JP2608214B2 - Cationic thickener - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to cationic thickeners. More specifically, it relates to a cationic thickener that can be suitably used in cosmetics and fragrances.

[0002]

2. Description of the Related Art Studies on gel bases have been conducted for a long time, and alkali neutralized salts of polyacrylic acid cross-linked polymers described in JP-B-32-4141 and JP-A-51-46586. Gel bases made of such materials are known as typical ones.

However, the gel base material is -COO.
Having a H groups in the polymer chain, part or all of the -COO H group NaOH, KOH, an anionic polymer that is E is neutralized with such amines because those based resin, in which It is difficult to add cosmetic materials for hair such as cationic setting polymers. For example, when a cationic setting polymer containing a quaternary amine is added to the polymer chain, the charge is neutralized between the anionic polymer and the cationic setting polymer, resulting in agglomeration, cloudiness or stagnation. There is. Therefore, the setting polymers that can be added are only nonionic setting polymers such as polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer, and anionic setting polymers typified by alkanolamine solutions of acrylic resins. Further, since the aqueous cosmetic in which the gel base material is used forms a hard film after drying, when this is used as a cosmetic for hair, for example, the film formed on the hair is Since the phenomenon of peeling, that is, the so-called flaking phenomenon occurs, its use is limited.

On the other hand, as a gel base material which forms a soft and flexible film after drying, a gel base material obtained by subjecting a crosslinked base monomer having an amino group to aqueous emulsion polymerization and adjusting the pH value is known. (Japanese Patent Laid-Open No. 57
-133145 discloses), crosslinked base monomer having an amino group are those susceptible to hydrolysis, when hydrolyzed is introduced cationic groups neutralized by acid treatment applied later However, since an anion group and a cation group coexist in the same polymer molecular chain, a uniform cationic polymer may not be obtained. Further, when N, N-dimethylaminoethyl methacrylate is used as a raw material monomer in the gel base material, a hydrolysis reaction occurs vigorously during the polymerization reaction, and a desired polymer cannot be obtained. In other words, this is widely used industrially,
In addition, it means that the above-mentioned N, N-dimethylaminoethyl methacrylate, which is known to have excellent characteristics as a raw material for cosmetics, cannot be used, which is very disadvantageous in selecting a raw material monomer for a gel base material. It tells that it is something. In addition, there is a drawback that impurities such as a surfactant cannot be avoided due to the nature of emulsion polymerization.

[0005]

In view of the above-mentioned problem, the present inventors can blend a cationic setting polymer, form a flexible film after drying, and reduce the amount of impurities mixed. As a result of earnestly researching a gel base material that can be used as a small amount of a cationic thickener, etc., such a gel base material has been found (Japanese Patent Application No. Hei 2-103913), but further intensive research is carried out. As a result,
It has excellent compatibility with water, and also has excellent compatibility with nonionic resins, cationic resins and amphoteric resins, and finally found a cationic thickener capable of imparting high gel viscosity, and finally reached the present invention. .

[0006]

The present invention provides (A) general formula
(I):

[0007]

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Wherein R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a methyl group, an ethyl group or a t-butyl group, and A represents an oxygen atom or
-NH- group, B is a straight-chain or side-chain having 1 to 1 carbon atoms
15 to 85% by weight of an amine-containing (meth) acrylic monomer represented by the formula 4).

[0009]

[Chemical 9]

(Wherein R ¹ is the same as above, and R ⁴ is a general formula:

[0011]

[Chemical 10]

A group represented by the formula (wherein p represents 3 or 4) or a formula:

[0013]

[Chemical 11]

0-80% by weight of a vinyl monomer represented by the following formula (C): (C) a general formula (III):

[0015]

[Chemical 12]

[0016] (wherein, R ¹ and A are as defined above, R ⁵
Is a linear or branched alkylene group having 1 to 17 carbon atoms;

[0017]

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(Wherein q represents an integer of 1 to 25) or a general formula:

[0019]

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(In the formula, r represents an integer of 1 to 25), R ⁶ represents a hydrogen atom or a methyl group, and 1 to 60% by weight of a (meth) acryloyl group-containing monomer represented by (D) 0.1 to 20% by weight of a crosslinkable vinyl monomer can be obtained by non-aqueous solution polymerization without using a surfactant.
A cationic thickener.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The cationic thickener of the present invention comprises, as described above, (A) a general formula (I):

[0022]

Embedded image

(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ are each independently a hydrogen atom, a methyl group, an ethyl group or a t-butyl group, A is an oxygen atom or
-NH- group, B is a straight-chain or side-chain having 1 to 1 carbon atoms
(B) the alkylene group represented by formula (4): 15 to 85% by weight of an amine-containing (meth) acrylic monomer;

[0024]

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(Wherein R ¹ is the same as above, R ⁴ is a general formula:

[0026]

Embedded image

(Wherein p represents 3 or 4) or a group represented by the formula:

[0028]

Embedded image

A vinyl monomer represented by the following formula): 0 to 80% by weight, (C) general formula (III):

[0030]

[Chemical 19]

(Wherein R ¹ and A are the same as described above, R ⁵
Is an alkylene group having a linear or side chain having 1 to 17 carbon atoms, a general formula:

[0032]

[Chemical 20]

(Wherein q represents an integer of 1 to 25) or a general formula:

[0034]

Embedded image

(Wherein r represents an integer of 1 to 25), R ⁶ represents a hydrogen atom or a methyl group, 1 to 60% by weight of a (meth) acryloyl group-containing monomer represented by the following formula: (D) 0.1 to 20% by weight of a crosslinkable vinyl monomer is a non-aqueous solution polymerized without using a surfactant .

The amine-containing (meth) acrylic monomer represented by the general formula (I) gives the copolymer an electrolytic property when the obtained copolymer is neutralized with a suitable acid. It is a component that has a role. Representative examples of such amine-containing (meth) acrylic monomers include, for example, N, N-dimethylaminoethyl acrylate, N, N
- (Meth) acrylate such as diethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-dimethylaminopropyl acrylate, N, N- The
Methylaminoethylacrylamide, N, N-diethyl
Aminoethylacrylamide, N, N-dimethylamino
Ethylmethacrylamide, N, N-diethylaminoethyl
Lumethacrylamido, N, N-dimethylaminopropyl
Methacrylamide, N, N-dimethylaminopropyl
Examples thereof include (meth) acrylamide such as acrylamide, but the present invention is not limited to only such examples. The amine-containing (meth) acrylic monomers are used alone or in combination of two or more.

The ratio of the amine-containing (meth) acrylic monomer in the monomers constituting the copolymer is 15 to
Adjusted to 85% by weight. When the proportion of the amine-containing (meth) acrylic monomer is less than 15% by weight, the amount of the amine-containing (meth) acrylic monomer part neutralized by the acid in the obtained copolymer is small. If it becomes too hard to obtain one with sufficient gel viscosity, and if it exceeds 85 % by weight,
The resulting cationic thickener will lose the flexibility of the film formed after drying.

The vinyl monomer represented by the general formula (II) is a component that gives flexibility, gloss and smoothness to a film formed after the cationic thickener is dried.

Representative examples of such vinyl monomers include:
For example, N-vinylpiperidone, N-vinylpyrrolidone, acrylamide, methacrylamide and the like can be mentioned, but the present invention is not limited only to such examples. In the present invention, the vinyl monomers are used alone or in combination of two or more.

The proportion of the vinyl monomer in the monomers constituting the copolymer is 0 to 80% by weight, preferably 20 to
Adjusted to be 60% by weight. When the proportion of the vinyl monomer exceeds 80% by weight, the gel viscosity of the obtained cationic thickener is remarkably lowered.
In addition, in order to sufficiently exhibit the effect exerted by blending the vinyl monomer, the ratio of the vinyl monomer is preferably 20% by weight or more, and more preferably 40% by weight or more.

The (meth) acryloyl group-containing monomer represented by the general formula (III) is a resin for improving the gloss of the film formed after the cationic thickener is dried, the gel viscosity and various setting resins. It is a component for improving the compatibility with the above.

Specific examples of the (meth) acryloyl group-containing monomer include, for example, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate,
Cyclohexyl (meth) acrylate, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, N-methyl (meth) acrylamide, hydroxyethyl (meth) acrylate, polyoxyethylene (q = 2 to 9) ) (Meth) acrylate, methoxypolyethylene glycol ( q = 2 to 23) (meth) acrylate, hydroxypropyl (meth) acrylate, polypropylene glycol ( r = 2 to 23) (meth) acrylate, and the like. It is not limited only to such an example. In the present invention, the (meth) acryloyl group-containing monomer may be used alone or
A mixture of more than one species is used.

The proportion of the (meth) acryloyl group-containing monomer in the monomers constituting the copolymer is 1 to 60% by weight, preferably 1 to 20% by weight, more preferably 2 to
It is adjusted to be 15% by weight. When the proportion of the (meth) acryloyl group-containing monomer exceeds 60% by weight, the proportion of the hydrophobic group in the obtained copolymer increases, and the solubility in water is low even after neutralization. When it is less than 1% by weight, the gel viscosity decreases, so it is necessary to increase the amount of the cationic thickening agent used and various setting resins. And the gloss of the film formed after the cationic thickener has dried is reduced.

The crosslinkable vinyl monomer is a compound having two or more carbon-carbon unsaturated double bonds in one molecule and has a property of crosslinking with other monomers. Representative examples of such crosslinking vinyl monomers, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, 1,2-ethane-diyl diacrylate, 1,2 Etanjiiruji Methacrylate, 1,10-decanediyl diacrylate, 1,10-decanediyl dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolethane triacrylate, trimethylol Ethane trimethacrylate, trimethylol propane triglycidyl triacrylate, trimethylol propane triglycidyl trimethacrylate , Poly (meth) acrylic compounds such as tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate; methylenebisacrylamide, methylenebismethacrylamide, 1,2-bisacrylamideethane, 1,2-bismethacrylamideethane, 1, 5-bisacrylamide pentane, 1,
5-bismethacrylamidopentane, 1,10-bisacrylamidododecane, 1,10-bismethacrylamidododecane, 1,1-bisacrylamido-1-phenylethane, 1,1-
Poly (meth) acrylamide-based compounds such as bismethacrylamide-1-phenylethane; divinylbenzene,
1,2-bis (p-vinylphenyl) ethane, 1,3-bis (p
Examples thereof include vinyl compounds such as vinylphenyl) propane and 1,4-bis (p-vinylphenyl) butane, but the present invention is not limited to these examples. In addition, in this invention, the said crosslinkable vinyl monomer is used 1 type or in mixture of 2 or more types.

The proportion of the crosslinkable vinyl monomer in the monomers constituting the copolymer is adjusted to be 0.1 to 20% by weight, preferably 1 to 10% by weight. When the proportion of the crosslinkable vinyl monomer is less than 0.1% by weight, the degree of crosslinking of the obtained cationic thickener becomes too small, so that the viscosity of the cationic thickener can be increased. If it exceeds 20% by weight, the viscosity of the cationic thickener itself becomes high, but fine aggregates may occur.

The amine-containing (meth) acrylic monomer, vinyl monomer, (meth) acryloyl group-containing monomer and crosslinkable vinyl monomer are polymerized in a non-aqueous solvent under an inert gas atmosphere such as nitrogen gas. Performed with warming.

In the present invention, the polymerization reaction is carried out in a non-aqueous solvent under an inert gas atmosphere in order to prevent hydrolysis of the ester group present in the monomer or the formed copolymer. Is.

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

In the present invention, the good solvent is used
This is because it is possible to control the formation of a homopolymer due to the different reactivity of each monomer and obtain a uniform copolymer.

In the present specification, the term "good solvent" refers to a compound of the general formula (I) at 25 ° C. per 100 ml of the good solvent.
The molecular weight of the amine-containing (meth) acrylic monomer represented by the formula (1), the vinyl monomer represented by the general formula (II), the (meth) acryloyl group-containing monomer represented by the general formula (III), and the crosslinkable vinyl monomer is 10,000. A solvent in which the above copolymer dissolves in a range of 20 g or more and no turbidity is observed. Specific examples of the good solvent include, for example, methanol, ethanol, isopropanol, acetone, ethyl acetate, benzene, toluene, xylene and the like. Among these good solvents, ethanol, isopropanol and benzene are particularly preferable because they can give a polymer having a relatively high molecular weight. The ethanol may be ethanol having a purity of 95% by volume or more, and more preferably ethanol having a purity of 99% by volume or more. When the cationic thickener of the present invention is used in cosmetics and the like, ethanol and isopropanol are most preferable because they are harmful to benzene and the like.

In the present invention, a poor solvent can be mixed with a good solvent in order to precipitate the produced polymer from the polymerization solution.

The above-mentioned poor solvent means the poor solvent at 25 ° C.
For 100 ml, there are 5 copolymers consisting of an amine-containing (meth) acrylic monomer represented by the general formula (I) and a vinyl monomer represented by the general formula (II) having a molecular weight of 10,000 or more.
It means a solvent that dissolves in the range of 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, straight-chain, branched-chain or cyclic aliphatic hydrocarbons having a relatively high boiling point and having 7 or less carbon atoms are preferable. Of these, straight-chain, branched-chain or cyclic aliphatic hydrocarbons having 6 or 7 carbon atoms have a high boiling point and are therefore particularly preferable. Further, n-hexane, cyclohexane and the like are preferred from the viewpoint that they are industrially inexpensive and have good handleability.

It is preferable to use a mixed solvent of the above-mentioned good solvent and poor solvent, and to mix both in an appropriate ratio so as not to impair the properties of the obtained cationic thickener. If the compounding ratio of the poor solvent is too large, the polymerization proceeds promptly, and it becomes difficult to obtain a cationic thickener having desired physical properties by depositing powder in a short time, The proportion of the poor solvent contained in the mixed solvent is preferably 98% by weight or less, and more preferably 97% by weight or less. Further, in order to promptly proceed the polymerization reaction and to prevent aggregation and solidification during the removal of the solvent after the polymerization, the ratio of the poor solvent contained in the mixed solvent is 80% by weight.
It is desirable that the amount is at least 90% by weight, preferably at least 90% by weight.

In order to efficiently obtain the cationic thickener from the reaction solution, a reaction device for improving the kneading state at the time of polymerization is necessary. When using a solution polymerization stirrer that is generally used as such a reactor,
The concentration of the total amount of the monomers is preferably 30% by weight 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 above 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 amount of the remaining monomer in the polymerization reaction is
At the time when the content becomes 10% by weight or less, it can be completed arbitrarily. The amount of the remaining monomer is, for example, PS
It can be determined by adding an oxygen to a double bond by a known method such as a DB method and measuring the double bond content.

A reaction solution containing a cationic thickener is thus obtained as a greasy substance.

The removal of the mixed solvent can be carried out, for example, by filtering the obtained precipitate of the cationic thickener and then vacuum-drying or distilling it under atmospheric pressure or reduced pressure.

A polymerization catalyst may be used in the polymerization reaction. Examples of such a polymerization catalyst include 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2
´-Azobisisobutyrate, 2,2´- Azobis (2,4-
Dimethylvaleronitrile) and the like. 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 it has good handleability. The amount of the polymerization catalyst used is 0.05 to 3% by weight, preferably 0.1 to 1% by weight, based on the total weight of the monomers.

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

[0061] when said Yo溶medium using only the present with the case of performing a general solution polymerization reaction similar appearance in the early stage of the polymerization reaction, crosslinking reaction is accompanied with the progress of the reaction Proceeds to give a gel state, and as the reaction proceeds, a grease-like product without a precipitate is obtained.

When a mixed solvent of a good solvent and a poor solvent is used, the initial stage of the polymerization reaction has the same appearance as that of a general solution polymerization reaction, but as the reaction proceeds, Then, the cross-linking reaction progresses, and a gel is formed. When the reaction proceeds further, the obtained cationic thickener can no longer be dissolved in the mixed solvent, becomes insoluble and precipitates as a precipitate.

Thus, a cationic thickener can be obtained,
The cationic thickener is used as it is, for example, by blending it with raw materials for various cosmetics or by forming it into a gel.

When the cationic thickener is used as a gel, for example, the content of the cationic thickener is usually 3.5% by weight or less to adjust the viscosity to a desired value.

When a gel is prepared using the above-mentioned cationic thickener, for example, mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, acetic acid, citric acid, lactic acid, amino acid, succinic acid, malic acid, Using an organic acid such as dimethyl sulfate or diethyl sulfate as a neutralizing agent, the cationic thickener
It is preferable to neutralize after diluting to not more than% by weight.

Next, the cationic thickener of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

Example 1 A three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube was charged with N, N-dimethylaminoethyl methacrylate.
39 g, N-vinylpyrrolidone 58.5 g, methoxypolyethylene glycol (23) methacrylate 2.5 g, ethylene glycol dimethacrylate 2 g, ethanol 33.4
g and a mixed solvent of 464.6 g of cyclohexane (mixing ratio (weight ratio) 6.7: 93.3) were added to adjust the monomer concentration to 17% by weight, and the mixture was refluxed at 80 ° C. under a nitrogen stream to 2 The mixture was stirred for a while and degassed.

Next, 0.3 g of 2,2′-azobisisobutyronitrile was added to a three-necked flask, and polymerization was started at 80 ° C.

After a polymerization reaction was carried out for about 10 hours while stirring under a nitrogen stream, the obtained polymer slurry solution was filtered under reduced pressure, and the solid content was dried under reduced pressure. A thickener was obtained.

Next, water was added to the obtained cationic thickener so as to have a concentration of 2% by weight, and then the pH was adjusted to 6.4 using lactic acid as a neutralizing agent, and kneaded sufficiently with a homogenizer. I got a gel. The physical properties of the obtained gel were examined for viscosity, texture, appearance, flexibility of the formed film and gloss of the formed film based on the following methods. Table 1 shows the results.

(A) Viscosity Using a Brookfield viscometer manufactured by Tokyo Keiki Co., Ltd.
The measurement was carried out at 25 ° C. under the conditions of rotor No. 4 and 4 to 10 rpm.

(B) Hand feeling About 2 ml of the obtained gel was picked up by fingers and rubbed with each other to check the hand feeling, and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: Smooth and light texture B: Slightly textured C: Slightly textured D: Rough texture is noticeable (C) Appearance The obtained gel is visually observed to see if impurities are mixed. It was examined and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: No contamination was found. B: Very slight inclusion of impurities is recognized. C: Contamination of impurities is slightly observed. D: Contaminant of impurities is conspicuous.

(D) Flexibility of formed film The obtained gel was applied to a vinyl chloride resin film using a bar coater to form a coating film having a thickness of 10 μm, and air-dried for 3 hours to form a film. The state of the formed film when the produced film was bent at random was examined and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: No change was observed. B: Very slight peeling is recognized. C: Partial peeling is observed. D: Complete peeling is recognized.

(E) Glossiness of formed film The film prepared in (d) above was visually observed and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: glossy film B: slightly glossy film C: dull film Examples 2 to 17 In Example 1, methoxypolyethylene glycol (2
3) A white powdered cationic thickener was obtained in the same manner as in Example 1 except that the (meth) acryloyl group-containing monomer shown in Table 1 was used instead of methacrylate.

Using the cationic thickening agent thus obtained, a gel was prepared in the same manner as in Example 1 and its physical properties were examined. Table 1 shows the results.

Comparative Example 1 N, N-dimethylaminoethyl methacrylate was placed in a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen inlet tube.
39 g, 61 g of N-vinylpyrrolidone and 2 g of ethylene glycol dimethacrylate, a mixed solvent of 33.4 g of ethanol and 464.6 g of cyclohexane were added to adjust the monomer concentration to 17% by weight, and the mixture was refluxed at 80 ° C. While stirring under a nitrogen stream for 2 hours, the mixture was deaerated.

[0081] then added to 2,2'-azobisisobutyronitrile 0.3 g into a flask with stirring at 80 ° C., it was carried out 10 hours a polymerization reaction under a stream of nitrogen gas.

The obtained polymer slurry solution was filtered under reduced pressure, and the solid content was dried under reduced pressure and then pulverized to obtain a thickening agent in the form of white powder.

Using the thickener thus obtained, a gel was prepared in the same manner as in Example 1 and its physical properties were examined. The results are shown in Table 1.

[0084]

[Table 1]

Example 18 N, N-dimeraminoethyl methacrylate 39 was placed in a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen inlet tube.
g, N-vinylpyrrolidone 55.9 g, methoxy polyethylene glycol (23) methacrylate 5.1 g and ethylene glycol dimethacrylate 2 g, and ethanol 33.4 g
A mixed solvent of 464.6 g of cyclohexane and 464.6 g of cyclohexane was added to adjust the monomer concentration to 17% by weight, and the mixture was degassed by stirring under a nitrogen stream for 2 hours while refluxing at 80 ° C.

[0086] then added to 2,2'-azobisisobutyronitrile 0.3 g into a flask with stirring at 80 ° C., it was carried out 10 hours a polymerization reaction under a stream of nitrogen gas.

The obtained polymer slurry solution was filtered under reduced pressure, and the solid content was dried under reduced pressure. The solid was dried and then pulverized to obtain a gel in the same manner as in Example 1 using a white powdered cationic thickener. making, it was examined and the physical properties thereof. Table 2 shows the results.
Shown in

Example 19 In Example 18, the amount of N-vinylpyrrolidone was 46 g,
A white powdered cationic thickener was obtained in the same manner as in Example 18, except that the amount of methoxypolyethylene glycol (23) methacrylate was changed to 15 g.

Example using the obtained cationic thickener
A gel was made in the same manner as in 18, and its physical properties were investigated. Table 2 shows the results.

Example 20 A three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube was charged with N, N -dimethylaminoethyl methacrylate.
46 g, N-vinylpyrrolidone 4 g, methoxypolyethylene glycol (23) methacrylate 50 g and ethylene glycol dimethacrylate 3.5 g, ethanol 389.4
g was added to adjust the monomer concentration to 21% by weight, and the mixture was degassed by stirring under a nitrogen stream for 2 hours while refluxing at 80 ° C.

Next, 0.3 g of 2,2′-azobisisobutyronitrile was added to the flask, and a polymerization reaction was carried out for 10 hours under a nitrogen stream while stirring at 80 ° C.

The obtained transparent grease-like polymer was dried on a stainless steel pallet and then pulverized to obtain a light yellow powdery cationic thickener.

Example using the obtained cationic thickener
A gel was made in the same manner as in 18, and its physical properties were investigated. Table 2 shows the results.

Comparative Example 2 N, N -dimethylaminoethyl methacrylate 30 was placed in a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen inlet tube.
g, N-vinylpyrrolidone 5 g, methoxypolyethylene glycol (23) methacrylate 65 g and ethylene glycol dimethacrylate 3.5 g, and ethanol 389.4 g
Was added to adjust the monomer concentration to 21% by weight, and the mixture was stirred for 2 hours under a nitrogen stream while refluxing at 80 ° C., followed by degassing.

Next, 0.3 g of 2,2'-azobisisobutyronitrile was added to the flask, and the polymerization reaction was carried out for 10 hours under a nitrogen stream while stirring at 80 ° C.

The obtained transparent, grease-like polymer was dried on a stainless steel pallet under reduced pressure and then pulverized to obtain a pale yellow powdery cationic thickener.

Using the obtained cationic thickener, a gel was prepared in the same manner as in Example 1, and the physical properties were examined. Table 2 shows the results.

[0098]

[Table 2]

Examples 21 to 23 The procedure of Example 1 was repeated except that 39 g of an amine-containing (meth) acrylic monomer shown in Table 3 was used instead of N, N-dimethylaminoethyl methacrylate. A cationic thickener in powder form was obtained.

Using the obtained cationic thickener, a gel was prepared in the same manner as in Example 1, and the physical properties were examined. The results are shown in Table 3.

[0101]

[Table 3]

Example 24 A three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube was charged with N, N-dimethylaminoethyl methacrylate.
80 g, methoxy polyethylene glycol (23) methacrylate 20 g and ethylene glycol dimethacrylate 3
g, ethanol 33.7 g and cyclohexane 469.2 g
The mixed solvent solution of was added to adjust the monomer concentration to 17% by weight, and the mixture was degassed while refluxing at 80 ° C. while stirring under a nitrogen stream for 2 hours.

Next, 0.3 g of 2,2′-azobisisobutyronitrile was added to the flask, and a polymerization reaction was carried out for 10 hours under a nitrogen stream while stirring at 80 ° C.

The obtained transparent grease-like polymer was cast on a stainless steel vat, dried under reduced pressure, and then pulverized to obtain a pale yellow powdery cationic thickener.

Using the cationic thickener thus obtained, a gel was prepared in the same manner as in Example 1 and its physical properties were examined. The results are shown in Table 4.

Example 25 N, N-dimethylaminoethyl methacrylate 45 was placed in a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen inlet tube.
g, methacrylamide 52.5 g, methoxy polyethylene glycol (23) methacrylate 2.5 g and ethylene glycol dimethacrylate 3.0 g, and ethanol 387.5 g
Was added to adjust the monomer concentration to be 21% by weight, and the mixture was degassed by stirring under a nitrogen stream for 2 hours while refluxing at 80 ° C.

Next, 0.3 g of 2,2'-azobisisobutyronitrile was added to the flask, and a polymerization reaction was carried out for 10 hours under a nitrogen stream while stirring at 80 ° C.

The obtained polymer slurry solution was filtered under reduced pressure, and the solid content was dried under reduced pressure and then pulverized to obtain a white powdery cationic thickener.

A gel was prepared using the obtained cationic thickener in the same manner as in Example 1, and the physical properties were examined. The results are shown in Table 4.

[0110]

[Table 4]

Formulation Examples 1-24 The cationic thickeners obtained in Example 1, Example 13, Example 16 or Comparative Example 1 were mixed with the amounts of water and ethanol shown in Tables 5-6, and The pH was adjusted to 6.5 using lactic acid, and the nonionic set resin (N
-Vinylpyrrolidone-Vinyl acetate copolymer: PVA6450 manufactured by Osaka Organic Chemical Industry Co., Ltd., cationic set resin (vinylpyrrolidone diethylsulfate-N, N-dimethylaminoethylmethacrylic acid copolymer: Osaka Organic Chemical Industry ( HCP-3A) or amphoteric set resin (N-
Methacryloylethyl-N, N-dimethylammonium
-α-N-methylcarboxybetaine-methacrylic acid ester copolymer: Mitsubishi Yuka Co., Ltd., Yukahomer AM
75) was added little by little in the amounts shown in Tables 5 to 6 and stirred with a stirrer having a disper-type stirring blade to prepare a uniform setting gel for hair.

The obtained hair setting gel was examined for physical properties such as viscosity, transparency, setting power, texture, flaking and hair washability according to the following methods.
The results are shown in Tables 5 and 6.

(A) Viscosity Using a Brookfield viscometer manufactured by Tokyo Keiki Co., Ltd.
The measurement was performed at 25 ° C. under the conditions of a rotor No. 4 and a rotation speed of 4 to 10 rpm.

(B) Transparency 30 g of the obtained setting gel was weighed in a glass cell for turbidity measurement, defoamed with an ultrasonic cleaner for 1 hour at room temperature, and manufactured by Hack Corporation, Ratio Turbidimeter 18900-00. A glass cell for turbidity measurement was set in the mold, and the measured value was stabilized for 15 minutes. After that, the value of turbidity was read and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: less than 3 NTU B: 3 NTU or more and less than 5 NTU C: 5 NTU or more (c) Setting force 3 g of setting gel was evenly applied to 2 g of hair having a length of 25 cm by hand. The hair was wound around a curler with an outer diameter of 1.2 cm and dried with warm air at 40 ° C for 60 minutes. Then, the hair was removed from the curler and suspended immediately in an atmosphere at a temperature of 30 ° C and a relative humidity of 80%. The length (L ₁ ) and the length after standing for 1 hour (L ₂ ) were measured, and the curl retention was calculated from the following formula.

[0116]

(Equation 1)

The larger the curl retention, the higher the set force. In the present invention, those having a curl retention of 60% or more satisfy the acceptance criteria.

(D) Hand feeling About 2 ml of the setting gel thus obtained was picked up by fingers and rubbed together to check the hand feeling, and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: Smooth and light texture B: Slightly rough texture C: Slightly rough texture D: Rough texture is noticeable (e) Flaking 3 g of setting gel is evenly applied to 25 cm long hair, and an extra amount is applied. I squeezed the gel with my hand and dropped it.

The hair was dried with warm air at 40 ° C. for 60 minutes, combed 10 times with a commercially available comb, and the peeled state of the resin was evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: No peeling is observed. B: Partial peeling is observed. C: Peeling is observed on the whole.

(F) Hair washability To 2 g of hair having a length of 25 cm, 3 g of setting gel was evenly applied by hand, and dried with warm air at 40 ° C for 60 minutes. This hair is 30% 0.5% commercial hair wash (shampoo)
It was immersed in the contained hot water, stirred and examined for the state of removal of the setting gel per unit time, and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: Hair can be completely removed without slimming within 30 minutes. B: The hair can be completely washed and removed without slimming within 40 minutes. C: There is some sliminess after 40 minutes, and some remains. D: Even after 40 minutes or more, slimming remains and hair washing cannot be removed.

In Tables 5 to 6, the ones marked with * in the viscosity column mean that no gel was formed.

[0125]

[Table 5]

[0126]

[Table 6]

As is clear from the results shown in Tables 5 and 6, the setting gel for hair using the cationic thickener of the present invention is excellent in hair washability, setting power, etc., and has a gel forming ability even in a small amount. Further, it can be seen that the composition is excellent in the degree of freedom of compounding with the setting resin.

[0128]

The cationic thickener of the present invention can impart a high viscosity, and therefore can be suitably used in a small amount, for example, for cosmetics.

Further, the cationic thickener of the present invention forms a film having excellent flexibility and has a low content of residues as impurities. Therefore, when it is used for a hair styling agent for hair, for example, It has the effect of giving an excellent setting effect.

Claims (1)

(57) [Claims] (A) General formula (I): (Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R
³ are each independently a hydrogen atom, a methyl group, an ethyl group or a t-butyl group, A is an oxygen atom or a -NH- group, B
Represents an alkylene group having 1 to 4 carbon atoms having a linear or side chain); 15 to 85% by weight of an amine-containing (meth) acrylic monomer represented by the following general formula (II): (In the formula, R ¹ is the same as described above, and R ⁴ is a general formula: (Wherein p represents 3 or 4) or a group represented by the formula: A vinyl monomer represented by
-80% by weight, (C) general formula (III): (In the formula, R ¹ and A are the same as described above, R ⁵ is a carbon number of 1 to
An alkylene group having 17 linear or side chains, a general formula: (Wherein q represents an integer of 1 to 25) or a general formula: (In the formula, r represents an integer of 1 to 25), a group R
Represented by (meth) acryloyl group-containing monomer 1 to 60% by weight ⁶ is a hydrogen atom or a methyl group), and 0.1 to 20 wt% (D) crosslinking vinyl monomer, a non-aqueous solution without using a surfactant Obtained by polymerization
Cationic thickener.