U.S. patent application number 10/827846 was filed with the patent office on 2004-10-07 for fatty acid esters composition of a polyglycerine, a process for the preparation thereof, a process for the preparation of a highly-purified fatty acid esters composition of a polyglycerine, a highly-purified fatty acid esters composition of a polyglycerine, an additive for food-stuffs, a resin compo.
Invention is credited to Daito, Terumasa, Endo, Toshio.
Application Number | 20040197460 10/827846 |
Document ID | / |
Family ID | 27586100 |
Filed Date | 2004-10-07 |
United States Patent
Application |
20040197460 |
Kind Code |
A1 |
Endo, Toshio ; et
al. |
October 7, 2004 |
Fatty acid esters composition of a polyglycerine, a process for the
preparation thereof, a process for the preparation of a
highly-purified fatty acid esters composition of a polyglycerine, a
highly-purified fatty acid esters composition of a polyglycerine,
an additive for food-stuffs, a resin composition, and a composition
for cosmetic or detergents
Abstract
Disclosed are a fatty acid esters composition of a polyglycerine
containing more than 70% of a fatty acid monoester which is defined
by a specified analysis method, a process for the preparation
thereof, a process for the preparation of a highly-purified fatty
acid esters composition of a polyglycerine, and a highly-purified
fatty acid esters composition of a polyglycerine having an oxirane
oxygen concentration of below 100 ppm which is defined by a
specified analysis method. The fatty acid esters compositions of a
polyglycerine are useful as additives for a variety of food-stuffs,
additives for a variety of thermoplastic resins, and as additives
for a variety of cosmetics or detergents.
Inventors: |
Endo, Toshio; (Ohtake-shi,
JP) ; Daito, Terumasa; (Sakai-shi, JP) |
Correspondence
Address: |
MORGAN & FINNEGAN, L.L.P.
345 Park Avenue
New York
NY
10154-0053
US
|
Family ID: |
27586100 |
Appl. No.: |
10/827846 |
Filed: |
April 20, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10827846 |
Apr 20, 2004 |
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10621202 |
Jul 15, 2003 |
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Current U.S.
Class: |
426/611 |
Current CPC
Class: |
A61Q 5/02 20130101; A61K
8/39 20130101; C11D 1/667 20130101; Y10S 516/06 20130101; C07C
69/33 20130101; C07C 69/33 20130101; C07C 67/26 20130101; C11D 1/04
20130101; C08K 5/103 20130101; Y10S 516/02 20130101; Y10S 516/01
20130101; C07C 67/26 20130101; A61Q 19/10 20130101; A61Q 11/00
20130101; A61Q 19/00 20130101 |
Class at
Publication: |
426/611 |
International
Class: |
A61K 007/06 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 11, 1995 |
JP |
227073/1995 |
Aug 21, 1995 |
JP |
233180/1995 |
Dec 6, 1995 |
JP |
344844/1995 |
Jan 18, 1996 |
JP |
6743/1996 |
Jan 22, 1996 |
JP |
8372/1996 |
Jan 22, 1996 |
JP |
8373/1996 |
Jan 25, 1996 |
JP |
10831/1996 |
Jan 25, 1996 |
JP |
10832/1996 |
Feb 1, 1996 |
JP |
16343/1996 |
Feb 1, 1996 |
JP |
16344/1996 |
Feb 1, 1996 |
JP |
16345/1996 |
Feb 5, 1996 |
JP |
18579/1996 |
Feb 5, 1996 |
JP |
18580/1996 |
Feb 5, 1996 |
JP |
18581/1996 |
Feb 8, 1996 |
JP |
22642/1996 |
Feb 8, 1996 |
JP |
22643/1996 |
Feb 8, 1996 |
JP |
22644/1996 |
Feb 8, 1996 |
JP |
22645/1996 |
Claims
1-54. (canceled)
55. A composition for tooth paste which comprises an abrasive, a
caking material, a wetting agent, and a fatty acid esters
composition of a polyglycerine or a highly-purified fatty acid
esters composition of a polyglycerine, wherein said fatty acid
esters composition of a polyglycerine contains more than 70% of a
fatty acid monoester represented by general formula (1) described
below: RCO--(OCH.sub.2CH(OH)CH.sub.2).sub.n--OH (1) wherein R is an
alkyl group, an alkenyl group, or a hydroxyl group-substituted
alkyl group which has a carbon number ranging from 6 to 21, and n
is an integer of at least 4 based on a peak area ratio detected
using an ultraviolet ray absorption detector in a high performance
liquid chromatographic analysis method; and said highly-purified
fatty acid esters composition of a polyglycerine has an oxirane
oxygen concentration of below 100 ppm, wherein said oxirane oxygen
concentration is defined by the titration method defined in Cd.
9-57 of Journal of American Oil Chemists' Society, or has a ratio
of below 0.01%, wherein said ratio is a peak area value of a
chemical shift between 2.7 ppm and 2.8 ppm assigned by methylene
proton derived from an oxirane group with respect to a peak area
value of a chemical shift between 3.4 ppm and 4.4 ppm assigned by
methylene proton and methine proton derived from a polyglycerine
with a proton NMR.
56. A composition for tooth paste as set forth in claim 55, wherein
said abrasive is at least one selected from the group consisting of
calcium secondary phosphate (dihydrate, anhydride), calcium
carbonate, silicates, and insoluble sodium metaphosphates.
57. A composition for tooth paste as set forth in claim 55, wherein
said caking material is at least one selected from the group
consisting of sodium carboxymethyl cellulose, sodium alginate,
bentonite, and silicate anhydride.
58. A composition for tooth paste as set forth in claim 55, wherein
said wetting agent is at least one selected from the group
consisting of glycerine, sorbitoi, propyleneglycol, sodium
pyrrolidone-carboxylate, and polyethyleneglycol, etc.
59. A cleaning agent composition which comprises (a) a
polycarboxylic acid ester of a monoglyceride or a salt thereof
represented by the general formula (3)
R.sup.1--COO--CH.sub.2--CHOZ.sup.1-CH.sub.2OZ.sup.2 (3) wherein R1
is an alkyl or alkenyl group having a carbon number ranging from 7
to 17, either Z1 or Z2is Z2 is a residual group of a polycarboxylic
acid or salt thereof, and another hydrogen atom or a residual group
of a polycarboxylic acid or a salt thereof, and (b) a fatty acid
esters composition of a polyglycerine or a highly-purified fatty
acid esters composition of a polyglycerine, (c) organic or
inorganic builders, (d) fluidity improvers, and additionally (e)
thickening agents, (f) perfumes, (g) coloring agents, (h)
sterilizers, (i) enzymes and (j) anti-inflammatory agents; wherein
said fatty acid esters composition of a polyglycerine contains more
than 70% of a fatty acid monoester represented by general formula
(1) described below: RCO--(OCH.sub.2CH(OH)CH.sub.2).sub.n--OH (1)
wherein R is an alkyl group an alkenyl group, or a hydroxyl
group-substituted alkyl group which has a carbon number ranging
from 6 to 21 and n is an integer of at least 4 based on a peak area
ratio detected using an ultraviolet ray absorption detector in a
high performance liquid chromatographic analysis method; and said
highly-purified fatty acid esters composition of a polyglycerine
has an oxirane oxygen concentration of below 100 ppm, wherein said
oxirane oxygen concentration is defined by the titration method
defined in Cd. 9-57 of Journal of American Oil Chemists' Society or
has a ratio of below 0.01% wherein said ratio is a peak area value
of a chemical shift between 2.7 ppm and 2.8 ppm assigned by
methylene proton derived from an oxirane group with respect to a
peak area value of a chemical shift between 3.4 ppm and 4.4 ppm
assigned by methylene proton and methine proton derived from a
polyglycerine with a proton NMR.
60. A cleaning agent composition as set forth in claim 59, wherein
said polycarboxylic acid is at least one selected from the group
consisting of citric acid, succinic acid, maleic acid, malic acid,
glutaric acid, adipic acid, tartaric acid, and diacetyl tartaric
acid.
61. A cleaning agent composition as set forth in claim 59, wherein
said organic or inorganic builders are at least one selected from
the group consisting of sodium pyrophosphate, sodium
tripolyphosphate, zeolite, sodium citrate, sodium malate,
nitrilotrisodium acetate, and a sodium polyacrylate, sodium
carbonate, sodium sulphate, sodium chloride, magnesium sulphate,
and calcium chloride.
62-64. (canceled)
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a fatty acid esters
composition of a polyglycerine containing more than 70% of a fatty
acid monoester and a process for the preparation thereof.
[0002] Furthermore, the present invention relates to a
highly-purified fatty acid esters composition of a polyglycerine
and a process for the preparation thereof.
[0003] Still further, the present invention relates to the use of
the fatty acid esters compositions of a polyglycerine for an
additive for food-stuffs.
[0004] In addition, the present invention relates to a resin
composition containing the fatty acid esters compositions of a
polyglycerine.
[0005] Besides, the present invention relates to compositions for
cosmetics or detergents containing the fatty acid esters
compositions of a polyglycerine.
[0006] In more detail, tile present invention relates to a fatty
acid esters composition of a polyglycerine having an excellent
emulsifying ability. The fatty acid esters compositions of a
polyglycerine are useful as an additive for food-stuffs, an
additive for thermoplastic resins, and an additive for cosmetics or
detergents, etc.
BACKGROUND OF THE INVENTION
[0007] In recent, fatty acid esters of a polyglycerine are
permitted as an additive such as an emulsifier for food-stuffs, and
demands in a market are getting increased. The fatty acid esters
composition of a polyglycerine have been usually employed in a
variety of fields, particularly such as foods, as an emulsifier or
an agent for adjusting a viscosity because esters having a wide
range of HLB values can be obtained by the combination of
polyglycerines having various molecular weight with fatty acids
having various chain length which are starting materials, and it
exhibits a higher stability in an acidic range.
[0008] As processes for preparing the fatty acid esters composition
of a polyglycerine, there are exemplified: (1) an esterification
reaction of a polyglycerine with a fatty acid, (2) a
transesterification reaction of a polyglycerine with a fatty acid
ester, (3) a transesterification reaction of a polyglycerine with
an oil and fatty acid, (4) an addition polymerization reaction of
glycidol to a monoglyceride of a fatty acid, and (5) an addition
polymerization reaction of glycidol to a fatty acid, etc. Of the
above-described reactions, the processes (2) and (3) are
problematic in the reactivity and the processes have many
limitations in quality and purity of the fatty acid ester of a
polyglycerine.
[0009] The process (1) is described in JAOCS (Journal of American
Oil Chemists' Society), Vol. 58, page 878 (1981), in which there is
carried out the esterification reaction of a polyglycerine with a
fatty acid in the presence of alkali catalysts to obtain a fatty
acid ester of the polyglycerine.
[0010] Furthermore, Japanese Patent Unexamined Publication (Kokai)
No. 41007/1994 discloses similar processes.
[0011] The process (5) is described in Japanese Patent Unexamined
Publication (Kokai) No. 65705/1976, in which there is prepared a
fatty acid monoester of glycerine. However, the Publication states
that there is obtained a carboxylic acid-1-monoglyceride having the
polymerization degree of glycerine of 1 with a high percentage in
the presence of an inert solvent, that is, it corresponds to a
compound having n of average 1 in the above-described chemical
formula [1]. Notwithstanding, there is not mentioned a fatty acid
esters composition of a polyglycerine at all in the
Publication.
[0012] As processes in which the addition polymerization reaction
of glycidol is employed, there are exemplified the addition
polymerization reaction (Japanese Patent Examined Publication
(Kokoku) No. 55254/1989, Japanese Patent Examined Publication
(Kokoku) No. 11532/1992, Japanese Patent Examined Publication
(Kokoku) No. 1291/1993 of glycidol to glycerine to obtain a
polyglycerine employed in the processes (1) to (3), the preparation
of a polyglycerine [Japanese Patent Examined Publication (Kokoku)
No. 69621/1992] by a hydrolysis reaction after the addition
polymerization reaction of glycidol to a fatty acid, and the
preparation of polyglycerine monoalkylether or the preparation of
polyglycerine monoalkylthioether [U.S. Pat. Nos. 3,821,372,
3,966,398, and 4,087,466], etc.
[0013] However, in the preparation process of a polyglycerine by a
hydrolysis reaction after the addition polymerization reaction of
glycidol to a fatty acid described in Japanese Patent Examined
Publication (Kokoku) No. 69621/1992, low fatty acids (a carbon
number of 2 to 6) are employed as fatty acids to prepare
polyglycerines, and a fatty acid ester of a polyglycerine is not
mentioned at all.
[0014] Heretofore, a fatty acid monoester of a polyglycerine has
been prepared by the above-described process (1). In the process,
it is pointed out that a polyglycerine having reactive hydroxyl
groups of 4 to 10 on an average is employed as a starting
polyglycerine, as a result, a resulting product contains an
unreacted polyglycerine, poly-substituted fatty acid esters such as
diester, triester, and tetraester, etc. other than the desired
fatty acid monoester of a polyglycerine [N. Garti, et al, Journal
of American Oil Chemists' Society, 59, 317-319 (1982)].
[0015] Furthermore, even in the process (4) in which glycidol is
addition polymerized to a fatty acid monoglyceride, a purity of a
reaction product remarkably depends upon the starting fatty acid
monoglyceride [c.f. U.S. Pat. No. 4,515,775]. Particularly, in the
case when there is employed a fatty acid monoglyceride obtained by
the reaction of glycerine with a fatty acid as a starting material,
the starting material contains unreacted glycerine as well as in
the above-described process (1), resulting in that a fatty acid
monoester of a polyglycerine obtained by the addition
polymerization of glycidol contains only approximately 40% of the
fatty acid monoester, and the residue of approximately 60% is
composed of unreacted glycerine and poly-substituted fatty acid
esters [Shigeru Tsuda, Monoglyceride, page 67(1985), Maki Book
Store].
[0016] As described above, there remain a large amount of unreacted
polyglycerine and poly-substituted fatty acid esters in the fatty
acid monoester of a polyglycerine employed until now. In the case
when such the fatty acid monoester is employed as surfactants or
emulsion stabilizers in food industries, it results in decrease of
surface tension, decrease of dispersibility, decrease of foaming
ability, and decrease of stability in emulsifying.
[0017] As a process for removing the unreacted polyglycerine,
Japanese Patent Unexamined Publication (Kokai) No. 23837/1988
discloses a process in which the unreacted polyglycerine is removed
by a liquid separation process using a mixed solvent composed of at
least one of water-soluble organic solvents or water and at least
one of water-insoluble organic solvents.
[0018] Furthermore, Japanese Patent Unexamined Publication (Kokai)
No. 81252/1991 discloses a process that the unreacted polyglycerine
is removed by an adsorption method in which a solution of a
reaction product in esterification is brought into contact with an
alkyl-silylated silicagel.
[0019] Still further, Japanese Patent Unexamined Publication
(Kokai) No. 41007/1994 discloses an extracting process in which the
unreacted polyglycerine is removed by employing a water-soluble
organic solvent such as n-butyl alcohol, n-propanol, or dioxane,
etc. together with water or an aqueous solution containing a
salting agent such as lithium, sodium, potassium or ammonium salts
of an organic acid or an inorganic acid such as sulfuric acid or
phosphoric acid.
[0020] And also, Japanese Patent Unexamined Publication (Kokai) No.
228052/1994 discloses an extracting process in which the unreacted
polyglycerine is removed by employing methylethylketone together
with water.
[0021] However, the process in Japanese Patent Unexamined
Publication (Kokai) No. 23837/1988 includes a problem in uses for
food-stuff from a viewpoint of safety because of aromatic
hydrocarbons such as benzene and toluene which are described as
examples of the water-insoluble organic solvents. Furthermore, in
the process, the reaction molar ratio of a fatty acid to a
polyglycerine is limited within 1, and there is not described the
effectiveness in the reaction molar ratio exceeding 1.
[0022] Still further, in the case of a toluene/methanol system, it
is observed that a large amount of a fatty acid ester of
polyglycerine having a high HLB value moves to methanol phase
containing water even in the reaction ratio below 1 and, further,
unreacted polyglycerine cannot be sufficiently removed, resulting
in that there are problems in industrial preparation.
[0023] In addition, the separation process disclosed in the Kokai
No. 81252/1991 includes disadvantages that operation costs are
expensive and operations are troublesome.
[0024] Besides, even though according to the prior arts including
the processes disclosed in the Kokai No. 41007/1994 and
228052/1994, although the unreacted polyglycerine can be removed,
poly-substituted esters of polyglycerine cannot be removed.
[0025] As described hereinabove, in the case when there is prepared
a fatty acid esters composition of a polyglycerine according to the
above-described processes (4) and (5) in which glycidol is
employed, preparation of polyglycerine can be prevented. However,
there is a problem that a small amount of unreacted glycidol
remains in the fatty acid esters composition of a
polyglycerine.
[0026] Even a small amount, unreacted residual glycidol itself does
not exhibit emulsifying ability, and unpreferably causes a
remarkable decrease of surface tension, dispersibility, foaming
ability, and stability in emulsifying in products including the
fatty acid esters composition of a polyglycerine.
[0027] In order to remove a small amount of unreacted glycidol from
the composition, there requires molecular distillation which is not
economical and not preferred from a viewpoint of industrial
applications. It is to be noted that glycidol is another name of an
epoxy alcohol.
[0028] In view of the above-described background, there has been
expected a fatty acid esters composition of a polyglycerine
containing high contents of a fatty acid monoester which exhibits
an improved surface tension, dispersibility, foaming ability, and
stability in emulsifying during uses as an emulsifying stabilizer
in the fields of surface active agents, food-stuffs, cosmetics, and
detergents.
[0029] Furthermore, the fatty acid esters composition of a
polyglycerine containing high contents of a fatty acid monoester in
the present invention effectively acts as a plasticizer, an
improver of a wetting ability for hydrophobic resins, an improver
of a printing property, an anti-static agent, a releasing agent. or
an anti-clouding agent, etc. for a variety of resins which include
a polyvinyl chloride resin, a styrene-based resin, a
methylmethacrylate-based resin, and a polyacetal resin.
[0030] For example, a polyvinyl chloride resin has been widely
employed as a wrapping film or a bottle for food-stuffs, cosmetics,
detergents, and other miscellaneous goods, materials for printing
such as a calendar and a poster because of its excellent rigidity,
transparency, moldability, printing ability.
[0031] In particular, uniaxially or biaxially oriented films are
employed as a shrinkable wrapping and a shrinkable label because of
the excellence in rigidity, a gloss, dimensional stability in
storage, and a shrinkable property.
[0032] However, similarly to other resins, a polyvinyl chloride
resin has a disadvantage that static electricity is very readily
charged, resulting in that it gives an unpleasant feeling to human
bodies and it readily catches dusts in air.
[0033] Accordingly, there is often carried out a process for
preventing static electricity.
[0034] The process for preventing static electricity includes
mixing an anti-static agent together with a thermal stabilizer, a
reinforcing material, and a slipping agent, etc. in the case of
molding a polyvinyl chloride resin, or coating an anti-static agent
after molding.
[0035] As the anti-static agent for vinyl chloride resins, there
have been conventionally employed a fatty acid ester of glycerine,
a fatty acid ester of sorbitan, a non-ionic surface active agent of
a higher alcohol, and an anionic surface active agent such as a
sodium alkylbenzene sulfonate and a sodium alkylsulfonate. However,
mixing of the anti-static agents cannot sufficiently give an effect
for preventing static electricity to films having thin thickness
such as thermally shrinkable oriented films, and transparency of
the films is occasionally decreased.
[0036] On the other hand, coating of the anti-static agents after
molding has disadvantages that an effect for preventing static
electricity is often decreased by rubbing or evaporation with a
long lapse of time, and further films themselves readily cause
blocking.
[0037] In JP Kokai No. 1861/1994, although there is disclosed the
use of a fatty acid esters composition of a polyglycerine for an
anti-static agent, the composition contains a large amount of a
residual polyglycerine and poly-substituted esters, unpreferably
resulting in that an effect for emulsifying and preventing static
electricity is remarkably small, whereby, a large amount of the
composition has to be employed.
[0038] Meanwhile, a styrene-based resin is excellent in
transparency, non-toxic, non-deodorant, and water-resistant.
[0039] However, there has been a problem that it is brittle in
spite of exhibiting strength and rigidness. Recently, the
brittleness in a styrene-based resin has been improved, whereby,
the styrene-based resin has been used as films for food-stuffs.
[0040] Particularly, the styrene-based resin films have a variety
of problems in the use as films for wrapping food-stuffs because of
non-affinity for water.
[0041] In the case when the styrene-based resin films are used for
wrapping food-stuffs and stored at low temperatures, moisture in
the food-stuffs such as vegetables or seat forms drops of water
over the films. There is a problem that the drops of water
adversely affect transparency of the films, unpreferably resulting
in that the food-stuffs in wrapping cannot be visually identified,
and it is not only visually unpreferred, but also it gives a bad
feeling.
[0042] In order to solve the problem, there has been thought out a
process for improving surface properties of the films.
[0043] As the process for improving surface properties of the
films, there are known processes that an anti-clouding agent is
coated on the films or mixed in preparing the films.
[0044] Although the coating process of the anti-clouding agent
provides an excellent anti-clouding effect for a short period after
coating, anti-clouding effect becomes decreased by rubbing with a
long time of lapse.
[0045] On the other hand, the mixing process of the anti-clouding
agent can provide the films with an excellent anti-clouding effect
for a long period after mixing.
[0046] As the anti-clouding agent for the styrene-based resin
films, there are known (1) fatty acid esters of glycerine (JP
Kokoku No. 4147/1963 and JP Kokoku No. 26532/1977), (2) fatty acid
esters of polyethyleneglycol (disclosed in JP Kokoku No.
21112/1964), and (3) fatty acid monoesters of polyglycerine (JP
Kokai No. 157558/1986), etc.
[0047] However, in the case when the fatty acid esters of glycerine
of (1) and the fatty acid esters of polyethyleneglycol of (2) are
employed as the anti-clouding agent for the styrene-based resin
films, a large amount of those must be employed in order to provide
an aimed anti-clouding effect, resulting in that mixing is
difficult.
[0048] In the case when the fatty acid monoesters of polyglycerine
of (3) is employed as the anti-clouding agent for the styrene-based
resin films, although an anti-clouding effect at ordinary
temperatures is excellent, an anti-clouding effect at low
temperatures is poor, and further miscibility and transparency are
poor, resulting in being not appropriate to wrapping for
food-stuffs at low temperatures.
[0049] It is to be noted that the fatty acid monoesters of
polyglycerine of the above-described (3) are prepared by the
esterification of polyglycerine with a fatty acid and the
purification by molecular distillation or solvent extraction, which
is different from a fatty acid esters composition of polyglycerine
in the present invention prepared by the addition polymerization
reaction of glycidol to a fatty acid.
[0050] Anti-clouding agent for the styrene-based resin films to be
employed for wrapping food-stuffs has to be excellent in a low
temperature property, a high temperature property, a recovery
property, and durability, etc. Particularly, it attaches importance
to an anti-clouding effect at a low temperature atmosphere for a
long time of period.
[0051] In order to make durability of an anti-clouding effect at
low temperatures exhibit, an anti-clouding agent to be mixed must
exhibit moderate miscibility with the styrene-based resins at low
temperatures.
[0052] An anti-clouding agent exhibiting a poor miscibility readily
moves to the surface of the film, and it oozes out of the film,
unpreferably resulting in causing blocking of the films in spite of
the presence of the anti-clouding effect.
[0053] On the other hand, an anti-clouding agent exhibiting an
excessive miscibility does not readily move to the surface of the
film, unpreferably resulting in not exhibiting the anti-clouding
effect. Accordingly, an anti-clouding agent must exhibit a
well-balanced miscibility with resins.
[0054] As a conventional anti-clouding agent for the styrene-based
resins has an excessive miscibility with the resins, it is involved
inside the resins, resulting in that there has been required a
large amount ranging from 7 to 8% by weight.
[0055] The problems can be solved by the use of the fatty acid
esters composition of a polyglycerine containing high contents of a
fatty acid monoester in the present invention.
[0056] Furthermore, although an article molded from the
styrene-based resin is particularly excellent in transparency,
there is a problem that it readily accumulates static electricity
induced by friction, and it does not readily disappear,
unpreferably resulting in that dust in air is drawn.
[0057] In order to prevent the accumulation of static electricity,
surface active agents have been mixed in the resin, or
silicone-based compounds have been coated on the surface of the
molded article.
[0058] However, there are problems that a small amount of the
surface active agents do not sufficiently provide an anti-static
effect and, unpreferably, a large amount of the surface active
agents adversely affect transparency of the resin, and coating
process of silicone-based compounds onto the surface of the molded
article results in increasing costs of production.
[0059] The problems can be solved by the use of the fatty acid
esters composition of a polyglycerine containing high contents of a
fatty acid monoester in the present invention.
[0060] In the meantime, a methylmethacrylate-based resin is widely
employed in a variety of fields which supply parts for automobiles
such as a cover for a variety of meters, optical parts such as
photo-magnetic disks and lenses, and a cover for an illuminating
lamp, etc., because of its excellence in transparency,
weatherability, and mechanical properties, etc.
[0061] The molded articles are usually prepared by an injection
molding and a compression molding. Particularly, the optical parts
such as photo-magnetic disks and lenses are molded by compression
molding with a precise mold, and a molded article is exceedingly
tightly in contact with the mold, whereby, release of the molded
article from the mold becomes insufficient, resulting in making a
productivity lower.
[0062] Therefore, it is proposed that a variety of releasing agents
are employed in molding a methylmethacrylate-based resin.
[0063] For example, JP Kokai No. 73754/1086 discloses a
methylmethacrylate resin in which there are mixed higher fatty acid
esters, polyvalent alcohols, higher alcohols, higher fatty acids,
amides of higher fatty acids, and metal salts of higher fatty acids
as releasing agents.
[0064] However, a releasing property is insufficient, and the
releasing agents move to the surface of molded articles,
unpreferably resulting in that the surface of the mold becomes
dirty, and commercial values remarkably decrease by coloration of
the molded article.
[0065] The additive which is the fatty acid esters composition of a
polyglycerine of the present invention can provide a
methylmethacrylate-based resin having an excellent releasing
property in spite of a small amount of use.
[0066] In the meantime, a polyacetal resin which is one of
engineering plastics has been exceedingly widely employed in a
variety of fields which supply parts for automobiles or bone
electric appliances, etc., because of its excellence in physical
properties such as mechanical properties and electric properties,
moldability, and chemical properties such as chemical resistance
and thermal stability.
[0067] However, as a polyacetal resin unprocessed is poor in a
printing property by a variety of inks, it has been used after a
treatment by corona discharge.
[0068] However, in the case when it is molded, for example, as a
shutter for a disk or a magnetic tape cartridge, as the shutter
itself is thin in thickness, bending or deformation is unpreferably
caused by a long time treatment or high-voltage treatment in corona
discharge, resulting in incapability of practically using.
[0069] In view of the situations, there has been expected a
material on which inks can be printed even by a short time
treatment or low-voltage treatment in corona discharge.
[0070] Although a process of a primer coating is known as a process
for improving a printing property, the primer process requires
solvents, unpreferably resulting in being problematic from
viewpoint of environmental pollution.
[0071] In JP Kokai No. 195155/1985, there is disclosed a process in
which a polyacetal resin is mixed with 0.01-3 parts by weight of
hindered amines together with 0.01-4 parts by weight of a specific
benztriazole-based ultraviolet absorbent in order to improve
weatherability.
[0072] However, a printing property cannot be sufficiently improved
by the process, and further, durability of the printing property is
almost not improved.
[0073] Furthermore, in JP Kokai No. 128740/1982, there is disclosed
a process in which a polyacetal resin is mixed with 0.01-5 parts by
weight of a fatty acid esters composition of a polyglycerine and/or
polyalkyleneglycol-alkylether.
[0074] However, even a printing property cannot be sufficiently
improved by the process because the fatty acid esters composition
of a polyglycerine is not prepared by the above-described glycidol
process (5).
[0075] Still further, in JP Kokoku No. 14709/1994, there is
disclosed a process in which a polyacetal resin is mixed with
0.01-3% by weight of a hindered amine compound together with an
effective amount (as an anti-static agent) a fatty acid ester of a
polyvalent alcohol.
[0076] However, even a printing property cannot be sufficiently
improved by the process, and further, durability of the printing
property is almost not improved.
[0077] In addition, in JP Kokai No. 41583/1986, there is disclosed
a process in which a polyacetal resin having the thickness of less
than 200 microns in skin layer.
[0078] However, even a printing property cannot also be
satisfactorily improved by the process, and further, durability of
the printing property is not occasionally improved.
[0079] The problems in the polyacetal resin can be solved by the
use of the fatty acid esters composition of a polyglycerine
containing high contents of a fatty acid monoester in the present
invention.
[0080] In addition, there is a problem that polyacetal resins or a
article molded therefrom do not exhibit a sufficient wetting
property to water and a liquid containing water such as
water-soluble inks, and blood, etc.
[0081] Wide applications of the polyacetal resins demand a variety
of special characteristics as materials. One of the special
characteristics is an improved wetting property to inks, etc.
[0082] Wetting property is prescribed in JIS K6768 in which it is
defined as a condition that liquid coated on the surface of a solid
is not repelled.
[0083] As a method for measuring the wetting property, there is
known a method measuring contact angle, and small contact angle
represents easiness of wetting.
[0084] Wetting property is required in a variety of molded
articles. For example, in an ink jet nozzle in a printer for a
personal computer, wetting property of the nozzle edge surface is
required in order to constantly control the direction jetting ink,
resulting in improving quality of printing.
[0085] Furthermore, in a carrier for a biosensor, improved wetting
property of a sample liquid is required in order to elevate a
sensitivity of measurement.
[0086] As methods for improving wetting property, there have been
put into practice plasma treatments, chemical treatments, and
surface coating by paints. However, the methods include a
disadvantage of inferior efficiency in production because a
highly-controlled technology is required in order to guarantee a
constant quality in surface treatment.
[0087] As methods for improving wetting property in a polyacetal
resin, although JP-A-257499/1994 discloses a method in which there
is mixed an additive such as polyethylene glycol for improving
wetting property, the method is insufficient.
[0088] Although JP-A-293856/1994 discloses a method in which there
is mixed a fatty acid esters composition of a polyglycerine for
improving wetting property, a large amount of the composition must
be employed in the method because a large amount of unreacted
polyglycerine remains in the composition.
[0089] Furthermore, a polyalkyleneglycol or a fatty acid esters
composition of a polyvalent alcohol is also insufficient from
viewpoint of improving wetting property, as shown in Comparative
Examples of the present invention which are described later.
[0090] Still further, a large amount of a compound improving
wetting property occasionally tends to adversely affect to
mechanical properties and moldability.
[0091] In addition, a polyacetal resin is used as a resin
composition by mixing a hindered phenol-based compound, inorganic
fibers having short length and other additives, in order to prepare
small or precise parts having thin thickness for precision
instruments such as a watch, a printer, and a desk top electronic
calculator, etc., because of being excellent in mechanical
properties and dimensional stability.
[0092] As the inorganic fibers having short length, there are
exemplified fiberglass and fibrous potassium titanate.
[0093] However, the fiberglass has the average fiber diameter
ranging from 6 to 13 microns and the average fiber length ranging
from 20 to 3000 microns. Accordingly, diameter and length are too
thick and too long, resulting in being incapable of employing, for
example, as gears for watch having the thickness of 50 or 60
microns.
[0094] On the other hand, the fibrous potassium titanate has the
average fiber diameter ranging from 0.2 to 2 microns and the
average fiber length ranging from 10 to 100 microns.
[0095] Accordingly, although the fibrous potassium titanate can be
employed as the gears, it often causes a problem of gate plugging
in a molding die.
[0096] Recently, micro-fibrous titanium oxide has been employed as
substitutes for fiberglass and fibrous potassium titanate.
[0097] For example, JP-A-113465/1989 teaches that micro fibrous
titanium oxide is employed to prepare a resin composition with
which there can be formed molded articles having excellent strength
and gloss of the surface.
[0098] However, the polyacetal resin composition in which
micro-fibrous titanium oxide is mixed has a drawback that releasing
property from a molding die is poor.
[0099] The poorness results in a poor profile property of the
surface in a molded article and a stain in a molding die.
[0100] Particularly, as the molding die for the precise parts is
small, cleaning of the stain requires a long maintenance time,
resulting in falling productivity.
[0101] The problems can be solved by the use of only a small amount
of the fatty acid esters composition of a polyglycerine having high
contents of a fatty acid monoester in the present invention.
[0102] In the meantime, a fatty acid esters composition of a
polyglycerine has been widely used as an additives for cosmetics,
toiletries, and detergents.
[0103] As a specific example of cosmetics, a water-in-oil
type-emulsified composition for cosmetics is used as an agent for
keeping moisture on human skin because outer layer is composed of
oil components, resulting in being capable of preventing dryness in
the human skin.
[0104] It is to be noted that a water-in-oil type-emulsified
composition for cosmetics is prepared by mixing a water-soluble
high viscous compound such as glycerine, oils and/or waxes, water,
and an emulsifier, etc.
[0105] As it does not have an affinity to water or sweat,
properties are not diminished by those, preferably resulting in
that the properties are durable for a long time of period.
[0106] Furthermore, an affinity to an oily makeup is high,
resulting in that it can be preferably employed as an excellent
cleansing for the purpose of removing the oily makeup.
[0107] However, there are disadvantages that a water-in-oil
type-emulsified composition for cosmetics unpreferably gives an
oily or sticky feel when it is applied on human skin because outer
layer is composed of oil components.
[0108] In order to solve the disadvantages, a water-in-oil
type-emulsified composition for cosmetics containing a large amount
of water has been numerously investigated, for example, as
described in JP-B-26366/1985, JP-A-302935/1988, and
JP-A-160709/1994.
[0109] However, the water-in-oil type-emulsified composition for
cosmetics containing a large amount of water is not suitable for
the purpose of removing the oily makeup because of high content of
water. Furthermore, the water-in-oil type-emulsified composition
for cosmetics containing a larger amount of water is not thinly
extended.
[0110] In the JP-A-160709/1994, it is described that a large amount
of silicone oils which are slippery are employed as oil components
for outer layer formed by a water-in-oil type-emulsified
composition, and further viscosity of the composition is controlled
within 20000 cps, whereby, thinness and an oily or sticky feel is
improved.
[0111] Still further, sorbitan fatty acid esters composition or
glycerine fatty acid esters composition which is a lipophilic
emulsifier has been employed in the presence or absence of metal
soaps of higher fatty acids for preparing the water-in-oil
type-emulsified composition for cosmetics. In addition, there are
recently employed organic compound-modified clays composition or
mixed emulsifiers containing alpha-monoglyceryl ether.
[0112] However, in the case when the composition or emulsifiers are
employed with a large amount of oils, viscosity thereof exceedingly
lowers, resulting in that there cannot be readily obtained a
water-in-oil type-emulsified composition for cosmetics having an
excellent feel in use and excellent stability for a long time of
period.
[0113] Besides, there is described a water-in-oil type-emulsified
composition for cosmetics having an excellent stability for a long
time of period in JP-A-128135/1994 in which a fatty acid esters
composition of a polyglycerine is employed. However, the
composition is prepared by an esterification reaction of a
polyglycerine with a fatty acid which is the preparation process
No. (1) described hereinabove.
[0114] As described hereinabove, the composition prepared by an
esterification reaction of a polyglycerine with a fatty acid has
problems.
[0115] The problems in the water-in-oil type-emulsified composition
for cosmetics can be solved by the use of the fatty acid esters
composition of a polyglycerine containing high contents of a fatty
acid monoester in the present invention.
[0116] As a specific example of cosmetics, a transparent liquid
composition for cosmetics has been used as an agent for keeping
moisture on human skin, cosmetics for bathroom, cosmetics for
cleansing, cosmetics for a massage, cosmetics for a facial pack,
cosmetics for hairs, and a base material for medicines, etc.
[0117] It is to be noted that a transparent liquid composition for
cosmetics is prepared by mixing an non-ionic surface active agent,
at least one of water-soluble compound having at least two hydroxyl
groups, oils, and water, etc.
[0118] The transparent liquid composition for cosmetics usually
contains oily components and plasticizers or emulsifiers which are
usually non-ionic surface active agents.
[0119] It is known that the non-ionic surface active agents are
relatively safe for human skin. Recently, the use of a fatty acid
esters composition of a polyglycerine is proposed similarly to a
fatty acid esters composition of sucrose instead of the non-ionic
surface active agents from viewpoint of irritating skin.
[0120] However, a conventional fatty acid esters composition of
polyglycerine is poorer in a solubilizing and emulsifying property
compared to non-ionic surface active agents having polyoxyethylene
chains. Particularly, it is difficult to solubilize a large amount
of oily components in water which is a base material, and as a
composition for cosmetics is highly viscous, there has been a
disadvantage that a feel in use is not heavy.
[0121] The problems in the transparent liquid composition for
cosmetics can be solved by the use of the fatty acid esters
composition of a polyglycerine containing high contents of a fatty
acid monoester in the present invention.
[0122] As a specific example of cosmetics, a gel-like emulsified
composition for cosmetics has been used as cosmetics for cleansing
and cosmetics for a massage, etc.
[0123] It is to be noted that a gel-like emulsified composition for
cosmetics is usually prepared by mixing glycerine, oils, a
polyvalent alcohol except glycerine, and an emulsifier, etc.
[0124] It has been conventionally difficult to prepare a gel-like
emulsified composition for cosmetics having a stability because of
characteristic properties thereof. In order to prepare a gel-like
emulsified composition having a stability, it has been uncommonly
tried to make the composition itself high viscous at the sacrifice
of a special characteristic and a feel in use.
[0125] Furthermore, although a gel-like emulsified composition for
cosmetics has been numerously investigated with development of a
hydrophilic fatty acid esters composition of a polyglycerine, there
is a problem that a conventional fatty acid esters composition of a
polyglycerine exhibits an unpleasant feel in use which is a poor
spreadability because of its sticky property.
[0126] As a method for solving the problem, for example,
JP-A-224507/1992 discloses an instance that there are employed a
fatty acid esters composition of polyoxyethylenesorbit and/or a
fatty acid esters composition of polyoxyethyleneglycerine together
with a fatty acid esters composition of diglycerine instead of a
hydrophilic fatty acid esters composition of a polyglycerine, and
JP-A-4911/1993 and JP-A-4912/1993 disclose instances that there are
employed natural surface active agents.
[0127] However, the compositions are insufficient from a viewpoint
of safety, there has been expected the development of a fatty acid
esters composition of a polyglycerine having excellent safety, an
excellent feel in use, and a special characteristic for a gel-like
emulsified composition.
[0128] The expectation can be attained by the fatty acid esters
composition of a polyglycerine containing high contents of a fatty
acid monoester in the present invention.
[0129] The problems in the gel-like emulsified composition for
cosmetics can be solved by the use of the fatty acid esters
composition of a polyglycerine containing high contents of a fatty
acid monoester in the present invention.
[0130] As a specific example of cosmetics, a composition for tooth
paste contains a foaming agent in order to give a refreshing feel,
a dispersing and emulsifying function, and a foaming function, and
a surface active agent is employed for giving functions.
[0131] It is to be noted that a composition for tooth paste is
usually prepared by mixing an abrasive such as secondary hydrated
calcium phosphate, water-soluble compounds having high molecular
weight such as a carboxymethyl cellulose, a wetting agent such as
glycerine, and medicinal components, etc.
[0132] The surface active agent to be employed for giving functions
is an essential component. The refreshing feel in teeth-brushing is
enhanced by a decrease of surface tension owing to mixing it.
Furthermore, the effect is enhanced by accelerating dispersion and
permeation of the medicinal components owing to mixing it. Still
further, the surface active agent sensuously gives stability by
foaming in use.
[0133] As the composition for tooth paste is used in mouth, not
only the surface active agent to be employed must possess excellent
ability for decreasing surface tension and excellent ability for
foaming, but also taste and odor must be satisfactorily
acceptable.
[0134] Therefore, there have been conventionally employed anion
surface active agents not having taste and odor such as a sodium
alkylsulphate, sodium acylsalkosinate, alpha-olefin sulphonate, and
a monoglyceride composed of sodium sulphate and a coconut oil,
etc.
[0135] However, the anionic surface active agents have
disadvantages that mucous membrane in mouth is Irritated, tastes of
foods are changed after using, and an effect by enzymes to be mixed
as medicinal components in tooth paste is decreased. Furthermore,
safeness has recently become problematic.
[0136] In view of situations, anionic surface active agents have
advantages of milder irritation to skin and mucous membrane
compared to anionic surface active agents. Furthermore, the anionic
surface active agents have an advantage of not decreasing the
effect by enzymes, and a fatty acid esters composition of sucrose
and a fatty acid esters composition of a polyglycerine are narrowly
approved as surface active agents for food processing.
[0137] Therefore, a fatty acid esters composition of sucrose and a
fatty acid esters composition of a polyglycerine are proposed as
surface active agents for mixing in tooth paste.
[0138] However, a fatty acid esters composition of sucrose and a
conventional fatty acid esters composition of a polyglycerine have
disadvantages that those do not sufficiently foam in use, and an
effect as tooth paste and a feel in use are exceedingly poor. It is
only known that monolaurate of sucrose and monomyristate of sucrose
were mixed [G. L. Fosol and P. Rovesti, (International Symposium on
Sugar-ester) Maison de la Chimie Paris, Jun. 8, 1960].
[0139] The problems in the composition for tooth paste can be
solved by the use of the fatty acid esters composition of a
polyglycerine containing high contents of a fatty acid monoester in
the present invention.
[0140] As a specific example of cosmetics, a cleaning agent
composition is widely used in a variety of fields. Particularly, a
cleaning agent composition importantly acts in food industries.
[0141] In the food industries, it is used for cleaning foods
themselves, starting materials for foods processing, apparatuses
for foods processing, and containers such as bottles or cans.
[0142] In the food industries, safeness of a cleaning agent
composition is severely demanded because it possibly remains in
apparatuses, containers, and foods themselves to be cleaned,
resulting in that it is taken together with foods or beverages in
human body.
[0143] Particularly, as a cleaning agent composition for the food
industries is often used for foods themselves, there have been used
a fatty acid esters composition of sucrose and a fatty acid esters
composition of glycerine which are also additives for foods from
viewpoint of safeness (Journal of Food Sanitation, vol. 18, No. 3,
page 217).
[0144] Furthermore, JP-A-158090/1994 discloses that there is used a
mixture composed of a monoglyceride composition of a polycarboxylic
acid ester and a fatty acid esters composition of glycerine which
are ionic surface active agents as a cleaning agent composition.
However, the cleaning agent composition in the Journal and the
mixture in the JP are not sufficient in cleaning ability.
[0145] The problems in the cleaning agent composition can be solved
by the use of the fatty acid esters composition of a polyglycerine
containing high contents of a fatty acid monoester in the present
invention.
[0146] The cleaning agent composition of the present invention is
harmless for human body and strong in cleaning ability, and it can
be preferably used as a cleaning agent composition for foods,
starting materials for foods, apparatuses for foods processing, and
bottles, containers, and cans in food industries.
[0147] As a specific example of cosmetics, a foaming composition
for cleaning is widely used as a cleaning agent in cosmetic fields
and a detergent for a kitchen or bathroom.
[0148] For example, hair washing with a shampoo requires rinsing by
water or warmed water after washing. However, in the case when a
person cannot have a bath or cannot wash with water because of an
injury, or in a place being incapable of using water, it is
difficult to clean hair.
[0149] Therefore, there is proposed a wiping type cleaning agent
which does not require rinsing.
[0150] Specifically, there are exemplified an aerosol type
water-based cleaning composition in JP-B-47960/1982, a foaming hair
cleaning agent in JP-A-289023/1986, a foaming hair cleaning agent
for wiping a shampoo in JP-A-205011/1987, a dry hair cleaning
method and an agent therefor in JP-A-14711/1988, and an aerosol
type shampoo composition in JP-A-190813/1988, etc.
[0151] However, conventional compositions in which an
electrolyte-based surface active agent is employed are not
sufficient in stimulation to head skin and hair by only wiping, and
spray-type conventional compositions in which a
non-electrolyte-based surface active agent is employed are not
satisfied because cleaning agents are scattered beyond necessary
portions, and foam-type conventional compositions in which a
non-electrolyte-based surface active agent is employed are not
satisfied in cleaning ability and refreshing feeling because a
mixing amount of alcohols is limited in order to prepare a foam
type one.
[0152] Furthermore, JP-A-100435/1994 discloses that a
non-electrolyte-based surface active agent such as a fatty acid
esters composition of a polyglycerine is employed in combination
with a higher alcohol to prepare a foaming composition for cleaning
containing a large amount of the higher alcohol.
[0153] However, the conventional fatty acid esters composition of a
polyglycerine is not prepared by the glycidol process (5) as
described hereinabove. Accordingly, the content of a fatty acid
monoester is low in the composition, resulting in that the foaming
composition for cleaning does not satisfactorily exhibit sufficient
stability for a long time of period, a cleaning effect, and a
refreshing feel.
[0154] The problems in the foaming composition for cleaning can be
solved by the use of the fatty acid esters composition of a
polyglycerine containing high contents of a fatty acid monoester in
the present invention.
[0155] As a result of an intensive investigation by the present
inventors, the present invention has been completed.
SUMMARY OF THE INVENTION
[0156] It is an object of the present invention to provide a fatty
acid esters composition of a polyglycerine containing more than 70%
of a fatty acid monoester and a process for the preparation
thereof.
[0157] It is another object of the present invention to provide a
highly-purified fatty acid esters composition of a polyglycerine
and a process for the preparation thereof.
[0158] It is other object of the present invention to provide the
use of a fatty acid esters composition of a polyglycerine as an
additive for food-stuffs, thermoplastic resins, cosmetics, and
detergents.
[0159] A first aspect of the present invention relates to a fatty
acid esters composition of a polyglycerine containing more than 70%
of a fatty acid monoester represented by general formula [1`
described below;
RCO--(OCH.sub.2CH(OH)CH.sub.2).sub.n--OH [1]
[0160] wherein R is an alkyl group, an alkenyl group, or a hydroxyl
group-substituted alkyl group which have a carbon number ranging
from 6 to 21, and n is an integer of at least 4, based on a peak
area ratio detected using an ultraviolet ray absorption detector in
a high performance liquid chromatographic analysis method.
[0161] A second aspect of the present invention relates to a
process for the preparation of a fatty acid esters composition of a
polyglycerine which comprises the reaction of a fatty acid
represented by general formula [2] described below:
RCOOH [2]
[0162] wherein R is an alkyl group, an alkenyl group, or a hydroxyl
group-substituted alkyl group which have a carbon number ranging
from 6 to 21, with glycidol in the presence of a phosphoric
acid-based acidic catalyst.
[0163] A third aspect of the present invention relates to a process
for the preparation of a highly-purified fatty acid esters
composition of a polyglycerine which comprises the steps:
[0164] (a) allowing to react a fatty acid with glycidol to obtain a
fatty acid esters composition of a polyglycerine,
[0165] (b) removing water after adding water into said fatty acid
esters composition of a polyglycerine, and then heating.
[0166] A fourth aspect of the present invention relates to a
highly-purified fatty acid esters composition of a polyglycerine
having an oxirane oxygen concentration of below 100 ppm, said
oxirane oxygen concentration is defined by the titration method
defined in Cd. 9-57 of Journal of American Oil Chemists' Society,
or having a ratio of below 0.01%, said ratio is a peak area value
of a chemical shift between 2.7 ppm and 2.8 ppm assigned by
methylene proton derived from an oxirane group with respect to a
peak area value of a chemical shift between 3.4 ppm and 4.4 ppm
assigned by methylene proton and methine proton derived from a
polyglycerine with a proton NMR.
[0167] A fifth aspect of the present invention relates to the use
of a fatty acid esters composition of a polyglycerine in the first
aspect or a highly-purified fatty acid esters composition of a
polyglycerine in the fourth aspect for an additive for
food-stuffs.
[0168] A sixth aspect of the present invention relates to a resin
composition which comprises a fatty acid esters composition of a
polyglycerine in the first aspect or a highly-purified fatty acid
esters composition of a polyglycerine in the fourth aspect, and a
thermoplastic resin.
[0169] A seventh aspect of the present invention relates to a
water-in-oil type-emulsified composition for cosmetics which
comprises glycerine, oils and/or waxes, water, and a fatty acid
esters composition of a polyglycerine in the first aspect or a
highly-purified fatty acid esters composition of a polyglycerine in
the fourth aspect.
[0170] An eighth aspect of the present invention relates to a
transparent liquid composition for a cleansing which comprises at
least one of an non-ionic surface active agent, at least one of
water-soluble compound having at least two hydroxyl groups, oily
components, water, and a fatty acid esters composition of a
polyglycerine in the first aspect or a highly-purified fatty acid
esters composition of a polyglycerine in the fourth aspect, a
highly-purified fatty acid esters composition of a polyglycerine in
the fourth aspect or a highly-purified fatty acid esters
composition of a polyglycerine in the fourth aspect, and an agent
for spraying said mixture.
[0171] A ninth aspect of the present invention relates to 3
gel-like emulsified composition for cosmetics which comprises
glycerine, liquid oily components, a polyvalent alcohol except
glycerine, and a fatty acid esters composition of a polyglycerine
in the first aspect or a highly-purified fatty acid esters
composition of a polyglycerine in the fourth aspect.
[0172] A tenth aspect of the present invention relates to a
composition for tooth paste which comprises an abrasive, a caking
material, a wetting agent, and a fatty acid esters composition of a
polyglycerine in the first aspect or a highly-purified fatty acid
esters composition of a polyglycerine in the fourth aspect.
[0173] An eleventh aspect of the present invention relates to a
cleaning agent composition which comprises (a) a polycarboxylic
acid ester of a monoglyceride or a salt thereof represented by
general formula [3]
R1-COO--CH.sub.2--CHOZ1-CH.sub.2OZ2 [3]
[0174] wherein R1 is an alkyl or alkenyl group having a carbon
number ranging from 7 to 17, either Z1 or Z2 is a residual group of
a polycarboxylic acid or salt thereof, and another hydrogen atom or
a residual group of a polycarboxylic acid or salt thereof, (b) a
fatty acid esters composition of a polyglycerine as set forth in
claim 1 or a highly-purified fatty acid esters composition of a
polyglycerine as set forth in claim 14, (c) organic or inorganic
builders, (d) fluidity improvers, and additionally (e) thickening
agents, (f) perfumes, (g) coloring agents, (h) sterilizers, (i)
enzymes, and (i) anti-inflammatory agents.
[0175] A twelfth aspect of the present invention relates to a
foaming composition for cleaning which comprises a mixture composed
of at least one of a lower monovalent alcohol having a carbon
number ranging from 1 to 3, water, at least one of a higher alcohol
having a carbon number ranging from 12 to 22, and a fatty acid
esters composition of a polyglycerine in the first aspect or a
highly-purified fatty acid esters composition of a polyglycerine in
the fourth aspect.
BRIEF DESCRIPTION OF THE DRAWINGS
[0176] FIG. 1 is a chart obtained by a high performance liquid
chromatography analysis (HPLC) relating to a lauric acid esters
composition of a polyglycerine obtained in Example 1.
[0177] FIG. 2 is a chart obtained by HPLC relating to a lauric acid
esters composition of a polyglycerine obtained in Example 2.
[0178] FIG. 3 is a chart obtained by HPLC relating to a lauric acid
esters composition of a polyglycerine obtained in Example 3.
[0179] FIG. 4 is a chart obtained by HPLC relating to a lauric acid
esters composition of a polyglycerine obtained in Example 4.
[0180] FIG. 5 is a chart obtained by HPLC relating to a lauric acid
esters composition of a polyglycerine obtained in Example 5.
[0181] FIG. 6 is a chart obtained by HPLC relating to a lauric acid
esters composition of a polyglycerine obtained in Comparative
Example 1.
[0182] FIG. 7 is a chart obtained by HPLC relating to a lauric acid
esters composition of a polyglycerine obtained in Comparative
Example 2.
[0183] FIG. 8 is a chart obtained by HPLC relating to a lauric acid
esters composition of a polyglycerine obtained in Comparative
Example 3.
[0184] FIG. 9 is a chart obtained by HPLC relating to a lauric acid
esters composition of a polyglycerine obtained in Comparative
Example 4.
[0185] FIG. 10 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 5.
[0186] FIG. 11 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 6.
[0187] FIG. 12 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 7.
[0188] FIG. 13 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 8.
[0189] FIG. 14 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 9.
[0190] FIG. 15 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 10.
[0191] FIG. 16 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 11.
[0192] FIG. 17 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 12.
[0193] FIG. 18 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 13.
[0194] FIG. 19 is a chart obtained by HPLC relating to commercially
supplied fatty acid esters composition of a polyglycerine employed
in Comparative Example 14.
[0195] FIGS. 20 and 21 (enlarged chart of 20) are a proton NMR
chart relating to the product obtained in Example 6 (first
step).
[0196] FIGS. 22 and 23 are a proton NMR chart relating to the
product obtained in Example 6 (second step).
[0197] FIG. 24 is a chart obtained by HPLC relating to PGMLEC
obtained in Example 28.
[0198] FIG. 25 is a chart obtained by HPLC relating to a
commercially supplied fatty acid esters composition of a
polyglycerine employed in Comparative Example 16.
[0199] FIG. 26 is a chart obtained by HPLC relating to a
commercially supplied fatty acid esters composition of a
polyglycerine employed in Comparative Example 17.
[0200] FIG. 27 is a chart obtained by HPLC relating to a
commercially supplied fatty acid esters composition of a
polyglycerine employed in Comparative Example 18.
DETAILED DESCRIPTION OF THE INVENTION
[0201] The present invention will be described hereinafter in more
detail.
[0202] According to a first aspect of the present invention, there
is provided a fatty acid esters composition of a polyglycerine
containing more than 70% of a fatty acid monoester represented by
general formula [1] described below:
RCO--(OCH.sub.2CH(OH)CH.sub.2).sub.n--OH [1]
[0203] wherein R is an alkyl group, an alkenyl group, or a hydroxyl
group-substituted alkyl group which have a carbon number ranging
from 6 to 21, and n is an integer of at least 4, based on a peak
area ratio detected using an ultraviolet ray absorption detector in
a high performance liquid chromatographic analysis method.
[0204] According to a second aspect of the present invention, there
is provided a process for the preparation of a fatty acid esters
composition of a polyglycerine which comprises the reaction of a
fatty acid represented by general formula [2] described below;
RCOOH [2]
[0205] wherein R is an alkyl group, an alkenyl group, or a hydroxyl
group-substituted alkyl group which have a carbon number ranging
from 6 to 21, with glycidol in the presence of a phosphoric
acid-based acidic catalyst.
[0206] The fatty acid esters composition of a polyglycerine
containing more than 70% of a fatty acid monoester represented by
the general formula [1] of the first aspect of the present
invention can be prepared by the process of the second aspect of
the present invention.
[0207] As the fatty acid represented by the general formula [2],
there are employed fatty acids having a carbon number ranging from
7 to 22 which may be a saturated or unsaturated acid, a linear
aliphatic or branched acid and, further a substituted fatty acid in
which hydroxyl groups are substituted for carbon chains. As an
example of the fatty acids, there are specifically exemplified
caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid,
lauric acid, isotridecanoic acid, myristic acid, palmitic acid,
palmitoreic acid, stearic acid, isostearic acid, oleic acid,
linoleic acid, behenic acid, erucic acid, licinoleic acid,
hydroxystearic acid, etc., which may be employed solely or in
combination. The fatty acid may be employed solely or in
combination.
[0208] It is to be noted that glycidol is another name of an epoxy
alcohol which has the chemical structure of 1
[0209] The fatty acid is allowed to react with glycidol in the
presence of a phosphoric acid-based acidic catalyst.
[0210] The phosphoric acid-based acidic catalyst to be essentially
employed in the present invention includes phosphoric acids or
esters thereof. Specifically, there are exemplified phosphoric
acids such as phosphoric acid, phosphoric anhydride, polyphosphoric
acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric
acid, triphosphoric acid, and tetraphosphoric acid, acidic esters
of phosphoric acid such as methyl acid phosphate, ethyl acid
phosphate, isopropyl acid phosphate, butyl acid phosphate, and
2-ethylhexyl acid phosphate, etc.
[0211] Furthermore, there can be also employed monoester compound,
diester compound, and an admixture thereof. Of those, phosphoric
acid and acidic esters of phosphoric acid are preferably employed.
The catalyst may be employed solely or in combination.
[0212] The catalysts are employed in an amount ranging from 0.01 to
10% by weight, preferably from 0.1 to 5% by weight based on the
fatty acid.
[0213] In the case when the amount is below 0.01% by weight, the
reaction rate is low and, on the contrary, even in the case when
the amount exceeds 10% by weight, the reaction rate is not promoted
and, it is not only meaningless, but also addition polymers of
glycidol itself unpreferably by-produce depending upon the
catalysts which act as initiators.
[0214] The reaction is carried out by charging the fatty acid into
a reaction vessel and adding the catalyst, followed by gradually
adding glycidol. The reaction is carried out in temperatures
ranging from 50 to 180.degree. C., preferably from 70 to
160.degree. C., and more preferably from 120 to 140.degree. C.
[0215] In the case when the temperature is below 50.degree. C., the
reaction rate is slow and, on the contrary, in the case when it
exceeds 180.degree. C., products remarkably color, and in the case
of exceeding 230.degree. C., glycidol decomposes and side reactions
are unpreferably caused. In order to prevent elevation of the
temperatures, there can be employed a solvent having a low-boiling
point which is inert to glycidol.
[0216] Furthermore, the reaction is preferably carried out under a
nitrogen gas atmosphere which may be optionally pressurized.
[0217] The reaction may be carried out by a batch type or
continuous type process.
[0218] The reaction molar ratio of glycidol to the fatty acid
ranges from 1 to 100, preferably from 1 to 50 and, more preferably
from 1 to 10.
[0219] In the case when the ratio is below 1, the fatty acid
unreacted unpreferably remains in a reaction product and, on the
contrary, in the case when the ratio exceeds below 100, there
cannot be obtained a desired fatty acid esters composition of a
polyglycerine.
[0220] Although solvents may be employed in the reaction, it is
preferred that solvents are not employed in the use as additives
for foods.
[0221] Examples of the solvents include an aromatic hydrocarbon
such as benzene, toluene, and xylene, a halogenated toluene such as
trifluorotoluene, an aliphatic ketone having a carbon number
ranging from 3 to 9 such as methylisopropyl ketone,
methyl-isobutylketone, diethylketone, and diisobutylketone,
etc.
[0222] Furthermore, there can be employed ethers such as
diisopropylether, etc. The solvent may be employed solely or in
combination. In the case when the solvent is employed, it is
employed in an amount of 2 times by weight at most based on the
total weight of starting materials.
[0223] According to the above-described process, there can be
obtained a fatty acid esters composition of a polyglycerine having
a high polymerization degree. The fatty acid esters composition of
a polyglycerine is an admixture composed of a monoester compound, a
diester compound, and a triester compound.
[0224] The fatty acid esters composition of a polyglycerine of the
present invention contains more than 70% of a fatty acid monoester
represented by the general formula [1] described hereinabove.
[0225] In order to define the content of a fatty acid monoester
compound in a fatty acid esters composition of a polyglycerine,
there is employed a high performance liquid chromatographic
analysis method (hereinafter, referred to as HPLC).
[0226] In the HPLC analysis method, a peak area ratio is detected
using an ultraviolet (UV) ray absorption detector. The analytical
condition may be selected from the following three conditions.
[0227] Analytical condition No. 1:
[0228] Column: 2 pieces (connected in series) of Wakosil 5C18
manufactured by Wako Jun-yaku Ltd. or equivalent, which is a
reversed phase distribution column (an ODS column) having an
octadecyl group as a functional group
[0229] Column size: 4.6 mm phi.times.250 mmL
[0230] Eluent for development; Methanol
[0231] Flow rate of the eluent; 0.05 to 1.0 ml/in (eg. 0.75
ml/min)
[0232] Column oven temperature; 30 to 60.degree. C. (eg. 40.degree.
C.)
[0233] Wave length in UV ray absorption detector; 210 nm
[0234] Sample concentration: 1 to 50% (eg. 5% in methanol
solution)
[0235] Sample volume: 0.1 to 20 micro liter (eg. 5 micro liter)
[0236] Retention time of polyglycerine; 8 minutes
[0237] Retention time of monoester compound; 8-12 minutes
[0238] Retention time of other ester compounds; >12 minutes
[0239] Retention time of methanol; exceeding 18 minutes
[0240] Analytical condition No. 2:
[0241] Column; Wakosil II 5C18HG manufactured by Wako Jun-yaku Ltd.
or equivalent, which is a reversed phase distribution column (an
ODS column) having an octadecyl group as a functional group
[0242] Column size; 4.6 mm phi.times.250 mmL
[0243] Eluent for development; Methanol
[0244] Flow rate of the eluent; 0.05 to 1.0 ml/min (eg. 0.20
ml/min)
[0245] Column oven temperature: 30 to 60.degree. C. (eg. 40.degree.
C.)
[0246] Wave length in UV ray absorption detector; 210 nm
[0247] Sample concentration; 1 to 50% (eg. 10% in methanol
solution)
[0248] Sample volume; 0.1 to 20 micro liter (eg. 10 micro
liter)
[0249] Retention time of polyglycerine; before 14 minutes
[0250] Retention time of monoester compound; 14-16.5 minutes
[0251] Retention time of other ester compounds; >16.5
minutes
[0252] Retention time of methanol; exceeding 18 minutes
[0253] Analytical condition No. 3:
[0254] Column; Wakosil 5C18 and Wakosil II 5C18HG (connected in
series) manufactured by Wako Jun-yaku Ltd. or equivalent, which is
a reversed phase distribution column (an ODS column) having an
octadecyl group as a functional group
[0255] Column size: 4.6 mm phi.times.250 mmL
[0256] Eluent for development; Ethanol
[0257] Flow rate of the eluent; 0.05 to 1.0 ml/minute (eg. 0.20
ml/min)
[0258] Column oven temperature; 30 to 60.degree. C. (eg. 40.degree.
C.)
[0259] Wave length in UV ray absorption detector; 210 nm
[0260] Sample concentration; 1 to 50% (eg. 5% in ethanol
solution)
[0261] Sample volume; 0.1 to 20 micro liter (eg. 10 micro
liter)
[0262] Retention time of polyglycerine: below 28.5 minutes
[0263] Retention time of monoester compound; 28.5-34 minutes
[0264] Retention time of other ester compounds; exceeding 34
minutes
[0265] Retention time of ethanol; 39 minutes
[0266] As an eluent for development, there can be preferably
employed an alcohol and a mixture composed of alcohol/water.
[0267] The eluent for development is selected depending upon the
kind of a fatty acid of which a fatty acid esters composition of a
polyglycerine is composed, and depending upon the amount of
glycidol introduced. For example, in the case when a lauric acid
esters composition of a polyglycerine is analyzed, methanol is
preferably employed as the eluent, and in the case when a stearic
acid esters composition of a polyglycerine is analyzed, ethanol is
preferably employed as the eluent.
[0268] Samples (as a solution of an eluent for development) in the
HPLC analysis method are employed in an amount ranging from 0.1 to
20 micro liter, preferably from 5 to 10 micro liter depending upon
the solubility of samples into the eluent and the kind of samples.
Sample concentration ranges from 1 to 50%, preferably from 5 to 10%
in the eluent.
[0269] In separation by the HPLC analysis method using a column (an
ODS column) having an octadecyl group, no-substituted polyglycerine
components which have a higher polarity are firstly detected, and
then fatty acid esters components of a polyglycerine are
detected.
[0270] In the fatty acid esters components, monoester compound is
firstly detected, and then diester compound is detected, and
further other ester (triester, tetraester, . . . ) compounds are
detected. The content of the monoester compound is calculated
according to the following equation.
Content of a monoester compound=[A/(B-C)].times.100 (%)
[0271] A: peak area from the beginning in detection of fatty acid
esters of a polyglycerine to detection of fatty acid monoester
compound
[0272] B: total peak area of all components
[0273] C: peak area of solvent
[0274] Speaking of peak area by a solvent, it is to be noted that
it is important to select a solvent so that a retention time by the
solvent does not overlap retention time by other components.
[0275] The above-described equation for calculating the content of
a monoester compound is based on the premise that a retention time
by the solvent is present before retention time by other
components.
[0276] There may be optionally refined the fatty acid esters
composition of a polyglycerine containing more than 70% of a fatty
acid monoester of the present invention.
[0277] As methods for refining, there are exemplified:
[0278] (1) A method for removing odor by a steam injection process
in which saturated steam is blown at reduced pressures.
[0279] (2) A method for decoloration by a bleaching process using
sodium hypophosphate or hydrogen peroxide.
[0280] According to a third aspect of the present invention, there
is provided a process for the preparation of a highly-purified
fatty acid esters composition of a polyglycerine which comprises
the steps;
[0281] (a) allowing to react a fatty acid with glycidol to obtain a
fatty acid esters composition of a polyglycerine,
[0282] (b) removing water after adding water into said fatty acid
esters composition of a polyglycerine, and then heating.
[0283] The highly-purified fatty acid esters composition of a
polyglycerine of the present invention is prepared by the two steps
(a) and (b).
[0284] The step (a) corresponds to the above-described reaction
process in the second aspect of the present invention.
[0285] A product obtained in the step (a) corresponds to the
above-described fatty acid esters composition of a polyglycerine in
the first aspect of the present invention.
[0286] It is to be noted that the fatty acid esters composition of
a polyglycerine obtained in the step (a) usually contains oxirane
oxygen ranging from 500 to 2000 ppm based on a titration method
described hereinafter.
[0287] The step (b) is described below in detail.
[0288] In the step (b), water is added into the fatty acid esters
composition of a polyglycerine obtained in the step (a), and then
the composition is heated, followed by removing water.
[0289] In the step (b), water is added in an amount ranging from
0.1 to 20% by weight, and preferably from 1 to 10% by weight based
on the weight of the above-described fatty acid esters composition
of a polyglycerine.
[0290] In the case when the amount of water is below 0.1%,
unreacted glycidol cannot be sufficiently decreased and, on the
contrary, in the case when the amount of water exceeds 20%, it
unpreferably requires a long time of period for removing water.
[0291] Unreacted glycidol is changed to glycerine by heating after
adding water. Heating temperature in the step (b) ranges from 60 to
200.degree. C., and preferably from 80 to 160.degree. C.
[0292] In the case when the temperature is below 60.degree. C.,
unreacted glycidol cannot be sufficiently decreased and, on the
contrary, in the case when the temperature exceeds 200.degree. C.,
there unpreferably colors the fatty acid esters composition of a
polyglycerine.
[0293] Heating time of period ranges from 0.5 to 15 hours, and
preferably from 1 to 7 hours depending upon heating
temperatures.
[0294] In the case when the heating time is below 0.5 hour,
glycidol cannot be sufficiently decreased and, on the contrary, in
the case when the time exceeds 15 hours, there unpreferably colors
the fatty acid esters composition of a polyglycerine.
[0295] In the step (b), water is removed after the completion of
heating to obtain the fatty acid esters composition of a
polyglycerine not containing unreacted glycidol.
[0296] Water can be removed by distillation, azeotropic
distillation, and distillation under reduced pressures.
[0297] Heating temperatures in distillation ranges from 100 to
200.degree. C., and preferably from 110 to 160.degree. C.
[0298] In the case when the distillation temperature is below
100.degree. C., water cannot be sufficiently removed and, on the
contrary, in the case when the temperature exceeds 200.degree. C.,
there unpreferably colors the fatty acid esters composition of a
polyglycerine.
[0299] Distillation time of period ranges from 1 to 10 hours, and
preferably from 1 to 6 hours depending upon temperatures and the
degree of reduced pressures in distillation.
[0300] In the case when the distillation time is below 1 hour,
water cannot be sufficiently removed and, on the contrary, in the
case when the time exceeds 10 hours, there unpreferably colors the
fatty acid esters composition of a polyglycerine.
[0301] In the case when a solvent is employed in the step (a), it
can be removed in the distillation together with water.
[0302] According to a fourth aspect of the present invention, there
is provided a highly-purified fatty acid esters composition of a
polyglycerine having an oxirane oxygen concentration of below 100
ppm, said oxirane oxygen concentration is defined by the titration
method defined in Cd. 9-57 of Journal of American Oil Chemists'
Society, or having a ratio of below 0.01%, said ratio is a peak
area value of a chemical shift between 2.7 ppm and 2.8 ppm assigned
by methylene proton derived from an oxirane group with respect to a
peak area value of a chemical shift between 3.4 ppm and 4.4 ppm
assigned by methylene proton and methine proton derived from a
polyglycerine with a proton NMR.
[0303] In order to determine the concentration value of oxirane
oxygen in the highly purified fatty acid esters composition of a
polyglycerine of the fourth aspect, there is employed the titration
method defined in Cd. 9-57 of Journal of American Oil Chemists'
Society, [Journal of American Oil Chemists' Society, 41, 86-87
(1964)] or having a ratio of below 0.01%, said ratio is a peak area
value of a chemical shift between 2.7 ppm and 2.8 ppm assigned by
methylene proton derived from an oxirane group with respect to a
peak area value of a chemical shift between 3.4 ppm and 4.4 ppm
assigned by methylene proton and methine proton derived from a
polyglycerine with a proton NMR.
[0304] The titration method defined in the tentative method Cd.
9-57, Oxirane Oxygen by D. S. Bolly et al and cited in the Journal
of American Oil Chemists' Society Volume 41, pp. 86-87 (1964) is a
method for measuring oxirane oxygen which is described below.
[0305] Definition: This method determines oxirane oxygen which is
the oxygen contained in the following grouping: 2
[0306] Under the prescribed conditions of this method, the oxygen
is titrated directly with hydrogen bromide in acetic acid.
[0307] Scope: Applicable to epoxidized fatty materials and epoxy
compounds in general.
[0308] A. Apparatus:
[0309] 1. Buret assembly of the Machlette type (gravity feed),
available from Scientific Glass Apparatus Co. Cat. No. JB6715 or
equivalent. Provide a closed system for titration to avoid loss of
hydrogen bromide attaching the titration flask to the buret tip
with a one-hole rubber stopper. The hole in the stopper should be
formed so as to take the buret tip snugly with a small side opening
to permit air to escape from the flask during titration.
[0310] 2. Flask: Erlenmeyer, 50 ml,
[0311] 3. A magnetic stirrer of any suitable type with round
magnetic stirring bars covered with "Teflon" or equivalent
protective covering.
[0312] B. Reagents:
[0313] 1. Glacial acetic acid, A.C.S. grade, acetic anhydride
free
[0314] 2. Hydrogen bromide gas, anhydrous, available in cylinders
from Matheson Company, Inc., Joliet, Illinois or 30-32% hydrogen
bromide in acetic acid available from Eastman Kodak Co.
[0315] 3. Crystal violet (Gentian violet), Eastman Kodak No. 1350
or equivalent.
[0316] 4. Acid potassium Phthalate, National Bureau of Standard,
Standard for Acidimetry. Dry for two hours at 120.degree. C. and
allow to cool in an efficient desiccator prior to use.
[0317] 5. Benzene, A.C.S. grade or chlorobenzene, analytical
reagent grade.
[0318] C. Solutions:
[0319] 1. Crystal violet indicator soln.; dissolve 0.1 g. of
crystal violet in 100 ml. of glacial acetic acid.
[0320] 2. Hydrogen bromide 0.1 N in acetic acid.
[0321] a. Prepare by bubbling hydrogen bromide gas through glacial
acetic acid to approximately 0.1N. A torsion type balance may be
use to estimate the amount of hydrogen bromide added.
[0322] b. or, prepare by diluting 30 to 32% (about 4N) hydrogen
bromide in acetic acid with glacial acetic acid to approximately
0.1N.
[0323] Standardization: Weigh accurately about 0.4 g. of dry acid
potassium phthalate and dissolve in 10 ml. glacial acetic acid.
Heat carefully dissolve, using a hot plate. Titration solution at
room temperature with hydrogen bromide using no more than 0.1 ml.
(5 drops from a fine dropper) of crystal violet indicator.
Standardization should be in duplicate with a difference not to
exceed 0.0004 N. Restandardize each day samples are analyzed.
Normality=(Weigh of Phthalate)/(0.2042.times.Titration)
[0324] D. Procedure:
[0325] 1. Weigh 0.3-0.5 g. (plus or minus 0.0001 g.) of the sample
into a 50 ml. Erlenmeyer flask. Dissolve the sample in 10 ml of
benzene or chlorobenzene (in case of epoxy resins use
chlorobenzene). Add stirring bar and crystal violet indicator
(maximum 0.1 ml. or 5 drops with a fine dropper).
[0326] 2. Place the rubber stopper in position and lower the tip of
the buret until it discharges just above the solution.
[0327] 3. Stir and titrate the sample (rapidly at first) with the
0.1 N hydrogen bromide solution to a bluish-green end point that
persists for 30 seconds. Control the rate of the magnetic stirrer
so as to avoid splashing.
[0328] E. Calculation:
Oxirane Oxygen, %=(Titration.times.N.times.1.60)/(Weight of
sample)
[0329] F. Responsibility:
[0330] The average variance of components calculated from the
collaborative data obtained by the investigating Committee indicate
the following 95% probability limits:
[0331] 1. The difference between duplicate determinations made
within a laboratory should not exceed . . . 0.8
[0332] 2. The difference between the average or duplicate
determinations made in different laboratories should not exceed . .
. 0.19
[0333] G. Note:
[0334] 1. This method is not applicable to oils containing alpha
and beta-unsaturated ketones, cyclopropenes-conjugated dienols,
oxidized fats, and soaps.
[0335] 2. Long standing has a deleterious effect on hydrogen
bromide solutions and should be avoided.
[0336] In the proton NMR method in order to determine the
concentration value of oxirane oxygen in the highly purified fatty
acid esters composition of a polyglycerine, methane-deuterium
chloride is employed as a solvent, the solution concentration of
the fatty acid esters composition of a polyglycerine is
approximately 5%, temperature for measuring is 40.degree. C. plus
or minus 0.5.degree. C., and JOEL270 Mz (manufactured by Nihon
Denshi, Ltd.) or equivalent is employed as an NMR apparatus.
[0337] Although starting materials for the highly-purified fatty
acid esters composition of a polyglycerine having an oxirane oxygen
concentration of below 100 ppm or having the ratio of below 0.01%
can be obtained by the process of the above-described second aspect
or the step (a) in the third aspect, preparation processes thereof
are not particularly limited.
[0338] Starting materials for the highly-purified fatty acid esters
composition of a polyglycerine having an oxirane oxygen
concentration of below 100 ppm or having the ratio of below 0.01%
may also be provided by any one of the above-described preparation
processes, that is, (1) an esterification reaction of a
polyglycerine with a fatty acid, (2) a transesterification reaction
of a polyglycerine with a fatty acid ester, (3) a
transesterification reaction of a polyglycerine with an oil and
fatty acid, (4) an addition polymerization reaction of glycidol to
a monoglyceride of a fatty acid including (5) an addition
polymerization reaction of glycidol to a fatty acid, etc.
[0339] The starting materials for the highly-purified fatty acid
esters composition of a polyglycerine contain an oxirane oxygen
ranging from 100 to 2000 ppm which is measured by the titration
method defined in the Cd. 9-57 of Journal of American Oil Chemists'
Society.
[0340] According to a fifth aspect of the present invention, there
is provided the use of a fatty acid esters composition of a
polyglycerine in the first aspect or a highly-purified fatty acid
esters composition of a polyglycerine in the fourth aspect for an
additive for food-stuffs.
[0341] As examples of the food-stuffs to be applied, there are
specifically exemplified a material for drinks such as a cacao,
coffee, and tea, a starch-based product such as noodles, kneaded
bread-stuffs or bread, cookies, and cake, a dairy product such as a
milk fermented by lactic acid, butter, and cheese, processed meat
or processed fish meat, and an oils & fats composition which is
composed of vegetable oils and/or hydrogenated animal or fish oils
and other additives, etc.
[0342] As an additive for a variety of the food-stuffs, the fatty
acid esters composition of a polyglycerine in the first or fourth
aspect is employed in an amount ranging from 0.01% to 5% by weight,
preferably from 0.05 to 2% by weight, and more preferably from 0.1
to 1% by weight based on the total amount of the food-stuffs
including water, although it depends upon the kind of the
food-stuffs.
[0343] In the case when the amount is below 0.01%, effect by the
use is meaninglessly small and, on the contrary, in the case when
the amount exceeds 5%, a taste or flavor inherently possessed in
the food-stuffs is adversely affected.
[0344] The fatty acid esters composition of a polyglycerine acts as
a stabilizer for emulsifying, an emulsifier or an accelerator
thereof, a surface active agent, a dispersant, a binder, or a
plasticizer for a variety of food-stuffs.
[0345] Effect by the use of the fatty acid esters composition of a
polyglycerine is more specifically described below relating to
respective food-stuffs.
[0346] In the case when the fatty acid esters composition of a
polyglycerine of the present invention is employed in kneaded
bread-stuffs, fermentation by yeast for bread is stabilized for
long time of period even without controlling temperatures,
resulting in that there can be prepared bread having an excellent
taste.
[0347] For the kneaded bread-stuffs which are one of the
starch-based product, the fatty acid esters composition of a
polyglycerine is employed in an amount of less than 0.5% by weight
together with other additives such as approximately 0.1% by weight
of calcium carbonate, approximately 0.1% by weight of powdered egg
white, and a small amount of salt, seasoning, and flavors, etc.
based on flour. Fermentation by yeast for bread of the kneaded
bread-stuffs is carried out at temperatures of 25 to 30.degree. C.
for 10 to 24 hours.
[0348] For noodles which are one of the starch-based products, the
fatty acid esters composition of a polyglycerine is employed in an
amount ranging from 0.1 to 0.5% by weight based on the weight of
flour together with other additives such as salt and egg white,
etc.
[0349] In the case when the fatty acid esters composition of a
polyglycerine of the present invention is employed in noodles, it
acts as a surface active agent, resulting in that adhering of
noodles itself can be prevented.
[0350] In the case when the fatty acid esters composition of a
polyglycerine of the present invention is employed in the dairy
product, it acts as a dispersant or an emulsifier, resulting in
that separation of fats can be prevented.
[0351] For the milk fermented by lactic acid which is one of the
dairy product, the fatty acid esters composition of a polyglycerine
is employed in an amount ranging from 0.02 to 0.15% by weight based
on the weight of milk together with other additives such as sugar,
etc.
[0352] Separation or flotation of fats is not caused in the milk
fermented by lactic acid in which the fatty acid esters composition
of a polyglycerine is mixed even at low temperatures such as
5.degree. C. or high temperatures such as 30.degree. C. for a long
time of period such as 3 months.
[0353] For meat or fish meat, the fatty acid esters composition of
a polyglycerine is employed in an amount ranging from 0.1 to 5% by
weight, preferably from 0.5 to 1% based on the weight of meat or
fish meat including moisture together with other additives such as
salt and egg white, etc.
[0354] In the case when the fatty acid esters composition of a
polyglycerine of the present invention is employed in the meat or
fish meat, it acts as a elasticity improver and a whiteness
improver.
[0355] The fatty acid esters composition of a polyglycerine of the
present invention can be employed together with a oils&fats
composition such as soy bean oil, etc. as an emulsifier for
bread-stuffs, cake, and cookies, etc. as described in
JP-A-22690/1994, together with an oils & fats composition for
butter cake as described in JP-A-53/1994, together with water,
sorbitol, lactose, and whey protein, etc. for sponge cake or snack
cake as described in JP-A-269244/1994, as an 0/W type-emulsified
oil&fat composition which contains water, oils & fats, a
glucide such as sorbitol, and an emulsifier as described in
JP-A-78672/1994, together with a fatty acid ester of sugar, a fatty
acid ester of glycerine, a fatty acid ester of sorbitan, a
crystallized cellulose, etc. as a stabilizer for emulsifying as
described in JP-A-125711/1994, together with cacao components, milk
components, a sweetening agent, and water as an emulsifier for a
cacao drink as described in JP-A-38682/1994, together with egg,
starch, and vegetable oils, etc. as an emulsifier for noodles as
described in JP-A-276972/1994 and JP-A-197717/1994, as an improver
for fish meal as described in JP-A-22730/1994, as an improver for
scallop meal as described in JP-A-90713/1994, as a plasticizer for
granules containing proteins as described in JP-A-133735/1994, as
an emulsifier for a W/0 type oil & fat composition as described
in JP-A-209704/1994, as a stabilizer for a wheat powder composition
as described in JP-A-253718/1994, as an emulsifier for an oils
& fats composition as described in JP-A-14711/1994, as an
emulsifier for a fermented milk or cheese as described in
JP-A-113799/1994, as a stabilizer for an extract from plants as
described in JP-A-153884/1994, as a stabilizer for starch-based
food-stuffs as described in JP-A-225684/1994, as a stabilizer for
an oils & fats-containing fermented drink, as described in
JP-A-62734/1994, as a stabilizer for a water-containing chocolate
base as described in JP-A-189682/1994, as a stabilizer for an oils
& fats composition as described in JP-A-90663/1994, and as an
emulsifier for food-stuffs containing proteins as described in
JP-A-113727/1994, etc.
[0356] According to a sixth aspect of the present invention, there
is provided a resin composition which comprises a fatty acid esters
composition of a polyglycerine in the first aspect or a
highly-purified fatty acid esters composition of a polyglycerine in
the fourth aspect, and a thermoplastic resin.
[0357] As examples of the thermoplastic resin to be applied, there
are specifically exemplified a polyvinyl chloride resin, a
styrene-based resin, a methylmethacrylate-based resin, and a
polyacetal resin, etc.
[0358] The fatty acid esters composition of a polyglycerine of the
first aspect and a highly-purified fatty acid esters composition of
a polyglycerine of the fourth aspect in the present invention act
as a plasticizer, an improver of a wetting ability for a
hydrophobic resin, an improver of a printing property, an
anti-static agent, a releasing agent, or an anti-clouding agent,
etc. for a variety of thermoplastic resins.
[0359] As an additive for a variety of thermoplastic resins, the
fatty acid esters composition of a polyglycerine in the first and
fourth aspects are employed in an amount ranging from 0.01% to 10%
by weight, preferably from 0.05 to 5% by weight, and more
preferably from 0.1 to 3% by weight based on the amount of the
resins, although it depends upon the kind of the thermoplastic
resins.
[0360] Mixing or kneading of the fatty acid esters composition of a
polyglycerine with the thermoplastic resins can be carried out
without any limitations by a single or twin screw extruder, a
kneader, a roll mixer, a tumble mixer, a Brabender type mixer, a
Henshell mixer, and a Banbury mixer which have been conventionally
employed.
[0361] Furthermore, monomers can also be polymerized in the
presence of the fatty acid esters composition of a polyglycerine
depending upon the kind of thermoplastic resins.
[0362] In the case when the fatty acid esters composition of a
polyglycerine is employed as an additive for a variety of
thermoplastic resins, it can be employed solely or in
combination.
[0363] Still further, in the case when the fatty acid esters
composition of a polyglycerine is employed as an additive for
thermoplastic resins, it can be employed together with other
conventional additives such as an anti-oxidant which includes a
hindered phenol-based or sulphur-based compound, a stabilizer, a
flame retardant, a slipping agent, a nucleating agent, an
ultraviolet absorbent, a releasing agent, a coloring agent,
pigments, fibers, and fillers such as fiber glass or glass beads,
etc., depending upon uses.
[0364] A resin composition in which a resin is mixed with the fatty
acid esters composition of a polyglycerine of the first aspect or
the fourth aspect in the present invention and other additives can
be molded by extruding molding, injection molding, compression
molding, vacuum molding, blow molding, and foamed molding, etc.
[0365] For example, in the case when the fatty acid esters
composition of a polyglycerine of the first aspect or fourth aspect
is employed as an additive for a polyvinyl chloride resin for the
purpose of preparing a resin composition, particularly, it
effectively acts as an anti-static agent.
[0366] A polyvinyl chloride resin may be molded as a film or a
molded article which includes a plasticized or rigid polyvinyl
chloride resin.
[0367] The fatty acid esters composition of a polyglycerine of the
first aspect or fourth aspect is employed in an amount ranging from
1 to 10 parts by weight, and preferably from 2 to 7 parts by weight
based on 100 parts of the polyvinyl chloride resin.
[0368] In the case when the amount is below 1 part by weight, an
anti-static effect is poor and, on the contrary, in the case when
the amount exceeds 10 part by weight, not only transparency of
films decreases but also workability in molding process of the
films unpreferably decreases.
[0369] The fatty acid esters composition of a polyglycerine of the
first aspect or the highly purified fatty acid esters composition
of a polyglycerine of the fourth aspect may be employed solely or
in combination, and further may be employed together with
conventional anti-static agents such as fatty acid esters of a
glycerine, fatty acid esters of sorbitan, and sodium
alkylsulfonates, etc.
[0370] The polyvinyl chloride resin to be employed in the present
invention includes homopolymers and copolymers with olefines such
as ethylene or propylene, vinyl acetate, and vinylidene
chloride.
[0371] Furthermore, the fatty acid esters composition of a
polyglycerine may be optionally employed together with conventional
additives such as thermal stabilizers, anti-oxidants, reinforcing
materials, processing agents, ultraviolet absorbents, slipping
agents, coloring materials such as dyes, and pigments, etc.
[0372] In the meantime, for example, in the case when the fatty
acid esters composition of a polyglycerine of the first aspect or
the highly purified fatty acid esters composition of a
polyglycerine of the fourth aspect is employed as an additive for a
styrene-based resin for the purpose of preparing a resin
composition, particularly, it effectively acts as an anti-clouding
agent or an anti-static agent.
[0373] As specific examples of the styrene-based resin, there are
exemplified a styrene homopolymer, a high impact polystyrene, an
acrylonitrile-styrene copolymer, a styrene-methylmethacrylate
copolymer, and a styrene-methylmethacrylate-acrylonitrile
copolymer.
[0374] In particular, in the case when it is employed as an
additive for a styrene-based resin film for the purpose of wrapping
food-stuffs, it is exceedingly effective.
[0375] The fatty acid esters composition of a polyglycerine of the
first aspect or the highly purified fatty acid esters composition
of a polyglycerine of the fourth aspect is employed in an amount
ranging from 0.5 to 8.0% by weight, and preferably from 1 to 5% by
weight based on the weight of the styrene-based resin.
[0376] In the case when the amount is below 0.8% by weight, an
anti-clouding effect is poor and, on the contrary, in the case when
the amount exceeds 8% by weight, the anti-clouding agent
excessively bleeds out of the films, resulting in that film
surfaces are unpreferably sticky.
[0377] In the case when the fatty acid esters composition of a
polyglycerine of the first aspect or the highly purified fatty acid
esters composition of a polyglycerine of the fourth aspect is
employed as an additive for a
styrene-methylmethacrylate-acrylonitrile resin which is one of the
styrene-based resin, particularly, it effectively acts as an
anti-static agent.
[0378] The styrene-based resin includes styrene units ranging from
100% to 20% by weight, and there may be included methyl
methacrylate units ranging from 0% to 80% by weight and
acrylonitrile units ranging from 0% to 20% by weight as other
units.
[0379] Furthermore, the styrene-based resin can be mixed with the
fatty acid esters composition of a polyglycerine of the first
aspect or the highly purified fatty acid esters composition of a
polyglycerine of the fourth aspect in combination with phosphorus
compounds and further optionally a polyalkylene glycol for the
purpose of preparing a transparent resin composition having an
excellent anti-static property.
[0380] As examples of the phosphorus compounds to be employed in
the present invention, there are exemplified tributyl phosphite,
triisooctyl phosphite, tribenzyl phosphite, triphenyl phosphite,
phenyldidecyl phosphite, diphenylisodecyl phosphite, trisnonyl
phenyl phosphite, tridecyl phosphite, trisstearyl phosphite,
distearylpentaerythritol diphosphite, and the like.
[0381] Of those, there are preferably employed tridecyl phosphite,
trisstearyl phosphite, and distearylpentaerythritol
diphosphite.
[0382] The fatty acid esters composition of a polyglycerine of the
first aspect or the highly purified fatty acid esters composition
of a polyglycerine of the fourth aspect is employed in an amount
ranging from 0.5 to 6.0 parts by weight, and preferably from 1.0 to
5.0 parts by weight based on 100 parts by weight of the transparent
resin composition.
[0383] In the case when the amount is below 0.6 part by weight, an
anti-static effect is poor and, on the contrary, in the case when
the amount exceeds 6.0 parts by weight, the esters composition
unpreferably bleeds out of articles, and further the surface of a
mold becomes unpreferably dirty.
[0384] The phosphorus compounds are employed in an amount ranging
from 0. 05 to 4.0 parts by weight, and preferably from 1.0 to 3.0
parts by weight based on 100 parts by weight of the transparent
resin composition.
[0385] In the case when the amount is below 0.05 part by weight, an
anti-static effect is unpreferably poor and, on the contrary, in
the case when the amount exceeds 4.0 parts by weight, the phosphite
compounds adhere to surface of a mold or a molded article,
unpreferably resulting in that a molded article becomes dirty.
[0386] The polyalkylene glycol which is an optional component is
employed in an amount ranging from 0.5 to 5.0 parts by weight, and
preferably from 1.0 to 4.0 parts by weight based on 100 parts by
weight of the transparent resin composition.
[0387] In the case when the amount is below 0.5 part by weight, an
effect for accelerating the anti-static is unpreferably poor and,
on the contrary, in the case when the amount exceeds 5.0 parts by
weight, the polyalkyleneglycol oozes out of an molded article,
unpreferably resulting in that a molded article becomes dirty.
[0388] The polyalkylene glycol has a molecular weight ranging from
200 to 1500, and preferably from 300 to 1000. In the case when the
molecular weight is below 200, compatibility with the resin becomes
unpreferably poor and, on the contrary, in the case when the
molecular weight exceeds 1500, an effect for accelerating the
anti-static becomes unpreferably poor.
[0389] The styrene-based resin, the fatty acid esters composition
of a polyglycerine, the phosphorus compounds, and optionally the
polyalkylene glycol can be mixed with the conventional mixers
described hereinabove.
[0390] In the meantime, for example, in the case when the fatty
acid esters composition of a polyglycerine of the first aspect or
the highly purified fatty acid esters composition of a
polyglycerine of the fourth aspect is employed as an additive for a
methyl-methacrylate-based resin for the purpose of preparing a
resin composition, particularly, it effectively acts a releasing
agent in a molding process.
[0391] Methylmethacrylate-based resin in the present invention
includes a methylmethacrylate homopolymer and a copolymer with
acrylates such as methylacrylate, ethylacrylate, butylacrylate,
methacrylates such as ethylmethacrylate, butylmethacrylate,
cyclohexylmethacrylate, acrylic acid, methacrylic acid, styrene,
acrylonitrile, diene-based monomers, glutaric acid anhydride, and
gulutarimide, etc.
[0392] In the case when the fatty acid esters composition of a
polyglycerine of the first aspect or the highly purified fatty acid
esters composition of a polyglycerine of the fourth aspect is
employed as a releasing agent for a methylmethacrylate-based resin,
it is preferably employed together with pentaerythritols or fatty
acid esters thereof in order to accelerate a releasing effect.
[0393] The pentaerythritols include monopentaerythritol,
dipenta-erythritol, tripentaerythritol, tetrapentaerythritol, and
adducts of 1 to 5 mol of ethyleneoxide or propyleneoxide with the
pentaerythritols.
[0394] Furthermore, the fatty acid esters thereof include esters of
the pentaerythritols with fatty acids such as caproic acid,
caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid,
isotridecanoic acid, myristic acid, palmitic acid, palmitoreic
acid, stearic acid, isostearic acid, oleic acid, linoleic acid,
behenic acid, erucic acid, licinoleic acid, and hydroxystearic
acid, etc.
[0395] The pentaerythritols or the fatty acid esters thereof are
employed in a ratio ranging from 10/90 to 90/10, and preferably
from 25/75 to 75/25 based on the weight of the fatty acid esters
composition of a polyglycerine.
[0396] The fatty acid esters composition of a polyglycerine of the
first aspect or fourth aspect or a mixture with the
penta-erythritols or the fatty acid esters thereof is employed in
an amount ranging from 0.01 to 0.5% by weight, and preferably from
0.1 to 0.2% by weight based on the weight of the
methyl-methacrylate-based resin.
[0397] In the case when the amount is below 0.01% by weight, a
releasing effect is insufficient and, on the contrary, in the case
when the amount exceeds 0.5% by weight, not only transparency of
the resin is unpreferably adversely affected, but also the
releasing agents move to the surface of molded articles,
unpreferably resulting in that the surface of the mold or molded
articles becomes dirty by excessive amounts of the releasing agent,
and commercial values remarkably decrease by coloration of the
molded article.
[0398] Furthermore, there may be optionally mixed conventional
additives such as hindered amine-based light stabilizers, hindered
phenol-based, phosphorus-based, and sulphur-based anti-oxidants,
reinforcing materials such as glass fibers, processing agents,
ultraviolet absorbents, slipping agents, flame-retardants,
weatherable agent, coloring agents such as dyes, and thermal
stabilizers, etc.
[0399] In the meantime, for example, in the case when the fatty
acid esters composition of a polyglycerine of the first aspect or
the highly purified fatty acid esters composition of a
polyglycerine of the fourth aspect can be employed as an additive
for a polyacetal resin for the purpose of preparing a resin
composition, particularly, it effectively acts as an agent for
improving a printing property, an agent for improving wetting
property to water, water-based inks, and an aqueous serum, and an
agent for improving releasing property from a molding die.
[0400] Furthermore, the excellent properties endure for a long time
of period.
[0401] In the case when the fatty acid esters composition of a
polyglycerine of the first aspect or the highly purified fatty acid
esters composition of a polyglycerine of the fourth aspect is
employed as an agent for improving a printing property, it is
employed in an amount ranging from 0.01 to 5 parts by weight, and
preferably from 0.03 to 1 parts by weight, and more preferably from
0.05 to 0.08 part by weight based on 100 parts of the polyacetal
resin.
[0402] In the case when the amount is below 0.01 part by weight, an
effect for improving printing property is small and, on the
contrary, in the case when the amount exceeds 5 parts by weight,
thermal stability unpreferably decreases, and silver streak is
caused by decomposed gases when molded, unpreferably resulting in
that outer appearances of molded articles become remarkably
poor.
[0403] In the case when the fatty acid esters composition of a
polyglycerine of the first aspect or the highly purified fatty acid
esters composition of a polyglycerine of the fourth aspect is
employed as an additive for improving a wetting property, it is
employed in an amount ranging from 0.01 to 0.4% by weight, and
preferably from 0.05 to 0.3% by weight, and more preferably from
based on the weight of the polyacetal resin.
[0404] In the case when the amount is below 0.01% by weight, an
effect for improving wetting property is small and, on the
contrary, in the case when the amount exceeds 0.4% by weight,
mechanical property unpreferably decreases, and melt viscosity
occasionally decreases, unpreferably resulting in that molding
conditions are remarkably limited for the purpose of manufacturing
a delicate part such as an ink jet nozzle in a printer for a
personal computer.
[0405] In the case when the fatty acid esters composition of a
polyglycerine of the first aspect or fourth aspect is mixed with
the polyacetal resin in an amount ranging from 0.01 to 0.4% by
weight, a resin composition has Melt Index (based on ASTM D1238-89)
of below 1.5, an article molded from the resin composition has a
contact angle of below 50, resulting in being preferred for the
purpose of manufacturing a delicate part such as an ink jet nozzle
in a printer for a personal computer.
[0406] The polyacetal resin to be employed in the present invention
includes a high molecular weight compound having oxymethylene
groups --CH.sub.2O--. More specifically, there are included an
oxymethylene homopolymer (--CH.sub.2O--).sub.n-- which is prepared
by polymerization of formaldehyde or a cyclic oligomer such as
trimer (trioxane) of formaldehyde and tetramer (tetraoxane) of
formaldehyde. Furthermore, there is included an oxymethylene
copolymer having a structure, for example, such as
(--CH.sub.2O--).sub.n----(--CH.sub.2--CH.sub.2O--).sub.m- -- having
0.1 to 20% by weight of oxyalkylene units containing a carbon
number ranging from 2 to 8.
[0407] The copolymer is prepared by a reaction of formaldehyde or a
cyclic oligomer such as trimer (trioxane) of formaldehyde and
tetramer (tetraoxane) of formaldehyde with a cyclic ether such as
ethylene oxide, propylene oxide, epichlorohydrin, 1,3-dioxolan, a
formal of a glycol, and a formal of a diglycol, etc.
[0408] Still further, there is included an oxymethylene block
copolymer having more than 50% by weight of recurring units a
branched oxymethylene copolymer or oxymethylene and less than 50%
by weight of other polymer units.
[0409] In addition, there can be blended at least one of an
oxymethylene homopolymer, an oxymethylene copolymer, a branched
polymer, and an oxymethylene block copolymer.
[0410] There is preferably employed a polyacetal resin having an FR
value (ASTM D1238-57E) of 20-100 g/10 minutes in the present
invention. In the case when the FR value is below 20 or exceeds
100, printing property cannot be improved.
[0411] In the polyacetal resin, there can be preferably mixed a
hindered amine compound together with the fatty acid esters
composition of a polyglycerine.
[0412] Hindered amine compound specifically includes
4-acetoxy-2,2,6,6-tetramethylpiperidine,
4-stearoiloxy-2,2,6,6-tetramethy- lpiperidine,
4-acryloiloxy-2,2,6,6-tetramethyl piperidine,
4-(phenylacetoxy)-2.2,6,6-tetramethylpiperidine,
4-benzoiloxy-2,2,6,6-tet- ramethylpiperidine,
4-methoxy-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethyl piperidine,
4-cyclohexyloxy-2,2,6,6-tetr- amethylpiperidine,
4-benzyloxy-2,2,6,6-tetramethylpiperidine,
4-phenoxy-2,2,6,6-tetramethylpiperidine,
4-ethylcarbamoyloxy-2,2,6,6-tetr- amethyl piperidine,
4-phenylcarbamoyloxy-2,2,6,6-tetramethylpiperidine,
bis(2,2,6,6-tetramethyl-4-piperidyl)-carbonate,
bis(2,2,6,6-tetramethyl-4- -piperidyl)-oxalate,
bis(2,2,6,6-tetramethyl-4-piperidyl)-malonate,
bis(2,2,6,6-tetramethyl-4-piperidyl)-adipate,
bis(2,2,6,6-tetramethyl-4-p- iperidyl)-terephthalate,
bis(2,2,6,6-tetramethyl-4-piperidyl)-ethane,
'-bis(2,2,6,6-tetramethyl-4-piperidyl)-p-xylene,
bis(2,2,6,6-tetramethyl-- 4-piperidyl)-tollylene-2,4-dicarbamate,
bis(2,2,6,6-tetramethyl-4-piperidy-
l)-hexamethylene-1,6-dicarbamate,
tris(2,2,6,6-tetramethyl-4-piperidyl)-be-
nzene-1,3,5-tricarboxylate, and
tris(2,2,6,6-tetramethyl-4-piperidyl)-benz-
ene-1,3,4-tricarboxylate, etc.
[0413] Furthermore, in the polyacetal resin, there can be
preferably mixed an additive such as beta-alanine polymer, a
polyamide such as 6,6-nylon, 6,10-nylon, thermal stabilizers such
as melamine, anti-oxidants such as
2,2'-methylenebis(4-methyl-6-t-butylphenol),
triethyleneglycol-bis[3-(3-t-
-butyl-5-methyl-4-hydroxyphenyl)propionate],
pentaerythritol-tetrakis[3-(3-
,5-di-t-butyl-4-hydroxyphenyl)propionate], slipping agents,
reinforcing materials such as glass fibers, carbon fibers,
inorganic fillers such as potassium titanate fibers, fibrous
titanium oxides, glass beads, talc, calcium carbonate, releasing
agents, plasticizers, carbon black, and pigments, etc., together
with the fatty acid esters composition of a polyglycerine.
[0414] In order to promote a printing ability of a resin
composition in which the polyacetal resin are mixed with the fatty
acid esters composition of a polyglycerine of the first aspect or
the highly purified fatty acid esters composition of a
polyglycerine of the fourth aspect, a hindered amine compound, and
other additives, the thickness of skin layer in a molded article is
preferably controlled within 15 microns.
[0415] The skin layer in the molded article means an outer surface
layer at side portion in a sliced sample through which light is not
polarized when observed by a light-transmittable type polarizing
microscope of 340-magnifications using a cross nicol.
[0416] The sliced sample is prepared by slicing cross section of a
molded article in the thickness of 10 microns with a microtome.
[0417] The thickness of the skin layer can be adjusted by
controlling crystallization time of resin or selecting an
appropriate molding method, or the combination thereof.
[0418] As the method for controlling crystallization time of resin,
there is a method in which crystallization time of molded articles
is controlled in a range of 20 to 100 seconds.
[0419] Crystallization time in the present invention means a time
of period (second) until an exothermal peak accompanied by
crystallization of polyacetal resin is detected after temperature
of a sample holder attained to 150.degree. C. as described
below.
[0420] The temperature of 5 mg of the polyacetal resin is heated to
200.degree. C. at the rate of 320.degree. C./minute, and maintained
at 200.degree. C. for 2 minutes, followed by cooling until
150.degree. C. at the rate of 80.degree. C./minute.
[0421] As the method for controlling crystallization time in a
range of 20 to 100 seconds, there is a method in which there are
mixed an appropriate amount of a nucleating agent such as talc,
silicate powder, hydrotalcite, calcium carbide, amine-based
compound such as melamine or dicyandiamide, nitrides such as boron
nitride, zinc oxide, titanium oxide, calcium oxide, magnesium
oxide, carbon black such as conducting carbon black, and an organic
nucleating agent such as a branched polyacetal copolymer,
polyamides such as 6,6-nylon, an ionic polymer of acrylamide, and
powder of vinyl polymers, etc.
[0422] Of those, there are preferably employed nitrides such as
boron nitride, and polyamides such as 6,6-nylon or an ionic polymer
of acrylamide, and most preferably boron nitride.
[0423] There is preferably employed a boron nitride having an
averaged particle size of from 1 to 10 microns, preferably from 2
to 7 microns.
[0424] Subsequently, there is described a method for controlling
the thickness of the skin layer by selecting an appropriate molding
method.
[0425] The process includes (1) a method in which molding is
carried out at mold temperatures ranging from 100 to 150.degree.
C., preferably from 110 to 140.degree. C., (2) a method in which
injection molding is carried out by selectively heating cavities in
a mold for injection molding with an induction heating method by
microwave, (3) a method in which an article is compressively molded
with a thermal roll, and then gradually cooled, and (4) a method in
which an article is molded at the mold temperature ranging from 10
to 100.degree. C., and then molded article is thermally annealed at
the temperature ranging from 150.degree. C. to a melting point of a
polyacetal resin.
[0426] Of those, the methods (1) and (2) are preferably employed
from viewpoint of productivity.
[0427] Polyacetal resin composition in which a polyacetal resin is
mixed with the fatty acid esters composition of a poly-glycerine of
the first aspect or the highly purified fatty acid esters
composition of a polyglycerine of the fourth aspect in the present
invention and other additives is preferably used as a lever, an
instrumental panel, a dial plate for a taping writer, a knob for a
combination switch, housings, and a shutter for a disk or a
magnetic tape cartridge. More preferably, it is employed as a
shutter for a disk or a magnetic tape cartridge.
[0428] Furthermore, polyacetal resin composition in which a
polyacetal resin is mixed with the fatty acid esters composition of
a polyglycerine of the first aspect or the highly purified fatty
acid esters composition of a polyglycerine of the fourth aspect in
the present invention in order to improve wetting property is
preferably employed as an ink jet nozzle in a printer for a
personal computer.
[0429] In order to prepare another polyacetal resin composition, in
the case when the fatty acid esters composition of a polyglycerine
of the first aspect or the highly purified fatty acid esters
composition of a polyglycerine of the fourth aspect is mixed
together with a hindered phenol-based compound, fibrous titanium
oxide, and at least one selected from the group consisting of a
compound having nitrogen, a hydroxide of alkaline metal or alkaline
earth metal, a metal salt of a carboxylic acid or an inorganic
acid, and a polyacetal resin, it acts as a releasing agent from a
molding die or an agent for improving fluidity in a molding
die.
[0430] The above-described polyacetal resin composition is
preferably employed as small or precise parts having thin thickness
for precision instruments such as a watch, a printer, and a
desk-top electronic calculator, etc., because of being excellent in
mechanical properties and dimensional stability.
[0431] In the above-described polyacetal resin composition for
precision instruments, although the polyacetal resin is not limited
regardless of homopolymers or copolymers described hereinabove and
polymerization degree thereof, there is preferably employed a
polyacetal resin having an FR value (ASTM D1238-57E) of more than 7
g/10 minutes.
[0432] The surface of the fibrous titanium oxide is preferably
processed. Unprocessed fibrous titanium oxide causes decomposition
and foaming in the resin composition during compounding and/or
molding.
[0433] The fibrous titanium oxide has preferably an aspect ratio of
more than 10. In the case when the ratio is below 10, an
reinforcing effect is not shown.
[0434] Average diameter of the fibrous titanium oxide preferably
ranges from 0.02 to 0.6 microns, and average length of the fibrous
titanium oxide preferably ranges from 1 to 20 microns.
[0435] The fibrous titanium oxide is preferably employed in an
amount ranging from 1 to 70 parts by weight, preferably from 10 to
50, more preferably from 20 to 40 based on 100 parts by weight of
the acetal resin.
[0436] In the case when the ratio is below 1, an reinforcing effect
is not shown, and in the case when the ratio exceeds 70, fluidity
is not only remarkably lowers but also thermal stability of the
resin composition unpreferably decreases.
[0437] As agents for processing the surface of the fibrous titanium
oxide, there can be limitlessly employed silan-based coupling
agents, titanate-based coupling agents, aluminum-based coupling
agents, and zirconate-based coupling agents which have been
conventionally employed.
[0438] Specifically, there are exemplified
N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-glycidoxypropyl
trimethoxysilane isopropyl tristearoyltitanate,
diisopropoxyaluminumethylacetate and n-butylzirconate, etc.
[0439] Furthermore, granulated fibrous titanium oxides are
particularly preferably employed because of more excellent
workability in a mixing process compared to no-granulated fibrous
titanium oxides. However, fibrous titanium oxides which are too
strongly granulated are not preferred because of not being
sufficiently loosened, unpreferably resulting in insufficient
dispersion of the fibrous titanium oxides and decrease of
mechanical properties in a molded article.
[0440] As the compound having nitrogen, there are specifically
exemplified polyamide polymers or copolymers such as nylon 12,
nylon 610, nylon 6, and nylon 66, polyamides having substituent
groups such as methylol group, nylon salts, polyamides such as
polyester amides which are prepared from caprolactones and
caprolactams, polyaminotriasol, dihydrazide dicarboxylate such as
hydrazide oxalate, hydrazide adipate, and hydrazide sebacate, a
condensate thermally prepared from urea, a condensed polymer having
nitrogen prepared from urea and diamines, uracyls, cyanoguanidines,
dicyandiamide, guanamine(2,4-diamino-sym-troadi- ne),
melamine(2,4,6-triamino-sym-triadine), N-butylmelamine,
N-phenylmelamine, N,N-diphenylmelamine, N,N-diallylmelamine,
N,N',N"-triallylmelamine, N,N',N"-trimethylolmelamine,
benzoguanamine(2,4-diamino-6-phenyl-sym-triadine),
2,4-diamino-6-methyl-sym-triadine,
2,4-diamino-6-butyl-sym-triadine,
2,4-diamino-6-benzyloxy-sym-triadine,
2,4-diamino-6-butoxy-sym-triadine,
2,4-diamino-6-cyclohexyl-sym-triadine,
2,4-diamino-6-chloro-sym-triadine,
2,4-diamino-6-mercapto-sym-triadine,
2,4-dioxy-6-amino-sym-triadine, 2-oxy-4,6-diamino-sym-triadine,
2,4-diamino-6-methyl-sym-triadine,
N,N',N',N'-tetracyanoethylbenzguanamine, and a
melamine-formaldehyde condensate, etc.
[0441] Of those, there are preferably employed a melamine, a
melamine derivative, and a melamine-formaldehyde condensate,
etc.
[0442] As the hydroxide of alkaline metal or alkaline earth metal,
the metal salt of a carboxylic acid or an inorganic acid, there are
specifically exemplified alkali metallic salts such as lithium
salts, sodium salts, and potassium salts, alkali earth metallic
salts such as magnesium salts, calcium salts, and barium salts,
inorganic acid salts such as carbonates, phosphates, and silicates.
As the carboxylic acids, there are specifically exemplified oxalic
acid, malonic acid, succinic acid, and higher fatty acids having a
carbon number ranging from 12 to 32 such as stearic acid and
behenic acid, and higher fatty acids having substituted group such
as hydroxyl group.
[0443] Of those, there are preferably employed the hydroxide of
lithium, magnesium, and calcium, carbonates, and more preferably
carboxylates.
[0444] As particularly preferred carboxylates containing metals,
there are exemplified calcium stearate, calcium
12-hydroxy-stearate, and calcium behenate.
[0445] The compound having nitrogen, the hydroxide of alkaline
metal or alkaline earth metal, and the metal salt of carboxylic
acid or inorganic acid may be employed solely or in
combination.
[0446] Those are employed in an amount ranging from 0.01 to 5 parts
by weight, preferably from 0.03 to 2 parts by weight, and more
preferably from 0.05 to 1 part by weight based on 100 parts by
weight of the polyacetal resin.
[0447] In the case when the amount is below 0.01 part by weight, a
releasing effect from a molding die, an effect for improving
fluidity in the molding die, and thermal stability of molded
articles become insufficient and, on the contrary, in the case when
the amount exceeds 5 parts by weight, those move to the surface of
molded articles, unpreferably resulting in that the surface of the
molding die or molded articles become dirty by excessive amounts of
those, and commercial values remarkably decrease by coloration of
the molded article.
[0448] Furthermore, hindered phenol-based compounds can be mixed
together with the above-described compound having nitrogen,
hydroxide of alkaline metal or alkaline earth metal, and metal salt
of carboxylic acid or inorganic acid in order to control thermal
decomposition of polyacetal resins.
[0449] As the hindered phenol-based compounds, there are
specifically exemplified 2,2-methylenebis(4-methyl-6-butyl phenol),
1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate],
pentaerythrityltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxy-benzyl)benzene,
n-octadecyl-3-(4'-hydroxy-3',5,-di-t-butylphenol)propionate,
4,4'-butylidene-bis-(6-t-butyl-3-methyl-phenol),
distearyl-3,5-di-t-butyl- -4-hydroxybenzyl phosphonate,
2-t-butyl-6-(3-t-butyl-5-methyl-2-hydroxyben-
zyl)-4-methylphenylacrylate, and
N,N'-hexamethylenebis(3,5-di-t-butyl-4-hy- droxy-hydroynamide).
[0450] Those may be employed solely or in combination.
[0451] Of those, there are particularly preferred 1,6-hexanediol
bis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate],
pentaerythrityltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)
propionate],
triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate]N,-
N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydroynamide).
[0452] The hindered phenol-based compounds are employed in an
amount ranging from 0.01 to 5 parts by weight, and preferably from
0.1 to 3 parts by weight based on 100 parts by weight of the
polyacetal resin.
[0453] In the case when the amount is below 0.01 part by weight,
thermal stability of molded articles become insufficient and, on
the contrary, in the case when the amount exceeds 5 parts by
weight, those move to the surface of molded articles, unpreferably
resulting in that the molded articles become dirty by excessive
amounts of those.
[0454] In the case when the fatty acid esters composition of a
polyglycerine of the first aspect or fourth aspect is employed as
an agent for improving a releasing property from a molding die or
an agent for improving fluidity in the molding die, it is employed
in an amount ranging from 0.01 to 5 parts by weight, and preferably
from 0.1 to 2 parts by weight based on 100 parts by weight of the
polyacetal resins.
[0455] In the case when the amount is below 0.01 part by weight, an
effect for improving the releasing property or fluidity is small
and, on the contrary, in the case when the amount exceeds 5 parts
by weight, bleeding in the surface of the molded articles is
unpreferably caused.
[0456] The above-described polyacetal resin composition is
preferably employed as small or precise parts having thin thickness
for precision instruments such as a watch, a printer, and a desk
top electronic calculator, etc., because of being excellent in
mechanical properties, thermal stability and dimensional
stability.
[0457] In the meantime, the fatty acid esters compositions of a
polyglycerine of the first aspect or fourth aspect in the present
invention are also useful as an additive for cosmetics, toiletries,
and detergents.
[0458] According to a seventh aspect of the present invention,
there is provided a water-in-oil type-emulsified composition for
cosmetics which comprises glycerine, oils and/or waxes, water, and
a fatty acid esters composition of a polyglycerine in the first
aspect or a highly-purified fatty acid esters composition of a
polyglycerine in the fourth aspect.
[0459] In the water-in-oil type-emulsified composition for
cosmetics, the fatty acid esters composition of a polyglycerine or
the highly-purified fatty acid esters composition of a
polyglycerine is employed in an amount ranging from 1.0 to 10.0% by
weight, preferably from 2.0 to 5.0%, and more preferably from 3 to
4% by weight based on the total weight of the water-in-oil
type-emulsified composition for cosmetics of the present
invention.
[0460] In the case when it is below 1.0% by weight, stability for
long time of period becomes worse and, on the contrary, in the case
when it exceeds 10.0% by weight, viscosity becomes high or
stability for long time of period becomes worse.
[0461] In the water-in-oil type-emulsified composition for
cosmetics, there is more preferably employed the highly-purified
fatty acid esters composition of a polyglycerine in the fourth
aspect from viewpoint of the use for human body.
[0462] In the water-in-oil type-emulsified composition for
cosmetics, glycerine is an essential component. Glycerine is
employed in an amount ranging from 5 to 25% by weight, preferably
from 10 to 20%, and more preferably approximately 15% by weight
based on the total weight of the water-in-oil type-emulsified
composition for cosmetics of the present invention.
[0463] In the case when it is below 5% by weight, stability for
long time of period becomes worse and, on the contrary, in the case
when it exceeds 25% by weight, a feel in use becomes worse because
of strong stickiness.
[0464] In the water-in-oil type-emulsified composition for
cosmetics, oils and/or waxes include hydrocarbons such as a liquid
paraffin, a solid paraffin, vaseline, and a microcrystalline wax,
esters such as isopropyl myristate, cetyl 2-ethylhexanate, cetyl
palmitate, myristyl myristate, propyleneglycol dicaprylate, and
tri(caprylic acid and capric acid)glyceryl, animal or vegetable
oils/waxes such as bees-waxes, whale-waxes, lanolin, olive oils,
etc. Of those, liquid paraffin and vaseline are employed in a
relatively larger amount.
[0465] The oils and/or waxes are employed in an amount ranging from
10 to 40% by weight, preferably from 15 to 30%, and more preferably
20 to 25% by weight based on the total weight of the water-in-oil
type-emulsified composition for cosmetics of the present
invention.
[0466] In the case when it is below 10% by weight, viscosity
becomes too high, resulting in that it is not thinly extended and,
on the contrary, in the case when it exceeds 40% by weight, an oily
feel becomes too strong and stability for a long time of period
becomes deteriorated.
[0467] Water is employed in an amount ranging from 25 to 50% by
weight, preferably from 30 to 40%, and more preferably 30 to 35% by
weight based on the total weight of the water-in-oil
type-emulsified composition for cosmetics of the present
invention.
[0468] In the case when it is below 25% by weight or in the case
when it exceeds 50% by weight, a good feel in use and stability for
a long time of period become unpreferably deteriorated.
[0469] Furthermore, the water-in-oil type-emulsified composition
for cosmetics of the present invention can optionally include other
surface active agents, water-soluble solvents such as
propyleneglycol and ethanol, organic or inorganic fillers such as
finely-sized titanium oxide, powdered nylon, talc, kaolin,
ultraviolet absorbents, antiseptics, anti-oxidants, water soluble
salts such as magnesium sulphate, medicinal components, coloring
agent, and perfumes, etc. which are conventionally employed as
additives for cosmetics.
[0470] The water-in-oil type-emulsified composition for cosmetics
of the present invention can be used for cleansings, face massage,
and an anti-sunburn agent for human body, etc.
[0471] According to an eighth aspect of the present invention,
there is provided a transparent liquid composition for cosmetics
which comprises at least one of an non-ionic surface active agent,
at least one of water-soluble compound having at least two hydroxyl
groups, oily components, water, and a fatty acid esters composition
of a polyglycerine in the first aspect or a highly-purified fatty
acid esters composition of a polyglycerine in the fourth
aspect.
[0472] In the eighth aspect of the present invention, there is more
preferably employed a highly-purified fatty acid esters composition
of a polyglycerine in the fourth aspect from viewpoint of the use
for human body.
[0473] As the non-ionic surface active agent, there are
specifically employed a fatty acid esters composition of sorbitan,
a fatty acid esters composition of glycerine, a fatty acid esters
composition of polyethyleneglycol, a polyoxyethylene alkylether, a
polyoxyethylene alkylphenylether, a hydrogenated castor oil of
polyoxyethylene, a fatty acid esters composition of polyoxyethylene
sorbitan, and a fatty acid esters composition of polyoxyethylene
sorbitol, etc.
[0474] In the transparent liquid composition for cosmetics of the
present invention, the fatty acid esters composition of a
polyglycerine or the highly-purified fatty acid esters composition
of a polyglycerine is employed in combination with at least one of
the non-ionic surface active agent in an amount ranging from 5 to
40% by weight, preferably from 15 to 30%, and more preferably 15 to
20% by weight based on the total weight of the transparent liquid
composition for cosmetics.
[0475] In the case when it is below 5% by weight or in the case
when it exceeds 40% by weight. the liquid composition unpreferably
decreases transparency, or it unpreferably gels.
[0476] HLB value ranges from 8 to 13, and preferably from 9 to 11
in a mixture composed of the fatty acid esters composition of a
polyglycerine or the highly-purified fatty acid esters composition
of a polyglycerine and at least one of the non-ionic surface active
agent. In the case when it is below 8, or in the case when it
exceeds 13, the liquid composition unpreferably decreases
transparency, or it unpreferably emulsifies or gels.
[0477] In the transparent liquid composition for cosmetics of the
present invention, as the water-soluble compound having at least
two hydroxyl groups, there are specifically employed propylene
glycol, 1,3-butanediol, dipropylene glycol, glycerine, diglycerine,
polyglycerine, trimethylolpropane, erythritol, pentaerythritol,
isopreneglycol, sorbitan, glucose, sorbitol maltitol, saccharose,
polyoxyethylene methylglucoside, diethyleneglycol, and
polyethyleneglycol. Of those, there are preferably employed
1,3-butanediol, propylene glycol, and dipropylene glycol.
[0478] At least one of the water-soluble compound having at least
two hydroxyl groups is employed in an amount ranging from 2 to 40%
by weight, preferably from 4 to 25% by weight based on the total
weight of the transparent liquid composition. In the case when it
is below 2%, or in the case when it exceeds 25%, the liquid
composition unpreferably decreases transparency, or it unpreferably
emulsifies or gels.
[0479] In the transparent liquid composition for cosmetics of the
present invention, the oily components include vegetable oils,
mineral oils, and ester oils.
[0480] More specifically, there are employed beef tallow, squalane,
olive oil, peanut oil, sweet almond oil, castor oil, corn oil, a
liquid paraffin, vaseline, tri(caprylic acid and capric
acid)glyceryl, isopropyl myristate, vitamin E acetate, pyridoxine
dioctanoate, myristyl myristate, octyldodecanol oleate, lanolin,
fatty acid derivatives of lanolin, methylpolysiloxane, and an
isostearyl cholesterylester, etc.
[0481] Those may be employed solely or in combination.
[0482] The oily components are employed in an amount ranging from 3
to 70% by weight, preferably from 10 to 60%, and more preferably 15
to 30% by weight based on the total weight of the transparent
liquid composition for cosmetics.
[0483] In the transparent liquid composition for cosmetics of the
present invention, water is employed in an amount ranging from 0.5
to 80% by weight, and preferably from 2 to 60% by weight based on
the total weight of the transparent liquid composition for
cosmetics. In the case when it is below 0.5%, or in the case when
it exceeds 80%, the liquid composition occasionally decreases
transparency.
[0484] The transparent liquid composition for cosmetics of the
present invention can be prepared by conventional mixing
methods.
[0485] As a preferred preparation method, there is exemplified a
method in which there are firstly mixed the fatty acid esters
composition of a polyglycerine or the highly-purified fatty acid
esters composition of a polyglycerine and at least one of the
non-ionic surface active agent, and then the oily components are
mixed, followed by gradually mixing water.
[0486] Although mixing can be carried out at room temperatures
without heating, when solid components are employed, mixing may be
carried out while heating.
[0487] Furthermore, the transparent liquid composition for
cosmetics of the present invention can optionally include medicinal
components, antiseptics, coloring agent, and perfumes, wetting
agent, anti-oxidants, ultraviolet absorbents, granules such as a
scrubbing material, ethanol, water-soluble or oil-soluble high
molecular weight compound in order to give a viscous property to
the composition, a cationic material in order to give a
conditioning effect to hair, etc. which are conventionally employed
as additives for cosmetics.
[0488] The transparent liquid composition for cosmetics of the
present invention can be used for cleansings, an agent for massage,
an agent for pack, cosmetics for hair, cosmetics for bathroom,
cosmetics for keeping moisture, and a base material for a medicine,
etc.
[0489] According to a ninth aspect of the present invention, there
is provided a gel-like emulsified composition for cosmetics which
comprises glycerine, liquid oily components, a polyvalent alcohol
except glycerine, and a fatty acid esters composition of a
polyglycerine in the first aspect or a highly-purified fatty acid
esters composition of a polyglycerine in the fourth aspect.
[0490] In the ninth aspect of the present invention, there is more
preferably employed a highly-purified fatty acid esters composition
of a polyglycerine in the fourth aspect from viewpoint of the use
for human body.
[0491] In the gel-like emulsified composition for cosmetics of the
present invention, glycerine is an essential component. Glycerine
is employed in an amount ranging from 20 to 60% by weight,
preferably from 30 to 60%, and more preferably from 35 to 45% by
weight based on the total weight of the gel-like emulsified
composition for cosmetics of the present invention.
[0492] In the case when it is below 20%, a feel in use is
deteriorated and, on the contrary, in the case when it exceeds 60%,
a feel in use is deteriorated because of a warmish feel.
[0493] As the liquid oily components, there are specifically
employed a hydrocarbon oil such as a liquid paraffin and squalane,
an ester oil such as cetyl octanate and isopropyl myristate, and a
fatty acid triglyceride such as trioctanic acid triglyceride and
olive oil, etc.
[0494] Liquid oils primarily containing higher alcohols and higher
fatty acids are not preferred because of instability at high
temperatures.
[0495] As the polyvalent alcohol except glycerine, there are
specifically employed propyleneglycol, 1,3-butylene glycol,
maltitol, and sorbitol, etc. Of those, there are preferably
employed propyleneglycol and 1,3-butylene glycol.
[0496] The polyvalent alcohol except glycerine are employed in an
amount ranging from 0.5 to 10% by weight, and preferably from 1 to
5% by weight based on the total weight of the gel-like emulsified
composition for cosmetics of the present invention.
[0497] In the gel-like emulsified composition for cosmetics, the
fatty acid esters composition of a polyglycerine or the
highly-purified fatty acid esters composition of a polyglycerine is
employed in an amount ranging from 1.0 to 6.0% by weight,
preferably from 2.0 to 5.0%, and more preferably approximately 3.5%
by weight based on the total weight of the gel-like emulsified
composition for cosmetics of the present invention.
[0498] HLB value is preferably more than 11 in the fatty acid
esters composition of a polyglycerine or the highly-purified fatty
acid esters composition of a polyglycerine. Of those, there are
preferably employed decaglyceryl monolaurate and hexaglyceryl
monolaurate having HLB value of 11 to 15.
[0499] The gel-like emulsified composition for cosmetics of the
present invention can be used for cleansings and cosmetics for
massage, etc.
[0500] Furthermore, the gel-like emulsified composition for
cosmetics of the present invention can optionally include
ultraviolet absorbents, antiseptics, anti-oxidants, coloring agent,
perfumes, and medicinal components, etc. which are conventionally
employed as additives for cosmetics or toiletries.
[0501] According to a tenth aspect of the present invention, there
is provided a composition for tooth paste which comprises an
abrasive, a caking material, a wetting agent, and a fatty acid
esters composition of a polyglycerine in the first aspect or a
highly-purified fatty acid esters composition of a polyglycerine in
the fourth aspect.
[0502] In the tenth aspect of the present invention, there is more
preferably employed a highly-purified fatty acid esters composition
of a polyglycerine in the fourth aspect from viewpoint of the use
for human body.
[0503] In the composition for tooth paste, the fatty acid esters
composition of a polyglycerine or the highly-purified fatty acid
esters composition of a polyglycerine is employed in an amount
ranging from 0.4 to 10% by weight, preferably from 1.0 to 3.0%, and
more preferably approximately 2.0% by weight based on the total
weight of the composition for tooth paste of the present invention.
It is to be noted that the fatty acid esters composition of a
polyglycerine or the highly-purified fatty acid esters composition
of a polyglycerine acts as a foaming agent.
[0504] The composition for tooth paste of the present invention
includes a paste, powder, ointment, and liquid type tooth
polisher.
[0505] As the abrasives, there are included calcium secondary
phosphate (dihydrate, anhydride), calcium carbonate, silicates, and
insoluble sodium metaphosphates.
[0506] As the caking material, there are included sodium
carboxy-methyl cellulose, carrageenan, sodium alginate, bentonite,
and silicate anhydride, etc.
[0507] As the wetting agent, there are included glycerine,
sorbitol, propyleneglycol, sodium pyrrolidone-carboxylate, and
polyethyleneglycol, etc.
[0508] The composition for tooth paste of the present invention may
include a variety of perfumes and medicinal components.
[0509] As the medicinal components to be employed, fluorides,
glycyrrhizinate, chlorohexydine, hinokitiol, dextranase, lysozyme,
edible salts, tranexamic acid, and epsilon-aminocaproic acid, etc.
which are conventionally employed for a tooth paste
composition.
[0510] According to an eleventh aspect of the present invention,
there is provided a cleaning agent composition which comprises (a)
a polycarboxylic acid ester of a monoglyceride or a salt thereof
represented by general formula [3]
R1-COO-CH.sub.2--CHOZ1-CH.sub.2OZ 2 [3]
[0511] wherein R1 is an alkyl or alkenyl group having a carbon
number ranging from 7 to 17, either Z1 or Z2is a residual group of
a polycarboxylic acid or salt thereof, and another hydrogen atom or
a residual group of a polycarboxylic acid or salt thereof, (b) a
fatty acid esters composition of a polyglycerine in the first
aspect or a highly-purified fatty acid esters composition of a
polyglycerine in the fourth aspect, (c) organic or inorganic
builders, (d) fluidity improvers, and additionally (e) thickening
agents, (f) perfumes, (g) coloring agents, (h) sterilizers, (i)
enzymes, and (j) anti-inflammatory agents.
[0512] In the cleaning agent composition, the component (b) which
is the fatty acid esters composition of a polyglycerine or the
highly-purified fatty acid esters composition of a polyglycerine is
employed in an amount ranging from 1.0 to 10.0% by weight,
preferably from 2.0 to 8.0%, and more preferably approximately 5%
by weight based on the total weight of the cleaning agent
composition.
[0513] In the case when the amount is below 1.0% by weight,
cleaning ability becomes poor and, on the contrary, even in the
case when the amount exceeds 10.0% by weight, cleaning ability does
not increase.
[0514] In the cleaning agent composition, the component (a) which
is the polycarboxylic acid ester of a monoglyceride or a salt
thereof is represented by the general formula [3].
[0515] In the formula [3], R1 is an alkyl or alkenyl group having a
carbon number ranging from 7 to 17 which may be linear or branched.
Specifically there are included heptyl group, nonyl group, undecyl
group, tridecyl group, pentadecyl group, heptadecyl group,
heptadecenyl group, etc. Of those, nonyl group, undecyl group, and
tridecyl group are preferably employed from viewpoint of cleaning
ability.
[0516] Z1 or Z 2is a residual group of a polycarboxylic acid or
salt thereof, and another hydrogen atom or a residual group of a
polycarboxylic acid. Specifically there are preferably employed
citric acid, succinic acid, maleic acid, malic acid, glutaric acid,
adipic acid, tartaric acid, diacetyl tartaric acid, and the salts
thereof. Of those, there are more preferably employed citric acid,
succinic acid, diacetyl tartaric acid, and the salts thereof.
[0517] As the salts, there are included alkali salts such as sodium
salts, potassium salts, lithium salts, alkali earth metal salts
such as magnesium salts, ammonium salts, lower amine salts such as
trimethylamine, triethylamine salts, lysine salts, mono-, di-, and
tri-lower alkanol amine salts such as monoethanol amine, diethanol
amine, and triethanol amine which are substituted or
non-substituted ammonium salts.
[0518] Furthermore, an acid type of the polycarboxylic acid esters
of a monoglyceride or the salts thereof exhibits an effect capable
of decreasing microorganisms in starting materials for processed
foods. On the other hand, the salts thereof exhibits high cleaning
ability. Accordingly, those are preferably employed by
appropriately mixing.
[0519] Still further, the polycarboxylic acid esters of a
monoglyceride or the salts may contain a position isomer in which
the polycarboxylic acid connects to primary or secondary hydroxyl
group in the monoglyceride and compounds in which 2 mol of the
polycarboxylic acid connects to the monoglyceride. It is to be
noted that the position isomer and the compounds are produced in a
refining process.
[0520] In the cleaning agent composition, the components (a)/(b)
are employed in a weight ratio ranging from 90/10 to 30/70, and
preferably from 80/20 to 40/60.
[0521] In the case when the ratio is below 30/70 or exceeds 90/10,
cleaning ability unpreferably decreases.
[0522] Furthermore, the cleaning agent composition of the present
invention can optionally include other additives which are
conventionally employed, as far as cleaning ability is not
deteriorated.
[0523] As the other additives, there are employed a sodium
phosphate of a polyoxyethylene alkylether, a fatty acid ester of
sucrose, a fatty acid ester of polyoxyethylene sorbitan, a fatty
acid monoethanolamide, a polyoxyethylene alkylether, a
polyoxyethylene alkylphenylether, a carboxybetaine type-, a
imidazolinium type-, a sulphobetaine type-, and an alanine
type-surface active agents which are harmless to human body.
[0524] As the other additives, there are further employed organic
builders such as sodium pyrophosphate, sodium tripolyphosphate,
zeolite, sodium citrate, sodium malate, nitrilotrisodium acetate,
and a sodium polyacrylate, inorganic builders such as sodium
carbonate, sodium sulphate, sodium chloride, magnesium sulphate,
and calcium chloride, fluidity improvers such as glycerine,
ethanol, propylene glycol, and a polyethyleneglycol, thickening
agents such as carboxymethyl cellulose and hydroxyethyl cellulose,
perfumes, coloring agents, sterilizers, enzymes, and
anti-inflammatory agents, etc.
[0525] According to a twelfth aspect of the present invention,
there is provided a foaming composition for cleaning which
comprises a mixture composed of at least one of a lower monovalent
alcohol having a carbon number ranging from 1 to 3, water, at least
one of a higher alcohol having a carbon number ranging from 12 to
22, and a fatty acid esters composition of a polyglycerine as set
forth in claim 1 or a highly-purified fatty acid esters composition
of a polyglycerine as set forth in claim 14, and an agent for
foaming the mixture.
[0526] In the foaming composition for cleaning, the fatty acid
esters composition of a polyglycerine or the highly-purified fatty
acid esters composition of a polyglycerine is employed in an amount
ranging from 0.5 to 10.0% by weight, and preferably from 1.0 to
5.0% based on the total weight of the foaming composition for
cleaning.
[0527] In the case when the amount is below 0.5% by weight, foaming
ability becomes poor and, on the contrary, in the case when the
amount exceeds 10.0% by weight, foaming ability does not only
increase but also foam is not readily broken, and a feel in use
becomes worse.
[0528] As the lower monovalent alcohol having a carbon number
ranging from 1 to 3, there are employed methanol, ethanol,
n-propanol, and iso-propanol. Of those, ethanol modified by
brucine, etc. from viewpoint of innoxious properties.
[0529] In the foaming composition for cleaning, the lower
monovalent alcohol having a carbon number ranging from 1 to 3 is
employed in an amount ranging from 20 to 70% by weight, and
preferably from 30 to 60% by weight based on the total weight of
the foaming composition for cleaning.
[0530] In the case when the amount is below 20% by weight, a
refreshing feel in use becomes not only insufficient but also
cleaning ability for fatty dirt on skin is insufficient and, on the
contrary, in the case when the amount exceeds 70% by weight,
durability of foam becomes not only worse but also a feel in use
becomes unpreferably worse.
[0531] As the higher alcohol having a carbon number ranging from 12
to 22, there are employed lauryl alcohol, myristyl alcohol,
palmityl alcohol, stearlyl alcohol, oleyl alcohol, cetyl alcohol,
and behenyl alcohol.
[0532] The higher alcohol having a carbon number ranging from 12 to
22 is employed in an amount ranging from 0.5 to 5% by weight, and
preferably from 1 to 3% by weight based on the total weight of the
foaming composition for cleaning. In the case when the amount is
below 0.5% by weight, foaming ability and stability of foam are
insufficient and, on the contrary, in the case when the amount
exceeds 5% by weight, stability of the composition and sol
therefrom becomes not only worse but also a feel in use becomes
unpreferably worse.
[0533] As the agent for foaming the mixture, there are employed
liquified petroleum gases such as propane, n-butane, i-butane,
n-pentane, i-pentane, and a mixture thereof with dimethylether.
[0534] The agent for foaming the mixture is employed in an amount
ranging from 2 to 15% by weight, and preferably from 3 to 10% by
weight based on the total weight of the foaming composition for
cleaning. In the case when the amount is below 2% by weight,
foaming ability is insufficient and, contrarily, in the case when
the amount exceeds 15% by weight, quality and stability of foam
become worse, and a feel in use becomes unpreferably worse.
[0535] The foaming composition for cleaning of the present
invention is an aerosol type, and may be a gas/liquid two Phases
type or gas/liquid/liquid three phases type.
[0536] Furthermore, the foaming composition for cleaning of the
present invention can optionally include polyvalent alcohols, high
molecular compounds, polysaccharides, protein derivatives, extracts
from plants, ultraviolet ray absorbents, medicinal components,
chelating agents, anti-oxidants, and perfumes as far as effects are
not deteriorated within an appropriate quantity and quality
depending upon purposes.
[0537] As the polyvalent alcohols, there are specifically employed
propylene glycol, 1,3-butyleneglycol, dipropylene glycol,
glycerine, diglycerine, sorbitan, sorbitol, maltitol, glucose,
sucrose, etc.
[0538] As the high molecular compounds, there are specifically
employed a cationic polymer such as poly(dimethyldiallyl
ammoniumhalide) [eg. Merquat 100, etc.], a copolymer of
dimethyldiallyl ammoniumhalide with an acrylic monomer [eg. Merquat
550, etc.], a condensate of
polyethyleneglycol/epichlorohydrin/propyleneamine [Polyquat II,
etc.], a quaternary nitrogen-containing cellulose [Polymer JR,
etc.], an anionic polymer such as xanthane gum, carrageenan, sodium
alginate, arabic gum, pectic substances, a carboxyvinyl Polymer, a
nonionic polymer such as a copolymer of vinyl acetate with
polyvinyl pyrrolidone, or vinyl pyrrolidone, a copolymer of vinyl
pyrrolidone with vinyl acetate and an acrylicaminoacrylate,
hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropyl
ethylcellulose, methylcellulose, dextrins, galactan, pullulan,
amphoretic polyelectrolytes such as Yukafoamer AM-75 in which there
are copolymerized dialkylaminoethylacrylate,
dialkylamino-ethylmethacrylate, and diacetone acrylamide with
alkylacrylates or alkylmethacrylates, and then modified by acetic
halides.
[0539] As the polysaccharides, there are specifically employed
hyaluronic acid, chondroitin, heparan sulphate, and salts
thereof.
[0540] As the ultraviolet ray absorbents, there are specifically
employed paraaminobenzoic acid, glycerylparaaminobenzoic acid,
ethyldihydroxypropylparaaminobenzoic acid, etc.
[0541] As the medicinal components, there are specifically employed
vitamin C, vitamin Es, amino acids, anti-inflammatory agent, and
sterilizers, etc.
[0542] The present invention is illustrated below by Examples and
Comparative Examples.
EXAMPLE 1
Preparation No. 1 of a Fatty Acid Esters Composition of a
Polyglycerine Containing more than 70% of a Fatty Acid
Monoester
[0543] A four-necked reaction vessel equipped with a tube for
supplying nitrogen gas, a stirrer, a cooler, a thermostat, and a
dropwise funnel was charged with 100.16 parts by weight of lauric
acid and 0.0622 part by weight of phosphoric acid (a purity of
85%), followed by heating to 140.degree. C. Subsequently, 222.24
parts by weight (molar ratio of glycidol/lauric acid=6) of glycidol
was added drowpwise over 5 hours to allow to react until oxirane
oxygen concentration in the reactant attains below 0.1% while
maintaining the reaction temperature at 140.degree. C.
[0544] After cooling, the reactant was taken out to obtain
approximately 300 parts by weight of a lauric acid esters
composition of a polyglycerine. The lauric acid esters composition
of a polyglycerine prepared was analyzed by the HPLC analytical
condition No. 1 as defined hereinabove.
[0545] The lauric acid esters composition of a polyglycerine
(hereinafter, referred to as PGMLEC) prepared was dissolved in
water to prepare an aqueous solution of 10%, followed by vibrating
with hands for 30 seconds to visually observe foaming ability and
appearance.
[0546] FIG. 1 is a chart obtained by the HPLC analysis relating to
the PGMLEC prepared. It was identified from the chart that the
composition (a hexaglycerine monolaurate composition) contains a
monolaurate of polyglycerine of 87.7% analyzed by the condition No.
1 in the HPLC analysis method.
EXAMPLE 2
Preparation No. 2 of a Fatty Acid Esters Composition of a
Polyglycerine Containing more than 70% of a Fatty Acid
Monoester
[0547] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 100.16 parts by weight of lauric acid and
0.0810 part by weight of phosphoric acid (85%), followed by heating
to 140.degree. C.
[0548] Subsequently, 222.24 parts by weight (molar ratio of
glycidol/lauric acid=6) of glycidol was added drowpwise over 5
hours to allow to react until oxirane oxygen concentration in the
reactant attains below 0.1% while maintaining the reaction
temperature at 140.degree. C. After cooling, the reactant was taken
out to obtain approximately 300 parts by weight of a lauric acid
esters composition of a polyglycerine. The lauric acid esters
composition of a polyglycerine prepared was analyzed by the HPLC
analytical conditions described hereinabove.
[0549] The lauric acid esters composition of a polyglycerine
(PGMLEC) prepared was dissolved in water to prepare an aqueous
solution of 10%, followed by vibrating with hands for 30 seconds to
visually observe foaming ability and appearance.
[0550] FIG. 2 is a chart obtained by the HPLC analysis relating to
PGMLEC prepared. It was identified from the chart that the
composition (a hexaglycerine monolaurate composition) contains a
monolaurate of polyglycerine of 90.8% analyzed by the condition No.
1 in HPLC analysis method.
EXAMPLE 3
Preparation No. 3 of a Fatty Acid Esters Composition of a
Polyglycerine Containing more than 70% of a Fatty Acid
Monoester
[0551] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 100.16 parts by weight of lauric acid and
0.0622 part by weight of phosphoric acid (85%), followed by heating
to 140.degree. C.
[0552] Subsequently, 296.32 parts by weight (molar ratio of
glycidol/lauric acid=8) of glycidol was added drowpwise over 5
hours to allow to react until oxirane oxygen concentration in the
reactant attains below 0.1% while maintaining the reaction
temperature at 140.degree. C. After cooling, the reactant was taken
out to obtain approximately 400 parts by weight of a lauric acid
esters composition of a polyglycerine. The lauric acid esters
composition of a polyglycerine prepared was analyzed by the HPLC
analytical condition No. 1 as described hereinabove.
[0553] The lauric acid esters composition of a polyglycerine
(PGMLEC) prepared was dissolved in water to prepare an aqueous
solution of 10%, followed by vibrating with hands for 30 seconds to
visually observe foaming ability and appearance.
[0554] FIG. 3 is a chart obtained by HPLC relating to PGMLEC
prepared. It was identified from the chart that the composition (an
octaglycerine monolaurate composition) contains a monolaurate of
polyglycerine of 84.5% analyzed by the condition No. 1 in HPLC
analysis method.
EXAMPLE 4
Preparation No. 4 of a Fatty Acid Esters Composition of a
Polyglycerine Containing more than 70% of a Fatty Acid
Monoester
[0555] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 100.16 parts by weight of lauric acid and
0.118 part by weight of phosphoric acid (85%), followed by heating
to 140.degree. C.
[0556] Subsequently, 370.40 parts by weight (molar ratio of
glycidol/lauric acid=10) of glycidol was added drowpwise over 5
hours to allow to react until oxirane oxygen concentration in the
reactant attains below 0.1% while maintaining the reaction
temperature at 140.degree. C. After cooling, the reactant was taken
out to obtain approximately 470 parts by weight of a lauric acid
esters composition of a polyglycerine. The lauric acid esters
composition of a polyglycerine prepared was analyzed by the HPLC
analytical conditions described hereinabove.
[0557] The lauric acid esters composition of a polyglycerine
(PGMLEC) prepared was dissolved in water to prepare an aqueous
solution of 10%, followed by vibrating with hands for 30 seconds to
visually observe foaming ability and appearance.
[0558] FIG. 4 is a chart obtained by the HPLC analysis relating to
the PGMLEC prepared. It was identified from the chart that the
composition (a decaglycerine monolaurate composition) contains a
monolaurate of polyglycerine of 77.2% analyzed by the condition No.
1 in the HPLC analysis method.
EXAMPLE 5
Preparation No. 5 of a Fatty Acid Esters Composition of a
Polyglycerine Containing more than 70% of a Fatty Acid
Monoester
[0559] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 100.16 parts by weight of lauric acid and
0.105 part of a mixture composed of monoethyl acid phosphate and
diethyl acid phosphate (EAP manufactured by Nihon Kagaku Kogyo,
Ltd.), followed by heating to 140.degree. C.
[0560] Subsequently, 370.04 parts by weight (molar ratio of
glycidol/lauric acid=10) of glycidol was added drowpwise over 5
hours to allow to react until oxirane oxygen concentration in the
reactant attains below 0.1% while maintaining the reaction
temperature at 140.degree. C. After cooling, the reactant was taken
out to obtain approximately 470 parts by weight of a lauric acid
esters composition of a polyglycerine. The lauric acid esters
composition of a polyglycerine prepared was analyzed by the HPLC
analytical condition No. 1 as described hereinabove.
[0561] The lauric acid esters composition of a Polyglycerine
(PGMLEC) prepared was dissolved in water to prepare an aqueous
solution of 10%, followed by vibrating with hands for 30 seconds to
visually observe foaming ability and appearance.
[0562] FIG. 5 is a chart obtained by the HPLC analysis relating to
the PGMLEC prepared. It was identified from the chart that the
composition (a decaglycerine monolaurate composition) contains a
monolaurate of polyglycerine of 77.2% analyzed by the condition No.
1 in HPLC analysis method.
COMPARATIVE EXAMPLE 1
Preparation in the Absence of Catalysts
[0563] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 100.16 parts by weight of lauric acid,
followed by heating to 140.degree. C.
[0564] Subsequently, 222.24 parts by weight (molar ratio of
glycidol/lauric acid=6) of glycidol was added drowpwise over 5
hours to allow to react until oxirane oxygen concentration in the
reactant attains below 0.1% while maintaining the reaction
temperature at 140.degree. C. After cooling, the reactant was taken
out to obtain approximately 300 parts by weight of a lauric acid
esters composition of a polyglycerine. The lauric acid esters
composition of a polyglycerine prepared was analyzed by the HPLC
analytical condition No. 1 as described hereinabove.
[0565] The lauric acid esters composition of a polyglycerine
(PGMLEC) prepared was dissolved in water to prepare an aqueous
solution of 10%, followed by vibrating with hands for 30 seconds to
visually observe foaming ability and appearance.
[0566] FIG. 6 is a chart obtained by the HPLC analysis relating to
the PGMLEC (a hexaglycerine monolaurate composition) prepared.
COMPARATIVE EXAMPLE 2
Preparation in the Presence of Paratoluene Sulfonic Acid
[0567] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 100.16 parts by weight of lauric acid and
0.371 part by weight of paratoluene sulfonic acid as a catalyst,
followed by heating to 140.degree. C. Subsequently, 222.24 parts by
weight (molar ratio of glycidol/lauric acid=6) of glycidol was
added drowpwise over 5 hours to allow to react until oxirane oxygen
concentration in the reactant attains below 0.1% while maintaining
the reaction temperature at 140.degree. C. After cooling, the
reactant was taken out to obtain approximately 300 parts by weight
of a lauric acid esters composition of a polyglycerine.
[0568] The lauric acid esters composition of a polyglycerine
prepared was analyzed by the HPLC analytical conditions described
hereinabove. The lauric acid esters composition of a polyglycerine
(PGMLEC) prepared was dissolved in water to prepare an aqueous
solution of 10%, followed by vibrating with hands for 30 seconds to
visually observe foaming ability and appearance.
[0569] FIG. 7 is a chart obtained by the HPLC analysis relating to
the PGMLEC (a hexaglycerine monolaurate composition) prepared.
COMPARATIVE EXAMPLE 3
Preparation by the Reaction of a Fatty Acid Monoglyceride with
Glycidol
[0570] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 137 parts by weight monoglyceride of lauric
acid and 0.45 part by weight of sodium methylate (methanol solution
having 28%) as a catalyst, followed by heating to 90.degree. C.
[0571] Subsequently, 185.2 parts by weight (molar ratio of
glycidol/monoglyceride of lauric acid=5) of glycidol was added
drowpwise over 5 hours to allow to react until oxirane oxygen
concentration in the reactant attains below 0.1% while maintaining
the reaction temperature at 140.degree. C. After cooling, the
reactant was taken out to obtain approximately 300 parts by weight
of a lauric acid esters composition of a polyglycerine.
[0572] The lauric acid esters composition of a polyglycerine
prepared was analyzed by the HPLC analytical condition No. 1 as
described hereinabove.
[0573] The lauric acid esters composition of a polyglycerine
(PGMLEC) prepared was dissolved in water to prepare an aqueous
solution of 10%, followed by vibrating with hands for 30 seconds to
visually observe foaming ability and appearance.
[0574] FIG. 8 is a chart obtained by the HPLC analysis relating to
the PGMLEC prepared.
COMPARATIVE EXAMPLE 4
Preparation by the Reaction of a Fatty Acid with Polyglycerine
[0575] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 175.3 parts by weight a polyglycerine
having a hydroxyl value of 960 (PGL06/a hexaglycerine manufactured
by Daicel Chemical Industries, Ltd., followed by heating to
80.degree. C. Subsequently, 100.16 parts by weight (molar ratio of
polyglycerine/lauric acid=1) of lauric acid was dissolved while
maintaining at 80.degree. C.
[0576] Subsequently, 0.75 part by weight of sodium carbonate and
0.25 part by weight of sodium hydrosulphite were added to allow to
react by esterification at 210.degree. C. After two hours, acid
value was changed to 0.89, followed by taking out a reaction
product after cooling at 100.degree. C.
[0577] The lauric acid esters composition of a Polyglycerine
prepared was analyzed by the HPLC analytical conditions described
hereinabove. It was identified from the chart that the lauric acid
esters composition of a polyglycerine prepared (a hexa glycerine
monolaurate composition) contains a monolaurate of polyglycerine of
55.1%.
[0578] The composition was dissolved in water to prepare an aqueous
solution of 10%, followed by vibrating with hands for 30 seconds to
visually observe foaming ability and appearance.
[0579] FIG. 9 is a chart obtained by the HPLC analysis relating to
the PGMLEC prepared. Results are shown in Table 1.
1 TABLE 1 Examples Comparative Example 1 2 3 4 5 1 2 3 4 A 6 6 8 10
10 10 10 10 8 B 12 12 12 12 12 12 12 12 12 C (1) 87.7 90.8 84.5
77.2 77.2 53.1 52.2 44.3 55.1 (2) 3.0 2.8 11.0 15.0 15.0 4.4 5.7
12.0 17.6 (3) 9.3 6.4 4.5 7.5 7.5 42.5 42.1 43.7 27.3 D Ex Ex Ex Ex
Ex P P P P E SW SW SW SW SW W W W W F FY FY FY FY FY Y Y Y Y G T T
T T T T T T T H O O O O O O O O O
COMPARATIVE EXAMPLES 5 to 14
Evaluation of Fatty Acid Esters Composition of a Polyglycerine
which are Commercially Supplied
[0580] Fatty acid esters composition of a polyglycerine which is
prepared by the reaction of a polyglycerine with a fatty acid was
evaluated by visually observing relating to foaming ability and
appearances similarly to Examples.
[0581] Furthermore, the lauric acid esters composition of a
polyglycerine prepared was analyzed by the HPLC analysis similarly
to Examples. FIGS. 10 to 19 are charts obtained by the HPLC
analysis No. 1 as described hereinabove relating to the PGMLEC
prepared, respectively.
[0582] Results are shown in Table 2.
2 TABLE 2 Comparative Example 5 6 7 8 9 10 11 12 13 14 PG (1) (2)
(3) (4) (5) (6) (7) (8) (9) (10) A 4 10 4 6 10 6 10 6 6 10 B 8 8 12
12 12 12 12 8 12 12 C (1) 50.0 41.5 47.5 52.0 44.3 65.5 53.1 53.2
52.2 55.1 (2) 2.0 4.1 1.4 6.8 12.0 3.8 4.4 3.8 5.7 17.6 (3) 48.0
54.4 51.1 41.2 43.7 30.7 42.5 43.0 42.1 27.3 D P P P P SP SP Ex P P
Ex E W W W W SW SW SW W W SW F Y Y Y Y Y FW FY FY FW FW G T T T T T
T T T T T H O O O O O O O O O O
[0583] In the Tables 1 and/or 2, alphabetical abbreviations and
numbering are as follows.
[0584] PG: fatty acid esters composition of a polyglycerine
commercially supplied
[0585] (1): SY Glystar MO-310 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[0586] (2): SY Glystar MO-750 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[0587] (3): SY Glystar ML-310 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[0588] (4): SY Glystar ML-500 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[0589] (5): SY Glystar MO-750 manufactured by Sakamoto Yakuhin
Kogyo. Ltd.
[0590] (6): Poem J-6021 manufactured by Riken Vitamin, Ltd.
[0591] (7): Poem J-0021 manufactured by Riken Vitamin, Ltd.
[0592] (8): Unigly GO-106 manufactured by Nihon Yushi, Ltd.
[0593] (9): Unigly GL-106 manufactured by Nihon Yushi, Ltd.
[0594] (10):Sunsoft Q12S manufactured by Taiyo Kagaku, Ltd.
[0595] A: the number of glycerine unit (pieces)
[0596] B: the carbon number of fatty acid
[0597] C: peak area ratio by HPLC (UV)
[0598] (1): fatty acid mono ester
[0599] (2): polyglycerine
[0600] (3): others
[0601] D: foaming ability (visual observation after vibration with
hands for 30 seconds relating to 10% aqueous solution)
[0602] Ex: excellent
[0603] P: poor
[0604] E: appearance (at standing still 10% aqueous solution)
[0605] SW: slightly whitening
[0606] W: whitening
[0607] F: color hue
[0608] FW: faintly white
[0609] FY: faintly yellow
[0610] Y: yellow
[0611] G: appearance (at heating)
[0612] T: transparent
[0613] H: appearance (at room temperatures)
[0614] O: opaque
EXAMPLE 6
Preparation No. 1 of a Highly-Purified Fatty Acid Esters
Composition of a Polyglycerine
First Step
[0615] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 100. 16 parts by weight of lauric acid and
0.0622 part by weight of phosphoric acid (a purity of 85%) followed
by heating to 140.degree. C. while stirring.
[0616] Subsequently, 222.24 parts by weight (molar ratio of
glycidol/lauric acid=6) of glycidol was added drowpwise over 5
hours to allow to react until oxirane oxygen concentration in the
reactant attains below 670 ppm while maintaining the reaction
temperature at 140.degree. C. to obtain a product. An acid value of
the product obtained in the first step was 0.13 (JIS 1557).
[0617] Furthermore, It was identified that the product (a
hexaglycerine monolaurate composition) contains a monolaurate of
polyglycerine of 87.7%.
[0618] Still further, the product was analyzed by the proton NMR in
which methanedeuterium chloride was employed as a solvent, the
solution concentration of the product was approximately 5%,
temperature for measuring is 40.degree. C., and JOEL270Mz
(manufactured by Nihon Denshi, Ltd.). Results are shown in Tables
20 and 21.
[0619] From the proton NMR analysis, it is identified that peak
area of a chemical shift between 2.7 ppm and 2.8 ppm assigned by
methylene proton in oxirane group is 0.5, and peak area of a
chemical shift between 3.4 ppm and 4.4 ppm assigned by methylene
proton in polyglycerine and methine proton is 962.6. Peak area
ratio is (0.551/962.6).times.100=0.52(%).
[0620] It is to be noted that the number 0.551 corresponds to
1.655/3 in which the denominator 3 corresponds to 3 protons (a, b,
and c), and the numerator 1.655 corresponds to peak area of 3
protons (a, b, and c).
Second Step
[0621] After the completion of the first step, water was added into
the flask in the amount of 2% by weight based on the product,
followed by heating to 135.degree. C. while stirring.
[0622] Subsequently, the temperature was maintained while refluxing
for 2 hours, followed by raising the temperature to 140.degree. C.
Subsequently, distillation was carried out to remove water in a
reduced pressure while maintaining the temperature at 140.degree.
C.
[0623] Reduced pressure degree after 4 hours distillation was 10
mmHg. Oxirane oxygen concentration and acid value in a
highly-purified fatty acid esters composition of a polyglycerine
obtained were 72 ppm and 0.45, respectively.
[0624] Still further, the product was analyzed by the proton NMR
similarly to the first step.
[0625] Results are shown in Tables 22 and 23.
[0626] From the proton NMR analysis, it is identified that peak
area of a chemical shift between 2.7 ppm and 2.8 ppm assigned by
methylene proton in oxirane group is not observed.
[0627] Accordingly, peak area ratio is zero.
EXAMPLE 7
Preparation No. 2 of a Highly-Purified Fatty Acid Esters
Composition of a Polyglycerine
First Step
[0628] Same procedures were repeated as in Example 6
Second Step
[0629] After the completion of the first step, water was added into
the flask in the amount of 2% by weight based on the product,
followed by heating to 120.degree. C. while stirring.
[0630] Subsequently, the temperature was maintained while refluxing
for 6 hours, followed by raising the temperature to 140.degree. C.
Subsequently, distillation was carried out to remove water in a
reduced pressure while maintaining the temperature at 140.degree.
C.
[0631] Reduced pressure degree after 4 hours distillation was 10
mmHg. Oxirane oxygen concentration and acid value in a
highly-purified fatty acid esters composition of a polyglycerine
obtained were 260 ppm and 0.45, respectively.
EXAMPLE 8
Preparation No. 3 of a Highly-Purified Fatty Acid Esters
Composition of a Polyglycerine
First Step
[0632] Same procedures were repeated as in Example 6
Second Step
[0633] After the completion of the above-described first step,
water was added into the flask in the amount of 2% by weight based
on the product, followed by heating to 120.degree. C. while
stirring. Subsequently, the temperature was maintained while
refluxing for 2 hours, followed by raising the temperature to
140.degree. C. Subsequently, distillation was carried out to remove
water in a reduced pressure while maintaining the temperature at
140.degree. C.
[0634] Reduced degree after 4 hours distillation was 10 mmHg.
[0635] Oxirane oxygen concentration and acid value in a
highly-purified fatty acid esters composition of a polyglycerine
obtained were 430 ppm and 0.45, respectively.
EXAMPLE 9
Preparation No. 4 of a Highly-Purified Fatty Acid Esters
Composition of a Polyglycerine
First Step
[0636] Same procedures were repeated as in Example 6
Second Step
[0637] After the completion of the first step, water was added into
the flask in the amount of 2% by weight based on the product,
followed by heating to 140.degree. C. while stirring.
[0638] Subsequently, the temperature was maintained while refluxing
for 2 hours. Subsequently, distillation was carried out to remove
water in a reduced pressure while maintaining the temperature.
Reduced pressure degree after 4 hours distillation was 10 mmHg.
Oxirane oxygen concentration and acid value in a highly-purified
fatty acid esters composition of a polyglycerine obtained were 72
ppm and 0.45, respectively.
[0639] It is to be noted that in Examples from 6 to 9, the
concentration value of oxirane oxygen in the fatty acid esters
composition of a polyglycerine was analyzed according to the
titration method defined in Cd. 9-57 of Journal of American Oil
Chemists Society, and it is to be noted that in Examples and
Comparative Examples, acid value was analyzed according to JIS
1557.
EXAMPLE 10
Preparation No. 1 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for a Thermoplastic Resin
[0640] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 284.49 parts by weight of stearic acid and
0.0622 part by weight of phosphoric acid (a purity of 85%),
followed by heating to 140.degree. C. Subsequently, 222.24 parts by
weight (molar ratio of glycidol/stearic acid=6) of glycidol was
added drowpwise over 5 hours to allow to react until oxirane oxygen
concentration in the reactant attains below 0.1% while maintaining
the reaction temperature at 140.degree. C., to obtain approximately
500 parts by weight of a fatty acid esters composition of a
polyglycerine (hexaglycerine monostearate composition).
EXAMPLE 11
Preparation No. 2 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for a Thermoplastic Resin
[0641] Same procedures were repeated as in Example 10 except that
296.32 parts by weight (molar ratio of glycidol/stearic acid=8) of
glycidol was employed to obtain approximately 575 parts by weight
of a fatty acid esters composition of a polyglycerine
(octaglycerine monostearate composition).
EXAMPLE 12
Preparation No. 3 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for a Thermoplastic Resin
[0642] Same procedures were repeated as in Example 10 except that
100.16 parts by weight (molar ratio of glycidol/lauric acid=6) of
lauric acid was employed to obtain approximately 320 parts by
weight of a atty acid esters composition of a polyglycerine
(hexaglycerine monolaurate composition).
EXAMPLE 13
Preparation No. 4 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for a Thermoplastic Resin
[0643] Same procedures were repeated as in Example 12 except that
296.32 parts by weight (molar ratio of glycidol/lauric acid=8) of
glycidol was employed to obtain approximately 390 parts by weight
of a fatty acid esters composition of a polyglycerine
(octaglycerine monolaurate composition).
APPLICATION EXAMPLES 1-4 AND COMPARATIVE APPLICATION EXAMPLES
1-3
THE USE OF PRODUCTS OBTAINED IN EXAMPLES 10-13 AS AN ANTI-STATIC
AGENT FOR A THERMOPLASTIC RESIN
[0644] There was prepared a mixture composed of 100 parts by weight
of a polyvinyl chloride (a homopolymer having a polymerization
degree of 700), 1.0 part by weight of a mercapt tinoctylate-based
stabilizer, 2.0 parts by weight of an epoxidized soy bean oil, 0.5
part by weight of stearic acid, and 10 parts of weight of a
reinforced material.
[0645] 4 parts by weight of respective products obtained in
Examples 10-13 and commercially supplied fatty acid esters of
polyglycerine as shown in Table 3 were mixed with the mixture to
obtain respective films by a calendar process, followed by being
biaxially-two fold oriented to obtain films having the thickness of
30 microns. There were measured surface resistance, transparency,
and workability in the calendar process of the oriented films.
Transparency was evaluated based on Haize value.
[0646] Results are shown in Table 3.
3 TABLE 3 Surface Resistance (ohm) Transparency Workability
Application Examples 1 A 3.0 .times. 1012 very good very good 2 B
2.0 .times. 1012 very good very good 3 C 1.0 .times. 1012 very good
very good 4 D 1.0 .times. 1012 very good very good Comparative
Application Examples 1 E 5.0 .times. 1013 good slightly good 2 F
3.0 .times. 1013 good slightly good 3 G 5.0 .times. 1014 good
slightly good
[0647] In the table 3, A, B, C, and D correspond to respective
products obtained in Examples 10, 11, 12, and 13, respectively, and
E, F, and G correspond to SY-GLYSTAR-MS-500, SY-GLYSTAR-ML-500
manufactured by Sakamoto Yakuhin, Ltd., and a glycerine
monostearate, respectively.
EXAMPLES 14
Preparation No. 4 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for a Thermoplastic Resin
[0648] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 100.16 parts by weight of lauric acid and
0.0622 part by weight of phosphoric acid (a purity of 85%),
followed by heating to 140.degree. C. Subsequently, 222.24 parts by
weight (molar ratio of glycidol/lauric acid=6) of glycidol was
added drowpwise over 5 hours to allow to react until oxirane oxygen
concentration in the reactant attains below 0.1% while maintaining
the reaction temperature at 140.degree. C. for 26 hours, to obtain
approximately 300 parts by weight of a fatty acid esters
composition of a polyglycerine (a hexaglycerine monolaurate
composition). Content of the monoester was 87.7% based on the HPLC
analytical condition No. 1 as described hereinabove.
EXAMPLE 15
Preparation No. 5 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for a Thermoplastic Resin
[0649] Same procedures were repeated as in Example 14 except that
296.32 parts by weight (molar ratio of glycidol/lauric acid=8) of
glycidol was employed to obtain approximately 400 parts by weight
of a fatty acid esters composition of a polyglycerine (an
octaglycerine monolaurate composition).
[0650] Content of the monoester was 84.5% based on the HPLC method
described hereinabove.
EXAMPLE 16
Preparation No. 6 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for a Thermoplastic Resin
[0651] Same procedures were repeated as in Example 14 except that
370.40 parts by weight (molar ratio of glycidol/lauric acid=10) of
glycidol was employed to obtain approximately 470 parts by weight
of a fatty acid esters composition of a polyglycerine (a
decaglycerine monolaurate composition).
[0652] Content of the monoester was 77.2% based on the HPLC
analytical condition No. 1 as described hereinabove.
COMPARATIVE EXAMPLE 15
Preparation No. 7 of a Fatty Acid Esters Composition of a
Polyglycerine not Derived from Glycidol as an Additive for a
Thermoplastic Resin)
[0653] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 175.3 parts by weight of a polyglycerine
(PGL06 having a hydroxyl value of 960 manufactured by Daicel
Chemical Industries, Ltd.), followed by heating at 80.degree. C.
Subsequently, 100.16 parts by weight (molar ratio of
polyglycerine/lauric acid=1) of lauric acid was dissolved while
maintaining 80.degree. C., followed by allowing to react for two
hours after adding 0.75 part by weight of sodium carbonate and 0.25
part by weight of sodium hydrogen sulfite at 210.degree. C. After
cooling to 100.degree. C., acid value attained 0.89, and a
polyglycerine monolaurate composition prepared was taken out.
Content of the monoester was 55.1% based on the HPLC analytical
condition No. 1 as described hereinabove.
APPLICATION EXAMPLE 5
Evaluations as an Agent for Improving Anti-Static Property of a
Styrene-Based Resin
[0654] 100 parts by weight of a styrene-based resin having styrene
unit of 100% was mixed with 4.0 parts by weight of a hexaglycerine
monostearate obtained by Example 1 and 2.0 parts by weight of
tristearyl phosphite (JP-318E manufactured by Johoku Kagaku Kogyo,
Ltd.) with a Henshel Mixer, followed by being pelletized with an
extruder having the cylinder diameter of 40 mm phi (manufactured by
Nakaya Kikai).
[0655] Pellets were molded by an injection machine (an N70A type
manufactured by Nihon Seiko) equipped with a flat molding die
[200L.times.70W.times.3t] at the cylinder temperature of
240.degree. C. and the molding die temperature of 50.degree. C.) to
prepare flat test pieces.
[0656] Maximum-charged voltage was 400V, the half period was 4.2
seconds, and intrinsic surface resistance was 72.times.10 ohm.
[0657] It is to be noted that anti-static property of a
styrene-based resin was evaluated by the half period of a maximum
charged pressure (Neostmeter 5-4104 manufactured by Shishido
Syokai), and an intrinsic surface resistance (an intrinsic surface
resistance meter, TR-8601 manufactured by Takeda Riken).
APPLICATION EXAMPLE 6
Evaluations as an Agent for Improving Anti-Static Property of a
Styrene-Based Resin
[0658] The same procedures as described in Application Example 5
were repeated except that there was further mixed 2.0 parts by
weight of a polyethyleneglycol having a molecular weight of
300.
[0659] Maximum-charged voltage was 380V, the half period was 3.2
seconds, and intrinsic surface resistance was 56.times.10 ohm.
APPLICATION EXAMPLE 7
Evaluations as an Agent for Improving Anti-Static Property of a
Styrene-Based Resin
[0660] The same procedures as described in Example 5 were repeated
except that there were employed 8.0 parts by weight of a
hexaglycerine monostearate obtained by Example 1 and 6.0 parts by
weight of a polyethyleneglycol having a molecular weight of 1000.
Maximum-charged voltage was 380V, the half period was 2.2 seconds,
and intrinsic surface resistance was 38.times.10 ohm.
[0661] In the case when the fatty acid esters composition of a
polyglycerine is mixed in an amount exceeding 6 parts by weight,
although the excellent anti-static property is given to a
styrene-based resin, bleeding is unpreferably caused as described
hereinabove.
APPLICATION EXAMPLES 8-11
Evaluations as an Agent for Improving Anti-Static Property of a
Styrene-Based Resin
[0662] Same procedures were repeated as in Application Example 5
except that components were mixed as shown in Table 4.
COMPARATIVE APPLICATION EXAMPLES 4-5
Evaluations as an Agent for Improving Anti-Static Property of a
Styrene-Based Resin
[0663] Same procedures were repeated as in Application Example 5
except that components were mixed as shown in Table 5.
4 TABLE 4 Application Example 8 9 10 11 Mixing components
Styrene-based resin St/MMA St/AN St/MMA/MA St/MMA/MA/CHMI Monomer
ratio (wt %) 50/50 60/40 40/56/4 10/70/5/15 PGLE MS06 MS06 MS06
MS06 (part by weight) (4) (4) (4) (4) Phosphorus compound DP SP DP
SP (part by weight) (2) (1) (3) (1) PAG 3E 10E 10P -- (part by
weight) (0.5) (1) (2) -- Properties MCV (v) 420 420 440 410 HP
(second) 4.2 5.3 4.0 3.9 S1R (.times.10 55 72 69 85
[0664]
5 TABLE 5 Comparative Application Example 4 5 Mixing components
Styrene-based resin St/MMA .sup. St/MMA Monomer ratio (wt %) 50/50
50/50 PGLE MS06 -- (part by weight) (4) -- Phosphorus compound --
SP.sup. (part by weight) -- .sup. (2) PAG -- -- Properties MCV (v)
500 540 HP (second) 92 .sup. 210< .sup. SIR (.times.10.sup.12)
1800 36000
[0665] In the Tables 4 and 5, abbreviations are as follows.
[0666] St: Styrene
[0667] MMA: Methylmethacrylate
[0668] AN: Acrylonitrile
[0669] MA: Methylacrylate
[0670] CHMI: Cyclohexylmaleimide
[0671] PGLE: Fatty acid esters composition of a polyglycerine
[0672] MS06: Hexaglycerine monostearate obtained in Example 2
[0673] DP: Tridecylphosphite
[0674] SP: Tristearylphosphite
[0675] PAG: Polyalkylene glycol
[0676] 3E: Polyethylene glycol having a molecular weight of 300
[0677] 10E: Polyethylene glycol having a molecular weight of
1000
[0678] 10P: Polypropylene glycol having a molecular weight of
1000
[0679] MCV: Maximum-charged voltage
[0680] HP: Half period
[0681] SIR: Surface intrinsic resistance
[0682] It is clearly identified from the values in Tables 4 and 5
that an excellent anti-static property is given to a styrene-based
resin by mixing an appropriate amount of the fatty acid esters
composition of a polyglycerine in the present invention.
APPLICATION EXAMPLE 12
Evaluation as a Releasing Agent for Methylmethacrylate-Based
Resin
[0683] There were mixed 100 parts by weight of a particle-state
methacrylic resin [Sumipex BL0 manufactured by Sumitomo Chemicals
Industries, Ltd.], 0.025 part by weight of dipentaerytliritol
tripalmitate, and 0.025 part by weight of the fatty acid esters
composition of a polyglycerine obtained in Example 1 with a Henshel
Mixer, followed by being extruded with a vent-type extruder having
the cylinder diameter of 40 mm phi to obtain pellets.
[0684] Pellets obtained were molded by a 13-ounces injection
machine (an M-140SJ type manufactured by Meiki Seisakusyo) equipped
with a molding die [25 mm.times.76.5 mm.times.3.2 mm] at the
cylinder temperature of 260.degree. C., molding die temperature of
60.degree. C. injection pressure of 80 kg/cm2-G, with interval of
60 seconds to evaluate a releasing property while continuously
preparing ASTM test pieces for 40 times.
[0685] The releasing property was evaluated by comparing the number
of broken or cracked pieces in the test pieces. Contamination
property in the molding die was evaluated by visually observing the
presence or absence of clouding portions in the inner surface of
the molding die according to the following levels.
[0686] N.C: no-clouding
[0687] X : clouding
[0688] Outer appearance in the test pieces was evaluated by
visually observing contamination or coloring in pieces.
APPLICATION EXAMPLES 13 to 19
Evaluation as a Releasing Agent for a Methylmethacrylate-Based
Resin
[0689] The same procedures were repeated as described in
Application Example 12 according to mixing ratio as shown in Table
6.
COMPARATIVE APPLICATION EXAMPLES 6 to 9
Evaluation as a Releasing Agent for a Methylmethacrylate-Based
Resin
[0690] The same procedures were repeated as described in Example 24
according to mixing ratio as shown in Table 6.
6 TABLE 6 mixing ratio RP CP OA Application Example 12 A (0.025)/E
(0.025) 7.6 NC G 13 A (0.05)/E (0.05) 6.4 NC G 14 A (0.1)/E (0.1)
5.0 NC G 15 A (0.03)/E (0.07) 6.3 NC G 16 A (0.07)/E (0.03) 6.4 NC
G 17 B (0.05)/E (0.05) 6.6 NC C 18 C (0.05)/E (0.05) 6.7 NC G 19 D
(0.05)/E (0.05) 6.7 NC G Comparative Application Example 6 -- --
15.0 NC G 7 A (0.1)/-- 12.3 NC G 8 -- /E (0.1) 12.3 NC G 9 A
(0.3)/E (0.3) 4.4 X SY
[0691] In the Table 6, abbreviations are as follows.
[0692] Dipentaerythritol tripalmitate
[0693] Dipentaerythritol hexabehenate
[0694] Monopentaerythritol
[0695] Tripentaerythritol
[0696] Fatty acid esters composition of a polyglycerine obtained in
Example 1
[0697] RP: Releasing property
[0698] CP: Contamination property
[0699] OA: Outer appearance
[0700] NC: No-clouding
[0701] X: Clouding
[0702] G: Good
[0703] SY: Slightly yellowing
[0704] It is clearly identified from the values in Table 5 that an
excellent relasing property is given to a methylmethacrylate-based
resin by mixing an appropriate amount of the fatty acid esters
composition of a polyglycerine in the present invention.
EXAMPLE 17
Preparation No. 8 of a Fatty Acid Esters Composition of a
Polyglycerine as an Agent for Improving Properties of a
Thermoplastic Resin
[0705] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 284.49 parts by weight of stearic acid and
0.0622 part by weight of phosphoric acid (a purity of 85%),
followed by heating to 140.degree. C. Subsequently, 222.24 parts by
weight (molar ratio of glycidol/stearic acid=6) of glycidol was
added drowpwise over 5 hours to allow to react until oxirane oxygen
concentration in the reactant attains below 0.1% while maintaining
the reaction temperature at 140.degree. C.
[0706] There was obtained approximately 500 parts by weight of a
fatty acid esters composition of a polyglycerine (a hexaglycerine
monostearate composition). The composition is designated E-1.
EXAMPLE 18
Preparation No. 9 of a Fatty Acid Esters Composition of a
Polyglycerine as an Agent for Improving Properties of a
Thermoplastic Resin
[0707] Same procedures were repeated as in Example 17 except that
296.32 parts by weight (molar ratio of glycidol/stearic acid=8) of
glycidol was employed to obtain approximately 565 parts by weight
of a fatty acid esters composition of a polyglycerine (an
octaglycerine monostearate composition).
[0708] The composition is designated E-2.
EXAMPLE 19
Preparation No. 10 of a Fatty Acid Esters Composition of a
Polyglycerine as an Agent for Improving Properties of a
Thermoplastic Resin
[0709] Same procedures were repeated as in Example 17 except that
370.40 parts by weight (molar ratio of glycidol/stearic acid=10) of
glycidol was employed to obtain approximately 650 parts by weight
of a fatty acid esters composition of a polyglycerine (a
decaglycerine monostearate composition).
[0710] The composition is designated E-3.
COMPARATIVE PREPARATION EXAMPLE 1
Preparation No. 11 of a Fatty Acid Esters Composition Obtained by
the Reaction of Fatty Acid with a Polyglycerine as an Agent for
Improving Properties of a Thermoplastic Resin
[0711] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 175.3 parts by weight of a hexaglycerine
having a hydroxyl value of 960 [PGL106 manufactured by Daicel
Chemical Industries, Ltd.], followed by heating to 80.degree. C.
Subsequently, 100.16 parts by weight (molar ratio of
hexaglycerine/lauric acid=1) of lauric acid was dissolved while
maintaining at 80.degree. C. Subsequently, 0.75 part by weight of
sodium carbonate and 0.25 part by weight of sodium hydrogen
sulphite were added, followed by allowing to react at 210.degree.
C. for 2 hours to obtain a product. After cooling to 100.degree.
C., there was taken out the product having an acid value of
0.89.
[0712] The product was analyzed by the HPLC analytical condition
No. 1 as described hereinabove to identify the content of a lauric
monoester compound of polyglycerine (a hexaglycerine monoester
composition) of 55.1%.
[0713] The product is designated E-4.
COMPARATIVE PREPARATION EXAMPLES 2 and 3
Measurement of the Content of Monoester Compound in Commercially
Supplied Fatty Acid Esters Composition
[0714] As a commercially supplied fatty acid esters composition
obtained by the reaction of fatty acid with a polyglycerine, there
were evaluated SY Glystar ML-500 and SY Glystar ML-750
(manufactured by Sakamoto Yakuhin Industries).
[0715] ML-500 exhibited the content of monoester compound of 52.0%,
and ML-750 exhibited the content of monoester compound of 44.3%.
ML-500 and ML-750 are designated E-5 and E-6.
[0716] Results are shown in Table 7.
PREPARATION EXAMPLE 1
Preparation No. 1 of a Polyacetal Resin
[0717] A polyacetal resin in which 2.8% of ethylene oxide is
copolymerized was prepared according to known processes described
in U.S. Pat. No. 3,027,352.
[0718] The polyacetal resin has an intrinsic viscosity of 1.0
(measured with a m-chlorophenol solution having 2.0% by weight of
alpha-pinene containing 0. 1 by weight of the polyacetal resin at
60.degree. C.) and melt index of 30.0 g/10 minutes (according to
ASTM D1238-57T). The polyacetal resin is designated P-1.
PREPARATION EXAMPLE 2
Preparation No. 2 of a Polyacetal Resin
[0719] The polyacetal resin having an intrinsic viscosity of 1.2
(measured with a m-chlorophenol solution having 2.0% by weight of
alpha-pinene containing 0.1% by weight of the polyacetal resin at
60.degree. C.) and melt index of 40.0 g/10 minutes (according to
ASTM D1238-57T) in which terminals are acetylated was prepared
according to known processes described in U.S. Pat. No.
2,998,409.
[0720] The polyacetal resin is designated P-2.
APPLICATION EXAMPLES 20 to 29
Preparation of Articles Molded from a Polyacetal Resin Composition
and Evaluations as an Agent for Improving a Printing Property by
the Fatty Acid Esters Composition of the Present Invention
[0721] There were mixed 0.2 part by weight of triethyleneglycolbis
(3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate), the
above-prepared polyacetal resins, a hindered amine compound, a
fatty acid esters composition of a polyglycerine, and a nucleating
agent in a mixing ratio as shown in Tables 4 and 5 under a nitrogen
atmosphere, followed by extruding with a L/D=25 single screw
extruder (the screw revolution of 100 rpm and the discharge amount
of 6 kg/hour) having a vent to prepare pellets.
[0722] The pellets were dried, and then molded (the mold
temperature of 100.degree. C. and the cooling time of period of 7
seconds) with a 5-ounces molding machine to prepare MFD
shutters.
[0723] The MFD shutters were irradiated by a corona discharging
lamp (irradiation energy of 90 watt, irradiation time of 0.2
second, discharging clearance of 7 mm, and discharging rate of 10
mm/sec). Subsequently, an ink (Tampo R double-liquid manufactured
by Tampo, Ltd.) was printed on a portion of the surface having
slightly more than 1 cm square in the respective MFD shutters.
Subsequently, curing was carried out at the heating temperature of
120.degree. C. for 20 minutes, followed by cooling at 23.degree. C.
and humidity of 50% for 24 hours.
[0724] After cooling, cross cut peeling tests were carried out
based on JIS K-5400 with cellophane tapes. Cross cut lines were
given with the interval of 1 mm by a cutter, respectively.
COMPARATIVE APPLICATION EXAMPLES 10 to 19
EVALUATION AS AN AGENT FOR IMPROVING A PRINTING PROPERTY BY THE
FATTY ACID ESTERS COMPOSITION OBTAINED IN COMPARATIVE EXAMPLE 1 AND
COMMERCIALLY SUPPLIED FATTY ACID ESTERS COMPOSITIONS
[0725] The same procedures were repeated as described in
Application Examples 20 to 29 except that there were employed the
hexaglycerine monostearate obtained in Comparative Example 1, SY
Glystar ML-500 (manufactured by Sakamoto Yakuhin Industries), and
SY Glystar ML-750 (manufactured by Sakamoto Yakuhin
Industries).
[0726] Evaluations of printing property were based on the following
6 stages.
[0727] 0: no-removed
[0728] 1: slightly removed (total length of removed ink of less
than 20 mm and width of less than 0.1 mm)
[0729] 2: slightly removed (total length of removed ink of 20 to 50
mm and width of 0.1-0.2 mm)
[0730] 3: fairly removed (total length of removed ink of 50< to
100 mm and width of 0.2< to 0.4 mm)
[0731] 4: further removed (total length of removed ink of 100<
to 150 mm and width of less than 0.4< to 0.5 mm)
[0732] 5: considerably removed (total length of removed ink of
exceeding 150 mm and width of exceeding 0.5 mm).
[0733] Printing properties after 1 hour and 1000 hours from
printing were evaluated. Results are shown in Tables 7 and 8.
7 TABLE 7 Example 20 21 22 23 24 25 26 27 28 29 (a) P-1 100 (b) D-1
D-4 D-5 D-1 D-2 D-3 D-4 D-5 D-5 D-5 0.01 0.01 0.05 3.0 0.1 0.1 0.01
0.01 0.08 3.0 (c) E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-2 E-3 0.05 4.0
0.1 1.0 0.2 3.0 0.01 0.5 0.2 0.2 (d) K-1 100 100 500 500 1000 500
500 800 800 300 (e) 15.0 15.0 3.0 3.0 1.1 3.0 3.0 1.5 1.5 7.0 (f) 1
1 1 0 0 0 1 1 0 0 (g) 1 1 1 0 0 0 1 1 0 0
[0734]
8 TABLE 8 Comparative Application Example 10 11 12 13 14 15 16 17
18 19 (a) P-1 100 (b) D-1 D-4 D-5 D-1 D-2 D-3 D-4 D-5 D-5 D-5 0.01
0.01 0.05 3.0 0.1 0.1 0.01 0.01 0.08 3.0 (C) E-4 E-4 E-4 E-4 E-4
E-4 E-4 E-4 E-5 E-6 0.05 4.0 0.1 1.0 0.2 3.0 0.01 0.5 0.2 0.2 (d)
K-1 100 100 500 500 1000 500 500 800 800 300 (e) 15.0 15.0 3.0 3.0
1.1 3.0 3.0 1.5 1.5 7.0 (f) 1 1 1 0 0 0 1 1 0 0 (g) 5 4 5 5 5 5 5 5
4 4
[0735] In the Tables 7 and 8, abbreviations and alphabetically
numbering are as follows.
[0736] (a): 100 parts by weight of P-1 (polyacetal polymer) was
employed in all the Application Examples and Comparative
Application Examples.
[0737] (b): Hindered amine compound (part by weight)
[0738] D-1: 3
[0739] wherein X is the formula described below, 4
[0740] m is 2, and n is 1.5,
[0741] and R is the formula described below. 5
[0742] Y is a hydrogen atom.
[0743] D-2: In the formula (4), Y is a methyl group, m is 2, and n
is 1.5.
[0744] D-3: In the formula (4), Y is a methyl group, m is 1 and n
is 1.5.
[0745] D-4: bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate
[0746] D-5: bis(2,2,6,6-tetramethyl-4-piperidyl)adipate
[0747] (c): E-1/hexaglycerine monostearate obtained in Example
17
[0748] E-2/octaglycerine monostearate obtained in Example 18
[0749] E-3/decaglycerine monostearate obtained in Example 19
[0750] E-4/hexaglycerine monostearate obtained in Comparative
Example 1
[0751] E-5/SY Glystar ML-500 (manufactured by Sakamoto Yakuhin
Industries)
[0752] E-6/SY Glystar ML-750 (manufactured by Sakamoto Yakuhin
Industries)
[0753] (d): K-1/Boron nitride having an average particle size of 2
microns as a nucleating agent (ppm).
[0754] (e): Thickness of skin layer (micron)
[0755] (f): Printing property after 1 hour
[0756] (g): Printing property after 1000 hours
[0757] By the values in (g) of Tables 7 and 8, it is clearly shown
that the fatty acid esters composition of the present invention
exhibits an effect for improving printing property in articles
molded from the polyacetal resin composition, compared to the fatty
acid esters composition obtained in Comparative Example 1 and the
commercially supplied fatty acid esters compositions.
EXAMPLE 20
Preparation No. 12 of a Fatty Acid Esters Composition of a
Polyglycerine as an Agent for Improving Properties of a
Thermoplastic Resin
[0758] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 100. 16 parts by weight of lauric acid and
0.0622 part by weight of phosphoric acid (a purity of 85%),
followed by heating to 140.degree. C. Subsequently, 222.24 parts by
weight (molar ratio of glycidol/lauric acid=6) of glycidol was
added drowpwise over 5 hours to allow to react until oxirane oxygen
concentration in the reactant attains below 0.1% while maintaining
the reaction temperature at 140.degree. C.
[0759] There was obtained approximately 320 parts by weight of a
fatty acid esters composition of a polyglycerine (a hexaglycerine
monolaurate composition).
[0760] The composition is designated E-1.
EXAMPLE 21
Preparation No. 13 of a Fatty Acid Esters Composition of a
Polyglycerine as an Agent for Improving Properties of a
Thermoplastic Resin
[0761] Same procedures were repeated as in Example 20 except that
296.32 parts by weight (molar ratio of glycidol/lauric acid=8) of
glycidol was employed to obtain approximately 390 parts by weight
of a fatty acid esters composition of a polyglycerine (an
octaglycerine monolaurate composition).
[0762] The composition is designated E-2.
EXAMPLE 22
Preparation No. 14 of a Fatty Acid Esters Composition of a
Polyglycerine as an Agent for Improving Properties of a
Thermoplastic Resin
[0763] Same procedures were repeated as in Example 20 except that
370.40 parts by weight (molar ratio of glycidol/lauric acid=10) of
glycidol was employed to obtain approximately 465 parts by weight
of a fatty acid esters composition of a polyglycerine (a
decaglycerine monolaurate composition).
[0764] The composition is designated E-3.
APPLICATION EXAMPLES 30 to 32
Evaluations as an Agent for Improving a Wetting Property of a
Polyacetal Resin by the Fatty Acid Esters Composition of the
Present Invention
[0765] Polyacetal resin (having a trade name of Duracon U10
manufactured by Polyplastics, Ltd.) was mixed with a variety of
additives according to respective mixing ratio as shown in Table 8
to prepare a polyacetal resin composition.
[0766] Mixing was carried out with a 30-mm twin screw extruder to
prepare pellets. Results are shown in Table 9.
9 TABLE 9 Application Example 30 31 32 Additives E-1 E-2 E-3 Amount
(% by weight) 0.2 0.2 0.2 Wetting property 38 40 41 (contact
angle/degree) Tensile strength 620 615 620 (kgf/cm2) Melt Index 1.0
1.0 1.0 (g/10 minutes)
COMPARATIVE APPLICATION EXAMPLES 20 to 28
EVALUATION AS AN AGENT FOR IMPROVING A PRINTING PROPERTY BY THE
FATTY ACID ESTERS COMPOSITION OBTAINED IN COMPARATIVE EXAMPLE 1 AND
COMMERCIALLY SUPPLIED FATTY ACID ESTERS COMPOSITIONS
[0767] The same procedures were repeated as in Application Examples
30 to 32 except that there were employed the fatty acid esters
composition obtained in Comparative Example 1 and commercially
supplied fatty acid esters compositions.
[0768] Results are shown in Table 10.
10 TABLE 10 Comparative Application Example 20 21 22 23 24 25 26 27
28 Additives A-1 A-1 A-2 A-3 -- B C C D Amount (% 0.2 0.5 0.5 0.5
-- 1.0 1.0 2.0 2.0 by weight) Wetting 65 41 40 38 72 70 70 58 60
property (contact angle/degree) Tensile 610 590 600 590 620 570 580
530 510 strength (kgf/cm2) Melt Index 1.0 1.1 1.0 1.0 1.0 1.2 1.0
1.8 1.6 (g/10 minutes)
[0769] In the Tables 9 and 10, abbreviations are as follows.
[0770] E-1: Fatty acid esters composition of a polyglycerine
obtained in Example 20 (a hexaglycerine monolaurate)
[0771] E-2: Fatty acid esters composition of a polyglycerine
obtained in Example 21 (an octaglycerine monostearate)
[0772] E-3: Fatty acid esters composition of a polyglycerine
obtained in Example 22 (a decaglycerine monolaurate)
[0773] A-1: Commercially supplied fatty acid esters composition of
a polyglycerine (a decaglycerine monolaurate)
[0774] A-2: Commercially supplied fatty acid esters composition of
a polyglycerine (a decaglycerine monostearate)
[0775] A-3: Commercially supplied fatty acid esters composition of
a polyglycerine (a octaglycerine monolaurate)
[0776] B: Glycerine monolaurate
[0777] C: Polyethyleneglycol having a molecular weight of 1000
[0778] D: Polyethyleneglycol having a molecular weight of 6000
EXAMPLE 23
Preparation No. 15 of a Fatty Acid Esters Composition of a
Polyglycerine as an Agent for Improving Properties of a
Thermoplastic Resin
[0779] A four-necked flask equipped with a tube for supplying
nitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise
funnel was charged with 142.25 parts by weight of stearic acid and
0.0622 part by weight of phosphoric acid (a purity of 85%),
followed by heating to 140.degree. C. Subsequently, 222.24 parts by
weight (molar ratio of glycidol/stearic acid=6) of glycidol was
added drowpwise over 5 hours to allow to react until oxirane oxygen
concentration in the reactant attains below 0.1% while maintaining
the reaction temperature at 140.degree. C.
[0780] There was obtained approximately 260 parts by weight of a
fatty acid esters composition of a polyglycerine (a hexaglycerine
monostearate composition). The composition is designated E1.
EXAMPLE 24
Preparation No. 16 of a Fatty Acid Esters Composition of a
Polyglycerine as an Agent for Improving Properties of a
Thermoplastic Resin
[0781] The same procedures were repeated as described in Example 23
except that 370.40 parts by weight (molar ratio of glycidol/stearic
acid=10) of glycidol was employed.
[0782] There was obtained approximately 380 parts by weight of a
fatty acid esters composition of a polyglycerine (a decaglycerine
monostearate composition). The composition is designated E2.
APPLICATION EXAMPLES 33 to 41
Evaluations as an Agent for Improving a Releasing Property of a
Polyacetal Resin by the Fatty Acid Esters Composition of the
Present Invention
[0783] Polyacetal resin (having a trade name of Duracon-M270
manufactured by Polyplastics, Ltd.) was mixed with a variety of
additives according to respective mixing ratio as shown in Table 10
to prepare polyacetal resin compositions.
[0784] The polyacetal resin composition was extruded with an
extruder to prepare pellets while visually observing the presence
or absence of foaming in strands before forming pellets.
[0785] Subsequently, the pellets were molded with an injection
machine to prepare test pieces. Respective methods for evaluating
properties are as follows.
[0786] Tensile Strength and Shear Strength:
[0787] The test pieces were placed at the conditions of the
temperature of 23.degree. C. and the humidity of 50% for 48 hours,
followed by measuring with a tensile strength tester (Tensilon
manufactured by Orientec, Ltd. ) based on ASTM-D638 and
ASTM-D732-85.
[0788] Amount of Gas in Melting:
[0789] There were stored 8 g of the pellets in a Melt Index tester
at 200.degree. C. for 5 minutes, followed by being discharged while
loading. Formaldehyde was caught while discharging under loading,
followed by being quantitatively measured. The amount of
formaldehyde is shown by ppm based on the unit weight of the
polyacetal resin.
[0790] Continuous Injection Test:
[0791] There was operated an injection machine (manufactured by
Toshiba Kikai Plastic Engineering, Ltd.) at the conditions of
cylinder temperature of 100.degree. C., injection pressure of
750kg/cm2, injection time of 4 seconds, cooling time of 3 seconds,
and molding die temperature of 30.degree. C. After continuously
molding articles having a specific shape at the conditions, the
amount of resin scraps adhered was visually measured to evaluate a
releasing property according to the following 5 stages.
[0792] A: resin scraps are not observed at all
[0793] S: a minor amount of resin scraps are only observed
[0794] C: resin scraps are slightly observed
[0795] D: resin scraps are relatively observed
[0796] E: resin scraps are considerably observed
[0797] Results are shown in Table 11.
11 TABLE 11 Application Example 33 34 35 36 37 38 39 40 41 Mixing
ratio and additives (A) 100 100 100 100 100 100 100 100 100 (B)
fibrous titanium oxide Average diameter 0.1 0.2 0.1 0.1 0.1 0.1 0.2
0.1 0.1 of fibrous titanium oxide (micron) Average length 8 12 8 8
8 8 8 8 8 of fibrous titanium oxide Agent for B1 B1 B2 B1 B1 B1 B1
B1 B1 processing the surface of fibrous titanium oxide (part by
weight) 25 25 25 45 25 25 25 25 25 (C) C1 C1 C1 C1 C2 C1 C1 C1 C1
(part by weight) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.4 0.2 (D) D1 D1 D1
D1 D1 D2 D1 D1 D1 (part by weight) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
0.4 (E) E1 E1 E1 E1 E1 E1 E2 E1 E1 (part by weight) 0.3 0.2 0.3 0.3
0.3 0.3 0.3 0.3 0.3 Properties Tensile strength 830 880 820 1050
840 830 825 820 820 (kg/cm2 ) Shear strength 590 625 580 730 600
595 590 580 590 (kg/cm2) Moldability Bubble in NB NB NB NB NB NB NB
NB B molding Continuous A A A B A A A A A injection test Amount of
100 70 105 120 95 95 120 60 70 gas (ppm)
COMPARATIVE APPLICATION EXAMPLES 29 to 34
Evaluations as an Agent for Improving a Releasing Property by
Commercially Supplied Fatty Acid Esters Compositions
[0798] The same procedures were repeated as described in
Application Examples 33 to 41 except that there were employed
commercially supplied fatty acid esters compositions.
12 TABLE 12 Comparative Application Example 29 30 31 32 33 34
Mixing ratio and additives (A) 100 100 100 100 100 100 (B) fibrous
titanium oxide Average diameter 0.3 0.3 0.1 0.1 0.1 0.1 of fibrous
titanium oxide (micron) Average length 15 15 8 8 8 8 of fibrous
titanium oxide Agent for B1 B1 B1 B1 B1 -- processing surface of
fibrous titanium oxide (part by weight) 25 45 25 25 25 -- (C) C1 C1
-- C1 C1 C1 (part by weight) 0.2 0.2 -- 0.2 0.2 0.2 (D) D1 D1 D1 --
D1 D1 (part by weight) 0.4 0.4 0.4 -- 0.4 0.4 (E) E1 E1 E1 E1 -- E1
(part by weight) 0.3 0.3 0.3 0.3 -- 0.3 Properties Tensile strength
900 1100 835 8300 835 -- (kg/cm2) Shear strength 590 630 590 570
580 -- (kg/cm2) Moldability Bubble in NB NB NB NB NB B molding
Continuous D E D D C impossible injection test Amount of 280 510
200 175 180 -- gas (ppm)
[0799] In the Tables 11 and 12, alphabetical abbreviations are as
follows.
[0800] (A): Polyacetal resin
[0801] (B): Titanium oxide whisker
[0802] B1: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane
[0803] B2: 3-glycidoxypropyltrimethoxysilane
[0804] (C): Compound having nitrogen
[0805] C1: Melamine
[0806] C2: Calcium stearate
[0807] (D): Hindered phenol compound
[0808] D1:
Pentaerythrityltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propi-
onate]
[0809] D2:
Triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)pro-
pionate]
[0810] (E): Fatty acid esters composition of a polyglycerine
[0811] E1: Fatty acid esters composition of a polyglycerine
(hexaglycerine monostearate composition) obtained in Example 23
[0812] E1: Fatty acid esters composition of a polyglycerine
(decaglycerine monostearate composition) obtained in Example 24
[0813] NB: Absence of bubble
[0814] B: Presence of bubble
EXAMPLE 25
Preparation No. 1 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for Cosmetics
[0815] A four-necked reaction vessel equipped with a tube for
supplying nitrogen gas, a stirrer, a cooler, a thermostat, and a
dropwise funnel was charged with 100.16 parts by weight of lauric
acid and 0.0622 part by weight of phosphoric acid (a purity of
85%), followed by heating to 140.degree. C. Subsequently, 222.24
parts by weight (molar ratio of glycidol/lauric acid=6) of glycidol
was added drowpwise over 5 hours to allow to react, followed by
further allowing to react for 26 hours while maintaining the
reaction temperature at 140.degree. C.
[0816] After cooling, the reactant was taken out to obtain
approximately 300 parts by weight of a lauric acid esters
composition of a polyglycerine. The lauric acid esters composition
of a polyglycerine prepared was analyzed by the analytical
condition No. 1 in the HPLC analysis as defined hereinabove. It was
identified from the chart that the composition (a hexaglycerine
monolaurate composition) contains a monolaurate of polyglycerine of
87.7%.
EXAMPLE26
Preparation No. 2 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for Cosmetics
[0817] The same procedures were repeated as described in Example
25. except that there was employed 296.32 parts by weight (molar
ratio of glycidol/lauric acid=8) of glycidol. It was identified
from the chart that the composition (an octaglycerine monolaurate
composition) contains a monolaurate of polyglycerine of 84.5% by
the analytical condition No. 1 in the HPLC analysis as defined
hereinabove.
Example 27
Preparation No. 3 of a Fatty Acid Esters Composition of a
Polyglycerine as an Additive for Cosmetics
[0818] The same procedures were repeated as described in Example
25, except that there was employed 370.4 parts by weight (molar
ratio of glycidol/lauric acid=10) of glycidol. It was identified
from the chart that the composition (a decaglycerine monolaurate
composition) contains a monolaurate of polyglycerine of 77.2% by
the analytical condition No. 1 in the HPLC analysis as defined
hereinabove.
APPLICATION EXAMPLES 42 to 44 AND COMPARATIVE APPLICATION EXAMPLES
35 to 37
Evaluations as a Water-in-Oil Type-Emulsified Composition for
Cosmetics
[0819] There was prepared a water-in-oil type-emulsified
composition for cosmetics based on the components and the mixing
ratio as described below, respectively.
[0820] Liquid paraffin (23% by weight)
[0821] Vaseline (6.5% by weight)
[0822] Micro-crystalline wax (0.2% by weight)
[0823] Lanolin (4.0% by weight)
[0824] Bleached bees wax (1.2% by weight)
[0825] Tri(caprylic-capric)glyceryl (12% by weight)
[0826] Butyl paraoxybenzoate (0.1% by weight)
[0827] Glycerine (15% by weight)
[0828] Ethyl paraoxybenzoate (0.1% by weight)
[0829] Perfume (0.2% by weight)
[0830] Purified water (34.2% by weight), (19.2% by weight only in
Comparative Application Example 36)
[0831] 1,3-butyleneglycol (15% by weight only in Comparative
Application Example 36)
[0832] Fatty acid esters composition of a polyglycerine (3.5% by
weight)
APPLICATION EXAMPLES
[0833] 42: Fatty acid esters composition of a polyglycerine (a
hexaglycerine monolaurate composition) prepared in Example 25
[0834] 43: Fatty acid esters composition of a polyglycerine (an
octaglycerine monolaurate composition) prepared in Example 26
[0835] 44: Fatty acid esters composition of a polyglycerine (a
decaglycerine monolaurate composition) prepared in Example 21
COMPARATIVE APPLICATION EXAMPLES
[0836] 35: Hexaglycerine monolaurate composition prepared in
Comparative Example 4 <by the reaction of a fatty acid with a
polyglycerine>
[0837] 36: SY Glystar ML-500 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[0838] 37: SY Glystar HO-750 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[0839] Total weight (100% by weight)
[0840] In Application Examples 42 to 44, an oily phase containing a
fatty acid esters composition of a polyglycerine and glycerine was
dissolved by heating to 75.degree. C. Independently, a water phase
containing purified water was heated to 75.degree. C.
[0841] The water phase was added into the oily phase to emulsify
while mixing with an emulsifier, followed by cooling and adding
perfumes at 45.degree. C., and then cooling to 30.degree. C.
[0842] In Comparative Application Examples, the same procedures
were repeated as employed in Application Examples except that
1,3-butyleneglycol was mixed only in Comparative Application
Example 36.
[0843] Results are shown in Table 13.
13 TABLE 13 Application Comparative Examples Application Example 42
43 44 35 36 37 Property Viscosity 1570 1830 1970 2540 2430 2660
immediately after prepared Viscosity after 1570 1830 1970 2540 2430
2660 3 months Stability for a long time of period (3 months) Room
temperature - - - + - - -5.degree. C. - - - - - - 40.degree. C. - -
- + .+-. .+-. Feel in use + + + + .+-. .+-.
[0844] In the Table 13, methods and standard for evaluation were
according to the following stages.
[0845] (a) Viscosity: It was measured with a Brookfield viscometer
at 25.degree. C.
[0846] (b) Stability after 3 months: It was visually evaluated
after placed at various temperatures for several months according
to the following stages.
[0847] -: presence of a separation in emulsified composition
[0848] .+-.: presence of a slight separation in emulsified
composition
[0849] +: presence of a remarkable separation in emulsified
composition
[0850] (c) Feel in use: Tackiness, spreadability, and oily touch
were evaluated by organoleptic tests of 10 professional
panelists.
[0851] -: a good feel in use
[0852] .+-.: a slightly unsatisfied feel in use
[0853] +: a slightly unsatisfied feel in use
APPLICATION EXAMPLES 45 to 48
Evaluations as a Water-in-Oil Type-Emulsified Composition for
Cosmetics
[0854] In Application Example 45, a water-in-oil type-emulsified
composition was evaluated as an emulsion for cleansing in which the
following components are mixed.
[0855] Liquid paraffin (23% by weight)
[0856] Vaseline (6.5% by weight)
[0857] Micro-crystalline wax (0.2% by weight)
[0858] Lanolin (4.0% by weight)
[0859] Tri(caprylic-capric)glyceryl (12% by weight)
[0860] Bleached bees wax (1.2% by weight)
[0861] Glycerine (15% by weight)
[0862] Fatty acid esters composition of a polyglycerine
[0863] prepared in Example 25 (3.5% by weight)
[0864] Butyl paraoxybenzoate (0.1% by weight)
[0865] Ethyl paraoxybenzoate (0.1% by weight)
[0866] Perfume (0.2% by weight)
[0867] Purified water (34.2% by weight)
[0868] Total (100% by weight)
[0869] In Application Example 46, a water-in-oil type-emulsified
composition was evaluated as an emulsion for body in which the
following components are mixed.
[0870] Squalane (15% by weight)
[0871] Liquid paraffin (8.0% by weight)
[0872] Vaseline (6.5% by weight)
[0873] Micro-crystalline wax (0.2% by weight)
[0874] Lanolin (4.0% by weight)
[0875] Lanolin cholestearyl of a fatty acid (0.5% by weight)
[0876] Olive oil (12.0% by weight)
[0877] Bleached bees wax (1.2% by weight)
[0878] Glycerine (15% by weight)
[0879] Fatty acid esters composition of a polyglycerine
[0880] prepared in Example 25 (3.5% by weight)
[0881] Decaglyceryl tristearate (0.5% by weight)
[0882] Butyl paraoxybenzoate (0.1% by weight)
[0883] Methyl paraoxybenzoate (0.1% by weight)
[0884] Perfume (0.2% by weight)
[0885] Purified water-(34.2% by weight)
[0886] Total (100% by weight)
[0887] In Application Example 47, a water-in-oil type-emulsified
composition was evaluated as an emulsion for preventing rough hands
in which the following components are mixed.
APPLICATION EXAMPLES 49 to 51 AND COMPARATIVE APPLICATION EXAMPLES
38 to 41
Evaluations as a Transparent Liquid Composition for Cosmetics
[0888] There was prepared a transparent liquid composition for
cosmetics based on the components and the mixing ratio as described
below, respectively.
[0889] POE oleylether (15.0% by weight)
[0890] 1,3-butyleneglycol (19.0% by weight)
[0891] Squalane (11.0% by weight)
[0892] Tri(caprylic-capric)glycerine (11.0% by weight)
[0893] Purified water (29.0% by weight)
[0894] Fatty acid esters composition of a polyglycerine or an other
additive (15.0% by weight)
APPLICATION EXAMPLES
[0895] 49: Fatty acid esters composition of a polyglycerine (a
hexaglycerine monolaurate composition) prepared in Example 25
[0896] 50: Fatty acid esters composition of a polyglycerine (an
octaglycerine monolaurate composition) prepared in Example 26
[0897] 51: Fatty acid esters composition of a polyglycerine (a
decaglycerine monolaurate composition) prepared in Example 27
COMPARATIVE APPLICATION EXAMPLES
[0898] 38: Hexaglycerine monolaurate composition prepared in
Comparative Example 4 <by the reaction of a fatty acid with a
polyglycerine>
[0899] 39: SY Glystar ML-500 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[0900] 40: SY Glystar MO-750 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[0901] 41: Sucrose laurate
[0902] Total weight (100% by weight)
[0903] Results are shown in Table 14.
14 TABLE 14 Application Comparative Examples Application Example 49
50 51 38 39 40 41 Property HLB 10.0 10.5 11.0 10.0 10.5 10.0 10.5
Appearance T T T ST T T ST L L L L C L L Spreadability G G G G P G
G Appearance T T T ST ST ST ST after 1 month L L L L C L L
[0904] In the Table 14, abbreviations are follows.
[0905] HLB: Hydrophile lipophile balance
[0906] T: Transparent
[0907] ST: Semi transparent
[0908] L: Liquid-state
[0909] C: Cream-state
[0910] G: Good
[0911] P: Poor
APPLICATION EXAMPLES 52 to 58
Evaluations as a Transparent Liquid Composition for Cosmetics
[0912] In Application Example 52, a transparent liquid Composition
for cosmetics was evaluated as a lotion for body in which the
following components are mixed. The components (a) to (c),
components (g) and (h) were homogeneously mixed, followed by
dispersing the components (d) to (f).
[0913] Subsequently, the component (i) was gradually added to
obtain a transparent lotion for body having HLB value of 10.5.
[0914] The transparent lotion for body was diluted with a proper
amount of warm water, resulting in exhibiting a wet and smooth feel
in use on body.
[0915] (a) Fatty acid esters composition of a polyglycerine
obtained in Example 27 (7.4% by weight)
[0916] (b) POE (3) oleylether having HLB value of 6.5 (8.1% by
weight)
[0917] (c) 1,3-butanediol (19.0% by weight)
[0918] (d) Tri(caprylic-capric)glycerine (5.5% by weight)
[0919] (e) Squalane (11.0% by weight)
[0920] (f) Hohoba oil (1.8% by weight)
[0921] (g) Perfumes (0.5% by weight)
[0922] (h) Antiseptic (0.4% by weight)
[0923] (i) Purified water (46.3% by weight)
[0924] In Application Example 53, a transparent liquid composition
for cosmetics was evaluated as a lotion for bathing in which the
following components are mixed. The components (a) to (c),
components (g) and (h) were homogeneously mixed, followed by
dispersing the components (d) to (f). Subsequently, the component
(i) was gradually added to obtain a transparent lotion for bathing
having HLB value of 10.5. The transparent lotion for bathing was
quickly dispersed, resulting in forming an emulsified liquid.
[0925] (a) Fatty acid esters composition of a polyglycerine
obtained in Example 27 (7.6% by weight)
[0926] (b) Diglycerine monooleate having HLB value of 6.5 (12.0% by
weight)
[0927] (c) 1,3-butanediol (13.0% by weight)
[0928] (d) Tri(caprylic-capric)glycerine (11.5% by weight)
[0929] (e) Squalane (11.0% by weight)
[0930] (f) Avocado oil (0.4% by weight)
[0931] (g) Perfumes (0.5% by weight)
[0932] (h) Antiseptic (0.3% by weight)
[0933] (i) Purified water (43.7% by weight)
[0934] In Application Example 54, a transparent liquid composition
for cosmetics was evaluated as a lotion for cleansing in which the
following components are mixed. The components (a) to (c),
components (g) and (h) were homogeneously mixed, followed by
dispersing the components (d) to (f). Subsequently, the component
(i) was gradually added to obtain a transparent lotion for
cleansing having HLB value of 10.0 which has a good spreadability
and a smooth feel in use on skin. Furthermore, washing with water
after cleansing was very readily, and it exhibited a refreshing
feel in use.
[0935] (a) Fatty acid esters composition of a polyglycerine
obtained in Example 27 (11.2% by weight)
[0936] (b) Sorbitan monoisostearate having HLB value of 5.0 (12.6%
by weight)
[0937] (c) 1,3-butanediol (17.5% by weight)
[0938] (d) Tri(2-ethylhexanic acid)glyceryl (16.0% by weight)
[0939] (e) Squalane (14.0% by weight)
[0940] (f) Nuts oil (0.5% by weight)
[0941] (g) Perfumes (0.3% by weight)
[0942] (h) Antiseptic (0.4% by weight)
[0943] (i) Purified water (27.5% by weight)
[0944] In Application Example 55, a transparent liquid composition
for cosmetics was evaluated as a lotion for massaging in which the
following components are mixed. The components (a) to (c),
components (g) and (h) were homogeneously mixed, followed by
dispersing the components (d) to (f). Subsequently, the component
(i) was gradually added to obtain a transparent lotion for
massaging having HLB value of 10.7 which has a good spreadability
and a smooth feel in use on skin. Furthermore, it was readily
washed with water after massaging, and was capable of providing a
fresh-looking skin.
[0945] (a) Fatty acid esters composition of a polyglycerine
obtained in Example 27 (12.0% by weight)
[0946] (b) POE(3)oleylether having HLB value of 6.5 (9.6% by
weight)
[0947] (c) 1,3-butanediol (19.0% by weight)
[0948] (d) Liquid paraffin (15.0% by weight)
[0949] (e) Squalane (10.0% by weight)
[0950] (f) Hohoba oil (2.0% by weight)
[0951] (g) Perfumes (0.3% by weight)
[0952] (h) Antiseptic (0.3% by weight)
[0953] (i) Purified water (31.8% by weight)
[0954] In Application Example 56, a transparent liquid composition
for cosmetics was evaluated as a lotion for an emollient pack in
which the following components are mixed. The components (a) to
(c), components (h) and (i) were homogeneously dissolved, followed
by dispersing the components (d) to (f). Subsequently, the
component (k) was gradually added, followed by adding the
components (g) and (i) to obtain a lotion for an emollient pack
having HLB value of 10.5 which has a good spreadability, an easy
coatability in using on face, and makes skin wet and smooth after
use. Furthermore, washing with water was very easy even after
packing.
[0955] (a) Fatty acid esters composition of a polyglycerine
obtained in Example 27 (8.9% by weight)
[0956] (b) Diglycerine monooleate having HLB value of 6.5 (14.0% by
weight)
[0957] (c) 1,3-butanediol (22.0% by weight)
[0958] (d) Tri(2-ethylhexanic acid)glyceryl (13.0% by weight)
[0959] (e) Squalane (12.0% by weight)
[0960] (f) Hohoba oil (2.5% by weight)
[0961] (g) Extracts from aloe (1.0% by weight)
[0962] (h) Perfumes (0.3% by weight)
[0963] (i) Antiseptic (0.3% by weight)
[0964] (j) Polyvinylpyrrolidone (0.3% by weight)
[0965] (k) Purified water (25.7% by weight)
[0966] In Application Example 57, a transparent liquid composition
for cosmetics was evaluated as a hair treatment in which the
following components are mixed. The components (a) to (d),
components (i) and (j) were homogeneously dissolved, followed by
dispersing the components (e) to (h). Subsequently, the component
(I) was gradually added, followed by adding the component (k) to
obtain a hair treatment having HLB value of 8.8 which is a
transparent liquid. The hair treatment can be directly employed for
wetted hairs, and also it was capable of rinsing with tepid water
even after lapse of an appropriate time. Hairs exhibited a neat
feel in touch.
[0967] (a) Fatty acid esters composition of a polyglycerine
obtained in Example 27 (4.6% by weight)
[0968] (b) Diglycerine monooleate having HLB value of 6.5 (16.2% by
weight)
[0969] (c) Dimethylammonium distearyl chloride (1.8% by weight)
[0970] (d) 1,3-butanediol (18.0% by weight)
[0971] (e) Dodecanol octylate (7.0% by weight)
[0972] (f) Squalane (16.0% by weight)
[0973] (g) Hohoba oil (2.3% by weight)
[0974] (h) Silicon oil (0.3% by weight)
[0975] (i) Perfumes (0.3% by weight)
[0976] (j) Antiseptic (0.3% by weight)
[0977] (k) Dyes (a proper amount)
[0978] (l) Purified water (33.3% by weight)
[0979] In Application Example 58, a transparent liquid composition
for cosmetics was evaluated as a base material for medicines in
which the following components are mixed. The components (a) to
(c), and the component (g) were homogeneously dissolved, followed
by dispersing the components (d) to (f). Subsequently, the
component (h) was gradually added to obtain a base material for
medicines. It was transparent, liquid, and excellent in
spreadability.
[0980] (a) Fatty acid esters composition of a polyglycerine
obtained in Example 27 (8.3% by weight)
[0981] (b) Diglycerine monooleate having HLB value of 6.5 (11.4% by
weight)
[0982] (c) 1,3-butanediol (13.0% by weight)
[0983] (d) Tri(caprylic-capric)glycerine (7.0% by weight)
[0984] (e) Squalane (15.0% by weight)
[0985] (f) Olive oil (1.0% by weight)
[0986] (g) Antiseptic (0.2% by weight)
[0987] (h) Purified water (44.1% by weight)
APPLICATION EXAMPLES 59 to 64 AND COMPARATIVE APPLICATION EXAMPLES
42 to 44
Evaluations as a Gel-like Emulsified Composition for Cosmetics
[0988] In the Application Examples and Comparative Application
Examples, methods and standard for evaluation were according to the
following stages.
[0989] (a) Stability after placing at 4020 C. for 60 days: It was
visually evaluated according to the following stages.
[0990] +: absence of a separation in composition
[0991] -: presence of a separation upper or lower layer in
composition
[0992] (b) Viscosity: It was measured with a Brookfield viscometer
(spindle #4) at 25.degree. C.
[0993] (c) Feel in use: It was evaluated by organoleptic tests of 5
professional panelists.
[0994] +: Good evaluation by all the members
[0995] -: Good evaluation by members not exceeding 4
[0996] There was prepared a gel-like emulsified composition for
cosmetics based on the components and the mixing ratio as described
below, respectively.
[0997] (a) 1,3-butanediol (3.0% by weight)
[0998] (b) Purified water (3.0% by weight)
[0999] (c) Liquid paraffin (75.0% by weight)
[1000] (d) Glycerine (15.0% by weight)
[1001] (e) Perfumes (0.50% by weight)
[1002] (g) Fatty acid esters composition of a polyglycerine (3.5%
by weight)
APPLICATION EXAMPLE 59
[1003] Composition obtained in Example 25
APPLICATION EXAMPLE 60
[1004] Composition obtained in Example 26
APPLICATION EXAMPLE 61
[1005] Composition obtained in Example 27
COMPARATIVE APPLICATION EXAMPLE 42
[1006] Hexaglycerine monolaurate composition prepared in
Comparative Example 4 (by the reaction of a fatty acid with a
polyglycerine)
COMPARATIVE APPLICATION EXAMPLE 43
[1007] SY Glystar ML-500 manufactured by Sakamoto Yakuhin Kogyo,
Ltd.
COMPARATIVE APPLICATION EXAMPLE 44
[1008] SY Glystar MO-750 manufactured by Sakamoto Yakuhin Kogyo,
Ltd.
15 TABLE 15 Comparative Application Examples Application Example 59
60 61 42 43 44 Property Stability (for + + + + + - 1 month at 40
C.) Viscosity (cps) 7000 7600 8100 9000 9500 9700 Feel in use + + +
- - +
[1009] In Application Example 62, there was prepared a gel-like
emulsified composition for cosmetics based on the components and
the mixing ratio as described below, respectively.
[1010] The composition was evaluated as gel for a cleansing.
[1011] (a) 1,3-butanediol (2.0% by weight)
[1012] (b) Purified water (1.6% by weight)
[1013] (c) Liquid paraffin (56.0% by weight)
[1014] (d) Glycerine (37.0% by weight)
[1015] (e) Sodium hyaluronate (0.002% by weight)
[1016] (f) Perfumes (0.20% by weight)
[1017] (g) Fatty acid esters composition of a polyglycerine
obtained in Example 27 (3.0% by weight)
[1018] In Application Example 63, there was prepared a gel-like
emulsified composition for cosmetics based on the components and
the mixing ratio as described below, respectively.
[1019] The composition was evaluated as a gel for massaging.
[1020] (a) 1,3-butanediol (2.0% by weight)
[1021] (b) Purified water (2.8% by weight)
[1022] (c) Liquid paraffin (25.0% by weight)
[1023] (d) Trioctanic glyceryl (25.0% by weight)
[1024] (e) Glycerine (42.0% by weight)
[1025] (f) Sodium hyaluronate (0.002% by weight)
[1026] (g) Perfumes (0.20% by weight)
[1027] (h) Fatty acid esters composition of a polyglycerine
obtained in Example 27 (3.0% by weight)
[1028] In Application Example 64, there was prepared a gel-like
emulsified composition for cosmetics based on the components and
the mixing ratio as described below, respectively.
[1029] The composition was evaluated as a wiping liquid for
making-up.
[1030] (a) Decaglycerylmonomilystate (1.5% by weight)
[1031] (b) 1,3-butanediol (2.0% by weight)
[1032] (c) Purified water (11.3% by weight)
[1033] (d) Liquid paraffin (40.0% by weight)
[1034] (e) Glycerine (42.0% by weight)
[1035] (f) Sodium hyaluronate (0.001% by weight)
[1036] (g) Perfumes (0.20% by weight)
[1037] (h) Fatty acid esters composition of a polyglycerine
obtained in Example 25 (3.0% by weight)
[1038] All the gel-like emulsified compositions for cosmetics in
Application Examples 62 to 64 exhibited an excellent stability and
excellent feel in use.
APPLICATION EXAMPLES 65 to 67 AND COMPARATIVE APPLICATION EXAMPLES
45 to 48
Evaluations as a Composition for Tooth Paste
[1039] In Application Example 65, there was prepared a composition
for tooth paste based on the components and the mixing ratio as
described below, respectively.
[1040] (a) Dihydrate of calcium secondary phosphate (45.00% by
weight)
[1041] (b) Carboxymethyl cellulose (0.50% by weight)
[1042] (c) Carrageenan (0.50% by weight)
[1043] (d) Glycerine (10.0% by weight)
[1044] (e) Sorbitol (10.0% by weight)
[1045] (f) Water (28.70% by weight)
[1046] (g) Fatty acid esters composition of a polyglycerine
obtained in Example 25 (2.00% by weight)
[1047] (h) Perfumes (1.00% by weight)
[1048] (i) Sodium saccharide (0.20% by weight)
[1049] (j) Sterilizer and Antiseptic (0.10% by weight)
[1050] In Application Example 66, the same components in
Application Example 65 were employed except that there was employed
the fatty acid esters composition of a polyglycerine obtained in
Example 26 as the component (g).
[1051] In Application Example 67, the same components in
Application Example 65 were employed except that there was employed
the fatty acid esters composition of a polyglycerine obtained in
Example 27 as the component (g).
[1052] In Comparative Application Example 45, the same components
in Application Example 65 were employed except that there was
employed the hexaglycerine monolaurate composition prepared in
Comparative Example 4 <by the reaction of a fatty acid with a
polyglycerine> as the component (g).
[1053] In Comparative Application Example 46, the same components
in Application Example 65 were employed except that there was
employed SY Glystar ML-500 manufactured by Sakamoto Yakuhin Kogyo,
Ltd. as the component (g).
[1054] In Comparative Application Example 47, the same components
in Application Example 65 were employed except that there was
employed SY Glystar ML-750 manufactured by Sakamoto Yakuhin Kogyo,
Ltd. as the component (g).
[1055] In Comparative Application Example 48, the same components
in Application Example 65 were employed except that there was
employed a sucrose laurate as the component (g).
[1056] Results are shown in Table 16.
16 TABLE 16 Comparative Application Examples Application Example 65
66 67 45 46 47 48 Foaming ability 480 500 460 290 300 260 250
Foamed volume G G G SP P SP SP feeling in mouth
[1057] In the Application Examples and Comparative Application
Examples, methods and standard for evaluation were according to the
following stages.
[1058] (a) Foaming ability: It was evaluated by measuring volume of
foam after agitating at 60V with a National mixer (MX-420) for 90
seconds. Beforehand, samples were prepared by suspending 5 g of
composition for tooth paste in 50 ml of water warmed at 30.degree.
C.
[1059] (b) Foamed volume feeling in mouth: It was evaluated by
organoleptic tests of 5 panelists.
[1060] G : Presence of foaming
[1061] SP: Presence of slightly foaming
[1062] : Absence of foaming
[1063] As shown in Table 16, there can be obtained a composition
for tooth paste having excellent foaming ability, a refreshing feel
in use, no-irritation at mucous membrane in mouth, no-depression of
enzymes by employing the fatty acid esters composition of a
polyglycerine specified in the present invention.
APPLICATION EXAMPLES 68 to 71 AND COMPARATIVE APPLICATION EXAMPLES
49 to 53
Evaluations as a Cleaning Agent Composition
[1064] In Application Example 68, there was prepared a cleaning
agent composition based on the components and the mixing ratio as
described below, respectively.
[1065] (a) Glycerine succinate monolaurate (5.0 parts by
weight)
[1066] (b) Fatty acid esters composition of a polyglycerine
obtained in Example 25 (11.0 parts by weight)
[1067] (c) Sodium tripolyphosphate (35.0 parts by weight)
[1068] (d) Sodium sulfuric anhydride (49.0 parts by weight)
[1069] (e) Deionized water (100 parts by weight)
[1070] The components (c) and (d) were mixed with a mixture
composed of (a) and (b), and further component (e) was added,
followed by mixing at 60.degree. C. to obtain a homogeneous
liquid.
[1071] Subsequently, sulfuric acid was added in order to adjust to
PH of 7.0, followed by spray-drying to obtain a cleaning agent
composition.
[1072] In a 500-ml beaker, 1.3 g of the cleaning agent composition
was dissolved in 400 ml of tap water at 25.degree. C. while
agitating with a magnetic stirrer to obtain a solution.
[1073] Separately, 4 glass plates having 5 cm L.times.2 cm
W.times.0.5 mm t were coated with 0.03-0.04 g of beef tallow,
respectively, into the solution for 5 minutes.
[1074] Cleaning ability was evaluated by the ratio (%) of area on
which beef tallow was washed with respect to total area,
[1075] Results are shown in Table 17.
17 TABLE 17 Component Component CP (b) (a) (%) Application Examples
68 No. 1 B1 A1 34 2 B2 A1 39 3 B3 A1 43 4 B3 A2 53 Comparative
Application Example 49 No. 1 B4 A1 25 2 B5 A1 23 3 B6 A1 21 4 B6 A2
24 5 B7 -- 2
[1076] In the Table 17, abbreviations are as follows.
[1077] B1: Fatty acid esters composition of a polyglycerine
obtained in Example 25
[1078] B2: Fatty acid esters composition of a polyglycerine
obtained in Example 26
[1079] B3: Fatty acid esters composition of a polyglycerine
obtained in Example 27
[1080] B4: Hexaglycerine monolaurate composition prepared in
Comparative Example 4 (by the reaction of a fatty acid with a
polyglycerine)
[1081] B5: SY Glystar ML-500 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[1082] B6: SY Glystar ML-750 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[1083] B7: Sucrose laurate
[1084] A1: Glycerine succinate monolaurate
[1085] A2: Glycerine succinate monodecanate
[1086] In Application Example 69, there was prepared a cleaning
agent composition based on the components and the mixing ratio as
described below, respectively.
[1087] (a) Glycerine succinate monolaurate (12.0 parts by
weight)
[1088] (b) Fatty acid esters composition of a polyglycerine
obtained in Example 25 (5.0 parts by weight)
[1089] (c) Sodium tripolyphosphate (35.0 parts by weight)
[1090] (d) citric acid (2.5 parts by weight)
[1091] (e) Sodium sulphate (45.5 parts by weight)
[1092] The cleaning agent composition was dissolved into water to
obtain an aqueous solution having 0.33% by weight.
[1093] The solution was employed to wash soy beans, resulting in
showing high washing power and sterilizing ability.
[1094] In Application Example 70, there was prepared a cleaning
agent composition based on the components and the mixing ratio as
described below, respectively.
[1095] (a) Glycerine succinate monomilystate (15.0 parts by
weight)
[1096] (b) Fatty acid esters composition of a polyglycerine
obtained in Example 25 (2.0 parts by weight)
[1097] (b) Fatty acid esters composition of a Polyglycerine
obtained in Example 27 (5.0 parts by weight)
[1098] (c) Sodium pyrophosphate (30.0 parts by weight)
[1099] (d) Phosphoric acid (2.0 parts by weight)
[1100] (e) Sodium sulphate (46.0 parts by weight)
[1101] The cleaning agent composition was dissolved into water to
obtain an aqueous solution having 0.20% by weight.
[1102] The solution was employed to wash tomatoes, resulting in
showing high washing ability.
[1103] In Application Example 71, there was prepared a cleaning
agent composition based on the components and the mixing ratio as
described below, respectively.
[1104] There was adjusted PH of an aqueous solution containing
0.10% by weight of glycerine succinate monolaurate and 0.030% by
weight of the fatty acid esters composition of a polyglycerine
obtained in Example 25 to 4, 5, and 7 with an aqueous solution of
sodium hydroxide to obtain three aqueous solutions having different
PHs. Sterilizing ability was evaluated as follows concerning the
three aqueous solutions having different PHs.
[1105] Triangular flasks containing 10 g of soy beans and 90 ml of
the respective aqueous solution were vibrated for 5 minutes.
[1106] After vibrated for 5 minutes, respective washed soy beans
were mixed with 90 ml of sterilized water in a 100-ml flask,
followed by placing in a thermostatically-controlled oven at
35.degree. C. for 20 hours.
[1107] After placing for 20 hours, soy beans were minutely crushed
together with sterilized water in a homogenizer, followed by
filtering with a sterilized gauze to separate solid.
[1108] A filtered liquid which is a starting liquid was diluted
into ten times, hundred times, and thousand times, respectively,
with a sterilized physiological aqueous solution of sodium
chloride. 1 ml of the starting liquid and 3 diluted liquid were
poured into 4 laboratory dishes, respectively.
[1109] Subsequently, there was poured 15-20 ml of a standard agar
culture medium which was kept at 50.degree. C. after sterilized in
a high pressure, followed by immediately mixing, respectively.
[1110] The 4 laboratory dishes were settled until the agar culture
media completely coagulate. After coagulated, the 4 laboratory
dishes were cultivated at 35.degree. C. for 2 days to count the
number of colonies by a conventional method. As a result, the
number of microorganisms was less than 10 per 1 g of soy beans in
all the laboratory dishes. For references, the same procedures were
repeated except that water having Ph of 7 was employed in place of
the solution containing the fatty acid esters composition of a
polyglycerine to obtain the number of microorganisms of
5.5.times.10.sup.6 per 1 g of soy beans.
APPLICATION EXAMPLES 72 to 77 AND COMPARATIVE APPLICATIONS EXAMPLES
54 to 56
Evaluations as a Foaming Composition for Cleaning
[1111]
18 TABLE 18 Comparative Application Examples Application Example 72
73 74 54 55 56 A1 1.0 A2 1.0 A3 1.0 A4 1.0 A5 1.0 A6 1.0 Property
Stability G G G P G G Stability E E E I E E (Deterioration ratio of
protein): It was Foaming ability G G G I I I Durability G G G I I I
of Foam (Stability of Foam) Feel in use G G G I G G
[1112] In the Table 18, A1 to A6 correspond to the following
composition, respectively.
[1113] A1: Fatty acid esters composition of a polyglycerine
obtained in Example 25
[1114] A2: Fatty acid esters composition of a polyglycerine
obtained in Example 26
[1115] A3: Fatty acid esters composition of a polyglycerine
obtained in Example 27
[1116] A4: Hexaglycerine monolaurate composition prepared in
Comparative Example 4 <by the reaction of a fatty acid with a
polyglycerine>
[1117] A5: SY Glystar ML-500 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[1118] A6: SY Glystar ML-750 manufactured by Sakamoto Yakuhin
Kogyo, Ltd.
[1119] In Application Examples 72-74 and Comparative Application
Examples 54-56, there was prepared a cleaning agent composition
based on the components and the mixing ratio as described below,
respectively.
[1120] Fatty acid esters composition of a polyglycerine (1.0% by
weight)
[1121] Cetyl alcohol (2.0% by weight)
[1122] Ethyl alcohol (50% by weight)
[1123] Purified water (42.0% by weight)
[1124] Liquified Petroleum Gas/L.P.G. (5.0% by weight)
[1125] In Application Example 75, there was prepared a cleaning
agent composition based on the components and the mixing ratio as
described below, respectively.
[1126] Fatty acid esters composition of a polyglycerine obtained in
Example 25 (2.5% by weight)
[1127] Cetstearyl alcohol (2.5% by weight)
[1128] Perfumes (0.2% by weight)
[1129] Purified water (53.5% by weight)
[1130] Ethyl alcohol (35.0% by weight)
[1131] Liquified Petroleum Gas/L.P.G. (7.0% by weight)
[1132] In Application Example 76, there was prepared a cleaning
agent composition based on the components and the mixing ratio as
described below, respectively.
[1133] Fatty acid esters composition of a polyglycerine obtained in
Example 25 (1.5% by weight)
[1134] Cetyl alcohol (3.0% by weight)
[1135] Saffron oil (0.1% by weight)
[1136] Perfumes (0.2% by weight)
[1137] Purified water (36.2% by weight)
[1138] Ethyl alcohol (55.0% by weight)
[1139] Liquified Petroleum Gas/L.P.G. (4.0% by weight)
[1140] In Application Example 77, there was prepared a cleaning
agent composition based on the components and the mixing ratio as
described below, respectively.
[1141] Fatty acid esters composition of a polyglycerine obtained in
Example 25 (1.2% by weight)
[1142] Behenyl alcohol (0.5% by weight)
[1143] POE(4)stearylether (1.0% by weight)
[1144] Orange oil (0.1% by weight)
[1145] Perfumes (0.2% by weight)
[1146] Purified water (47.1% by weight)
[1147] Ethyl alcohol (45.0% by weight)
[1148] Liquified Petroleum Gas/L.P.G. (5.0% by weight)
[1149] The cleaning agent composition in Application Examples 75-77
exhibited an excellent stability, foaming ability, durability of
foam, and cleaning ability.
[1150] In the Application Examples and Comparative Application
Examples, methods and standard for evaluation were according to the
following stages.
[1151] (a) Stability (Deterioration ratio of protein): It was
evaluated by deterioration ratio (HDR %) of hemoglobin.
[1152] It exhibited a good relationship with an irritating
intensity for eyes according to a Draze method.
HDR%=((LAOC-LAOD)/(LAOC)).times.100
[1153] LAOC: Light absorption degree by a control sample
[1154] LAOD: Light absorption degree after deteriorating by a test
sample
[1155] E: HDR of <5%
[1156] G: HDR of 5% to <15%
[1157] I: HDR of 15% to 21 50%
[1158] B: HDR of not less than 50%
[1159] (b) Cleaning ability: It was measured by a cleaning process
in which a fixed amount of artificial fatty skin dirt containing an
ultraviolet ray absorbent was coated on a rubber plate, and then
rubbing was carried out at three cycles with a paper towel
containing a sample liquid under a fixed loading. The artificial
fatty skin dirt after cleaning was recovered with a solvent, and
then the amount of the ultraviolet ray absorbent was measured to
evaluate as follows.
[1160] G: Cleaning ability of not less than 60%
[1161] I: Cleaning ability of 40% to <60%
[1162] B: Cleaning ability of not more than 40%
[1163] (c) Foaming ability: It was evaluated by a process that
there were mixed an agent for foaming (spraying) a mixture and the
mixture in a fixed ratio to prepare an aerosol, and the aerosol was
filled in a can for spraying, and then the aerosol was sprayed onto
hands at --b 5.degree. C., 25.degree. C., and 30.degree. C.,
respectively. Foaming ability was evaluated by organoleptic
tests.
[1164] G: Good
[1165] I: Insufficient
[1166] (d) Durability of Foam (Stability of Foam): It was evaluated
by a process that the aerosol was sprayed, there was measured a
ratio (Fr %) between the volume of foam immediately after spraying
and the volume after 30 minutes.
Fr %=[(Volume of foam after 30 minutes)/(Volume of foam immediately
after spraying)].times.100
[1167] G: Fr of not less than 80%
[1168] I: Fr of 50% to <80%
[1169] B: Fr of <50%
[1170] (e) Feel in use: It was evaluated by a method that 5 g of
respective sample was employed for washing hairs, and then wiped
with towels. At 30 minutes after wiping, a refreshing feel in hairs
was evaluated by organoleptic tests of 8 panelists according to the
following 5 stages.
[1171] Excellent: Good: 4
[1172] Normal: 3
[1173] Slightly poor: 2
[1174] Poor: 1
[1175] Evaluations were shown by average points of the 8
panelists.
[1176] (a) Stability: It was evaluated by a method that samples
were preserved at temperatures of -5.degree. C., 0.degree. C.,
25.degree. C., and 30.degree. C. for 1 month, and the samples were
sprayed, conditions of foam at the temperatures and at the
25.degree. C. were visually observed to evaluate by the following
stages.
[1177] G: Appropriate as a foaming composition for cleaning
[1178] P: Inappropriate as a foaming composition for cleaning
EXAMPLE 28
PREPARATION OF A HIGHLY-PURIFIED FATTY ACID ESTERS COMPOSITION OF A
POLYGLYCERINE FROM THE COMPOSITION (A DECAGLYCERINE MONOLAURATE
COMPOSITION) OBTAINED IN EXAMPLE 5
[1179] The composition obtained in Example 5 and 2% by weight of
water was charged into a flask. Subsequently, the flask was heated
to 135.degree. C. while stirring under refluxing, followed by
maintaining at the temperature for 2 hours. Subsequently, the flask
was heated to 140.degree. C. Distillation in reduced pressures was
carried out while maintaining at the temperature in order to remove
water for 4 hours to obtain a highly-purified fatty acid esters
composition of a polyglycerine. Reduced pressure degree was finally
10 mmHg.
[1180] There was carried out HPLC analysis with the analytical
condition No. 2 relating to the highly-purified fatty acid esters
composition of a polyglycerine. FIG. 24 (ML-10) is a chart obtained
by the HPLC analysis. It was identified from the chart that the
composition contains a monolaurate of polyglycerine of 81.26% by
weight, polyglycerine of 8.20% by weight, and other components of
10.54% by weight by the analytical condition No. 2 in the HPLC
analysis as defined hereinabove.
COMPARATIVE EXAMPLES 16 AND 17
HPLC Analysis by the Analytical Condition No. 2 Relating to a Fatty
Acid Esters Composition of a Polyglycerine which is Commercially
Supplied
[1181] As fatty acid esters composition which is commercially
supplied prepared by the reaction of a polyglycerine with a fatty
acid, SY Glystar ML-750 manufactured by Sakamoto Yakuhin, Ltd. and
Sunsoft Q-12S manufactured by Taiyo Kagaku, Ltd. were analyzed by
the analytical condition No. 2 in HPLC analysis. FIGS. 25 (ML-750)
and 26 (Q-12S) are a respective chart obtained by the HPLC
analysis.
[1182] It was identified from the charts that the respective
compositions contain a monolaurate of polyglycerine of 44.92% by
weight, polyglycerine of 14.16% by weight, and other components of
40.82% by weight, and a monolaurate of polyglycerine of 48.80% by
weight, polyglycerine of 26.88% by weight, and other components of
24.32% by weight by the analytical condition No. 2 in the HPLC
analysis as defined hereinabove.
COMPARATIVE EXAMPLE 18
HPLC Analysis by the Analytical Condition No. 3 Relating to a Fatty
Acid Esters Composition of a Polyglycerine which is Commercially
Supplied
[1183] As fatty acid esters composition which is commercially
supplied prepared by the reaction of a polyglycerine with a fatty
acid, SY Glystar ML-500 manufactured by Sakamoto Yakuhin, Ltd. was
analyzed by the analytical condition No. 3 in HPLC analysis.
[1184] FIG. 27 is a chart obtained by the HPLC analysis. It was
identified from the charts that the respective compositions contain
a monolaurate of polyglycerine of 38.20% by weight, polyglycerine
of 6.17% by weight, and other components of 55.64% by weight.
[1185] While the invention has been described in detail and with
reference to the specific embodiments thereof, it will be apparent
to those skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope
thereof.
* * * * *