U.S. patent application number 12/669045 was filed with the patent office on 2010-08-12 for organopolysiloxane.
This patent application is currently assigned to KAO CORPORATION. Invention is credited to Masayoshi Ehara, Kazuhisa Fukuhara, Kayoko Kitada, Takashi Kodate, Kenichi Ueyama.
Application Number | 20100203002 12/669045 |
Document ID | / |
Family ID | 41508558 |
Filed Date | 2010-08-12 |
United States Patent
Application |
20100203002 |
Kind Code |
A1 |
Fukuhara; Kazuhisa ; et
al. |
August 12, 2010 |
ORGANOPOLYSILOXANE
Abstract
There is provided an organopolysiloxane which is excellent in
extensibility as well as solubility and dispersibility in water and
lower alcohols. There is provided an organopolysiloxane with a
poly(N-acylalkyleneimine) segment having a repeating unit
represented by the following general formula (1): wherein R.sup.1
represents a hydrogen atom or an alkyl group, an aralkyl group, or
an aryl group each having 1 to 22 carbon atoms, and n is 2 or 3,
wherein the segment is bound to each of at least two silicon atoms
of an organopolysiloxane segment as a main chain via an alkylene
group containing a hetero atom, and wherein the number-average
molecular weight of the segment is 800 to 1600, the mass ratio of
the organopolysiloxane segment as a main chain and the
poly(N-acylalkyleneimine) segment is 65/35 to 82/18, and the
weight-average molecular weight of the organopolysiloxane segment
as a main chain is 10,000 to 100,000. ##STR00001##
Inventors: |
Fukuhara; Kazuhisa; (Tokyo,
JP) ; Kodate; Takashi; (Wakayama, JP) ;
Kitada; Kayoko; (Tokyo, JP) ; Ueyama; Kenichi;
(Tokyo, JP) ; Ehara; Masayoshi; (Darmstadt,
DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, L.L.P.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
KAO CORPORATION
Tokyo
JP
|
Family ID: |
41508558 |
Appl. No.: |
12/669045 |
Filed: |
July 18, 2008 |
PCT Filed: |
July 18, 2008 |
PCT NO: |
PCT/JP2008/063474 |
371 Date: |
January 14, 2010 |
Current U.S.
Class: |
424/70.122 ;
528/26 |
Current CPC
Class: |
A61K 2800/54 20130101;
C08G 81/00 20130101; C08G 77/26 20130101; A61Q 5/06 20130101; A61K
8/898 20130101; C08G 77/452 20130101 |
Class at
Publication: |
424/70.122 ;
528/26 |
International
Class: |
A61K 8/89 20060101
A61K008/89; A61Q 5/12 20060101 A61Q005/12; C08G 77/04 20060101
C08G077/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 20, 2007 |
JP |
2007-190244 |
Jul 20, 2007 |
JP |
2007-190245 |
Dec 7, 2007 |
JP |
2007-316589 |
Claims
1. An organopolysiloxane comprising a poly(N-acylalkyleneimine)
segment having a repeating unit represented by the following
general formula (1): ##STR00011## wherein R.sup.1 represents a
hydrogen atom or an alkyl group, an aralkyl group, or an aryl group
each having 1 to 22 carbon atoms, and n is 2 or 3, wherein said
segment is bound to each of at least two silicon atoms of an
organopolysiloxane segment as a main chain via an alkylene group
comprising a hetero atom, and wherein the number-average molecular
weight of the poly(N-acylalkyleneimine) segment is 800 to 1600, the
mass ratio (a/b) of the organopolysiloxane segment (a) as a main
chain and the poly(N-acylalkyleneimine) segment (b) is 65/35 to
82/18, and the weight-average molecular weight of the
organopolysiloxane segment as a main chain is 10,000 to
100,000.
2. A hair cosmetic comprising the organopolysiloxane according to
claim 1.
3. The hair cosmetic according to claim 2 further comprising one or
more organic solvents selected from the group consisting of the
following (b1) to (b5): (b1) a compound represented by the general
formula (2) ##STR00012## wherein R.sup.2 represents a hydrogen
atom, an alkyl group having 1 to 6 carbon atoms, or a group
R.sup.3-Ph-R.sup.4--, wherein R.sup.3 represents a hydrogen atom, a
methyl group, or a methoxy group; R.sup.4 represents a bond or a
saturated or unsaturated divalent hydrocarbon group having 1 to 3
carbon atoms; and Ph represents a paraphenylene group, A represents
a bond or a saturated divalent hydrocarbon group having 1 to 4
carbon atoms, Y and Z each independently represent a hydrogen atom
or a hydroxy group, and p and q each independently are an integer
of 0 to 5, provided that when p=q=0, Z represents a hydroxy group,
and R.sup.2 is not either a hydrogen atom or a group R.sup.3-Ph-;
(b2) N-alkylpyrrolidone or N-alkenylpyrrolidone in which an alkyl
group or an alkenyl group having 1 to 18 carbon atoms binds to a
nitrogen atom; (b3) an alkylene carbonate having 2 to 4 carbon
atoms; (b4) a polypropylene glycol having a number-average
molecular weight of 100 to 1000; and (b5) a lactone or a cyclic
ketone represented by the general formula (3), (4), or (5):
##STR00013## wherein X represents a methylene group or an oxygen
atom, R.sup.5 and R.sup.6 represent substituents different from
each other, and a and b each independently are 0 or 1.
4. The hair cosmetic according to claim 3, wherein the organic
solvent is at least one selected from dipropylene glycol,
1,3-butanediol, benzyl alcohol, phenoxyethanol, 2-benzyloxyethanol,
propylene carbonate, and polypropylene glycol (number-average
molecular weight, 300 to 500).
5. The hair cosmetic according to claim 3, wherein the organic
solvent is a lower alcohol having 1 to 6 carbon atoms.
6. The hair cosmetic according to claim 4 comprising an organic
carboxylic acid which may have a hydroxy group or a salt
thereof.
7. The hair cosmetic according to claim 6, wherein the organic
carboxylic acid which may have a hydroxy group is a
hydroxycarboxylic acid having 2 to 6 carbon atoms.
8. The hair cosmetic according to any one of claims 2 to 7 further
comprising a set polymer.
9. The hair cosmetic according to claim 6 or 7, wherein the pH is
2.5 to 4.5 at 25.degree. C. when diluted 20-fold by mass with
water.
10. The hair cosmetic according to any one of claims 2 to 9, which
is a semisolid styling composition.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a novel organopolysiloxane
and a hair cosmetic containing the same.
BACKGROUND OF THE INVENTION
[0002] Since organopolysiloxanes (hereinafter sometimes referred to
as "silicones") have many features such as low surface tension,
excellent lubricating property and mold releasing property, high
thermal stability, generally very low glass transition points, and
excellent gas permeability, silicones in various forms are very
widely used as lubricants, heat medium, electric insulators, paint
leveling agents, mold releasing agents, cosmetic additives, textile
treating agents, shock buffering materials, sealing materials,
molding materials, polishing agents, foam stabilizers, and
defoaming agents.
[0003] The cosmetic field is no exception, and silicones are often
used as feel improving agents or the like in cosmetic products such
as skin care agents, foundations, shampoos, and conditioners. As an
example of silicones that can be used in cosmetics,
organopolysiloxanes that do not break or are not plastically
deformed at extension rates in the range of 0 to 15% at a
temperature of 20.degree. C. and a relative humidity of 65% have
been disclosed in Patent Document 1. Hair cosmetics containing
these organopolysiloxanes have excellent hair setting ability and
set holding performance, can impart a favorable feel such as
flexibility and no stiffness to the hair after setting, and can be
easily washed off by shampooing the hair. Thus, the
organopolysiloxanes described in Patent Document 1 were superior to
conventional set polymers.
[0004] In recent years, however, required performance and
preference in hair cosmetics have been greatly changed, and
conventional set polymers or silicones cannot adequately respond to
them. Specifically, hair cosmetics are required to impart a
flexible feel, have set characteristics that the hair style is not
disintegrated after passing fingers through the hair, and, in
addition, achieve a more natural finish.
[0005] Meanwhile, it is said that chemical treatment with hair
color or the like and physical treatment such as blowing cause
abrasion of cuticles on the hair surface and hollowing of the hair
due to the leakage of lipids from the inside of the hair, resulting
in overly dry hair, uneasy finger passing, poor hair manageability,
and loss of luster.
[0006] To impart manageability to the hair and prevent overly dry
hair, hair cosmetics mainly used at present include waxes,
emulsified products such as hair creams containing oil solutions
such as a higher alcohol, a surfactant, and the like, gels
containing a membrane formation polymer (set polymer), and so
forth. Such hair cosmetics attach oils and fats or polymers to the
hair surface to solve problems such as poor manageability and
overly dry hair only temporarily, but could not achieve essential
improvement.
[0007] Several hair cosmetics for reforming the hair are known, and
some of these use specific organic acids and organic solvents for
reforming the hair by acting on the inside of the hair. However,
while such hair cosmetics have excellent reforming effects to
improve luster and manageability of the hair, they suffer from such
problems that flexibility is hard to impart, the applied hair
becomes greasy, and so forth. Therefore, common silicones are mixed
as feel improving agents. However, although the feel to the touch
is improved, a problem arises that hair reforming effects
(improvement of manageability, etc.) by organic acids and organic
solvents are impaired.
[0008] To solve such problems, a hair cosmetic has been proposed in
which an organopolysiloxane having a specific structure is used in
combination with a specific organic acid and a specific organic
solvent (Patent Document 2).
[0009] Furthermore, due to diversified and individualized hair
styles in recent years, hair cosmetics are desired wherein a
desired hair style can be easily set, the set hair style can be
held for a long time, and a flexible feel and a more natural finish
can be imparted. While the above-mentioned hair cosmetic of Patent
Document 2 can impart a favorable feel (softness, no greasiness,
etc.) without impairing hair reforming effects (improvement of
manageability, etc.), neither of styling properties, setting
performance and set holding performance, is necessarily adequate,
and these properties have room to improve.
[Patent Document 1] JP-A-07-133352
[Patent Document 2] JP-A-2006-69899
SUMMARY OF THE INVENTION
[0010] The present invention provides an organopolysiloxane with a
poly(N-acylalkyleneimine) segment having a repeating unit
represented by the following general formula (1) bound to each of
at least two silicon atoms of an organopolysiloxane segment as a
main chain via an alkylene group containing a hetero atom,
wherein
[0011] the number-average molecular weight of the
poly(N-acylalkyleneimine) segment is 800 to 1600,
[0012] the mass ratio (a/b) of the organopolysiloxane segment (a)
as a main chain and the poly(N-acylalkyleneimine) segment (b) is
65/35 to 82/18, and
[0013] the weight-average molecular weight of the
organopolysiloxane segment as a main chain is 10,000 to
100,000.
##STR00002##
wherein R.sup.1 represents a hydrogen atom or an alkyl group, an
aralkyl group, or an aryl group each having 1 to 22 carbon atoms,
and n is 2 or 3.
[0014] Furthermore, the present invention provides a hair cosmetic
containing the above-mentioned organopolysiloxane.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The present invention provides an organopolysiloxane having
excellent extensibility and excellent solubility and dispersibility
in water and lower alcohols, and a hair cosmetic containing the
same.
[0016] The inventors of the present invention found that, among
organopolysiloxanes having a structure similar to that of the
organopolysiloxanes described in the above-mentioned Patent
Document 1, those in a specific scope have properties totally
different from the organopolysiloxanes described in Patent Document
1, specifically, they cause plastic deformation and exhibit much
superior extensibility.
[0017] Conventionally, polymers causing plastic deformation have an
inadequate set holding performance and have been thought to be
unsuitable as polymers for hair setting. Unexpectedly, however, it
has been found that, when an organopolysiloxane that causes plastic
deformation and has high extensibility is added to a hair cosmetic,
a flexible feel can be imparted, the set hair is minimally
disintegrated even when fingers are passed through the hair or
external factors such as wind and vibration are applied, a natural
finish is achieved, and a favorable wash property is exhibited.
[0018] According to the present invention, an organopolysiloxane
having excellent extensibility and excellent solubility in water
and lower alcohols is provided.
[0019] Furthermore, a hair cosmetic containing this
organopolysiloxane can impart a flexible feel, the set hair is
minimally disintegrated even when fingers are passed through the
hair or external factors such as wind and vibration are applied,
and a natural finish is achieved.
[0020] When the hair cosmetic of the present invention contains a
specific organic carboxylic acid and a specific organic solvent, it
imparts an excellent feel to the hair after application (softness,
no greasiness, etc.) without impairing hair reforming effects
(improvement of manageability, etc.) of the organic acid and the
organic solvent and can further improve styling properties, setting
performance and set holding performance. Consequently, there is
provided a hair cosmetic that essentially reforms the hair, imparts
excellent hair manageability and feel to the touch (softness, no
greasiness), and is greatly superior in styling properties, setting
performance immediately after getting permed and set holding
performance.
[0021] Therefore, the hair cosmetic of the present invention is
useful particularly as a hair cosmetic such as a hair styling agent
and a hair conditioning agent.
Organopolysiloxanes
[0022] The organopolysiloxane of the present invention is composed
of a poly(N-acylalkyleneimine) segment having a repeating unit
represented by the above-mentioned general formula (1) bound to
each of at least two silicon atoms in an organopolysiloxane segment
as a main chain via an alkylene group containing a hetero atom, as
with the organopolysiloxanes described in the above-mentioned
Patent Document 1, and is characterized in that it causes plastic
deformation at extension rates in the range of 0 to 15% and does
not break at an extension rate of 300%. In contrast, the
organopolysiloxanes described in Patent Document 1 do not cause
plastic deformation and break under the same conditions. Therefore,
the organopolysiloxane of the present invention has properties
totally different from those of the organopolysiloxanes described
in Patent Document 1.
[0023] In the present specification, whether plastic deformation
occurs at extension rates in the range of 0 to 15% is determined by
the following test method. Specifically, a sample section having a
thickness of approx. 0.2 mm, a length of 20 mm, and a width of 5 mm
is prepared, extended 3 mm (15%) at a crosshead speed of 20 mm/min
at a temperature of 20.degree. C. and a relative humidity of 65%,
and then immediately the crosshead is returned to the original
position at the same speed, while recording a stress-strain curve.
Then, 10 minutes later, the sample section is extended again. As a
result, when the stress-strain curve at the second extension
follows the trajectory of the first curve, it is determined that
plastic deformation does not occur. On the other hand, when the
stress-strain curve does not follow the same trajectory, it is
determined that plastic deformation has occurred. Furthermore,
whether a break occurs at an extension rate of 300% is determined
based on the appearance of a test sample section having a length of
20 mm, a width of 5 mm, and a thickness of 1.0 mm after extending
it 300% in the longitudinal direction at an extension speed of 50
mm/min with a tensile tester (Tensilon Tensile Tester, Model
RTC-1210A, Orientech Co., Ltd.) at a temperature of 20.degree. C.
and a relative humidity 65% and leaving it for 3 min.
[0024] The organopolysiloxane of the present invention causes
plastic deformation and has high extensibility as described above,
and these characteristics are exhibited only by providing
structural characteristics of the following i) to iv).
i) A poly(N-acylalkyleneimine) segment binds to at least two
silicon atoms in an organopolysiloxane segment as a main chain. ii)
The number-average molecular weight of the
poly(N-acylalkyleneimine) segment is 800 to 1600. iii) The mass
ratio (a/b) of the organopolysiloxane segment (a) as a main chain
and the poly(N-acylalkyleneimine) segment (b) is 65/35 to 82/18.
iv) The weight-average molecular weight of the organopolysiloxane
as a main chain is 10,000 to 100,000.
[0025] The poly(N-acylalkyleneimine) segment can bind to at least
two arbitrary silicon atoms constituting the organopolysiloxane
segment via an alkylene group containing a hetero atom, but
preferably binds to one or more silicon atoms that are not either
terminus via the above-mentioned alkylene group, more preferably to
two or more silicon atoms that are not either terminus via the
above-mentioned alkylene group.
[0026] The alkylene group containing a hetero atom functions as a
linking group of the poly(N-acylalkyleneimine) segment. Examples of
the alkylene group include alkylene groups having 2 to 20 carbon
atoms which contain 1 to 3 nitrogen atoms, oxygen atoms, or sulfur
atoms. Among these, those represented by the following formulas (i)
to (vii) are preferable, and those represented by the following
formulas (i) and (ii) are more preferable. In the formulas,
An.sup.- represents a counter ion of a quaternary ammonium salt,
and examples thereof include an ethyl sulfate ion, a methyl sulfate
ion, a chloride ion, an iodide ion, a sulfate ion, a
toluenesulfonate ion, and a perchlorate ion.
##STR00003##
[0027] The N-acylalkyleneimine unit constituting the
poly(N-acylalkyleneimine) segment is represented by the
above-mentioned general formula (1). Definitions of the symbols in
the formula will be explained below.
[0028] Examples of the alkyl group having 1 to 22 carbon atoms for
R.sup.1 include straight, branched or cyclic alkyl groups each
having 1 to 22 carbon atoms, and specific examples thereof include
a methyl group, an ethyl group, an n-propyl group, an isopropyl
group, an n-butyl group, a tert-butyl group, a pentyl group, a
hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a
nonyl group, a decyl group, an undecyl group, an dodecyl group, an
octadecyl group, a nonadecyl group, an eicosyl group, a docosyl
group, and so forth. Among these, alkyl groups having 1 to 10
carbon atoms are preferable, and alkyl groups having 1 to 6 carbon
atoms are more preferable.
[0029] Examples of the aralkyl group include aralkyl groups having
7 to 15 carbon atoms, and specific examples thereof include a
benzyl group, a phenethyl group, a trityl group, a naphthylmethyl
group, an anthracenylmethyl group, and so forth. Among these,
aralkyl groups having 7 to 14 carbon atoms are preferable, and
aralkyl groups having 7 to 10 carbon atoms are more preferable.
[0030] Examples of the aryl group include aryl groups having 6 to
14 carbon atoms, and specific examples thereof include a phenyl
group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl
group, an anthryl group, a phenanthryl group, and so forth. Among
these, aryl groups having 6 to 12 carbon atoms are preferable, and
aryl groups having 6 to 9 carbon atoms are more preferable.
[0031] Among these, alkyl groups having 1 to 6 carbon atoms are
even more preferable as R.sup.1.
[0032] The mass ratio (a/b) of the organopolysiloxane segment (a)
and the poly(N-acylalkyleneimine) segment (b) is 65/35 to 82/18,
but is preferably 68/32 to 80/20, more preferably 70/30 to 79/21 in
view of not breaking and exhibiting plastic deformation even at
extension rates of 300% or higher, ensuring sufficient membrane
strength, and improving styling properties, setting performance and
set holding performance, in use as the hair cosmetic described
later.
[0033] In the present specification, the mass ratio (a/b) is a
value obtained by dissolving 5% by mass of the organopolysiloxane
of the present invention in deuterated chloroform and performing a
nuclear magnetic resonance (.sup.1-NMR) analysis to obtain the
integral ratio of an alkyl group or a phenyl group in the
organopolysiloxane segment and a methylene group in the
poly(N-acylalkyleneimine) segment.
[0034] Furthermore, the weight-average molecular weight (MWg) of an
organopolysiloxane segment between adjacent
poly(N-acylalkyleneimine) segments is preferably 1500 to 3500,
preferably 1600 to 3200, more preferably 1700 to 3000 in view of
not breaking and exhibiting plastic deformation even at extension
rates of 300% or higher, ensuring sufficient membrane strength, and
improving styling properties, setting performance and set holding
performance, in use as the hair cosmetic described later.
[0035] In the present specification, the "organopolysiloxane
segment between adjacent poly(N-acylalkyleneimine) segments" means
a segment surrounded by the broken line between two points, the
binding point of a poly(N-acylalkyleneimine) segment to an
organopolysiloxane segment (binding point a) and the binding point
(binding point .beta.) of an adjacent poly(N-acylalkyleneimine)
segment, as shown in the following formula (6), which consists of
one unit of R.sup.7SiO, one R.sup.11, and y+1 units of
R.sup.7.sub.2SiO. Furthermore, the "poly(N-acylalkyleneimine)
segment" refers to W, which binds to the above-mentioned
R.sup.11.
##STR00004##
[0036] In the above-mentioned general formula (6), R.sup.7 each
independently represents an alkyl group or a phenyl group each
having 1 to 22 carbon atoms, R.sup.11 represents an alkylene group
containing a hetero atom, W represents a poly(N-acylalkyleneimine)
segment, R.sup.12 represents a residue of a polymerization
initiator, and y is a positive number.
[0037] MWg is the molecular weight of the portion surrounded by the
broken line in the above-mentioned general formula (6) and can be
understood as the mass (g/mol) of an organopolysiloxane segment per
mole of the poly(N-acylalkyleneimine) segment. When 100% of a
functional group of a modified organopolysiloxane, a starting
compound, is replaced with poly(N-acylalkyleneimine), the value is
equal to the functional group equivalent (g/mol) of the modified
organopolysiloxane.
[0038] The molecular weight (MWox) of a poly(N-acylalkyleneimine)
segment can be measured by a method of calculating from the
molecular weight and the polymerization degree of a
N-acylalkyleneimine unit or a measuring method by gel permeation
chromatography (GPC) described later. In the present invention, the
number-average molecular weight is measured by a measuring method
by GPC and is preferably 800 to 1600, more preferably 850 to 1500,
even more preferably 900 to 1400. Consequently, the
organopolysiloxane does not break and plastic deformation is
exhibited even at extension rates of 300% or higher, and sufficient
membrane strength can be ensured. Furthermore, styling properties,
setting performance and set holding performance, can be further
improved in use as the hair cosmetic described later.
[0039] Furthermore, MWg can be obtained from the following formula
(1) using the content percentage (Csi) of an organopolysiloxane
segment as a main chain.
MWg = Csi .times. MWox 100 - Csi ( I ) ##EQU00001##
[0040] The weight-average molecular weight (MWsi) of an
organopolysiloxane segment as a main chain is 10,000 to 100,000,
preferably 20,000 to 80,000, more preferably 30,000 to 60,000 in
view of not breaking and exhibiting plastic deformation at
extension rates of 300% or higher, ensuring sufficient membrane
strength, and further solubility in polar solvents such as water
and easiness to handle after dissolution. To have a skeleton common
to that of a modified organopolysiloxane, the starting compound,
MWsi is nearly the same as the weight-average molecular weight of
the modified organopolysiloxane, the starting compound. The average
molecular weight of modified organopolysiloxane, the starting
compound, is the polystyrene-equivalent weight-average molecular
weight obtained by GPC under the following conditions.
[0041] Column: Super HZ4000 Super HZ2000 (Tosoh Corporation)
[0042] Eluent: 1 mM triethylamine/THF
[0043] Flow rate: 0.35 mL/min
[0044] Column temperature: 40.degree. C.
[0045] Detector: UV
[0046] Sample: 50 .mu.L
[0047] The weight-average molecular weight (MWt) of the
organopolysiloxane of the present invention is preferably 12,000 to
150,000, more preferably 24,000 to 120,000, even more preferably
37,000 to 92,000. Consequently, the organopolysiloxane does not
break and plastic deformation exhibited even at extension rates of
300% or higher, sufficient membrane strength can be ensured, and,
in addition, excellent solubility in polar solvents such as water
is achieved. Furthermore, styling properties, setting performance
and set holding performance, can be further improved in use as the
hair cosmetic described later. In the present specification, MWt
can be obtained from the weight-average molecular weight of a
modified organopolysiloxane, the starting compound, and the
above-mentioned mass ratio (a/b).
[0048] Methods for producing the organopolysiloxane of the present
invention will be explained below.
[0049] For example, the organopolysiloxane of the present invention
is produced by reacting a modified organopolysiloxane represented
by the following general formula (7):
##STR00005##
wherein R.sup.7 has the same meaning as defined above, and R.sup.8
and R.sup.9 each represent a group identical to R.sup.7 or a
monovalent group represented by any of the following formulas
(viii) to (xiii):
##STR00006##
wherein R.sup.10 represents a monovalent group represented by any
of the above-mentioned formulas (viii) to (xiii), d is an integer
of 135 to 1350, and e is an integer of 3 to 57) and a terminal
reactive poly(N-acylalkyleneimine) obtained by ring-opening
polymerization of a cyclic imino ether represented by the following
general formula (8):
##STR00007##
wherein R.sup.1 and n have the same meaning as defined above.
[0050] It is desirable to use a modified organopolysiloxane whose
functional group equivalent is preferably 1700 to 3500, more
preferably 1800 to 3200, even more preferably 2000 to 3000, and
whose weight-average molecular weight is preferably 10,000 to
100,000, more preferably 20,000 to 80,000, even more preferably
30,000 to 60,000.
[0051] Furthermore, it is desirable to adjust the molecular weight
of the terminal reactive poly(N-acylalkyleneimine) to preferably
800 to 1600, more preferably 850 to 1500, even more preferably 900
to 1400.
[0052] The ring-opening polymerization of a cyclic imino ether (8)
can be performed using a polymerization initiator. Examples of the
polymerization initiator include compounds having strong
electrophilic reactivity, for example, alkyl esters of strong acids
such as alkyl benzenesulfonates, alkyl p-toluenesulfonates, alkyl
trifluoromethanesulfonates, alkyl trifluoroacetates, dialkyl
sulfates, and the like. Among these, dialkyl sulfates are
preferably used. The amount of the polymerization initiator used is
usually 1 mol based on 2 to 100 mol of a cyclic imino ether
(8).
[0053] Examples of the polymerization solvent include acetic acid
esters such as ethyl acetate and propyl acetate, ethers such as
diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran,
ketones such as acetone and methyl ethyl ketone, halogen solvents
such as chloroform and methylene chloride, nitrile solvents such as
acetonitrile and benzonitrile, and aprotonic polar solvents such as
N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl
sulfoxide. Among these, acetic acid esters are preferably used. The
amount of a solvent used is usually 20 to 2000 parts by mass based
on 100 parts by mass of a cyclic imino ether (8).
[0054] The polymerization temperature is usually 30 to 170.degree.
C., preferably 40 to 150.degree. C. The polymerization time is not
uniform depending on the polymerization temperature and the like,
but is usually 1 to 60 h.
[0055] When a 2-substituted-2-oxazoline is used as a cyclic imino
ether (8), for example, poly(N-acylethyleneimine) with n=2 in the
above-mentioned general formula (1) is obtained. When a
2-substituted-dihydro-2-oxazine is used, poly(N-acylpropyleneimine)
with n=3 in the above-mentioned general formula (1) is
obtained.
[0056] Examples of the method for linking poly(N-acylalkyleneimine)
and an organopolysiloxane segment include the following
methods.
1) A method of reacting a modified organopolysiloxane represented
by the above-mentioned general formula (7) with a terminal reactive
poly(N-acylalkyleneimine) obtained by living polymerization of a
cyclic imino ether 2) Formation reaction of an ester by
condensation of a carboxyl group and a hydroxy group 3) Formation
reaction of an amide by condensation of a carboxyl group and an
amino group 4) Formation reaction of a secondary, tertiary, or
quaternary ammonium from a halogenated alkyl group and a primary,
secondary, or tertiary amino group 5) Addition reaction of a vinyl
group to an Si--H group of an organopolysiloxane 6) Formation
reaction of a .beta.-hydroxy amine from an epoxy group and an amino
group
[0057] Among these, the method of the above-mentioned 1) is most
effective in that the degree of polymerization can be easily
regulated by the amounts of a cyclic imino ether (8) and a
polymerization initiator used as shown in the following theoretical
formula (II) [MWi, molecular weight of poly(N-acylpropyleneimine)],
and that nearly-monodispersed poly(N-acylalkyleneimine) with a
narrower molecular weight distribution than in usual radical
polymerization can be obtained.
Mwi = Number of moles of cyclic imino ether Number of moles of
polymerization initiator .times. Molecular weight of cyclic imino
ether + Molecular weight of polymerization initiator ( II )
##EQU00002##
[0058] The organopolysiloxane of the present invention has a unique
structure in which a poly(N-acylalkyleneimine) segment binds to at
least two silicon atoms of an organopolysiloxane segment having a
predetermined molecular weight via an alkylene group containing a
hetero atom at a predetermined interval and a predetermined ratio.
Consequently, the organopolysiloxane of the present invention is
suitably added to a hair cosmetic since plastic deformation is
exhibited, both high extensibility and high membrane strength are
achieved, and it can be dissolved in polar solvents such as water
and lower alcohols.
[0059] Examples of the organopolysiloxane of the present invention
include poly(N-formylethyleneimine)organosiloxane,
poly(N-acetylethyleneimine) organosiloxane,
poly(N-propionylethyleneimine)organosiloxane, and so forth.
Hair Cosmetic
[0060] The hair cosmetic of the present invention is characterized
in that the organopolysiloxane of the present invention described
above is contained. Consequently, a flexible feel, setting
performance that the hair style is not disintegrated after passing
fingers through hair, and a more natural finish can be
obtained.
[0061] The organopolysiloxane of the present invention can be used
solely or two or more thereof can be used in combination. The
content thereof is preferably 0.05 to 20% by mass, more preferably
0.1 to 15% by mass, even more preferably 0.1 to 10% by mass, even
more preferably 0.5 to 5% by mass based on the total mass of the
hair cosmetic in view of hair setting performance, set holding
performance, and wash property by shampooing. Furthermore, with
such contents, when organic solvents and organic acids or salts
thereof described later are used in combination, styling
properties, setting performance and set holding performance, can be
further improved without impairing hair reforming effects
(improvement of manageability, etc.) of the organic acids and the
organic solvents.
[0062] Furthermore, the hair cosmetic of the present invention can
further contain an organic solvent selected from the following (b1)
to (b5) (hereinafter, referred to as "component (B)") as a
preferred component.
(b1) Compound represented by general formula (2)
##STR00008##
wherein R.sup.2 represents a hydrogen atom, an alkyl group having 1
to 6 carbon atoms or a group R.sup.3-Ph-R.sup.4-- (wherein R.sup.3
represents a hydrogen atom, a methyl group, or a methoxy group;
R.sup.4 represents a bond or a saturated or unsaturated divalent
hydrocarbon group having 1 to 3 carbon atoms; and Ph represents a
paraphenylene group), A represents a bond or a saturated divalent
hydrocarbon group having 1 to 4 carbon atoms, Y and Z each
independently represent a hydrogen atom or a hydroxy group, and p
and q are each independently an integer of 0 to 5, provided that
when p=q=0, Z represents a hydroxy group, and R.sup.2 is not either
a hydrogen atom or a group R.sup.3-Ph-; (b2) N-alkylpyrrolidone or
N-alkenylpyrrolidone in which an alkyl group or an alkenyl group
having 1 to 18 carbon atoms binds to a nitrogen atom; (b3) Alkylene
carbonate having 2 to 4 carbon atoms; (b4) Polypropylene glycol
having a number-average molecular weight of 100 to 1000; and (b5)
Lactone or cyclic ketone represented by the following general
formula (3), (4), or (5)
##STR00009##
wherein X represents a methylene group or an oxygen atom, R.sup.5
and R.sup.6 represent different substituents, and a and b are each
independently 0 or 1.
[0063] Among the organic solvents, components (B), examples of (b1)
include straight or branched C1 to C6 lower alcohols such as
ethanol, isopropanol, butanol, and isobutanol, ethylene glycol,
propylene glycol, dipropylene glycol, 1,3-butane diol, benzyl
alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol,
p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol,
methylcarbitol, ethylcarbitol, propylcarbitol, butylcarbitol,
triethylene glycol monoethyl ether, triethylene glycol monobutyl
ether, and so forth.
[0064] Examples of (b2) include N-methylpyrrolidone,
N-octylpyrrolidone, N-laurylpyrrolidone, and so forth.
[0065] Examples of (b3) include ethylene carbonate, propylene
carbonate, and so forth.
[0066] As the polypropylene glycol having a number-average
molecular weight of 100 to 1000, (b4), those having a
number-average molecular weight of 300 to 500 are preferable. Here,
the number-average molecular weight means a number-average
molecular weight in terms of polystyrene measured by GPC.
[0067] In (b5), preferable examples of R.sup.5 and R.sup.6 in the
general formulas (3) to (5) include straight, branched, or cyclic
alkyl groups, a hydroxy group, a sulfonate group, a phosphate
group, a carboxy group, a phenyl group, a sulfoalkyl group, an
alkyl phosphate group, a carboxyalkyl group, and so forth. Among
these, straight or branched alkyl groups having 1 to 6 carbon
atoms, for example, a methyl group, an ethyl group, a propyl group,
an isopropyl group, and a butyl group are preferable. These groups
are preferably substituted at the .gamma.y-position in
.gamma.-lactone and at the .delta.-position in .delta.-lactone
(specifically, methylene adjacent to a heterooxygen atom).
Furthermore, when water-solubility of compounds (3) to (5) needs to
be increased, these compounds preferably have an acidic group such
as a sulfonate group, a phosphate group, and a carboxy group or an
alkyl group substituted by these groups as R.sup.5 or R.sup.6.
Among (b5), examples of lactones include .gamma.-butyrolactone,
.gamma.-caprolactone, .gamma.-valerolactone, .delta.-valerolactone,
.delta.-caprolactone, .delta.-heptanolactone, and so forth. In view
of stability of lactone, .gamma.-lactone, in particular,
.gamma.-butyrolactoneand .gamma.-caprolactone are preferable. Among
(b5), examples of cyclic ketones include cyclopentanone,
cyclohexanone, cycloheptanone, 4-methyl cycloheptanone, and so
forth.
[0068] Furthermore, the component (B) used in the present invention
is preferably liquid at 25.degree. C., and C log P is preferably -2
to 3, more preferably -1 to 2 in view of penetration enhancement.
Here, C log P is an octanol-water-distribution coefficient (log P)
defined by the following formula (III), a measure of distribution
of a substance between the octanol phase and the aqueous phase, and
an example thereof is described in Chemical Reviews, Vol. 71, No. 6
(1971).
log P=log([substance].sub.Octanol/[substance].sub.Water) (III)
wherein [substance].sub.Octanol represents a molar concentration of
a substance in the 1-octanol phase, and [substance].sub.Water
represents a molar concentration of the substance in the aqueous
phase.
[0069] Specific C log P of the representative components (B) are
dipropylene glycol (-0.67), 1,3-butanediol (-0.29), benzyl alcohol
(1.1), 2-benzyloxyethanol (1.2), 2-phenylethanol (1.2),
1-phenoxy-2-propanol (1.1), polypropylene glycol 400 (0.9),
propylene carbonate (-0.41), and .gamma.-butyrolactone (-0.64).
[0070] Two or more of components (B) may be used in combination,
and the total content thereof is preferably 0.1 to 40% by mass of
the hair cosmetic of the present invention, more preferably 0.5 to
10% by mass, even more preferably 1 to 5% by mass in view of
effects of improving firmness and body after shampooing, effects of
improving softness and manageability of the hair, and promotion of
reforming effects (improvement of elasticity and moisture
resistance, etc.).
[0071] Furthermore, the hair cosmetic of the present invention can
contain water or a straight or branched saturated or unsaturated C1
to C6 alcohol as a solvent in view of hair setting performance,
favorable usability, and promotion of solubility during the
preparation of a hair cosmetic. The solvent can be used solely, or
two or more thereof can be used in combination. Among these, water
and C1 to C6 lower alcohols such as ethanol and isopropanol are
preferable, and water and ethanol are more preferable. The total
content of water and alcohols is preferably 0.1 to 98% by mass of
the total mass of a hair cosmetic, more preferably 1 to 90% by
mass, even more preferably 5 to 60% by mass.
[0072] Furthermore, the hair cosmetic of the present invention can
contain an organic carboxylic acid or a salt thereof (hereinafter,
referred to as "component (A)") that may have a hydroxy group,
together with a component (B). In this case, particularly
preferable examples of the component (B) include dipropylene
glycol, 1,3-butane diol, benzyl alcohol, phenoxyethanol,
2-benzyloxyethanol, propylene carbonate, and polypropylene glycol
(a number-average molecular weight of 300 to 500, more preferably
400).
[0073] Organic carboxylic acids having 2 to 8 carbon atoms are
preferable as components (A), and specific examples thereof include
monocarboxylic acids such as acetic acid and propionic acid,
dicarboxylic acids such as malonic acid, succinic acid, glutaric
acid, adipic acid, maleic acid, fumaric acid, and phthalic acid,
polycarboxylic acids such as polyglutamic acid, hydroxycarboxylic
acids such as glycolic acid, lactic acid, hydroxyacrylic acid,
glyceric acid, malic acid, tartaric acid, and citric acid, acidic
amino acids such as glutamic acid and aspartic acid, and so forth.
Among these, hydroxycarboxylic acids having 2 to 6 carbon atoms are
preferable, and lactic acid and malic acid are more preferable.
Examples salts of these organic carboxylic acids include salts with
alkali metals, alkaline earth metals, ammonia, and organic amine
compounds.
[0074] Two or more of these components (A) may be used in
combination, and the total content thereof is preferably 0.1 to 30%
by mass of the hair cosmetic of the present invention, more
preferably 0.5 to 20% by mass, even more preferably 0.5 to 10% by
mass in view of effects of reforming the inside of the hair
(repairing hollows, etc.), effects of improving firmness and body
after shampooing, and effects of improving softness and
manageability of the hair.
[0075] The mass ratio of an organic carboxylic acid or a salt
thereof as component (A) and an organic solvent as component (B) is
preferably in the range of (A):(B)=10:1 to 1:7, more preferably 4:1
to 1:3 to effectively exhibit effects of reforming the inside of
the hair (repairing hollows, etc.), effects of improving firmness
and body after shampooing, and effects of improving softness and
manageability of the hair.
[0076] Furthermore, when a set polymer is added to the hair
cosmetic of the present invention, the set holding performance is
further improved, and the smooth feel of the hair becomes
favorable.
[0077] Examples of the set polymer include those shown in the
following 1) to 8). These polymers can be used solely, or two or
more thereof can be used in combination.
1) Vinylpyrrolidone Polymers
Polyvinylpyrrolidones
[0078] Examples thereof include marketed products such as Luviskol
K12 and K30 (BASF) and PVP K15 and K30 (GAF Corporation).
Vinylpyrrolidone/Vinyl Acetate Copolymers
[0079] Examples thereof include marketed products such as Luviskol
VA28 and VA73 (BASF) and PVP/VA E-735 and S-630 (GAF
Corporation).
Vinylpyrrolidone/Vinyl Acetate/Vinyl Propionate Ternary
Copolymer
[0080] Examples thereof include marketed products such as Luviskol
VAP343 (BASF).
Vinylpyrrolidone/Alkyl Aminoacrylate Copolymer
[0081] Examples thereof include marketed products such as Luviflex
(BASF) and copolymers 845, 937, and 958 (GAF Corporation).
Vinylpyrrolidone/Acrylate/(Meth)Acrylic Acid Copolymer
[0082] Examples thereof include marketed products such as Luviflex
VBM35 (BASF).
Vinylpyrrolidone/Alkyl Aminoacrylate/Vinyl Caprolactam
Copolymer
[0083] Examples thereof include marketed products such as copolymer
VC-713 (GAF Corporation).
2) Acidic Vinyl Ether Polymers
Methyl Vinyl Ether/Maleic Anhydride Alkyl Half-Ester Copolymers
[0084] Examples thereof include marketed products such as Gantrez
ES-225, ES-425, and SP-215 (GAF Corporation).
3) Acidic Polyvinyl Acetate Polymers
Vinyl Acetate/Crotonic Acid Copolymers
[0085] Examples thereof include marketed products such as resin
28-1310 (National Starch and Chemical Company) and Luviset CA66
(BASF).
Vinyl Acetate/Crotonic Acid/Vinyl Neodecanoate Copolymer
[0086] Examples thereof include marketed products such as resin
28-2930 (National Starch and Chemical Company).
Vinyl Acetate/Crotonic Acid/Vinyl Propionate Copolymers
[0087] Examples thereof include marketed products such as Luviset
CAP (BASF).
4) Acidic Acrylic Polymers
(Meth)Acrylate/(Meth)Acrylate Ester Copolymers
[0088] Examples thereof include marketed products such as Plus Size
L53P (Goo Chemical Co., Ltd.) and Diahold (Mitsubishi Petrochemical
Co., Ltd.).
Acrylate/Alkyl Acrylate Ester/Alkyl Acrylamide Copolymers
[0089] Examples thereof include marketed products such as Ultra
Hold 8 (BASF) and Unfoamer V-42 (National Starch and Chemical
Company).
5) Ampholytic Acrylic Polymers (Meth)acryl ethyl betaine/alkyl
(meth)acrylate copolymers
[0090] Examples thereof include copolymers of
N-methacryloyloxyethyl-N,N-dimethylammonium-.alpha.-N-methylcarboxybetain-
e and alkyl (meth)acrylate, for example, marketed products such as
Yukafoamer M-75, SM (Mitsubishi Petrochemical Co., Ltd.).
Alkyl Acrylate/Butylaminoethyl Methacrylate/Octyl Acrylate Amide
Copolymers
[0091] Examples thereof include octyl
acrylamide/acrylate/butylaminoethyl methacrylate copolymers, for
example, marketed products such as Unfoamer 28-4910 (National
Starch and Chemical Company).
6) Basic Acrylic Polymers
Acrylamide Acryl Ester Copolymers
[0092] Examples thereof include those in the examples of
JP-A-02-180911 and JP-A-08-291206.
7) Cellulose Derivatives
Cationic Cellulose Derivatives
[0093] Examples thereof include marketed products such as Celquat
H-100, L-200 (National Starch and Chemical Company).
8) Chitin or Chitosan Derivatives
Hydroxypropyl Chitosan
[0094] Examples thereof include marketed products such as
Chitofilmer (Ichimaru Pharcos Co., Ltd.).
[0095] Salts of carboxymethyl chitin, carboxymethyl chitosan,
chitosan with monovalent acids such as pyrrolidonecarboxylic acid,
lactic acid, and glycolic acid or with divalent acids such as
adipic acid and succinic acid
[0096] Examples thereof include marketed products such as Chitomer
PC (pyrrolidonecarboxylic acid salt) and Chitomer L (lactic acid
salt) (Union Carbide).
[0097] Among these set polymers, set polymers selected from acrylic
polymers and vinylpyrrolidone polymers are particularly preferable.
The content of a set polymer is preferably 0.05 to 20% by mass of
the total mass of a hair cosmetic, more preferably 0.1 to 10% by
mass, even more preferably 0.3 to 5% by mass.
[0098] To further improve the conditioning effect, the hair
cosmetic of the present invention can contain an oil solution and a
conditioning component selected from silicones other than the
above-mentioned organopolysiloxanes.
[0099] Oil solutions are used to improve manageability and the
feeling of dried hair. Examples of oil solutions include
hydrocarbons such as squalene, squalane, liquid isoparaffin, light
liquid isoparaffin, heavy liquid isoparaffin, .alpha.-olefin
oligomers, liquid paraffin, and cycloparaffin, glycerides such as
caster oil, cacao oil, mink oil, avocado oil, and olive oil, waxes
such as beeswax, spermaceti, lanolin, microcrystalline wax, ceresin
wax, and carunauba wax; higher alcohols such as cetyl alcohol,
oleyl alcohol, stearyl alcohol, isostearyl alcohol, and
2-octyldodecanol, esters such as octyldodecyl myristate, hexyl
laurate, cetyl lactate, monostearate propylene glycol, oleyl
oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, and
tridecyl isononanoate, higher fatty acids such as caprynic acid,
lauric acid, myristic acid, palmitic acid, stearic acid, behenic
acid, oleic acid, coconut oil fatty acids, isostearylic acid, and
isopalmitic acid, solid fats such as cholesterol, Vaseline,
cholesteryl isostearate, and sphingo lipid, as well as jojoba oil,
isostearyl glyceryl ether, polyoxypropylene butyl ether, and so
forth. Among these, branched hydrocarbons such as squalene,
squalane, liquid isoparaffin, light liquid isoparaffin, heavy
liquid isoparaffin, and .alpha.-olefin oligomers are particularly
preferable.
[0100] The content of an oil solution is preferably 0.05 to 20% by
mass of the hair cosmetic of the present invention, more preferably
0.1 to 10% by mass, even more preferably 0.5 to 5% by mass in view
of favorable manageability and no greasiness.
[0101] Examples of silicones include dimethyl polysiloxane,
polyether-modified silicones, amino-modified silicones,
carboxy-modified silicones, methylphenylpolysiloxane, fatty
acid-modified silicones, alcohol-modified silicones, aliphatic
alcohol-modified silicones, epoxy-modified silicones,
fluorine-modified silicones, cyclic silicones, alkyl-modified
silicones, and so forth. Among these, dimethylpolysiloxane,
polyether-modified silicones, and amino-modified silicones are
preferable.
[0102] Dimethylpolysiloxane can impart a favorable lubricating
property to the hair, polyether-modified silicones can impart
smoothness to the hair, and amino-modified silicones can impart a
moistening feel to hair. In the present invention, various
silicones can be used solely, or two or more thereof can be used in
combination depending on the required performance.
[0103] Dimethylpolysiloxane having a viscosity of approx. 5
mm.sup.2/s to approx. 10,000,000 mm.sup.2/s often provided as
emulsifiers can be used depending on the required feel, and those
having a viscosity of 5000 to 10,000,000 mm.sup.2/s, particularly a
viscosity of 50,000 to 10,000,000 mm.sup.2/s are preferable.
[0104] Polyether-modified silicones are not limited so long as they
are silicones having a polyoxyalkylene group, and examples of
groups constituting the polyoxyalkylene group include an
oxyethylene group and an oxypropylene group. More specific examples
thereof include KF-6015, KF-945A, KF-6005, KF-6009, KF-6013,
KF-6019, KF-6029, KF-6017, KF-6043, KF-353A, KF-354A, and KF-355A
(Shin-Etsu Chemical Co., Ltd.), FE-2404, SS-2805, FZ-2411, FZ-2412,
SH3771M, SH3772M, SH3773M, SH3775M, SH3749, SS-280X series,
BY22-008M, BY11-030, and BY25-337 (Dow Corning Toray Co., Ltd.),
and so forth.
[0105] Amino-modified silicones having an average molecular weight
of approx. 3000 to 100,000, described under the name of
amodimethicone in the Cosmetic, Toiletry and Fragrance Association
(CTFA) Dictionary (U.S., Cosmetic Ingredient Dictionary) 3rd
Edition are preferable. Examples thereof include marketed products
such as SM 8704C (Dow Corning Toray Co., Ltd.), DC 929 (Dow Corning
Corporation), KT 1989 (GE Toshiba Silicones), 8500 Conditioning
Agent, DOW CORNING TORAY SS-3588, DOW CORNING TORAY SILSTYLE
104(Dow Corning Toray Co., Ltd.), and so forth.
[0106] The content of silicones is preferably 0.05 to 20% by mass
of the hair cosmetic of the present invention, more preferably 0.1
to 10% by mass, even more preferably 0.5 to 5% by mass in view of
the finger passing property and no greasiness.
[0107] The hair cosmetic of the present invention can contain a
surfactant in view of the system stability including solubility,
dispersibility, and the like of a solvent and improvement of the
feel. As a surfactant, any of cationic surfactants, nonionic
surfactants, ampholytic surfactants, and anionic surfactants can be
used.
[0108] Examples of cationic surfactants include quaternary ammonium
salts represented by the following general formula (9):
##STR00010##
wherein R.sup.13 and R.sup.14 each independently represent a
hydrogen atom or an alkyl group or a benzyl group having 1 to 28
carbon atoms and are not a hydrogen atom, a benzyl group, or a
lower alkyl group having 1 to 3 carbon atoms or any combination
thereof at the same time, and An.sup.- has the same meaning as
defined above.
[0109] Here, one of R.sup.13 and R.sup.14 represents preferably an
alkyl group having 16 to 24 carbon atoms, more preferably having 22
carbon atoms, even more preferably a straight alkyl group, and the
other one preferably represents a lower alkyl group having 1 to 3
carbon atoms, more preferably a methyl group.
[0110] As cationic surfactants, mono-long chain alkyl quaternary
ammonium salts are preferable, and specific examples thereof
include cetyltrimethyl ammonium chloride, stearyltrimethyl ammonium
chloride, alkyltrimethyl ammonium chloride, behenyltrimethyl
ammonium chloride, alkyl benzalkonium chloride, and so forth.
Stearyltrimethyl ammonium chloride and behenyltrimethyl ammonium
chloride are particularly preferable.
[0111] Examples of nonionic surfactants include polyoxyalkylene
alkyl ethers, polyoxyalkylene alkenyl ethers, higher fatty acid
sucrose esters, polyglycerine fatty acid esters, higher fatty acid
mono or diethanol amides, polyoxyethylene hydrogenated caster oil,
polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit
fatty acid esters, alkyl saccharide surfactants, alkyl amine
oxides, alkyl amide amine oxides, and so forth. Among these,
polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated caster
oil are preferable, and polyoxyethylene alkyl ethers and
polyoxyethylene.cndot.polyoxypropylene alkyl ethers are
particularly preferable.
[0112] Examples of ampholytic surfactants include imidazoline
surfactants, carbobetaine surfactants, amidobetaine surfactants,
sulfobetaine surfactants, hydroxysulfobetaine surfactants,
amidosulfobetaine surfactants, and so forth. Among these, betaine
surfactants such as alkyl dimethyl aminoacetic acid betaines and
fatty acid amidopropyl betaines are preferable, and fatty acid
amidopropyl betaines are more preferable. Fatty acid amidopropyl
betaines having 8 to 18 carbon atoms, in particular, those
containing an acyl group having 10 to 16 carbon atoms are
preferable. More preferable examples thereof include lauric acid
amidopropyl betaines, palm kernel oil fatty acid amidopropyl
betaines, coconut oil fatty acid amidopropyl betaines, and so
forth.
[0113] Examples of anionic surfactants include
alkylbenzenesulfonates, alkyl or alkenyl ether sulfates, alkyl or
alkenyl sulfuric acid salts, olefinsulfonates, alkanesulfonates,
saturated or unsaturated fatty acid salts, alkyl or alkenyl ether
carboxylic acid salts, .alpha.-sulfone fatty acid salts,
N-acylamino acid surfactants, phosphate mono or diester
surfactants, sulfosuccinic acid esters, and so forth. Examples of
counter ions of anionic residues of the above-mentioned surfactants
include alkali metal ions such as a sodium ion and a potassium ion,
alkaline earth metal ions such as a calcium ion and a magnesium
ion, an ammonium ion, and alkanol amine containing 1 to 3 alkanol
groups having 2 or 3 carbon atoms (for example, monoethanolamine,
diethanolamine, triethanolamine, triisopropanolamine, etc.).
Furthermore, examples of counter ions of cationic residues include
halide ions such as a chloride ion, a bromide ion, and an iodide
ion, a methosulfate ion, and a saccharinate ion.
[0114] Among these, cationic surfactants and nonionic surfactants
are preferable in view of its feel to the touch. Surfactants can be
used solely, or two or more thereof can be used in combination. In
view of the system stability including solubilization of a solvent
and emulsification of an oil solution, the content is preferably
0.01 to 10% by mass, more preferably 0.05 to 5% by mass of the hair
cosmetic of the present invention.
[0115] Furthermore, the hair cosmetic of the present invention can
contain polyhydric alcohols other than components (B). Polyhydric
alcohols contribute to solubilization and stable distribution of
components (B) and act synergistically with components (B) to
promote improvement of luster and hair reforming effects. Examples
of the polyhydric alcohols include ethylene glycol, glycerine, and
sorbitol, and glycerine is particularly preferable. Polyhydric
alcohols can be used solely, or two or more thereof can be used in
combination. The content thereof is preferably 0.1 to 10% by mass,
more preferably 0.5 to 5% by mass in the hair cosmetic of the
present invention.
[0116] In addition to the above-mentioned components, components
usually used in hair cosmetics can be suitably mixed in the hair
cosmetic of the present invention depending on the objective,
purpose, form, and the like. Examples of such components include
anti-dandruff agents such as zinc pyrithione and octopirox, vitamin
agents, disinfectants such as triclosan and trichlorocarban,
anti-inflammatory agents such as dipotassium glycyrrhizinate and
tocopherol acetate, preservatives such as methylparaben and
butylparaben, chelating agents, moisturizing agents such as
panthenol, coloring materials such as dyes and pigments, viscosity
modifiers such as hydroxyethylcellulose, methylcellulose,
polyethylene glycol, and clay minerals, organic acids other than
components (A), pH modifiers such as sodium hydroxide and potassium
hydroxide, plant extracts, pearlescents, perfumes, coloring
matters, ultraviolet absorbers, antioxidants, and other components
described in Encyclopedia of Shampoo Ingredients (Micelle
Press).
[0117] The hair cosmetic of the present invention can be prepared
in various forms by usual methods, for example, not only in liquid
compositions such as mists, lotions, and tonics but also in
semisolid compositions such as gels, pastes, creams, and waxes.
Liquid compositions using water and/or a lower alcohol, in
particular, water and a lower C1 to C3 alcohol as a solvent are
preferable. Examples of such lower alcohols include ethanol,
1-propanol, 2-propanol, and so forth, and, among these, ethanol is
preferable.
[0118] By suitably selecting a form and mixed components depending
on the purpose, for example, the hair cosmetic of the present
invention can be prepared as shampoo compositions, hair
conditioning compositions, and further semisolid styling
compositions.
[0119] Measures for applying these hair cosmetics to the hair are
not uniform depending on the form, but usually jetting such as
spraying, application by hand, a combination there of, and the like
are employed. Furthermore, a solvent after application is
preferably removed by natural drying, heating, or the like. To set
the hair in a desired shape, it is desirable to shape the hair
before drying after application. Shaping is performed usually by a
method using a brush, a dryer, a flat iron, or a curler or the
like.
[0120] Furthermore, a propellant may be added to the hair cosmetic
of the present invention to prepare an aerosol hair cosmetic. The
propellants are not particularly limited, so long as they are
usually used in aerosol-type cosmetics, and examples thereof
include saturated lower hydrocarbons such as propane, butane, or
mixtures thereof (including a liquefied petroleum gas), ethers such
as dimethyl ether, a nitrogen gas, carbon dioxide, a nitrous oxide
gas, and so forth. These can be used solely, or two or more thereof
can be used in combination. The content of a propellant is
preferably 0.01 to 50% by mass of the hair cosmetic of the present
invention, more preferably 5 to 20% by mass.
[0121] Furthermore, the hair cosmetic of the present invention can
be prepared as a non-aerosol-type hair cosmetic by filling a
composition containing the above-mentioned organopolysiloxane and
components (A) and (B) in a foam discharge container. The foam
discharge containers are not particularly limited, so long as the
composition is mixed with air and discharged as a foam. Examples
thereof include squeeze foamers, which are used by pressing the
body of a soft container with fingers, pump foamers, which have a
pump mechanism and are used by pressing the head of the cap with a
finger, trigger types, and so forth.
[0122] Examples of squeeze foamers includes those described in
JP-Y2-62-042785, JP-Y2-62-042786, and JP-Y2-62-042787 and those
similar thereto. Examples of pump foamers include those described
in JP-A-07-315463 and JP-A-08-230961 and those similar thereto.
These containers are often provided with a mesh body at the
discharge port to improve the quality of foam. Among these, those
provided with one or two mesh bodies having 100 to 300 meshes are
preferable.
[0123] Such hair cosmetics are preferably used as hair styling
agents, hair conditioning agents, and the like. As the form
thereof, pump spray, aerosol spray, pump foam, aerosol foam, gel,
lotion, mist, cream, and the like are preferable. Among these, pump
spray, pump foam, and aerosol foam are preferable.
[0124] Furthermore, after application of the above-mentioned
organopolysiloxane containing components (A) and (B) to the hair,
penetration of components (A) and (B) into the hair can be promoted
by heating a hair cosmetic. Heating can be performed by using a
hair iron, a dryer, a heater, a hair singer, or the like. The
temperature is preferably 60.degree. C. or higher, more preferably
70.degree. C. or higher.
[0125] Furthermore, in everyday life, by treating the hair with the
hair cosmetic of the present invention at least once daily and
continuing the treatment for preferably 7 days or longer, more
preferably 14 days or longer, softness and manageability of the
hair and styling properties, setting performance and set holding
performance, can be improved.
EXAMPLES
[0126] Hereafter, the present invention will be explained
specifically with reference to the examples. However, the scope of
the present invention is not limited to these examples. In the
following examples, the content percentage of an organopolysiloxane
segment is a value obtained by the nuclear magnetic resonance
method (.sup.1H-NMR), and a weight-average molecular weight of the
final product is a calculated value. The molecular weight of
poly(N-propionylethyleneimine) is a number-average molecular weight
obtained by gel permeation chromatography (GPC).
Column: K-804L+K-804L, Showa Denko K.K.
[0127] Eluent: 1 mmol/L FARMIN DM20 (Kao Corporation)/chloroform
Flow rate: 1.0 mL/min Column temperature: 40.degree. C.
Detector: RI
[0128] Sample amount: 5 mg/mL, 100 .mu.L
In Terms of Polystyrene
Example 1
[0129] 8.1 g (0.053 mol) of diethyl sulfate and 45.8 g (0.48 mol)
of 2-ethyl-2-oxazoline were dissolved in 115 g of dehydrated ethyl
acetate, and the mixture was heated to reflux for 8 hours under a
nitrogen atmosphere to synthesize a terminal reactive
poly(N-propionylethyleneimine). The number-average molecular weight
was 1400 by GPC. A solution of 100 g of side-chain primary
aminopropyl-modified polydimethylsiloxane (weight-average molecular
weight, 32,000; amine equivalent, 2000) in 33% ethyl acetate was
added to the mixture in a batch, and the mixture was heated to
reflux for 10 hours. The reaction mixture was vacuum concentrated
to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as
a light yellow rubber-like semisolid (150 g, yield 97%). The
content percentage of an organopolysiloxane segment in the final
product was 65% by mass, and the weight-average molecular weight
was 49,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 2
[0130] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1100 was obtained from 9.3 g (0.060 mol) of diethyl
sulfate, 37.8 g (0.40 mol) of 2-ethyl-2-oxazoline, and 100 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 32,000; amine equivalent, 1750), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like semisolid (141 g, yield 96%). The
content percentage of an organopolysiloxane segment in the final
product was 68% by mass, and the weight-average molecular weight
was 47,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 3
[0131] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1400 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 36.4 g (0.39 mol) of 2-ethyl-2-oxazoline, and 91 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 20,000; amine equivalent 2500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like semisolid (137 g, yield 96%). The
content percentage of an organopolysiloxane segment in the final
product was 70% by mass, and the weight-average molecular weight
was 29,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 4
[0132] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1300 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline, and 87 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 40,000; amine equivalent, 2500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like semisolid (138 g, yield 98%). The
content percentage of an organopolysiloxane segment in the final
product was 71% by mass, and the weight-average molecular weight
was 56,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 5
[0133] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 900 was obtained from 6.2 g (0.040 mol) of diethyl
sulfate, 20.4 g (0.22 mol) of 2-ethyl-2-oxazoline, and 57 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 35,000; amine equivalent, 2600), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow viscous semisolid (123 g, yield 97%). The content
percentage of an organopolysiloxane segment in the final product
was 79% by mass, and the weight-average molecular weight was
51,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 6
[0134] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1200 was obtained from 8.1 g (0.053 mol) of diethyl
sulfate, 39.0 g (0.41 mol) of 2-ethyl-2-oxazoline, and 100 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 32,000; amine equivalent, 2000), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like semisolid (143 g, yield 97%). The
content percentage of an organopolysiloxane segment in the final
product was 68% by mass, and the weight-average molecular weight
was 46,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 7
[0135] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1000 was obtained from 4.6 g (0.030 mol) of diethyl
sulfate, 17.3 g (0.18 mol) of 2-ethyl-2-oxazoline, and 47 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 65,000; amine equivalent, 3500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow viscous semisolid (118 g, yield 97%). The content
percentage of an organopolysiloxane segment in the final product
was 82% by mass, and the weight-average molecular weight was
79,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 8
[0136] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1500 was obtained from 4.6 g (0.030 mol) of diethyl
sulfate, 28.7 g (0.30 mol) of 2-ethyl-2-oxazoline, and 71 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight 37,000, amine equivalent 3500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow viscous semisolid (129 g, yield 97%). The content
percentage of an organopolysiloxane segment in the final product
was 75% by mass, and the weight-average molecular weight was
49,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 9
[0137] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1400 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 36.4 g (0.39 mol) of 2-ethyl-2-oxazoline, and 91 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight 70,000, amine equivalent 2500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like semisolid (140 g, yield 98%). The
content percentage of an organopolysiloxane segment in the final
product was 70% by mass, and the weight-average molecular weight
was 100,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 10
[0138] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1300 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline, and 87 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 32,000; amine equivalent, 2000), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like semisolid (138 g, yield 98%). The
content percentage of an organopolysiloxane segment in the final
product was 71% by mass, and the weight-average molecular weight
was 46,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that approx. 22% by mole of amino
groups remained.
Example 11
[0139] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 900 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 20.1 g (0.21 mol) of 2-ethyl-2-oxazoline, and 57 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 36,000; amine equivalent, 2000), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow viscous semisolid (124 g, yield 98%). The content
percentage of an organopolysiloxane segment in the final product
was 79% by mass, and the weight-average molecular weight was
46,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that approx. 21% by mole of amino
groups remained.
Example 12
[0140] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1100 was obtained from 10.1 g (0.066 mol) of diethyl
sulfate, 43.7 g (0.46 mol) of 2-ethyl-2-oxazoline, and 115 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 32,000; amine equivalent, 1600), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like semisolid (148 g, yield 96%). The
content percentage of an organopolysiloxane segment in the final
product was 65% by mass, and the weight-average molecular weight
was 49,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 13
[0141] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 900 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 20.1 g (0.21 mol) of 2-ethyl-2-oxazoline, and 57 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 19,000, amine equivalent 2500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow viscous semisolid (122 g, yield 96%). The content
percentage of an organopolysiloxane segment in the final product
was 79% by mass, and the weight-average molecular weight was
25,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 14
[0142] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1300 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline, and 87 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 19,000; amine equivalent, 2500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow viscous semisolid (135 g, yield 96%). The content
percentage of an organopolysiloxane segment in the final product
was 71% by mass, and the weight-average molecular weight was
27,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Example 15
[0143] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1300 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline, and 87 g
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 80,000; amine equivalent, 2500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like semisolid (135 g, yield 96%). The
content percentage of an organopolysiloxane segment in the final
product was 71% by mass, and the weight-average molecular weight
was 113,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Comparative Example 1
[0144] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1600 was obtained from 8.7 g (0.056 mol) of diethyl
sulfate, 55.3 g (0.59 mol) of 2-ethyl-2-oxazoline, and 136 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 90,000; amine equivalent, 1870), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (159 g, yield 97%). The content
percentage of an organopolysiloxane segment in the final product
was 61% by mass, and the weight-average molecular weight was
148,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Comparative Example 2
[0145] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1500 was obtained from 8.1 g (0.053 mol) of diethyl
sulfate, 50.6 g (0.54 mol) of 2-ethyl-2-oxazoline, and 125 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 32,000; amine equivalent, 2000), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (154 g, yield 97%). The content
percentage of an organopolysiloxane segment in the final product
was 63% by mass, and the weight-average molecular weight was
51,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Comparative Example 3
[0146] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1300 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline, and 87 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 8000; amine equivalent, 2500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow viscous semisolid (137 g, yield 97%). The content
percentage of an organopolysiloxane segment in the final product
was 71% by mass, and the weight-average molecular weight of
organopolysiloxane was 11,000. Neutralization titration with
hydrochloric acid using methanol as a solvent showed that no amino
group remained.
Comparative Example 4
[0147] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1300 was obtained from 6.5 g (0.042 mol) of diethyl
sulfate, 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline, and 87 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight 110,000, amine equivalent 2500), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (135 g, yield 96%). The content
percentage of an organopolysiloxane segment in the final product
was 71% by mass, and the weight-average molecular weight of
organopolysiloxane was 155,000. Neutralization titration with
hydrochloric acid using methanol as a solvent showed that no amino
group remained.
Comparative Example 5
[0148] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 500 was obtained from 8.1 g (0.053 mol) of diethyl
sulfate, 12.4 g (0.13 mol) of 2-ethyl-2-oxazoline, and 44 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 40,000; amine equivalent, 2000), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (116 g, yield 96%). This product
was a solid insoluble in various solvents.
Comparative Example 6
[0149] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 5800 was obtained from 1.5 g (0.010 mol) of diethyl
sulfate, 39.4 g (0.42 mol) of 2-ethyl-2-oxazoline, and 87 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 26,000; amine equivalent, 11,000), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (135 g, yield 96%). The content
percentage of an organopolysiloxane segment in the final product
was 71% by mass, and the average molecular weight was 37,000.
Neutralization titration with hydrochloric acid using methanol as a
solvent showed that no amino group remained.
Comparative Example 7
[0150] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1900 was obtained from 4.5 g (0.029 mol) of diethyl
sulfate, 36.3 g (0.39 mol) of 2-ethyl-2-oxazoline, and 87 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight 35,000; amine equivalent, 3600), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (135 g, yield 96%). The content
percentage of an organopolysiloxane segment in the final product
was 71% by mass, and the weight-average molecular weight was
49,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Comparative Example 8
[0151] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 700 was obtained from 8.1 g (0.053 mol) of diethyl
sulfate, 18.5 g (0.20 mol) of 2-ethyl-2-oxazoline, and 57 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 80,000; amine equivalent, 2000), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (120 g, yield 95%). This product
was a solid insoluble in various solvents.
Comparative Example 9
[0152] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 5200 was obtained from 3.2 g (0.021 mol) of diethyl
sulfate, 92.8 g (0.98 mol) of 2-ethyl-2-oxazoline, and 205 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight, 50,000; amine equivalent, 3800),
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (188 g, yield 96%). The content
percentage of an organopolysiloxane segment in the final product
was 51% by mass, and the weight-average molecular weight was
98,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that approx. 24% by mole of amino
groups remained.
Comparative Example 10
[0153] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight 2700 was obtained from 0.8 g (0.005 mol) of diethyl sulfate,
12.8 g (0.14 mol) of 2-ethyl-2-oxazoline, and 29 g of dehydrated
ethyl acetate. Further, using 100 g of a side-chain primary
aminopropyl-modified polydimethylsiloxane (weight-average molecular
weight 100,000, amine equivalent 20,000), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (111 g, yield 98%). The content
percentage of an organopolysiloxane segment in the final product
was 88% by mass, and the weight-average molecular weight was
114,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that no amino group remained.
Comparative Example 11
[0154] By the same method as in Example 1,
poly(N-propionylethyleneimine) having a number-average molecular
weight of 1200 was obtained from 0.6 g (0.004 mol) of diethyl
sulfate, 3.6 g (0.04 mol) of 2-ethyl-2-oxazoline, and 9 g of
dehydrated ethyl acetate. Further, using 100 g of a side-chain
primary aminopropyl-modified polydimethylsiloxane (weight-average
molecular weight 100,000, amine equivalent 20,000), an
N-propionylethyleneimine-dimethylsiloxane copolymer was obtained as
a light yellow rubber-like solid (95 g, yield 95%). The content
percentage of an organopolysiloxane segment in the final product
was 96% by mass, and the weight-average molecular weight was
104,000. Neutralization titration with hydrochloric acid using
methanol as a solvent showed that approx. 30% by mole of amino
groups remained.
[0155] Physical properties of the organopolysiloxanes obtained in
Examples 1 to 15 are shown in Table 1. Physical properties of the
organopolysiloxanes obtained in Comparative Examples 1 to 11 are
shown in Table 2.
TABLE-US-00001 TABLE 1 Examples 1 2 3 4 5 6 7 8 9 a/b 65/35 68/32
70/30 71/29 79/21 68/32 82/18 75/25 70/30 MWsi 32000 32000 20000
40000 35000 32000 65000 37000 70000 MWox 1400 1100 1400 1300 900
1200 1000 1500 1400 MWg 2000 1750 2500 2500 2600 2000 3500 3500
2500 MWt 49000 47000 29000 56000 51000 46000 79000 49000 100000
Examples 10 11 12 13 14 15 a/b 71/29 79/21 65/35 79/21 71/29 71/29
MWsi 32000 36000 32000 19000 19000 80000 MWox 1300 900 1100 900
1300 1300 MWg 2500 2500 1600 2500 2500 2500 MWt 46000 46000 49000
25000 27000 113000
TABLE-US-00002 TABLE 2 Comparative Examples 1 2 3 4 5 6 7 8 9 10 11
a/b 61/39 63/37 71/29 71/29 -- 71/29 71/29 -- 51/49 88/12 96/4 MWsi
90000 32000 8000 110000 40000 26000 35000 80000 50000 100000 100000
MWox 1600 1500 1300 1300 500 5800 1900 700 5200 2700 1200 MWg 1870
2000 2500 2500 -- 11000 3600 -- 5000 20000 28600 MWt 148000 51000
11000 155000 -- 37000 49000 -- 98000 114000 104000 a/b: Mass ratio
of an organopolysiloxane segment (a) and a
poly(N-acylalkyleneimine) segment (b) MWsi: Weight-average
molecular weight of an organopolysiloxane segment as a main chain
MWox: Number-average molecular weight of a
poly(N-acylalkyleneimine) segment MWg: Weight-average molecular
weight of an organopolysiloxane segment between adjacent
poly(N-acylalkyleneimine) segments MWt: Weight-average molecular
weight of an organopolysiloxane
Evaluation Test
[0156] The organopolysiloxanes obtained in Examples 1 to 15 and
Comparative Examples 1 to 11 were evaluated for the following
properties. The results of Examples 1 to 15 are shown in Table 4.
The results of Comparative Examples 1 to 11 are shown in Table
5.
(1) Extensibility
[0157] A solution of 10% by mass organopolysiloxane in ethanol was
prepared, and ethanol was spontaneously evaporated to prepare a
polymer membrane having a length of 20 mm, a width of 5 mm, and a
thickness of 1.0 mm.
[0158] This membrane was extended 300% in the longitudinal
direction at an extension speed of 50 mm/min at a temperature of
20.degree. C. and a relative humidity of 65% using a tensile tester
(Tensilon Tensile Tester, Model RTC-1210A, Orientech Co., Ltd.).
Membranes that did not break after being left at an extension rate
of 300% for 3 minutes were rated as B, and those that broke were
rated as D.
(2) Curl Maintaining Ability
[0159] A bundle of untreated straight Japanese hair having a length
25 cm (L0) and a mass of 4 g was washed with a model shampoo having
the composition shown in Table 3 (the model shampoo mentioned below
had the same composition) and dried with a towel.
[0160] Subsequently, 0.4 g of a solution of organopolysiloxane in
ethanol having a concentration of 5% by mass was made into a mist
and applied uniformly to the above-mentioned hair bundle, and the
bundle was wound on a glass cylinder having a diameter of 2 cm. The
bundle was air-dried over 8 hours at a temperature of 20.degree. C.
and a relative humidity of 60%, removed from the cylinder, and hung
with one end thereof fixed, and the length (L1) was measured. Then,
a fine styling comb (New Delrin Comb, Uehara Cell) was carefully
passed through the hair bundle 10 times, and hung with one end
thereof fixed, and the length (L2) was measured.
[0161] The curl maintaining rate (%) was obtained by the following
formula (IV) from the measured values. Evaluation was made by
rating 82% or higher as A, lower than 82% and 77% or higher as B,
lower than 77% and 75% or higher as C, and lower than 75% as D.
[(L0-L2)/(L0-L1)].times.100 (IV)
TABLE-US-00003 TABLE 3 Composition of model shampoo Mixture amount
Model shampoo (% by mass) 25% aqueous solution of polyoxyethylene
62.00 (2.5 E.O) sodium lauryl ether sulfate Lauric diethanolamide
2.28 Disodium edetate 0.10 Sodium benzoate 0.50 Oxybenzone 0.03
Phosphoric acid (75% aqueous solution) 0.10 Dibutylated
hydroxytoluene 0.01 Sodium chloride 0.80 Red No. 106 0.00012
Perfume 0.26 Purified water Balance
(3) Softness of Hair
[0162] A bundle of permed Japanese hair having a length of 20 cm
and a weight of 4 g was washed with the model shampoo and dried
with a towel.
[0163] Subsequently, 0.4 g of a solution of organopolysiloxane in
ethanol having a concentration of 5% by mass was made into a mist,
applied uniformly to the above-mentioned hair bundle, and air-dried
over 4 hours, and sensory evaluation was made by a panel of five
experts. Evaluation was made by rating "Feels soft" as 5 points,
"Feels slightly soft" as 4 points, "Undecided" as 3 points, "Feels
not very soft" as 2 points, and "Does not feel soft" as 1 point. A
was given with the total score of the five experts being 22 points
or higher, B with lower than 22 points and 17 points or higher, C
with lower than 17 points and 11 points or higher, and D with lower
than 11 points.
(4) Wash Property
[0164] A bundle of dried permed Japanese hair having a length of 25
cm and a weight of 4 g was prepared, and 0.4 g of a solution of
organopolysiloxane in ethanol having a concentration of 5% by mass
was made into a mist, applied uniformly to the above-mentioned hair
bundle, and dried with a dryer. Then, 1 g of the model shampoo was
applied, rinsed with tap water at 40.degree. C., and dried with a
dryer.
[0165] This procedure was repeated 14 times, and the feel to the
touch was compared with that of a hair bundle untreated with a
polymer as a control hair bundle to evaluate the degree of residual
organopolysiloxanes. Sensory evaluation was made by a panel of five
experts. Evaluation was made by rating "No difference" as 5 points,
"Not much difference" as 4 points, "Undecided" as 3 points, "Slight
difference" as 2 points, "Different" as 1 point, as compared with
the control hair bundle. A was given with the total score of the
five experts being 22 points or higher, B with lower than 22 points
and 17 points or highe, C with lower than 17 points and 11 points
or higher, and D with lower than 11 points.
(5) Ethanol Solubility
[0166] Evaluation was made by rating an organopolysiloxane that
could be dissolved in ethanol at 40% by mass or more or uniformly
dispersed as B and others as D.
(6) Water Dispersibility
[0167] Evaluation was made by rating an organopolysiloxane that
could be dissolved in purified water at 30% by mass or more or
uniformly dispersed as B, and others were rated as D.
TABLE-US-00004 TABLE 4 Examples 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Extensibility B B B B B B B B B B B B B B B Curl A B B A B A B B A
A B A C B A maintaining ability Softness of C A A A A B A B B A A B
A A B hair Wash property A B B B B B C A B A B B B B B Ethanol B B
B B B B B B B B B B B B B solvability Water B B B B B B B B B B B B
B B B dispersibility
TABLE-US-00005 TABLE 5 Comparative Examples 1 2 3 4 5 6 7 8 9 10 11
Extensibility D D D B -- D D -- D D D Curl D D D C -- D C -- D C D
maintaining ability Softness of C C C C -- D D -- D C C hair Wash
property C C C D -- C C -- B B B Ethanol B B B B D B B D B B D
solvability Water B B B D D B B D B B D dispersibility --:
Immeasurable
Examples 16 to 20 and Comparative Examples 12 and 13
[0168] Hair cosmetics having compositions shown in Table 6 were
prepared and evaluated for "setting performance," "set holding
performance," and "softness of hair after setting" according to the
following methods and criteria. The evaluation results are also
shown in Table 6. In the table, the mixture amount of each
component is expressed with % by mass.
Evaluation Methods
1) Evaluation of "Setting Performance"
[0169] The head hair of five experts of a panel with permed hair of
a medium length (length of hair reaching the shoulder or so) was
washed with the model shampoo and dried with a dryer, and a
hairdresser applied a styling wax as required and set the hair.
[0170] Then, sensory evaluation of the setting performance was made
by each expert. Evaluation was made by rating "Feel good setting
performance" as 5 points, "Feel slightly good setting performance"
as 4 points, "Undecided" as 3 points, "Feel not very good setting
performance" as 2 points, and "Feel not good setting performance"
as 1 point. A was given with the total score of the five experts
being 22 points or higher, B with lower than 22 points and 17
points or higher, C with lower than 17 points and 11 points or
higher, and D with lower than 11 points.
2) Evaluation of "set Holding Performance"
[0171] The head hair of five experts of a panel with permed hair of
a medium length (length of hair reaching the shoulder or so) was
washed with a model shampoo and dried with a dryer, and a
hairdresser applied a styling wax as required and set the hair.
[0172] Then, the experts were instructed to have normal activity
for 4 hours, and sensory evaluation was made by each panelist
regarding the set holding performance. Evaluation was made by
rating "Feel good set hold" as 5 points, "Feel slightly good set
hold" as 4 points, "Undecided" as 3 points, "Feel not very good set
hold" as 2 points, and "Feel no good set hold" as 1 point. A was
given with the total score of the five experts being 22 points or
higher, B with lower than 22 points and 17 points or higher, C with
lower than 17 points and 11 points or higher, and D with lower than
11 points.
3) Evaluation of "Softness of Hair After Setting"
[0173] The head hair of five experts of a panel with permed hair of
a medium length (length of hair reaching the shoulder or so) was
washed with the model shampoo and dried with a dryer, and a
hairdresser applied a styling wax as required and set the hair.
[0174] Then, sensory evaluation was made by each panelist regarding
softness of hair after setting. Evaluation was made by rating "Hair
feels soft" as 5 points, "hair feels slightly soft" as 4 points,
"Undecided" as 3 points, "Hair feels not very soft" as 2 points,
and "Hair feels not soft" as 1 point. A was given with the total
score of the five experts being 22 points or higher, B with lower
than 22 points and 17 points or higher, C with lower than 17 points
and 11 points or higher, and D with lower than 11 points.
TABLE-US-00006 TABLE 6 Examples Comparative Examples 16 17 18 19 20
12 13 Organopolysiloxane A*.sup.1 2.5 -- 1.5 -- 2.0 -- --
Organopolysiloxane B*.sup.2 -- 2.5 -- 1.5 1.5 -- --
Organopolysiloxane C*.sup.3 -- -- -- -- -- 2.5 -- Acrylic
acid-alkyl methacrylate copolymer*.sup.4 -- -- 0.5 0.5 0.5 0.5 1.0
Dimethyl polysiloxane*.sup.5 5.0 5.0 5.0 5.0 5.0 5.0 5.0
Polyoxyethylene isocetyl ether (20 E.O.) 1.5 1.5 1.5 1.5 1.5 1.5
1.5 Polyoxyethylene lauryl ether (23 E.O.) 1.5 1.5 1.5 1.5 1.5 1.5
1.5 Isopropyl palmitate 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Vaseline 1.0
1.0 1.0 1.0 1.0 1.0 1.0 Ethanol 6.0 6.0 5.0 5.0 6.0 6.0 5.0
Disodium edetate 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Glycerine 5.0 5.0 5.0
5.0 5.0 5.0 5.0 Sodium hydroxide As required As required As
required As required As required As required As required Methyl
paraoxybenzoate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Perfume 0.1 0.1 0.1 0.1
0.1 0.1 0.1 Water Balance Balance Balance Balance Balance Balance
Balance Setting performance B A C B A C C Set holding performance
after setting A B B C A D D Softness of hair after setting B B A A
B A C *.sup.1Organopolysiloxane obtained in Example 10
*.sup.2Organopolysiloxane obtained in Example 11
*.sup.3Organopolysiloxane obtained in Comparative Example 6
*.sup.4Carbopol ETD-2020 (Noveon, Inc.) *.sup.5Silicone SH200C
FLUID 5000CS (Dow Corning Toray Co., Ltd.)
Examples 21 to 23 and Comparative Example 14
[0175] Hair cosmetics having compositions shown in Table 7
(emulsified cream type, soft) were prepared and evaluated for
"setting performance" and "set holding performance" according to
the above-mentioned methods and criteria and for "smoothness of
hair after setting" according to the following method and criteria.
The evaluation results are also shown in Table 7. In the table, the
mixture amount of each component is expressed with % by mass.
Evaluation of "Smoothness of Hair After Setting" Evaluation
Method
[0176] The head hair of five experts of a panel with permed hair of
a medium length (length of hair reaching the shoulder or so) was
washed with the model shampoo and dried with a dryer, and a
hairdresser applied a styling wax as required and set the hair.
[0177] Then, sensory evaluation was made by each panelist regarding
smoothness of the hair after setting. Evaluation was made by rating
"Hair feels smooth" as 5 points, "Hair feels slightly smooth" as 4
points, "Undecided" as 3 points, "Hair feels not very smooth" as 2
points, and "Hair feels not smooth" as 1 point. A was given with
the total score of the five experts being 22 points or higher, B
with lower than 22 points and 17 points or higher, C with lower
than 17 points and 11 points or higher, and D with lower than 11
points.
TABLE-US-00007 TABLE 7 Comparative Examples Example 21 22 23 14
Organopolysiloxane A*.sup.1 0.5 -- 0.3 -- Organopolysiloxane
B*.sup.2 -- 0.5 0.2 -- Liquid paraffin 3.0 3.0 3.0 5.0 Dimethyl
polysiloxane*.sup.5 3.0 3.0 3.0 3.0 Polyoxyethylene sorbitan 2.0
2.0 2.0 2.0 monostearate (20 EO) Lipophilic glyceryl 3.0 3.0 3.0
5.0 monostearate*.sup.6 Behenyl alcohol 8.0 8.0 8.0 8.0 Paraffin
5.0 5.0 5.0 5.0 Disodium edetate 0.1 0.1 0.1 0.1 1,3-Butylene
glycol 5.0 5.0 5.0 5.0 Phenoxyethanol 0.3 0.3 0.3 0.3 Ethanol 0.5
0.5 0.5 0.5 Perfume 0.1 0.1 0.1 0.1 Water Balance Balance Balance
Balance Setting performance B A A C Set holding performance after A
B A C setting Smoothness of hair after B B B D setting
*.sup.1Organopolysiloxane obtained in Example 10
*.sup.2Organopolysiloxane obtained in Example 11 *.sup.5Silicone
SH200C FLUID 5000CS (Dow Corning Toray Co., Ltd.) *.sup.6RHEODOL
MS-60 (Kao Corporation)
Examples 24 to 26 and Comparative Examples 15 and 16
[0178] Hair cosmetics having the compositions shown in Table 8
(emulsified cream type, hard) were prepared, and "setting
performance" and "set holding performance" were evaluated according
to the above-mentioned method and criteria. Further, "no greasiness
of hair after setting" was evaluated according to the following
method and criteria. The evaluation results combined are also shown
in Table 8. The mixture amount of each component in the table is
expressed with % by mass.
Evaluation of "No Greasiness of Hair After Setting" Evaluation
Method
[0179] The head hair of five experts of a panel with permed hair of
a medium length (length of hair reaching the shoulder or so) was
washed with the model shampoo and dried with a dryer, and a
hairdresser applied a styling wax as required and set the hair.
[0180] Then, sensory evaluation was made by each expert panelist
regarding greasiness of hair after setting. Evaluation was made by
rating "Feels not greasy" as 5 points, "Feel not very greasy" as 4
points, "Undecided" as 3 points, "Feels slightly greasy" as 2
points, and "Feels greasy" as 1 point. A was given with the total
score of the five experts being 22 points or higher, B with lower
than 22 points and 17 points or higher, C with lower than 17 points
and 11 points or higher, and D with lower than 11 points.
TABLE-US-00008 TABLE 8 Comparative Examples Examples 24 25 26 15 16
Organopolysiloxane A*.sup.1 1.5 -- 0.7 -- -- Organopolysiloxane
B*.sup.2 -- 1.5 0.7 -- -- Organopolysiloxane C*.sup.3 -- -- -- 1.5
-- Liquid paraffin 3.0 3.0 3.0 3.0 3.0 Microcrystalline wax 5.0 5.0
5.0 5.0 5.0 Polyoxyethylene sorbitan 2.0 2.0 2.0 2.0 2.0
monostearate (20 EO) Lipophilic glyceryl 5.0 5.0 5.0 5.0 5.0
monostearate*.sup.6 Cetanol 8.0 8.0 8.0 8.0 8.0 Vaseline 1.5 1.5
1.5 1.5 3.0 Beeswax 1.5 1.5 1.5 1.5 3.0 Disodium edetate 0.1 0.1
0.1 0.1 0.1 1,3-Butylene glycol 5.0 5.0 5.0 5.0 5.0 Phenoxyethanol
0.3 0.3 0.3 0.3 0.3 Ethanol 1.8 1.8 1.8 1.8 1.8 Perfume 0.1 0.1 0.1
0.1 0.1 Water Balance Balance Balance Balance Balance Setting
performance A A A D C Holding performance A B A C C after setting
No greasiness of hair B A A C D after setting
*.sup.1Organopolysiloxane obtained in Example 10
*.sup.2Organopolysiloxane obtained in Example 11
*.sup.3Organopolysiloxane obtained in Comparative Example 6
*.sup.6RHEODOL MS-60 (Kao Corporation)
Examples 31 to 56 and Reference Examples 31 to 54
[0181] Hair cosmetics having the compositions shown in Tables 9 to
12 were prepared by a usual method. The hair cosmetics having the
compositions shown in Tables 9 and 11 were aerosol-type foamy hair
cosmetics. The hair cosmetics having the compositions shown in
Tables 10 and 12 were non-aerosol-type mists. pH is the value when
the composition was diluted 20-fold by mass with water at
25.degree. C. The mixture ratio of each component in Tables 9 to 12
is expressed with % by mass.
TABLE-US-00009 TABLE 9 Examples 31 32 33 34 35 36 37 38 Aqueous
malic acid (50% by mass 3.5 3.5 aqueous solution) Lactic acid (90%
by mass aqueous 2.0 2.0 solution) Glycolic acid (70% by mass
aqueous 2.5 2.5 solution) Citric acid (50% by mass aqueous 3.5 3.5
solution) Benzyl alcohol 1.0 1.0 1.0 1.0 0.2 0.2 0.2 0.2
Dipropylene glycol 0.8 0.8 0.8 0.8 1,3-Butylene glycol
Phenoxyethanol Benzyloxyethanol Organopolysiloxane A*.sup.1 2.5 2.5
2.5 2.5 1.0 1.0 Organopolysiloxane B*.sup.2 0.2 1.5 0.2 1.5
Organopolysiloxane D*.sup.7 Organopolysiloxane E*.sup.8
Vinylpyrrolidone-N,N- 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
dimethylaminoethyl methacrylic acid copolymer diethyl sulfate
Stearyl trimethyl ammonium chloride 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
(30% by mass aqueous solution) Polyoxyethylene tridecyl
ether*.sup.9 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Polyoxyethylene-polyoxypropylene 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
stearyl ether*.sup.10 Polyoxyethylene cetyl ether*.sup.11 0.5 0.5
0.5 0.5 0.5 0.5 0.5 0.5 Polyoxyethylene-methyl polysiloxane
copolymer*.sup.12 95% synthetic ethylalcohol 12.0 12.0 12.0 12.0
12.0 12.0 12.0 12.0 Neopentyl glycol dicaprate Isopropyl palmitate
Purified water Balance Balance Balance Balance Balance Balance
Balance Balance Sodium hydroxide As As As As As As As As required
required required required required required required required
Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Propellant (LPG, 4.4 Pa)
7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 pH 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7
Examples 39 40 41 42 43 44 45 46 Aqueous malic acid (50% by mass
1.0 0.5 0.5 0.3 0.2 0.2 aqueous solution) Lactic acid (90% by mass
aqueous 1.5 1.5 1.5 1.0 2.5 2.1 1.5 1.5 solution) Glycolic acid
(70% by mass aqueous 1.5 0.2 solution) Citric acid (50% by mass
aqueous 1.0 2.0 0.2 solution) Benzyl alcohol 0.2 0.2 0.1 0.2
Dipropylene glycol 1.5 1.5 0.3 0.5 0.3 1,3-Butylene glycol 0.2 0.2
0.7 0.5 0.5 0.5 Phenoxyethanol 0.1 0.1 Benzyloxyethanol 1.0 1.0 0.2
Organopolysiloxane A*.sup.1 1.5 1.5 1.5 1.5 1.5 1.2 2.5 3.0
Organopolysiloxane B*.sup.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Organopolysiloxane D*.sup.7 0.5 0.5 0.5 0.5 0.5 0.2 0.1 0.1
Organopolysiloxane E*.sup.8 0.2 Vinylpyrrolidone-N,N- 0.5 0.5 0.5
0.5 0.4 1.0 1.2 1.2 dimethylaminoethyl methacrylic acid copolymer
diethyl sulfate Stearyl trimethyl ammonium chloride 1.5 1.5 1.5 1.5
1.5 1.5 1.5 1.5 (30% by mass aqueous solution) Polyoxyethylene
tridecyl ether*.sup.9 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Polyoxyethylene-polyoxypropylene 2.0 2.0 2.0 2.0 2.0 2.0 stearyl
ether*.sup.10 Polyoxyethylene cetyl ether*.sup.11 0.5 0.5 0.5 0.5
0.5 0.5 0.5 0.5 Polyoxyethylene-methyl polysiloxane 0.3 0.5
copolymer*.sup.12 95% synthetic ethylalcohol 12.0 12.0 12.0 12.0
12.0 12.0 12.0 12.0 Neopentyl glycol dicaprate 2.0 1.0 Isopropyl
palmitate 0.5 0.5 Purified water Balance Balance Balance Balance
Balance Balance Balance Balance Sodium hydroxide As As As As As As
As As required required required required required required
required required Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Propellant (LPG, 4.4 Pa) 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 pH 3.7 3.7
3.7 3.7 3.7 3.7 3.7 3.7
TABLE-US-00010 TABLE 10 Examples 47 48 49 50 51 52 53 54 55 56
Aqueous malic acid (50% by mass 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 1.8
1.8 aqueous solution) Lactic acid (90% by mass aqueous 1.4 1.4 1.4
1.4 1.4 1.4 1.4 1.4 1.0 1.0 solution) Glycolic acid (70% by mass
aqueous solution) Citric acid (50% by mass aqueous solution) Benzyl
alcohol 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Dipropylene glycol
1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1,3-Butylene glycol
Phenoxyethanol Benzyloxyethanol Organopolysiloxane A*.sup.1 0.4 1.9
0.5 2.0 0.5 2.0 1.0 4.0 0.5 2.0 Organopolysiloxane B*.sup.2 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 Organopolysiloxane D*.sup.7 1.5 1.3 0.5 0.5
3.0 3.0 1.5 1.5 1.5 1.5 Organopolysiloxane E*.sup.8
Vinylpyrrolidone-N,N- 0.2 1.0 0.2 1.0 0.2 1.0 0.2 1.0 0.2 1.0
dimethylaminoethyl methacrylic acid copolymer diethyl sulfate
Stearyl trimethyl ammonium chloride 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
0.8 0.8 (30% by mass aqueous solution) Polyoxyethylene tridecyl
ether*.sup.9 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4
Polyoxyethylene-polyoxypropylene stearyl ether*.sup.10
Polyoxyethylene cetyl ether*.sup.11 Polyoxyethylene-methyl
polysiloxane 0.6 0.6 0.6 0.6 0.6 copolymer*.sup.12
Aminoethylaminopropylsiloxane- 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
0.4 dimethylsiloxane copolymer emulsion*.sup.13 95% synthetic
ethylalcohol 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0
Neopentyl glycol dicaprate Isopropyl palmitate Polyethylene glycol
0.2 0.2 0.2 0.2 0.2 Glycerine 1.0 1.0 1.0 1.0 1.0 Purified water
Balance Balance Balance Balance Balance Balance Balance Balance
Balance Balance Sodium hydroxide As As As As As As As As As As
required required required required required required required
required required required Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
0.1 0.1 Propellant (LPG, 4.4 MPa) pH 3.7 3.7 3.7 3.7 3.7 3.7 3.7
3.7 3.7 3.7
TABLE-US-00011 TABLE 11 Reference Examples 31 32 33 34 35 36 37 38
39 40 41 42 Aqueous malic acid (50% by mass 3.5 1.0 3.5 3.5 aqueous
solution) Lactic acid (90% by mass aqueous 2.0 1.5 2.0 solution)
Glycolic acid (70% by mass 2.5 aqueous solution) Citric acid (50%
by mass aqueous solution) Benzyl alcohol 1.0 0.2 0.2 0.2 0.2 0.2
Dipropylene glycol 0.8 0.8 0.8 0.8 0.8 1,3-Butylene glycol 0.2
Phenoxyethanol 0.1 Benzyloxyethanol 1.0 Organopolysiloxane A*.sup.1
2.5 2.5 2.5 2.5 2.5 2.5 2.5 Organopolysiloxane B*.sup.2 0.1 0.1 0.1
0.1 0.1 0.1 0.1 Organopolysiloxane D*.sup.7 2.5 2.5 2.0 0.1
Organopolysiloxane E*.sup.8 1.0 0.1 Vinylpyrrolidone-N,N- 0.5 0.5
0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.5 dimethylaminoethyl
methacrylic acid copolymer diethyl sulfate Stearyl trimethyl
ammonium 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2.5 chloride
(30% by mass aqueous solution) Polyoxyethylene tridecyl
ether*.sup.9 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.5
Polyoxyethylene-polyoxypropylene 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
2.0 2.0 2.0 3.0 stearyl ether*.sup.10 Polyoxyethylene cetyl
ether*.sup.11 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.5
Polyoxyethylene- methylpolysiloxane copolymer*.sup.12 95% synthetic
ethylalcohol 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0
13.0 Neopentyl glycol dicaprate Isopropyl palmitate Purified water
Balance Balance Balance Balance Balance Balance Balance Balance
Balance Balance Balance Balance Sodium hydroxide As As As As As As
As As As As As As required required required required required
required required required required required required required
Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 1.1 Propellant
(LPG, 4.4 MPa) 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 8.0 pH
3.7 3.7 3.7 6.0 6.0 6.0 3.7 3.7 3.7 3.7 6.0 6.0
TABLE-US-00012 TABLE 12 Reference Examples 43 44 45 46 47 48 49 50
51 52 53 54 Aqueous malic acid (50% by mass 2.5 2.5 2.5 2.5 2.5 2.5
aqueous solution) Lactic acid (90% by mass aqueous 1.4 1.4 1.4 1.4
1.4 1.4 solution) Glycolic acid (70% by mass aqueous solution)
Citric acid (50% by mass aqueous solution) Benzyl alcohol 0.2 0.2
0.2 0.2 0.2 0.2 Dipropylene glycol 1.0 1.0 1.0 1.0 1.0 1.0
1,3-Butylene glycol Phenoxyethanol Benzyloxyethanol
Organopolysiloxane A*.sup.1 0.4 1.9 0.4 1.9 0.4 1.9
Organopolysiloxane B*.sup.2 Organopolysiloxane D*.sup.7 1.5 1.3 1.5
1.3 1.5 1.3 Organopolysiloxane E*.sup.8 Vinylpyrrolidone-N,N- 0.2
1.0 0.2 1.0 0.2 1.0 0.2 1.0 0.2 1.0 0.2 1.0 dimethylaminoethyl
methacrylic acid copolymer diethyl sulfate Stearyl trimethyl
ammonium 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 chloride
(30% by mass aqueous solution) Polyoxyethylene tridecyl
ether*.sup.9 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4
Polyoxyethylene-polyoxypropylene stearyl ether*.sup.10
Polyoxyethylene cetyl ether*.sup.11 Polyoxyethylene-methyl 0.6 0.6
0.6 0.6 0.6 0.6 polysiloxane copolymer*.sup.12
Aminoethylaminopropylsiloxane- 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
0.4 0.4 0.4 dimethylsiloxane copolymer emulsion*.sup.13 95%
synthetic ethylalcohol 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0
15.0 15.0 15.0 Neopentyl glycol dicaprate Isopropyl palmitate
Polyethylene glycol 0.2 0.2 0.2 0.2 0.2 0.2 Glycerine 1.0 1.0 1.0
1.0 1.0 1.0 Purified water Balance Balance Balance Balance Balance
Balance Balance Balance Balance Balance Balance Balance Sodium
hydroxide As As As As As As As As As As As As required required
required required required required required required required
required required required Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 Propellant (LPG, 4.4 MPa) pH 3.7 3.7 3.7 3.7 3.7
3.7 3.7 3.7 3.7 3.7 3.7 3.7 *.sup.1Organopolysiloxane obtained in
Example 10 *.sup.2Organopolysiloxane obtained in Example 11
*.sup.7Organopolysiloxane obtained in Comparative Example 10
*.sup.8Organopolysiloxane obtained in Comparative Example 9
*.sup.9SOFTANOL 90 (Nippon Shokubai Co., Ltd.) *.sup.10UNILUBE
YM-250 (NOF Corporation) *.sup.11Nikkol BC-20TX (Nihon Surfactant
Kogyo K.K.) *.sup.12KF6029 (Shin-Etsu Chemical Co., Ltd.)
*.sup.13SM8704C (Dow Corning Toray Co., Ltd.)
[0182] The foam-type hair cosmetics obtained in these examples and
reference examples were evaluated for "setting performance," "set
holding performance," "softness of hair," "manageability," "no
greasiness," "effects of improving firmness and body after
shampooing," and "manageability after shampooing" according to the
following method and criteria.
Evaluation Method
[0183] A panel of five female experts with hair longer than the
shoulder (medium length, long) who had permanent wave within three
months received a foam-type hair cosmetic obtained in each example
or reference example on the head hair as required (3 to 5 g) and
made evaluation as follows.
(1) Setting Performance
[0184] After styling, setting performance was evaluated with the
completely dried hair.
(2) Set Holding Performance
[0185] After styling, the hair was dried completely and left for 4
hours, and then setting performance was evaluated.
(3) Softness of Hair
[0186] After styling, softness of hair was evaluated with the
completely dried hair.
(4) Manageability
[0187] After styling, hair manageability was evaluated with the
completely dried hair.
(5) No Greasiness
[0188] After styling, hair greasiness was evaluated with the
completely dried hair.
(6) Effects Improving Firmness and Body after Shampooing
[0189] After evaluations of (1) to (5), the hair was washed with
the model shampoo shown in Table 3, effects of improving firmness
and body were evaluated with the air-dried hair.
(7) Manageability After Shampooing
[0190] After evaluations of (1) to (5), the hair was washed with
the model shampooing shown in Table 3, manageability was evaluated
with the air-dried hair.
Evaluation Criteria
[0191] Sensory evaluation was made by a panel of five experts
according to the criteria shown in Table 13, evaluation points of
each expert were added up, and evaluation was made according to the
criteria shown below. The results of Examples 31 to 46 are shown in
Table 14. The results of Examples 47 to 56 are shown in Table 15.
The results of Reference Examples 31 to 42 are shown in Table 16.
The results of Reference Examples 43 to 54 are shown in Table
17.
TABLE-US-00013 TABLE 13 (Setting performance) 5: Setting
performance observed 4: Slight setting performance observed 3:
Undecided 2: Minimal setting performance observed 1: No setting
performance observed (Set holding performance) 5: Holding
performance observed 4: Slight Holding performance observed 3:
Undecided 2: Minimal holding performance observed 1: No holding
performance observed (Softness of hair) 5: Soft 4: Slightly soft 3:
Undecided 2: Not very soft 1: Not soft (No greasiness) 5: Not
greasy 4: Not very greasy 3: Undecided 2: Slightly greasy 1: Greasy
(Manageability) 5: Manageable 4: Slightly manageable 3: Undecided
2: Slightly poor manageability 1: Poor manageability (Effects
improving firmness and body after shampooing) 5: Feel firmness and
body effects 4: Feel slight firmness and body effects 3: Undecided
2: Feel not much firmness and body effects 1: Feel no firmness and
body effects (Manageability after shampooing) 5: Feel manageability
4: Feel slight manageability 3: Undecided 2: Feel minimal
manageability 1: Feel no manageability
Evaluation Criteria
[0192] A: The total score is 22 points or higher.
[0193] B: The total score is lower than 22 points and 17 points or
higher.
[0194] C: The total score is lower than 17 points and 11 points or
higher.
[0195] D: The total score is lower than 11 points.
TABLE-US-00014 TABLE 14 Examples 31 32 33 34 35 36 37 38 39 40 41
42 43 44 45 46 Setting performance A A A A B B B B A A A B A A A A
Set holding A A B B A B A B A A A A A B A A performance Softness of
hair B B B B A A A A B B B B A A B B Manageability B B B B B A B A
B B B A A B B A No greasiness A A A A A C B C B B B B B A A C
Effects of improving A A B B B B B B B C A A A B B B firmness and
body after shampooing Manageability after B B B B B B A B C B C B A
B B A shampooing
TABLE-US-00015 TABLE 15 Examples 47 48 49 50 51 52 53 54 55 56
Setting performance B A B A B B B A B A Set holding performance A A
A A B B B A A A Softness of hair A B B B A A A B A B Manageability
B A B B A A A A B A No greasiness A B B C B B C C A B Effects of
improving A A A A B B A A B B firmness and body after shampooing
Manageability after A A A A B B A A B B shampooing
TABLE-US-00016 TABLE 16 Reference Examples 31 32 33 34 35 36 37 38
39 40 41 42 Setting performance B B B B B B C C C D D A Set holding
performance B B B B B B D D D D D B Softness of hair C C C C C C B
B A D D B Manageability B B B B B B C C C D D B No greasiness B B B
B B B B B B C C B Effects of improving firmness D D D D D D B B B D
D D and body after shampooing Manageability after shampooing D D D
C C C B B B D C D
TABLE-US-00017 TABLE 17 Reference Examples 43 44 45 46 47 48 49 50
51 52 53 54 Setting performance D D C B D D C C D D D B Set holding
performance D D C C D D D C D D D C Softness of hair D C B C D D B
C D D C C Manageability D D B B D D C B D D C C No greasiness D C B
C C C C D C C C C Effects of improving firmness B B D D D D C C D D
D D and body after shampooing Manageability after shampooing B B D
D D D C C D D D D
[0196] Preparation examples of hair cosmetics containing the
organopolysiloxane of the present invention will be shown
below.
Preparation Example 1 (Pump spray)
TABLE-US-00018 (% by mass) Organopolysiloxane A (Example 10) 0.5
Stearyltrimethyl ammonium chloride 0.25 Glycerine 1.0 Ethanol 4.5
Perfume 0.02 Water Balance
Preparation Example 2 (Pump mist)
TABLE-US-00019 (% by mass) Organopolysiloxane A (Example 10) 0.2
Organopolysiloxane B (Example 11) 0.2 Polyvinylpyrrolidone 3.0
Ethanol 10.0 Perfume 0.05 Water Balance
Preparation Example 3 (Hair gel)
TABLE-US-00020 (% by mass) Organopolysiloxane A (Example 10) 1.2
Organopolysiloxane F (Example 6) 1.5 Glycerine 2.0
Hydroxyethylcellulose 2.0 Ethanol 10.0 Perfume 0.05 Water
Balance
Preparation Example 4(hair lotion)
TABLE-US-00021 (% by mass) Organopolysiloxane A (Example 10) 0.2
Organopolysiloxane G (Example 4) 0.2 Glycerine 1.0 Ethanol 10.0
Perfume 0.02 Water Balance
Preparation Example 5 (Hair lotion)
TABLE-US-00022 (% by mass) Organopolysiloxane B (Example 11) 0.2
Stearyltrimethyl ammonium chloride 0.1 Polyethylene glycol 400 0.45
Ethanol 4.5 Water Balance
Preparation Example 6 (Pump foam)
TABLE-US-00023 (% by mass) Organopolysiloxane A (Example 10) 1.0
Polyoxyethylene lauryl ether (16 E.O.) 1.0 Stearyltrimethyl
ammonium chloride 0.1 Glycerine 1.0 Ethanol 4.0 Perfume 0.02 Water
Balance
Preparation Example 7 (Styling pump mist)
TABLE-US-00024 (% by mass) Malic acid 2.0 Benzyl alcohol 0.5
Organopolysiloxane A (Example 10) 1.1 Stearyltrimethyl ammonium
chloride 0.3 Glycerine 2.0 Ethanol 9.5 Perfume 0.01 Water Balance
Sodium hydroxide (pH modifier) Adjusted to pH 3.7
Preparation Example 8 (Styling pump mist)
TABLE-US-00025 (% by mass) Malic acid 1.5 Lactic acid 2.0
2-Benzyloxyethanol 1.0 Dipropylene glycol 0.5
Polyoctanium-11*.sup.14 0.7 Organopolysiloxane A (Example 10) 2.8
Organopolysiloxane B (Example 11) 0.2 Ethanol 12.0 Perfume 0.01
Water Balance Sodium hydroxide (pH modifier) Adjusted to pH 3.7
*.sup.14GAFQUATS 755N, ISP Japan Ltd.
Preparation Example 9 (Styling gel)
TABLE-US-00026 (% by mass) Malic acid 1.5 Citric acid 1.5 Glycerine
2.0 Benzyl alcohol 0.3 1,3-Butylene glycol 1.0 Organopolysiloxane A
(Example 10) 1.5 Organopolysiloxane B (Example 11) 0.5
Hydroxyethylcellulose*.sup.15 2.0 Ethanol 25.0 perfume 0.02 Water
Balance Sodium hydroxide (pH modifier) Adjusted to pH 3.7
*.sup.15HEC Daicel SE850K, Daicel Chemical Industries, Ltd.
Preparation Example 10 (Styling lotion)
TABLE-US-00027 (% by mass) Malic acid 1.2 Lactic acid 1.0 Benzyl
alcohol 0.3 Dipropylene glycol 0.5 Organopolysiloxane A (Example
10) 1.6 Organopolysiloxane D (Comparative 0.5 Example 10) Glycerine
1.0 Ethanol 12.0 Perfume 0.02 Water Balance Sodium hydroxide (pH
modifier) Adjusted to pH 3.7
Preparation Example 11 (styling lotion)
TABLE-US-00028 (% by mass) Malic acid 1.5 Glycolic acid 1.0 Benzyl
alcohol 0.5 Phenoxyethanol 0.3 Organopolysiloxane B (Example 11)
0.8 Organopolysiloxane C (Example 6) 0.5 Polyethylene glycol (MW =
400)*.sup.16 0.45 Stearyltrimethyl ammonium chloride 0.1 Ethanol
7.5 Water Balance Sodium hydroxide (pH modifier) Adjusted to pH 3.7
*.sup.16ADEKA PEG400, ADEKA Corporation
Preparation Example 12 (styling pump foam)
TABLE-US-00029 (% by mass) Malic acid 1.0 Lactic acid 1.5 Glycerine
1.0 Benzyl alcohol 0.2 Dipropylene glycol 0.7 1,3-Butylene glycol
0.3 Organopolysiloxane A (Example 10) 1.2 Organopolysiloxane B
(Example 11) 0.7 Organopolysiloxane D 0.5 (Comparative Example 10)
Polyoctanium-11*.sup.14 0.5 Polyoxyethylene tridecyl ether 1.0
Stearyltrimethyl ammonium chloride 0.2 Ethanol 5.5 Perfume 0.01
Water Balance Sodium hydroxide (pH modifier) Adjusted to pH 3.7
*.sup.14GAFQUATS 755N, ISP Japan Ltd.
Preparation Example 13 (Hair cream, pH 3.7)
TABLE-US-00030 (% by mass) Organopolysiloxane A (Example 10) 0.7
Organopolysiloxane B (Example 11) 0.3 Organopolysiloxane D 0.3
(Comparative Example 10) Behenyltrimethyl ammonium chloride 0.24
Malic acid 0.5 Benzyl alcohol 0.2 Dipropylene glycol 2.0
N,N-Dimethyloctadecyloxypropylamine 0.2 Cetanol 1.6 Isopropyl
palmitate 0.5 Dimethicone (Dow Corning Toray Co., 0.5 Ltd.,
BY22-060) Perfume 0.1 pH modifier (sodium hydroxide, As required
lactic acid) Water Balance
* * * * *