JP2001106732A - Cationic polymer, cationic polymer fine particle and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer having a cationic hydrophilic group and hydrophobic group simultaneously, and a high cationic group density, and to provide a method for producing cationic polymer fine particles having a high cation density, high safety for a living body and low environmental load. SOLUTION: This polymer having a cationic hydrophilic group and hydrophobic group simultaneously is produced by imparting both cationic hydrophilic group and hydrophobic group to a monomer itself by introducing an alkyl group having 5-20 number of carbon atoms into an N-substituted aminoalkyl (meth)acrylate or N-substituted aminoalkyl(method)acrylamide, and polymerizing them with another radically polymerizable monomer. Further, by using the cationic polymer as a protective colloid and polymerizing a vinyl monomer, new cationic polymer particles having both hydrophilicity and hydrophobicity on the surface of the fine particles and having a high cationic group density can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationic polymer and a method for producing the same, and cationic polymer fine particles using the cationic polymer and a method for producing the same. More specifically, a cationic polymer having both a quaternary ammonium base and a long-chain alkyl group in the same molecule and usable as a polymeric surfactant and a solubilizer, and a method for producing the same,
The cationic polymer is used as a protective colloid to obtain a vinyl monomer by emulsion polymerization. In various fields such as cosmetics, paints, electronic information materials, and papermaking additives, antistatic, viscosity control, pigment dispersion, The present invention relates to cationic polymer fine particles that can be used for fixing and improving the papermaking yield, and a method for producing the same.

[0002]

2. Description of the Related Art When a polymer having both a cationic hydrophilic group and a hydrophobic group is produced, a vinyl compound having a tertiary amino group and a hydrophobic vinyl compound are first copolymerized, and then the tertiary amino group is alkylated with an alkylating agent. It is common to quaternize the groups. However, in this method, since the alkylation step is a polymer reaction, it is difficult to perform a quantitative reaction, and it is difficult to obtain a polymer having a desired cation density. In addition, since the alkylating agent generally dislikes water, strict process control is required, and there is a problem that the production conditions are greatly restricted. JP-A-8-2
No. 52447 discloses a hydrophilic monomer (meth) acrylamidoalkylsulfonic acid and a hydrophobic monomer N
A method for copolymerizing an alkyl-substituted (meth) acrylamide in N, N-dimethylformamide is disclosed. In this method, it is possible to polymerize a monomer having contradictory properties of hydrophilicity and hydrophobicity in a homogeneous system by using a polar solvent having a strong dissolving power. However, this method requires reprecipitation and purification of the polymer with a poor solvent, which is not suitable for industrial production.

On the other hand, cationic polymer fine particles are generally prepared by emulsion polymerization of a vinyl monomer using a cationic emulsifier, emulsion polymerization of a vinyl monomer using a polymer having a cationic group as a protective colloid, or cationic water-soluble polymer. It is produced by reverse-phase emulsion polymerization of a reactive monomer. JP-A-8-2
No. 7349, by polymerizing a monomer having an ionic functional group and an unsaturated double bond in an organic solvent, and then subjecting the solvent to an aqueous medium, and adding an ethylenically unsaturated monomer to carry out emulsion polymerization. A method for obtaining an aqueous emulsion of cationic polymer microparticles is disclosed. However, this method not only causes an increase in cost due to a complicated manufacturing process, but also
It is not preferable because there is a concern about residual solvent. JP 9
In -195170, a quaternary ammonium salt-containing vinyl monomer is polymerized in a cationic polymer protective colloid aqueous solution to form an aqueous solution of a quaternary ammonium salt polymer, and the vinyl monomer is added to the aqueous solution. There is disclosed a cationic emulsion comprising cationic vinyl polymer particles obtained by polymerization and a method for producing the same. In this method, the cationic polymer is adsorbed on the particle surface, but there is a problem that a sufficient cationic group density cannot be obtained due to the structure of the cationic polymer.

[0004]

An object of the present invention is to provide a method for industrially producing a polymer having both a cationic hydrophilic group and a hydrophobic group, and to provide a cationic group having a high cationic group density and a high emulsion stability. An object of the present invention is to provide a method for producing polymer fine particles.

[0005]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that N-substituted aminoalkyl (meth) acrylates or N-substituted aminoalkyl (meth) acrylamides have carbon atoms. By introducing an alkyl chain of 5 to 20, both a cationic hydrophilic group and a hydrophobic group are imparted to the monomer itself, and the monomer is polymerized with another radically polymerizable vinyl compound to form a cationic hydrophilic group. It has been found that a polymer having both a hydrophobic group and a hydrophobic group can be easily obtained. Further, by using the cationic polymer of the present invention, it is possible to obtain a stable cationic emulsion, which has been difficult to produce in the prior art, and to stably emulsify and disperse an oil-soluble substance in an aqueous medium to obtain a conventional cationic polymer. It has been found that it has an emulsifying and dispersing ability exceeding that of a surfactant. Furthermore, the cationic polymer having a high cationic group density is obtained by emulsion-polymerizing a vinyl monomer by using a cationic polymer having a quaternary ammonium base and a long-chain alkyl group in the same molecule of the present invention as a protective colloid. The present inventors have found that fine particles can be obtained and completed the present invention.

That is, the first invention of the present invention relates to the following general formula (1)

Embedded image(R¹Represents a hydrogen atom or a methyl group;²Is a methyl group
Or an ethyl group. A is O or NH, and P is
X is an alkylene group having 10 or less carbon atoms, X is Cl, Br,
F, I, BF₄, CH₃SO₄, CH₃CH₂SO₄,
CH₃C₆H₄SO ₃Is shown. n is an integer of 5 to 20
10 to 80 parts by weight of the compound (I) represented by
General formula (2)

Embedded image (R ³ is a hydrogen atom or a methyl group, R ⁴ is a methyl group,
R ⁵ represents a methyl group, an ethyl group or a benzyl group; B is O or NH; Q is an alkylene group having 10 or less carbon atoms; Y is Cl, Br, F, I, BF ₄ , CH ₃
SO ₄ , CH ₃ CH ₂ SO ₄ , and CH ₃ C ₆ H ₄ SO ₃ are shown. 20) to 90 parts by weight of the compound (II) represented by the formula (1) and radical polymerizable monomers 0 to 7 copolymerizable therewith.
A cationic polymer obtained by copolymerizing 0 parts by weight (however,
The total of the compounds (I) and (II) and the radical polymerizable monomer copolymerizable therewith is 100 parts by weight. ) ”.

The second invention of the present invention has a gist of "cationic polymer fine particles obtained by emulsion-polymerizing a vinyl monomer using the cationic polymer obtained in the first invention as a protective colloid".

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The compound (I) serving as a basic structural unit of the cationic polymer of the present invention includes N-substituted aminoalkyl (meth) acrylate such as dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate;
Alternatively, it is produced by quaternizing an N-substituted aminoalkyl (meth) acrylamide such as (meth) acrylamidodimethylaminopropyl with an alkylating agent having 5 to 20 carbon atoms. Octyl chloride as an alkylating agent,
Examples include octyl bromide, dodecyl chloride, dodecyl bromide, tetradecyl chloride, tetradecyl bromide, hexadecyl chloride, hexadecyl bromide and the like. If the alkylating agent has less than 5 carbon atoms, the cationic polymer after polymerization is too strong in hydrophilicity, which is not preferable. On the other hand, if the number of carbons exceeds 20, the hydrophobicity is too strong.

The compound (I) is produced by mixing and reacting N-substituted aminoalkyl (meth) acrylate or N-substituted aminoalkyl (meth) acrylamide with the above alkylating agent in a polar organic solvent. . Examples of the polar organic solvent used include methyl alcohol, ethyl alcohol, isopropyl alcohol, protic solvents such as n-butyl alcohol, acetone, acetonitrile, dimethylformamide, aprotic solvents such as dimethyl sulfoxide, and the like. Acetone and acetonitrile are preferred.

The molar ratio of the reaction is as follows: 1 mole of N-substituted aminoalkyl (meth) acrylate or 1 mole of N-substituted aminoalkyl (meth) acrylamide to 0.1 mole of alkylating agent.
The range is 5 to 2.0 mol, and more preferably 1.0 to 2.0 mol.
The range is 1.5. If the amount is less than 0.5 mol, the N-substituted aminoalkyl (meth) acrylate or N-substituted aminoalkyl (meth) acrylamide having high polymerizability may remain excessively after the alkylating agent is consumed to form a homopolymer. Is undesirably high. Also,
If it exceeds 2.0 moles, an expensive alkylating agent remains in excess, which is disadvantageous in cost and is not preferred.

Specific examples of compound (I) include (meth)
Acryloyloxyethyl dimethyloctyl ammonium chloride, (meth) acryloyloxyethyl dimethyl octyl ammonium bromide, (meth) acryloyloxyethyl dimethyl dodecyl ammonium chloride, (meth) acryloyloxyethyl dimethyl dodecyl ammonium bromide, (meth) acryloyloxyethyl dimethyl hexadecyl Ammonium chloride, (meth) acryloyloxyethyldimethylhexadecylammonium bromide, (meth) acryloyloxyethyldiethyloctylammonium chloride, (meth) acryloyloxyethyldiethyloctylammonium bromide, (meth) acryloyloxyethyldiethyldodecylammonium chloride,
(Meth) acryloyloxyethyl diethyldodecyl ammonium bromide, (meth) acryloyloxyethyl diethylhexadecyl ammonium chloride,
(Meth) acryloyloxyethyl diethylhexadecyl ammonium bromide, (meth) acryloylaminopropyldimethyloctylammonium chloride,
(Meth) acryloylaminopropyldimethyloctylammonium bromide, (meth) acryloylaminopropyldimethyldodecylammonium chloride, (meth) acryloylaminopropyldimethyldodecylammonium bromide, (meth) acryloylaminopropyldimethylhexadecylammonium chloride, ( (Meth) acryloylaminopropyldimethylhexadecylammonium bromide and the like.

Specific examples of compound (II) include (meth)
Acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethyltrimethylammonium methylsulfate, (meth) acryloyloxyethyldimethylethylammoniumethylsulfate, (meth) acryloyloxyethyl Trimethylammonium p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, (meth) acryloylaminopropyltrimethylammonium methylsulfate, (meth) acryloylaminopropyldimethylethylammoniumethyl Sulfate, (meta Acryloylamino trimethylammonium p- toluenesulfonate and the like. Of these, methacryloyloxyethyltrimethylammonium chloride and (meth) acryloylaminoproltrimethylammonium chloride are particularly preferred.

The radical polymerizable monomer copolymerizable with the compounds (I) and (II) is not particularly limited, but styrene, α-methylstyrene, (meth) acrolein, methyl (meth) acrylate, ( (Meth) ethyl acrylate,
N-butyl (meth) acrylate, i (meth) acrylate
so-butyl, tert-butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) ) Phenyl acrylate, benzyl (meth) acrylate, N-
Isopropyl (meth) acrylamide, N-tert-
Butyl (meth) acrylamide, lauryl (meth) acrylamide, vinyl acetate, styrene sulfonic acid (sodium salt), (meth) acrylic acid (sodium salt), 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylic acid Hydroxypropyl, (meth) acrylic acid 4-
Hydroxyethyl, 6-hydroxyhexyl (meth) acrylate, vinylsulfonic acid (sodium salt), allylsulfonic acid (sodium salt), methallylsulfonic acid (sodium salt), (meth) acrylamide, N-methylol (meth) acrylamide , N-vinylpyrrolidone, N
-Vinylformamide, N-vinylacetamide and the like.

The monomer unit constituting the cationic polymer of the present invention is compound (I) 10 to 10 parts by weight in total.
80 parts by weight, 20 to 90 parts by weight of compound (II), 0 to 7 vinyl monomers copolymerizable with compounds (I) and (II)
Each is used in a range of 0 parts by weight. Cationic polymer
Is used as a protective colloid, when compound (I) is 10
If the amount is less than part by weight, the hydrophilicity of the protective colloid is too strong,
It is not preferable because the emulsion cannot be stabilized during the emulsion polymerization. On the other hand, if the amount exceeds 80 parts by weight, the hydrophobicity of the protective colloid is too strong, and the protective colloid becomes insoluble in water, which is not preferable. If the amount of the compound (II) is less than 20 parts by weight, the hydrophilicity of the protective colloid becomes insufficient and the protective colloid becomes insoluble in water, which is not preferable. Also, 90
Exceeding the weight part is not preferred because the hydrophilicity of the protective colloid is too strong and the emulsion cannot be stabilized during emulsion polymerization. On the other hand, if the amount of the vinyl monomer copolymerizable with the compounds (I) and (II) exceeds 70 parts by weight, the emulsifying and dispersing function of the protective colloid is unpreferably reduced.

The cationic polymer of the present invention can be produced by a known polymerization method, but is particularly preferably produced by polymerization in an aqueous medium using a radical polymerization initiator.
The term “aqueous medium” used herein refers to a solvent in which water is 100% or a mixture of water and a polar organic solvent at an arbitrary ratio. The polar organic solvent may be any as long as it can be mixed with water at any ratio.Specifically, methanol, ethanol, a protic solvent such as isopropanol, acetonitrile, acetone,
Aprotic solvents such as dimethylformamide and dityl sulfoxide are exemplified. Of these, methyl alcohol, ethyl alcohol and isopropyl alcohol are particularly preferred. These media may be a single medium composed of only one type, or a mixed medium composed of two or more types.

The radical polymerization initiator is not particularly limited, and can be arbitrarily selected from known ones. Specifically, benzoyl peroxide, tert-butyl hydroperoxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, azobisisobutyronitrile,
2,2′-azobis (2-aminodipropane) dihydrochloride, 2,2′-azobis (2-aminobutane) hydrochloride,
Examples thereof include 2,2′-azobis (2,4-dimethylvaleronitrile), and among them, 2,2′-azobis (2-aminodipropane) dihydrochloride is particularly preferable.

The cationic polymer of the present invention can be used as a surfactant. Specific examples include a cationic protective colloid used for emulsion polymerization, and an emulsifying dispersant for dispersing an oil-soluble substance in an aqueous medium.

When the cationic polymer of the present invention is used as a protective colloid for emulsion polymerization, it may be prepared by aqueous solution polymerization immediately before emulsion polymerization and used directly as an emulsion polymerization medium, or it may be prepared in advance by solution polymerization to obtain a powder. It may be taken out and stored as a body, and redissolved in water as needed to prepare an emulsion polymerization medium.

The cationic polymer fine particles according to the second invention of the present invention are produced by adding a vinyl monomer to an aqueous protective colloid solution of the cationic polymer and performing emulsion polymerization. Examples of the vinyl monomer used in the emulsion polymerization include styrene, α-methylstyrene, (meth) acrolein, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylate. ) Iso-butyl acrylate, t- (meth) acrylate
tert-butyl, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, (meth)
Glycidyl acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxypropyl, (meth) acrylic acid 4-
Examples include hydroxyethyl, 6-hydroxyhexyl (meth) acrylate, crotonic acid, maleic acid and the like. Of these, (meth) acrylates such as methyl methacrylate are particularly preferred.

The radical polymerization initiator used in the emulsion polymerization is not particularly limited, but is preferably a water-soluble one, such as tert-butyl hydroperoxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, etc. 2,2'-azobis (2-amidinopropane)
Dihydrochloride, 2,2'-azobis (2-amidinobutane)
An azo-based polymerization initiator such as dihydrochloride may be used, and may be used alone or as a mixture of two or more. Further, a redox-based polymerization initiator obtained by combining a reducing agent such as a tertiary amine, a sulfite, or a ferrous salt with the above-described peroxide, or a combination of a redox-based polymerization initiator and an azo-based polymerization initiator is used. And a polymerization initiator. The amount of the radical polymerization initiator used is 0.0
It is 0.01 to 10% by weight, preferably 0.01 to 1% by weight, and more preferably 0.05 to 0.5% by weight. The polymerization temperature is usually in the range of room temperature to 100 ° C,
Preferably, it is carried out in the range of 60 to 80 ° C.

Examples of the polymerization method include a method in which a vinyl monomer and other components are charged at once, a method in which a part or all of the vinyl monomer is dropped, and a method in which the vinyl monomer is dropped. Controlling the polymerization temperature is easy and preferable. By the above method, cationic polymer fine particles having an average particle diameter of 10 μm or less and a high cationic group density can be produced.

[0022]

EXAMPLES Examples of the cationic polymer and cationic polymer fine particles of the present invention will be described below in more detail, but the present invention is not limited to these examples. -Physical property analysis-<Weight average molecular weight> The weight average molecular weight of the cationic polymer is determined by using an apparatus: HPLC8010 series manufactured by Tosoh Corporation, and a column: TSKgelG4000P manufactured by Tosoh Corporation.
W, detector: RI8000 (differential refractometer) manufactured by Tosoh Corporation, eluent: 1.0 M acetate buffer (pH 4.5), standard substance: polyethylene glycol, gel permeation chromatography (GPC) ). <Cation group density> The cation group density is a theoretical value calculated by the following equation. Cation group density = cation monomer-component amount (mol) /
<Emulsion particle size> per 1 g of polymer (solid content) The particle size of the cationic polymer fine particles was determined by diluting the obtained emulsion to a concentration of 1 to 3%, and then ultrasonically dispersing the emulsion for 1 hour. The average particle size was measured by -130 (laser diffraction method).

<Synthesis Example 1> 157 g of dimethylaminoethyl methacrylate (acryester DM, manufactured by Mitsubishi Rayon Co., Ltd.) and octyl bromide (in a 2 L four-necked flask equipped with a stirrer, thermometer, temperature controller, nitrogen inlet tube, and condenser) 193 g of acetone (manufactured by Wako Pure Chemical Industries, Ltd.) and 700 g of acetone were charged and reacted at 40 ° C. for 20 hours in a nitrogen stream. After completion of the reaction, acetone was distilled off under reduced pressure, and a large excess of ethyl acetate was added to the obtained crystals, followed by stirring for 30 minutes. The crystals were filtered off with suction, washed three times with ethyl acetate and dried under reduced pressure, and 262 g of white crystals of a cationic monomer, methacryloyloxyethyldimethyloctyl ammonium bromide (CM1).
(Yield: 75%) was obtained.

<Synthesis Example 2> A cationic monomer, methacryloyloxyethyldimethyl, was prepared in the same manner as in Synthesis Example 1 except that 305 g of hexadecyl bromide (manufactured by Wako Pure Chemical Industries) was used instead of 157 g of octyl bromide. 300 g (65% yield) of white crystals of hexadecyl ammonium bromide (CM2) were obtained.

<Synthesis Example 3> A cationic monomer, methacryloylaminoethyldimethyloctyl ammonium bromide (CM3) was prepared in the same manner as in Synthesis Example 1 except that methacrylamidodimethylaminopropyl was used instead of dimethylaminoethyl methacrylate. ) Was obtained in an amount of 252 g (yield: 72%).

<Synthesis Example 4> The procedure of Synthesis Example 2 was repeated, except that methacrylamidodimethylaminopropyl was used instead of dimethylaminoethyl methacrylate, and a cationic monomer, methacryloylaminoethyldimethylhexadecyl ammonium bromide ( CM
286 g (yield: 62%) of white crystals of 4) were obtained.

Example 1 A cationic monomer (CM1) 10 was placed in a 300 ml separable flask equipped with a stirrer, thermometer, temperature controller, nitrogen inlet tube, and condenser.
g, methacryloylaminopropyltrimethylammonium chloride (MAPTAC, manufactured by Nitto Riken Kogyo) 10
g, 80 g of demineralized water, and nitrogen bubbling for 30 minutes at room temperature with stirring.
2'-azobis (2-amidinopropane) dihydrochloride (V
-50) (Wako Pure Chemical Industries, Ltd.) (0.1 g) was added and polymerized for 5 hours. After concentrating the polymerization solution under reduced pressure, a large excess of ethyl acetate was added to precipitate the polymer. This was separated by filtration, washed and dried under reduced pressure, and the cationic polymer Poly (CM1-
Co-MAPTAC) 17 g (yield: 85)
%, Weight average molecular weight: 72000, cationic group density 3.
7 × 10 ⁻³ mol / g).

Example 2 In the same apparatus as in Example 1, 5 g of a cationic monomer (CM2), 15 g of methacryloyloxyethyltrimethylammonium chloride (acrylic ester DMC, manufactured by Mitsubishi Rayon), and 40 parts of demineralized water
g, and methanol 40 g, and stirred at room temperature for 3 hours.
After nitrogen bubbling for 0 minutes, the internal temperature was raised to 50 ° C,
0.1 g of V-50 was added and polymerized for 5 hours. When the polymerization solution was concentrated under reduced pressure and a large excess of acetone was added, the polymer precipitated. This was separated by filtration, washed and dried under reduced pressure, and 14.6 g (yield: 73%, weight average molecular weight) of a white powder of a cationic polymer Poly (CM2-co-DMC) was obtained.
68000, cation group density 5.4 × 10 ⁻³ mol /
g) was obtained.

Example 3 In the same apparatus as in Example 1, 10 g of a cationic monomer (CM3) and MAPTAC10
g, 80 g of demineralized water, and nitrogen bubbling for 30 minutes at room temperature with stirring. Then, the internal temperature was raised to 50 ° C., and V-
50 0.1 g was added and polymerization was carried out for 5 hours. When the polymerization solution was concentrated under reduced pressure and a large excess of acetone was added, the polymer precipitated. This is separated by filtration, washed and dried under reduced pressure, and cationic polymer Poly (CM3-co-MAPTAC)
Of white powder (yield: 77%, weight average molecular weight: 120,000, cationic group density: 4.3 × 10 ⁻³ m)
ol / g).

Example 4 In the same apparatus as in Example 1, 5 g of a cationic monomer (CM4), 15 g of methacryloyloxyethyltrimethylammonium chloride (acrylester DMC, manufactured by Mitsubishi Rayon Co., Ltd.), and methanol 4
0 g and demineralized water (40 g) were added and stirred at room temperature for 30 g.
After bubbling nitrogen for 5 minutes, the internal temperature was raised to 50 ° C.
0.1 g of -50 was added and polymerization was carried out for 5 hours. When the polymerization solution was concentrated under reduced pressure and a large excess of acetone was added, the polymer precipitated. This was separated by filtration, washed and dried under reduced pressure, and 16.8 g (yield: 84%, weight average molecular weight: 6) of a cationic polymer Poly (CM4-co-DMC) white powder.
7000, cation group density 5.8 × 10 ⁻³ mol /
g) was obtained.

Comparative Example 1 In the same apparatus as in Example 1, 10 g of acrylester DMC and 10 parts of lauryl methacrylate (acrylester L, LMA manufactured by Mitsubishi Rayon) were added.
g of methanol and 80 g of methanol.
After nitrogen bubbling for 0 minutes, the internal temperature was raised to 50 ° C and V
0.1 g of -50 was added and polymerization was carried out for 5 hours. After concentrating the polymerization solution under reduced pressure, a large excess of ethyl acetate was added to precipitate the polymer. This was separated by filtration, washed and dried under reduced pressure, and 17.0 g (yield: 85%, weight average molecular weight) of a white powder of a cationic polymer Poly (DMC-co-LMA):
320,000). The cationic group density of this polymer was 3.1 × 10 ⁻³ mol / g, and it was hardly soluble in water.

Comparative Example 2 An apparatus similar to that of Example 1
15 g of APTAC, 5 g of stearyl methacrylate (acrylester SL, SLMA, manufactured by Mitsubishi Rayon) and 80 g of methanol were charged, and the mixture was bubbled with nitrogen at room temperature for 30 minutes with stirring.
0.1 g was added and polymerization was carried out for 5 hours. After concentrating the polymerization solution under reduced pressure, a large excess of ethyl acetate was added to precipitate the polymer. This was separated by filtration, washed and dried under reduced pressure, and 15.0 g (yield: 75%, weight average molecular weight: 24) of a white powder of a cationic polymer Poly (DMC-co-SLMA) was obtained.
0000). The cationic group density of this polymer was 3.3 × 10 ⁻³ mol / g.

Example 5 Use Example 1 as Surfactant Demineralized water 500 was placed in a 1 L separable flask equipped with a stirrer, thermometer, temperature controller, nitrogen inlet tube, and condenser.
g, the cationic polymer Poly obtained in Example 2
After charging 10 g of (CM2-co-DMC) and 100 g of MMA and bubbling nitrogen at 70 ° C. with stirring at 70 ° C., 0.05 g of V-50 was added and emulsion polymerization was carried out for 5 hours to obtain a stable emulsion. Obtained. When the obtained emulsion particle diameter was measured by LS-130 (laser diffraction method) manufactured by Coulter, the average particle diameter was 2.0.
μm.

Example 6 Use Example 2 as Surfactant In a 200 ml beaker, 100 g of demineralized water, 1.0 g of limonene (oil-soluble fragrance): The cationic polymer Poly (CM2-co) obtained in Example 2 -DMC) was weighed out and mixed with stirring at room temperature for 60 minutes, whereby limonene was emulsified and dispersed to form a stable emulsion. On the other hand, in the blank in which the cationic polymer was not added, limonene remained separated on the water surface even after stirring and mixing.

Example 7 A 300 ml separable flask equipped with a stirrer, a thermometer, a temperature controller, a nitrogen inlet tube, and a condenser was charged with 50 g of methacryloyloxyethyldimethyloctyl ammonium bromide (CM1).
Methacryloyloxyethyltrimethylammonium chloride (acrylester DMC, manufactured by Mitsubishi Rayon) 50
g and 300 g of methanol, nitrogen gas was bubbled at room temperature for 30 minutes while stirring, the internal temperature was raised to 50 ° C., 0.1 g of V-50 was added, and polymerization was carried out for 5 hours. When the polymerization solution was concentrated under reduced pressure and a large excess of acetone was added, a polymer precipitated. This was separated by filtration, washed and dried under reduced pressure, and 91 g of a white powder of cationic polymer (CP1) (yield:
91%, weight average molecular weight: 123000).

Example 8 A reaction apparatus similar to that of Example 7 was charged with 25 g of methacryloyloxyethyldimethylhexadecylammonium bromide (CM2), 75 g of methacryloyloxyethyltrimethylammonium chloride (DMC), and 300 g of methanol. After bubbling nitrogen for 30 minutes at room temperature,
The temperature was raised to 0 ° C, 0.1 g of V-50 was added, and polymerization was carried out for 5 hours. When the polymerization solution was concentrated under reduced pressure and a large excess of acetone was added, a polymer precipitated. This was separated by filtration, washed and dried under reduced pressure, and 85 g of a white powder of a cationic polymer (CP2) (yield: 85%, weight average molecular weight: 68000)
I got

Example 9 A 1 L flat bottom flask equipped with a stirrer, thermometer, temperature controller, nitrogen inlet tube, and condenser was charged with 500 ml of deionized water and cationic polymer (CP).
1) 10 g, methyl methacrylate (acrylic ester M,
MMA, manufactured by Mitsubishi Rayon Co., Ltd.), 20 g, and nitrogen bubbling at 70 ° C. for 30 minutes with stirring.
After addition of 0.1 g and emulsion polymerization for 0.5 hours,
80 g of MMA was added dropwise over 1 hour to continue emulsion polymerization.
After completion of the dropwise addition, the mixture was aged for 2 hours while maintaining the temperature at 70 ° C. to obtain a milky white emulsion of cationic polymer fine particles. 5
1 g of this emulsion was weighed and placed in a 0 ml beaker, diluted 10 times with demineralized water, and dispersed in an ultrasonic water tank for 1 hour. The particle size was measured by a laser diffraction method. The average particle size was 0.45 μm. Was. The cationic group density was 3.5 × 10 ⁻⁴ mol / g.

<Embodiment 10> An apparatus similar to that of Embodiment 9 is used.
500 ml of demineralized water, 5 g of methacryloyloxyethyldimethyloctylammonium bromide (CM1) and 5 g of methacryloyloxyethyltrimethylammonium chloride (DMC) were charged, and the mixture was bubbled with nitrogen at 50 ° C. for 30 minutes with stirring, and 0.1 g of V-50 was added. Then, the aqueous solution was polymerized for 3 hours to prepare an aqueous protective colloid solution. Thereafter, the temperature was raised to 70 ° C., MMA 20 g, V-50
After adding 0.1 g and performing emulsion polymerization for 0.5 hour,
80 g of MMA was added dropwise over 1 hour to continue emulsion polymerization.
After completion of the dropwise addition, the mixture was aged for 2 hours while maintaining the temperature at 70 ° C. to obtain a milky white emulsion of cationic polymer fine particles. When the particle size was measured in the same manner as in Example 9, the average particle size was 0.41 μm. The cationic group density was 5.3 × 10 ⁻⁴ mol / g.

Example 11 In the same reactor as in Example 9, 500 ml of demineralized water and cationic polymer (CP2) were added.
10 g and 20 g of methyl methacrylate were charged, and nitrogen bubbling was performed at 70 ° C. for 30 minutes with stirring.
After addition of 0.1 g and emulsion polymerization for 0.5 hours,
80 g of MMA was added dropwise over 1 hour to continue emulsion polymerization.
After completion of the dropwise addition, the mixture was aged for 2 hours while maintaining the temperature at 70 ° C. to obtain a milky white emulsion of cationic polymer fine particles. When the particle size was measured in the same manner as in the example, the average particle size was 0.72 μm. The cationic group density was 5.3 × 10 ⁻⁴ mol / g. Examples 9 to
Emulsion No. 11 was stable without any aggregates or sediments even after 4 weeks.

Comparative Example 3 The same apparatus as in Example 9 was charged with 500 ml of demineralized water and 10 g of methacryloyloxyethyltrimethylammonium chloride (DMC).
After nitrogen bubbling at 50 ° C. for 30 minutes with stirring,
An aqueous solution of protective colloid was prepared by adding 0.1 g of -50 and polymerizing the aqueous solution for 3 hours. Thereafter, the temperature was raised to 70 ° C.
After adding 20 g of MA and 0.1 g of V-50 and emulsion-polymerizing for 0.5 hour, 80 g of MMA was further added dropwise to continue the emulsion polymerization, but as the polymerization progressed, aggregates increased and stable cationic polymer fine particles were obtained. Could not be obtained.

Comparative Example 4 In the same apparatus as in Example 9, 500 ml of demineralized water and cation-modified polyvinyl alcohol 1 were added.
0 g was charged, and nitrogen bubbling was performed at 70 ° C. for 30 minutes with stirring to prepare an aqueous protective colloid solution. After this, MMA
After adding 20 g and 0.1 g of V-50 and performing emulsion polymerization for 0.5 hour, 80 g of MMA was further added dropwise to continue emulsion polymerization. After completion of the dropwise addition, the mixture was aged for 2 hours while maintaining the temperature at 70 ° C. to obtain a milky white emulsion. When the particle size was measured in the same manner as in the example, the average particle size was 0.31 μm. The cation group density is 0.4 × 10 ⁻⁴ mol /
g. After 4 weeks, a slight amount of sediment was observed in the obtained emulsion.

Comparative Example 5 50 ml of demineralized water, 100 g of MMA, and 3 g of trimethylhexadecyl ammonium chloride were weighed into a 300 ml tall beaker, and were weighed at 13,000 rpm using an emulsifier (T-25 basic manufactured by IKA).
The mixture was emulsified at pm for 3 minutes to prepare an emulsion. In the same apparatus as in Example 9, 450 ml of demineralized water and 30 ml of the above-mentioned emulsion were charged and nitrogen bubbling was performed at 70 ° C. for 30 minutes with stirring. Then, immediately after adding 0.1 g of V-50, the remaining emulsion was removed. It was added dropwise to carry out emulsion polymerization. After completion of the dropwise addition, the mixture was aged for 2 hours while maintaining the temperature at 70 ° C. to obtain a milky white emulsion. When the particle diameter was measured in the same manner as in the example, the average particle diameter was 0.11 μm. The cationic group density was 0.9 × 10 ⁻⁴ mmol / g. In the obtained emulsion, sedimentation of particles was observed after 2 weeks.

[0043]

According to the present invention, a novel cationic polymer having both hydrophilicity and hydrophobicity in the same molecule and having a high cationic group density can be obtained. The cationic polymer can be used as a polymer surfactant, a solubilizer, a viscosity modifier and the like, and is expected to be applied in a wide range of industrial fields such as cosmetics and paints. Further, according to the cationic polymer of the present invention, novel cationic polymer fine particles having both hydrophilicity and hydrophobicity on the surface of the fine particles and having a high cationic group density can be obtained. The cationic polymer fine particles are used in various fields such as cosmetics, paints, electronic information materials, and papermaking additives, for moisturizing properties, conditioning effects, antistatic, viscosity control, pigment dispersion / fixing, and improving papermaking yield. It is possible.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J011 KA15 KB08 KB29 4J100 AB02R AB07R AG04R AJ02R AK08R AL03R AL04R AL05R AL08P AL08Q AL08R AL09R AL10R AL11R AM15R AM17R AM21P AM21Q AM21R AN04R AP01R BAQR38 BC03 DA55 JA01 JA13 JA15 JA43 JA61

Claims (6)

[Claims] [Claim 1] The following general formula (1)(R¹Represents a hydrogen atom or a methyl group;²Is a methyl group
Or an ethyl group. A is O or NH, and P is
X is an alkylene group having 10 or less carbon atoms, X is Cl, Br,
F, I, BF₄, CH₃SO₄, CH₃CH₂SO₄,
CH₃C₆H₄SO ₃Is shown. n is an integer of 5 to 20
10 to 80 parts by weight of the compound (I) represented by
General formula (2)(R³Represents a hydrogen atom or a methyl group;⁴Is a methyl group,
An ethyl group is represented by R⁵Represents a methyl, ethyl, or benzyl group
Show. B represents O or NH, and Q represents an alkyl having 10 or less carbon atoms.
Y represents Cl, Br, F, I, BF₄, CH₃
SO₄, CH₃CH₂SO₄, CH₃C₆H₄SO₃To
Show. 20) to 90 parts by weight of the compound (II) represented by
And radical polymerizable monomers 0 to 7 copolymerizable therewith.
A cationic polymer obtained by copolymerizing 0 parts by weight. (However
And compounds (I) and (II) and copolymerizable with them
The total amount of the radical polymerizable monomers is 100 parts by weight. ) 2. The compound (II) is (meth) acryloyloxyethyltrimethylammonium chloride or (meth) acryloylaminopropyltrimethylammonium chloride, and the polymer has a cationic group density of 3.5 × 10 ⁻³ mol / mol. 2. The cationic polymer according to claim 1, wherein the amount is at least g. 3. A compound according to claim 1, wherein the compounds (I) and (II) and the radical polymerizable monomer copolymerizable therewith are polymerized in an aqueous medium using a radical polymerization initiator. A method for producing a cationic polymer. 4. Cationic polymer fine particles obtained by emulsion-polymerizing a vinyl monomer using the cationic polymer according to claim 1 as a protective colloid. 5. The cationic polymer particles according to claim 4, wherein the vinyl monomer is a (meth) acrylate. 6. A method for producing cationic polymer fine particles, wherein a vinyl monomer is emulsion-polymerized using the cationic polymer according to claim 1 as a protective colloid.