JP3221851B2 - Cationic group-containing copolymer and thickener - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cationic group-containing copolymer and a thickener comprising the same. More specifically, the present invention relates to a cationic group-containing copolymer which can be suitably used as an additive for chemicals and cosmetics, particularly a thickener having a good feeling in use, and a thickener comprising the same.

[0002]

2. Description of the Related Art
Various thickeners are used in various industrial fields. As such a thickener, for example, natural polymers such as carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, starch, xanthan gum, and sodium alginate are known. However, they generally have poor thixotropy, and their application properties are not very good when used as cosmetic additives.

Japanese Patent Application Laid-Open No. 51-46586 discloses an alkali metal salt of a polyacrylic acid crosslinked polymer. In this case, although it has a thixotropic property and its coatability is not bad, it has a touch. This is not so preferable, and is particularly remarkable when applied to hair or the like.

Japanese Patent Application Laid-Open No. 4-20584 proposes a compound obtained by copolymerizing a cationic vinyl monomer and an N-vinyl type nonionic monomer in the presence of a crosslinking agent. However, the crosslinking agent described in this publication does not have good copolymerizability with an N-vinyl type nonionic monomer, and it is difficult to introduce a crosslinking point uniformly into the polymer molecular chain from the initial stage to the end of the polymerization. For this reason, since the crosslinking agent is not used effectively and is not sufficiently crosslinked, a very uneven gel tends to be formed when added to water.

On the other hand, JP-A-5-140531, JP-A-4-1853
Japanese Patent No. 3772 proposes a compound obtained by polymerizing an amine-containing (meth) acrylic monomer or other vinyl monomer in the presence of a crosslinking agent and then neutralizing the polymer. Since the group is neutralized with an acid compound or the like to be cationized, the thixotropy of the hydrogel is liable to change greatly depending on the pH or the like in the system. Further, when the compound was used as an additive for cosmetics, it did not have high usability (easy to spread at the time of application and strong feeling of residual hydrogel).

[0006] Accordingly, the problem to be solved by the present invention is to have excellent thixotropic properties and high adsorptivity to the skin, hair, etc., and to provide a very good feeling of use (when applied) It is an object of the present invention to provide a copolymer exhibiting ease of spreading and good feeling of the residue of the hydrogel, and a thickener comprising the same.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that a cationic group-containing copolymer having a specific thixotropic property has high adsorption to skin, hair and the like. When used in cosmetics and the like as a thickener, it has a very good feeling of use (ease of application,
The present inventors have found that the feeling of the residue of the hydrogel is good, etc.) and completed the present invention.

That is, according to the present invention, the viscosity at 25 ° C. when added to ion-exchanged water so as to be 0.5% by weight is 0.3 to 20 Pa · sec when the shear rate is 1 sec ⁻¹ , When the rate is 10 sec ^-1 , it is 0.01 to 5 Pa · sec.
And the viscosity at a shear rate of 1 sec ^-1 is the shear rate
An object of the present invention is to provide a cationic group-containing copolymer characterized by having a viscosity higher than 10 sec ^-1 and a thickener comprising the same.

[0009] The present invention also relates to at least one kind of a vinyl monomer having a cationic group and at least one kind of a vinyl monomer having a hydrophilic nonionic group represented by the general formula (I) or (II). , Vinyl group, acryloyl group, methacryloyl
A crosslinkable vinyl monomer having at least two groups selected from a group and an allyl group in a molecule (hereinafter referred to as at least two groups)
Generic name for crosslinkable vinyl monomers having a vinyl group in the molecule
The present invention provides a cationic group-containing copolymer obtained by radical polymerization of at least one of the above as an essential constituent monomer and a thickener comprising the same.

[0010]

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Wherein R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ are the same or different and each represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms; Is shown. ]

[0012]

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[Wherein R ¹ has the meaning described above, and A ¹ and A ²
They are the same or different, formula _{- (CH 2) n - (} n is an integer of 2 to 6) represents a group represented by, B is -O- or -CH ₂ - shows a group. ]

[0014]

Embodiments of the present invention will be described below in detail.

[Cationic Group-Containing Copolymer] The cationic group-containing copolymer of the present invention must be contained in an ion-exchanged water in an amount of 0.5% by weight in order to exhibit a good feeling of use desired by the present invention. The viscosity at 25 ° C when added, the shear rate 1
When sec ^-1, a 0.3~20Pa · sec, when the shear rate 10 sec ^-1, a 0.01~5Pa · sec, and the viscosity is shear rate at the shear rate of 1 sec ^-1 10 sec ^-1
It is necessary to exhibit a thixotropic property such that the viscosity is higher than the viscosity at the time of (1). A copolymer having a viscosity behavior out of the above range makes it difficult to apply the composition to the skin or the like, does not give a feeling of remaining on the skin, and cannot provide a good feeling of use.

The preferred viscosity behavior of the cationic group-containing copolymer of the present invention is that the viscosity at 25 ° C. when added to ion-exchanged water so as to be 0.5% by weight has a shear rate of 1
When sec ^-1 , 0.4 to 10Pasec, share rate
When 10 sec ^-1, a 0.05~3Pa · sec, and the viscosity at a shear rate of 1 sec ^-1 is higher than the viscosity at a shear rate 10 sec ^-1.

Further, when the physical property value obtained by dynamic viscoelasticity of an aqueous solution at 25 ° C. when added to ion-exchanged water so as to be 0.5% by weight is a complex at a frequency of 6.28 rad / sec and a strain of 1%, The elastic modulus is 1 N / m ² or more and 300 N / m ² or less,
Loss tangent (tan [delta) is 2 or less, preferably 1.5 or less, more preferably it is 1 or less, the frequency 6.28 rad / sec, when the strain 500%, modulus of elasticity is 0.01 N / m ² or more 30 N / m ² or less When the loss tangent (tan δ) is 1 or more, a very good feeling in use can be exhibited.

The cationic group-containing copolymer of the present invention can also increase the viscosity of a hydrophilic solvent such as ethanol and isopropyl alcohol (giving thixotropic properties). In these organogels, the viscosity at 25 ° C. when added to ethanol at 2.0% by weight is determined by the shear rate in order to express the good feeling of use desired by the present invention.
When 1 sec ^-1, a 0.3~20Pa · sec, when the shear rate 10 sec ^-1, a 0.01~5Pa · sec, and the viscosity is shear rate at the shear rate of 1 sec ^-1 10 sec
It is preferable to exhibit a thixotropy higher than the viscosity at ^-1 .

The cationic group-containing copolymer of the present invention having such performance is prepared by using an aqueous medium or a lower alcohol having 1 to 3 carbon atoms (ethanol, isopropyl alcohol, etc.).
Is extremely useful as a thickener in a hydrophilic medium or a mixed medium thereof.

The above-mentioned thixotropic cationic group-containing copolymer includes, for example, at least one cationic group-containing vinyl monomer and a hydrophilic monomer represented by the above general formula (I) or (II). At least one selected from a group of nonionic group-containing vinyl monomers and at least one type of a crosslinkable vinyl monomer having at least two vinyl groups in a molecule are subjected to radical polymerization. And a cationic group-containing copolymer obtained thereby. Such a cationic group-containing copolymer will be described below.

[Cationic group-containing vinyl monomer] Among the monomers constituting the cationic group-containing copolymer of the present invention,
Examples of the cationic group-containing vinyl monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylaminoethyl (meth) acrylate , Diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide,
Diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylaminopropyl (meth) acrylamide (Meth) acrylic acid ester or (meth) acrylamides having a dialkylamino group such as dimethylaminostyrene,
Styrenes having a dialkylamino group such as dimethylaminomethylstyrene, vinylpyridines such as 4-vinylpyridine and 2-vinylpyridine, N-vinyl heterocyclic compounds such as N-vinylimidazole, aminoethyl vinyl ether, dimethylaminoethyl Acid-neutralized or quaternary ammonium salts of monomers having an amino group such as vinyl ethers such as vinyl ethers; diallyl-type quaternary ammonium salts such as dimethyldiallylammonium chloride and diethyldiallylammonium chloride;

Preferred as these cationic group-containing vinyl monomers are at least one selected from compounds represented by the general formula (III) or (IV).

[0023]

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[R ¹ has the same meaning as above, R ⁴ and R ⁵ are the same or different and each represents an alkyl or alkenyl group having 1 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or a 1 to 4 carbon atoms. an alkyl group, Y is -O -, - NH- or _{-O-CH 2 CH (OH)} - represents a group, Z is a straight or branched alkylene group having 1 to 4 carbon atoms, X Represents a conjugate base of an acid, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms. ]

[0025]

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Wherein R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or a methyl group; R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Has the above-mentioned meaning. As specific examples of the compound represented by the general formula (III),
The acid-neutralized product obtained by neutralizing the (meth) acrylic acid ester or the (meth) acrylamide having a dialkylamino group with an acid described above or a quaternary ammonium salt obtained by quaternizing with a quaternizing agent is exemplified. Specific examples of the compound represented by the general formula (IV) include the diallyl type 4 exemplified above.
Secondary ammonium salts.

Preferred acids for obtaining the above acid-neutralized products include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, maleic acid,
Examples include fumaric acid, citric acid, tartaric acid, adipic acid, sulfamic acid, toluenesulfonic acid, lactic acid, pyrrolidone-2-carboxylic acid, and succinic acid. Preferred quaternizing agents for obtaining the quaternary ammonium salt include And alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide, and general alkylating agents such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate.

Among the compounds represented by formula (III) or (IV), more preferred are dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, Diethylaminopropyl (meth)
A quaternary ammonium salt obtained by quaternizing acrylamide with the above-described quaternizing agent, or dimethyldiallylammonium chloride can be used. Here, the acid neutralized monomer has a disadvantage that the stability of the viscosity is low because the neutralized acid is dissociated due to the pH of the system and the polymer structure is changed. From this viewpoint, a quaternary ammonium salt type monomer is more preferable.

[Hydrophilic nonionic group-containing vinyl monomer]
Among the monomers constituting the cationic group-containing copolymer of the present invention, as the hydrophilic nonionic group-containing vinyl monomer represented by the general formula (I), (meth) acrylamide,
N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt
-Butyl (meth) acrylamide, N-isobutyl (meth) acrylamide and the like. Examples of the hydrophilic nonionic group-containing vinyl monomer represented by the general formula (II) include N
-(Meth) acroyl morpholine and the like,
The present invention is not limited to the above examples, and these hydrophilic nonionic group-containing vinyl monomers can be used alone or in combination of two or more.

Among these hydrophilic nonionic group-containing vinyl monomers, use of N, N-disubstituted acrylamide is particularly preferable in terms of use. Further, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta)
Acrylamide can gel an aqueous solution of ethanol or an aqueous solution of an anionic activator, so that the range of application is wide and preferable.

[Crosslinkable vinyl monomer having at least two vinyl groups in the molecule] Among the monomers constituting the cationic group-containing copolymer of the present invention, at least two vinyl groups are used in the molecule. Examples of the crosslinkable vinyl monomer having ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, 1,2-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin Tori (meta) Relate, trimethylolpropane tri (meth) acrylate, polyhydric alcohol (meth) acrylic acid esters such as pentaerythritol tetra (meth) acrylate; N- methyl-allyl acrylamide, N- vinyl acrylamide, N, N '
Acrylamides such as methylenebis (meth) acrylamide and bisacrylamideacetic acid; divinylbenzene,
Divinyl compounds such as divinyl ether and divinyl ethylene urea; diallyl phthalate, diallyl maleate, diallylamine, triallylamine, triallyl ammonium salt, allyl etherified pentaerythritol, and sucrose having at least two allyl ether units in the molecule. Polyallyl compounds such as allyl etherified products;
(Meth) acrylic acid esters of unsaturated alcohols such as vinyl (meth) acrylate, allyl (meth) acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth) acrylate.

Among these crosslinkable vinyl monomers, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether are preferred.

[Blending Ratio of Monomer Component] The blending ratio of the cationic group-containing vinyl monomer and the hydrophilic nonionic group-containing vinyl monomer, which is preferable for obtaining the cationic group-containing copolymer of the present invention. Is a cationic group-containing vinyl monomer / hydrophilic nonionic group-containing vinyl monomer (molar ratio), 98 /
It is 2/2/98, more preferably 60 / 40-3 / 97. When the compounding ratio of these monomers deviates from the range shown here, for example, when the compounding ratio of the cationic group-containing vinyl monomer exceeds the range shown here, the thixotropic property is reduced. It tends to lack. In addition, when the mixing ratio of the hydrophilic nonionic group-containing vinyl monomer exceeds the range shown here, the viscosity at a low shear rate tends to be low.

The ratio of the crosslinkable vinyl monomer having at least two vinyl groups in the molecule constituting the cationic group-containing copolymer of the present invention is based on the total amount of the monomer. 0.002 to 5% by weight, preferably 0.002% by weight or more
Less than 0.1% by weight is particularly preferred. When the proportion of the crosslinkable vinyl monomer having at least two vinyl groups in the molecule is less than 0.002% by weight, the degree of crosslinking of the resulting cationic group-containing copolymer becomes too small. When the viscosity of the hydrogel formed from the cationic group-containing copolymer cannot be increased, and when the content exceeds 5% by weight, the hydrogel has a hard feel when touched by hand and has poor slippage. Is easily obtained.

[Other Monomer Components] The cationic group-containing copolymer of the present invention is a copolymer containing the above three kinds of vinyl monomers as essential components. Other vinyl monomers copolymerizable with the above can also be constituents.

As other vinyl monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate A) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, cyclopentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) A) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acryl Over DOO, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, xylyl (meth) acrylate, benzyl (meth) acrylate, 2
-Ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxy (meth)
Acrylate, 2-methoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2
(Meth) acrylic acid derivatives such as ethoxypropyl (meth) acrylate and 3-ethoxypropyl (meth) acrylate; 2-acrylamido-2-methylpropanesulfonic acid, sodium styrenesulfonate, acrylic acid, methacrylic acid, Anionic group-containing monomers such as sulfoethyl methacrylate; N- (3-sulfopropyl) -N-acryloyloxyethyl-N, N-dimethylammonium betaine, N- (3-sulfopropyl) -N-methacryloylamidopropyl -N, N-dimethylammonium betaine, N- (3-carboxymethyl) -N-methacryloylamidopropyl-N, N-
Dimethylammonium betaine, N- (3-sulfopropyl) -N-methacryloyloxyethyl-N, N-dimethylammonium betaine, N-carboxymethyl-
Betaines such as N-methacryloyloxyethyl-N, N-dimethylammonium betaine;

[Polymerization method] The method for producing the cationic group-containing copolymer of the present invention is not necessarily limited. However, it is usually carried out by a method such as an aqueous solution polymerization method, a reverse phase suspension polymerization method or a precipitation polymerization method. Is preferred. For example, as an aqueous solution polymerization method, a monomer component and a crosslinking agent are uniformly dissolved in a solvent such as water or a hydrophilic organic solvent which can be uniformly mixed with water or a mixed solvent thereof, and nitrogen, carbon dioxide gas or the like is used. After removing dissolved oxygen in the system by replacement with an inert gas or the like, a method of reacting by adding a polymerization initiator may be mentioned. The polymerization initiation temperature is usually about 20 to 90 ° C., and the reaction time is about 1 to 10 hours. When a component that is hardly soluble in water is used as a monomer, it is desirable to use a hydrophilic organic solvent in combination.

Representative examples of the above hydrophilic organic solvents include, for example, lower alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol, cyclic ethers such as tetrahydrofuran and dioxane, acetone, acetonitrile, dimethylformamide, dimethylacetamide and dimethylacetate. Sulfoxide and the like. Among them, particularly preferred are tetrahydrofuran, acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like.

As the polymerization initiator, a peroxide, an organic or inorganic peracid or a salt thereof, which is homogeneously dissolved in a solvent, and a redox-based azobis compound alone or in combination with a reducing agent are used. As typical examples thereof, for example, t-butyl peroxide, t-
Amyl peroxide, cumyl peroxide, acetyl peroxide, propionyl peroxide, benzoyl peroxide, benzoyl isobutyryl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cyclohexyl hydroperoxide, tetralin hydroperoxide, t-butyl Peracetate, t-butyl perbenzoate, bis (2-ethylhexylperoxydicarbonate), 2,
2'-azobisisobutyronitrile, phenylazotriphenylmethane, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2
-Imidazolin-2-yl) propane] dihydrochloride, 2,2 '
-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, sodium persulfate, potassium persulfate,
Examples include a combination of ammonium persulfate, hydrogen peroxide, a persulfate with a tertiary amine such as triethylamine, triethanolamine, dimethylaniline and the like.

Among these, t-butyl peroxide, benzoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2 ' -Azobis [2- (5-methyl-2
-Imidazolin-2-yl) propane] dihydrochloride, 2,2 '
-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, sodium persulfate, potassium persulfate or ammonium persulfate alone, or a mixture of these persulfates with triethylamine, triethanolamine or dimethylaniline; Combinations with tertiary amines are preferred.

The polymerization apparatus used for producing the copolymer of the present invention is not particularly limited. In the aqueous solution polymerization method, for example, a container having a plurality of rotating stirring arms is used. The container having a plurality of rotary stirring arms needs to be capable of imparting a shearing force to the hydrogel polymer produced with the progress of the polymerization when the monomer mixture is polymerized in an aqueous solution by rotating the rotary stirring arms. is there. It is necessary to have a plurality of rotary stirring arms, and as such a container, for example, a device such as a double-arm kneader (hereinafter simply referred to as a kneader) can be mentioned. When using a kneader, two rotating stirring arms are used by rotating them in opposite directions at a constant speed or at a constant speed.
In the case of constant velocity, the rotating radii of the two rotary stirring arms are used in a state where they have overlapping portions, and in the case of non-uniform velocity, the rotating radii of the two rotary stirring arms are used without overlapping. The rotary stirring arm may be any of a sigma type, an S type, a Banbury type or a fish tail type.

One example of the procedure for producing the copolymer of the present invention is as follows.
A 50% by weight aqueous solution is fed in, the system is replaced with an inert gas such as nitrogen if necessary, a water-soluble radical polymerization initiator is added, and polymerization is carried out at room temperature or at 30 to 70 ° C. The method may be a method in which the polymerization is started, and the polymerization is completed while the hydrogel polymer produced with the progress of the polymerization is finely divided by the shearing force caused by the rotation of the blades of the kneader. Of course, the scope of the present invention is not limited by this example. The initial concentration of the monomer mixture aqueous solution used here is preferably 10 to 50% by weight.

The amount of the polymerization initiator to be used is in the range of 0.01 to 5 mol%, preferably 0.01 to 3 mol%, particularly preferably 0.01 to 1 mol%, based on the monomer component. By the way, when the amount of the polymerization initiator used is more than 5 mol% based on the monomer component, the degree of polymerization of the main chain polymer chain does not increase, and the ratio of non-crosslinked polymer chains increases, and water and Expected performance cannot be exhibited because it is easily dissolved in organic solvents. On the other hand, when it is less than 0.01 mol%, the reaction rate of the polymerization reaction does not increase, and there is a problem that the amount of the residual monomer increases.

The reaction product is in the form of a gel containing the solvent used in the reaction, and is usually pulverized with a rotary cutter or the like.
The solvent is removed by a method such as heating and reduced pressure, and the powder is dried and pulverized and classified to obtain a powder.

In the reverse phase suspension polymerization method, a monomer component and a crosslinking agent are uniformly dissolved in water, and the suspension is emulsified or suspended in an organic solvent which is not uniformly mixed with water using a dispersant or the like. Perform the reaction. As the polymerization initiator, not only a water-soluble polymerization initiator but also a polymerization initiator soluble in an organic solvent is used. As the organic solvent used here, in addition to the above,
For example, hydrocarbon organic solvents such as hexane, cyclohexane, heptane, octane, benzene, toluene, xylene and ethylbenzene, halogenated hydrocarbon organic solvents such as carbon tetrachloride and dichloroethane, and mineral oils such as Isobar are also used.

Examples of the dispersing agent include sorbitan monostearate, sorbitan monopalmitate, polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, sugar ester (Mitsubishi Chemical Corporation)
Product name).

The removal of dissolved oxygen in the system, the treatment of the reaction product, and the like are the same as described above, and the reaction conditions are not necessarily limited, but are generally as follows. Amount of solvent used: Equivalent to 20-fold, preferably equivalent to 10-fold as aqueous monomer solution, Amount of polymerization initiator used: 0.01 to 5 mol%, preferably 0.01 to 3 mol% based on monomer component The polymerization initiation temperature is about 10 to 90 ° C., and the reaction time is about 1 to 10 hours.

[Measurement Method of Viscosity and Dynamic Viscoelasticity] The cationic group-containing copolymer of the present invention has good thixotropic properties,
That is, when the viscosity at 25 ° C. when added to ion-exchanged water so as to be 0.5% by weight has a shear rate of 1 sec ⁻¹ ,
0.3 to 20 Pa · sec, and when the share rate is 10 sec ⁻¹ , it is 0.01 to 5 Pa · sec, and the share rate is 1 sec.
^Although the viscosity at ^-1 shows a thixotropic property higher than the viscosity at a shear rate of 10 sec ^-1 , the viscosity in the present invention was measured by the following method.

That is, the copolymer was added to ion-exchanged water such that the concentration of the cationic group-containing copolymer having an average particle diameter of 50 μm or less was 0.5% by weight, and left at 50 ° C. for half a day to obtain a hydrogel. For the hydrogel, a coaxial double cylinder type of a sensor system SV-DIN was used as a rotor using a viscometer manufactured by HAAKE, Rotovisco RV-20, and a measuring head M10. Store the hydrogel stored at 25 ° C in the rotor for 10-15.
Then, the measurement was started at 25 ° C. Share rate (se
The c- ¹ ) time program reduces the share rate to 0s in 2 minutes.
It was raised from ec ^-1 to 15 sec ^-1 . During this time, 60 points of data were stored using software. Program used was a Rotation Version 2.3, shear rate was calculated viscosity at a 1 sec ^-1 and 10 sec ^-1 eta a (Pa · sec).

When the cationic group-containing copolymer of the present invention is added to ethanol and the viscosity is measured, the same conditions and methods as in the case of ion-exchanged water are used except that the addition concentration is 2.0% by weight. Was.

Further, the dynamic viscoelasticity of the cationic group-containing copolymer of the present invention was measured by the following method. A hydrogel is prepared by adding the cationic group-containing copolymer having an average particle size of 50 μm or less to ion-exchanged water so that the concentration becomes 0.5% by weight. At 25 ° C., a dynamic viscoelasticity measurement device (Rheometrics, Fluids Spectrometer RF
S-II) in Dynamic Strain Sweep mode, using a cone plate with a diameter of 50 mm, a gap of 0.05 mm, a cone angle of 0.04 rad, a strain frequency of 6.28 rad / sec and a strain of Dynamic viscoelasticity measurements were made with the change set at 0.5-500%.

[0052]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 A methyl chloride adduct of dimethylaminopropyl methacrylamide (MAPTAC: MAPTAC: 1 liter) was placed in a stainless steel kneader having an internal volume of 1 liter and two sigma-type stirring arms in which oil at 55 ° C. was externally circulated in a jacket. Nitto Chemical Industry Co., Ltd.
17.58 g, N, N-dimethylacrylamide 71.37
g, polyethylene glycol dimethacrylate (NK-9
G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.0429 g, ion-exchanged water 350
g of a monomer aqueous solution which had been replaced with nitrogen in advance, and nitrogen gas was further blown therein for 20 to 40 minutes to raise the temperature of the monomer aqueous solution while replacing the inside of the reaction system with nitrogen. Next, 0.22 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added as a polymerization initiator. The polymerization started 30 minutes to 1 hour after the addition of the polymerization initiator, and the whole became a soft gel. Stirring was continued as it was, and the lid was removed 4 hours after the addition of the polymerization initiator, to terminate the polymerization. The mochi-like content was taken out, washed with stirring in 5 liters of ethanol for 5 to 10 minutes, and dried. Then, it was pulverized with a coffee mill and a jet mill. The pulverized crosslinked particles were classified with a high volter to obtain a cationic group-containing copolymer.

Example 2 In Example 1, the methyl chloride adduct of dimethylaminopropyl methacrylamide was added to 24.92 g of methacryloyloxyethyltrimethylammonium chloride (QDM: manufactured by Nitto Chemical Industry Co., Ltd.), and N, N-dimethylacrylamide was added. To 67.41 g, and polyethylene glycol dimethacrylate to pentaerythritol triallyl ether.
The same operation was performed except that the amount was changed to 0.0103 g, to obtain a cationic group-containing copolymer.

When the infrared absorption spectrum of this copolymer was measured, a spectrum as shown in FIG. 1 was obtained. The spectrum was 1620 to 1650 cm ^-1 (C = O expansion and contraction) derived from the tertiary amide structure, and 1730 to 1730 cm ^-1 derived from the ester bond. 1740cm ^-1 (C = O stretching), methyl,
2900-3000cm ^-1 (CH ₂ , CH ₃ stretch) derived from methylene bond
Was observed, indicating that the desired copolymer was obtained.

Example 3 In Example 1, the amount of the methyl chloride adduct of dimethylaminopropyl methacrylamide was increased to 123.1 g, and N, N-
The same operation was carried out except that the amount of dimethylacrylamide was changed to 23.8 g and the amount of polyethylene glycol dimethacrylate was changed to 0.107 g, to obtain a cationic group-containing copolymer.

Example 4 In Example 1, the amount of methyl chloride adduct of dimethylaminopropyl methacrylamide was adjusted to 17.58 g, and N, N
-Dimethylacrylamide in a mixture of 67.8 g of N, N-dimethylacrylamide and 4.58 g of Nt-butylacrylamide, and 0.0429 g of polyethylene glycol dimethacrylate (NK-1G: manufactured by Shin-Nakamura Chemical Co., Ltd.) The same operation was carried out except that the copolymer was changed to a copolymer having a cationic group.

Example 5 In Example 1, N, N-dimethylacrylamide was added to 29.85 g of a 65% aqueous solution of diallyldimethylammonium chloride (DADMAC: manufactured by Daiso Co., Ltd.) using the methyl chloride adduct of dimethylaminopropyl methacrylamide. The same operation was performed except that the amount of polyethylene glycol dimethacrylate was changed to 0.0214 g to 57.8 g of N-methylacrylamide to obtain a cationic group-containing copolymer.

Example 6 In Example 1, a methyl chloride adduct of dimethylaminopropyl methacrylamide was added to 93.42 g of an 80% aqueous solution of dimethylaminoethyl methacrylate diethyl sulfate (MOEDES: manufactured by Nitto Chemical Industry Co., Ltd.), and N was added. , N-dimethylacrylamide was converted to N-acroylmorpholine (ACMO: manufactured by Kojin Co., Ltd.) 79.07 g and the amount of polyethylene glycol dimethacrylate was changed to 0.129 g, and the same operation was carried out to obtain a cationic group-containing compound. A copolymer was obtained.

Comparative Example 1 In Example 1, the amount of methyl chloride adduct of dimethylaminopropyl methacrylamide was changed to 8.79 g, and N, N-
A similar operation was carried out except that the amount of dimethylacrylamide was changed to 75.34 g and polyethylene glycol dimethacrylate was not added, to obtain a cationic group-containing copolymer.

Comparative Example 2 In Example 1, without adding the methyl chloride adduct of dimethylaminopropyl methacrylamide, the amount of N, N-dimethylacrylamide was increased to 75.34 g, and polyethylene glycol dimethacrylate was replaced with ethylene glycol dimethacrylate (NK). -1G: manufactured by Shin-Nakamura Chemical Co., Ltd.) A copolymer was obtained in the same manner except that the amount was changed to 1.072 g.

Comparative Example 3 In Example 1, the amount of the methyl chloride adduct of dimethylaminopropyl methacrylamide was changed to 43.96 g, and N, N
-Dimethylacrylamide is converted to methoxypolyethylene glycol methacrylate (M-90G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 9
The same operation was performed except that the amount of polyethylene glycol dimethacrylate was changed to 0.0214 g to 3.6 g to obtain a cationic group-containing copolymer.

Comparative Example 4 Anionic group-containing polymer BF manufactured by BF Goodrich
ARBOPOL941 (polyacrylic acid crosslinked polymer) was used as a comparative sample as it was.

Test Example 1 Using the copolymers obtained in Examples 1 to 6 and Comparative Examples 1 to 4, the viscosity at 25 ° C. when added to ion-exchanged water so as to be 0.5% by weight, Viscosity at 25 ° C when added to 2.0 wt%, and
The dynamic viscoelasticity of the aqueous solution at 25 ° C. when added to 0.5% by weight was measured by the above method. Table 1 shows the results.

[0065]

[Table 1]

Test Example 2 The copolymers obtained in Examples 1 to 6 and Comparative Examples 1 to 4
It was added to ion-exchanged water so as to be 1.0% by weight and left at 50 ° C. for half a day to obtain a viscous hydrogel. The resulting hydrogel was examined for ease of application and residual strength according to the methods described below. Table 2 shows the results.

<Ease of application> 5 ml of the obtained hydrogel was placed on the right forearm of 10 panelists, and the ease of application (ease of spreading) was slowly extended with the palm of the left hand. Was evaluated based on the following evaluation criteria.

Evaluation criteria 1: Very easy to apply 2: Easy to apply 3: Slightly easy to apply 4: Difficult to apply <Strength of residual feeling> Take 5 ml of the obtained hydrogel by hand, Put it on the right forearm of a human paneler, with the left palm,
The skin was slowly spread, left for 5 minutes, washed thoroughly with tap water and wiped with a towel, and the skin texture was examined based on the following evaluation criteria.

Evaluation criteria A: Strong residual feeling B: Some residual feeling C: Somewhat residual feeling D: No residual feeling felt In this case, the stronger the residual feeling of the hydrogel,
preferable.

[0070]

[Table 2]

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the cationic group-containing copolymer obtained in Example 2.

────────────────────────────────────────────────── ─── Continued on the front page (72) Koji Yui, Inventor 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Laboratory (56) References JP-A-4-241197 (JP, A) JP-A-62-44270 (JP, A) JP-A-8-3229 (JP, A) JP-A-2-196806 (JP, A) JP-A-63-120710 (JP, A) JP-A-2-24359 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C08F 220/00-220/70 C08F 226/00-226/12

Claims (8)

(57) [Claims] 1. A cationic nonionic group-containing vinyl monomer represented by the general formula (III) or (IV), and a hydrophilic nonionic group represented by the general formula (I) or (II): At least one kind of vinyl monomer containing a vinyl group, acryloy
Methacryloyl and allyl groups
A cationic group-containing copolymer obtained by radical polymerization of at least one kind of crosslinkable vinyl monomer having at least two groups in a molecule as an essential constituent monomer .
A Ranaru thickener, a viscosity at 25 ° C. upon addition to 0.5 wt% in deionized water, shear rate
When 1 sec ^-1, a 0.3~20Pa · sec, when the shear rate 10 sec ^-1, a 0.01~5Pa · sec, and the viscosity is shear rate at the shear rate of 1 sec ^-1 10 sec
^A thickener comprising a cationic group-containing copolymer, which is higher in viscosity than ^-1 . Embedded image [In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms. [Chemical formula 2] [In the formula, R ¹ has the same meaning as above, A ¹ and A ² are the same or different and represent a group represented by the formula-(CH ₂ ) _n- (n represents an integer of 2 to 6) , B is -O- or -CH ₂ - shows a group. [Chemical formula 3] (R ¹ has the above meaning, R ⁴ and R ⁵ are the same or different and each represent an alkyl group or an alkenyl group having 1 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. shows, Y is -O -, - NH- or _{-O-CH 2 CH (OH)} - represents a group, Z is a straight or branched alkylene group having 1 to 4 carbon atoms, X is the acid Conjugated base, halogen atom or 1-4 carbon atoms
Represents an alkyl sulfate group. [Formula 4] Wherein R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or a methyl group; R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Show meaning. ] 2. The physical properties obtained by dynamic viscoelasticity of an aqueous solution at 25 ° C. when added to ion-exchanged water so as to be 0.5% by weight are as follows: frequency: 6.28 rad / sec, strain: 1%
, The complex elastic modulus is 1 N / m ² or more and 300 N / m ² or less, the loss tangent (tan δ) is 2 or less, the frequency is 6.28 rad / sec,
When the 500% strain, the complex elastic modulus is 0.01 N / m ² or more 30 N / m
² or less, consisting of cationic group-containing copolymer according to claim 1, wherein the loss tangent (tan [delta) is greater than 1
Thickener . 3. The physical properties obtained by dynamic viscoelasticity of an aqueous solution at 25 ° C. when added to ion-exchanged water so as to be 0.5% by weight are as follows: frequency: 6.28 rad / sec, strain: 1%
, The complex elastic modulus is 1 N / m ² or more and 300 N / m ² or less, the loss tangent (tan δ) is 1.5 or less, and the frequency is 6.28 rad / sec.
When the strain is 500%, the complex elastic modulus is 0.01N / m ² or more and 30N /
^3. The cationic group-containing copolymer according to claim 1, wherein the loss tangent (tan δ) is 1 or more.
A thickener consisting of 4. The physical properties obtained by dynamic viscoelasticity of an aqueous solution at 25 ° C. when added to ion-exchanged water at 0.5% by weight are as follows: frequency 6.28 rad / sec, strain 1%
, The complex elastic modulus is 1 N / m ² or more and 300 N / m ² or less, the loss tangent (tan δ) is 1 or less, and the frequency is 6.28 rad / sec.
When the 500% strain, the complex elastic modulus is 0.01 N / m ² or more 30 N / m
^The thickener comprising the cationic group-containing copolymer according to any one of claims 1 to 3, wherein a loss tangent (tan δ) is ² or less. 5. The method according to claim 5, wherein the hydrophilic nonionic group-containing vinyl monomer comprises N, N-dimethyl (meth) acrylamide and N, N
Increasing consisting cationic group-containing copolymer according to claim 1, characterized in that at least one selected from N- diethyl (meth) acrylamide
Adhesive . 6. A vinyl group, acryloyl group, methacryloyl
2. The amount of the crosslinkable vinyl monomer having at least two groups selected from an yl group and an allyl group in a molecule is 0.002 to 5% by weight based on the total amount of the monomer. A thickener comprising the cationic group-containing copolymer according to any one of claims 1 to 5. 7. A vinyl group, acryloyl group, methacrylo
The amount of the crosslinkable vinyl monomer having at least two groups selected from an yl group and an allyl group in the molecule is not less than 0.002% by weight and less than 0.1% by weight based on the total amount of the monomer. A thickener comprising the cationic group-containing copolymer according to any one of claims 1 to 6. 8. The viscosity at 25 ° C. when added to ethanol at 2.0% by weight is 0.3 to 20 Pa · sec when the shear rate is 1 sec ⁻¹ , and the shear rate is 10 sec.
^{When -1} , it is 0.01-5Pa · sec, and the share rate
Thickening consists cationic group-containing copolymer according to any one of claims 1 to 7, the viscosity at a 1 sec ^-1 is equal to or higher than the viscosity at a shear rate of 10 sec ^-1
Agent .