JP3179044B2 - Resin particles and their uses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to resin particles and uses thereof. More specifically, the present invention suppresses the generation of by-product fine particles due to concurrent emulsion polymerization during the polymerization of a polymerizable monomer containing a (meth) acrylic monomer as a main component, and the physical properties of the obtained particles. It is related to technology for improving the quality. Further, the present invention relates to a technique for improving the heat stability of (meth) acrylic resin particles.

[0002]

2. Description of the Related Art (Meth) acrylic resin particles, particularly those having an average particle diameter of about 0.1 to 500 .mu.m, include, for example, anti-blocking agents for resin films, additives for toners for developing electrostatic images, and powders. It is expected to be used in applications such as paints and water-dispersed paints, decorative board additives, artificial marble additives, cosmetic fillers, and chromatographic column fillers.

[0003] Conventionally, as a method for producing resin particles, a method using mechanical pulverization, a method using suspension polymerization, a method using emulsion polymerization, and the like are known. Among them, the method using mechanical pulverization requires a large amount of energy for pulverization, and further requires a multi-stage classification process in order to obtain fine particles having a uniform particle size. Further, since the fine particles obtained by this method are amorphous, problems remain in fluidity, coagulation resistance and the like. In the method by emulsion polymerization, fine particles having a uniform particle size can be obtained.
It is about 1 μm, and cannot be directly used for the above-mentioned applications. On the other hand, the method using suspension polymerization prepares and polymerizes suspended particles of a monomer by mechanical stirring, so that resin particles having a desired particle size can be obtained relatively easily, and a solvent is used. It has advantages such as not being used and easy reaction control.

[0004] However, it is known that fine particles are secondary formed by emulsion polymerization in an aqueous phase during suspension polymerization. As a result, the yield and polymerization stability decrease, and the emulsion polymerization fine particles thus formed adhere to a large amount at the interface of the suspension polymerization particles and are difficult to completely remove. This results in a decrease in the physical properties of the particles. In particular, the resin particle size to be obtained by suspension polymerization is finer, for example, 0.1 to 500 μm
In the case of about the same level, the amount of the dispersion stabilizer added to the aqueous phase in order to stabilize the suspended fine particles is larger than in the case of general suspension polymerization. In the process, the amount of the polymerizable monomer dissolved in the aqueous phase is increased, and there is a problem of by-product of fine particles due to such emulsion polymerization.

[0005] In the suspension polymerization method, as a method for preventing emulsion polymerization occurring simultaneously in the aqueous phase, it is known to add an inorganic water-soluble inhibitor to the system. 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, cupric chloride and the like.
JP-A No. 302-205108 discloses that vanadium pentoxide and / or cupric chloride may be added together with a dispersion stabilizer, and JP-A-62-205108 discloses sodium nitrite, potassium nitrite, cupric chloride and the like. 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 all vinyl monomers. A polymerization initiator comprising a water-soluble inhibitor such as nitrite and an organic peroxide is disclosed in JP-A-2-284905. The suspension polymerization is carried out by 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, hydroquinone and the like.

Further, as disclosed in JP-A-61-255323, a technique of adding a water-soluble mercaptan compound in order to prevent simultaneous occurrence of emulsion polymerization in aqueous suspension polymerization is also known. Examples of the water-soluble mercaptan compound include 2-mercaptoethanol, thioglycolic acid, cysteine, glutathione, dimercaprol, 1,4-dithiothreitol, dimercaptosuccinic acid, and 2,3-dimercapto-1-propanesulfonic acid. Are disclosed.

Further, Japanese Patent Application Laid-Open No. 52-102391 discloses that

[0008]

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

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

When simultaneous occurrence of emulsion polymerization is prevented by using a water-soluble mercaptan compound, an unpleasant odor adheres to resin particles or waste water obtained due to the mercaptan compound, and this unpleasant odor is easily obtained even after washing. Could not be 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.

By the way, the (meth) acrylic resin particles may be used in various forms as described above. For example, when the (meth) acrylic resin particles are used as an anti-blocking agent for a resin film, the desired properties include the addition of The refractive index is close to that of the resin system to be used, and the heat stability is good. Hereinafter, this point will be described in more detail.

Polyolefin films are used as packaging materials for packaging various articles including foods. When the films are laminated, the films adhere to each other, so-called blocking, and the workability of packaging and the like is remarkably increased. It has the disadvantage of lowering. Conventionally, as a means of preventing blocking in a polyolefin film and improving the slipperiness, a method of uniformly mixing fine particles of an inorganic substance such as fine powder of silica and talc in the film has been generally practiced. It is necessary to mix a large amount of inorganic substances in order to impart sufficient blocking resistance and slipperiness to the polyolefin film using, and when a polyolefin film mixed with the inorganic substances is stretched, voids around the inorganic substances are generated. Occurs
There has been a problem that the transparency and mechanical strength of the film are reduced.

It has also been proposed to use polyamide fine powder or a condensed resin spherical body having a triazine ring in place of the above-mentioned inorganic substances. The method of using polyamide fine powder is effective in preventing a decrease in transparency, but it requires a large amount of mixing, resulting in a problem that the strength of the obtained film is reduced and the cost is increased. Also, the method of using the spherical body of the condensation type resin having a triazine ring has a difference in the refractive index between the polyolefin and the condensation type resin having the triazine ring, and there is a problem in preventing a decrease in transparency. Unreacted volatiles such as unreacted formalin remaining in the mold resin form voids during the stretching process, which has the disadvantage of lowering the transparency or mechanical strength of the film. Furthermore, when such resin particles are blended, if the heat resistance of the resin particles is not sufficient, the resin particles are decomposed during the melt-kneading of the resin for the film, and the decomposition components generate odors and form voids. Since there is a risk of contamination and deterioration of mechanical and optical characteristics, improvement of heat resistance has been desired.

[0016]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide improved resin particles and various uses to which the resin particles are applied. Another object of the present invention is to provide resin particles having excellent physical properties obtained by suspension-polymerizing a polymerizable monomer containing a (meth) acrylic monomer as a main component. Another object of the present invention is to provide (meth) acrylic resin particles particularly excellent in heat stability and uses thereof.

[0017]

SUMMARY OF THE INVENTION The above-mentioned objects are to provide a crosslinking property.
(Meth) acrylic monomer containing (meth) acrylic monomer
50-100% by weight of the monomer and copolymerized with the monomer
A polymer particle obtained by polymerizing a polymerizable monomer (A) comprising 50 to 0% by weight of another monomer obtained , wherein the particle material is kept at 270 ° C. for 40 hours in the air. Polymer components originating from the polymerizable monomer of the polymer (hereinafter simply
The resin particles are characterized in that the rate of weight loss due to decomposition of the organic components is 60% by weight or less.

The present invention is also a polyolefin polymer composition obtained by blending the above resin particles with a polyolefin.

The present invention is also a polyolefin polymer film obtained by blending the above resin particles with a polyolefin.

The present invention is also a cosmetic product comprising the above resin particles as a filler.

The present invention is also a coating composition comprising the above resin particles blended in a binder.

[0022]

The present inventors have found that in the case where resin particles are obtained by carrying out aqueous suspension polymerization of a polymerizable monomer (A) containing a (meth) acrylic monomer as a main component, the suspension polymerization is carried out. As a result of intensive research focusing on the fact that such emulsion polymerization occurs mainly at the interface of suspended particles, it has a specific structural unit, and When the compound (B) which is substantially insoluble and hardly soluble in the polymerizable monomer is present in the aqueous suspension polymerization, the compound (B) is brought into contact with the suspension particles in the aqueous suspension polymerization. It has been found that they can be efficiently arranged, thereby effectively suppressing emulsion polymerization occurring at the interface of suspended particles.

The (meth) obtained in this way
It was found that the acrylic polymer resin particles had much higher heat stability than conventional ones. The exact reason for this point is not clear, and it was unexpected that the compound (B) suppresses the emulsion polymerization generated at the interface of the suspended particles and improves the heat resistance of the obtained resin particles.

Hereinafter, the present invention will be described in detail based on embodiments.

The resin particles according to the present invention are polymer particles obtained by polymerizing a polymerizable monomer (A) having a (meth) acrylic monomer as a main component, and have extremely high heat resistance. It has.

The polymerizable monomer (A) used for obtaining such resin particles contains a (meth) acrylic monomer as a main component, and preferably contains a (meth) acrylic monomer in an amount of 50 to 50%. 100% by weight, more preferably 60%
-100% by weight. In addition, if the compounding ratio of the (meth) acrylic monomer in the polymerizable monomer (A) is extremely small, the effect of inhibiting the emulsion polymerization by the compound (B) described below cannot be expected much. From this point, it is further desired that the SP (dissolution parameter) value of the polymerizable monomer (A) is 9.0 or less.

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

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 do. As such a crosslinkable (meth) acrylic monomer,
Trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, pentadecaethylene glycol dimethacrylate, pentacontaethylene glycol dimethacrylate, diethylene glycol dimethacrylate Methacrylic acid 1,3
-(Meth) acrylic monomers such as butylene, allyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and diethylene glycol dimethacrylate phthalate, and a plurality of these can be used in combination. . Further, an aromatic divinyl compound such as divinylbenzene, divinylnaphthalene, or a derivative thereof, N, N-divinyl, or the like, as long as the mixing ratio of the (meth) acrylic monomer in the polymerizable monomer (A) is not impaired. Crosslinking agents such as aniline, divinyl ether, divinyl sulfide, divinyl sulfonic acid, etc., as well as polybutadiene, polyisoprene unsaturated polyester and JP-B-57-5-5
No. 6,507, JP-A-59-221304, JP-A-59-221305, and JP-A-59-221305.
It is also possible to use reactive polymers described in JP-A-221,306 and JP-A-59-221307.

On the other hand, other monomers that can be contained in the polymerizable monomer (A) used in the present invention may be any as long as they are copolymerizable with the (meth) acrylic monomer as described above. For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, Examples include styrene-based monomers such as p-chlorostyrene, ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, methacrylamide, N-vinylpyrrolidone, and the like.

To produce the resin particles having excellent heat resistance according to the present invention, the polymerizable monomer (A) as described above is used.
Is subjected to aqueous suspension polymerization, a compound (B) which is substantially insoluble in water and hardly soluble in the polymerizable monomer (A) is added to the suspension polymerization system.

As described above, the compound (B) used in the present invention is substantially insoluble in water and hardly soluble in the polymerizable monomer (A). The compound (B) is present at the interface of the suspension particles by the action of a dispersion stabilizer such as a surfactant described below added to the suspension polymerization system, and the emulsification that occurs at the interface of the suspension particles Effectively suppress polymerization. If the solubility of the compound (B) in water is high, the compound (B) migrates to the aqueous phase which is a continuous phase during suspension polymerization, so that emulsion polymerization cannot be prevented. When the solubility for the monomer (A) is high, suspended particles (monomer)
In this case, chain transfer easily occurs, and the degree of polymerization of the obtained resin particles does not increase.

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

The compound (B) satisfying the solubility conditions for water and the polymerizable monomer (A) includes, for example, -SH, -SS-, -COOH, -NO2 and-
Those having at least one or more structural units selected from the group consisting of OH are preferably used.

Specific examples of the compound having a -SH group include thiocresol, thiophenol, methyl thioglycolate, ethyl thioglycolate, butyl thioglycolate, 2-ethylhexyl thioglycolate, and trimethylolpropane trithioglycolate. , Dithiohydroquinone, xylene dithiol, 2-mercaptonaphthalene, and the like. Specific examples of the compound having a -SS- group include diallyl disulfide, dioctyl dithiodipropionate, and the like. Examples of the compound include cinnamic acid, benzoic acid, chlorobenzoic acid, phthalic acid, isophthalic acid, and the like,
Compounds having a -NO ₂ group include nitrobenzene,
Nitrotoluene, nitroxylene, nitronaphthalene,
Examples of the compound having an OH group include aminocresol, aminonaphthol, and m-nitroaniline.
-Cresol, oxyanthracene, oxyanthraquinone, oxantrone, 3-oxy-9-anthrone,
Oxynaphthoquinone, dioxyanthracene, dioxyanthraquinone, 1,5-dioxynaphthalene, 1,8
-Dioxynaphthalene, 2,6-dioxynaphthalene,
3,5-dimethylphenol, naphthol and the like.

The compound (B) used in the present invention includes -SH, -SS-, -COOH,-
Particularly preferred are those having two or more structural units selected from the group consisting of NO ₂ and —OH, specifically, for example, salicylic acid, thiosalicylic acid, dithiosalicylic acid, nitrobenzoic acid, 3,4-dinitrobenzoic acid, nitro Phenol and the like.

In the aqueous suspension polymerization according to the present invention, the amount of the compound (B) to be added also depends on the type of the compound (B) used, the composition of the polymerizable monomer (A) and the like. However, 2 to the polymerizable monomer (A)
0 to 0.0001% by weight, more preferably 10 to 0.0%
It is preferably about 01% by weight, more preferably about 5 to 0.01% by weight. If the amount of the compound (B) is less than 0.0001% by weight, the effect of inhibiting the emulsion polymerization is so small that the generation of fine particles cannot be prevented. In this case, chain transfer easily occurs, and the degree of polymerization of the obtained resin particles does not increase.

The method of adding such a compound (B) is not particularly limited, and it may be added to the polymerizable monomer (A), added to the aqueous phase, or dissolved in a solvent such as methanol. Thereafter, a method of dispersing in an aqueous phase or the like can be used.

The polymerization temperature in the production of the resin fine particles according to the present invention is 10 to 90 ° C., preferably 30 to 8 ° C.
About 0 ° C. is appropriate. In this suspension polymerization, it is preferable to carry out the reaction after regulating the particle diameter of the polymerizable monomer (A) suspension particles or while regulating the particle diameter. Particularly, the particle diameter is regulated. It is preferred to carry out the reaction later. The regulation of the particle size is, for example, as follows: a suspension in which a predetermined component is dispersed in an aqueous medium is subjected to T.V. K. Stir with a homomixer. Alternatively, it is carried out by passing once or several times through a high-speed stirrer such as a line mixer (for example, Ebara Milder).

In the suspension polymerization, a dispersion stabilizer may be added to stabilize the suspended particles. As dispersion stabilizers, polyvinyl alcohol, gelatin,
Water soluble polymers such as tragacanth, starch, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, sodium polyacrylate, sodium polymethacrylate, anionic surfactant, cationic surfactant, zwitterionic surfactant, nonionic surfactant There are activators, etc.Alginates, zein, casein, barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay, diatomaceous earth, bentonite, titanium hydroxide, titanium hydroxide, metal oxide powder, etc. Is used.

Examples of the anionic surfactant include fatty acid oils such as sodium oleate and castor oil, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene. Sulfonate, alkane sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl sulfate, and the like. As nonionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether,
Examples include polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxysorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethylene-oxypropylene block polymers, 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 amphoteric surfactant include lauryl dimethylamine oxide.

These dispersion stabilizers have a predetermined particle size, for example, from 0.1 to 500 μm, preferably from 0.5 to 100 μm, and more preferably from 0.5 to 100 μm.
It should be used by appropriately adjusting its composition and amount so as to be 30 to 30 μm, for example, 0.01 to 29% by weight, preferably 0.1 to 29% by weight, based on the polymerizable monomer (A).
It is used in an amount of 1 to 10% by weight.

As the polymerization initiator used for the polymerization, oil-soluble peroxide-based or azo-based initiators usually used for suspension polymerization can be used. By way of example, for example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide,
Peroxide initiators such as diisopropylperoxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 2,2′-azobisisobutyronitrile, 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-methix-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), Dimethyl-2,2'-azobisisobutyrate and the like. 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, at the time of suspension polymerization, a colorant such as a pigment or a dye, or other additives may be blended or added into the polymerizable monomer (A) or the aqueous phase, if necessary. Can also.

Examples of the pigment include inorganic pigments such as lead white, lead red, graphite, carbon black, ultramarine, zinc oxide, cobalt oxide, titanium dioxide, iron oxide, silica, titanium yellow and titanium black, and isoindolinone. , Quinacridone, dioxane violet, phthalocyanine blue,
Organic pigments such as perinone pigments, perylene pigments, insoluble azo pigments, soluble azo pigments and dye lakes are used.

Examples of the dye include nitroso dye, nitro dye, azo dye, stilbene azo dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye,
Polymethine dyes, thiazole dyes, indamine dyes, indophenol dyes, azine dyes, oxazine dyes, thiazine dyes, sulfur dyes and the like are used.

Other additives include a plasticizer, a polymerization stabilizer, a fluorescent brightener, a magnetic powder, an ultraviolet absorber, an antistatic agent and a flame retardant.

These colorants and other additives may be surface-treated by various methods for the purpose of improving dispersibility in the polymerizable monomer (A).
As a surface treatment method, stearic acid, a method of treating with a long-chain hydrocarbon such as oleic acid, acrylic acid, a method of treating with a polymerizable monomer having a polar group such as methacrylic acid,
A method of treating with a polyhydric alcohol such as trimethylolpropane, a method of treating with amines such as triethanolamine, a method of treating with various coupling agents, or a coloring agent or other additive and a functional group on their surface A polymer having a reactive group such as an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group, a thioepoxy group, an isocyanate group, a vinyl group, a silicon-based hydrolyzable group, or an amino group that can react with 20 to 350 ° C. And a method of grafting a polymer onto the surface of a coloring agent or other additives.

In the resin particles obtained by the above-described method, during the suspension polymerization, the emulsion polymerization which occurs at the interface between the suspended particles and the aqueous phase is suppressed by the action of the compound (B). Therefore, there is no generation of by-product fine particles due to emulsion polymerization, and the average particle size is 0.1 to 500 μm, especially 0.1 to 500 μm.
The particle size distribution is extremely narrow at 5 to 100 μm, more particularly about 0.5 to 30 μm. The obtained resin particles have extremely high heat resistance, and typically, a ratio of weight loss due to decomposition of an organic component of a polymer when held at 270 ° C. in air for 40 minutes (hereinafter, “organic component”). Is referred to as "decomposition rate" of 60% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less.

The decomposition rate of the organic component kept at a low temperature described in the present specification is as follows: the temperature is raised from room temperature to 200 ° C. at a rate of about 40 ° C./min, and thereafter the rate of temperature rise is gradually reduced. Thus, the time required to reach 270 ° C. from room temperature was adjusted to 20 minutes, the time at which the temperature reached 270 ° C. was set to time 0, and the weight loss was measured after holding for 40 minutes. The sample amount was about 20 mg, and the measurement was carried out under the condition that clean air was flowed at a rate of about 40 ml / min. Further, the organic component described here refers only to a polymer component derived from a polymerizable monomer, and excludes components such as an organic colorant added as necessary in resin particles and is considered. . How to measure weight loss due to the above pyrolysis
The method consists of differential thermal analysis (DTA) and thermogravimetry (TG).
Combined, usually differential thermogravimetry (DT
G).

The resin particles or the suspension of the resin particles according to the present invention have excellent properties such as excellent heat stability and a very narrow particle size distribution as described above.
It is suitably used in various applications.

For example, the resin particles according to the present invention are suitable as an anti-blocking agent for a film molded product, in particular, an anti-blocking agent for a polyolefin film.

The polyolefin polymer composition according to the present invention is obtained by blending the above resin particles with a polyolefin. This polyolefin-based polymer composition can be used as it is, or a polyolefin-based polymer film can be obtained by blending a polyolefin with the composition and forming it into a film. Further, the polyolefin-based polymer film according to the present invention is obtained by blending the above resin particles with a polyolefin. The polyolefin polymer film obtained by blending the resin particles in this manner has blocking resistance, slipperiness,
It is very excellent in transparency and mechanical strength.

When the above resin particles are arranged in a polyolefin, the components constituting the resin particles are decomposed at the time of melt-kneading in film forming and volatile components are generated due to high heat stability of the resin particles as described above. There is no danger of voids, no deterioration in optical and mechanical properties of the film, and no danger of environmental pollution due to such volatile odor.

The resin particles according to the present invention have an index of refraction of 1.45 to 1.45 when no coloring agent or the like is added.
It is in the range of 1.55 and is close to the refractive index of polyolefin. For this reason, when the resin particles according to the present invention are disposed in the polyolefin-based polymer as the anti-blocking agent, there is no fear that the transparency is reduced. Generally, when any additive is used to improve the heat resistance of the resin particles, the refractive index is likely to be outside the above range, but in the resin particles according to the present invention, such an additive is used. It has a preferred refractive index because it is not needed. In addition, as the refractive index of the resin particles when blended as a blocking inhibitor in the polyolefin as described above,
Furthermore, it is desirable that it is 1.47 to 1.53, especially 1.48 to 1.52.

In addition, the resin particles according to the present invention preferably have a crosslinked structure.
For example, it has a relatively low pencil hardness of 5H or less, preferably 4H or less, and exhibits good scratch resistance when blended in a polyolefin film.

The compounding amount of the resin particles in the polyolefin polymer composition of the present invention is 0.001 to 40% by weight, preferably 0.005 to 3% by weight based on the polyolefin.
About 5% by weight is appropriate. The compounding amount of the resin particles in the polyolefin polymer film is 0.001 to 5% by weight, preferably 0.005 to 3% by weight, more preferably 0.01 to 2% by weight based on the polyolefin.
A suitable amount is about weight%. The polyolefin-based polymer film of the present invention can obtain good blocking resistance and slipperiness by adding a relatively small amount of resin particles as described above. When the amount of the resin particles as described above is 0.
When the amount is less than 001% by weight, the blocking resistance and the slipperiness of the film are hardly developed, and when the amount is more than 5% by weight, the film strength is reduced.

When used as such an antiblocking agent, the average particle size of the resin particles of the present invention is as follows:
It is desirable that the thickness be 0.1 to 30 μm, preferably 0.3 to 25 μm, and more preferably 0.5 to 20 μm.
When the average particle size is smaller than 0.1 μm, the blocking resistance effect and the slipperiness improving effect are not sufficiently exhibited, so that a large amount of addition is required and the mechanical strength of the film may be impaired. On the other hand, when the average particle diameter is larger than 30 μm, the particles easily fall off the film, and there is a possibility that the mechanical strength is reduced.

The polyolefin used in the polyolefin polymer composition or the polyolefin polymer film of the present invention includes homopolymers, random copolymers and block copolymers of α-olefins such as ethylene, propylene and butylene. Alternatively, a mixture thereof may, for example, be mentioned. Among them, a polymer containing ethylene and / or propylene as a main component is preferably used. The polyolefin polymer composition or the polyolefin polymer film of the present invention may contain various additives within a range that does not adversely affect the effects of the resin particles. Examples of these additives include various stabilizers such as an antioxidant and an ultraviolet absorber, a flame retardant, an antistatic agent, a coloring agent, and an inorganic filler. Also,
A conventionally used blocking inhibitor such as silica may be used in combination.

In order to mix and disperse the resin particles according to the present invention in the polyolefin resin, a conventionally known mixer such as a ribbon blender, a Banbury mixer, a super mixer, an extruder, etc. may be used. As a method of adjusting the content of, a method of producing a high-concentration masterbatch by the above method and diluting the masterbatch with a polyolefin resin to form a film is preferable because the resin particles are more uniformly dispersed.

The polyolefin polymer film of the present invention can be produced by, for example,
It can be obtained by various conventionally known production methods such as die processing, and may be a single-layer film having a single composition or a laminated film laminated with the same or different kinds of films. As a method of obtaining a laminated film, a method of forming each film and then laminating by dry lamination, a heat laminating method, a method of extruding and laminating a resin on a previously formed film, and simultaneously forming a laminated film by a multilayer coextrusion method And the like.

The film obtained by these methods can be further stretched to obtain a stretched polyolefin film. Further, if necessary, at least one surface of the polyolefin polymer film may be subjected to corona discharge treatment. By corona discharge treatment, characteristics such as blocking resistance and slipperiness may be improved.

Further, the resin particles of the present invention, particularly particles containing titanium oxide or an ultraviolet absorber, show good ultraviolet absorption characteristics and weather resistance, and are suitably used in cosmetics. Specific examples of cosmetics include, for example, a powder foundation, a creamy foundation, and O / W.
Or foundations such as W / O type emulsion foundation, O / W or W / O type oil cake type foundation, cream emulsions such as O / W or W / O type cream, O / W or W / O type emulsion Lip balm, sun care oil, blusher, eyeshadow, mascara, etc., in addition to suspension cosmetics in which particles are dispersed in a liquid such as water, aqueous alcohol, oil and the like.

The cosmetic of the present invention can be obtained by mixing the resin particles with a general cosmetic base in a conventional manner.
Examples of suitable bases for cosmetics include, for example, silicone oils such as dimethylpolysiloxane, methylpolysiloxane, dimethylcyclopolysiloxane, and methylhydrogenpolysiloxane, solid or liquid paraffin, crystal oil, ceresin, Hydrocarbons such as ozokerite and montan wax, olive oil, ground wax, carnauba wax, lanolin, whale wax and other vegetable oils or animal fats and oils, waxes, stearic acid, palmitic acid, oleic acid, glycerin monostearate, isopropyl Fatty acids such as myristate, isopropylstearate and butylstearate, and esters thereof, ethyl alcohol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, Palmityl alcohol, and alcohols such as hexyl dodecyl alcohol.
Polyhydric alcohols having a moisturizing effect, such as glycol, glycerin, and sorbitol, can also be used. Examples of the powder include extenders such as mica, talc, sericite, kaolin, and nylon powder; inorganic pigments such as titanium oxide, zinc white, iron oxide, and pearl;
Organic pigments such as 26, yellow 4, and aluminum lake are used. Further, as these powders, powders which have been subjected to a known hydrophobic surface treatment such as a silicon treatment, a metal soap treatment, and an N-acylglutamic acid treatment can be used. Further, water, a surfactant, a thickener, a preservative, an antioxidant and the like which are usually used in cosmetics can also be blended.

The amount of the resin particles according to the present invention in the cosmetic varies depending on the type of the cosmetic, but is 0.1 to 70% by weight, preferably 0.5 to 50% by weight, and more preferably 1 to 25% by weight. % By weight.

The use of the resin particles according to the present invention includes:
There are also coating compositions. As a specific example of the coating composition, it is suitably used as a coating agent for imparting blocking resistance and slipperiness of an outer film of various coatings. The binder used in the coating composition is a thermoplastic resin, a thermosetting resin, or a reactive resin capable of forming a film by coating on various substrates, and one or more of these resins may be used depending on the application. A mixture is used.

The thermoplastic resin has an average molecular weight of 1,0.
Those having about 100 to 1,000,000 are preferably used. Specific examples thereof include vinyl chloride polymers, vinyl chloride resins such as vinyl chloride-vinylidene chloride copolymers, vinyl acetate polymers, and vinyl acetate-ethylene copolymers. Polymers, vinyl acetate resins such as vinyl acetate-methyl methacrylate copolymer, (meth) acrylate (co) polymer, (meth) acrylate-acrylonitrile copolymer,
(Meth) acrylic acid ester resin such as (meth) acrylic acid ester-styrene copolymer, styrene resin such as styrene-butadiene-acrylonitrile copolymer,
Poly (ε-caprolactam), polyamide resins such as condensates of adipic acid and hexamethylenediamine, polyester resins such as condensates of terephthalic acid and ethylene glycol, condensates of adipic acid and ethylene glycol, polyethylene, Chlorinated polypropylene, carboxyl-modified polyethylene, polyisobutylene, polyolefin resins such as polybutadiene, cellulose acetate,
Examples include cellulose derivatives such as cellulose propionate and nitrocellulose, and butyral resins.
As these resins, commercially available products may be used as they are, or resins synthesized by a generally known method may be used.

The thermosetting resin or the reactive resin can form a crosslinked structure caused by an addition reaction, a condensation reaction, or the like by heating, irradiating with active energy rays, drying or other means during or after the film formation. Specifically, for example, phenolic resins such as novolak resins and resol resins, urea resins, melamine resins, amino resins such as benzoguanamine resins, various alkyd resins, unsaturated polyester resins, curable acrylic resins, isocyanates Examples include urethane-modified resins such as group-containing polyesters and isocyanate group-containing polyethers, polyamine resins, and epoxy resins.

The binder should be selected according to the adhesion and wettability to the substrate to be coated, hardness, flexibility, chemical resistance, stain resistance, weather resistance, etc., required for the coating. Yes, alone or in consideration of the intended use of the coating composition
Used in combination of more than one species.

The resin particle-containing coating composition of the present invention can be obtained by a method in which the resin particles are dispersed in various binders. The use ratio of the binder and the resin particles in the coating composition is not particularly limited, but the content of the binder is 100 parts by weight in order to sufficiently express the characteristics of the coating composition and not to impair the performance as a coating. 0.01 to 300 parts by weight, preferably 0.05 to 200 parts by weight
Parts by weight of resin particles are used. Further, the resin particle-containing coating composition of the present invention may contain, in addition to the above components, well-known additives to the coating composition so far as the effect is not impaired. Examples of such additives include metal soaps, dispersing aids such as surfactants, film forming aids, antistatic agents, defoamers, and inorganic pigments such as silica, talc, calcium carbonate, and titanium oxide. No.

The resin particles of the present invention may further include, for example, an additive for a toner for developing an electrostatic image, an additive for a decorative plate,
It is suitably used as an additive for artificial marble, a column filler for chromatography, a gap adjusting agent for a liquid crystal display panel, a display particle for a Coulter counter, a carrier for immunodiagnostic agents, and the like.

[0071]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but these examples do not limit the present invention in any way. Further, "parts" described in the examples described below all represent parts by weight.

Example 1 A flask equipped with a stirrer, an inert gas inlet tube, a reflux condenser and a thermometer was charged with polyoxyethylene alkyl sulfonammonium (HYTENOL N-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). 900 parts of deionized water in which 0.5 part was dissolved was charged. 90 parts of methyl methacrylate and trimethylolpropane trimethacrylate previously prepared therein
, A mixture of 1 part of azoisobutyronitrile and 1 part of 3,4-dinitrobenzoic acid was charged. K. 8000 with a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.)
The suspension was stirred at rpm for 5 minutes to form a uniform suspension.

The temperature of 3,4-dinitrobenzoic acid at 23 ° C.
The solubility in water at 760 Torr was 0.29%, and the solubility in the polymerizable monomer used was 16%.

Next, while blowing in nitrogen gas, the temperature is raised to 75 ° C.
The suspension was 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 resin particles (1). At this time, the nonvolatile content (emulsion polymerization fine particles) contained in the filtrate was 1.48 parts.

The obtained resin particles (1) were measured by a Coulter counter (aperture: 100 μm), and as a result, the average particle diameter was 3.47 μm, and the standard deviation was 1.4 μm. The resin particles (1) were colorless and odorless.

The resin particles (1) were heated at 270 ° C. in air for 4 hours.
The decomposition rate of the organic components when held for 0 minutes was measured using a thermogravimetric analyzer DTG-40 manufactured by Shimadzu Corporation.
%Met. In this measurement, the temperature was raised from room temperature to 200 ° C. at a rate of about 40 ° C./min. Thereafter, the temperature was gradually lowered to adjust the time to reach 270 ° C. from room temperature to 20 minutes. When the temperature reaches ℃, time 0
Was calculated by measuring the weight loss after holding for 40 minutes. The amount of resin sample at this time is about 20 mg
Further, in the measurement, the measurement was performed under the condition that the clean air was flowed at a rate of 40 ml / min.

Example 2 The procedure of Example 1 was repeated, except that 1 part of thiosalicylic acid was used in place of 1 part of 3,4-dinitrobenzoic acid used in Example 1. K. Resin particles (2) were obtained by repeating the same method as in Example 1 except that the homogenizer was stirred at 6000 rpm for 3 minutes.
I got

The thiosalicylic acid was heated at 23 ° C. and 760
The solubility in water under the condition of rr is 0.03% or less, and the solubility in the polymerizable monomer used is 1.
6%.

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

Example 3 The polymerizable monomer components used in Example 1 were 70 parts of butyl acrylate and 30 parts of styrene, and 5 parts of p-nitrobenzoic acid was used instead of 1 part of 3,4-dinitrobenzoic acid. Was used to obtain resin particles (3).

Incidentally, p-nitrobenzoic acid at 23 ° C. and 760
The solubility in water under the condition of Torr is 0.03.
% Or less, and the solubility in the polymerizable monomer used was 0.48%.

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

Example 4 The same flask as used in Example 1 was charged with polyoxyethylene alkyl sulfonammonium (Hydenol N
-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 900 parts of deionized water in which 0.5 part of a deionized water was dissolved was charged. To the polymerizable monomer component composed of 75 parts of methyl methacrylate and 5 parts of ethylene glycol dimethacrylate prepared beforehand, titanium oxide (Taipec CR-60-2, manufactured by Ishihara Sangyo Co., Ltd.) as a coloring agent 20), a mixture of 1 part of azoisobutyronitrile and 1 part of thiosalicylic acid was charged, and the same method as in Example 1 was repeated to obtain resin particles (4).

The thiosalicylic acid at 23 ° C. and 760 To
The solubility in the polymerizable monomer used under the condition of rr was 1.6%.

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

Synthesis Example 1 Polyvinyl alcohol (PVA-20) was placed in a flask equipped with a stirrer, an inert gas inlet tube, a reflux condenser, and a thermometer.
5, Kuraray Co., Ltd.) was dissolved in 200 parts of deionized water. A mixture prepared by dissolving 8 parts of benzoyl peroxide in a previously prepared polymerizable monomer composed of 97 parts of styrene and 3 parts of glycidyl methacrylate was added thereto, and stirred at a high speed to form a uniform suspension. Then, the mixture was heated to 80 ° C. while blowing in nitrogen gas, stirred at this temperature for 5 hours to carry out a polymerization reaction, and then cooled to obtain a polymer suspension. The polymer suspension was filtered, washed, and dried to obtain a polymer having an epoxy group as a reactive group.

The polymer having an epoxy group as a reactive group (40 parts) and carbon black MA-100R (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) (20 parts) were combined using a Labo Plastomill (Toyo Seiki Co., Ltd.) for 160 parts. The mixture was kneaded under the conditions of 100 ° C. and 100 rpm, reacted, cooled and pulverized to obtain a carbon black graft polymer (1).

Example 5 The same flask as used in Example 1 was charged with polyoxyethylene alkyl sulfonammonium (Hytenol N).
-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 900 parts of deionized water in which 0.5 part of a deionized water was dissolved was charged. A carbon black graft polymer (1) as a colorant obtained in Synthesis Example 1 was added to a polymerizable monomer component, which was prepared in advance and consisted of 76 parts of methyl methacrylate and 9 parts of trimethylolpropane trimethacrylate. 15), a mixture of 1 part of azoisobutyronitrile and 1 part of 2,2-dithiosalicylic acid was charged, and the same method as in Example 1 was repeated to obtain resin particles (5).

The temperature of 2,2-dithiosalicylic acid at 23 ° C.
The solubility in water at 760 Torr was 0.03% or less, and the solubility in the polymerizable monomer used was 0.03% or less.

The properties of the obtained resin particles (5) and the amount of by-produced emulsion polymerized fine particles were examined in the same manner as in Example 1, and the results are shown in Table 1.

Example 6 In the same flask as used in Example 1, 0.5 parts of polyoxyethylene nonylphenyl ether (Nonipol 200, manufactured by Sanyo Chemical Industries, Ltd.) was dissolved in deionized water 9
00 parts were charged. A polymerizable monomer component composed of 80 parts of methyl methacrylate and 19 parts of ethylene glycol dimethacrylate prepared in advance therein, 1 part of a fluorescent brightener Ubitex OB (manufactured by Ciba-Geigy), and azoisobutyro 0.5 parts of nitrile and o-nitrobenzyl alcohol 2
The mixture containing the components was charged, and the same method as in Example 1 was repeated to obtain resin particles (6).

Incidentally, 23 of o-nitrobenzyl alcohol
The solubility in water was 0.48% under the conditions of 760 Torr at ℃, and the solubility in the polymerizable monomer used was 23%.

The properties of the obtained resin particles (6) and the amount of emulsion polymerized fine particles produced as a by-product were examined in the same manner as in Example 1, and the results are shown in Table 2.

Example 7 The same flask as 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. To the polymerizable monomer component composed of 70 parts of methyl methacrylate and 9 parts of trimethylolpropane trimethacrylate prepared in advance, titanium oxide (Taipec CR-
60-2, manufactured by Ishihara Sangyo Co., Ltd.), a mixture of 20 parts of the optical brightener Ubitex OB (manufactured by Ciba-Geigy), 1 part of azoisobutyronitrile and 1 part of thiosalicylic acid was charged and carried out. The same method as in Example 1 was repeated to obtain resin particles (7).

The temperature of thiosalicylic acid at 23 ° C., 760 T
The solubility in the polymerizable monomer used under the conditions of orr was 1.6%.

The properties of the obtained resin particles (7) and the amount of emulsion polymerized fine particles produced as a by-product were examined in the same manner as in Example 1, and the results are shown in Table 2.

Comparative Example 1 The same flask as 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. A mixture prepared in advance by mixing 90 parts of methyl methacrylate, 10 parts of ethylene glycol dimethacrylate, and 1 part of azoisobutyronitrile was added thereto. K. Comparative resin particles (1) were obtained by repeating the same method as in Example 1 except that the mixture was stirred with a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 6000 rpm for 3 minutes to obtain a uniform suspension.

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

Comparative Example 2 In the same flask as used in Example 1, a polyoxyethylene alkyl sulfonammonium (Hytenol N) was added.
-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 900 parts of deionized water in which 0.5 part of a deionized water was dissolved was charged. A mixture prepared by mixing 90 parts of methyl methacrylate prepared in advance, 10 parts of trimethylolpropane trimethacrylate, and 1 part of azoisobutyronitrile was charged therein, and the same method as in Example 1 was repeated. The dispersion stability of the suspension during the polymerization reaction was poor, and most of the non-volatile components were aggregated and settled at the bottom of the flask.

Comparative Example 3 In a flask similar to that used in Example 1, polyoxyethylene alkyl sulfonammonium (Hytenol N) was added.
-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 900 parts of deionized water in which 1 part of cupric chloride was dissolved.
90 parts of methyl methacrylate prepared in advance there,
A mixture prepared by mixing 10 parts of trimethylolpropane trimethacrylate and 1 part of azoisobutyronitrile was charged, and the same method as in Example 1 was repeated. As a result, the dispersion stability of the suspension during the polymerization reaction was poor. Most of the non-volatile components aggregated and settled at the bottom of the flask.

Comparative Example 4 In a flask similar to that used in Example 1, polyoxyethylene alkyl sulfonammonium (Hytenol N) was added.
-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 900 parts of deionized water in which 1 part of thioglycolic acid was dissolved. Methyl methacrylate 9 previously prepared there
0 parts, trimethylolpropane trimethacrylate 10
And a mixture prepared by mixing 1 part of azoisobutyronitrile was charged, and the same method as in Example 1 was repeated to obtain comparative resin particles (4).

The properties of the comparative resin particles (4) and the amount of emulsion polymerized fine particles produced as a by-product were examined in the same manner as in Example 1, and the results are shown in Table 3.

Comparative Example 5 In Example 1, dodecyl mercaptan was used in place of 1 part of 4-nitrophthalic acid (dissolved in any ratio in the polymerizable monomer components methyl methacrylate and trimethylolpropane trimethacrylate). When one part was used and the same method as in Example 1 was repeated, the polymerization reaction was delayed, and most of the non-volatile components aggregated and settled at the bottom of the flask.

[0104]

[Table 1]

[0105]

[Table 2]

[0106]

[Table 3]

Example 8 Polypropylene (Melt Flow Index (MI) 2
g / 10 min, 3 parts of heptane-soluble component) and 99 parts of the resin particles (1) obtained in Example 1 were blended and kneaded into pellets at 230 ° C. with a Banbury mixer to form colorless pellets ( 1) was obtained. Next, 10 parts of these pellets and 90 parts by weight of the above polypropylene were mixed and mixed with an extruder.
It was extruded into a sheet at 0 ° C, stretched 5 times and 9 times vertically at a stretching temperature of 140 ° C and a stretching temperature of 175 ° C, and then one surface of the film was subjected to corona discharge treatment to give a stretched polypropylene film (1 ) Got.

The obtained stretched polypropylene film (1) was measured for thickness, turbidity, coefficient of kinetic friction, blocking strength and tensile modulus. Table 4 shows the results. The blocking strength and the kinetic friction coefficient were measured for the corona discharge treated surface and the non-treated surface, respectively.

The turbidity, dynamic friction coefficient, blocking strength and tensile modulus of the film were analyzed and evaluated by the following methods.

Turbidity Measured using a colorimetric colorimeter NDH-1001DP (turbidity meter) manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K6714.

Coefficient of dynamic friction Two films having a sample width of 50 mm were stacked on each other and the load was 200 g.
One side of the film was slid under a friction speed of 35 mm / min, a resistance value (g) was measured, and a coefficient was obtained from the following equation. The resistance was measured using a slip tester manufactured by Toyo Seiki.

Dynamic friction coefficient = (chart scale (g)) / (200 g) Blocking strength (g / cm 2) A film having a sample size of 120 mm × 120 mm is overlaid and an atmosphere of 40 ° C. and 90% RH under a load of 73 g / cm 2. After 24 hours in the sample, the blocking area was 1
It was cut out to have a size of 2 cm @ 2, and the shear peel strength (g) was measured by an autograph and determined by the following equation.

Blocking strength = (shear peel strength (g)) / (12 cm 2) Tensile modulus (kg / mm 2) Measured according to ASTM D-882.

Synthesis Example 2 150 parts of benzoguanamine and 37% formalin 13 were placed in a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer.
0 parts and a 10% strength aqueous solution of sodium carbonate 0.52
Parts were charged and mixed. The pH of the system was adjusted to 8.0, the temperature was raised to 95 ° C. with stirring, and the mixture was reacted for 4 hours to obtain a soluble fusible resin.

In addition to this, polyvinyl alcohol (PV
A-205, 8 parts of Kuraray Co., Ltd.) was dissolved in 750 parts of water, and this aqueous solution was heated to 90 ° C. and stirred using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The soluble fusible resin was added to the aqueous solution under stirring to obtain a white emulsion. The emulsion was cooled to 40 ° C, 2 parts of dodecylbenzenesulfonic acid was added, and the mixture was kept at 40 ° C for 2 hours while gently stirring with an anchor stirrer.
The mixture was stirred and cured at a temperature of 90 ° C. and 2 hours, respectively, to obtain a suspension of finely cured resin. The suspension was filtered and dried to obtain comparative resin particles (6).

The obtained comparative resin particles (6) had an average particle size of 3.32 μm and a particle size distribution of 1.6 μm.

Comparative Example 6 The same polypropylene as in Example 8 was used with respect to 99 parts by weight of polypropylene.
One part of the comparative resin particles (6) obtained in Synthesis Example 2 was blended, kneaded and pelletized at 230 ° C. with a Banbury mixer to obtain pale yellow comparative pellets (1). Then, 10 parts of this comparative pellet (1) and 90 parts of the above polypropylene were mixed and extruded into a sheet at 260 ° C. with an extruder. After stretching the film by 9 times and 9 times the width, one surface of the film was subjected to corona discharge treatment to obtain a stretched polypropylene film for comparison (1).

The thickness, turbidity, kinetic friction coefficient, blocking strength and tensile modulus of the obtained comparative oriented polypropylene film (1) were measured in the same manner as in Example 8. Table 4 shows the results.

Example 9 Low density polyethylene (melt flow index (M
I) 2.0 g / 10 min, density 0.92 g / cm3) 75
25 parts by weight of the resin particles (2) obtained in Example 2 were blended with the parts by weight, and kneaded and pelletized at 220 ° C. with a Banbury mixer to obtain colorless pellets (2). Then, 2 parts by weight of the pellet (2) and 98 parts by weight of the low-density polyethylene were mixed and extruded in a sheet form at 200 ° C. from a T-die using an extruder to obtain a polyethylene film (1).

The thickness, turbidity, dynamic friction coefficient, blocking strength and tensile modulus of the obtained polyethylene film (1) were measured. Table 4 shows the results.

Comparative Example 7 25 parts by weight of the comparative resin particles (1) obtained in Comparative Example 1 were mixed with 75 parts by weight of the same low-density polyethylene as in Example 9, and kneaded at 220 ° C. with a Banbury mixer. Pellets were obtained to obtain pale yellow comparative pellets (2). Then
2 parts of this comparative pellet (2) and 98 parts of the above low-density polyethylene were mixed and extruded into a sheet at 200 ° C. using an extruder.
The mixture was extruded from a die to obtain a comparative polyethylene film (1).

The thickness, turbidity, dynamic friction coefficient, blocking strength and tensile modulus of the obtained comparative polyethylene film (1) were measured in the same manner as in Example 8. Table 4 shows the results.

[0123]

[Table 4]

Example 10 and Comparative Example 8 An acrylic polymer (Dianal BR-113, manufactured by Mitsubishi Rayon Co., Ltd.) was mixed with ethyl acetate / toluene = 50/50.
Dissolved in the solution, then the resin particles (1) obtained in Example 1
And polymethyl sesquioxane particles (Tospearl 13
0, manufactured by Toshiba Silicone Co., Ltd., average particle size 3.0 μm)
Was added in the amounts shown in Table 3 and sufficiently stirred to obtain a coating composition (1) and a comparative coating composition (1).

10 parts of a polyester polymer (AD1010, manufactured by Toyo Morton Co., Ltd., 50% ethyl acetate solution) and polyisocyanate (Cat10, Toyo Morton Co., Ltd.)
Co., Ltd., 75% ethyl acetate solution), and apply and dry the above-mentioned coating composition to a stretched polypropylene film coated with an undercoat diluted with ethyl acetate and dried.
A coating layer of 7 μm was provided to obtain a coating film. The test results are as shown in Table 5.

[0126]

[Table 5]

As is clear from Table 5, the coating composition of the present invention has excellent scratch resistance.

Example 11 and Comparative Example 9 Vinyl chloride-vinyl acetate copolymer (400X-110A, manufactured by Nippon Bion Co., Ltd.) as a binder, polyurethane (Nipporan 2301, Nippon Polyurethane Co., Ltd.)
) And polyisocyanate (Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) were dissolved in methyl ethyl ketone in the composition shown in Table 4, and then the resin particles (5) obtained in Example 5 and carbon black (Asahi # 60, (Asahi Carbon Co., Ltd.) were added in the amounts shown in Table 3 and sufficiently stirred to obtain a coating composition (2) and a comparative coating composition (2). The test results were as shown in Table 6.

[0129]

[Table 6]

As is clear from Table 6, the coating composition of the present invention has good dispersibility, and is excellent in antistatic properties, slip properties, abrasion resistance and matting properties.

Each test in Table 6 is performed by the following method.

Antistatic property: The surface electric resistance of the coated article kept in an atmosphere of 25 ° C. and 60% RH for 24 hours was measured.

Coefficient of friction: The dynamic friction coefficient (at 3.3 cm / sec) μ of the stainless steel ball was measured by surface measurement.

Abrasion resistance: The wear state after 100 reciprocations according to the JIS L-1084445R method was visually evaluated using a Gakushin-type dyeing wear fastness tester.

…: No abrasion ×: abrasion matte: visually determined.

…: Good mattability ×: poor mattability Example 12 and Comparative Example 10 Zinc white, mica, talc, iron oxide and the resin particles (4) or titanium dioxide obtained in Example 4 are shown in Table 7. The powders were added in the amounts shown, and mixed with a Henschel mixer to obtain mixed powder. On the other hand, liquid paraffin, sorbitan sesquiolate, ethyl paraben, vitamin E, and a fragrance were heat-dissolved in the amounts shown in Table 7 at 80 ° C., sprayed on the mixed powder, and further mixed with a Henschel mixer. Was. Subsequently, it was pulverized by an atomizer, sieved, and molded into a medium plate by compression molding to obtain a cosmetic (1) and a comparative cosmetic (1).

When each cosmetic was subjected to a sensory evaluation by 10 panelists, the results shown in Table 7 were obtained.

[0138]

[Table 7]

As is clear from Table 7, it can be seen that the cosmetic of the present invention is excellent in the feeling of adhesion to the skin, sticking to the skin, spreading, and stickiness.

The symbols in Table 7 are as follows:…: 8 to 10 people judged good usability Δ: 5 to 7 people judged good usability ×: 0 to 4 people judged good usability Show.

[0141]

As described above, since the present invention is a (meth) acrylic resin particle having excellent heat resistance, it can be suitably used for various applications.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08F 20/06-20/18 C08F 2/18 C08L 33/00 C09D 133/00

Claims (5)

(57) [Claims] Claims: 1. A composition comprising a crosslinkable (meth) acrylic monomer.
(Meth) acrylic monomer 50 to 100% by weight and
And 50 to 0 weight of another monomer copolymerizable with the monomer
% Of the polymerizable monomer (A) obtained by polymerizing the polymerizable monomer (A),
Weight caused by polymerizable monomer of polymer
Resin particles characterized in that the rate of weight loss due to decomposition of the combined component is 60% by weight or less. 2. A polyolefin polymer composition obtained by blending the resin particles according to claim 1 with a polyolefin. 3. A polyolefin polymer film obtained by blending the resin particles according to claim 1 with a polyolefin. 4. A cosmetic comprising the resin particles according to claim 1 as a filler. 5. A coating composition comprising the resin particles according to claim 1 and a binder.