JP2908555B2 - Cationic gel base - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a cationic gel base material. More specifically, the present invention relates to a cationic gel base material that can be suitably used for cosmetics, fragrances, and the like.

[Prior art] Research on gel base materials has been conducted for a long time.
A gel base comprising an alkali neutralized salt of a polyacrylic acid crosslinked polymer described in JP-B No. 32-4141 and JP-A-51-46586 is known as a representative one.

 However, the gel base material is -COO Base polymer
-COO Part or all of the group is NaOH, KO
Anionic poly obtained by neutralization with H, amines, etc.
Is used as a base resin.
Cosmetic materials for hair, such as
It is difficult to add. For example, 4
Addition of cationic setting polymer containing secondary amine
When added, these anionic polymers and cations
Neutralization of charge occurs between polymer for system setting,
May cause agglomeration, clouding or smelling. But
Thus, the setting polymer that can be added is polyvinyl.
Pyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer
Nonionic setting polymer for body, acrylic tree
Anionic cell represented by fatty alkanolamine liquid
Only the setting polymer. In addition, the gel base material
Aqueous cosmetics are used to form a hard film after drying.
Because it forms
When used as a film, a film formed on the hair
Peeling phenomenon, that is, the so-called flaking phenomenon
As a result, its use was limited.

On the other hand, as a gel base material that forms a soft and flexible film after drying, there is known a gel base material obtained by subjecting a crosslinked base monomer having an amino group to aqueous emulsion polymerization and adjusting the pH value thereof ( JP-A-57-133145), the crosslinked base monomer having an amino group is
It is easily hydrolyzed, and when hydrolyzed, it is neutralized by an acid treatment performed later to introduce a cationic group, and an anionic group and a cationic group coexist in the same polymer molecular chain. May not be a uniform cationic polymer. Further, when N, N-dimethylaminoethyl methacrylate is used as a raw material monomer in the gel base material, a hydrolysis reaction occurs violently during the polymerization reaction, and a desired polymer cannot be obtained. This means
In other words, the N, which is widely used industrially and is known to have excellent characteristics as a raw material for cosmetics
It means that N-dimethylaminoethyl methacrylate cannot be used, which means that it is very disadvantageous in selecting a raw material monomer for a gel base. In addition, there is a drawback that impurities such as surfactants cannot be avoided from being mixed due to the nature of emulsion polymerization.

[Problems to be Solved by the Invention] In view of the above conventional art, the present inventors can blend a cationic setting polymer,
After drying, a flexible film was formed, and as a result of intensive studies to obtain a gel base material with a small amount of impurities, a cationic gel base which satisfies all of these physical properties and can be suitably used for the gel base material. We finally found the material and completed the present invention.

[Means for Solving the Problems] That is, the present invention provides (A) a general formula (I): (Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each represent a methyl group or an ethyl group, and A represents a linear or branched alkylene group having 1 to 4 carbon atoms). (Meth) acrylic acid ester, (B) general formula (II): (Wherein m represents 3 or 4) and (C) 1,10-decanediyl diacrylate, 1,10-decanediyl dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , Pentaerythritol triacrylate, pentaerythritol trimethacrylate,
Trimethylol ethane triacrylate, trimethylol ethane trimethacrylate, trimethylol propane triglycidyl triacrylate, trimethylol propane triglycidyl trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, methylene bis acrylamide, methylene bis methacrylamide, 1 , 2-bisacrylamidoethane, 1,2-bismethacrylamidoethane,
1,5-bisacrylamidopentane, 1,5-bismethacrylamidopentane, 1,10-bisacrylamidododecane, 1,10-bismethacrylamidododecane, 1,1-bisacrylamido-1-phenylethane, 1,1- Bismethacrylamide-1-phenylethane, divinylbenzene, 1,2-bis (p-vinylphenyl) ethane, 1,3-bis (p-vinylphenyl) propane, 1,4-bis (p-
At least one selected from vinylphenyl) butane, 2,2-bis [4- (acryldiethoxy) phenyl] propane and dipentaerythritol hexaacrylate
The present invention relates to a cationic gel base comprising a copolymer obtained by polymerizing a kind of crosslinkable polyvinyl compound.

[Action and Examples] As described above, the cationic gel base material of the present invention comprises: (A) a general formula (I): (Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each represent a methyl group or an ethyl group, and A represents a linear or branched alkylene group having 1 to 4 carbon atoms). (Meth) acrylic acid ester, (B) general formula (II): (Wherein m represents 3 or 4) and (C) 1,10-decanediyl diacrylate, 1,10-decanediyl dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , Pentaerythritol triacrylate, pentaerythritol trimethacrylate,
Trimethylol ethane triacrylate, trimethylol ethane trimethacrylate, trimethylol propane triglycidyl triacrylate, trimethylol propane triglycidyl trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, methylene bis acrylamide, methylene bis methacrylamide, 1 , 2-bisacrylamidoethane, 1,2-bismethacrylamidoethane,
1,5-bisacrylamidopentane, 1,5-bismethacrylamidopentane, 1,10-bisacrylamidododecane, 1,10-bismethacrylamidododecane, 1,1-bisacrylamido-1-phenylethane, 1,1- Bismethacrylamide-1-phenylethane, divinylbenzene, 1,2-bis (p-vinylphenyl) ethane, 1,3-bis (p-vinylphenyl) propane, 1,4-bis (p-
At least one selected from vinylphenyl) butane, 2,2-bis [4- (acryldiethoxy) phenyl] propane and dipentaerythritol hexaacrylate
It is composed of a copolymer obtained by polymerizing various kinds of crosslinkable polyvinyl compounds.

The (meth) acrylic acid ester represented by the general formula (I) has a role of imparting an electrolytic ability to the copolymer by neutralizing with a suitable acid when obtaining the desired copolymer in the present invention. Component. Representative examples of such (meth) acrylates include, for example, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate and the like. However, the present invention is not limited only to such an example. In the present invention, the (meth) acrylate is used alone or in combination of two or more.

The composition ratio of the (meth) acrylate in the monomer constituting the copolymer is adjusted to 15 to 85% (% by weight, the same applies hereinafter), and preferably 30 to 60%.
When the composition ratio of the (meth) acrylic ester is less than 15%, the amount of the (meth) acrylic ester portion neutralized by the acid in the obtained copolymer is so small that it is insufficient. If the gel base exceeds 80%, the flexibility of the film formed after the obtained gel base material is dried will be lost.

The vinyl monomer represented by the general formula (II) has flexibility in a film formed after the gel base material is dried,
It is a component that gives gloss and smoothness.

Representative examples of such vinyl monomers include, for example, N
-Vinylpiperidone, N-vinylpyrrolidone and the like, but the present invention is not limited only to these examples. In the present invention, the vinyl monomers are used alone or in combination of two or more.

The composition ratio of the vinyl monomer in the monomer constituting the copolymer is adjusted to be 0 to 80%, preferably 20 to 60%. The composition ratio of such vinyl monomer is 80%
If the amount exceeds the above range, the gel strength of the obtained gel base material will be significantly reduced.

The crosslinkable polyvinyl compound is a compound having two or more carbon-carbon unsaturated double bonds in one molecule and having a property of crosslinking with another monomer, and is 1,10-decanediyl diacrylate. 1,1,10-decanediyl dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triglycidyl tri Acrylate, trimethylolpropane triglycidyl trimethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethanetetramethacrylate, methylenebisacrylamide, Bismethacrylamide, 1,
2-bisacrylamidoethane, 1,2-bismethacrylamidoethane, 1,5-bisacrylamidopentane, 1,5-
Bismethacrylamidopentane, 1,10-bisacrylamidododecane, 1,10-bismethacrylamidododecane,
1,1-bisacrylamide-1-phenylethane, 1,1-
Bismethacrylamide-1-phenylethane, divinylbenzene, 1,2-bis (p-vinylphenyl) ethane,
Selected from 1,3-bis (p-vinylphenyl) propane, 1,4-bis (p-vinylphenyl) butane, 2,2-bis [4- (acryldiethoxy) phenyl] propane and dipentaerythritol hexaacrylate At least one of them.

The composition ratio of the crosslinkable polyvinyl compound in the monomer constituting the copolymer is 0.1 to 20%, preferably 1 to 1%.
Adjusted to be 0%. When the composition ratio of the crosslinkable polyvinyl compound is less than 0.1%, the strength of the obtained gel base material becomes too small, so that it is impossible to increase the viscosity of the gel itself, and 20% If this is exceeded, the viscosity of the gel itself will increase, but fine aggregates may form in the gel.

The polymerization of the (meth) acrylate, the vinyl monomer and the crosslinkable polyvinyl compound is carried out while heating in a non-aqueous solvent under an atmosphere of an inert gas such as nitrogen gas.

In the present invention, the reason why the polymerization reaction is carried out in a non-aqueous solvent under an inert gas atmosphere is to prevent the ester group present in the monomer or the formed copolymer from being hydrolyzed.

In the present invention, a mixed solvent of a good solvent and a poor solvent is used as the non-aqueous solvent.

The reason why a good solvent is used in the present invention is to suppress the formation of a homopolymer due to the difference in reactivity of each monomer and to obtain a uniform copolymer.

In the present specification, the good solvent is a mixture of a (meth) acrylic acid ester represented by the general formula (I) and a vinyl monomer represented by the general formula (II) at 25 ° C. with respect to 100 ml of the good solvent. A solvent in which a copolymer having a molecular weight of 10,000 or more dissolves in a range of 20 g or more and does not show turbidity. Specific examples of the good solvent include methanol, ethanol, isopropanol, acetone, chloroform, ethyl acetate, benzene, toluene, xylene and the like. Among these good solvents, ethanol, isopropanol, and benzene are particularly preferable because they can produce a polymer having a relatively high molecular weight. The ethanol may be ethanol having a purity of 95% by volume or more.
Ethanol in volume% or more is preferred. In the case where the gel base material of the present invention is used for cosmetics and the like, ethanol and isopropanol are most preferable because benzene and the like are harmful.

The reason why the poor solvent is used in the present invention is to precipitate the produced polymer from the polymerization solution.

In the present specification, the poor solvent refers to a mixture of a (meth) acrylic acid ester represented by the general formula (I) and a vinyl monomer represented by the general formula (II) with respect to 100 ml of the poor solvent at 25 ° C. A solvent in which a copolymer having a molecular weight of 10,000 or more dissolves in a range of 5 g or less. Specific examples of the poor solvent include linear, branched or cyclic aliphatic hydrocarbons having 15 or less carbon atoms, such as n-pentane, n-hexane and cyclohexane. Among these poor solvents, linear, branched or cyclic aliphatic hydrocarbons having a relatively high boiling point and 7 or less carbon atoms are preferred. Among them, straight-chain, branched-chain or cyclic aliphatic hydrocarbons having 6 or 7 carbon atoms are particularly preferable because of their high boiling points. Further, n-hexane, cyclohexane and the like are preferable from the viewpoint that they are industrially inexpensive and have good handleability.

In order to synthesize a gel base material without deteriorating the properties of the obtained gel base material, the good solvent and the poor solvent must be blended in an appropriate ratio, for example, using the good solvent and the poor solvent alone. If so, the object of the present invention is not achieved.

The mixing ratio of the good solvent and the poor solvent is preferably adjusted so that the ratio of the good solvent / the poor solvent (weight ratio) is 2/98 to 20/80, especially 3/97 to 10/90. When the ratio of good solvent / poor solvent (weight ratio) is less than 2/98, polymerization starts immediately and powder is precipitated in a short time to obtain a gel base material having desired physical properties. If it exceeds 20/80, powdering for improving copolymerizability does not proceed, and coagulation and solidification is likely to occur during removal of the solvent after polymerization.

In order to efficiently obtain the gel base material from the reaction solution, a reaction device for improving the kneading state during polymerization is required. When a stirrer for solution polymerization generally used as such a reaction apparatus is used, the concentration of the total amount of the monomers is preferably 30% or less. At the time of the reaction, it is preferable to sufficiently stir the mixture with a stirrer or the like so that the reaction solution does not stay.

The polymerization reaction is preferably carried out under heating at 50 to 100 ° C., and is generally carried out at the reflux temperature of the volatile solvent used in the reaction.

The time required for the polymerization reaction is usually 10 hours or more. The polymerization reaction can be arbitrarily completed when the amount of the remaining monomer becomes 10% or less. In addition, the amount of the remaining monomer can be determined by, for example, adding sulfur to the double bond by a known method such as the PSDB method and measuring the double bond content.

Thus, a reaction solution containing the precipitate of the gel base material is obtained.The mixed solvent may be removed, for example, by filtering the obtained precipitate of the gel base material, followed by vacuum drying, or under normal pressure or reduced pressure. By distillation.

In the polymerization reaction, a polymerization catalyst may be used. Such polymerization catalysts include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2 '
Azobisisobutyrate, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide,
Examples include diisopropyl purge carbonate and t-butyl perisobutyrate. The type of the polymerization catalyst varies depending on the boiling point of the solvent used. For example, when ethanol or benzene is used, 2,2'-azobisisobutyronitrile is the most preferable because of its good handleability. The amount of the polymerization catalyst used is 0.05-3%, preferably 0.1-1%, based on the total weight of the monomers.

In the process of polymerizing the monomer, various aspects are exhibited.

At the beginning of the polymerization reaction, the appearance is similar to that of a general solution polymerization, but the crosslinking reaction proceeds with the progress of the reaction, and the gel is formed. As the reaction further proceeds, the obtained gel base material can no longer be dissolved in the mixed solvent, and is insolubilized and precipitates as a precipitate.

Thus, a gel base material is obtained, and the gel base material is mixed with raw materials for various cosmetics as it is,
Or it is used by making it into a gel.

When the gel base is used as a gel, for example, the content of the gel base is usually adjusted to a desired viscosity at 2% or less.

When a gel is prepared using the gel base material, for example, sulfuric acid, hydrochloric acid, mineral acids such as phosphoric acid, acetic acid,
It is preferable to neutralize the gel base material after diluting the gel base material to 2% or less with water using an organic acid such as citric acid, lactic acid, amino acid, succinic acid, malic acid, dimethyl sulfate or diethyl sulfate as a neutralizing agent. .

Next, the cationic gel substrate of the present invention will be described in more detail based on Examples, but the present invention is not limited to only these Examples.

Example 1 N, N-dimethylaminoethyl methacrylate 120 was placed in a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen inlet tube.
g, 180 g of N-vinylpyrrolidone and 7.5 g of methylenebisacrylamide in a 20% ethanol / cyclohexane mixed solvent (mixing ratio (weight ratio) = 7/93), and refluxed at 80 ° C. while flowing nitrogen gas. And degassed by stirring for 2 hours.

Next, 0.9 g of 2,2'-azobisisobutyronitrile was added to the three-necked flask, and polymerization was started at 80 ° C. The reaction solution became cloudy 10 minutes after the initiation of polymerization, and a precipitate was formed after a lapse of 10 minutes. About 10 hours after the start of mixing, the reaction was completed. Elemental analysis of the obtained gel base material was performed. The results are shown below.

(Measurement results of elemental analysis) Calculated value: C63.14, H8.69, N11.3 (%) Measured value: C63.52, H8.91, N11.55 (%) Next, the gel base material obtained Was added to water to form a 2% aqueous slurry solution, the pH was adjusted to 6.4 using lactic acid as a neutralizing agent, and the mixture was sufficiently kneaded with a homogenizer to obtain a gel (viscosity (20 ° C.): 1000 P). The physical properties of the obtained gel were examined, and the appearance and flexibility of the formed film were examined based on the following methods. Table 1 shows the results.

(A) Texture The texture was examined by rubbing the obtained gel with about 2 ml of the finger, and evaluated based on the following evaluation criteria.

(Evaluation criteria) ：: Smooth and light texture ○: Smooth texture △: Slightly rough ×: Smoothness is noticeable (b) Appearance The obtained gel is visually observed to see if there is any contamination with impurities. The evaluation was performed based on the evaluation criteria described above.

(Evaluation Criteria) 不純 物: No contamination of impurities was observed. ○: Very slight contamination of impurities was observed. △: Mixing of impurities was slightly observed. ×: Mixing of impurities was noticeable. (C) Flexibility of formed film. The gel was coated on a vinyl chloride film with a bar coater to a thickness of 10 μm using a bar coater, air-dried for 3 hours to form a film, and the state of the formed film when the vinyl chloride film was randomly bent was examined. The evaluation was made based on the following evaluation criteria.

(Evaluation criteria): No change is observed ○: Very slight peeling is observed △: Partial peeling is observed ×: Complete peeling is observed Example 2 Thermometer, reflux tube and nitrogen inlet tube N, N-dimethylaminoethyl methacrylate 1 in a three-necked flask equipped with
20 g of 18 g of 2,2-bis [4- (acryldiethoxy) phenyl] propane and 180 g of N-vinylpyrrolidone
% Ethanol / cyclohexane mixed solvent (mixing ratio (weight ratio) = 7/93) was added, and the mixture was stirred for 2 hours under a nitrogen stream while refluxing at 80 ° C to be degassed.

Next, 0.9 g of 2,2'-azobisisobutyronitrile was added to the three-necked flask, and polymerization was started at 80 ° C. After a lapse of 30 minutes from the start of the polymerization, the reaction solution became a gel and became a uniform slurry solution as the polymerization proceeded.

About 2 hours after the start of mixing, a powdery substance starts to form,
The reaction was completed after about 10 hours.

Elemental analysis of the obtained gel base material was performed. The results are shown below.

(Measurement results of elemental analysis) Calculated value: C63.98, H8.63, N10.5 (%) Actual measured value: C67.32, H8.99, N10.35 (%) A gel (viscosity (20 ° C.): 1750 P) was prepared in the same manner as in Example 1, and the physical properties of the gel were examined in the same manner as in Example 1. Table 1 shows the results.

Example 3 3.75 g of pentaerythritol triacrylate (Viscoat ^# 300 manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used in place of 2,2-bis [4- (acryldiethoxy) phenyl] propane used in Example 2. A gel base material was obtained in the same manner as in Example 2 except for using.

Elemental analysis of the obtained gel base material was performed. The results are shown below.

(Measurement results of elemental analysis) Calculated value: C63.29, H8.72, N10.99 (%) Actual measured value: C63.53, H9.01, N10.79 (%) Next, the gel base material obtained A gel (viscosity (20 ° C.): 1300 P) was prepared in the same manner as in Example 1, and the physical properties of the gel were examined in the same manner as in Example 1. The result is
It is shown in the table.

Example 4 Instead of 2,2-bis [4- (acryldiethoxy) phenyl] propane used in Example 2, 1,3-bis (p-
Example 2 except that 18 g of (vinylphenyl) propane was used.
A gel substrate was obtained in the same manner as described above.

Elemental analysis of the obtained gel base material was performed. The results are shown below.

(Measurement results of elemental analysis) Calculated value: C64.99, H8.71, N10.50 (%) Actual measured value: C65.30, H9.02, N10.66 (%) A gel (viscosity (20 ° C.): 1050 P) was prepared in the same manner as in Example 1, and the physical properties of the gel were examined in the same manner as in Example 1. Table 1 shows the results.

Example 5 Example 2 was repeated except that 1.5 g of dipentaerythritol hexaacrylate was used in place of 2,2-bis [4- (acryldiethoxy) phenyl] propane used in Example 2.
A gel substrate was obtained in the same manner as described above.

Elemental analysis of the obtained gel base material was performed. The results are shown below.

(Measurement results of elemental analysis) Calculated values: C63.33, H8.73, N11.07 (%) Measured values: C62.81, H8.55, N11.42 (%) A gel (viscosity (20 ° C.): 940P) was prepared in the same manner as in Example 1, and the physical properties of the gel were examined in the same manner as in Example 1. Table 1 shows the results.

[Effect of the Invention] The cationic gel base material of the present invention is not only a nonionic polymer widely used as a setting polymer, but also a
It has good compatibility with the cationic polymer, and can be widely used, for example, as a gel base material for hair cosmetics.

In addition, since the cationic gel base material of the present invention comprises a vinyl monomer such as N-vinyl lactam as a component, it forms a coating film having excellent flexibility on, for example, the hair, and has an excellent setting. It is effective.

Claims (1)

(57) [Claims] (A) General formula (I): (Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each represent a methyl group or an ethyl group, and A represents a linear or branched alkylene group having 1 to 4 carbon atoms). (Meth) acrylic acid ester, (B) general formula (II): (Wherein m represents 3 or 4) and (C) 1,10-decanediyl diacrylate, 1,10-decanediyl dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , Pentaerythritol triacrylate, pentaerythritol trimethacrylate,
Trimethylol ethane triacrylate, trimethylol ethane trimethacrylate, trimethylol propane triglycidyl triacrylate, trimethylol propane triglycidyl trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, methylene bis acrylamide, methylene bis methacrylamide, 1 , 2-bisacrylamidoethane, 1,2-bismethacrylamidoethane,
1,5-bisacrylamidopentane, 1,5-bismethacrylamidopentane, 1,10-bisacrylamidododecane, 1,10-bismethacrylamidododecane, 1,1-bisacrylamido-1-phenylethane, 1,1- Bismethacrylamide-1-phenylethane, divinylbenzene, 1,2-bis (p-vinylphenyl) ethane, 1,3-bis (p-vinylphenyl) propane, 1,4-bis (p-
At least one selected from vinylphenyl) butane, 2,2-bis [4- (acryldiethoxy) phenyl] propane and dipentaerythritol hexaacrylate
A cationic gel base comprising a copolymer obtained by polymerizing a kind of crosslinkable polyvinyl compound.