JP2010195897A - Method for producing acrylic polymer particle having positively charging property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing acrylic polymer particles having an excellent positively charging property. <P>SOLUTION: In the method for producing the polymer particles including a step for producing an acrylic polymer particles by making an acrylic polymerizable monomer absorbed in seed particles in the presence of the seed particles in an aqueous medium to perform seed emulsion polymerization, the seed particles are vinyl polymer particles, the acrylic polymerizable monomer is a compound having 40 to 100 wt.% (meth)acrylate-based monomer and 0 to 60 wt.% vinyl polymerizable monomer which can be polymerized together with the (meth)acrylate-based monomer, a substituent of an ester part of the (meth)acrylate-based monomer has the number of carbons of 4 to 10 and the acrylic polymer particles have +30 to +80 μC/g blow-off charge amount. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing positively chargeable polymer particles. More specifically, the present invention is obtained by seed emulsion polymerization by absorbing a (meth) acrylic ester monomer in the presence of seed particles, and has a blow-off charge amount of +30 to +80 μC / g. The present invention relates to a method for producing polymer particles.

Acrylic polymer resin particles are widely used as paint additives, adhesives, cosmetic additives, toner additives, light diffusing agents, liquid crystal spacers, binders, rheology modifiers, extenders, coating film performance improvers, etc. Yes. Such polymer resin particles often have a negatively chargeable or positively chargeable charge on the surface. For example, a positively chargeable polymer particle having a positive charge on the surface is a positively chargeable property of an electrophotographic toner. It is known that it can be used as an additive for imparting. Also, a crosslinking agent that forms a uniform and strong cross-linked structure in the film by adding it to a film such as a resin and reacting with a negatively charged reactive site, or a surface of a film such as a resin or a fiber such as cellulose. It is also used as a surface modifying agent that adheres to the surface and imparts slipperiness, matting properties, and the like, and substrate particles for plating with various metals (substrate particles of conductive particles). Furthermore, it has a wide range of application fields such as paints, civil engineering top coats, sealers, ink jet recording materials, and electrodeposition paints, and its utility value is high.
As a method for obtaining positively chargeable polymer particles, a method using a salt of an amino group-containing vinyl monomer (Japanese Patent Laid-Open Nos. 59-150531, 2004-10645), a method using a graft copolymer of an amino group-containing vinyl monomer ( Japanese Patent Laid-Open No. 63-90508) has been proposed.

JP 59-150531 A JP 2004-10645 A JP-A 63-90508

  However, in these positively chargeable polymer particles, the amount of charge is not sufficient, and the polymer particles of the amino group-containing polymerizable monomer contain a large amount of amino groups, which makes it easier to adsorb moisture. The resulting positively chargeable polymer resin particles will have increased hygroscopicity, for example, lowering the charge amount under high humidity, and affecting various physical properties such as dispersibility and fluidity. There was a problem. For this reason, there arises a problem that the use of toner additives used for electrostatic charge image development is limited depending on the application. Further, when a large amount of amino group-containing vinyl monomer was present during emulsion polymerization, the polymerization stability during emulsion polymerization was very poor, and the desired positively chargeable polymer particles could not be obtained.

  The inventors of the present invention have intensively studied to solve the above-mentioned problems. As a result, in the presence of seed particles, the amino acid-containing vinyl monomer is not an amino group-containing vinyl monomer, and the ester particles have 4 to 10 carbon atoms in the ester portion ( It has been found that positively charged polymer particles having a high charge amount can be obtained by absorbing a polymerizable monomer containing 40 to 100% by weight of a (meth) acrylic ester monomer and performing seed emulsion polymerization. Invented.

Thus, according to the present invention, in the presence of seed particles in an aqueous medium, the seed particles are allowed to absorb an acrylic polymerizable monomer, and seed emulsion polymerization is performed to produce acrylic polymer particles.
The seed particles are vinyl polymer particles, the acrylic polymerizable monomer is 40 to 100% by weight of a (meth) acrylic ester monomer, and the vinyl polymerizable monomer copolymerizable with the (meth) acrylic ester monomer. 0-60% by weight formulation,
The carbon number of the substituent of the ester part of the (meth) acrylic ester monomer is 4 or more and 10 or less,
There is provided a method for producing polymer particles, wherein the acrylic polymer particles have a blow-off charge amount of +30 to +80 μC / g.

The positively chargeable polymer particles of the present invention have a feature that the blowoff charge amount is +30 to +80 μC / g and excellent in positive chargeability. Therefore, it can be used as an external additive for toners used in electrostatic image development (used as an external additive for electrophotographic toners), paint additives, adhesives, cosmetic additives, toner additives, light Suitable as a diffusing agent, a liquid crystal spacer, a binder, a rheology modifier, a bulking agent, a coating film performance improving agent, and the like.
In addition, since no amino group is contained in the polymer particles of the acrylic polymerizable monomer, moisture is not adsorbed, and the resulting positively chargeable polymer resin particles can suppress hygroscopicity. Therefore, it is possible to prevent, for example, a reduction in the charge amount under high humidity and influence on various physical properties such as dispersibility and fluidity. Moreover, the polymerization stability at the time of emulsion polymerization is good, and the target positively chargeable polymer particle is obtained.

  In the present invention, vinyl polymer particles that are seed particles are allowed to absorb an acrylic polymerizable monomer containing 40 to 100% by weight of a (meth) acrylic ester monomer having an ester part having 4 to 10 carbon atoms, This is a method for obtaining polymer particles obtained by seed emulsion polymerization, wherein the blow-off charge amount is +30 to +80 μC / g. Here, “(meth) acryl” means acrylic or methacrylic.

(Seed particles)
The seed particle used in the present invention is a polymer obtained by polymerizing a vinyl monomer. Specifically, aromatic vinyl monomers such as styrene and α-methylstyrene, (meth) acrylic acid monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and vinyl acetate alone Examples thereof include block polymers, random blocks, and graft copolymers with polymers or monomers copolymerizable therewith. In addition, the polymer containing a (meth) acrylic ester monomer is preferable in that the absorbability of the acrylic polymerizable monomer is excellent.

The method for producing the seed particles is not particularly limited, and a method such as emulsion polymerization, soap-free emulsion polymerization or suspension polymerization can be used. In view of the uniformity of the seed particle size and the simplicity of the production method, emulsion polymerization and soap-free emulsion polymerization are preferred.
The weight average molecular weight of the seed particles of the present invention is not particularly limited, but is preferably 10,000 or more, more preferably 12,000 to 500,000, as measured by gel permeation chromatography. Such seed particles preferably have a uniform particle size in order to make the obtained polymer particles have a uniform particle size.
If the average particle size of the seed particles of the present invention is too small, the absorption of the acrylic polymerizable monomer into the seed particles may be insufficient, and the polymerization stability may be significantly reduced, and if too large, the use of the acrylic polymerizable monomer is too large. Since it is necessary to reduce the amount and productivity is lowered, 0.05 to 0.4 μm is preferable.
If the amount of seed particles used is small, the polymerization may proceed on the seed particles or other than in the seed particles, and the resulting fine particles and coarse particles may increase, and the resulting polymer has a uniform particle size. If the amount is too large, the particles may be deformed due to phase separation from the polymer forming the seed particles, and the sphericity of the polymer particles may be decreased. The amount of seed particles used is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and particularly preferably 5 to 15 parts by weight with respect to 100 parts by weight of the acrylic polymerizable monomer.

(Acrylic polymerizable monomer)
The acrylic polymerizable monomer used in the present invention includes 40 to 100% by weight of a (meth) acrylic ester monomer having 4 to 10 carbon atoms in the substituent of the ester portion, and the (meth) acrylic ester monomer. Is a blend of 0 to 60% by weight of a vinyl-based polymerizable monomer copolymerizable with. The acrylic polymerizable monomer used in the present invention is good even when the amount of the (meth) acrylic ester monomer having 4 to 10 carbon atoms in the substituent of the ester portion is 100% by weight. When used as a mixture, the charge amount is good.

In the present invention, a (meth) acrylic ester monomer having 4 to 10 carbon atoms in the substituent of the ester moiety is used. When the number of carbon atoms of the substituent in the ester portion is 3 or less, the charge amount is lowered although the stability during polymerization is good. Moreover, when carbon number of the substituent of an ester part is 11 or more, stability at the time of superposition | polymerization may deteriorate and a particle diameter may become large. More specifically, examples of the (meth) acrylic ester monomer having 4 to 10 carbon atoms in the substituent of the ester moiety used in the present invention include n-butyl (meth) acrylate and (meth) acrylic acid. Examples include isobutyl, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and the like. In particular, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and isobornyl (meth) acrylate are more preferable in that a high charge amount can be obtained. . These (meth) acrylic ester monomers may be used alone or in combination of two or more.
When the amount of the (meth) acrylic ester monomer having 4 or more and 10 or less carbon atoms in the substituent of the ester portion is small, the polymerization stability is good but the charge amount is lowered. It is 40 to 100% by weight based on the monomer. 70-100 weight% is more preferable.

Examples of the monomer copolymerizable with the (meth) acrylic ester monomer having 4 to 10 carbon atoms in the substituent of the ester portion of the present invention include aromatic vinyl monomers such as styrene and α-methylstyrene, (meth) Examples include (meth) acrylic ester monomers such as methyl acrylate and ethyl (meth) acrylate, vinyl acetate, and the like, and methyl (meth) acrylate is particularly preferable.
The amount of the vinyl polymerizable monomer copolymerizable with the (meth) acrylic ester monomer having 4 to 10 carbon atoms in the substituent of the ester moiety used in the present invention is the same for the same reason. It is 0 to 60% by weight based on the polymerizable monomer. 0 to 30% by weight is preferred.

  A chain transfer agent may be added to the acrylic polymerizable monomer. Specific examples of the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, α-methylstyrene dimer, 2,6-di- Acrylic polymerizable monomers include phenolic compounds such as t-butyl-4-methylphenol and styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrachloride. It is preferable to use 0.1 to 5 parts by weight with respect to 100 parts by weight of the blend. More preferably, it is 0.3-3 weight part.

Other monomers and additives may be added to the acrylic polymerizable monomer as long as the effects of the present invention are not impaired.
Examples of the other monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, and chlorostyrene.
Still other monomers include bifunctional polymerizable vinyl monomers. Specific examples include divinylbenzene and alkylene glycol dimethacrylate (alkylene preferably has 2 to 4 carbon atoms). The mixing ratio of the bifunctional polymerizable vinyl monomer is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the acrylic polymerizable monomer blend.
Examples of other additives include light stabilizers, ultraviolet absorbers, pigments, dyes, antifoaming agents, thickeners, heat stabilizers, leveling agents, lubricants, antistatic agents, and the like.

(Aqueous medium)
Emulsion polymerization is performed in an aqueous medium. Although it does not specifically limit as an aqueous medium, The mixture of water, water, and a water-soluble organic solvent (for example, lower alcohol) etc. are mentioned. Of these, water with less wastewater treatment problems is preferred.

(Seed emulsion polymerization)
The acrylic polymerizable monomer is subjected to seed emulsion polymerization in the presence of seed particles in an aqueous medium.
In the present invention, when the acrylic polymerizable monomer as described above is absorbed into the seed particles and seed emulsion polymerization is performed, the acrylic polymerizable monomer is mixed and stirred with a cationic surfactant as described later, and an aqueous medium. Then, it is preferably emulsified to obtain an emulsion dispersion (O / W emulsion) in which an acrylic polymerizable monomer is dispersed in an aqueous medium, and an aqueous dispersion of seed particles is added to the emulsion dispersion.
The use ratio (parts by weight / parts by weight) of the acrylic polymerizable monomer and the aqueous medium when adjusting the emulsified dispersion is preferably in the range of 1:20 to 1: 2. When the ratio of the acrylic polymerizable monomer blend is less than 1:20, productivity may be deteriorated, which is not preferable. When the ratio of the acrylic polymerizable monomer compound is more than 1: 2, the stability of the particles during polymerization is deteriorated, and aggregates of polymer particles after polymerization may occur, which is not preferable. A more preferable use ratio (parts by weight / parts by weight) is 1:15 to 1: 3.
The time for absorbing the acrylic polymerizable monomer in the seed particles is not particularly limited, but is preferably 10 minutes to 3 hours.

The cationic surfactant that can be used in the present invention is not particularly limited, and any known cationic surfactant can be used. For example, alkylamine or a salt thereof, ammonium salt having polyalkylene oxide, pyridinium salt, amino alcohol fatty acid derivative, polyamine fatty acid derivative, imidazoline, alkyltrimethylamine, or ammonium salt thereof, dialkyldimethylamine or ammonium salt thereof, alkyldimethylbenzyl Examples thereof include amines, ammonium salts thereof, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride. Of these, ammonium salts such as ammonium hydrochloride, ammonium sulfate, ammonium sulfonate, ammonium paratoluene sulfonate, and ammonium acetate are preferable. For example, lauryltrimethylammonium hydrochloride, stearyltrimethylammonium hydrochloride, cetylmethylammonium hydrochloride, and distearyldimethylammonium chloride N-polyoxyalkylene-N, N, N-trialkylammonium paratoluenesulfonate are more preferable. . These may be used alone or in combination of two or more.
If the amount of the cationic surfactant used is too small, absorption of the acrylic polymerizable monomer into the seed particles may be insufficient, and the polymerization stability may be significantly reduced. If the amount is too large, polymerization in the aqueous phase is likely to occur and a large amount of fine particles are generated, and the yield of the target polymer particles may be reduced. It is preferable that it is 0.01-0.5 weight part, and 0.02-0.2 weight part is more preferable.

Instead of the cationic surfactant that can be used in the present invention, a cationic water-soluble polymer may be used. Specific examples include amino group-modified polyvinyl alcohol, polydiallyldimethylammonium chloride, and cationized hydroxyethyl cellulose. Amino group-modified polyvinyl alcohol and polydiallyldimethylammonium chloride are particularly preferable. These may be used alone or in combination of two or more.
If the amount of the cationic water-soluble polymer used is too small, the acrylic polymerizable monomer may not be sufficiently absorbed by the seed particles, and the polymerization stability may be significantly reduced. If the amount is too large, polymerization in the aqueous phase is likely to occur and a large amount of fine particles may be generated, which may reduce the yield of the target polymer particles. The amount is preferably 0.01 to 0.5 parts by weight and more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the monomer blend.

As the polymerization initiator in the present invention, either a water-soluble polymerization initiator or an oil-soluble polymerization initiator can be used. A water-soluble polymerization initiator is preferable from the viewpoint of polymerization stability.
As the water-soluble polymerization initiator that can be used in the present invention, a cationic water-soluble polymerization initiator can be more preferably used. Specific examples of the cationic water-soluble polymerization initiator used in the present invention include 2,2-azobis (2-amidinopropane) hydrogen dichloride, 2,2-azobis [2- (2-imidazolin-2-yl). Propane] disulfide dihydrate, 2,2-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2-azobis {2- [1- (2-hydroxyethyl) ) -2-imidazolin-2-yl] propane} hydrogen dichloride, 2,2-azobis [2- (2-imidazolin-2-yl) propane], 2,2-azobis (1-imino-1-pyrrolidino- 2-ethylpropane) hydrogen dichloride, 2,2-azobis {2-methyl-N [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2-azobis [2-methyl- N- (2-Hide Xylethyl) propionamide], 2,2-azobis (N-hydroxyethylisobutyramide), 4,4-azobis (4-cyanopentanoic acid), azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile) And other azo compounds. The persulfates and organic peroxides include sodium sulfooxylate formaldehyde, sodium bisulfite, ammonium bisulfite, sodium thiosulfate, ammonium thiosulfate, hydrogen peroxide, sodium hydroxymethanesulfinate, L-ascorbic acid, And redox initiators using a reducing agent such as a salt thereof, a cuprous salt, and a ferrous salt in combination with a polymerization initiator.

Examples of the oil-soluble polymerization initiator include benzoyl peroxide, t-butyl peroxide, lauryl peroxide, t-butyl hydroxy peroxide, cumene hydroxy peroxide, t-butyl perbenzoate, t-butyl peroxyisopropyl carbonate, Examples thereof include peroxides such as methyl ethyl ketone peroxide, isopropyl peroxycarbonate, dioctanoyl peroxide, and azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile, and azobiscyclohexanecarbonitrile.
Although the usage-amount of a polymerization initiator changes with kinds, it is preferable to use 0.1-5 weight part with respect to 100 weight part of acrylic polymerizable monomer compounds. More preferably, it is 0.3 to 3 parts by weight.

The stirring rotation speed of the polymerization system is preferably 100 to 500 rpm, for example, when a 5 liter reactor is used. Moreover, although superposition | polymerization temperature changes with kinds of the monomer and polymerization initiator to be used, it is preferable that it is 30-100 degreeC, and it is preferable that superposition | polymerization time is 2 to 10 hours.
In addition, the polymer particles can be isolated from the aqueous medium by a known method, such as a spray drying method typified by a spray dryer, or a method of drying by adhering to a heated rotating drum typified by a drum dryer. It can be performed by freeze-drying or the like. Further, it is desirable that the dried polymer particles are crushed by a pulverizer or a pulverizer.

  The polymer particles of the present invention have an average particle size of 0.1 to 1.0 μm. If it is less than 0.1 μm, the cohesive force of the polymer particles may increase, and the chargeability is lowered, which is not preferable. On the other hand, if it exceeds 1.0 μm, the specific surface area of the polymer particles becomes small and the charge amount is lowered, which is not preferable. A more preferable average particle diameter is 0.15 to 0.8 μm. In addition, the measuring method of an average particle diameter is described in the Example column.

  Furthermore, the polymer particles of the present invention have a blow-off charge amount of +30 to +80 μC / g. When it is less than +30 μC / g, for example, when it is used as an additive for toner used for electrostatic image development, the charge amount is not sufficiently applied. If it is greater than +80 μC / g, for example, when it is used as an additive for toner used in electrostatic image development, the toner cleaning property may be deteriorated due to the excessive charge amount. Preferably, it is +35 to +80 μC / g.

  The polymer particles of the present invention are acrylic polymer particles excellent in low hygroscopicity with suppressed moisture adsorption rate in a high humidity environment, and can be used for desired applications. As such an application, it can be used as an external additive for toners used for electrostatic image development, paints, additives for ink pressure-sensitive adhesives, adhesives, artificial marble, paper processing agents, It is suitable as a packing material for cosmetics, a column packing material for chromatography, an anti-blocking agent for film, a light diffusing agent and the like.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. In addition, the measuring method of the average particle diameter in Example and a comparative example, polymerization stability, a water | moisture-content adsorption rate, and a charge amount is described below.

(Moisture adsorption rate)
Here, the moisture adsorption rate means a value calculated from the amount of weight change before and after storage after storing the polymer particles in a constant temperature and humidity environment for a predetermined time. That is, the polymer particles were previously dried at 55 ° C. for 24 hours, and 1 g of the dried polymer particles was stored in an atmosphere at a temperature of 20 ° C. and a relative humidity of 80% for 1 hour, and then the weight (g) of the polymer particles was determined. Weigh. This value was defined as W, and the value obtained by calculation from the following formula was defined as the water adsorption rate of the polymer particles.

Moisture adsorption rate (%) = (W−1) × 100

(Average particle size)
The average particle diameter here means a particle diameter measured using a method called a dynamic light scattering method or a photon correlation method. That is, an aqueous dispersion of polymer particles adjusted to 0.1 vol% is irradiated with laser light at 25 ° C., and the intensity of scattered light scattered from the polymer particles is measured with a time change in units of microseconds. It is an average particle size obtained by a cumulant analysis method for calculating an average particle size by applying a scattering intensity distribution caused by the detected polymer resin particles to a normal distribution. This type of average particle diameter can be easily measured with a commercially available measuring apparatus. In this example, “Zeta Sizer Nano ZS” commercially available from Malvern is used for measurement.
The above-described commercially available measurement apparatus is equipped with data analysis software, and can automatically analyze measurement data.

(Polymerization stability)
Polymerization stability here refers to the total amount of the obtained aqueous dispersion of polymer particles passed through a stainless steel sieve having an opening of 100 μm, and the residue on the sieve was dried at 50 ° C. for 24 hours, and then the weight of the residue was determined. Weigh (Wa). From this value (Wa), the agglomerate production rate is calculated by the following formula, and when the obtained value is less than 5%, the polymerization stability is very excellent (◎), when it is 5 to 10% The polymerization stability was excellent (◯), and when it exceeded 10%, the polymerization stability was judged to be poor (x).

Aggregate production rate (%) = (Wa / polymerizable monomer use amount) × 100

(Blow-off charge measurement)
Here, the blow-off charge amount means a charge amount measured by a contact charging method using a blow-off method. Specifically, the polymer particles to be measured were externally added to styrene-acrylic polymer particles produced by a synthesis method described later (hereinafter referred to as pseudo toner), and the charge amount of the pseudo toner was measured. Hereinafter, measurement examples will be described.
A mixture of 15 g of particles having an average particle diameter of 10 μm, which is a styrene-butyl methacrylate copolymer produced in the synthesis example described later, and 0.45 g of a measurement sample is mixed for 5 seconds with a mill mixer (National product number MX-X57-Y fiber mixer). Treated and then left to stand for 1 minute. Again, mixing for 5 seconds and standing for 1 minute were repeated for a total of 5 times.
0.5 g of the pseudo toner obtained by the above method and 9.5 g of standard carrier N-02 (manufactured by the Imaging Society of Japan) were put in a 50 cc polypropylene container, sealed, and then mixed by shaking up and down 200 times. Thereafter, the container was opened and allowed to stand for 24 hours under constant temperature and humidity of 20 ° C. and a relative humidity of 60%. Next, 0.2 g of the sample was weighed and put into a measurement sample chamber containing a 400 mesh screen to measure the blow-off charge amount. In addition, this kind of blow-off charge amount can be easily measured with a commercially available measuring apparatus, and TB-203 commercially available from Kyocera Chemical Co., Ltd. was used in this example. The measurement was performed under constant temperature and humidity of 20 ° C. and a relative humidity of 60%, nitrogen gas was used for blowing, the blowing pressure was 10 kPa, and the suction pressure was 9 kPa.

<Synthesis example>
The production of styrene-acrylic polymer particles used for blow-off charge measurement will be described. In a 5 L autoclave, 2600 parts by weight of water, 910 parts by weight of styrene, 390 parts by weight of butyl methacrylate, 26 parts by weight of magnesium pyrophosphate, 0.07 parts by weight of sodium nitrite, sodium polyoxyethylene alkylphenyl ether phosphate (Toho Chemical company "Phosphanol LO-529") 0.52 parts by weight of 10% aqueous solution, 10.4 parts by weight of azobisisobutyronitrile and 3.9 parts by weight of benzoyl peroxide are fed and stirred at 250 rpm The mixture was heated at 60 ° C. for 6 hours while stirring with a number. Next, the polymerization was carried out while heating to 80 ° C. and continuing stirring for another hour. Thereafter, the mixture was cooled to room temperature and dehydrated and dried to obtain styrene-acrylic polymer particles. The average particle diameter of the obtained styrene-acrylic polymer particles was 10 μm.

(Synthesis method 1 of seed particles used in Examples 1 to 8)
Supply 3600 parts by weight of water, 1.429 parts by weight of stearyltrimethylammonium chloride 28% aqueous solution (“Cotamine 86W” manufactured by Kao Corporation), 400 parts by weight of methyl methacrylate, and 8 parts by weight of normal octyl mercaptan to a 5 L autoclave. Then, it was heated to 70 ° C. while stirring at a stirring rotational speed of 250 rpm. Next, 2 parts by weight of 2,2′-azobis (2-amidinopropane) dihydrochloride (“V-50” manufactured by Wako Pure Chemical Industries, Ltd.) was supplied and stirred at 70 ° C. for 3 hours. The emulsion polymerization was carried out while heating to 0 ° C. and continuing stirring for another hour. Thereafter, the emulsion was cooled to room temperature to obtain an aqueous dispersion of polymer particles. The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.12 μm. The weight average molecular weight was 36,900.

(Synthesis method 2 of seed particles of Example 9)
The synthesis was performed in the same manner as in Synthesis Method 1 except that 400 parts by weight of methyl methacrylate was a mixture of 120 parts by weight of methyl methacrylate and 280 parts by weight of isobutyl methacrylate. The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.13 μm. The weight average molecular weight was 14,700.

Example 1
In a 5L autoclave, 2740 parts by weight of water, 0.571 parts by weight of a 28% aqueous solution of stearyltrimethylammonium chloride (“Cotamine 86W” manufactured by Kao Corporation), 240 parts by weight of methyl methacrylate, 560 parts by weight of isobutyl methacrylate, normal 8 parts by weight of dodecyl mercaptan was supplied, and after emulsifying and stirring with a homogenizer at a stirring speed of 7000 rpm for 10 minutes, 400 parts by weight of an aqueous dispersion of polymer particles produced by Synthesis Method 1 was supplied, and then for 1 hour. Stir at room temperature. After heating to 70 ° C., 2 parts by weight of 2,2′-azobis (2-amidinopropane) dihydrochloride (“V-50” manufactured by Wako Pure Chemical Industries, Ltd.) was supplied and stirred for 3 hours. The emulsion polymerization was performed while continuing stirring at 80 ° C. for 1 hour. Thereafter, the emulsion was cooled to room temperature to obtain an aqueous dispersion of polymer particles. The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.28 μm. Further, the obtained aqueous dispersion of polymer particles was treated with a spray dryer at an air supply temperature of 105 ° C. and an exhaust temperature of 55 ° C., and then treated with a jet mill to obtain polymer particle powder. Table 1 shows the types and amounts of raw materials used. Since the charge amount of the obtained polymer particles was +53.1 μC / g, the positive chargeability was excellent.
The agglomerate production rate evaluated by a stainless sieve having an aperture of 100 μm in the obtained aqueous dispersion of polymer particles was 1.5%, which was very excellent in polymerization stability.

(Example 2)
The same procedure as in Example 1 was carried out except that tertiary butyl methacrylate (TBMA; carbon number of ester part 4) (“light ester TB” manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of isobutyl methacrylate.
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.32 μm. The charge amount was +61.1 μC / g, and the positive chargeability was excellent.
The agglomerate formation rate evaluated by a stainless sieve having an aperture of 100 μm in the aqueous dispersion of the obtained polymer particles was 1.7%, which was very excellent in polymerization stability.

(Example 3)
The same procedure as in Example 1 was performed except that cyclohexyl methacrylate (CHMA; ester part carbon number 6) (manufactured by Kyoeisha Chemical Co., Ltd .; “light ester CH”) was used instead of isobutyl methacrylate.
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.36 μm. The charge amount was +48.9 μC / g, and the positive chargeability was excellent.
The agglomerate production rate evaluated by a stainless sieve having an aperture of 100 μm of the obtained aqueous dispersion of polymer particles was 1.9%, which was very excellent in polymerization stability.

Example 4
The same procedure as in Example 1 was conducted except that benzyl methacrylate (BZMA; ester part carbon number 7) (manufactured by Kyoeisha Chemical Co., Ltd .; “Light Ester BZ”) was used instead of isobutyl methacrylate.
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.33 μm. The charge amount was +38.2 μC / g, and the positive chargeability was excellent.
The agglomerate formation rate evaluated by a stainless sieve having an aperture of 100 μm in the aqueous dispersion of the obtained polymer particles was 2.0%, which was very excellent in polymerization stability.

(Example 5)
The same procedure as in Example 1 was performed except that cyclohexyl methacrylate was used instead of methyl methacrylate.
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.34 μm. The charge amount was +54.2 μC / g, and the positive chargeability was excellent.
The agglomerate formation rate evaluated by a stainless sieve having an aperture of 100 μm in the aqueous dispersion of the obtained polymer particles was 2.1%, which was very excellent in polymerization stability.

(Example 6)
The same procedure as in Example 1 was performed except that 120 parts by weight instead of 240 parts by weight of methyl methacrylate and 680 parts by weight instead of 560 parts by weight of isobutyl methacrylate were used.
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.34 μm. The charge amount was +55.5 μC / g, and the positive chargeability was excellent.
The agglomerate formation rate evaluated by a stainless sieve having an aperture of 100 μm in the aqueous dispersion of the obtained polymer particles was 2.1%, which was very excellent in polymerization stability.

(Example 7)
The same procedure as in Example 1 was performed except that 400 parts by weight was used instead of 240 parts by weight of methyl methacrylate and 400 parts by weight was used instead of 560 parts by weight of isobutyl methacrylate.
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.31 μm. The charge amount was +31.3 μC / g, and the positive chargeability was excellent.
The agglomerate production rate evaluated with a stainless sieve having an aperture of 100 μm in the obtained aqueous dispersion of polymer particles was 1.2%, which was very excellent in polymerization stability.

(Example 8)
In the same manner as in Example 1 except that 560 parts by weight of isobutyl methacrylate (IBA; ester part carbon number 10) (manufactured by Kyoeisha Chemical Co., Ltd .; “Light Ester IB-XA”) was used instead of 560 parts by weight of isobutyl methacrylate. went.
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.35 μm. The charge amount was +48.4 μC / g, and the positive chargeability was excellent.
The agglomerate formation rate evaluated by a stainless sieve having an aperture of 100 μm in the aqueous dispersion of the obtained polymer particles was 3.4%, which was very excellent in polymerization stability.

Example 9
The same procedure as in Example 1 was carried out except that the seed particles produced by the synthesis method 2 were used instead of the seed particles produced by the synthesis method 1.
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.36 μm. The charge amount was +54.5 μC / g, and the positive chargeability was excellent.
The agglomerate production rate evaluated by a stainless sieve having an aperture of 100 μm of the obtained aqueous dispersion of polymer particles was 1.9%, which was very excellent in polymerization stability.

(Comparative Example 1)
The same procedure as in Example 1 was conducted except that 800 parts by weight of methyl methacrylate was used instead of isobutyl methacrylate.
The average particle diameter of the polymer particles in the obtained aqueous dispersant was 0.26 μm, but the charge amount was +27.6 μC / g, and the positive chargeability was not excellent.
The agglomerate formation rate evaluated by a stainless sieve having an aperture of 100 μm in the aqueous dispersion of the obtained polymer particles was 0.5%, which was very excellent in polymerization stability.

(Comparative Example 2)
The same procedure as in Example 1 was performed, except that 640 parts by weight instead of 240 parts by weight of methyl methacrylate and 160 parts by weight instead of 560 parts by weight of isobutyl methacrylate were used.
The average particle diameter of the polymer particles in the obtained aqueous dispersant was 0.27 μm, but the charge amount was +28.6 μC / g, and the positive chargeability was not excellent.
The agglomerate production rate evaluated by a stainless sieve having an aperture of 100 μm in the obtained aqueous dispersion of polymer particles was 0.7%, which was very excellent in polymerization stability.

(Comparative Example 3)
The same procedure as in Example 1 was performed except that 560 parts by weight of stearyl methacrylate (STMA; ester part carbon number 18) (manufactured by Kyoeisha Chemical Co., Ltd .; light ester ST) was used instead of 560 parts by weight of isobutyl methacrylate.
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 1.85 μm, which was not a desired size. The charge amount was +22.4 μC / g, and the positive chargeability was not excellent.
The aggregate formation rate evaluated by a stainless sieve having an aperture of 100 μm in the aqueous dispersion of the obtained polymer particles was 12.6%, and the polymerization stability was very poor.

(Comparative Example 4)
The same procedure as in Example 1 was performed except that emulsion polymerization was performed without using seed particles.
The average particle diameter of the polymer particles in the obtained aqueous dispersant was 0.32 μm, but the charge amount was +28.3 μC / g, and the positive chargeability was not excellent.
The agglomerate formation rate evaluated by a stainless sieve having an aperture of 100 μm in the obtained aqueous dispersion of polymer particles was 7.4%, which was excellent in polymerization stability.

(Comparative Example 5)
The same procedure as in Example 1 was carried out except that 160 parts by weight of methyl methacrylate and 80 parts by weight of dimethylaminoethyl methacrylate (DMAEMA) (manufactured by Kyoeisha Chemical Co., Ltd .; Light Ester DM) were used instead of 240 parts by weight of methyl methacrylate. .
The average particle diameter of the polymer particles in the obtained aqueous dispersion was 0.40 μm. The charge amount was +29.1 μC / g, and the positive chargeability was not excellent.
The aggregate formation rate evaluated by a stainless sieve having an aperture of 100 μm in the obtained aqueous dispersion of polymer particles was 2.1%, and the polymerization stability was very excellent.
In Comparative Example 5, the amino group-containing polymerizable monomer contains a large amount of 2.1% of amino groups, so that it easily adsorbs moisture, and the positively charged polymer resin particles absorb moisture. Sexuality is increasing.

  The polymer particles of the present invention are characterized in that the polymer particles have an average particle diameter of 0.1 to 1 μm and are excellent in positive chargeability. Therefore, it can be used as an external additive for toners used in electrostatic image development, as well as additives for paints, ink pressure-sensitive adhesives, adhesives, artificial marble, paper processing agents, cosmetics, etc. It can be used as a filler, a column filler for chromatography, an additive for toner used for developing electrostatic images, an antiblocking agent for film, a light diffusing agent, and the like.

Claims (4)

In an aqueous medium, in the presence of seed particles, the seed particles absorb an acrylic polymerizable monomer, and perform seed emulsion polymerization to produce acrylic polymer particles,
The seed particles are vinyl polymer particles;
The acrylic polymerizable monomer is a blend of 40 to 100% by weight of a (meth) acrylic ester monomer and 0 to 60% by weight of a vinyl polymerizable monomer copolymerizable with the (meth) acrylic ester monomer. ,
The carbon number of the substituent of the ester part of the (meth) acrylic ester monomer is 4 or more and 10 or less,
The method for producing positively chargeable acrylic polymer particles, wherein the acrylic polymer particles have a blow-off charge amount of +30 to +80 μC / g.   The substituent of the ester part of the (meth) acrylic ester monomer is one or more of isobutyl, t-butyl, benzyl, cyclohexyl group, and isobornyl group. A method for producing positively chargeable acrylic polymer particles.   3. The method for producing positively chargeable acrylic polymer particles according to claim 1, wherein the average particle size is 0.1 to 1.0 μm.   The acrylic polymer particles obtained by the production method according to claim 1, which is used as an external additive for toner used in electrostatic image development.