JPS61159412A - Production of cationic emulsion - Google Patents

Abstract

PURPOSE:To obtain the title emulsion excellent in adsorptivity of a negatively charged substance and suitable as an adhesive or the like, by polymerizing a vinyl monomer in the presence of a cationic acrylic copolymer containing a polymerizable quat. ammonium salt. CONSTITUTION:A cationic copolymer is prepared which comprises a quat. ammonium nitrogen-containing polymerizable quat. ammonium salt of the formula (wherein R and R' are each a 1-20C alkyl, R'' is a 1-20C alkyl, a 6-15C aromatic group of the like group and R''' is a 2-6C ethylene bond-containing aliphatic hydrocarbon), e.g, 2-hydroxy-3-methacryloxypropyltrimethyl-ammonium chloride) and a monomer selected from among (meth)-acrylate, styrene, acrylonitrile, butadiene, vinyl acetate, etc. A vinyl monomer (e.g, vinyl acetate) is polymerized in the presence of this copolymer to obtain the title emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Industrial Field of Application The present invention relates to a method for producing a cationic emulsion, more particularly containing a quaternary nitrogen atom and having the general formula (where R and R' are carbon atoms). R'' represents an alkyl group having 1 to 20 carbon atoms, or an aromatic or alicyclic group having 6 to 15 carbon atoms, and R'' represents a carbon atom. 2-6
represents an aliphatic hydrocarbon group having one ethylene bond, and X represents a chlorine or bromine atom. ) and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate 5 ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid In the presence of a cationic copolymer consisting of an acrylate monomer such as hydroxy-7-ethyl, and at least one of styrene, acrylonitrile, butadiene, isoprene, vinyl chloride, or vinyl acetate.

Related to a method for producing a cationic emulsion characterized by polymerizing vinyl monomers OB, Conventional technology Conventionally, cationic emulsions obtained by polymerizing vinyl monomers in the presence of a cationic emulsifier are Although it has many potential uses, at present it is hardly produced on an industrial scale. There are various reasons for this, but one is that it lacks stability throughout the entire chassis process and tends to generate a large amount of coagulum. Although it is not impossible to solve this problem, the cationic emulsifiers selected for this purpose are highly toxic, which not only causes problems in the treatment of emulsion waste liquid, but also may cause cationic emulsifiers depending on the application of the emulsion. Even pollution due to the release of the emulsifier is expected.

In addition, cationic emulsions obtained by polymerizing vinyl monomers in the presence of a cationic emulsifier or polymerizing vinyl monomers in the presence of a nonionic emulsifier or using a hydrophilic polymer substance as a protective colloid are also available. Cationic emulsions obtained by adding cationic emulsifiers to emulsions often have serious deficiencies when used to take advantage of their cationic properties. That is, upon adsorption to an anionic substance, the cationic emulsifier is preferentially removed from the surface of the emulsion particles, causing destabilization of the emulsion particles. As a result, homogeneous adsorption of the emulsion particles to the anionic substance does not occur, making it impossible to achieve the objective.

On the other hand, in emulsions in which cationic groups are chemically bonded or strongly adsorbed to the particle surface, the above phenomenon is not observed and adsorption to anionic substances occurs homogeneously, but there are cases where the desired performance cannot be obtained. Often. This is often a problem with the particle size of the emulsion, and if the emulsion is simply cationic, adsorption will occur but sufficient performance will not be obtained in many cases.

Problems to be Solved by the C0 Invention In view of the above-mentioned drawbacks of the prior art, the present invention is significantly superior in adsorption ability to negatively charged substances.

Stable. The present invention also provides a method for producing a cationic emulsion with a small particle size.

Means for Solving Problem D1 In view of the above-mentioned drawbacks of the prior art, the present inventors have developed a method that is significantly superior in adsorption ability to negatively charged substances. As a result of intensive study on a method for producing a stable cationic emulsion with small particle size, we found that it contains a quaternary nitrogen atom and has the general formula OOHR. R'' represents an alkyl group having 1 to 20 carbon atoms or an aromatic or alicyclic group having 6 to 15 carbon atoms; R'' represents an alkyl group having 2 to 20 carbon atoms; ~6
represents an aliphatic hydrocarbon group having one ethylene bond, and X represents a chlorine or bromine atom. ) and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and methyl methacrylate.

Ethyl methacrylate, propyl methacrylate.

At least one hydrophobic polymerizable monomer selected from acrylic ester monomers such as butyl methacrylate and hydroquinethyl methacrylate, styrene, acrylonitrile, butadiene, isoprene, vinyl chloride, and vinyl acetate. The present inventors have discovered that the above-mentioned objective can be achieved by polymerizing a vinyl monomer in the presence of a cationic copolymer consisting of a vinyl monomer and a cationic copolymer, and have completed the present invention.

Cationic copolymer used in the present invention
containing a class nitrogen atom and having the general formula (where R and R' represent an alkyl group having 1 to 20 carbon atoms, and R'' represents an alkyl group having 1 to 20 carbon atoms or an alkyl group having 6 to 15 carbon atoms). represents an aromatic or alicyclic group having 2 to 2 carbon atoms.
It represents an aliphatic hydrocarbon group having six atom and one ethylene bond, and X represents a chlorine or bromine atom. ) and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and methyl methacrylate.

Acrylic acid ester monomers such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, hydroxoethyl methacrylate, styrene, acrylonitrile, butadiene, isoprene, vinyl chloride or vinyl acetate. Both mean a copolymer with a kind of hydrophobic polymerizable monomer.

Specific examples of the polymerizable quaternary ammonium salt represented by the above general formula include 2-hydroquine-3-methacryloxypropyltrimethylammonium chloride, 2-hydroxy-3-acryloxypropyltrimethylammonium chloride, and 2-hydroxy/-3 -methacryloxyglobiltriethylammonium bromide, 2-hydroxy-3-methacryloxypropyltributylammonium chloride, 2-hydrogine-3-methacryloxypropylmethyletherpterammonium chloride, 2-hydroxy-3-methacryloxypropyldimethylphenylammonium chloride, 2-hydroxy-3-methacryloquinepropyldimethylcyclohexylammonium chloride, and the like.

These can be used alone or in combination of two or more,
Among them, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride is preferably used.

The cationic copolymer used in the present invention includes the polymerizable quaternary ammonium salt, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylate. Acrylic acid ester monomers such as propyl acid, butyl methacrylate, hydroxyethyl methacrylate, styrene, acrylonitrile, butadiene, isoprene,
Vinyl chloride can be obtained by radical copolymerization with at least one hydrophobic polymerizable monomer selected from vinyl acetate using a polymerization initiator.

As the polymerization initiator, any compound that generates cationic or nonionic free radicals can be used, such as 2,2-azobis(2-amidinopropane) hydrochloride, hydrogen peroxide, or the like. and a reducing agent, cumene hydroperoxide and t
-butyl hydroperoxide or a combination thereof with a reducing agent. Other known anionic polymerization initiators can also be used as long as they do not impair the intended effects of the present invention. Any commonly used polymerization solvent can be used, but water is preferably used because it can proceed directly to the nibble John polymerization of the present invention after producing the cationic copolymer.

A preferred example of the cationic copolymer used is one or more of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride and an acrylic ester monomer, styrene or vinyl acetate. Copolymers with the monomers are particularly preferably used to obtain the desired stable cationic emulsion with small particle diameters.

Polymerizable quaternary ammonium salts and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate in a copolymer with at least one hydrophobic polymerizable monomer selected from acrylic acid ester monomers such as styrene, acrylonitrile, butadiene, isopre, vinyl chloride or vinyl acetate. The content of the polymerizable quaternary ammonium salt is preferably 10% by weight to 90% by weight in the copolymer, particularly 20% by weight S
~85% by weight is more preferred, especially 35. It's arrogant~
Particularly preferred is 85 layers.

Furthermore, for the purpose of imparting cationic properties to the target emulsion particles, all polymers in the emulsion were added. 90
．． It is preferable that the vinyl tertiary polymer used in the emulsion polymerization of the present invention is present in an amount of 0.01% by weight or more, such as vinyl acetate, vinyl globionate, vinyl persate, vinyl chloride, vinylidene chloride, These can be used alone or in combination of two or more, but vinyl acetate is most preferably used. In addition, styrene, substituted styrene,
Acrylic acid or methacrylic acid with an alcohol having 1 to 12 carbon atoms, acrylonitrile, butadiene, imprene, etc. can be used, but these are preferably used in combination with the above-mentioned vinyl acetate, etc. In some cases, the stability of the emulsicone is improved. In addition, for the purpose of modifying the emulsion mentioned above, ethylene,
There is no problem even if isobutyne, acrylamide, N-methylolacrylamide, N,N-dimethylmethacrylamide, methacrylonitrile, divinylbenzene, ethylene glycol dimethyl acrylate, etc. are copolymerized. Furthermore, cationic monomers such as dimethylaminoethyl methacrylate, diethylamine ethyl methacrylate, and 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride can also be used as polymerizable monomers.

The emulsion polymerization method in the present invention includes polymerizable 4R ammonium salts and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methacrylic acid. Acrylic acid ester monomers such as butyl, hydroxyethyl methacrylate, styrene, acrylonitrile, butadiene, isoprene,
The clear method involves first synthesizing a copolymer with at least one hydrophobic polymerizable monomer selected from vinyl chloride or vinyl acetate, and then emulsion polymerizing a vinyl monomer in the presence of the copolymer. Methods consisting of separate steps are preferred, but the following methods are also included. That is, for example, when a polymerizable quaternary ammonium salt is copolymerized with hinyl acetate to be polymerized in an aqueous medium, an apparent emulsion is obtained; As the polymerization progresses, the content of polymerizable quaternary ammonium salt in the newly formed copolymer decreases, and in some cases, the final polymer becomes substantially hydrophilic. There are books out there that are made of polyvinyl acetate.

In this case, the extremely hydrophilic copolymer containing polymerizable quaternary ammonium formed initially becomes a kind of protective colloid, and emulsion shore polymerization proceeds. When present, stability during polymerization is improved.

Polymerization agents used here include polymerizable quaternary ammonium salts, methyl acrylate, ethyl acrylate,
Acrylic acid ester monomers such as propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, styrene/,
The same one used for the copolymerization with at least one hydrophobic polymerizable monomer selected from acrylonitrile, butadiene, isoprene, vinyl chloride or vinyl acetate is used.

The cationic copolymer conveniently used in the present invention is 0.01 to 20 parts by weight, preferably 0.05 to 1 part by weight, per 100 parts by weight of the vinyl monomer to be emulsion polymerized.
It is used in a range of 0 parts by weight.

In addition, in order to maintain stability during polymerization, other protective colloids, such as water-soluble polymeric substances such as polyvinyl alcohol and its derivatives, cellulose derivatives such as hydroxyl ethyl cellulose, and methyl cellulose, may be added to the polymerization system as necessary. be able to. Furthermore, known nonionic emulsifiers and cationic emulsifiers can be added as long as they do not impair the spirit of the present invention.

The emulsion obtained by the present invention has a remarkable ability to adsorb negatively charged substances, is stable, and has small particle diameters, and the film made from it has excellent water resistance. That being said, K also has one characteristic.

In addition, compared to emulsions normally produced using G' emulsifiers or emulsions using a hydrophilic polymeric substance such as polyvinyl alcohol as a protective colloid, the method of the present invention has the advantage that emulsifiers or hydrophilic Another feature is that even if a polymeric substance is used, only a small amount is required.

80 Actions and Effects of the Invention The cationic emulsion obtained by the present invention has the features of outstanding adsorption ability to negatively charged substances, good stability, and small particle size.
Useful for adhesives, cement joints, etc. It may be appropriate to add a substance such as dibutyl phthalate to the emulsion as an external plasticizer for the polymer in the emulsion during or after the polymerization, depending on the final purpose. The present invention will be explained in more detail, but the present invention is not limited to these Examples. In the examples, "parts" means "parts by weight" unless otherwise specified.

Example 1 After purging a separable flask equipped with a stirrer and a nitrogen inlet tube with nitrogen, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (
Below are the monomers [! ] and abbreviated as suru. ) and 0.5 parts of methyl methacrylate monomer were added with 70 parts of ion-exchanged water that had been purged with nitrogen in advance, and dissolved at room temperature.

After raising the temperature to 70°C, an aqueous initiator solution of 0.5 parts of 2,2'-azobis(2-amidinopropane) sulfate and 5 parts of ion-exchanged water was added and polymerized for 1 hour to obtain [1]. An aqueous copolymer solution with methyl methacrylate was obtained. Then 60
℃, add 5 parts of vinyl acetate monomer, and add 3 parts of vinyl acetate monomer.
After polymerizing for 0 minutes, 90 parts of vinyl acetate monomer was added to 1
The mixture was added continuously for 00 minutes and polymerized. 10 minutes after the start of addition of vinyl acetate monomer in A, 10%
30 parts of an aqueous solution of Newport PK-68 (nonionic emulsifier, Sanyo Chemical Industries, Ltd.) was added at once. Nine days after the continuous addition of vinyl acetate monomer was completed, the temperature was raised to 70°C.
The reaction was aged for 1 hour to complete the polymerization.

The resulting emulsion was stable and had a solids concentration of 48.
0%, and the particle size was 0.1 to 0.3μ.

Example 2 A separate flask equipped with a stirrer and a nitrogen inlet tube was purged with nitrogen, and then 70 parts of ion-exchanged water, which had been purged with nitrogen in advance, was added to 2.0 parts of monomer [I] and 0.5 parts of vinyl acetate monomer, and dissolved at room temperature. did.

After raising the temperature to 70°C, an aqueous initiator solution consisting of 0.5 parts of 2.2-azobis(2-amidinopropane) hydrochloride and 5 parts of ion-exchanged water was added and allowed to stand for 1 hour. A copolymer with vinyl was obtained. Next, the temperature was adjusted to 60°C, 5 parts of vinyl acetate monomer was added, and after stirring for 30 minutes, the temperature was adjusted to 60°C.
of vinyl acetate monomer was continuously added over 100 minutes for polymerization. 30 minutes after the start of the addition of vinyl acetate monomer, 20 parts of a 10% (by weight) aqueous solution of polyvinyl alcohol (partially saponified product, degree of polymerization 500) was continuously added, and 70 minutes after the continuous addition of vinyl acetate monomer was completed. The temperature was raised to °C and the reaction was aged for 1 hour to complete the polymerization.

The resulting emulsion is stable and has a high solids content! 47.
9%, and the particle size was as small as 0.1-0.3μ.

Example 3 A separable flask equipped with a stirrer and a nitrogen inlet tube was purged with nitrogen, and then 70 parts of ion-exchanged water, which had been smoothed and purged with nitrogen, was added to 2.0 parts of monomer [1] and 1.0 part of methyl acrylate monomer. Dissolved at room temperature. After raising the temperature to 70°C, an initiator aqueous solution of 0.5 parts of 2,2-azobis(2-amidinopropane) hydrochloride and 5 parts of ion-exchanged water was added and polymerized for 1 hour to form (I) and methyl acrylate. A copolymer was obtained.

Subsequently, the temperature was adjusted to 60°C and 5 parts of vinyl acetate was added.
was added and polymerized for 30 minutes, and then 90 parts of vinyl acetate monomer was continuously added and polymerized over 100 minutes. 30 minutes after the start of addition of vinyl acetate monomer, 1
After the continuous addition of 20 parts of 0% (weight it) polyvinyl alcohol (partially saponified product, degree of polymerization 500) aqueous solution and the continuous addition of vinyl acetate monomer was completed, the temperature was raised to 70°C and reaction aging was performed for 1 hour to polymerize. was completed.

The resulting emulsion was stable and had a solid content of 48,
The 1%1 particle size was as small as 0.1 to 0.3μ.

Comparative Example 1 After purging the same reactor as in Example 1 with nitrogen, 70 parts of ion-exchanged water, which had been purged with nitrogen in advance, was added to 2.0 parts of monomer (1) and dissolved at room temperature. After heating to 70°C, , 2. Add an initiator aqueous solution of 0.5 parts of 2'-azobis(2-amidinopropane) hydrochloride and 10 parts of ion-exchanged water, and mix for 1 hour to obtain [1] with [η] of 0.18. An aqueous homopolymer solution was obtained. Subsequently, the temperature was adjusted to 60°C, 5 parts of vinyl acetate monomer was added, and after polymerization for 30 minutes, 9
0 parts of vinyl acetate monomer was continuously added over 100 minutes to perform one polymerization. Halfway through, 30 minutes after the start of addition of vinyl acetate monomer, 10% (fi) polyvinyl alcohol (partially saponified product 1 polymerization [500) water solution #20
The addition of acetic acid and nyl monomer was started at the same time as the addition of 100% of the monomer. Continuous addition ended at 570
The temperature was raised to 'C' and reaction aging was carried out for 1 hour to complete one polymerization.

Although the obtained emulsion (solid content concentration 50.2%) showed good stability, the particle diameter was relatively large at 0.2-0.4μ.

Comparative Example 2 The same reactor as in Example 1 was replaced with nitrogen, and the hole diameter, monomer [
1] and 0.75 parts of acrylamide as a hydrophilic polymerizable monomer were added with 70 parts of ion-exchanged water that had been previously substituted with nitrogen, and dissolved at room temperature. After raising the temperature to 70℃, 2.2'-azobis(2-amidinopropane)
An aqueous initiator solution containing 0.25 parts of hydrochloride and 5 parts of ion-exchanged water was added and polymerized for 1 hour to obtain a copolymer of (1) and acrylamide as a hydrophilic polymerizable monomer. Subsequently, the temperature was adjusted to 60°C, 3 parts of acetic acid and vinyl monomer were added, and after polymerization for 30 minutes, 92 parts of vinyl acetate monomer was continuously added over 100 minutes.

I hope it polymerizes. 10 minutes after the start of the addition of acetic acid and nil monomer, 20 parts of a 10% (by weight) aqueous solution of polyvinyl alcohol (partially saponified product, degree of polymerization 500) was added all at once. After finishing the continuous addition of vinyl acetate monomer, the temperature was raised to 70°C.
The temperature was raised to 1, and aging was performed for 1 hour to complete one polymerization.

Although the obtained emulsion (solid content concentration: 49.8%) was stable, the particle diameter was quite large, ranging from 0.5 to 1.0 .mu.m.

Comparative Example 3 A separable flask equipped with a stirrer 1 and a nitrogen inlet tube was purged with nitrogen, and then monomer (1) 2. 70 parts of ion-exchanged water which had been previously substituted with nitrogen was added to part O and 0.1 part of methyl methacrylate heptamer and dissolved at room temperature. After raising the temperature to 70°C, an initiator aqueous solution of 0.5 parts of 2,2'-azobis(2-amidinopropane) hydrochloride and 5 parts of ion-exchanged water was added and polymerized for 1 hour to form [1] and methacrylic acid. A copolymer with methyl was obtained.

The temperature was carefully adjusted to 60°C, 5 parts of acetic acid and vinyl monomer were added, and the mixture was combined for 30 minutes. After that, 90 parts of vinyl acetate monomer was continuously added and combined over 100 minutes. During the process, 10 minutes after the start of addition of the vinyl acetate monomer, 30 parts of 10% (by weight) New Ball PE-68 (nonionic emulsifier, manufactured by Sanyo Chemical Industries, Ltd.) in water was added all at once. 7 after the addition is complete
The temperature was raised to 0'C, and the reaction was aged for 1 hour to complete the combination.The resulting emulsion was stable and had a solid content concentration of 47.
The effect of copolymerizing 9%1 particle size of 0.2 to 0.4 μ and methyl methacrylate was not observed.

Comparative Example 4 A separable flask equipped with a stirrer and a nitrogen inlet tube was purged with nitrogen, and then 70 parts of ion-exchanged water, which had been previously purged with nitrogen, was added to 0.1 s part of monomer CI and 2.0 parts of methyl methacrylate monomer, and dissolved at room temperature. did. After raising the temperature to 70°C, an initiator aqueous solution of 0.5 parts of 2,2-azobis(2-amidinopropane) hydrochloride and 5 parts of ion-exchanged water was added and polymerized for 1 hour to form CI) and methyl methacrylate. A copolymer was obtained. The temperature was then adjusted to 60°C, 5 parts of vinyl acetate monomer was added, and the mixture was polymerized for 30 minutes. After that, 90 parts of vinyl acetate monomer was continuously added and polymerized over 100 minutes. Halfway through, 30 minutes after the start of the addition of vinyl acetate monomer, 10% (by weight) of two-knee ball PE-
68C nonionic emulsifier, manufactured by Sanyo Chemical Industries ■] Aqueous solution 3
0 parts were added all at once. However, at the end of the continuous addition of vinyl acetate monomer, coagulation occurred and a stable emulsion could not be obtained.

Next, in order to examine the effects of the psychokinetic thionic emulsions obtained in the above Examples and Comparative Examples, the following two tests were conducted.

+IJ Adhesion Test Example 1. Each of the emulsions of Comparative Example 1 and Comparative Example 2 was diluted to a solid content concentration of 40% by adding 10 wt% of dibutyl phthalate based on the solid content, and applied on an asbestos slate board so that the dry film was 200 μm. Then, a cotton cloth was placed thereon as a reinforcing material and air-dried for 3 days to form a film. Width this film with a cutter knife! A cut was made at n, and the temperature and humidity were controlled for 3 days at a temperature of 206 G and a relative humidity of 65% RH, and the gouge strength was measured on an autograph at an angle of r90°. The results are shown in Table 1.

Table 1 As is clear from Table 1, the cationic emulsion with small particle size obtained by the present invention has extremely excellent adhesion to asbestos slate, whereas 2-hydroquine-3- When a homopolymer of methacryloxypropyltrimethylammonium chloride was used (Comparative Example 1), fc was.

Even when using a copolymer of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, if the other component of the copolymerization is a hydrophilic polymerizable monomer such as acrylamide (comparative example) 2),
The particle size of the resulting cationic emulsion is 0.5 to 1.
．． It is found that it is quite large at 0μ, and has only poor adhesion to the asbestos slate board.

(2) Water resistance test The emulsion obtained by the present invention, in particular the polyvinyl acetate emulsion that uses polyvinyl alcohol as part of the stabilizer, has excellent water resistance of the film, unlike ordinary polyvinyl acetate emulsion. In comparison with commercially available polyvinyl acetate emulsions, Examples 1 and 2
The emulsions obtained in 3 and 3 are shown below. The test method is J
According to IS K6828-1977 water drop test. (Second
Table) Table 2

Claims (1)

[Claims] (1) Contains a quaternary nitrogen atom and has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R and R' represent an alkyl group having 1 to 20 carbon atoms, R'' represents an alkyl group having 1 to 20 carbon atoms or an aromatic or alicyclic group having 6 to 15 carbon atoms, and R'' represents an alkyl group having 1 to 20 carbon atoms;
It represents an aliphatic hydrocarbon group having six atom groups and one ethylene bond, and X represents a chlorine or bromine atom. ) and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid In the presence of a cationic copolymer consisting of an acrylic acid ester monomer such as hydroxyethyl, styrene, acrylonitrile, butadiene, isoprene, vinyl chloride or vinyl acetate,
A method for producing a cationic emulsion, which comprises polymerizing a vinyl thread monomer. (2) A patent claim in which the polymerizable quaternary ammonium salt containing a quaternary nitrogen atom and having the general formula ▲ has a mathematical formula, chemical formula, table, etc. ▼ is 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride. The manufacturing method described in Scope 1. (8) The production method according to claim 1, wherein the vinyl monomer is vinyl acetate. (4) The production according to claim 1, wherein the cationic polymer is a copolymer of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride and vinyl acetate, and the vinyl monomer is vinyl acetate. Law. (5) The production method according to claim 1, wherein the content of the polymerizable quaternary ammonium salt in the cationic copolymer is 10% by weight to 90% by weight.