JPH07165847A - Composite resin particle, its production, and its use - Google Patents

Abstract

PURPOSE:To obtain a composite resin particle of excellent properties in a good yield while preventing the formation of fine particles as a by-product caused by emulsion polymerization concurring with the suspension polymerization of a (meth)acrylic monomer. CONSTITUTION:An oil phase comprising a polymerizable monomer based on a (meth)acrylic monomer and a resin is subjected to aqueous suspension polymerization in the presence of a compound which is substantially insoluble in water and hardly soluble in the polymerizable monomer and has at least one structural unit selected from the group consisting of-SH,-S-S-,-COOH,-NO2 and-OH.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to resin composite particles, a method for producing the same, and uses thereof. More specifically, the present invention relates to the suspension polymerization of an oil phase composed of a polymerizable monomer containing a (meth) acrylic monomer as a main component and a resin,
The present invention relates to a technique for suppressing the generation of by-product fine particles due to concurrent emulsion polymerization and improving the polymerization stability, yield, and physical properties of the obtained particles.

[0002]

2. Description of the Related Art (Meth) acrylic resin composite particles, especially those having an average particle size of about 0.01 to 500 .mu.m,
For example, powder coatings and water-dispersible coatings, inks, adhesives, artificial marble additives, paper treatment agents, cosmetic fillers,
It is expected to be applied to applications such as column packings for chromatography and additives for toners for electrostatic image development.

Conventionally, as a method for producing resin composite particles,
Known methods include mechanical pulverization, suspension polymerization, and emulsion polymerization. Among them, the method by mechanical pulverization limits the resins that can be uniformly compounded and rubbed with the (meth) acrylic resin in the production of the resin as the raw material, and further requires a large amount of energy for pulverization. Moreover, in order to make the obtained fine particles have a uniform particle size, a multi-stage classification treatment is required, and since the obtained particles are of irregular shape, problems such as fluidity and aggregation resistance remain. there were. Further, in the method by emulsion polymerization, the resin that can be compounded with the (meth) acrylic resin is limited due to the mechanism of the polymerization, and the resin composite particles can be obtained only in a specific range. On the other hand, the suspension polymerization method is a method in which suspended particles of a monomer are prepared by mechanical stirring and then polymerized, and if the resin can be dissolved or dispersed in the monomer, a composite Particles can be obtained. Further, it has advantages that a desired particle size can be obtained relatively easily, that a solvent is not used, and that reaction control is easy.

However, it is known that fine particles by emulsion polymerization are secondarily formed in suspension polymerization. Therefore, the yield is lowered, the polymerization stability is lowered, and the emulsion-polymerized fine particles thus formed are hardly complexed, and moreover, they are often adhered to the interface of the suspension-polymerized particles and completely removed. Since it is difficult to obtain the resin composite particles, the physical properties of the obtained resin composite particles are deteriorated. In particular, when the resin particle size to be obtained by suspension polymerization is made finer, for example, to be about 0.01 to 500 μm, a dispersion added to the aqueous phase in order to stabilize the suspended fine particles. Since the amount of the stabilizer is larger than that in the case of general suspension polymerization, the amount of the polymerizable monomer dissolved in the aqueous phase in the dispersion step and the polymerization step increases, and such fine particles due to emulsion polymerization Is a problem.

In the suspension polymerization method, it is known to add an inorganic water-soluble inhibitor to the system as a method for preventing emulsion polymerization which occurs concurrently in the aqueous phase. For example, in JP-A-55-82125, 0.01 to 0.01
It is also possible to add 10% by weight of a water-soluble inhibitor such as ammonium thiocyanate and cupric chloride.
No. 302 discloses addition of vanadium pentoxide and / or cupric chloride together with a dispersion stabilizer, and JP-A No. 62-205108 discloses that sodium nitrite, potassium nitrite, cupric chloride, etc. It is disclosed in JP-A-2-284905 that such a water-soluble inhibitor can be dissolved in water in an amount of 10 ppm or more based on the total amount of vinyl monomers, and a polymerization initiator comprising a water-soluble inhibitor such as nitrite and an organic peroxide. It is further known that suspension polymerization is carried out using
No. 237105 discloses that suspension polymerization is carried out in a continuous aqueous phase containing water, a water-miscible organic solvent and a water-soluble polymerization inhibitor such as sodium nitrite and hydroquinone.
Each is shown.

Further, as disclosed in JP-A-61-255323, a technique of adding a water-soluble mercaptan compound in order to prevent concurrent emulsion polymerization in aqueous suspension polymerization is known. The water-soluble mercaptan compound includes 2-mercaptoethanol, thioglycolic acid, cysteine, glutathione, dimercaprol, 1,4-dithiothreitol, dimercaptosuccinic acid, and 2,3-dimercapto-1-propanesulfonic acid. Etc. are disclosed.

Further, in Japanese Patent Laid-Open No. 52-102391,

[0008]

[Chemical 1]

A water-soluble inhibitor selected from borohydrides, alkali metal nitrites, alkaline earth metal nitrites or ammonium nitrite represented by about 0.0005 to about 0.02 per 100 parts by weight of the monomer. It is disclosed that about 0.0001 to about 0.005 part by weight of an oil-soluble inhibitor consisting of oil-soluble and alcohol-soluble nigrosine is added.

However, even if an inorganic water-soluble inhibitor is added during suspension polymerization of a polymerizable monomer containing a (meth) acrylic monomer as a main component, its emulsion polymerization inhibitory effect is weak and a large amount is added. The need arises. Especially, the smaller the particle size of the fine particles to be obtained by suspension polymerization, the more remarkable this tendency.

When the water-soluble mercaptan compound is used to prevent the concurrent occurrence of emulsion polymerization, an unpleasant odor adheres to the resin composite particles or the waste water obtained due to the mercaptan compound, and the unpleasant odor is washed. It could not be easily removed.

Further, the use of a borohydride as a water-soluble inhibitor makes it difficult to handle the compound itself and requires strict control of suspension polymerization conditions and the like.

[0013]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide an improved resin composite particle, a method for producing the same, and various uses to which the resin composite particle is applied. The present invention also provides resin composite particles having excellent physical properties obtained by suspension polymerization of an oil phase composed of a polymerizable monomer having a (meth) acrylic monomer as a main component and a resin, and a method for producing the same. The purpose is. Another object of the present invention is to provide suspension-polymerized resin composite particles in which the presence of by-product fine particles due to emulsion polymerization is small and a method for producing the same. The present invention further suppresses the generation of by-product fine particles due to emulsion polymerization which occurs concurrently at the suspension particle interface during suspension polymerization of an oil phase composed of a polymerizable monomer having a (meth) acrylic monomer as a main component and a resin. It is an object of the present invention to provide a method for producing resin composite particles, which can suppress the polymerization stability, improve the yield, and improve the physical properties of the obtained particles.

[0014]

[Means for Solving the Problems] The above-mentioned objects are (meta)
Polymerizable monomer (A) containing acrylic monomer as a main component
And an oil phase consisting of the resin (B), -SH, -SS
It has at least one structural unit selected from the group consisting of —, —COOH, —NO ₂ and —OH, is substantially insoluble in water, and is difficult for the polymerizable monomer (A). This is achieved by a method for producing resin composite particles, which comprises performing aqueous suspension polymerization in the presence of a soluble compound (C).

As the compound (C), especially -S
H, -SS-, -COOH, -NO ₂And -OH
Having two or more structural units selected from the group consisting of
Is desired. The amount of compound (C) added is
20 to 0.0001% by weight based on the polymerizable monomer (A)
Is desired. Note that suspension polymerization is possible.
Plasticizer, polymerization stabilizer, colorant, optical brightener, magnetic powder, ultraviolet
Additives such as line absorbers, antistatic agents and flame retardants
It doesn't matter.

The present invention is also a coating composition using the above resin composite particles as a binder.

The present invention further provides an ink composition containing the above resin composite particles.

The present invention also provides an adhesive composition containing resin composite particles.

[0019]

The inventors of the present invention have been able to suppress emulsion polymerization that occurs concurrently when suspension polymerization of an oil phase composed of a polymerizable monomer having a (meth) acrylic monomer as a main component and a resin is performed. As a result of diligent study focusing on the point that such emulsion polymerization mainly occurs at the suspension particle interface, it has a specific structural unit as described above, and is substantially insoluble in water and When the compound (C) which is hardly soluble in the polymerizable monomer is allowed to exist during the aqueous suspension polymerization, the compound (C) can be efficiently arranged at the interface of the suspended particles during the aqueous suspension polymerization. It was found that the emulsion polymerization that occurs at the interface of suspended particles can be efficiently suppressed by this.

The present invention will be described in detail below based on embodiments.

The polymerizable monomer (A) used in the present invention contains a (meth) acrylic monomer as a main component, preferably 50 to 100% by weight of a (meth) acrylic monomer, more preferably Is contained in an amount of 60 to 100% by weight. When the compounding ratio of the (meth) acrylic monomer in the polymerizable monomer (A) is extremely low, the effect of preventing the emulsion polymerization by the compound (C) described below cannot be expected so much. From this point,
The SP (solubility parameter) value of the polymerizable monomer (A) is desired to be 9.0 or less.

Examples of (meth) acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, and acrylic. Acid tetrahydrofurfuryl, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc. Can be mentioned,
Of course, it is not limited to these. It is also possible to use a combination of a plurality of these (meth) acrylic monomers.

Further, in order to obtain resin particles having a crosslinked structure between molecules, a (meth) acrylic monomer having a plurality of polymerizable double bond groups in the molecule is copolymerized with the above (meth) acrylic monomer. It is possible to As such a crosslinkable (meth) acrylic monomer,
Trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, pentadecaethylene glycol dimethacrylate, pentacontahector ethylene glycol dimethacrylate, dimethacrylate Methacrylic acid 1,3
-(Meth) acrylic monomers such as butylene, allyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and diethylene glycol dimethacrylate phthalate are listed, and it is possible to use a combination of two or more of them. . In addition, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and their derivatives, N, N,-, within a range that does not hinder the mixing ratio of the (meth) acrylic monomer in the polymerizable monomer (A). Divinyl aniline, divinyl ether, divinyl sulfide,
Cross-linking agents such as divinyl sulfonic acid, polybutadiene, polyisoprene, unsaturated polyester and JP-B-57-56,507, and JP-A-59-221,30.
4, JP-A-59-221,305, JP-A-59-221-306, and JP-A-59-221,3.
It is also possible to use the reactive polymers and the like described in JP-A No. 07.

On the other hand, the other monomer that can be contained in the polymerizable monomer (A) used in the present invention may be any one that can be copolymerized with the above-mentioned (meth) acrylic monomer, for example, , Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-
Butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene and other styrene monomers, ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, methacrylamide, N-vinyl. Examples thereof include pyrrolidone.

The resin (B) that forms an oil phase with the polymerizable monomer (A) is not particularly limited, and may be a thermoplastic resin, a thermosetting resin or a resin that is dissolved or dispersed in the polymerizable monomer (A). As the reactive resin, one kind or a mixture of two or more kinds thereof is used depending on the use of the resin composite fine particles.

The thermoplastic resin has an average molecular weight of 1,0.
About 100 to 1,000,000 are preferably used, and specific examples thereof include vinyl chloride polymers such as vinyl chloride polymers and vinyl chloride-vinylidene chloride copolymers, vinyl acetate polymers, vinyl acetate-ethylene copolymers. Vinyl ester resins such as polymers, (meth) acrylic acid ester (co)
Polymers, (meth) acrylic ester-acrylonitrile copolymers, (meth) acrylic ester-based resins such as (meth) acrylic ester-styrene copolymers, styrene polymers, styrene-acrylonitrile copolymers, styrene- Styrene resins such as butadiene-acrylonitrile copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, poly (ε-
Caprolactam), polyamide resins such as condensation products of adipic acid and hexamethylenediamine, polyester resins such as condensation products of terephthalic acid and ethylene glycol, condensation products of adipic acid and ethylene glycol, polyethylene, polypropylene, chlorinated polyethylene Polyolefin resins such as chlorinated polypropylene, carboxyl modified polyethylene, polyisobutylene and polybutadiene,
Cellulose acetate, cellulose propionate, cellulose derivatives such as nitrocellulose, butyral resin, cyclized rubber and the like can be mentioned. As these resins, commercially available products may be used as they are, or those synthesized by a generally known method may be used.

The thermosetting resin or reactive resin is heated,
It is possible to form a crosslinked structure due to addition reaction, condensation reaction, etc. by active energy ray irradiation, drying or other means, and specifically, for example, phenolic resins such as novolac resins and resole resins, urea resins, melamine. Resins, amino resins such as benzoguanamine resins, various alkyd resins, unsaturated polyester resins, curable acrylic resins, isocyanate group-containing polyesters, urethane group-modified resins such as isocyanate group-containing polyethers,
Examples thereof include polyamine resins and epoxy resins.

The resin (B) is selected according to various physical properties required for the resin composite particles,
In particular, at least one resin selected from the group consisting of polyester resin, polyolefin resin, urethane resin, epoxy resin, and cyclized rubber is preferable, and at least selected from the group consisting of chlorinated polyethylene, chlorinated polypropylene, and carboxyl-modified polyethylene. One type of resin is more preferable, and one type or a combination of two or more types can be used in consideration of the purpose of use of the resin composite particles.

The mixing ratio of the polymerizable monomer (A) and the resin (B) is not particularly limited, but the characteristics of the resin composite particles are sufficiently exhibited and the stability of suspension polymerization is not impaired. In order to obtain 100 parts by weight of polymer (A)
The resin (B) is used in an amount of 1 to 400 parts by weight, preferably 0.1 to 300 parts by weight.

In the production of the resin composite particles of the present invention,
In the aqueous suspension polymerization of the oil phase comprising the polymerizable monomer (A) and the resin (B) as described above, it is substantially insoluble in water and the polymerizable monomer (A) is added. And the sparingly soluble compound (C) is added to the suspension polymerization system.

As described above, since the compound (C) used in the present invention is substantially insoluble in water and hardly soluble in the polymerizable monomer (A), it is a suspension polymerization system. In the above, the compound (C) is present at the interface of suspended particles due to the action of a dispersion stabilizer such as a surfactant, which will be described later, added to the suspension polymerization system, and the emulsification occurring at the interface of suspended particles. Effectively suppress polymerization. When the solubility of the compound (C) in water is high, during the suspension polymerization, the compound (C) migrates to the continuous aqueous phase and emulsion polymerization cannot be prevented. When the solubility in the monomer (A) is high, chain transfer is likely to occur in the monomer, and the resulting resin particles do not have a high degree of polymerization.

Further, the solubility of this compound (C) in water is preferably 0 to 1% by weight, more preferably 0 to 0.1% by weight under the conditions of 25 ° C. ± 5 ° C. and 760 Torr. On the other hand, the solubility of the polymerizable monomer (A) is 25 ° C ± 5 ° C 760T.
Under the condition of orr, 0 to 50% by weight, more preferably 0.01 to 20% by weight, still more preferably 0.01 to 20% by weight.
It is preferably about 10% by weight.

As the compound (C) satisfying the solubility in water and the polymerizable monomer (A), --S
H, -S-S -, - COOH, -NO 2, are preferably used those having a structure unit selected from the group consisting of -OH least one, particularly preferably, -SH,
Those having two or more kinds of structural units selected from the group consisting of —SS—, —COOH, —NO ₂ and —OH are used, and examples thereof include thiosalicylic acid, dithiosalicylic acid, nitrobenzoic acid, and 3,4-dinitrobenzoic acid. Acid, nitrophenol and the like are preferably used.

In the aqueous suspension polymerization according to the present invention, such a compound (C) is appropriately selected so as to satisfy the solubility condition for the polymerizable monomer (A), and the addition amount of the compound (C) is Depends on the kind of the compound (C) used and the composition of the polymerizable monomer (A), but is 20 to 0.000 relative to the polymerizable monomer (A).
It is more preferably 1 to 10% by weight, more preferably 10 to 0.001% by weight, and further preferably 5 to 0.01% by weight. If the addition amount of the compound (C) is less than 0.0001% by weight, the inhibiting effect on emulsion polymerization is small and the generation of fine particles cannot be prevented. On the other hand, if the addition amount exceeds 20% by weight, chain transfer occurs in the monomer. The degree of polymerization of the resulting resin particles does not increase, and the degree of polymerization does not increase.

The method of adding such a compound (C) is not particularly limited, and it is a method of adding it to the polymerizable monomer (A), a method of adding it to the aqueous phase, and a method of dissolving it in a solvent such as methanol. A method of dispersing in an aqueous phase can be used.

In the method for producing resin composite particles according to the present invention, the above-mentioned oil phase comprising the polymerizable monomer (A) containing the (meth) acrylic monomer as a main component and the resin (B) is used as described above. The aqueous suspension polymerization is carried out in the presence of the compound (C). The polymerization temperature is 10 to 9
A temperature of 0 ° C., preferably 30 to 80 ° C. is suitable. In this suspension polymerization, it is desirable to carry out the reaction after controlling the particle size of the oil phase suspension particles composed of the polymerizable monomer (A) and the resin (B), or while controlling the particle size. It is preferable to carry out the reaction after controlling the particle size.
The regulation of the particle size is carried out, for example, by using a suspension prepared by dispersing a predetermined component in an aqueous medium in T. K. Stir with a homomixer. Alternatively, it is carried out by passing it through a high-speed stirrer such as a line mixer (for example, Ebara Milder) once or several times.

In suspension polymerization, a dispersion stabilizer can be added to stabilize the suspension polymerization. As the dispersion stabilizer, polyvinyl alcohol, gelatin,
Water-soluble polymers such as tragacanth, starch, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, sodium polyacrylate, sodium polymethacrylate; anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants. There are surfactants such as agents, and other alginates, zein, casein, barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay, diatomaceous earth, bentonite, titanium hydroxide, etc.
Sodium hydroxide, metal oxide powder or the like is used.

Examples of the anionic surfactant include fatty acid salts such as sodium oleate and potassium castor oil, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene. Examples thereof include sulfonate, alkane sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkylphenyl ether sulfate ester salt, polyoxyethylene alkyl sulfate ester salt and the like. As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether,
There are polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine; glycerin fatty acid ester, oxyethylene-oxypropylene block polymer and the like. Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride. Examples of the zwitterionic surfactant include lauryl dimethylamine oxide.

In these dispersion stabilizers, the resin composite particles obtained have a predetermined particle size, for example, 0.01 to 500.
μm, preferably 0.01 to 100 μm,
The composition and the amount to be used should be appropriately adjusted and used, for example, 0.01 to 29% by weight, preferably 0. Used in an amount of 1-10% by weight.

The polymerization initiator used for the polymerization is
An oil-soluble peroxide type or azo type initiator which is usually used in suspension polymerization can be used. To give an example, for example,
Benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl orthochloroperoxide, benzoyl orthomethoxy peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide Peroxide initiators such as propylbenzene hydroperoxide, 2,2'-azobisisobutyronitrile, 2,2 '
-Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (2,3-dimethylbutyronitrile),
2,2'-azobis (2-methylbutyronitrile),
2,2'-azobis (2,3,3-trimethylbutyronitrile), 2,2'-azobis (2-isopropylbutyronitrile), 1,1'-azobis (cyclohexane-)
1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), Examples include dimethyl-2,2'-azobisisobutyrate. The polymerization initiator is preferably used in an amount of 0.01 to 20% by weight, particularly 0.1 to 10% by weight, based on the polymerizable monomer (A).

Further, in suspension polymerization, a colorant such as a pigment or dye, or a plasticizer may be added in the oil phase or the water phase composed of the polymerizable monomer (A) and the resin (B), if necessary. Further, additives such as a polymerization stabilizer, a fluorescent whitening agent, a magnetic powder, an ultraviolet absorber, an antistatic agent and a flame retardant can be compounded or added.

These colorants and additives are those surface-treated by various methods for the purpose of improving the dispersibility in the oil phase comprising the polymerizable monomer (A) and the resin (B). It may be. The surface treatment method includes a method of treating with a long-chain hydrocarbon such as stearic acid and oleic acid, a method of treating with a polymerizable monomer having a polar group such as acrylic acid and methacrylic acid, and an amine such as triethanolamine. Or the like, a method of treating with various coupling agents, or an aziridine group or an oxazoline group capable of reacting with a colorant or an additive and a functional group on the surface thereof,
20 to 3 polymers each having a reactive group such as an N-hydroxyalkylamide group, an epoxy group, a thioepoxy group, an isocyanate group, a vinyl group, a silicon-based hydrolyzable group, and an amino group.
Examples thereof include a method of reacting at a temperature of 50 ° C. and grafting a polymer on the surface of a colorant or an additive.

The resin composite particles obtained by the method for producing resin composite particles of the present invention as described above are sub-polymerized at the interface between the suspension particles and the aqueous phase by the action of the compound (C) during suspension polymerization. Since subsequent emulsion polymerization is suppressed, by-product fine particles are not generated by emulsion polymerization, and the average particle size is 0.01 to 500 μm, particularly 0.01 to 100 μm, and the particle size distribution is extremely narrow. .

The resin composite particles or the suspension of the resin composite particles obtained by the production method of the present invention has excellent characteristics such as an extremely narrow particle size distribution, and is therefore preferably used in various applications.

For example, the resin composite particles according to the present invention are preferably used as a binder of a coating composition.

In the coating composition of the present invention, the above resin composite particles are dispersed or dissolved in a solvent, and an extender pigment, a coloring pigment, and other additives commonly used in the art are added thereto, and a suitable stirrer or pigment is used. A coating composition is prepared by uniformly dispersing and mixing with a disperser or a three-roll mill. As the solvent of the coating composition, benzene, toluene, aromatic solvents such as xylene, ethyl acetate, ester solvents such as butyl acetate,
A ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone, an alcohol solvent such as methanol, ethanol, isopropanol and n-butanol, water and the like can be used alone or in combination, but when water is used as a main agent, polymerization is performed. It is preferable since the subsequent suspension of resin composite particles can be directly used.

In the coating composition of the present invention, the polymer composed of the polymerizable monomer (A) and the resin (B) are finely mixed in a particle unit, and therefore the adhesion to a metal substrate, a plastic substrate, etc. It also has excellent properties such as weather resistance, ozone resistance, chemical resistance, and water resistance.
It is widely used as a coating material for exteriors and interiors, and also as an ink composition for printing.

The ink composition of the present invention is produced by the same method as the above-mentioned coating composition, and printed on various substrates by a known method such as a gravure method and a flexo method.

In addition to the above, the resin composite particles of the present invention include, for example, artificial marble additives, paper treating agents, cosmetic fillers, chromatography column fillers, electrostatic charge image developing toner additives, and powders. It is preferably used as a body paint, a gap adjusting agent for liquid crystal display panels, display particles for Coulter counters, carriers for immunodiagnostic agents, and the like.

[0050]

EXAMPLES The present invention will now be described in more detail with reference to examples, but these examples do not limit the present invention in any way. In addition, all "parts" described in the following examples represent parts by weight.

Example 1 A flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser and a thermometer was charged with polyoxyethylene alkylsulfoammonium (Hitenol N-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0 900 parts of deionized water in which 0.5 part was dissolved was charged. 64 parts of methyl methacrylate and 16 parts of n-butyl methacrylate epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 2 prepared in advance.
A mixture containing 0 parts, 1 part of azoisobutyronitrile and 1 part of 3,4-dinitrobenzoic acid was charged, and T.I. K.
800 by a homogenizer (made by Tokushu Kika Kogyo Co., Ltd.)
The mixture was stirred at 0 rpm for 5 minutes to form a uniform suspension.

Next, blowing nitrogen gas at 75 ° C.
The mixture was heated to 0 ° C., stirred at this temperature for 5 hours to carry out a suspension polymerization reaction, and then cooled. The suspension was filtered and dried to obtain fine particles (1). The ratio of emulsion-polymerized particles calculated from the nonvolatile content contained in the filtrate is 1.08% (vs total solid content).
Met.

The fine particles (1) thus obtained were measured with a Coulter counter (aperture 100 μm). As a result, the average particle diameter was 3.53 μm and the standard deviation value was 1.2 μm. The fine particles (1) were colorless and odorless.

Example 2 A flask similar to that used in Example 1 was charged with 900 parts of deionized water in which 0.5 part of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) was dissolved. 27 parts of styrene, 63 parts of n-butyl acrylate and polyester (Kurapol P-2010,
A mixture containing 10 parts of Kuraray Co., Ltd., 1 part of azoisobutyronitrile and 5 parts of p-nitrobenzoic acid was charged, and the same method as in Example 1 was repeated to obtain fine particles (2).

The properties of the resulting fine particles (2) and the amount of emulsion-polymerized particles by-produced were examined in the same manner as in Example 1 and the results are shown in Table 1.
Shown in.

Example 3 In a flask similar to that used in Example 1, 1 part of polyoxyethylene nonylphenyl ether (Nonipol 200, manufactured by Sanyo Chemical Industries, Ltd.) was dissolved in deionized water 900.
The department was set up. 60 parts of methyl methacrylate, 20 parts of n-butyl acrylate prepared in advance therein, 20 parts of urethane resin (Samprene 1100, Sanyo Chemical Industry Co., Ltd. desolvated), azoisobutyronitrile 1 Part and 2,2-dithiosalicylic acid (1 part) were added to the mixture, and T. K. Homogenizer (Special Kika Kogyo Co., Ltd.)
Product) to stir at 8000 rpm for 30 minutes to form a uniform suspension.

Next, blowing nitrogen gas at 75 ° C.
The mixture was heated to 0 ° C., stirred at this temperature for 5 hours to carry out a suspension polymerization reaction, and then cooled to obtain a suspension (3). Part of the suspension was filtered and then dried to obtain fine particles (3).

The properties of the resulting fine particles (3) and the proportion of emulsion-polymerized particles by-produced were examined in the same manner as in Example 1 and the results are shown in Table 1.

Example 4 A flask similar to that used in Example 1 was charged with polyoxyethylene alkylsulfoammonium (Hitenol N
-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 1 part was charged with 900 parts of deionized water. 50 parts of methyl methacrylate and 20 parts of n-butyl acrylate prepared in advance.
Parts, chlorinated polypropylene (Supercron L-20
6, a desolventized product of Nippon Paper Industries Co., Ltd.), 30 parts, a mixture of 1 part of azoisobutyronitrile and 1 part of thiosalicylic acid were charged, and the same method as in Example 3 was repeated to obtain fine particles (4). Got

The properties of the resulting fine particles (4) and the amount of emulsion-polymerized particles by-produced were examined in the same manner as in Example 1 and the results are shown in Table 1.
Shown in.

Comparative Example 1 A flask similar to that used in Example 1 was charged with polyoxyethylene alkylsulfoammonium (Hitenol N
-08, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., was charged with 900 parts of deionized water in which 0.5 part was dissolved. 64 parts of methyl methacrylate and n-butyl acrylate 1 prepared in advance
A mixture containing 6 parts, 20 parts of an epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.), and 1 part of azoisobutyronitrile was charged, and the same method as in Example 1 was repeated. The dispersion stability of the suspension was poor, and most of the non-volatile matter aggregated and settled to the bottom of the flask.

Comparative Example 2 A flask similar to that used in Example 1 was charged with polyoxyethylene alkylsulfoammonium (Hitenol N
-08, 0.5 part by Dai-ichi Kogyo Seiyaku Co., Ltd., and 900 parts of deionized water in which 1 part of cupric chloride was dissolved were charged.
64 parts of methyl methacrylate prepared in advance,
A mixture containing 16 parts of n-butyl acrylate, 20 parts of epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.), and 1 part of azoisobutyronitrile was charged, and the same method as in Example 1 was repeated. However, the dispersion stability of the suspension during the polymerization reaction was poor, and most of the non-volatile components were aggregated and settled to the bottom of the flask.

Comparative Example 3 A flask similar to that used in Example 1 was charged with polyoxyethylene alkylsulfoammonium (Hitenol N
-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and 900 parts of deionized water in which 1 part of thioglycolic acid was dissolved were charged. Methyl methacrylate 6 prepared in advance there
4 parts, n-butyl acrylate 16 parts, epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 20
Part and azoisobutyronitrile 1 part were mixed and the same method as in Example 1 was repeated to obtain comparative fine particles (3).

The properties of the comparative fine particles (3) and the amount of emulsion-polymerized particles by-produced were examined in the same manner as in Example 1 and the results are shown in Table 2.

Comparative Example 4 In Example 1, 1 part of 3,4-dinitrobenzoic acid was replaced with dodecyl mercaptan (dissolved in methyl methacrylate and n-butyl acrylate, which are polymerizable monomers, at an arbitrary ratio. 1) was used and the same procedure as in Example 1 was repeated, the polymerization reaction was delayed, and most of the non-volatile components were aggregated and settled to the bottom of the flask.

Comparative Synthesis Example 1 A flask similar to that used in Example 1 was charged with polyoxyethylene alkylsulfoammonium (Hitenol N).
-08, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., 2 parts, and polyoxyethylene nonylphenyl ether (Nonipol 20)
0, 150 parts of deionized water in which 0.5 part of Sanyo Chemical Industry Co., Ltd. was dissolved was charged. 75 parts of methyl methacrylate and 25 parts of n-butyl acrylate prepared in advance.
4.5 parts at 90 ° C.
The emulsion polymerization was carried out for a period of time to obtain a comparative suspension (1) having a solid content concentration of 40%.

[0067]

[Table 1]

[0068]

[Table 2]

Example 5 and Comparative Example 5 With respect to 100 parts by weight of the resin solid content of the suspension (3) obtained in Example 3 and the comparative suspension (1) obtained in Comparative Synthesis Example 1, 3 parts by weight thickener, 0.8 parts by weight wetting agent, 2 parts by weight defoaming agent, 14 parts by weight film-forming aid and pigment volume concentration (P
A pigment was added so that the VC) would be about 21% to obtain a coating composition (1) and a comparative coating composition (1). The test results are shown in Table 3.

As is clear from Table 3, the coating composition of the present invention was found to have excellent water resistance and adhesion.

Each test in Table 3 is performed by the following method.

Gloss: A glass plate was wet coated with the coating composition to a thickness of 150 μm and dried at 85 ° C. for 3 hours.
0 ° specular gloss was measured Water resistance: The coating composition was wet coated onto a PET film treated with corona discharge to a thickness of 100 μm and then at 85 ° C. for 3 days.
After drying for one hour, the state of the coating film after 7 days of immersion in water was visually evaluated.

○: No blister △: Partially blistered ×: Overall blister Adhesion: A test piece prepared in the same manner as in the water resistance evaluation was subjected to a peeling test with an adhesive tape to obtain a coating film. Was visually evaluated.

◯: No peeling △: Partially peeling ×: Whole surface peeling

[0075]

[Table 3]

Comparative Synthesis Example 2 A flask similar to that used in Example 1 was charged with polyoxyethylene alkylsulfoammonium (Hitenol N
-08, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., 2 parts, and polyoxyethylene nonylphenyl ether (Nonipol 20)
0, 150 parts of deionized water in which 0.5 part of Sanyo Chemical Industry Co., Ltd. was dissolved was charged. 70 parts of methyl methacrylate and 30 parts of n-butyl acrylate prepared in advance
4.5 parts at 90 ° C.
Emulsion polymerization was carried out for a time to obtain a comparative suspension (2) having a solid content concentration of 40%.

Example 6 and Comparative Example 6 For 100 parts by weight of resin solid content of the suspension (4) obtained in Example 4 and the comparative suspension (2) obtained in Comparative Synthesis Example 2, After mixing 30 parts of a blue pigment (Rionol Blue ES, manufactured by Toyo Ink Mfg. Co., Ltd.) and dispersing with an attritor for 30 minutes, Zahn Cup No. The viscosity was adjusted to 4 for 10 seconds to obtain an ink composition (1) and a comparative ink composition (1). These ink composition (1) and comparative ink composition (1) were used in a gravure printing machine and
The m plate was printed on an easy-adhesion polypropylene film (YS-41, manufactured by Toray Industries, Inc.). The test results are shown in Table 4.

As is clear from Table 4, the coating composition of the present invention was found to have excellent water resistance and adhesion.

Each test in Table 4 is performed by the following method.

Water resistance: The number of times the ink surface is rubbed with water-containing absorbent cotton, and the film drops off ..... 50 times or more ..... 20 to 49 times ..... 19 times or less. Was visually evaluated.

◯: No peeling Δ: Partially peeling ×: Whole surface peeling

[0082]

[Table 4]

[0083]

As described above, according to the present invention, the oil phase composed of the polymerizable monomer (A) containing the (meth) acrylic monomer as the main component and the resin (B) is replaced with -SH,- S
It has at least one structural unit selected from the group consisting of —S—, —COOH, —NO ₂ and —OH, and is substantially insoluble in water and relative to the polymerizable monomer (A). Since it is an aqueous suspension polymerization in the presence of a poorly soluble compound (C), it is possible to suppress emulsion polymerization as a by-product due to the polymerizable monomer (A) partially dissolved in the aqueous phase, Polymerization stability, yield, and physical properties of the obtained particles can be improved.

Claims (10)

[Claims] The method according to claim 1 (meth) oil phase consisting of a polymerizable monomer composed mainly of acrylic-based monomer (A) and the resin (B), -SH, -S- S -, - COOH, -NO 2 And the presence of a compound (C) having at least one structural unit selected from the group consisting of -OH, which is substantially insoluble in water and hardly soluble in the polymerizable monomer (A). Resin composite particles obtained by performing aqueous suspension polymerization below. 2. The compound (C) is --SH, --SS--,
The resin composite particle according to claim 1, which has two or more kinds of structural units selected from the group consisting of —COOH, —NO ₂ and —OH. 3. The resin composite according to claim 1, wherein the resin (B) is at least one resin selected from the group consisting of polyester resins, polyolefin resins, urethane resins, epoxy resins, and cyclized rubbers. particle. 4. The resin composite particles according to claim 1, wherein the resin (B) is at least one resin selected from the group consisting of chlorinated polyethylene, chlorinated polypropylene, and carboxyl-modified polyethylene. 5. The resin composite particles according to claim 1, which have an average particle diameter of 0.01 to 500 μm. 6. A (meth) oil phase consisting of a polymerizable monomer composed mainly of acrylic-based monomer (A) and the resin (B), -SH, -S- S -, - COOH, -NO 2 And the presence of a compound (C) having at least one structural unit selected from the group consisting of -OH, which is substantially insoluble in water and hardly soluble in the polymerizable monomer (A). A method for producing resin composite particles, which comprises performing aqueous suspension polymerization below. 7. The compound (C) is --SH, --SS--,
The method for producing resin composite particles according to claim 6, which has two or more structural units selected from the group consisting of —COOH, —NO ₂ and —OH. 8. The method for producing resin composite particles according to claim 6, wherein the amount of the compound (C) added is 20 to 0.0001% by weight based on the polymerizable monomer (A). 9. A coating composition using the resin composite particles according to claim 1 as a binder. 10. An ink composition using the resin composite particles according to claim 1 as a binder.