U.S. patent application number 10/588514 was filed with the patent office on 2007-07-19 for water-soluble resin, hair cosmetic material containing the same, and silicone oil adsorption assistant.
This patent application is currently assigned to MITSUBISHI CHEMICAL CORPORATION. Invention is credited to Tomoaki Hiwatashi, Shoya Yoda, Yuko Yoda.
Application Number | 20070167593 10/588514 |
Document ID | / |
Family ID | 34840170 |
Filed Date | 2007-07-19 |
United States Patent
Application |
20070167593 |
Kind Code |
A1 |
Yoda; Shoya ; et
al. |
July 19, 2007 |
Water-soluble resin, hair cosmetic material containing the same,
and silicone oil adsorption assistant
Abstract
Provided is a water-soluble resin which gives a conditioning
effect when it is used in a hair cosmetic material containing an
anionic surfactant, or the like. A water-soluble resin having a
structure corresponding to a copolymer of a monomer mixture
containing a vinylic monomer (A) having a hydroxyl group and an
amido bond, and a vinylic monomer (B) having a cationic group.
Inventors: |
Yoda; Shoya; (Mie, JP)
; Hiwatashi; Tomoaki; (Mie, JP) ; Yoda; Yuko;
(Mie, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
MITSUBISHI CHEMICAL
CORPORATION
33-8, Shiba 5-chome
Minato-ku, Tokyo
JP
108-0014
|
Family ID: |
34840170 |
Appl. No.: |
10/588514 |
Filed: |
February 9, 2005 |
PCT Filed: |
February 9, 2005 |
PCT NO: |
PCT/JP05/02367 |
371 Date: |
November 17, 2006 |
Current U.S.
Class: |
526/303.1 ;
526/311; 526/312 |
Current CPC
Class: |
A61Q 5/12 20130101; C08F
220/58 20130101; A61Q 5/02 20130101; A61K 8/8158 20130101; C08F
220/28 20130101 |
Class at
Publication: |
526/303.1 ;
526/311; 526/312 |
International
Class: |
C08F 120/00 20060101
C08F120/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 9, 2004 |
JP |
2004-032203 |
Jan 25, 2005 |
JP |
2005-016988 |
Claims
1. A water-soluble resin having a structure corresponding to a
copolymer of a monomer mixture containing a vinylic monomer (A)
having a hydroxyl group and an amido bond, and a vinylic monomer
(B) having a cationic group.
2. The water-soluble resin of claim 1, wherein the vinylic monomer
(A) having a hydroxyl group and an amido bond is represented by the
formula (1):
CH.sub.2.dbd.C(R.sup.1)--CO--NR.sup.2--(CH.sub.2).sub.a--OH (1)
wherein R.sup.1 represents a hydrogen atom, or a methyl group;
R.sup.2 represents a hydrogen atom, or an alkyl group or a
hydroxyalkyl group having 1 to 4 carbon atoms; a is an integer from
1 to 4.
3. The water-soluble resin of claim 2, wherein a in the formula (1)
is 2.
4. The water-soluble resin of claim 1, wherein the vinylic monomer
(A) having a hydroxyl group and an amido bond is hydroxyethyl
acrylamide, or hydroxyethyl methacrylamide.
5. The water-soluble resin of any one of claim 1, wherein the
vinylic monomer (B) having a cationic group is represented by the
formula (2)
CH.sub.2.dbd.C(R.sup.3)--CO(O).sub.b--(NH).sub.1-b--(CH.sub.2).sub.c--N.s-
up.+R.sup.4R.sup.5R.sup.6.X.sup.- (2) wherein R.sup.3 represents a
hydrogen atom, or a methyl group; R.sup.4 and R.sup.5 each
independently represent an alkyl group or an aryl group or an
aralkyl group having 1 to 24 carbon atoms; R.sup.6 represents a
hydrogen atom, an alkyl group or an aryl group or an aralkyl group
having 1 to 24 carbon atoms, or
CH.sub.2--CH(OH)--CH.sub.2--N.sup.+R.sup.7R.sup.8R.sup.9.Y.sup.-;
R.sup.7 to R.sup.9 each independently represent an alkyl group or
an aryl group or an aralkyl group having 1 to 24 carbon atoms;
X.sup.- and Y.sup.- each independently represent an anion; b
represents 0, or 1; and c represents an integer from 1 to 10.
6. The water-soluble resin of claim 1, wherein the vinylic monomer
(B) having a cationic group is at least one selected from the group
consisting of meth acroyloxyethyl-trimethylammonium chloride,
acroylaminopropyl-trimethylammonium chloride, and meth
acroylaminopropyl-trimethylammonium chloride.
7. The water-soluble resin of claim 1, wherein the monomer mixture
containing a vinylic monomer (A) having a hydroxyl group and an
amido bond, and a vinylic monomer (B) having a cationic group
contains 20 to 90% by weight of the vinylic monomer (A) having a
hydroxyl group and an amido bond, and 10 to 80% by weight of the
vinylic monomer (B) having a cationic group.
8. The water-soluble resin of claim 1, wherein weight average
molecular weight is 5,000 to 5,000,000.
9. The water-soluble resin of claim 1, wherein the water
soluble-resin can form an aqueous solution having a concentration
of at least 5% by weight.
10. The water-soluble resin of claim 1, wherein the vinylic monomer
(A) having a hydroxyl group and an amido bond is hydroxyethyl
acrylamide, and the vinylic monomer (B) having a cationic group is
at least one selected from the group consisting of
(meth)acroyloxyethyltrimethylammonium chloride,
acroylaminopropyltrimethylammonium chloride, and
(meth)acroylaminopropyltrimethylammonium chloride.
11. A hair cosmetic material containing the water-soluble resin of
any one of claim 1.
12. The hair cosmetic material of claim 11, further containing an
anionic surfactant.
13. The hair cosmetic material of claim 12, which is an aqueous
solution containing 0.05 to 5% by weight of the water-soluble resin
and 5 to 40% by weight of the anionic surfactant.
14. A silicone oil adsorption assistant comprising the
water-soluble resin of claim 1.
15. The hair cosmetic material of claim 11, wherein the vinylic
monomer (A) having a hydroxyl group and an amido bond is
represented by the formula (1):
CH.sub.2.dbd.C(R.sup.1)--CO--NR.sup.2--(CH.sub.2).sub.a--OH (1)
wherein R.sup.1 represents a hydrogen atom, or a methyl group;
R.sup.2 represents a hydrogen atom, or an alkyl group or a
hydroxyalkyl group having 1 to 4 carbon atoms; a is an integer from
1 to 4.
16. The hair cosmetic material of claim 11, wherein the vinylic
monomer (B) having a cationic group is represented by the formula
(2):
CH.sub.2.dbd.C(R.sup.3)--CO(O).sub.b--(NH).sub.1-b--(CH.sub.2).sub.c--N.s-
up.+R.sup.4R.sup.5R.sup.6.X.sup.- (2) wherein R.sup.3 represents a
hydrogen atom, or a methyl group; R.sup.4 and R.sup.5 each
independently represent an alkyl group or an aryl group or an
aralkyl group having 1 to 24 carbon atoms; R.sup.6 represents a
hydrogen atom, an alkyl group or an aryl group or an aralkyl group
having 1 to 24 carbon atoms, or
CH.sub.2--CH(OH)--CH.sub.2--N.sup.+R.sup.7R.sup.8R.sup.9.Y.sup.-;
R.sup.7 to R.sup.9 each independently represent an alkyl group or
an aryl group or an aralkyl group having 1 to 24 carbon atoms;
X.sup.- and Y.sup.- each independently represent an anion; b
represents 0, or 1; and c represents an integer from 1 to 10.
17. The silicone oil adsorption assistant of claim 14, wherein the
vinylic monomer (A) having a hydroxyl group and an amido bond is
represented by the formula (1):
CH.sub.2.dbd.C(R.sup.1)--CO--NR.sup.2--(CH.sub.2).sub.a--OH (1)
wherein R.sup.1 represents a hydrogen atom, or a methyl group;
R.sup.2 represents a hydrogen atom, or an alkyl group or a
hydroxyalkyl group having 1 to 4 carbon atoms; a is an integer from
1 to 4.
18. The silicone oil adsorption assistant of claim 14, wherein the
vinylic monomer (B) having a cationic group is represented by the
formula (2):
CH.sub.2.dbd.C(R.sup.3)--CO(O).sub.b--(NH).sub.1-b--(CH.sub.2).sub.-
c--N.sup.+R.sup.4R.sup.5R.sup.6.X.sup.- (2) wherein R.sup.3
represents a hydrogen atom, or a methyl group; R.sup.4 and R.sup.5
each independently represent an alkyl group or an aryl group or an
aralkyl group having 1 to 24 carbon atoms; R.sup.6 represents a
hydrogen atom, an alkyl group or an aryl group or an aralkyl group
having 1 to 24 carbon atoms, or
CH.sub.2--CH(OH)--CH.sub.2--N.sup.+R.sup.7R.sup.8R.sup.9.Y.sup.-;
R.sup.7 to R.sup.9 each independently represent an alkyl group or
an aryl group or an aralkyl group having 1 to 24 carbon atoms;
X.sup.- and Y.sup.- each independently represent an anion; b
represents 0, or 1; and c represents an integer from 1 to 10.
19. The water-soluble resin of claim 2, wherein the vinylic monomer
(B) having a cationic group is represented by the formula (2):
CH.sub.2.dbd.C(R.sup.3)--CO(O).sub.b--(NH).sub.1-b--(CH.sub.2).sub.c--N.s-
up.+R.sup.4R.sup.5R.sup.6.X.sup.- (2) wherein R.sup.3 represents a
hydrogen atom, or a methyl group; R.sup.4 and R.sup.5 each
independently represent an alkyl group or an aryl group or an
aralkyl group having 1 to 24 carbon atoms; R.sup.6 represents a
hydrogen atom, an alkyl group or an aryl group or an aralkyl group
having 1 to 24 carbon atoms, or
CH.sub.2--CH(OH)--CH.sub.2--N.sup.+R.sup.7R.sup.8R.sup.9.Y.sup.31 ;
R.sup.7 to R.sup.9 each independently represent an alkyl group or
an aryl group or an aralkyl group having 1 to 24 carbon atoms;
X.sup.- and Y.sup.- each independently represent an anion; b
represents 0, or 1; and c represents an integer from 1 to 10.
Description
TECHNICAL FIELD
[0001] The present invention relates to a water-soluble resin, and
in particular, it relates to a water-soluble resin, when used as a
hair cosmetic material containing an anionic surfactant, which
gives conditioning effects such as good touch in finger-combing in
rinsing, a smooth feel after dried and a silky feel after dried, to
hairs treated with the hair cosmetic material.
BACKGROUND ART
[0002] A conditioner is blended with a hair cosmetic material such
as shampoo, hair rinse, hair treatment, and hair styling products
in order to improve a touch in finger-combing in rinsing, a touch
in combing after washed, a soft feel after washed, and other feels.
For example, it is known to blend a cationated hydroxycellulose, a
cationated guar gum, a dimethyldiallylammonium chloride/acrylamide
copolymer, or the like as a conditioner with a shampoo.
[0003] A shampoo having a cationated hydroxylcellulose or the like
blended therewith has a good touch in finger-combing in rinsing,
but hairs after dried may have a rough feel and a stiff feel.
Therefore, to improve this, addition of an oil, co-use of a
surfactant, and the like are investigated. Above all, it is known
that feels after dried greatly varies by adding a silicone oil (for
example, JP-A-2003-212733).
[0004] Further, because it is essential that a conditioner is
adsorbed on hairs, an amino acid-modified cationated polymer is
proposed as a conditioner having improved a sticky feel and a slimy
feel, while having proper absorbability, and sustaining the
conditioning effect without washing out in rinsing (for example,
JP-A-2003-34704).
DISCLOSURE OF THE INVENTION
[0005] However, according to the investigations by the present
inventors, further high conditioning effect may be required.
Further, if a silicone oil is added to the hair cosmetic material,
a large amount of a cationated hydroxyethyl cellulose or the like
is required in order to adhere a sufficient amount of the silicone
oil on hairs. As a result, the hair cosmetic material also gives a
rough feel. Further, in the case of hairs damaged by bleaching,
coloring or the like (hereinafter sometimes referred to as "damaged
hairs"), an adsorption amount of the silicone oil may be small, and
thus a sufficient conditioning effect was not obtained.
[0006] The present invention is to solve the above problems, and it
is, for example, an object to provide a water-soluble resin which
gives a conditioning effect when it is used in a hair cosmetic
material containing an anionic surfactant, or the like.
[0007] As a result of keen investigations in view of the above
problems, the present inventors have found that hair cosmetic
material containing a water-soluble resin having a structure
corresponding to a copolymer of a vinylic monomer having a hydroxyl
group and an amido bond, and a vinylic monomer having a cationic
group show good conditioning effects, and further increases an
adsorption amount of a silicone oil when the silicone oil is used
together, and have completed the invention.
[0008] That is, a gist of the invention resides in a water-soluble
resin having a structure corresponding to a polymerized product of
a monomer mixture containing a vinylic monomer (A) having a
hydroxyl group and an amido bond, and a vinylic monomer (B) having
a cationic group.
[0009] Another gist of the invention is a hair cosmetic material
containing the water-soluble resin, an anionic surfactant and
water.
[0010] Specifically, the invention has been achieved by the
following means.
[0011] (1) A water-soluble resin having a structure corresponding
to a copolymer of a monomer mixture containing a vinylic monomer
(A) having a hydroxyl group and an amido bond, and a vinylic
monomer (B) having a cationic group.
[0012] (2) The water-soluble resin of (1), wherein the vinylic
monomer (A) having a hydroxyl group and an amido bond is
represented by the formula (1):
CH.sub.2.dbd.C(R.sup.1)--CO--NR.sup.2--(CH.sub.2).sub.a--OH (1)
wherein R.sup.1 represents a hydrogen atom, or a methyl group;
R.sup.2 represents a hydrogen atom, or an alkyl group or a
hydroxyalkyl group having 1 to 4 carbon atoms; a is an integer from
1 to 4.
[0013] (3) The water-soluble resin of (2), wherein a in the formula
(1) is 2.
[0014] (4) The water-soluble resin of any one of (1) to (3),
wherein the vinylic monomer (A) having a hydroxyl group and an
amido bond is hydroxyethyl acrylamide, or hydroxyethyl
methacrylamide.
[0015] (5) The water-soluble resin of any one of (1) to (4),
wherein the vinylic monomer (B) having a cationic group is
represented by the formula (2):
CH.sub.2.dbd.C(R.sup.3)--CO(O).sub.b--(NH).sub.1-b--(CH.sub.2).sub.c-
--N.sup.+R.sup.4R.sup.5R.sup.6.X.sup.- (2) wherein R.sup.3
represents a hydrogen atom, or a methyl group; R.sup.4 and R.sup.5
each independently represent an alkyl group or an aryl group or an
aralkyl group having 1 to 24 carbon atoms; R.sup.6 represents a
hydrogen atom, an alkyl group or an aryl group or an aralkyl group
having 1 to 24 carbon atoms, or
CH.sub.2--CH(OH)--CH.sub.2--N.sup.+R.sup.7R.sup.8R.sup.9.Y.sup.-;
R.sup.7 to R.sup.9 each independently represent an alkyl group or
an aryl group or an aralkyl group having 1 to 24 carbon atoms;
X.sup.- and Y.sup.- each independently represent an anion; b
represents 0, or 1; and c represents an integer from 1 to 10.
[0016] (6) The water-soluble resin of any one of (1) to (5),
wherein the vinylic monomer (B) having a cationic group is at least
one selected from the group consisting of meth
acroyloxyethyl-trimethylammonium chloride,
acroylaminopropyl-trimethylammonium chloride, and meth
acroylaminopropyl-trimethylammonium chloride.
[0017] (7) The water-soluble resin of any one of (1) to (6),
wherein the monomer mixture containing a vinylic monomer (A) having
a hydroxyl group and an amido bond, and a vinylic monomer (B)
having a cationic group contains 20 to 90% by weight of the vinylic
monomer (A) having a hydroxyl group and an amido bond, and 10 to
80% by weight of the vinylic monomer (B) having a cationic
group.
[0018] (8) The water-soluble resin of any one of (1) to (7),
wherein weight average molecular weight is 5,000 to 5,000,000.
[0019] (9) The water-soluble resin of any one of (1) to (8),
wherein the water soluble-resin can form an aqueous solution having
a concentration of at least 5% by weight.
[0020] (10) The water-soluble resin of any one of (1) to (9),
wherein the vinylic monomer (A) having a hydroxyl group and an
amido bond is hydroxyethyl acrylamide, and the vinylic monomer (B)
having a cationic group is at least one selected from the group
consisting of (meth)acroyloxyethyltrimethylammonium chloride,
acroylaminopropyltrimethylammonium chloride, and
(meth)acroylaminopropyltrimethylammonium chloride.
[0021] (11) A hair cosmetic material containing the water-soluble
resin of any one of (1) to (10).
[0022] (12) The hair cosmetic material of (11), further containing
an anionic surfactant.
[0023] (13) The hair cosmetic material of (12), which is an aqueous
solution containing 0.05 to 5% by weight of the water-soluble resin
and 5 to 40% by weight of the anionic surfactant.
[0024] (14) A silicone oil adsorption assistant comprising the
water-soluble resin of any one of (1) to (10).
DETAILED DESCRIPTION OF THE INVENTION
[0025] The invention is described in detail hereinafter. In the
present specification, the expression "to" is used in the meaning
of including the numerical values described at positions before and
after the expression as the lower limit and the upper limit. Unless
otherwise specifically indicated, the concentration as referred to
herein is at 25.degree. C.
[0026] The water-soluble resin relate to the invention has a
structure corresponding to a copolymer of a monomer mixture
containing a vinylic monomer (A) having a hydroxyl group and an
amido bond, and a vinylic monomer (B) having a cationic group. The
vinylic monomer (A) having a hydroxyl group and an amido bond is
preferablely a hydroxyalkyl (meth)acrylamide monomer ("(meth)acryl"
as referred means acryl and methacryl).
CH.sub.2.dbd.C(R.sup.1)--CO--NR.sup.2--(CH.sub.2).sub.a--OH (1)
wherein R.sup.1 represents a hydrogen atom or a methyl group;
R.sup.2 represents a hydrogen atom, or an alkyl group or a
hydroxyalkyl group having 1 to 4 carbon atoms; a is an integer from
1 to 4.
[0027] R.sup.1 is preferably a hydrogen atom. R.sup.2 is preferably
a hydrogen atom, or a methyl group, with a hydrogen atom being more
preferable. a is preferably 2.
[0028] The vinylic monomer (A) having a hydroxyl group and an amido
bond of the formula (1) includes N-hydroxyalkyl (meth)acrylamides
such as N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl
(meth)acrylamide, and N,N-dihydroxyethyl (meth)acrylamide. Of
those, preferred is N-hydroxyethyl (meth)acrylamide, as its
solubility in water is high and the solubility in water of the
polymer obtained from it is also high.
[0029] Preferably, the content of the structural unit corresponding
to the vinylic monomer (A) having a hydroxyl group and an amido
bond in the copolymer is from 20 to 90% by weight, more preferably
from 30 to 80% by weight, even more preferably from 40 to 70% by
weight. It is considered that the structural unit corresponding to
the vinylic monomer (A) having a hydroxyl group and an amido bond
increases the effect of adsorbing on hairs by the action of a
hydrogen bond derived from the amido bond portion. It is believed
that, when an anionic surfactant is used in hair cosmetic material,
the anionic surfactant and a water-soluble resin in the material
may form a complex, and when the hair cosmetic material is applied
to hair or while the hair is shampooed or rinsed with it, then the
complex may deposits and adhere to the hair. In the water-soluble
resin of the invention, however, after a structural unit
corresponding to the vinylic monomer (B) having a cationic group in
the copolymer has formed the complex with the anionic surfactant
used together, the copolymer may still keep its solubility in water
owing to the hydrophilicity of the structural unit corresponding to
the vinylic monomer (A) having a hydroxyl group and an amido
bond.
[0030] When the content of the structural unit corresponding to the
vinylic monomer (A) having a hydroxyl group and an amido bond is at
least 20% by weight, adsorption force to hairs or the like may
effectively be kept, and, a smooth feel and a silky feel of dried
hair are further improved. When it is at least 90% by weight, the
content of the structural unit corresponding the vinylic monomer
(B) having a cationic group is further sufficiently kept, further
sufficient complex with the anionic surfactant can be formed,
adsorption amount to hairs is improved, and it is more effective
by, for example, a smooth feel of hair in rinsing.
[0031] The vinylic monomer (B) having a cationic group includes
diallyl-type quaternary ammonium salts such as
N,N-dimethyl-N,N-diallylammoniumchloride; (meth)acrylester-type
quaternary ammonium salts such as
N-methacryloyloxyethyl-N,N,N-trimethylammonium chloride;
(meth)acrylamide-type quaternary ammonium salts such as
N-mathacryloylaminopropyl-N,N,N-trimethylammonium chloride; amino
acid-type cation species such as reaction product of L-arginine and
glycidyl methacrylate; and the like. Of those, more preferred are
(meth)acryl quaternary ammonium salt monomers. In particular, more
preferred are (meth) acryl quaternary ammonium salt monomers of the
formula (2).
CH.sub.2.dbd.C(R.sup.3)--CO(O).sub.b--(NH).sub.1-b--(CH.sub.2).sub.c--N.s-
up.+R.sup.4R.sup.5R.sup.6.X.sup.- (2) wherein R.sup.3 represents a
hydrogen atom, or a methyl group; R.sup.4 and R.sup.5 each
independently represent an alkyl group or an aryl group or an
aralkyl group having 1 to 24 carbon atoms; R.sup.6 represents a
hydrogen atom, an alkyl group or an aryl group or an aralkyl group
having 1 to 24 carbon atoms, or
CH.sub.2--CH(OH)--CH.sub.2--N.sup.+R.sup.7R.sup.8R.sup.9.Y.sup.-;
R.sup.7 to R.sup.9 each independently represent an alkyl group or
an aryl group or an aralkyl group having 1 to 24 carbon atoms;
X.sup.- and Y.sup.- each independently represent an anion; b
represents 0, or 1; and c represents an integer from 1 to 10.
[0032] Preferably, R.sup.3 is a methyl group. Preferably, R.sup.4
and R.sup.5 are each independently a methyl group or an ethyl
group, and more preferably a methyl group. Preferably, R.sup.6 is a
methyl group, an ethyl group or a butyl group, and more preferably
a methyl group. Preferably, R.sup.7 to R.sup.9 are each
independently a methyl group or an ethyl group, and more preferably
a methyl group. Preferably the anions for X.sup.- and Y.sup.- are
each independently a chlorine ion, an iodine ion or a bromine ion.
Preferably, b is 0. Preferably, c is an integer from 1 to 5, and
more preferably 3.
[0033] Some vinylic monomers having a cationic group of the formula
(2) are exemplified below; cationic group having (meth)acrylic
esters, such as N-(meth)acryloyloxyethyl-N,N,N-trimethylammonium
chloride, N-(meth)
acryloyloxyethyl-N-ethyl-N,N-dimethylammonium=monoethyl sulfate
salt, N-(meth)acryloyloxyethyl-N,N,N-triethylammonium=monoethyl
sulfate salt,
N-[3-{N'-(meth)acryloyloxyethyl-N',N'-dimethylammonium}-2-hydroxypropyl]--
N,N,N-trimethylammonium chloride,
N-[3-{N'-(meth)acryloyloxyethyl-N',N'-diethylammonium}-2-hydroxypropyl]-N-
,N,N-trimethylammonium chloride; and cationic group-having (meth)
acrylamides such as
N-(meth)acryloylaminopropyl-N,N,N-trimethylammonium chloride,
N-(meth)acryloylaminopropyl-N-methyl-N,N-dimethylammonium=monoe-
thyl sulfate salt,
N-(meth)acryloylaminopropyl-N,N-diethyl-N-methylammonium chloride,
N-(meth)acryloylaminopropyl-N,N-diethyl-N-methylammonium=monomethyl
sulfate salt,
N-[3-{N'-(meth)acryloylaminopropyl-N',N'-dimethylammonium}-2-hydroxypropy-
l]-N,N,N-trimethylammonium chloride, and
N-[3-{N'-(meth)acryloylaminopropyl-N',N'-diethylammonium}-2-hydroxypropyl-
]-N,N,N-trimethylammonium chloride; and the like.
[0034] Of those, preferred are
N-(meth)acryloyloxyethyl-N,N,N-trimethylammonium chloride and
N-(meth)acryloylaminopropyl-N,N,N-trimethylammonium chloride, and
more preferred is
N-(meth)acryloylaminopropyl-N,N,N-trimethylammonium chloride.
[0035] The structure corresponding to the copolymer of the cationic
group-having vinylic monomer (B) may be prepared, for example, by
copolymerizing with vinylic monomer precursor having a cationic
group of the formula (3), and then by converting into the
corresponding structure having a cationic group by a cationating
agent.
CH.sub.2.dbd.C(R.sup.3)--CO(O).sub.b--(NH).sub.1-b--(CH.sub.2).sub.c--NR.-
sup.4R.sup.5 (3) wherein, R.sup.3to R.sup.5, b and c are the same
as defined in the formula (2), and the preferable range is also the
same as defined therein.
[0036] The cationic vinylic monomer precursor includes, for
example, (meth)acrylates esters having a tertiary amine such as
N-(meth)acryloyloxyethyl-N,N-dimethylamine,
N-(meth)acryloyloxyethyl-N,N-diethylamine; and (meth)acrylamides
having a tertiary amine such as
N-(meth)acryloylaminopropyl-N,N-dimethylamine,
N-(meth)acryloylaminopropyl-N,N-diethylamine; and the like.
[0037] The cationating agent includes an alkyl halide such as
methyl chloride; a cationating agents having cationic group such as
3-chloro-2-hydroxypropyl-N,N,N-trimethylammonium chloride, and the
like. Cationaion can be conducted, for example, by adding the
cationating agent to a solution of a polymer, and reacting them at
the conditions 20 to 100.degree. C. and 1 to 20 hours.
[0038] One or more different types of cationic vinylic monomers or
their precursors may be used herein singly or as combined.
[0039] Preferably, the content of the structural unit corresponding
to the vinylic monomer (B) having a cationic group in the copolymer
is 10 to 80% by weight, more preferably 20 to 70% by weight, and
particularly more preferably 30 to 60% by weight. The structural
unit corresponding to the vinylic monomer (B) having a cationic
group may form a complex with the anionic surfactant in hair
cosmetic material, thereby making the copolymer more adhere to
hair. When the content of the structural unit corresponding to the
vinylic monomer (B) having a cationic group is at least 10% by
weight, then it may form a sufficient complex with the anionic
surfactant, for example, the hair cosmetic material may be more
effective for keeping the shampooed hair smooth during rinsing.
When the content of the structural unit is at most 80% by weight,
adsorption force to hairs and the like can further sufficiently be
kept better, and as a result, a smooth feel and a silky feel of
hair after dried can further effectively be kept.
[0040] The copolymer may further contain a structural unit derived
from other vinylic monomer. However, if an anionic functional group
is present in the copolymer, then it may interfere with the
formation of the complex with the above-described anionic
surfactant. Therefore, it is desirable that the amount of such an
anionic functional group in the copolymer is as small as
possible(for example, at most 10% of the total functional groups in
the copolymer). More preferably, the copolymer does not
substantially contain the group. The term "not substantially
contain" means, for example, not showing anionic property at pH 3
to 8. Any other vinylic monomer includes esters of (meth) acrylic
acid with an alcohol having from 1 to 22 carbon atoms; amides of
(meth) acrylic acid with an alkylamine having from 1 to 22 carbon
atoms; monoesters of ethylene glycol or 1,3-propylene glycol or the
like with (meth) acrylic acid; esters derived from the monoesters
by etherifying the hydroxyl group therein with methanol ethanol or
the like; nonionic monomers such as (meth) acryloylmorpholine;
amphoteric monomers such as betaine group-having (meth)acryl
esters, betaine group-having (meth)acrylamides; semi-polar monomers
such as amine oxide group-having (meth)acryl esters, amine oxide
group-having (meth)acrylamides; and the like.
[0041] The content of the structural unit derived from the other
vinylic monomer may appropriately be determined within a range
within the scope which does not overlap the subject matter of the
invention. For example, the content may appropriately be determined
within a range not disturbing solubility of the water-soluble
resin, conditioning effect where used in hair cosmetic material,
and the like. Preferably, the content of the other vinylic
copolymer is at most 30% by weight.
[0042] The contents of the structural unit corresponding to the
vinylic monomer (A) having a hydroxyl group and an amido bond, the
structural unit corresponding to the vinylic monomer (B) having a
cationic group, and the structural unit derived from the other
vinylic monomer, in the copolymer can be determined by IR
absorption of a hydroxyl group or an amido bond site, .sup.1H-NMR
of a hydroxyl group, an amido bond site, or a methyl group adjacent
to the cationic group, .sup.13C-NMR of those, and the like.
[0043] Preferably, the water-soluble resin of the invention is a
resin capable of forming an aqueous solution having a concentration
of at least 5% by weight at an ordinary temperature, i.e.,
25.degree. C., that is, a resin in which an aqueous solution having
a concentration of at least 5% by weight has a transmission (550
nm) of at least 80%, and the aqueous solution is uniform and
stable. More preferably, the resin may from an aqueous solution
having a concentration of at least 20% by weight.
[0044] The water-soluble resin according to the present invention
may be prepared, for example, by mixing monomers or their
precursors giving the respective structural units, copolymerizing
by a method such as solution polymerization, suspension
polymerization or emulsion polymerization, and then, optionally,
cationating the resulting copolymer.
[0045] Preferably the polymerization is conducted in a hydrophilic
solvent. The hydrophilic solvent includes ketone solvents such as
acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohol
solvents such as methanol, ethanol, n-propanol, i-propanol,
n-butanol, i-butanol and sec-butanol; and water. One or more of
these may be used herein either singly or as combined. Preferred
are alcohol solvents or water.
[0046] The polymerization initiator usable herein is not
specifically defined, including, azo compounds such as
2,2'-azobisisobutyronitrile,
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
dimethyl-2,2'-azobisisobutyronitrile,
2,2'-azobis(2-methylbutyronitrile),
1,1'-azobis(1-cyclohexanecarbonitrile),
2,2'-azobis(2-methyl-N-(2-hydroxyethyl)-propionamide),
2,2'-azobis(2-amidinopropane) dihydrochloride; peroxides such as
benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl
peroxide; persulfates; and their redox type agent; and the like.
Preferably the amount of the polymerization initiator to be used is
from 0.01 to 5% by weight of all the monomers.
[0047] The polymerization may be conducted in an inert gas
atmosphere such as nitrogen or argon, at preferably 30 to
120.degree. C., and more preferably 40 to 100.degree. C., for 1 to
30 hours. After completion of the polymerization, the copolymer
formed may be isolated from the reaction solution in an appropriate
method such as solvent distilling off or addition of poor solvent.
The copolymer may be used to the production of hair cosmetic
material and the like according to the invention directly or after
further purification. The purification maybe conducted by an
appropriate method such as reprecipitation, solvent washing or
membrane separation, or by combing the methods thereof.
[0048] Weight average molecular weigh of the copolymer of the
invention is preferably 5,000 to 5,000,000, more preferably 10,000
to 2,000,000, and further preferably 20,000 to 1,000,000. When the
weight average molecular is at least 5,000, adsorption force to
hairs can be increased, and conditioning effect can further
effectively be kept. When the weight average molecular weigh is at
most 5,000,000, viscosity can appropriately be kept, resulting in
easy handling on production. The weight average molecular weight of
the copolymer may be determined by gel permeation chromatography
(for example, using water/methanol/acetic acid/sodium acetate as a
developing solvent).
[0049] The water-soluble resin of the invention increases
adsorption amount of a silicone oil on hairs, and can be used as a
silicone oil adsorption assistant. It is preferable that the
silicone oil adsorption amount on hairs is preferably 70 ppm or
more, with being more preferably 100 ppm or more.
[0050] Further, the silicone oil adsorption amount on hairs is
preferably 5,000 ppm or less, and more preferably 2,000 ppm or
less. By making the amount be 5,000 ppm or less, hairs after dried
can be prevented from being sticky, which is preferable.
[0051] Further, preferably, the silicone oil adsorption amount on
bleach-treated hairs is within the above range.
[0052] The hair cosmetic material of the invention may be prepared
by blending a necessary amount of the water-soluble resin obtained
by the above method with a formulation. Other components to be
contained in the hair cosmetic material are not particularly
limited, and may be blended within a range which does not disturb
the object and effect of the invention. Concretely, such other
components are an anionic surfactant, a cationic surfactant, a
nonionic surfactant, a water-soluble polymer other than the
water-soluble resin of the invention, cationic polymer, an anionic
polymer, a nonionic polymer, an amphoteric polymer, an oil
component, a pearly agent, and the like.
[0053] When the water-soluble resin obtained by the above method
is, for example, used in a shampoo or the like, it can be prepared
by dissolving the water-soluble resin into water. In this case, the
concentration of the anionic surfactant is preferably 5 to 40% by
weight, and more preferably 10 to 30% by weight, and the
concentration of the water-soluble resin is preferably 0.05 to 5%
by weight, and more preferably 0.1 to 1% by weight. When the
anionic surfactant and the water-soluble resin is within the above
concentration ranges, the anionic surfactant and the water-soluble
resin forms a complex in the hair cosmetic material obtained, and
this complex deposits to adhere on hairs in shampooing or rinsing,
thereby giving a good touch of hair in finger-combing.
[0054] When the concentration of the anionic surfactant is at less
5% by weight, the hair cosmetic material can further effectively
exhibit the function, and reversely when it is at most 40% by
weight, viscosity can appropriately be kept, making it easy to
handle. When the concentration of the water-soluble resin is at
least 0.05% by weight, the conditioning effect can further
effectively be exhibited, thereby improving a touch of hair in
finger-combing and the like.
[0055] The anionic surfactant includes materials that are generally
used in hair cosmetic material, such as .alpha.-olefin sulfonic
acid salt, a higher alcohol sulfuric ester salt, a polyoxyethyl
alkyl ether sulfuric ester salt, a paraffin sulfonate, a
polyoxyethylene alkyl ether carboxylic ester salt, an
alkylsulfosuccinate, N-acyl-.beta.-alanine salt, N-acylglutamate,
and acylmethyltaurinate. The counter ion of those anionic
surfactants includes sodium, potassium, ammonium, triethanolamine,
diethanolamine, and the like. The anionic surfactants may be used
in combination of several kinds.
[0056] Other optional components that can be blended with hair
cosmetic material are exemplified below.
[0057] The cationic surfactant includes stearyl trimethylammonium
chloride, behenyl trimethylammonium chloride and the like. The
cationic surfactant can effectively improve feels. Preferably, an
amount of the cationic surfactant is 0.1 to 3% by weight.
[0058] The nonionic surfactant includes alkanol amide, glycerin
fatty acid ester, polyoxyethyelene-hardened caster oil,
polyoxyethylene alkyl ether and the like. The amphoteric surfactant
includes alkylamide propyl betaine, alkylcarboxybetaine,
alkylsulfobetaine and the like. Preferably an amount of those is 1
to 10% by weight.
[0059] The water-soluble polymer other than the water-soluble resin
of the invention includes methyl cellulose, hydroxymethyl cellulose
and the like. The cationic polymer includes a cation-modified
cellulose ester derivative, a polydimethyldiallylammonium halide, a
copolymer of dimethyldiallylammonium halide and acrylamide, and the
like. The anionic polymer includes an acrylic acid derivative (a
polyacrylic acid and its salt, an acrylic acid-acrylamide-ethyl
acrylate copolymer and its salt, etc.), a methacrylic acid
derivative, a crotonic acid derivative, and the like. The nonionic
polymer includes an acrylic acid derivative (a hydroxyethyl
acrylate-methoxyethyl acrylate copolymer, a polyacrylamide, etc.),
and a vinylpyrrolidone derivative (a polyvinylpyrrolidone, a
vinylpyrrolidone-vinyl acetate copolymer, etc.). The amphoteric
polymer includes a dimethyldiallylammonium chloride derivative (an
acrylamide-acrylic acid-dimethyldiallylammonium chloride copolymer,
an acrylic acid-dimethyldiallylammonium chloride copolymer, etc.),
and the like. Preferably, an amount of those is 0.1 to 1% by
weight.
[0060] The oil component includes a higher alcohol, a silicone oil,
an olive oil, a jojoba oil, a liquid paraffin, a fatty acid alkyl
ester oil, and the like. Of those, when a silicone oil is blended,
a silky feel after dried is further improved. Therefore, the
silicone oil is particularly useful. The silicone oil desirably is
used involatile polydimethylsiloxanes. Preferably, an amount of the
oil component is 0.1 to 2% by weight.
[0061] A pearly agent includes ethylene glycol fatty acid, and the
like, and a suspending agent includes a polystyrene-emulsified
product and the like. Preferably, an amount of those is 0.1 to 2%
by weight.
[0062] As other component, natural extracts of animals and plants,
and their derivatives, an inorganic salt such as sodium chloride, a
solubilizing agent (ethanol, ethylene glycol, propylene glycol,
etc.), a moisturizer (glycerin, sorbitol, maltitol, dipropylene
glycol, 1,3-butyrene glycol, hyaluronic acid, etc.), an
antioxidant, a higher fatty acid, a thickening agent, a
sequestering agent (edentate, etc.), a pH regulator, an ultraviolet
absorber, a sterilizer, a preservative, a dyestuff, a perfume, a
lathering booster, and the like may appropriately be blended in a
range that does not disturb the effect of the invention.
EXAMPLE
[0063] The present invention is further specifically described
below using the examples, but the invention is not limited by the
following examples so long as it is not beyond the gist of the
invention.
Example 1
(Production of Copolymer (1))
[0064] 300 parts by weight of distilled water were placed in a
reactor equipped with a reflux condenser, a dropping funnel, a
thermometer, a nitrogen gas introduction pipe, and a stirring
means, and a monomer mixed liquid of monomers (copolymer (1)) in
Table 1 and 100 parts by weight of distilled water was placed in
the dropping funnel. The reactor was replaced with nitrogen, and
heated up to 70.degree. C. 0.5 part by weight of 2,2'-azobis
(2-amidinopropane)dihydrochloride was introduced into the reactor,
and the monomer mixture was then added dropwise over 1 hour. After
conducted the reaction for 4 hours from the addition of dropwise,
the reactor was heated to 80.degree. C., and reaction was further
conducted for 2 hours.
[0065] Weight average molecular weight of the copolymer obtained
was determined using a gel permeation chromatography (apparatus,
Tosoh's SC8010, SD8022, RI8020, C08011, PS8010; column, Wako
Jun-yaku's Wakopack (Wakobeads G-50); developer solvent:
water/methanol/acetic acid/sodium acetate=6/4/0.3/0.41). The
results are shown in Table 1.
[0066] Water solubility of the copolymer obtained was conducted
according to the following criteria by preparing a 5 wt % aqueous
solution and a 20 wt % aqueous solution at 25.degree. C. and
measuring its transmission (550 nm, 10 mm glass cell). The results
are shown in Table 1.
[0067] .largecircle.: 80% or more
[0068] .DELTA.: 50% or more to less than 80%
[0069] x: Less than 50% TABLE-US-00001 TABLE 1 Monomer composition
(parts by weight) Monomer (B) Average 5% 20% DMAP DMAP DAD GMA
Monomer (A) DMAP molecular Water Water- Copolymer DMC AAC MAC MAC
Arg HEAA NMAA MAO HEA weight solubility solubility (1) 20 -- -- --
-- 80 -- -- -- 450000 .largecircle. .largecircle. (2) 40 -- -- --
-- 60 -- -- -- 420000 .largecircle. .largecircle. (3) 60 -- -- --
-- 40 -- -- -- 360000 .largecircle. .largecircle. (4) -- 40 -- --
-- 60 -- -- -- 400000 .largecircle. .largecircle. (5) -- -- 40 --
-- 60 -- -- -- 300000 .largecircle. .largecircle. (6) 5 -- -- -- --
95 -- -- -- 320000 .largecircle. .largecircle. (7) 90 -- -- -- --
10 -- -- -- 500000 .largecircle. .largecircle. (8) -- -- -- 40 --
60 -- -- -- 120000 .largecircle. .largecircle. (9) -- -- -- -- 40
60 -- -- -- 280000 .largecircle. .largecircle. (10) -- 40 -- -- --
-- 60 -- -- 300000 .largecircle. .largecircle. (11) -- -- 40 -- --
-- -- 60 -- 320000 .largecircle. .largecircle. (12) -- 40 -- -- --
-- -- -- 60 100000 .largecircle. .largecircle. DMC:
N-Methacryloyloxyethyl-N,N,N-trimethylammonium chloride DMAPAAC:
N-Acryloylaminopropyl-N,N,N-trimethylammonium chloride DMAPMAC:
N-Methacryloylaminopropyl-N,N,N-trimethylammonium chloride DADMAC:
N,N-Dimethyl-N,N-diallylammonium chloride GMAArg: Reaction product
of L-arginine and glycidyl methacrylate HEAA: N-Hydroxyethyl
acrylamide NMAA: N-Methylol acrylamide DMAPMAO:
N-Methacryloylaminopropyl-N,N-dimethylamine oxide HEA: Hydroxyethyl
acrylate
(Preparation of Hair Cosmetic Material)
[0070] A shampoo having this composition was prepared by using the
copolymer (1) as a resin shown in Table 2. The preparation was
conducted by mixing components other than a silicone oil, and then
blending the silicone oil with the resulting mixture. Using the
shampoo prepared, lathering, a smooth feel in rinsing, a silky feel
of hair after dried, a smooth feel of hair after dried and silicone
oil adsorption amount were evaluated by the methods described
below. TABLE-US-00002 TABLE 2 Formulation wt % as solid content
Resin 0.3 Anionic surfactant *1 10 Lauroylamidopropyl betaine 5
Silicone oil *2 2 MARCOAT 550 *3 0.5 Stearyltrimethylammonium
chloride *4 1 Distilled water Remnant (Total 100) *1:
Polyoxyethylene (3) lauryl ether sodium sulfate, LES-Na (a product
of Lion Corporation) *2: Silicone oil emulsion BY22029 (a product
of Dow Corning Toray Co., concentration: 50%) *3: Copolymer of
dimethyldiallylammonium halide and acrylamide (a product of Merck
& Co., Inc.) *4: Stearyltrimetylammonium chloride, ARCARD T-28
(a product of Lion Chemical Corporation)
(Evaluation of Hair Cosmetic Material)
[0071] The hair cosmetic material obtained by the above method was
evaluated by the following method. The evaluation results when
non-processed hair bundles were used as a hair bundle are shown in
Table 3, and the evaluation results when damaged hairs were used as
a hair bundle are shown in Table 4.
Examples 2 to 9
(Production of Copolymers (2) to (9))
[0072] Copolymers (2) to (9) were produced in the same manner as
the production of the copolymer (1), except for using monomer
compositions shown in Table 1 (copolymer (2) to (9)). Weight
average molecular weight of the copolymers obtained is shown in
Table 1.
(Preparation and Evaluation of Hair Cosmetic Material)
[0073] Preparation and evaluation of the hair cosmetic material
were conducted in the same manners as described in Example 1. The
evaluation results are shown in Tables 3 and 4.
Example 10
(Production of Copolymer (10))
[0074] Copolymer (10) was produced in the same manner as the
production of the copolymer (1), except for using the monomer
composition described in Table 1 (copolymer (10)) and changing the
amount of distilled water introduced into the reactor at the
initial stage to 500 parts by weight. Weight average molecular
weight of the copolymer obtained is shown in Table 1.
(Preparation and Evaluation of Hair Cosmetic Material)
[0075] Preparation and evaluation of the hair cosmetic material
were conducted in the same manners as described in Example 1. The
evaluation results are shown in Tables 3 and 4.
Comparative Example 1
(Production of Copolymer (11))
[0076] Copolymer (11) was produced in the same manner as the
production of the copolymer (1), except for using the monomer
composition described in Table 1 (copolymer (11)). Weight average
molecular weight of the copolymer obtained is shown in Table 1.
(Preparation and Evaluation of Hair Cosmetic Material)
[0077] Preparation and evaluation of the hair cosmetic material
were conducted in the same manners as described in Example 1. The
evaluation results are shown in Tables 3 and 4.
Comparative Example 2
(Production of Copolymer (12))
[0078] Copolymer (12) was produced in the same manner as the
production of the copolymer (1), except for using the monomer
composition described in Table 1 (copolymer (12)), using ethanol as
a solvent, and using dimethyl-2,2'-azobisisobutyrate as a
polymerization initiator. Distilled water was added to the
copolymer obtained, and ethanol was distilled off to obtain an
aqueous solution. Weight average molecular weight of the copolymer
obtained is shown in Table 1.
(Preparation and Evaluation of Hair Cosmetic Material)
[0079] Preparation and evaluation of the hair cosmetic material
were conducted in the same manners as described in Example 1. The
evaluation results are shown in Tables 3 and 4.
Comparative Example 3
(Preparation and Evaluation of Hair Cosmetic Material)
[0080] Preparation and evaluation of hair cosmetic material were
conducted in the same manners as described in Example 1, except for
using a cationated hydroxyethyl cellulose as resin described in
Table 2 (Calgon's JR400). The evaluation results are shown in
Tables 3 and 4.
Comparative Example 4
Standard
(Preparation and Evaluation of Hair Cosmetic Material)
[0081] Preparation and evaluation of hair cosmetic material were
conducted in the same manners as described in Example 1, except
that the resin described in Table 2 was not blended. The evaluation
results are shown in Tables 3 and 4.
(Evaluation Method)
[0082] Each shampoo composition was applied to a hair bundle
provided, and the following items were evaluated respectively. As
the hair bundle, "root-trimmed human black hair (100%)"
(non-processed hair bundles: 10 g.times.30 cm), by Viewlax)" was
used as "non-processed hair bundles". Further, hairs obtained by
subjecting "non-processed hair bundles" to the following bleach
treatment were used as "damaged hairs". The bleach treatment was
conducted by applying a mixture of 12 g of Milbon's Promatis Brave
Oxitan 6.0 (hydrogen peroxide 6% cream), and 6 g of Melos
Chemical's Powder Bleach MR2, as a bleaching agent to one hair
bundle, allowing the same to stand for 30 minutes, washing with
water, applying polyoxyethylene (3) lauroyl ether sodium sulfate,
and washing.
(1) Lathering
[0083] Water was contained in 10 g of a hair bundle with flowing
water of 40.degree. C., excess water was removed, and 1 g of a
shampoo was applied, and foamed. Degrees of speed of lathering and
fineness of foams formed in such a case were evaluated by four
levels and ranked.
[0084] +2: The sample is better than the standard (with no resin)
in point of both the lathering speed and the texture of the
later.
[0085] +1: The sample is better than the standard in point of
either the lathering speed or the texture of the later.
[0086] 0: The sample is on the same level as the standard.
[0087] -1: The sample is inferior to the standard.
(2) Smooth Feel in Rinsing
[0088] After evaluation of lathering, smooth feel in finger-through
combing in rinsing the hair bundle with flowing water of 40.degree.
C., and sustainability of its smooth feel were evaluated by four
levels.
[0089] +2: The sample is better than the standard in point of the
smooth feel, and its smooth feel lasts for 1 minute or more.
[0090] +1: The sample is better than the standard in point of
either the smooth feel or the smooth feel durability.
[0091] 0: The sample is on the same level as the standard.
[0092] -1: The sample is inferior to the standard.
(3) Silky Feel after Dried
[0093] The hair bundle after evaluation of smooth feel in rinsing
was dried in a thermostatic chamber at 23.degree. C. and 60% RH
overnight, and silky feel of the hair bundle was evaluated by four
levels.
[0094] +2: The sample is much better than the standard in point of
the silky feel.
[0095] +1: The sample is better than the standard in point of the
silky feel.
[0096] 0: The sample is on the same level as the standard.
[0097] -1: The sample is inferior to the standard.
(4) Softness after Dried
[0098] Using the hair bundle after evaluation of Silky feel,
softness after dried was evaluated by four levels.
[0099] +2: As compared with the standard, the sample does not
almost have a rough feel.
[0100] +1: The sample has a rough feel in some degree, though
better than the standard.
[0101] 0: The sample is on the same level as the standard.
[0102] -1: The sample is inferior to the standard.
(5) Silicone Oil Adsorption
[0103] After wetting 10 g of a hair bundle with flowing water of
40.degree. C., water drip was conducted until not dropping water
droplets. 1 g of a shampoo was applied to the hair bundle, and the
hair bundle was comb 100 times for 1 minute to foam. The hair
bundle thus treated was rinsed with flowing water of 40.degree. C.
for 30 seconds, and then dried overnight. After repeating this
treatment two times, the silicone oil adsorbed on the hairs was
extracted, and an adsorption amount was evaluated by NMR
measurement (quantitative determination of H in Si--CH.sub.3 by
.sup.1H-NMR) of the extract.
[0104] The extraction was conducted by dipping a hair bundle in a
solvent of chloroform/methanol=4/1, treating with ultrasonic wave,
drying the solvent in reduced pressure, dissolving in heavy
chloroform, adding dimethyl terephthalate as an internal standard,
and determining a concentration. TABLE-US-00003 TABLE 3 Evaluation
result with untreated hair Silicone oil Resin Smooth feel Silky
feel after Softness after adsorption (In Table 2) Lathering in
rinsing dried dried amount (ppm) Example 1 Copolymer (1) +2 +1 +2
+2 500 Example 2 Copolymer (2) +2 +1 +2 +2 700 Example 3 Copolymer
(3) +2 +1 +2 +1 680 Example 4 Copolymer (4) +2 +2 +2 +2 800 Example
5 Copolymer (5) +2 +2 +2 +2 750 Example 6 Copolymer (6) +1 +1 +1 +2
400 Example 7 Copolymer (7) +2 +1 +2 +1 420 Example 8 Copolymer (8)
+2 +1 +1 +1 350 Example 9 Copolymer (9) +2 +1 +1 +1 350 Example 10
Copolymer (10) +2 +2 +1 +1 400 Comparative Example 1 Copolymer (11)
+2 +2 +2 +2 700 Comparative Example 2 Copolymer (12) 0 -1 -1 -1 280
Comparative Example 3 JR400 +2 +2 +1 -1 750 Comparative Example 4
(None) 0 0 0 0 300 (Standard) JR400: Cationated hydroxyethyl
cellulose "None" in the Table means that a resin is not
blended.
[0105] TABLE-US-00004 TABLE 4 Evaluation result with damaged hair
Silicone oil Resin Smooth feel Silky feel after Softness after
adsorption (In Table 2) Lathering in rinsing dried dried amount
(ppm) Example 1 Copolymer (1) +2 +1 +2 +2 200 Example 2 Copolymer
(2) +2 +1 +2 +2 300 Example 3 Copolymer (3) +2 +1 +2 +1 250 Example
4 Copolymer (4) +2 +2 +2 +2 400 Example 5 Copolymer (5) +2 +2 +2 +2
300 Example 6 Copolymer (6) +1 +1 +1 +1 120 Example 7 Copolymer (7)
+2 +1 +1 +1 150 Example 8 Copolymer (8) +2 0 +1 +1 80 Example 9
Copolymer (9) +2 +1 +1 0 90 Example 10 Copolymer (10) +2 0 +1 0 70
Comparative Example 1 Copolymer (11) +2 +1 0 +1 50 Comparative
Example 2 Copolymer (12) 0 -1 -1 -1 45 Comparative Example 3 JR400
+2 +1 0 -1 60 Comparative Example 4 (None) 0 0 0 0 50
(Evaluation of Results) [0106] 1) Comprehensively evaluating,
Examples 1 to 5 obtained most preferable results, Examples 6 and 7
obtained second preferable results, and Examples 8 to 10 obtained
third preferable results. [0107] 2) Because Comparative Example 1
uses N-methacryloylaminopropyl-N,N-dimethylamine oxide in the
production of a water-soluble resin, the structural unit of the
water-soluble resin does not have a hydroxyl group. For this
reason, the silicone oil adsorption amount on the damaged hairs is
low, and silky feel of hair after dried is poor. [0108] 3) Because
Comparative Example 2 uses hydroxyethyl acrylate in the production
of a water-soluble resin, the structural unit of the water-soluble
resin does not have an amido bond. For this reason, lathering,
smooth feel in rinsing, silky feel after dried, softness after
dried, and silicone oil adsorption amount in non-processed hair
bundles and damaged hairs are poor. [0109] 4) Because Comparative
Example 3 uses cationated hydroxyethyl cellulose which does not
have an amido bond as the water-soluble resin, softness after dried
is poor in non-processed hair bundles and damaged hairs. [0110] 5)
Because Comparative Example 4 (standard sample) does not contain a
resin, lathering, smooth feel in rinsing, silky feel after dried,
softness after dried, and silicone oil adsorption amount in
non-processed hair bundles and damaged hairs are poor as compared
with the hair cosmetic material having blended therein the
water-soluble resin of the invention.
[0111] When the water-soluble resin of the invention is used in,
for example, hair cosmetic material comprising an anionic
surfactant as a main component, the water-soluble resin gives
conditioning effects, such as a good touch of hair in
finger-combing in rinsing, smooth feel after dried, silky feel and
softness, to hairs treated with the hair cosmetic material, and
thus the industrial value of the invention is remarkable.
Advantage of the Invention
[0112] The water-soluble resin of the invention is excellent in
lathering, smooth feel in rinsing, silky feel after dried, softness
after dried, and silicone oil adsorption amount. For this reason,
conditioning effects and the like when used in hair cosmetic
material are excellent.
* * * * *