JPS60126212A - Modified polyvinyl alcohol polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to skin conditioning polymers that, when applied to the skin, form a moisture-retentive film that helps reduce water loss from the skin.

The present invention relates generally to derivatives of film-forming polyvinyl alcohol polymers, and specifically to polyvinyl alcohols having certain amine and quaternary ammonium nitrogen-containing side groups or combinations of these nitrogen-containing side groups. Regarding derivatives. Of particular interest are those having a polyvinyl alcohol backbone (i.e. basic silver) with nitrogen-containing side chains distributed randomly across the backbone and bonded via oxygen, and containing quaternary amines, quaternary amines, class ammonium, alkyl,
arylalkyl, hydroxyalkyl, alkyl acid,
and at least 2 selected from hydroxyalkyl acids
It is a polymer containing side chain groups of ridges.

As a result of the presence of quaternary ammonium groups in the polymer, the thin film coating on the skin penetrates the outer layers of the skin and provides sufficient adhesion, while being sufficiently flexible to avoid discomfort after drying. maintain sexuality.

The thin film acts as a partially impermeable barrier to prevent water loss by evaporation and also by the formation of hydrates that can occur at the quaternary ammonium sites and by hydrogen bonding to the hydrophilic polymer matrix. By inclusion, it also behaves as a moisture retention agent. Other groups selected from tertiary amines and alkyl groups serving as side groups on the polyvinyl alcohol chain may aid in the compatibility of the dry film with the skin, as these groups may confer miscibility with certain solvents. provides a means to adjust the hydrophilic/lipophilic balance,
The polymers can thus be incorporated into a wide variety of skin conditioning, cosmetic and pharmaceutical formulations. Additionally, the polymer acts as a suspending agent for the drizzled pigments and medicinal ingredients that are present in high concentrations in such formulations.

One object of the present invention is to provide a polyvinyl alcohol polymer base chain (
at least 2,000 and preferably about 200 before denaturation.
,000 or less); and a plurality of side groups bonded via oxygen, selected from at least two of the general formulas (a) to (C1) of F; The object of the present invention is to provide a quaternary nitrogen or tertiary amine-functionalized polyvinyl alcohol polymer having a total nitrogen content of 0.01 to 7.0% by weight: (a) -R-N R,R2H,A- ( b) -R-NR, R, and fcJ -R4 where R is an alkylene group, a substituted alkyref group (preferably a hydroxyalkylene group), or an acylene group having 14 to about 3,000 substitutions, and RI r R2+ R3
are an alkyl or arylalkyl group, which may be the same or different and have 1 to 20 carbon atoms, A is an anion, and -R, is an alkyl group, an arylalkyl group, or an alkyl or arylalkyl group having a specified substituent.

Such polymers have (a+b) groups, (a+c) groups, (b+c
) groups or (a+b+c) groups. Another object of the invention is to provide a preferred method for synthesizing such polymers. Yet another object of the invention is an aqueous solution useful in the formulation of skin conditioning lotions, creams, cosmetics and pharmaceuticals for application to the hair, skin and nails, comprising: .1 to 30% by weight. Yet another object of the present invention is to provide a film-forming polymer that also acts as a dispersant for insoluble particulates in formulations such as those described above.

R in the above general formula is an alkylene group (e.g. methylene, ethylene, propylene, butylene, pentylev, hexylene, ethylhexylene, dodecylene, tetradecylne, hexadecylne, octadecylne) or a direct alkylene group (e.g. hydroxypropylene, hydroxybutylene, acetyl, (gropionyl, butyryl, octadecanoyl, octadecanoyl and equivalents thereof).

RI+R2 and R3 are from alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, phenyl group, benzyl group and their equivalents. You can choose.

A'' is a chlorine ion, bromide ion, ice ion, hydroxide ion, lower alkyl (C
+ to C,) can be selected from a number of anions such as sulfate, tetrafluoroborate, nitrate and perchlorate.

R4 is about 3000 substitutions or less, preferably 1000 substitutions
From many groups such as the following alkyl groups, alkylaryl groups, substituted alkyl groups, substituted alkylaryl groups, (especially alkyl groups or alkylaryl groups having a dihydroxyl group, a carboxyl group, or a combination of both groups) You can choose.

The total formula weight of side chain groups is 0.01 to 7% by weight of total nitrogen.
It is adjusted during polymer synthesis so that

The overall proportion of R2 groups attached to the polyvinyl alcohol bases is adjusted such that the total formula weight of those groups constitutes 0.5-50% by weight of the total weight of the polymer; The ratio (b/a) of total formula weight of amine groups: total formula weight of quaternary ammonium-containing groups can vary between 0 and 90% by weight. -R-N R,R2 Depending on the amount of R8A and -R1 groups, -R-N-R,
The presence of the R2 group may not be required. If side groups of type R4 with hydroxy or carboxy groups are bonded to the polyvinyl alcohol base prior to reaction with quaternary ammonium or tertiary amine-containing groups, quaternary Some of the primary ammonium or tertiary amine-containing groups are oxygenated to the polyvinyl alcohol bases.
jr may not be directly bonded, but may be bonded to the -R4 side chain group via oxygen.

The R4 group is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyldecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, hydroxyethyl, mono- or dihydroxyglobil, mono- or poly-hydroxybutyl, mono- - or poly-hydroxypentyl, mono- or polyhydroxyhexyl, mono- or polyhydroxyquindecyl, mono- or poly-hydroxydodecyl, mono- or poly-hydroxytetradecyl, mono- or poly-hydroxyhexadecyl, mono- or poly-
Hydroxyoctadecyl, carboxymethylene, carboxyethylene, carboxypropylene, carboxybutylene, carboxyethylene, carboxyhexylene,
Carboxyethylene, carboxyethylene, carboxyethylene, carboxyethylene, carboxypropylene, carboxytetradecylev, carboxypentadecylef, carboxyhexylene, carboxypropylene, carboxyoctadecylef, carboxy (hydroxyethylene), carboxy (hydroxyethylene), Carboxy (hydroxybutylene), carboxy (hydroxyethylene), carboxy (hydroxyhexylene)
, carboxy(hydroxyhebutylene), carboxy(
hydroxyethylene), carboxin (hydroxyethylene), carboxy (hydroxyethylene), carboxy (hydroxyhexylene), carboxy (hydroxytetradecylev), carboxy (hydroxybentadecylef), carboxy (hydroxyhexylene), carboxy (hydroxy heptadecylef), carboxy (hydroxyoctadecyle/) groups, and the like.

The quaternary nitrogen-containing polyvinyl alcohol polymer of the present invention is
Idealized, it can be represented by typical polymer segments having the following two structural formulas.

-[(-CH,CHORN+R,R,R8A)(-0
H20HOH me, (CH, CHOR4) (cH2CHO
H) m, (cH, cHORN+-R, R2R3A-)]
-or-[(CH2CHORN R,R2H,A)(CH2CHORN R,R2H,A)
CHCN)p, (CH2CHORNR,H,)(CH2
0k(OH)pz (OH2CHOR4)-(C'H2
C'HOH)pm(CH,CHORNR,R2R3A
)]-]rr++, ms=0-65 0t+mx==(650 pl, p snow, pm=0-650' p+ +pz+ps==(650 RT RI I R2+ R3+ R4 and A- are as defined above.

Typical examples of quaternary and tertiary amine groups and nitrogen-free groups in units randomly distributed in the polyvinyl alcohol basic chain include the following:

tl) -0H,0H(OH)Cl,N(OH3)3
017(2t(C1(2CH[C!H2s”-(CH3
), al-]o), pHt OH(OH)CH, l
J+(CH,)3 C1= (θ=1~20) (31-(C=O)CH2N+(CH20H3)3 B
r-t4) -0H2CH(OH)OH2N+(OH8
)2(OH2Ph)Ol-(51-CH,0H2N+
(CH8)(C)I,Cl-1,)(CH2Ph)CH
,SO,-(6J 7CH[(CH2)70H,]OC
HOH)(CH2)rc'H20H(7) -CH((
CH,)7CH3)cH(OH)(CnH2),C! H
,ocH20H(OH)OH2N (OH8)3C1- t81 C)(tcH(CI42N+(C)13)3C
'l )OOHL(CH2)fucH,)OH(OH)(
OH2), CH20H (91-OH,0H(OH)OH.

+101-C! H2CH(OH8)(ocH2C!H(
OH)CH2N (OH3)3clOυ-CH2CHC
N, N (CnH3), C1-[:OCH, 0H(OH
)CH3,111 -CH20H(OH)CH2N(O
H2Ph)OH.

C31-0H2C! H(OOH2aH(oH)CH2N
+(0H2ph +cn3)CH2N (C!H,),
C! 1- C41-aH2aH[ocH2an(oH)ah2N+
(CH3)3c1]0H2N(OH,Ph)CH8 (151-C!HC(OH,),a)(,]ea(oc
n, cl((ol()cl(2N+(CH3)3CI
E(CH2), CH20-CH, (1!H(OH)C
I42N+(c)i3), C"L-(Rule-(C=O)(
CH2),,CH.

Uη-(C=O)(OH2), CH(OH,)70H3
(1-(C=O)(CH,)7CH= CH(OH2)
7cl(3(II-(0=O)(CH2), 0H(
OH)CH(OH)(CnH2)70H3 (ph=phenyl group) The above values are attached to the basic chain of polyvinyl alcohol.
These examples are illustrative of the types of side chain groups that can be used; however, it will be apparent to those skilled in the art that many others with similar chemical structures may be included. Each of the above types of radicals has 1
or in combination with others as a substituent on the polyvinyl alcohol basic chain (especially when the nitrogen content in the final product is between 0.001 and 7% by weight)
It has been found that this may result in a desired combination of products with useful moisture barrier properties. Depending on the type of group attached to the nitrogen of the quaternary group, the effective range of nitrogen content can be more specific. For example, R1 in the above general formula
．． It has been discovered that when all of R2 and R8 are methyl groups, the effective nitrogen content will range from 0.1 to 5 parts by weight.

Although many methods have been used to add substituent groups to modify polymeric raw materials or change their hydrophilic/lipophilic balance (HLB), there are four methods for adding substituent groups to polyvinyl alcohol. A preferred method is to combine the hydroxyl groups of the polyvinyl alcohol basic chain;
oxirane) groups or halohydrin groups (in aqueous solution), or low molecular weight alkyl alcohol esters of substituents in dipolar aprotic solution, or acid halides in dipolar aprotic solvents or two-phase systems; presence of a base or acid catalyst).

Although a number of methods can be used for the manufacture of the PVA g-conductors of the present invention, and the use of non-aqueous solvents such as dimethylformamide or similar polar substances is possible, these solvents are not commonly used in the final product. must be completely removed from the object. Although the use of aqueous solvents or mixed aqueous systems is preferred, in this case the competitive reaction of the quaternary ammonium compound with water and the PVA hydroxyl groups in the presence of a catalyst takes place, and the yield needs to be optimized. be.

Improved yield increases once the PVA in water
This can be obtained by adding the oxira/compound as a concentrate and minimizing the amount of base used to catalyze the addition reaction. Salts formed during the reaction are selectively removed from the final product. This is because such salts can have an adverse effect on the skin's moisture barrier properties as well as its formulation. induced PV
It has also been found that the pH of A affects the skin moisture barrier properties as well as its persistence on the skin. Generally, 2 to 1
A pH range of 0, preferably 5 to 9 is desirable.

The product is obtained in dry form by precipitation, filtration, drying and crushing. Precipitation can be carried out by adding the reaction mixture to a non-solvent such as acetone, methanol, ethanol, etc. The products can also be used as aqueous solutions or suspensions. Such aqueous solutions or suspensions are preferably obtained by dialysis of the reactants to remove salts and low molecular weight unreacted intermediates therefrom. In order to provide a better understanding of the method which has been found to be most satisfactory, the following general and specific methods are described. However, these are illustrative of the invention and are not intended to limit it (all additional doses are "by weight" unless otherwise indicated).

General production method 1 A flask equipped with a water-cooled condenser, a mechanical stirrer, and a thermometer is charged with polyvinyl alcohol and distilled water.
: Make a cloudy liquid or slurry. Polyvinyl alcohol, a commercial product typically prepared by hydrolysis of polyvinyl acetate, may contain from 0 to 35% by weight, preferably from 2 to 15 weight percent, of residual vinyl acetate groups. The number average molecular weight of this starting material ranges from 2,000 to 20 U, 000 or more, preferably from 25,000 to i5o,
It can be in the range o o o. Additionally, and for the purposes of the present invention, the polyvinyl alcohol basic chain is 25
Other comonomers, such as vinyl pyrrolidone, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, may be included in weight percentages.

The aqueous slurry is heated to 80 DEG to 100 DEG C. and then catalyzed with a catalytic amount of an alkaline hydroxide (e.g., sodium hydroxide, potassium hydroxide), or an acidic substance if appropriate. This solution is then cooled to near ambient temperature when the propylene oxide is to be dissolved, or 50 to 75 mL when the aliphatic epoxidized or tertiary amine epoxy compound is to be applied. Cool to ℃. These reagents may be used alone or in combination in amounts of 90 to 0.95 moles, preferably 0.001 to 0.05 moles per mole of hydroxyl groups on the polyvinyl alcohol base mirror.

The entire solution is then typically treated with a quaternary ammonium reagent (if used) at 80-90°C, usually for 3-24 hours, preferably 5-10 hours. 2
, 3-epoxypropyltrialkylammonium halide or (chlorhydroquiprovir) trimethylammonium halide, in small portions or all at once, in the form of a water bath solution or crystals.
JD L, stir at a temperature of 40-90°C, preferably 60-70°C for about 4 hours or until the reaction is complete.

These quaternary ammonium no-ride reagents are typically used at a concentration of 1) 0.0. (JO3~0.95
It is translated in amounts of moles, preferably from 0.1 to 0.3 moles.

The reaction mixture is subjected to total dialysis or ultrafiltration to remove all compounds below a certain molecular weight. Two methods can be used, one method being a static method and the other method being a dynamic method. In a static method, the reaction mixture is placed inside commercially available semi-elongated dialysis tubing and the tubing is soaked in distilled water for typically 12 to 48 hours. The contents of the dialysis tube are then collected. The product can be used as is or dried.

In a dynamic system, a pressure pump is used to valve a semi-elongated membrane to remove water from the reaction mixture. The water carries away all minerals and low molecular weight organics: vB.

The resulting concentrated product can then be collected and used directly in cosmetic formulations or dried to a highly dispersed solid in conventional manner.

-Membrane manufacturing method■ A flask equipped with a water-cooled condenser, a mechanical stirrer, and a thermometer is charged with polyvinyl alcohol and water to make an aqueous suspension or slurry. Polyvinyl alcohol, which is a commercial product usually produced by oral decomposition of polyvinyl acetate, may contain from θ to 35% by weight, preferably from 2 to 15% by weight of residual vinyl acetate groups. The number average molecular weight of this starting material may range from 2,000 to 200,000 or more, preferably from 25,000 to 150,000. Additionally, and for the purposes of the present invention, the polyvinyl alcohol base chain contains up to 25% by weight of its flu comonomers, such as vinylpyrrolidone,
It may contain acrylic acid, acrylic ester, methacrylic acid, and methacrylic ester.

The aqueous slurry is heated to 80-100°C and then a catalytic amount of alkaline hydroxide (e.g. sodium hydroxide,
potassium hydroxide)' or an acidic substance if appropriate,
Added as a catalyst. The entire solution is then usually
Quaternary ammonium reagent (when using this, V (:4
The treatment is carried out at a temperature of 0 to 90°C, usually for 3 to 24 hours, preferably for 5 to 10 hours. A quaternary ammonium reagent such as 2,3-epoxypropyltrialkylammonium halide or (chlorohydroxypropyl)trimethylammonium halide is added in small amounts or all at once in the form of an aqueous solution or crystals, and the mixture is heated at 40 to 90°C.
The mixture is preferably stirred at a temperature of 60-70°C for about 4 hours or until the reaction is complete.

These quaternary ammonium halide reagents are typically used in an amount of 0.003 to 0.95 mole, preferably 0.1 to 0.3 mole, per mole of unreacted hydroxyl groups remaining on the polyvinyl alcohol base steel. used in quantity.

The reaction mixture is then purified by dialysis or ultrafiltration.
All chemicals below a certain molecular weight are removed.

To this end, two methods can be used. One method is a static method and the other is a dynamic method. In the static method, the reaction mixture is placed inside commercially available semi-elongated dialysis tubing and the tubing is placed in distilled water with a
Soak for an hour.

The contents of the dialysis tube are then collected. The product can be used as is or dried. In a dynamic system, water is removed from the reaction mixture using a semi-elongated membrane using a pressure pump. Any minerals and low molecular weight organics are carried away.The resulting concentrate can then be collected and used as such in cosmetic formulations or alkylated as described above.

The solution is then cooled to near ambient temperature if propylene oxide is to be added, or an aliphatic epoxy compound or a tertiary amine epoxy compound! ! I.J.
When adding water, cool to 50-75°C.

These reagents may be used alone or in combination in amounts of from 90 to 0.95 mole, preferably from o,ooi to 0.5 mole per mole of basic inhibiting hydroxyl group. A catalytic amount of alkaline hydroxide is used.

To obtain optimal moisture barrier properties, the resulting solution is freed from the catalyst by dialysis or ultrafiltration to prepare an aqueous dispersion. This dispersion can be used as is or may be recovered by precipitation.

Example 1 -R4: -OH, -0H(OH,)OH; -RN+R
,R2T(,A"-=-(!H2-C!H(OH)C
! H2N (CH,), C! A flask equipped with a mechanical stirrer, thermometer, efficiency condenser, and dropping capacity was charged with commercially available polyvinyl alcohol (88, OF) and distilled water (500 z/). The polyvinyl alcohol contained 2% residual vinyl acetate base and had a number average molecular weight of 126,000. The slurry was heated to 85-90℃.
Potassium hydroxide (15 m/3.0 m water) was heated for 1 hour.
OF) was added. The solution was cooled to 35° C. and propylene oxide (35, OF) was added at a rate such that no reflux occurred. At the end of the lab/JLI, the temperature was increased to 50°C for an additional 4+4 days. This hot solution was then poured into acetone. The precipitate was collected by filtration, washed with acetone and methanol, and dried under vacuum. The yield was 113y.

This C′ loboxylated polyvinyl alcohol (56,5y>
t, then add water (5 ml) to another flask equipped as above.
00Rt), potassium hydroxide (3,OF) and H(chlorohydroxypropyl)trimethylammonium chloride (48% water bath solution 80-). The entire solution was then stirred at 60°C for 16 hours. The product was recovered by precipitation from acetone as described above. Its nitrogen content was 0.88 inches.

Example 2 -R4=-0H20H(OH)CH.

-R-N0R, R2R', A, =-(!H20H(O
H) OH2-N(CHs) 301 thermometer, mechanical stirrer,
Condenser and nitrogen sparger (spargeer)'f: Add polyvinyl alcohol (hydrolysis rate 98% i
MW=126,000i88, OF) and distilled water (7
00d) was prepared.

Add potassium hydroxide (25 m/3.0 ji in water),
The flask contents were stirred at 35°C for 1 hour. Propylene oxide (58.0P; 1.0 mol) was then added dropwise. Due to heat generation during the addition of calories,
The contents temperature rose to 55°C. At the end of this introduction,
The temperature was maintained at 55°C for an additional 4 hours. Product recovery was performed by precipitation with acetone as described above. Yield is 1
It was 34.5F.

This propoxylated polyvinyl alcohol (72,2yL
) was then charged with distilled water (500x/) into another flask equipped as above. The contents of the flask are 5
It was warmed to 5°C, and potassium hydroxide (25 d in 3.0 ml of water) was added. After 1 hour, 2,3-epoxytrimethylammonium chloride (48% aqueous solution, 78 ml) was added to the solution. Heat the whole thing for another 12 hours (55
°C], Shita. Product recovery was carried out by precipitation from acetone as described above, yielding a raw NZ product with a nitrogen content of 1.71%.

Example 3 -R,=-C! H((C!H2), C1Hs)OH(O
H) (C!H2)80H or -C! H((CH,),
0HICH(OH)(C!H,)7C! H3-RN''
-R, R2H, A-=-C! H,0H(OH)C! H,
N (CH3), C! 1 Oleyl alcohol (20
0p.

Purity 85%) and methylene chloride (600Rt) were charged, and the mixture was cooled to 5-10°C. 3-Chlorperoxybenzoic benzoin Lf (135P; 85% purity) was then added via powder ejector in four equal portions at 20 minute intervals.

The slurry was stirred for an additional 3 hours while the temperature was gradually increased to ambient temperature. The solution is
(10% bicarbonate) Pti aqueous solution (5%
00a/3 times) and water (500a/2 times).

The organic layer was then collected, dried over anhydrous magnesium sulfate, and concentrated under vacuum to give a pale yellow oil (yield: 212yi99y). When left to stand, this oil solidified into a colorless waxy substance. This wax was used without further purification.

Polyvinyl alcohol (500Pi98
% skin water decomposition rate; MW=126,000) and distilled water (
3,700t/) was charged. The slurry was heated to 85° C. and maintained at that temperature until dissolution was complete. Potassium hydroxide (100+x/31.5y in water) was added and the flask contents were cooled to 70°C. 9,10-epoxyoctadecane-1-ol (235y; 0.83 mol)
After all additions were made, the flask contents were cooled to 60°C. The cloudy solution was stirred at 60° C. for an additional 3 hours and gradually cooled to ambient temperature.

The resulting latex solution was diluted with a small amount of 6 M -H2SO.
.

It was neutralized and bottled. Half the volume of this solution was then charged to a similarly equipped 32 flask and heated to 80°C. Potassium hydroxide (15.0F in 50ttl water)
The contents of the flask were cooled to 60°C. Then 48% (chlorohydroxyf).

lopyl) trimethylammonium chloride ° aqueous solution (
331,0d) were added all at once. The whole cell was heated at 60° C. for a further 4 hours and the product was recovered by precipitation with acetone.

Example 4 -R4=-C! HC(OH2), OH]CH(OH)
(C!H2), 0H5-RN+R, R2H, A? -(:
In a flask equipped with a mechanical stirrer, a thermometer, and a condenser, polyvinyl alcohol (44,0y; 98% water decomposition rate i
MW=126,000) and water (400a/) were charged. The contents were heated to 185°C for 1 hour+h' and then cooled to 80°C. Potassium hydroxide (15a water/3a medium)
．． Oy) was added to the flask, and the contents of the flask were cooled to 60°C. Glycisyl monomethylammonium chloride (
75,81) was added and the resulting solution was stirred for an additional 5 hours. The product was mixed with acetone (1500 t
/) was recovered by precipitation. The yield was 1101, and the nitrogen content was 4.66%.

This quaternized polymer (40y) was then charged to a similarly equipped flask along with water (400wg).

The flask contents were heated to 60-65° C. and potassium hydroxide (2.0F in 5 d of water) was added. 9,10-Epoxyoctadecanol (same as 8,5jii Example 3) was added and the solution was stirred at 60°C for 16 hours. The product was then recovered by precipitation from acetone. Its nitrogen content was 0.97%.

Example 5 -R4=-0H20H(OH)C! H.

-RN+R,R2R3A7=-OH2C1((O)()
In a flask equipped with OH2N (OH8), C1 mechanical stirrer, condenser, thermometer and addition funnel, polyvinyl alcohol (44, Oji+, 100% hydrolysis rate; MW=
78,000 ) and water (400a/) were charged. To 85-qnr' of this bath solution, heated 1-1 sodium hydroxide (2.6F in 20°C gl of water) was added. The solution was then cooled to 30°C. Propylene oxide (15
, OF) were added all at once. The solution was stirred at 30°C for 1 hour and then warmed to 70°C. 9,10-Epoxyoctadecanol (10,0y) was added along with glycicylate monomethylammonium chloride (30,0y). The entire solution was then stirred at 70° C. for 3 hours, cooled to ambient temperature and stored overnight. The product was recovered by precipitation with methanol.

Example 6 -RNR,R,-=-cH,6H(oH)cH,s+
(ca, )'(aH2Ph)-RN+R,R,R3A
-=-CH, CH(OH)OH, N+(OH,), C1
A flask equipped as in Example 5 was charged with polyvinyl alcohol (44, OF) and water (400 a/m),
Heated to 85°C. After 1 hour, add ihipotassium hydroxide (water 1
3.11) in 5al and diluted the contents of the flask to 65%.
Cooled to ℃. Glycisyl methylammonium chloride (30,0F) a--all at once was added and the flask contents were stirred for 1 hour.

Be/Giroux (2,3-epoxy 7° autohypertensive) methylamine was then added dropwise over 30 minutes and the entire solution was stirred for a further 3 hours. The product was recovered by precipitation from a methanol/acetone mixture. The yield was 62y.

Its nitrogen content was 1.20%.

Example 7 -RNR,R2=-CH,-0H(OH)CH,N(O
H3) (C!H2Ph) Polyvinyl alcohol (
44,0yi hydrolysis rate 98chi, MW=126,000
) and water (400a/) were charged. Add this slurry to 1
Heat to 90℃ for 4 days, add potassium hydroxide (15ffl water)
#3.0y) is Ju L. The solution was cooled to 75°C and freshly distilled benzyl-(2,3-
epoxypropyl) methylamine (44,37) t, a
.

It was applied dropwise over a period of minutes. This entire solution is 60~
Stirred for an additional 3 hours at 65°C and recovered the product from the acetone. The yield is 49. OF and nitrogen content is 0.25
It was Chi.

Example 8 A flask equipped as in the general example was charged with polyvinyl alcohol (44,0y;/J; water decomposition rate 100%, MW
= 86,000) and water (400d') k preparation, 85
Heat iJu to ~90°C. A catalytic amount of aqueous potassium hydroxide solution was added and the contents of the flask were cooled to 60°C. Crystalline 2,3-epoxyprobyltrimethylammonium chloride <151.51; 1.0 mol) was then added and the reaction mixture was stirred for a further 4 hours at 60<0>C. The product could be recovered by precipitation or ultrafiltration. The nitrogen content of the product was 84% yield:
It was 5.5%.

Example 9 Ite 75.8 II' (0,
50 mol) and repeating Example 8, the yield was 8.
A product with a nitrogen content of 4.5%, based on 0%, is obtained.

Example IO A flask equipped as in Example 5 is charged with polyvinyl alcohol and water. The aqueous slurry is heated to 80 DEG-90 DEG C. and held at that temperature for 1 hour, or until the polymer is completely dispersed or solvated. Add a catalytic amount of sulfuric acid or any protic acid or Lewis acid or aluminum hydrogen silicate to the flask contents?
! Cool to -40-90°C. At this point, 9.10-
Add epoxy octadecanol and the reaction mixture f
: Stir for 1 hour. The 2,3-epoxyprobyl trialkylammonium halide is then added in portions or all at once. The total content of these two types of epoxy compounds is 0.05 to 1.0 mol, preferably 0.1 to 0.3 mol, per 1 mol of hydroxyl groups on the polyvinyl alcohol base steel.
Can be used in molar proportions. The entire reaction mixture was then heated to 60
C. for a period of typically 4 hours. The product can be recovered by one of the methods described above.

Example 11 illustrates the impact of salts produced by neutralization with HC'I on skin moisture barrier properties I#. It should be noted that the substantial improvement in results obtained is based on the final dialyzed product.

Example 11 A flask equipped as in the general example was charged with polyvinyl alcohol (,44,Oy; MW=86.00
0; 100% hydrolysis) and water (400 a/ml) were charged and heated to 85-90°C for 1 hour.

The flask contents were cooled to 80° C. and potassium hydroxide (5.6 P in 15 kg of water) km was added. The contents of the flask were cooled to 60°C over 1 hour, and 3-chloro-2-hydroxypropyltrimethylammonium chloride (18,
8F)'. The solution was stirred at 60° C. for 4 hours and dialyzed through a raw potato porous membrane for 5 hours. Nitrogen content was 0.15%. (Improvement of product yield and significant reduction of reaction time can be achieved by using all oxirane derivatives,
This can then be achieved by adding to a concentrated PVA solution. ) The solution was then charged to a flask equipped as in the general example and heated to 80-85°C. Potassium hydroxide (0.56 g/10 m of water) was added to solution 1 and stirred for 1 hour. 9.10 while cooling to 60℃
-Epoxyoctadecane-1-ol (10,27)e
and the entire solution was stirred at 60° C. for 3 hours. The resulting white dispersion was divided into two parts (volumes). One of the solutions, A, was neutralized with a small amount of concentrated Hc1. This product was found to reduce moisture wicking through the paper barrier by 42 inches. The other solution B was dialyzed for 48 hours through a raw potato porous membrane to pH=
It was set at 7.9. This product was found to reduce moisture wicking in paper barriers by 83%.

Moisture Barrier Testing on Paper The modified polyvinyl alcohol polymers of the present invention are best tested on live animal skin for moisture retention, permanence and moisture barrier film formation. An indication of the effectiveness of polyvinyl alcohol polymers as moisture barriers is obtained by testing on P paper. In this test, Whatmman (Whatm
an ) /7: 2.5 inch (6,3
5crn) of the modified polymer obtained in the example.
It is treated with an aqueous solution containing 10% by weight to give a polymer film deposit of about 0.1y when dried at room temperature. The test is carried out by taking approximately 2 years of an aqueous solution of the modified polymer and dropping it onto the entire side of a circular piece of f-paper moistened with water. Dry the saturated paper overnight at room temperature and weigh.

Depending on the concentration of the solution, each paper is treated with substantially the same amount of polymer until the weight gain is about 0.1 no.
The above operation may be repeated. The drying paper was sealed over the opening of a test cell containing 100F water and heated at 40% relative humidity for 7 hours.
Leave it in a constant humidity greenhouse for 100 hours at below 0°C (21.1°C). The weight of water passing through the p-paper under such conditions is determined by weighing the amount of water remaining in the test cell. Each test employs a control test cell sealed with the same single paper material that is not treated with the polymer. Assuming that the weight loss (transpiration water content) of such untreated paper is 100, the reduction rate of water evaporation is calculated from the amount of water remaining in the cell. Such a paper test provides a rough indication of the moisture effect for further testing on animal skin.

When the modified polymers made in Examples 1-7 were screened in the moisture barrier test described above, they exhibited evaporation reductions of 35 to about 50%. These values are well comparable to the 40-50% values obtained with unmodified polyvinyl alcohol films.

Among these, the one of Example 3 gave an evaporation reduction rate of 48%. In an in vitro test on animal skin coated with 5% by weight of the modified vinyl alcohol polymer of the present invention, it was found that Results comparable to unmodified polyvinyl alcohol films in terms of water vapor transmission (WVT) were obtained. For example, when testing the stratum corneum with 5 tympanic films of the polymer prepared in Example 3, unmodified PVA (molecular t = 126,000
) compared to a water vapor transmission reduction rate of 66.7 cm.
A water vapor transmission reduction rate of 22% is obtained.

Such films can be applied to the skin surface without adversely affecting elasticity. For example, the modified polymer obtained in Example 3 had a film coverage of 11 when subjected to thermomechanical analysis after application to pig skin at a film coverage of 5.
It gives a value of 4, compared to petroleum jelly which gives a maximum elasticity of 28.

The polymers of this invention can be modified to control film-forming and formulation properties over a wide range, depending on the molecular weight of the PVA, the concentration of quaternary nitrogen, and the concentration of lipophilic groups attached to the PVA base. The exact hydrophilicity/oleophilicity ratio to achieve the balance of water retention, film properties, skin retention, wash removability and compoundability of the polymers of the present invention can be determined experimentally. In general, modified PVA polymers with a high ratio of polyalkylene:quaternary groups in the side chains are more lipophilic and less sensitive to moisture, whereas modified PV polymers with high concentrations of nitrogen-containing side groups
The A polymer becomes more hydrophilic and therefore easier to distribute in systems containing high total concentrations of water, glycerin, or other hydrophilic substances. There is no upper limit to the molecular weight of PVA that can be used to make the modified polymers of this invention. It has been found that, generally at molecular weights of a few thousand and above, the film properties of modified PVA are good enough to give a viable product. Molecular weight 2
00.000 or more has excellent film properties and can be preferably used in the practice of the present invention.

However, the practical unavailability of such raw materials and high working viscosities make such molecular weight materials somewhat less interesting.

Some of the products of the invention can be both moisture barriers and polymeric surfactants, so they can be formulated with or without low molecular weight surfactants in a variety of compositions. There is. The choice of surfactant will depend on the specific formulation and properties desired and will depend on the molecular weight of the PvA, the quaternary nitrogen content, the proportion of lipophilic side chains in the polymer, and the It depends on the desired oil or moisture concentration. With these experimental parameters and guidelines, a wide variety of formulations can be made utilizing the polymers of this invention. Examples of such applications include, for example, soap formulations; skin products; vehicles for pigments, powders, dyes, etc. in cosmetic formulations;

The modified polymers of the present invention are biocides, fungicides; light-blocking (light-absorbing) agents; and other biologically or chemically active substances that protect sunburned skin from moisture loss or fungal infection in film or granular form. It can also be used as a vehicle for inclusion in formulations.

Traditionally, unmodified polyvinyl alcohol has been used with limited success in film-forming ointment pastes and creams used to protect the skin from the effects of external stimuli. (J
, B. Ward and G. J.

5perandio ; r Am
ericanPθ"rfumer and Cosme
tics J Volume 79 (1964) No. 53-5s3f
fl':l. Fill with polyvinyl alcohol.

It is difficult to produce lume-forming creams.

This is because their blending properties are poor and they form poor films, making them difficult to formulate. Lotions and creams made with polyvinyl alcohol are usually not cleansing, i.e., the in vitro films formed from ointments and lotions containing about 15% polyvinyl alcohol are slow to dry and have a greasy appearance. and become sticky,
Finally, it leaves behind a hard crusty film. Furthermore, PVA's good moisture barrier film is very difficult to remove from the skin as it is usually difficult to remove with soap and water.

The problems associated with the use of unmodified PVA in film-forming bases are that the modified polymers of the present invention are readily dispersible in water, scales, and compatible with typical lotion formulations, as well as the skin surface. This is substantially overcome by forming a soft, smooth film that dries quickly when applied to the surface of the substrate, retains its integrity over a long period of time, and is easily removable with soap and water. The comfort of the formulation was tested by applying a typical moisture barrier lotion formulation to the back of the hand and evaluating ease of application, feel on the skin,
This is done by making observations on drying time, film durability, ease of removal, and subjective factors.

In most cases, the formulations evaluated do not adversely affect the film forming properties of the modified polyvinyl alcohol polymers of the present invention.

Aqueous moisture barrier compositions according to the invention typically have the consistency of a lotion and may be in the form of an oil-in-water or water-in-oil emulsion. The former oil-in-water type is preferred because it has more satisfactory cosmetic properties. Preferably, the lotion is manufactured by first forming an oil phase, then forming an aqueous phase, and then adding the aqueous phase to the oil phase. Typically, the aqueous phase is heated to about 75-100°C and then added gradually to the oil phase (heated to about the same temperature) with stirring.

Oil phase components can include various materials such as emulsifiers, emollients, oils, waxes, fragrances, lanolin, polyalkylenes, stearol, and the like.

The aqueous phase components include a humectant, a modified polyvinyl alcohol moisture barrier agent of the present invention, proteins and polypeptides, a preservative,
It may contain many materials such as alkalinizing agents, thickening agents, flavoring agents, stabilizers, and disinfectants.

The skin conditioning lotions and ointments according to the invention may contain, as an essential ingredient, 1 to 15% by weight, preferably 05 to 5% by weight, of the modified polyvinyl alcohol polymer 'kO' according to the invention. The modified polyvinyl alcohol polymer can be added in the form of an aqueous composition or in the form of a dry powder.

The lotion may contain about 0.05% to 8%, preferably about 0.25% to 5%, of an emulsifier to emulsify its oil components. Typical emulsifiers include polyethoxylated fatty acids, such as polyethoxylated fatty acids, non-ethoxylated sugar esters, polyoxyethylene fatty ether phosphates, fatty acid amides, phospholipids, etc. in an amount of up to about 30 moles per mole of fatty acid.
selected from the group consisting of polypropoxylated aliphatic ethers, acrylates, polyethoxylated polyoxy7propylene glycols, polypropoxylated polyethylene glycols, polyoxyethylene, polyoxypropylene ethylene dimers, soaps and mixtures thereof.

Examples of such emulsifiers include polyoxyethylene (
8) Stearate, myristylethoxy (3) myristate, myristylethoxy (3) palmitate, methyl glucose sesquistearate, sucrose distearate, sucrose laurate, sorbitan monolaurate, polyoxyethylene (31 oleyl ether phosph) ate, polyoxyethylene (II oleyl ether phosphate, lauric acid jetinylamide, stearic acid monoethylamide, lecithin, lanolin alcohol propoxylate, sodium stearoyl-2-lactate, calcium stearoyl-2-lactate,
and Pluronics (trademark HBASF Wyan
dotte company). Examples of soaps such as alkaline metal or triethanolamine salts of long chain fatty acids include sodium stearate, triethanolamine stearate and similar salts of lanolin fatty acids. A preferred emulsifier is polyoxyethylene (2112f'71
It is J le ether.

Lotion formulation is an emollient (relaxant) gold 0.2-2
5 inches, often 1 to 8 inches (by weight).

One function of the emollient is to fractionate (disperse) the modified polyvinyl alcohol polymer sufficiently so that it forms a film on the surface of the skin. Typical emollients include fatty alcohols, about 24
branched-chain esters with a total number of carbon atoms of more than about 24 (e.g. cetearyl octoate), squalef, mixtures of fatty acids with liquid or solid paraffins,
and mixtures thereof. Examples of typical alcohols and fatty acids that may be used include cetyl alcohol, myristyl alcohol, stearyl alcohol, stearic acid, and valmitic acid.
Some have 2 to 22 carbon atoms. Examples of paraffins are mineral oil, petrolatum and paraffin wax.

Lotions and ointments are particularly stable and effective when adjusted to a pH of 6-8.

Because the polymers of the present invention have a high amine content, some of the polymers of the present invention may undergo degradation in sunlight or air to form products that impart an undesirable odor to the formulation. sell. To overcome this problem, small amounts of decomposition inhibitors should be added with the polymer. Examples of such decomposition inhibitors/antioxidants include nordihydroguaiaretic acid, citric acid, ascorbic acid, hydroquinone, butylated hydroxyanisole, butylated hydroxytoluene, and other suitable antioxidants. be.

The formulations below are illustrative of, but not limited to, formulations containing the modified polyvinyl alcohol film-forming moisture barrier polymers of the present invention. A typical lotion comprises the modified P of the present invention in an aqueous emulsion.
0.1-5.0% VA polymer, 2% aliphatic alcohol
~5% and 2-5% emulsifier.

Example A An aqueous solution containing 0.5 Pa of modified polyvinyl alcohol polymer prepared according to Example 4 was diluted with water to give 2.41
! of cetyl alcohol, 1.6y of stearyl alcohol and 3.0y of polyoxyethylene 0υ stearyl ether (trademark BRIJ721J of IC Eamerica, Inc.)
emulsifier). Further water was added to make the water concentration 92.5%.

After stirring at 75° C. for about 5 minutes, the resulting emulsion was allowed to cool to room temperature and stored. A makeup comfort test was conducted by applying this lotion to Kaneko and the back of the arm. It gave a smooth, silky feel, had a drying time of less than 15 minutes and a film durability of more than 2 days.

Residual film and lotion could be easily removed from the skin with soap and water.

As mentioned above, the polymers of the invention have advantageous properties which allow them to be used for preparing cosmetic formulations in the form of direct use or diluted concentrates. Cosmetic formulations can therefore contain the modified PVA polymers of the invention from 0.01 to
15% by weight. Solutions of modified PVA polymers of the present invention (alone or with other active ingredients) are particularly useful when applied to hair during shampooing, shampooing, etc. The modified PVA polymers of the present invention significantly improve hair quality. When used in hair treatment, modified PVA polymers promote the detangling action of wet hair and do not leave a sticky residue on dry hair. In some cases, modified PVA polymers are believed to provide dry hair with increased longevity, softness, shine, and anti-tangle properties.

Hair treatment formulations containing rehydrating, alcoholic or dilute alcoholic solutions of modified PVA polymers can be used. Furthermore, the modified I'VA polymers can be used as IJ-mes, lotions, gels or aerosol sprays.

Modified PVA polymers can be used in combination with perfumes, dyes, preservatives, sequestrants, thickeners, emulsifiers, and the like.

Example B 5 y of the modified polymer of Example 8, 7 y of cetyl alcohol, 7 y of cicada-like polyoxyethylated C+ o -CIa aliphatic alcohol 3 y, 1 casein derivative 2 y, 0.55 E of tetradecyltrimethylammonium chloride and 82.5 y of water.
Typical hair conditioner formulations containing , as well as trace amounts of hair dye, can be used to treat the hair, giving it an improved appearance and antistatic properties.

Example C 2.5f of modified polymer of Example 9, 1 part of benzyl alcohol
0y, oleic acid 20f, polyoxyethylene (to) oleocetyl alcohol 3y, oleic acid jetanolamide 7y, 2-octyldodecanol 7.5F, lauric acid triethanolamine sa/L'7: r--t2.
5p, ethanol 10P11 ammonia water 18M/,N
, N-bis(2-hydroxy-ethanol)paraphenylenediamine 1y russorcin 0.4F, hydroquinone 0.1y, ethylenediamine tetracetate 0.245
E, m-amine phenol 0.15F, alpha naphthol 0.4F, sodium bisulfate 1 mA' and the whole x
A typical oxidized hair dye solution containing 130F of water in an amount of It forms a composition. The hair treated with the hair dye obtained in this way is
It is believed that leaving the hair for 0 minutes and then rinsing it again will easily detangle the hair and give it a silky feel.

The modified polyvinyl alcohol polymers of the present invention are used to improve the comfort and stability of cosmetic products such as liquid and bar soaps, shaving creams, bath products, antiperspirants, sunscreens, and cleansing creams. It can also be used as a suspending agent for insoluble pigments and medicinal ingredients. When the modified PVA polymers of the present invention are used in 0.5 to 5% by weight conventional formulations (see examples below), improvements are generally observed.

Examples A portion of the aqueous solution obtained in Example 3 (i.e., aliphatic alcohol-modified quaternized polyvinyl alcohol) was added to 0.5F
4. OPQ stearic acid, 2
．． 5. Oji's polyoxyethylene 0υ stearyl ether (ARLAMOL: Trademark of Koch America, Inc.); 5.
OF's glycerol monostearate and polyoxyclef stearate) (ARLAC of XC Air America, Inc.)
KL: Trademark) and 10. OF was added to an aqueous solution containing a 70% sorbitol solution (trademark 5ORBO of Industrial Chemistry America, Inc.).

After stirring at 75° C. for about 5 minutes, the emulsion was allowed to cool to room temperature and stored. When this lotion was applied to the hands and backs of arms to test its cosmetic comfort, it gave a clean, silky feel, took less than 15 minutes to dry, and the film was durable for more than 2 days. Ta. The residual film and lotion are easily removed from the skin with soap and water.

Example E Ingredients % (w/w) Example 3 Polymer 40 Water (deionized) 34.76 T)owicil 200 (trademark: Dow Chemical Company) 0
．． 1”zr f)5popvpa4 YV71x-0”7
・57. □4Rezol 36G (Reheis) Example F Aerosol type shaving ream Ingredients % (w/w) Example 3 Polymer 5,0 Cetyl alcohol 4.3 Polyoxyethylene (2) stearyl ether 22 Sorbic acid 0・17 Water 74.9 Air freshener 0.08 Water 13.35 Example G Oil-in-water type sunscreen lotion ingredients Ch (w/w) Mineral oil 18.8 Cetyl alcohol 5.0 ArlOcel 60 (trademark) ) Emulsifier 2.5rwee
n 60 (trademark) Emulsifier 7.5 Amyl para-dimethylaminobenzoic acid 1,2 Example 4 Polymer 2.0 Water 63.0 Preservative appropriate amount Example H Ingredients (w/w) Mineral oil 10 Beeswax 1 .5 Oevesin Wax 1.0 Arlac
el 186 (trademark) emulsifier 3.2 Sorbo (trademark) nlubitol 28.8 Tie2 and other pigments 20.0 Water 33.5 Example 6 polymer 2.0 Example ingredients Blend amount Carmine 80 Zinc white 805j Bentonite magma 250a+/ Incorporated (5 others) Continued from page 1 ■Int, CI,' Identification code Internal reference number 0 Inventor George Keikuichi φ United States of America Delitatus Yamplain Abbey State 19804. Wilmington, Chinew 81
5

Claims (1)

[Scope of Claims] (1) The following general formula % Formula % (R is a group selected from an alkylene group, a substituted alkylene group, or an acylene group, and R1l R2+ R3 is an alkyl group having 1 to 20 carbon atoms) or an arylalkyl group, where R4 is an alkyl group; an alkylaryl group; or a substituted alkyl, alkylaryl, or arylalkyl group having a hydroxy or carboxyl group, or a combination of a hydroxy group and a carboxyl group; A is an anion, and A is an anion, and A is an anion. is 0. O1-7.0% by weight
A modified polyvinyl alcohol polymer useful in skin conditioning, cosmetic and pharmaceutical formulations. (2) Polyvinyl alcohol base silver is 2,000 to 2
A polymer according to claim 1 having a number average molecular weight within the range of 00.000. (The total amount of all 31R4 groups is 0.5 of the polymer.
50% by weight of a polymer according to claim 1. (4) [-RNR, total formula valuable amount of all R2 groups]: (
The polymer according to claim 1, wherein the ratio of -RN+R,R2R3A total formula weight of the fund part is in the range of 0 to 90M. (5) R is -(!H, -CHOH-OH2 and -[a
H2aH(aH2NR,R2R3A)O]. CH20
H(OH)CH2- [R1, R2 and R3 are alkyl or arylalkyl groups having 1 to 20 carbon atoms, A- is a halogen ion or (lower alkyl) S04, θ = 1 to 20] A polymer according to claim 1 selected from the group consisting of: (6) (a) The group is -COC! H2N R, R2R3A
The polymer according to claim 1, which is (7) The side chain groups -R, -NR, R2 are -CH2CHOH-0H2NR, R, and [nee0H2
cJcH2NR,R2)-o]cH2-aH(oH)-
OH2N R, R2 (where R and R2 are alkyl or arylalkyl groups containing 1 to 20 carbon atoms, and θ=1-
20). The polymer according to claim 1, which is selected from the group consisting of: (8) Side chain group -R-NR,R, is -GOOL-121
, IR, R2, wherein R and R2 are alkyl or arylalkyl groups having from 1 to 20 carbon atoms. (9) R1, R2 and R3 are -OH3, -CH20H3
The polymer according to claim 1 selected from the group consisting of ゜-CH20H2G)(3,-(J(-(3H, or -〇H, Ph (herein, ph is a phenyl group) . R4 is 1,9-dihydroxydioctadecane and 1,1
A polymer according to claim 1 selected from the group consisting of 0-dihydroxydioctadecane. αυ -R is octadecanoic acid, 9-hydroxyoctadecanoic acid, lO-hydroxyoctadecanoic acid, 9.10-
A polymer according to claim 1 selected from the group consisting of dihydroxydioctadecanoic acid and salts or esters thereof. (1211,9- or l,10-Dihydroxydioctadecane has one or both hydroxy groups via oxygen of the general formula -R-NR,R, and/or -R-N+R,
9. A polymer according to claim 9, which is bonded to the group R2R3A (R, R, , R2, R, and i as defined in claim 1). (13) The polymer according to claim 5, wherein R4 is selected from the group consisting of 1,9-dihydroxydioctadecane and 1,10-dihydroxydioctadecane. One or both hydroxy groups of the dihydroxydioctadecane are bonded via oxygen to a group selected from the general formula % (R8 and i are as defined in claim 1). The polymer according to claim 13. (15) R4 is -C-(CH2)7CH=CH-(CH2), -cl(
3. The polymer according to claim 1, selected from the group consisting of 3 and 3. Some or all of the hydroxy groups on ue R4 valve oxygen to form -R-NR, R, and/or -R-NR,
RtR, A group (R* RI + R2r RR and i
(as defined in Claim 1). C7) Some or all of the hydroxyl groups on the -R4 side chain groups may be substituted with oxygen to form -RNR, R2 and/or -R
N+R, R2R3A- group (R, R,, R,, R3 and A
- is as defined in claim 1)). The polymer according to claim 1, wherein αS RI IR2 and R8 are methyl groups, and the nitrogen content is 0.05 to 3% by weight. tiIfal Equimolar amounts of epichlorohydrin and trimethylamine aqueous solution are reacted at a temperature of 25°C or less; (
b) number average molecular weight 2, containing a catalytic amount of potassium hydroxide;
000 to 200,000 polyvinyl alcohol in water; (C) Step @ the solution obtained in step (a) and step (b)
and (dl alkyl epoxy compound or -4-substituted alkyl epoxy compound) with the product obtained in step (C1) at a temperature of 40 to 90°C;
Mixing at 30-90<0>C; Polymer according to claim 1 made by steps. υ fa) reacting an alkyl epoxy compound or a substituted alkyl epoxy compound with an aqueous solution of polyvinyl alcohol having a number average molecular weight of 25,000 to 150,000 containing a catalytic amount of potassium hydroxide at a temperature of 30 to 90°C; b) Reacting epichlorohydrin with an aqueous trimethylamine solution at a temperature of 25°C or lower - (c) Step (-
A polymer according to claim 1 made by the steps of: reacting the product of step 8(b) with the product of step 8(b) at a temperature of 40 to 90<0>C. eυ (a) (chlorohydroxypropyl)trialkylammonium chloride in aqueous solution or crystalline state is dissolved in the presence of a catalytic amount of potassium hydroxide to 2,000
and (b
1. A polymer as claimed in claim 1 made by the steps of reacting the water bath liquid of step (a) with an alkyl epoxy compound at a temperature of 30 to 90<0>C. c! c ta) Alkyl epoxy compound or substituted alkyl epoxy compound with a number average molecular weight of 2,000 to 2
00,000 polyvinyl alcohol water bath solution at 30-90°C in the presence of a catalytic amount of potassium hydroxide;
and tb+ reacting the product of step (a) with (chlorohydroxypropyl)trimethylammonium chloride in aqueous solution or crystalline state at a temperature of 40 to 90°C; Polymers described. I231 fat 25,000~15 U,000 number average molecular weight solution of polyvinyl alcohol, 2,
A catalytic amount of 3-epoxyprobyltrialkylammonium noride was added to the water bath solution in an amount such that the molar ratio of the ammonium nolide per mole of hydroxyl group of the polyvinyl alcohol was 0.003 to 1. (b) reacting the product of step (a) with the alkyl epoxy compound at a temperature of 30 to 90°C; claims made by the steps; The polymer according to item 1. (24) (al Alkyl epoxy compound or substituted alkyl epoxy compound, 25,000 to 150,0
a polyvinyl alcohol aqueous solution with a number average molecular weight of 00;
react to completion in the presence of a catalytic amount of potassium hydroxide at a temperature of 30-90°C; and (b) 2°3-eboxyglobil triplekylammonium halide in step (
The molar ratio of the product of a) to the ammonium halide per mole of hydroxyl group of the polyvinyl alcohol is 0.
．． Polymers according to claim 1, prepared by a process of reaction in the presence of a catalytic amount of base at a temperature of 40 to 90°C in an amount such that 003 to 1. 4 la) polyvinyl alcohol with a number average molecular weight of 25,000 to 150,000 and trimethylethoxycarbonylmethylammonium halide in the presence of a catalytic amount of magnesium acetate in a dipolar aprotic solution.
and (b) reacting the product of step (1)) with the alkyl epoxy compound or the substituted alkyl epoxy compound in an aqueous reaction medium; The polymer according to item 1. @(al) Polyvinyl alcohol having a number average molecular weight of 25,000 to 150,000 is reacted with an alkyl epoxy compound in an aqueous solution containing a catalytic amount of alkaline hydroxide; and (1)) Step (product of al) and trimethylethoxycarbonylmethylammonium halide in a dipolar aprotic solution in the presence of a catalytic amount of magnesium acetate at a temperature of 70 to 150°C; Polymer. +27) According to claim 21 or 22, the ammonium nolide is (chlorohydroxypropyl)trimethylammonium chloride, and the alkyl epoxy compound is 9,10-epoxyoctadecane-1-ol. polymer. (to) Claim 23 or 24, wherein the ammonium nolide is 2,3-epoxypropyltrimethylammonium chloride, and the alkyl epoxy compound is 9,10-epoxyoctadecane-1-ol.
Polymers described in Section. (2I A polyvinyl alcohol polymer having a number average molecular weight of 25,000 to 150,000, 9,10-epoxyoctadecanol and 2,3-epoxypropyltrialkylammonium halide, [total number of moles of both epoxy compounds] : [Polyviny A/7/L/Near-
The ratio of the number of moles of combined hydroxyl groups is 000
40 to 1 in the presence of a catalytic amount of acid in an amount such that 3 to 1
A polymer according to claim 1 made by reacting at a temperature of 90°C. (7) The polymer according to claim 1, which has been prepared by dialysis or ultrafiltration in an aqueous solution. C (11) 0.1% of the polymer described in claim 1
Aqueous dispersion containing ~30% by weight. Country 1 to 5% by weight of the polymer tube described in claim 1, 2 to 5% by weight of an emulsifier, and 2 to 5% by weight of a skin softener.
An aqueous skin conditioning composition containing 5% by weight. +3:i The polymer according to claim 1 is added to 0.
An aqueous hair conditioning composition containing 1 to 5% by weight. (0.5% of the polymer described in claim 1)
Cosmetic compositions containing ~5% by weight. 61 The polymer according to claim 1 has a concentration of 0.5 to
A pharmaceutical composition comprising 5% by weight. (g) The following general formula % formula % (where R is selected from the group consisting of an alkylene group, a substituted alkylene group, or an acylene group, and RI and R2 are 1 to
a plurality of side groups selected from the group consisting of alkyl or arylalkyl groups having 20 carbon atoms,
consisting of polyvinyl alcohol base silver bonded via oxygen and with a total nitrogen content of 0.01 to 7% by weight, for use in skin conditioning, cosmetic and pharmaceutical formulations. Amine-modified polyvinyl alcohol polymer. A modified polymer according to claim 1, wherein the C371 polyvinyl alcohol is a copolymer containing up to 25 volumes of vinyl acetate, vinyl acrylate, vinyl methacrylate and vinyl pyrrolidone.