JPH06316510A - Production of cationic thickening agent - Google Patents

Abstract

PURPOSE:To produce a cationic thickening agent capable of being blended with a cationic setting polymer, forming a flexible film after drying, having a small amount of impurities admixed. CONSTITUTION:Polymer components comprising (A) 15-85wt.% of an amine- containing (meth)acrylic monomer of formula I (R<1> is H or methyl; R<2> and R<3> are respectively H, methyl, ethyl or t-butyl; A is O or NH; N is a 1-14C alkylene) such as N,N-dimethylaminoethyl acrylate, (B) 0-80wt.% of a vinyl monomer of formula II [R<4> is a group of formula III ((p) is 3 or 4) or a group of formula IV] such as N-vinylpyrrolidone, (C) 1-60wt.% of a (meth)acryloyl group-containing monomer of the formula V [R<5> is a 1-17C alkylene, (C2H4O)q or (C3H6O)r ((q) and (r) are respectively 1-25); R<6> is H or methyl] such as methoxypolyethylene glycol (23) methacrylate and (D) 0.1-20wt.% of a cross- linkable vinyl monomer such as ethylene glycol dimethacrylate, are polymerized in an atmosphere of an inert gas in a nonaqueous solvent and the prepared reaction solution is powdered.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a cationic thickener. More specifically, it relates to a method for producing 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. A gel base material composed of, for example, is known as a typical one.

However, the gel base material is -COO.
Since the base resin is an anionic polymer having H groups in the polymer chain and obtained by neutralizing a part or all of the --COOH groups with NaOH, KOH, amines, etc. It is difficult to add cosmetic materials for hair such as polymers for system setting. 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 and polyvinylpyrrolidone-vinyl acetate copolymer, and anionic setting polymers represented by acrylic resin alkanolamine solution. In addition, since the aqueous cosmetic using the gel base material forms a hard film after drying, when it 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 substrate for forming a soft and flexible film after drying, there is known a gel substrate which is thickened by aqueous emulsion polymerization of a crosslinkable base monomer having an amino group and adjusting the pH value. (Japanese Patent Laid-Open No. 57
-133145), the crosslinkable base monomer having an amino group is easily hydrolyzed, and when hydrolyzed, the cationic group is neutralized by an acid treatment performed later. Since it is introduced and an anion group and a cation group coexist in the same polymer molecular chain, it 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 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 N, N-dimethylaminoethyl methacrylate, which is known to have excellent characteristics as a raw material for cosmetics, cannot be used, which is extremely disadvantageous in selecting a raw material monomer for a gel base material. It tells us 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]

Therefore, in view of the above-mentioned prior art, the present inventors have been able to 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 method for producing a cationic thickener capable of imparting a high gel viscosity, and finally found the present invention. Arrived

[0006]

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

[0007]

[Chemical 8]

(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 linear or side chain having 1 to 1 carbon atoms
5 to 85% by weight of an amine-containing (meth) acrylic monomer represented by the formula (I).
I):

[0009]

[Chemical 9]

(Wherein R ¹ is the same as above, 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]

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

[0015]

[Chemical 12]

(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:

[0017]

[Chemical 13]

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

[0019]

[Chemical 14]

(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) A polymerization component containing 0.1 to 20% by weight of a crosslinkable vinyl monomer is polymerized while heating in a non-aqueous solvent under an inert gas atmosphere, and then the obtained reaction liquid is powdered. And a method for producing a cationic thickener.

[0021]

ACTIONS AND EXAMPLES As described above, the method for producing the cationic thickener of the present invention comprises: (A) general formula (I):

[0022]

[Chemical 15]

(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 linear or side chain having 1 to 1 carbon atoms
5 to 85% by weight of an amine-containing (meth) acrylic monomer represented by the formula (I).
I):

[0024]

[Chemical 16]

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

[0026]

[Chemical 17]

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

[0028]

[Chemical 18]

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]

[Chemical 21]

(In the formula, r represents an integer of 1 to 25), R ⁶ represents a hydrogen atom or a methyl group, and a (meth) acryloyl group-containing monomer is contained in an amount of 1 to 60% by weight, and (D) A polymerization component containing 0.1 to 20% by weight of a crosslinkable vinyl monomer is polymerized while heating in a non-aqueous solvent under an inert gas atmosphere, and then the obtained reaction liquid is powdered. It is what

The amine-containing (meth) acrylic monomer represented by the general formula (I) imparts an electrolytic property to the obtained copolymer when the 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- Dimethylaminoethylacrylamide, N, N-diethylaminoethylacrylamide, N, N-dimethylaminoethylmethacrylamide, N, N-diethylaminoethylmethacrylamide, N, N-dimethylaminopropylmethacrylamide, N, N-dimethylaminopropylacrylamide (Meth) acrylamide and the like, but the present invention is not limited to these examples. In addition, the said amine-containing (meth) acrylic-type monomer is used individually or in mixture of 2 or more types.

The proportion of the amine-containing (meth) acrylic monomer in the polymerization component constituting the copolymer is 15 to
It is adjusted to be 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 exceeds 85% by weight, it becomes difficult to obtain a gel 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 imparts flexibility, gloss and smoothness to the film formed after the cationic thickener is dried.

As a typical example of such vinyl monomer,
Examples thereof include N-vinylpiperidone, N-vinylpyrrolidone, acrylamide, and methacrylamide, but the present invention is not limited to these examples. In addition, in this invention, the said vinyl monomer is used individually or in mixture of 2 or more types.

The proportion of the vinyl monomer in the polymerization component constituting the copolymer is 0 to 80% by weight, preferably 20 to
It is 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.
The content of the vinyl monomer is preferably 20% by weight or more, and more preferably 40% by weight or more in order to sufficiently bring out the effect exhibited by blending the vinyl monomer.

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 compatibility with.

Specific examples of the (meth) acryloyl group-containing monomer include 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 (n = 2 to 23) (meth) acrylate, hydroxypropyl (meth) acrylate, polypropylene glycol (n = 2 to 23) (meth) acrylate, and the like. The present invention is not limited to this example. In the present invention, the (meth) acryloyl group-containing monomer may be used alone or
It is used as a mixture of two or more species.

The proportion of the (meth) acryloyl group-containing monomer in the polymerization component 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 becomes large and the solubility in water is small 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. At the same time that the compounding amount of (3) is reduced, the gloss of the film formed after the cationic thickener is 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. Typical examples of such crosslinkable vinyl monomers include, for example, ethylene glycol diacrylate, ethylene glycol methacrylate, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1,2-ethanediyl diacrylate. Acrylate, 1,2-ethanediyldimethacrylate, 1,10-decanediyldiacrylate, 1,10-decanediyldimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate , Trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane tri Glycidyl triacrylate,
Poly (meth) acrylic compounds such as trimethylolpropane triglycidyl trimethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate; methylenebisacrylamide, methylenebismethacrylamide, 1,2-bisacrylamideethane, 1,2- Bismethacrylamidoethane, 1,5-
Bisacrylamide pentane, 1,5-bismethacrylamide pentane, 1,10-bisacrylamide dodecane, 1,10
-Bismethacrylamide dodecane, 1,1-bisacrylamide-1-phenylethane, 1,1-bismethacrylamide-1-
Poly (meth) acrylamide compounds such as phenylethane; divinylbenzene, 1,2-bis (p-vinylphenyl) ethane, 1,3-bis (p-vinylphenyl) propane, 1,4-bis (p-vinyl) Examples thereof include vinyl compounds such as phenyl) 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 polymerization component composing the copolymer is adjusted to 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.

A polymerization component containing the amine-containing (meth) acrylic monomer, vinyl monomer, (meth) acryloyl group-containing monomer and crosslinkable vinyl monomer is added to a non-aqueous solvent under an inert gas atmosphere such as nitrogen gas. After the polymerization is carried out while heating in the medium, the obtained reaction liquid is pulverized to obtain a cationic thickener.

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

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

In the present specification, the good solvent means the compound represented by the general formula (I) with respect to 100 ml of the good solvent at 25 ° C.
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 and the like having 1 to 10 carbon atoms.
Examples thereof include monohydric alcohol of 3, acetone, ethyl acetate, benzene, toluene and xylene. 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 obtained by the method 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 may be added to the good solvent in order to precipitate the produced copolymer from the reaction solution.

The poor solvent is the poor solvent at 25 ° C.
A solvent in which a copolymer 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 dissolves in 100 ml per 5 g or less. Say. 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. In addition, n-hexane, cyclohexane and the like are preferable because they are industrially inexpensive and have good handleability.

As a combination of the good solvent and the poor solvent, it is said that the chain transferability of the solvent is suitable and the degree of polymerization between the polymerization components can be preferably adjusted before the copolymer starts to precipitate. From the viewpoint, a combination of a monohydric alcohol having 1 to 3 carbon atoms and a linear, branched or cyclic aliphatic hydrocarbon having 15 or less carbon atoms is preferable, and a combination of ethanol and cyclohexane is particularly preferable. .

It should be noted that it is preferable to use a mixed solvent of the good solvent and the poor solvent, and to mix both in an appropriate ratio so as not to impair the characteristics of the obtained cationic thickener. If the blending 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. In addition, the polymerization reaction proceeds promptly,
In order to prevent aggregation and solidification during removal of the solvent after the polymerization, the proportion of the poor solvent contained in the mixed solvent is preferably 80% by weight or more, and more preferably 90% by weight or more.

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 a stirrer for solution polymerization, which is generally used as such a reactor, is used, the concentration of the total amount of the above-mentioned polymerization components is preferably 30% by weight or less. During the reaction, it is preferable to sufficiently stir with a stirrer or the like in order to prevent the reaction solution from being stagnant.

The polymerization reaction is preferably carried out under heating at about 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 preferably 10 hours or more. The polymerization reaction can be optionally completed when the amount of the remaining monomer is 10% by weight or less. The amount of the remaining monomer can be determined by adding bromine to the double bond by a known method such as the PSDB method and measuring the double bond content.

Thus, a reaction liquid containing the copolymer is obtained.

When the good solvent is used, for example, the reaction solution is dried to volatilize and remove the good solvent from the reaction solution, and then powdered to obtain a cationic thickener. .

When the above mixed solvent is used,
A cationic thickener can be obtained by filtering the deposited precipitate of the copolymer and then pulverizing it by, for example, performing vacuum drying or drying under normal 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-
Examples include 2,2'-azobisisobutyrate and 2,2'-azobis (2,4-dimethylvaleronitrile). The type of the polymerization catalyst varies depending on the boiling point of the solvent used, and when ethanol or benzene is used, 2,2′-azobisisobutyronitrile is the most preferable because it is easy to handle. . The amount of the polymerization catalyst used is preferably 0.05 to 3% by weight, more preferably 0.1 to 1% by weight, based on the total amount of the polymerization components.

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

When only the above-mentioned good solvent is used, at the initial stage of the polymerization reaction, an aspect similar to that in the case of carrying out a general solution polymerization reaction is exhibited, but as the reaction progresses, a crosslinking reaction occurs. It progresses and becomes gel-like, and as the reaction proceeds further, a grease-like product having no precipitate is obtained.

When the mixed solvent of the good solvent and the poor solvent is used, the same phase as in the case of carrying out a general solution polymerization reaction is exhibited in the initial stage of the polymerization reaction, but the reaction progresses. Along with this, the cross-linking reaction progresses, and a gel is formed. When the reaction proceeds further, the obtained copolymer can no longer be dissolved in the mixed solvent and becomes insoluble and precipitates as a precipitate.

Thus, a cationic thickener can be obtained,
The cationic thickener is used in the state of being powdered as it is, for example, by blending it as a raw material for various cosmetics or by making it into a gel.

When the above cationic thickener is used as a gel, for example, the desired viscosity is usually adjusted with the content of the cationic thickener being about 3.5% by weight or less.

When a gel is prepared using the above cationic thickener, for example, mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid, lactic acid, amino acids, succinic acid, malic acid, The organic thickener such as dimethylsulfate and diethylsulfate is used as a neutralizing agent, and the cationic thickener is diluted with water.
It is preferable to neutralize after diluting to less than or equal to wt%.

Next, the method for producing the cationic thickener of the present invention will be described in more detail based on examples, but the present invention is not limited to 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, methoxy polyethylene glycol (23) methacrylate 2.5 g and ethylene glycol dimethacrylate 2 g, and 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 initiated at 80 ° C.

After carrying out a polymerization reaction for about 10 hours while stirring under a nitrogen stream, the obtained polymer slurry solution was filtered under reduced pressure, the solid content was dried under reduced pressure, and then pulverized to obtain a white powdery cation. I got a sex thickener.

Next, water was added to the obtained cationic thickener so that the concentration was 2% by weight, and then the pH was adjusted to 6.4 using lactic acid as a neutralizing agent, and the mixture was sufficiently kneaded 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. The results are shown in Table 1.

(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: Roughness is noticeable (C) Appearance The obtained gel is visually observed to see if impurities are mixed. The examination was performed and the evaluation was performed based on the following evaluation criteria.

(Evaluation Criteria) A: No inclusion of impurities is recognized. B: Very slight inclusion of impurities is recognized. C: Some mixing of impurities is recognized. D: Contaminant of impurities is noticeable.

(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: Some peeling is recognized. 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: Matte film Examples 2 to 17 In Example 1, methoxypolyethylene glycol (2
3) A white powdery 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.

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

Comparative 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, 61 g of N-vinylpyrrolidone and 2 g of ethylene glycol dimethacrylate, and 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.

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

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.

[0086]

[Table 1]

Example 18 A three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introducing tube was charged with N, N-dimeraminoethyl methacrylate 39.
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.

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 polymer slurry solution was filtered under reduced pressure, the solid content was dried under reduced pressure, and then pulverized to obtain a gel in the same manner as in Example 1 using a white powdered cationic thickener. I made it up and investigated its physical properties. The results are shown in Table 2.
Shown in.

Example 19 In Example 18, the amount of N-vinylpyrrolidone was 46 g,
A white powdery 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. The results are shown in Table 2.

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, methoxy polyethylene glycol (23) methacrylate 50 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 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 the polymerization reaction was carried out for 10 hours under a nitrogen stream while stirring at 80 ° C.

The obtained transparent and grease-like polymer was dried on a stainless steel pallet and then pulverized to obtain a pale 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. The results are shown in Table 2.

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 introduction tube.
g, N-vinylpyrrolidone 5 g, methoxy polyethylene 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 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 the polymerization reaction was carried out for 10 hours under a nitrogen stream while stirring at 80 ° C.

The obtained transparent and grease-like polymer was dried under reduced pressure on a stainless steel pallet 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 2.

[0100]

[Table 2]

Examples 21 to 23 White color was obtained in the same manner as in Example 1 except that 39 g of the amine-containing (meth) acrylic monomer shown in Table 3 was used in place of N, N-dimethylaminoethyl methacrylate. A powdered cationic thickener was obtained.

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 3.

[0103]

[Table 3]

Example 24 A three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introducing 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 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 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 introducing 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 the 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.

Using the obtained cationic thickener, 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.

[0112]

[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 physical properties of the obtained setting gel for hair were examined according to the methods described below for viscosity, transparency, setting power, texture, flaking and washability.
The results are shown in Tables 5-6.

(A) Viscosity Using a Brookfield viscometer manufactured by Tokyo Keiki Co., Ltd.
The measurement was carried out at 25 ° C. under the condition of rotor No. 4 and 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 Company, Ratio Turbidity Meter 18900-00. A glass cell for turbidity measurement was set in the mold, the measured value was stabilized for 15 minutes, the turbidity value 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 power 2 g of hair having a length of 25 cm was uniformly coated with 3 g of the setting gel by hand. Wrap this hair in a curler with an outer diameter of 1.2 cm, dry it with hot air at 40 ° C for 60 minutes, remove the hair from the curler, and hang it vertically in an atmosphere with 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.

[0118]

[Equation 1]

It should be noted that the greater the curl retention, the greater the setting force. In the present invention, the curl retention of 60% or more satisfies the acceptance criteria.

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

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

The hair was dried with warm air of 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: Peeling is partially observed. C: Peeling is observed on the whole.

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

(Evaluation Criteria) A: Hair can be completely washed off within 30 minutes without slimy skin. B: It is possible to completely wash and remove hair without slimyness within 40 minutes. C: There is some sliminess after 40 minutes, and some remains. D: Even after 40 minutes or more, sliminess remains and hair cannot be removed by washing.

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

[0127]

[Table 5]

[0128]

[Table 6]

As is clear from the results shown in Tables 5 to 6, the setting gel for hair using the cationic thickening agent obtained by the method of the present invention is excellent in hair washability, setting power and the like, and even in a small amount. It can be seen that it has a gel-forming ability and is excellent in the degree of freedom of blending with the resin for setting.

[0130]

EFFECT OF THE INVENTION By the production method of the present invention, a high viscosity can be imparted, and a cationic thickener which can be suitably used in a small amount, for example, for cosmetics can be easily obtained.

The cationic thickener obtained by the production method of the present invention forms a film having excellent flexibility,
Since the content of the residue, which is an impurity, is small, it has an effect of imparting an excellent setting effect when it is used, for example, as a hair styling agent for hair.

Claims (5)

[Claims] 1. (A) General formula (I): (In the formula, 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
Is a linear or side chain alkylene group having 1 to 4 carbon atoms) represented by the formula: 15 to 85% by weight of an amine-containing (meth) acrylic monomer, and (B) a general formula (II): (In the formula, R ¹ is the same as 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
⁶ represents a hydrogen atom or a methyl group), and a (meth) acryloyl group-containing monomer (1 to 60% by weight) and (D) a crosslinkable vinyl monomer (0.1 to 20% by weight) were added to a polymerization component under an inert gas atmosphere. A method for producing a cationic thickening agent, which comprises polymerizing while heating in a non-aqueous solvent, and then pulverizing the obtained reaction solution. 2. A non-aqueous solvent comprising (A) an amine-containing (meth) acrylic monomer represented by the general formula (I),
(B) a vinyl monomer represented by the general formula (II), (C)
Using a good solvent for a copolymer having a molecular weight of 10,000 or more composed of a (meth) acryloyl group-containing monomer represented by the general formula (III) and (D) a crosslinkable vinyl monomer, and volatilizing and removing the good solvent from the reaction solution. The method for producing a cationic thickener according to claim 1, wherein the cationic thickener is powdered by. 3. The method for producing a cationic thickener according to claim 2, wherein the good solvent is a monohydric alcohol having 1 to 3 carbon atoms. 4. A non-aqueous solvent, (A) an amine-containing (meth) acrylic monomer represented by the general formula (I),
(B) a vinyl monomer represented by the general formula (II), (C)
Containing a good solvent for a copolymer consisting of a (meth) acryloyl group-containing monomer represented by general formula (III) and a crosslinkable vinyl monomer (D) having a molecular weight of 10,000 or more, and (A) containing an amine represented by general formula (I) Precipitating a copolymer from a reaction solution by using a mixed solvent of a poor solvent for a copolymer having a molecular weight of 10,000 or more composed of a (meth) acrylic monomer and (B) a vinyl monomer represented by the general formula (II) The method for producing a cationic thickener according to claim 1, wherein the cationic thickener is powdered by. 5. The cation according to claim 4, wherein the mixed solvent is a mixed solvent of a monohydric alcohol having 1 to 3 carbon atoms and a linear, branched or cyclic aliphatic hydrocarbon having 15 or less carbon atoms. Of producing a thickening agent.