JP2000026665A - Crosslinked polymer particle and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide crosslinked polymer particles excellent in sliding properties, mar resistance of molded articles and external appearance of molded particles. SOLUTION: In the presence of (C) 10-90 pts.wt. crosslinked particles obtained by polymerizing (A) 5-100 wt.% crosslinkable monomer and (B) 95-0 wt.% [provided that (A)+(B)=100 wt.%] at least one vinyl type monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a methacrylate ester compound and, if necessary, another vinyl type monomer copolymerizable with these monomers, (D) 90-10 pts.wt. [provided that (C)+(D)=100 pts.wt.] monomer component composed of 0-2 wt.% component (A) and 100-98 wt.% component (B) is graft-polymerized with a graft ratio of not less than 5 wt.% to obtain crosslinked polymer particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to crosslinked polymer particles having excellent slidability, scratch resistance on the surface of a molded article, and excellent surface appearance of the molded article, and a method for producing the same.

[0002]

2. Description of the Related Art Copolymers of styrene and acrylonitrile are generally referred to as AS resins, and have excellent physical properties, mechanical properties, electrical properties, and moldability. Widely used for. However, this AS resin has drawbacks such as poor slidability and the surface of a molded article is easily damaged.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is intended to provide a crosslinked polymer particle having excellent slidability, a surface of a molded article which is hardly damaged, and an excellent surface appearance of the molded article. It is intended to provide a manufacturing method.

[0004]

According to the present invention, there is provided (A) 5 to 100% by weight of a crosslinkable monomer, and (B) at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a methacrylate ester. 95 to 0% by weight of a monomer component composed of various vinyl monomers and other vinyl monomers copolymerizable therewith if necessary.
(A) + (B) = 100% by weight] (C)
In the presence of 10 to 90 parts by weight of the crosslinked particles, 90 to 10 parts by weight of the (D) monomer component consisting of the component (A) / component (B) = 0 to 2/100 to 98% by weight [( C) +
(D) = 100 parts by weight], and the graft ratio is 5% by weight or more. The present invention also provides a method for producing the above-mentioned crosslinked polymer particles, wherein the crosslinked polymer particles are obtained by emulsion graft polymerization or suspension graft polymerization.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The crosslinked particles (C) of the present invention are:
(A) 5 to 100% by weight of a crosslinkable monomer, and (B) at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a methacrylate ester.
95 to 0% by weight of a monomer component composed of various kinds of vinyl monomers and other vinyl monomers copolymerizable therewith if necessary [(A) + (B) = 100% by weight] ] Is polymerized. Here, (A) as the crosslinkable monomer,
Polyethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-butylene glycol diacrylate, 1,6-hexane glycol diacrylate, neopentyl glycol diacrylate, polypropylene glycol diacrylate, 2,
2'-bis (4-acryloxypropyloxyphenyl)
Diacrylate compounds such as propane and 2,2'-bis (4-acryloxydiethoxyphenyl) propane; triacrylate compounds such as trimethylolpropane triacrylate, trimethylolethane triacrylate and tetramethylolmethane triacrylate; and ditrimethylolpropane Tetraacrylate compounds such as tetraacrylate, tetramethylolmethanetetraacrylate, and pentaerythritol tetraacrylate;
Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol methacrylate, 1,3-butylene glycol dimethacrylate,
1,4-butylene glycol dimethacrylate, 1,6
Methacrylate compounds such as hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4-methacryloxydiethoxyphenyl) propane,
Examples include trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethanetrimethacrylate, methylenebisacrylamide, and divinylbenzene.

Among the crosslinkable monomers (A), ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and divinylbenzene are preferred.
Particularly preferred are trimethylolpropane trimethacrylate and divinylbenzene. The crosslinkable monomer (A) may be used singly or as a mixture of two or more.

The amount of the crosslinkable monomer (A) used in the crosslinked particles (C) of the present invention is 5 to 100% by weight,
Preferably 10 to 90% by weight, more preferably 10 to 90% by weight.
When it is used in an amount of less than 5% by weight, the slidability and the scratch resistance of the molded product surface are poor.

The aromatic vinyl compound used for the monomer component (B) includes, for example, styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, 1,1-diphenylstyrene, N , N-diethyl-
p-aminomethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene,
Fluorostyrene, vinyl naphthalene, and the like,
Particularly, styrene and α-methylstyrene are preferred. The aromatic vinyl compounds can be used alone or in combination of two or more.

The vinyl cyanide compound used in the monomer component (B) includes acrylonitrile, methacrylonitrile, etc., and acrylonitrile is particularly preferred. The above vinyl cyanide compounds can be used alone or in combination of two or more. Further, as the methacrylic acid ester used for the monomer component (B), methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate,
Examples thereof include dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate, with methyl methacrylate being particularly preferred. The above methacrylic acid esters can be used alone or in combination of two or more.

[0010] In the (C) crosslinked particles of the present invention, at least one vinyl monomer selected from the group consisting of the above-mentioned aromatic vinyl compound, vinyl cyanide compound and methacrylate ester in the monomer component (B). The amount of body used is preferably greater than 50% by weight, more preferably 70% by weight.
Is an amount that exceeds If the used amount is 50% by weight or less, the molded article surface has poor scratch resistance.

Further, other vinyl monomers that may be used as the monomer component (B) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, and the like. Acrylic esters such as 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; acrylic acid, methacrylic acid, etc. Unsaturated acids such as maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; Of alpha, imide compound of β- unsaturated dicarboxylic acid; glycidyl methacrylate, epoxy group-containing unsaturated compound such as allyl glycidyl ether;
Unsaturated carboxylic acid amides such as acrylamide and methacrylamide; unsaturated compounds containing an amino group such as acrylamine, aminomethyl methacrylate, aminoether methacrylate, aminopropyl methacrylate and aminostyrene; 3-hydroxy-1-propene; -Hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate Hydroxyl-containing unsaturated compounds such as styrene and hydroxystyrene; oxazoline-containing unsaturated compounds such as vinyloxazoline; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-
Examples thereof include conjugated dienes such as methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and chloroprene. The other copolymerizable vinyl monomers can be used alone or as a mixture of two or more.

The amount of the other copolymerizable vinyl polymer in the component (B) in the crosslinked particles (C) of the present invention is preferably 50% by weight or less, more preferably 30% by weight or less. When the amount exceeds 50% by weight, the viscosity at the time of melting increases, and the appearance of the molded product is significantly reduced.

Preferred combinations of vinyl monomers of the monomer component (B) are as follows. (1) Styrene (2) Styrene / acrylonitrile (3) Methyl methacrylate (4) Styrene / methyl methacrylate (5) Styrene / methyl methacrylate / acrylonitrile

The amount of the monomer component (B) used in the crosslinked particles (C) of the present invention is 0 to 95% by weight, preferably 10 to 90% by weight, and more preferably 30 to 90% by weight. If it exceeds 95% by weight, the slidability and the scratch resistance of the molded product surface are inferior.

The (C) crosslinked particles of the present invention can be obtained by combining the above (A) crosslinkable monomer and (B) monomer component with a known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, or a combination thereof. Can be produced by a conventional polymerization method.
Preferably, it is emulsion polymerization. At this time, for emulsion polymerization,
A polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used. In the case of emulsion polymerization, a part or all of the (A) crosslinkable monomer and the (B) monomer component are added and polymerized, and then the remaining monomers are added or polymerized continuously or divided, and the present invention is carried out. (C) Crosslinked particles can be obtained.

Examples of the polymerization initiator include organic hydroperoxides represented by cumene hydroxyperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like, sugar-containing pyrophosphoric acid formulations, sulfoxylate formulations and the like. A redox system in combination with a reducing agent, or a persulfate such as potassium persulfate, or a peroxide such as azobisisobutyronitrile or benzoyl peroxide is used. Preferred are persulfates and oil-soluble initiators, potassium persulfate for persulfates, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and sugar containing for oil-soluble initiators. A redox system based on a combination with a reducing agent represented by a pyrophosphoric acid formulation, a sulfoxylate formulation or the like is preferred. Moreover, you may combine the said oil-soluble initiator and a water-soluble initiator. When combined, the addition ratio of the water-soluble initiator is preferably 50% by weight or less, more preferably 25% by weight or less of the total amount. Further, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator used is usually 0.05 to 5% by weight, preferably 0.1 to 5% by weight, based on the monomer component.
３3% by weight.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethylthiuram sulfide, and the like. Examples thereof include hydrocarbons such as carbon tetrachloride, ethylene bromide and pentaphenylethane, or dimers of acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, and α-methylstyrene. These chain transfer agents can be used alone or in combination of two or more. The method of using the chain transfer agent may be any of batch addition, divisional addition, and continuous addition. The amount of the chain transfer agent is usually about 0.05 to 2.0% by weight based on the monomer component.

Examples of the emulsifier include an anionic surfactant,
Nonionic surfactants, and amphoteric surfactants are included. Among them, examples of the anionic surfactant include a higher alcohol sulfate, an alkylbenzene sulfonate, a fatty acid sulfonate, a phosphoric acid, and a fatty acid salt. As the nonionic surfactant, an alkyl ester type, an alkyl ether type, an alkyl phenyl ether type or the like of ordinary polyethylene glycol is used. Further, as an amphoteric surfactant,
Examples thereof include those having a carboxylate, sulfate, sulfonate, or phosphate as an anion portion, and amine salts, quaternary ammonium salts, or the like as a cation portion. The amount of emulsifier used is usually
It is about 0.3 to 5.0% by weight.

When the (A) crosslinkable monomer and the (B) monomer component are emulsion-polymerized to obtain (C) crosslinked particles, a polymerization temperature of 40 to 95 ° C., preferably 50 to 80 ° C. It is desirable to carry out emulsion polymerization in the above. The crosslinked particles (C) of the present invention are subjected to a recovery step such as coagulation-washing, dehydration-desolubilization, etc. after emulsion polymerization, and then dried to form powders or granules.

The term "crosslinked particles" used herein means that the gel content (toluene-insoluble content) measured by the following method is 50% by weight or more, preferably 75% by weight or more.
The crosslinked polymer particles of the present invention using the crosslinked particles (C) having a gel content in the above range are excellent in slidability and scratch resistance on the surface of the molded article.

The method for measuring the gel content (toluene-insoluble matter) is described below. That is, about 1 g (X) of the powder of the crosslinked particles (C) of the present invention is placed in a 100 ml Meyer flask.
g) After weighing, add 50 ml of toluene and leave at room temperature for 24 hours. Next, the mixture is filtered with filter paper, and 10 ml of the filtrate is collected, transferred to an aluminum dish (Yg), and then toluene is evaporated (Zg). The gel content is determined by the following equation (1). Gel content (% by weight) = [1- (Z−Y) × 5 / X] / 100 (1)

The average particle size of the crosslinked particles (C) of the present invention is as follows:
The range is preferably 50 nm to 2 mm, more preferably 50 nm to 1,000 nm, and particularly preferably 60 nm.
５００500 nm. If it is less than 50 nm, the viscosity of the latex increases, and handling is difficult. Meanwhile, 2
If it exceeds mm, the dispersibility in other resins is inferior, and as a result, the molded appearance is significantly inferior.

The crosslinked polymer particles of the present invention can be used in the presence of the component (A) in the presence of 10 to 90 parts by weight of the crosslinked particles (C).
(B) component = 0 to 2/100 to 98% by weight (D) 90 to 10 parts by weight of a monomer component (provided that (C) +
(D) = 100 parts by weight].
(C) The amount of the crosslinked particles used is 10 to 90 parts by weight, preferably 20 to 90 parts by weight, per 100 parts by weight of the crosslinked polymer particles of the present invention.
90 parts by weight, more preferably 40 to 80 parts by weight, particularly preferably 45 to 80 parts by weight. If the amount is less than 10 parts by weight, the slidability and the scratch resistance of the molded product surface are poor. On the other hand, if it exceeds 90 parts by weight, the slidability, the scratch resistance of the molded product surface and the appearance of the molded product surface are inferior.

Among the (D) monomer components graft-polymerized on the (C) crosslinked particles, all of the above-mentioned components (A) and (B) can be used. The ratio of the component (A) to the component (B) in the component (D) is represented by the ratio of the component (A) /
Component (B) = 0 to 2/100 to 98% by weight, preferably only component (B). Here, when the use amount of the component (A) is more than 2% by weight, the surface appearance of the molded product is inferior.
The amount of the component (D) used is determined by the amount of the crosslinked polymer particles 10 of the present invention.
10 to 90 parts by weight, preferably 10 to 80 parts by weight in 0 parts by weight
Parts by weight, more preferably 20 to 60 parts by weight, particularly preferably 20 to 55 parts by weight. If less than 10 parts by weight,
The slidability, the scratch resistance of the molded article, and the appearance of the molded article surface are poor. On the other hand, if it exceeds 90 parts by weight, the slidability and the scratch resistance of the molded article surface are poor.

The crosslinked polymer particles of the present invention can be obtained by graft polymerization of the monomer component (D) in the presence of the crosslinked particles (C). Examples of the polymerization method include known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, and a combination of these known polymerization methods. Preferably,
Emulsion polymerization or suspension polymerization, particularly preferably emulsion polymerization. In the case of emulsion polymerization, after (A) a part or all of the crosslinkable monomer and (B) monomer components are added and polymerized, the remaining monomers are continuously or dividedly added and polymerized. After obtaining the crosslinked particles, the crosslinked polymer particles of the present invention can be obtained by performing polymerization while adding (D) a monomer component for graft polymerization all at once, dividedly or continuously.

The polymerization initiator used in the emulsion polymerization or suspension polymerization is not particularly limited as long as it is used in ordinary emulsion polymerization or suspension polymerization. For example, an oxidizing agent consisting of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, t-butylperoxylaurate, sugar-containing iron pyrophosphate formulation, sulfoxylate formulation , Redox initiators in combination with reducing agents such as a mixture of sugar-containing iron pyrophosphate formulation / sulfoxylate formulation; persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate; azobisisobutyro Nitrile, dimethyl-2,
Azo compounds such as 2'-azobisisobutyrate and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide; and aqueous solutions such as potassium persulfate are preferred. It is a sex initiator.

The amount of these radical polymerization initiators used is
Usually, 0.1 part by weight per 100 parts by weight of the monomer component used.
It is about 0.5 to 5 parts by weight, preferably about 0.1 to 3 parts by weight. If the amount is less than 0.05 part by weight, the polymerization is inactivated, and the monomer conversion rate is reduced.

In the above emulsion polymerization and suspension polymerization, a surfactant or a suspension protective agent is used to increase the stability of the polymerization reaction system. As the surfactant, for example, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium diphenylether disulfonate,
Sodium succinate sodium sulfonate, sodium or potassium salt of aliphatic carboxylic acid having 10 to 20 carbon atoms, sodium or potassium salt of rosin acid, known anionic surfactant such as reactive emulsifier, polyoxyethylene Nonionic surfactants such as nonyl phenyl ether, polyethylene glycol monostearate, polyoxyethylene alkylpropenyl phenyl ether, sorbitan monostearate, octaethylene glycol monohexadecyl ether, and hexaethylene glycol monododecyl ether are exemplified.

Preferred suspension protective agents include polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, sodium polyacrylate, hydroxypropyl cellulose and (meth) acrylic acid.
(Meth) acrylic acid ester copolymers and the like. The amount of the surfactant or suspension protective agent used is 0.1 to 5 parts by weight, based on 100 parts by weight of the monomer component used.
Preferably it is 0.2 to 3 parts by weight. If the amount is less than 0.1 part by weight, instability in the polymerization system occurs, and the polymerization mode deteriorates. On the other hand, when the amount exceeds 5 parts by weight, new particles are generated, so that the graft ratio decreases.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, and tetraethyl. Thiuram sulfide, carbon tetrachloride, ethylene bromide,
Examples thereof include hydrocarbon salts such as pentaphenylethane, terpenes, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, and α-methylstyrene dimer. These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent to be used is generally 0 to 3 parts by weight based on 100 parts by weight of the monomer component. When the amount exceeds 3 parts by weight, the molecular weight of the graft portion decreases, so that the compatibility with other resins decreases. In the graft polymerization for obtaining the crosslinked polymer particles of the present invention, in addition to the polymerization initiator, the surfactant, the suspension protective agent, the chain transfer agent, and the like, various electrolytes, a pH adjuster, and the like are used as needed. be able to.

The amount of water used in the emulsion polymerization is usually 100 parts by weight based on 100 parts by weight of the monomer component used.
To 500 parts by weight, preferably 100 to 300 parts by weight, more preferably 100 to 250 parts by weight. If the amount is less than 100 parts by weight, the heat generated by the polymerization cannot be removed,
It is difficult to control the polymerization. On the other hand, if it exceeds 500 parts by weight, the productivity is greatly reduced.

The polymerization temperature during the emulsion polymerization is from 40 to
90 ° C, preferably 40 to 80 ° C. In the polymerization, it is preferable to keep the internal temperature constant within this polymerization temperature range. If the polymerization temperature is lower than 40 ° C., the polymerization reaction is slow and the monomer conversion is low. Further, the polymerization time is preferably set to 1 to 10 hours. If it is less than 1 hour, the monomer conversion is low, while if it exceeds 10 hours, the productivity is greatly reduced.

The conditions of the suspension polymerization are the same as those of the above emulsion polymerization except that the polymerization is carried out with stirring at 400 rpm using polyvinyl alcohol as a dispersant.

When the crosslinked polymer particles of the present invention are obtained by emulsion polymerization, they are purified and recovered by coagulation, washing and drying. After spray drying, if necessary, the product may be purified and recovered by washing with water and drying. Coagulants used in the coagulation process include sodium chloride, calcium chloride, aluminum chloride, magnesium sulfate, ferrous sulfate, ferric sulfate, ferric chloride, aluminum sulfate, activated silica, calcium phosphate, sulfuric acid, and acetic acid. Is mentioned.

When the crosslinked polymer particles of the present invention are obtained by suspension polymerization, after completion of the polymerization, the granular polymer is separated by filtration, washed with water, and dried at 60 to 80 ° C.

The crosslinked polymer particles of the present invention are obtained by grafting a thermoplastic polymer onto crosslinked particles (C) having substantially no thermoplasticity. Therefore, the crosslinked polymer particles of the present invention include (C) a crosslinked particle graft obtained by grafting a thermoplastic polymer onto the crosslinked particles and a non-grafted (ungrafted) thermoplastic polymer. The amount of the thermoplastic polymer grafted to the crosslinked particles (C) in the crosslinked polymer particles, that is, the graft ratio is 5% by weight or more, preferably 5 to 400% by weight, more preferably 10 to 150% by weight, and particularly preferably. Is from 20 to 150% by weight. If the graft ratio is less than 5% by weight, slidability,
Poor scratch resistance and appearance of the molded product surface.

Here, the above-mentioned graft ratio refers to that represented by the following formula (2). Graft ratio (%) = [(weight of (D) component subjected to graft polymerization) / {weight of (C) component}] × 100 (2) The graft ratio is determined as described below. Desired. From the amount of the crosslinked particles (C) used during the graft polymerization and the polymerization conversion of the graft component, the content (W) (% by weight) of the component (C) in the crosslinked polymer particles of the present invention is obtained. When the crosslinked polymer particles of the present invention are fractionated by gel permeation chromatography (hereinafter referred to as “GPC”), a peak of the crosslinked particle graft is detected in a polymer region exceeding the exclusion limit of GPC. On the other hand, for the ungrafted thermoplastic polymer, a peak is detected in a normal region. From the peak area (A ₁ ) of the peak attributed to the crosslinked particle graft, the peak area (A ₂ ) of the peak attributed to the ungrafted thermoplastic polymer, and the component (C) content (W), the following formula (3) ), The above graft ratio can be calculated. Graft ratio (%) = [100−W− {A ₂ × 100 / (A ₁ + A ₂ )}] × 100 / W (3)

At the time of graft polymerization, the unreacted component of the crosslinkable monomer (A) used in the production of the crosslinked particles (C) of the present invention serves as a graft crossing agent, and is therefore considered to be a graft point. Since it is considered that a monomer is graft-polymerized to a polymer having a double bond, the control of the ratio (graft ratio) of the monomer contributing to the graft polymerization is controlled by a general AB.
It is possible by the same method as the control method in S. That is,
This is a method of adjusting the type and amount of the polymerization initiator, the type and amount of the chain transfer agent, the polymerization temperature, the method for adding the vinyl monomer to be graft-polymerized, the addition time, and the like.

The molecular weight (Mw; weight average molecular weight in terms of polystyrene by GPC measurement) of the ungrafted thermoplastic polymer in the crosslinked polymer particles is preferably in the range of 30,000 to 8,000,000. More preferably, 50,000-
It is 1,000,000, particularly preferably 50,000 to 500,000. If it is outside this range, the compatibility with other resins will be reduced.

The average particle size of the crosslinked polymer particles of the present invention is preferably in the range of 50 nm to 2 mm, more preferably 50 nm to 1000 nm, and particularly preferably 60 nm.
m to 500 nm. If it is less than 50 nm, the viscosity of the latex increases and handling becomes difficult. On the other hand, if it exceeds 2 mm, the dispersibility in other resins is inferior and the appearance of the molded article is significantly inferior.

The crosslinked polymer particles of the present invention may contain, if necessary, known stabilizers, plasticizers, lubricants, coloring agents, foaming agents, wood flour, paper, inorganic fillers, antioxidants, weather resistance (light )
Agents, metal powders, flame retardants, flame retardant aids, antibacterial agents, fungicides, silicone oils, coupling agents, and the like.

The crosslinked polymer particles of the present invention can be blended with other known polymers. Here, as other known polymers, for example, ABS resin, MBS resin, HI
PS, AES resin, ASA resin, AS resin, PS resin,
PMMA, MS resin, PBT, PET, polyarylate, polyamide resin, PPS resin, liquid crystal polyester,
Polycarbonate, acrylic rubber, silicone rubber, fluorine rubber, butyl rubber, butadiene rubber, ethylene
α-olefin copolymer rubber, NBR, SBR, SB
S, SEPS, SEBS, thermoplastic polyurethane, PT
FE, polypropylene, polyethylene, polyamide elastomer, polyester elastomer and the like. These other known polymers can be used alone or as a mixture of two or more.

The crosslinked polymer particles of the present invention can be kneaded together with various components using various extruders, Banbury mixers, kneaders, rolls, ribbon blenders, Henschel mixers and the like. A preferred method is a method using a twin screw extruder or a Banbury mixer. When kneading with each component, each component may be kneaded at once or may be kneaded by a multi-stage addition method.

With the crosslinked polymer particles of the present invention, good molded articles can be obtained by various processing methods. Examples of the processing method include (foaming) extrusion molding, blow molding, injection molding, press molding, calendering, vacuum molding, inflation molding, and lamination molding. Various molded products obtained by the above molding method, utilizing their excellent properties,
It can be used for a wide range of applications, such as various parts such as OA / home electric appliances, vehicle field, sanitary field, building material field, daily miscellaneous goods field.

[0045]

EXAMPLES The present invention will now be described more specifically with reference to examples. Parts and% in Examples are parts by weight and% by weight unless otherwise specified. During the implementation, various measurement items were as described below. Measurement of gel content (toluene-insoluble matter); described in the text.

As the average particle diameter of the dispersed particles, the particle diameters of the crosslinked particles (C) and the crosslinked polymer particles in the latex synthesized by emulsion polymerization were measured by a light scattering method. The measuring device is a laser particle size analysis system LPA-3100 manufactured by Otsuka Electronics Co., Ltd.
And the average particle diameter (nm) was measured using the cumulant method by integrating 70 times. Graft ratio and weight ratio of ungrafted thermoplastic polymer
Average molecular weight (Mw) of Waters Co., gel permeation chromatography (GPC-244), Tosoh as column Corporation
Manufactured by TSK-gel-GMH-HR-H30 microns ×
1. Using tetrahydrofuran (THF) as a solvent,
The measurement was performed at a flow rate of 0.5 ml / min and a temperature of 23 ° C., and calibrated based on polystyrene.

[0047] Using the slidability Suzuki type slide tester, as the mating member with steel (S45C). The test piece had an outer diameter of 25.6 mm,
A ring-shaped press-formed product having an inner diameter of 20.0 mm was used, and a counterpart material having the same shape was used. The measurement conditions for the dynamic friction coefficient are as follows: a load of 0.5 was applied in an atmosphere at room temperature 23 ° C. and 50% humidity.
kg, the peripheral speed was 500 mm / sec, and the running distance was 3 km, and the dynamic friction coefficient and the amount of wear were measured. The dynamic friction coefficient was calculated by the following equation (4). mu = ^{_{[3 × F × (r 2 2}} -r 1 2) ] / _{^{[P × (r 2 3 -r 1}} 3) ] ..... (4) (wherein, mu is the dynamic friction coefficient, F is The force applied to the load cell,
P represents a load, R represents an arm length to a load cell, r ₁ represents an inner diameter, and r ₂ represents an outer diameter. )

A flat test piece was formed by press forming with scratch resistance (resistance to scratching) . The test piece surface was strongly wiped with gauze, and the degree of surface damage was visually evaluated according to the following evaluation criteria. ；: No damage (good). ×: Scratched (poor). A flat test piece was formed by press molding of the surface of the molded product . The test piece surface was visually evaluated according to the following evaluation criteria. ；: Good without unevenness on the surface X: The surface is uneven and defective.

Reference Example 1 [(C) Preparation of Crosslinked Particles] (1) C-1 After replacing a stainless steel reaction vessel equipped with a stirrer with nitrogen,
1.4 parts of potassium stearate, 0.1 part of sodium hydroxide.
3 parts, 2.6 parts of potassium rosinate, 600 ion-exchanged water
Parts were added. Next, 15 parts of divinylbenzene, 62 parts of styrene and 23 parts of acrylonitrile were added in a nitrogen stream with stirring, and then the temperature was raised while circulating hot water at 65 ° C. through the jacket. When the internal temperature reaches 55 ° C,
0.6 parts of potassium persulfate was added as a 2% aqueous solution to initiate a polymerization reaction. After 2 hours, the polymerization was terminated to obtain crosslinked particles (C-1). The polymerization conversion was 98%.
The gel content of -1) was 93%, and the average particle size was 62 nm. FIG. 1 shows the GPC measurement result of (C-1).

(2) C-2 In the polymerization method of the above (C-1), except that the amount of each monomer used was changed to 50 parts of divinylbenzene, 36.5 parts of styrene and 13.5 parts of acrylonitrile. Polymerization was performed in the same manner to obtain (C-2). Polymerization conversion rate is 97
%, And the gel content of the obtained crosslinked particles (C-2) is 89.
%, And the average particle diameter was 55 nm. (3) C-3 In the polymerization method of (C-1), the same procedure was carried out except that (A) the crosslinkable monomer was changed from 15 parts of divinylbenzene to 15 parts of trimethylolpropane trimethacrylate. I got The polymerization conversion was 98%, the gel content of the obtained crosslinked particles (C-3) was 95%, and the average particle size was 60 nm.

(4) C-4 In the polymerization method of the above (C-1), except that all 23 parts of acrylonitrile were replaced with 23 parts of styrene, (C-4) was obtained. The polymerization conversion was 96%, the gel content of the obtained crosslinked particles (C-4) was 93%, and the average particle size was 66 nm. (5) C-5 Polymerization was carried out in the same manner as in the above polymerization method (C-1), except that the amount of each monomer was changed to 2 parts of divinylbenzene, 71.5 parts of styrene and 26.5 parts of acrylonitrile. Was carried out to obtain (C-5). The polymerization conversion rate is 98%,
The gel content of the obtained crosslinked particles (C-3) was 91%, and the average particle size was 75 nm.

Examples 1 to 8 and Comparative Examples 1 to 5 [Preparation and Evaluation of Crosslinked Polymer Particles (E-1 to 12)] E-1 After replacing a stainless steel reaction vessel equipped with a stirrer with nitrogen,
50 parts of (C-1) were added as crosslinked particles, and the temperature was raised while circulating warm water through the jacket while stirring. Inner temperature 65
When the temperature reached ° C, 0.13 parts of potassium persulfate was added as a 2% aqueous solution. Styrene 36.5 in a stream of nitrogen
Parts and 13.5 parts of acrylonitrile were added continuously over 3 hours to carry out graft polymerization. Then, after stirring was continued for 2 hours, cold water was circulated through the jacket to cool the internal temperature to room temperature. The obtained crosslinked polymer particle latex was coagulated with sulfuric acid, washed with water and dried to obtain a crosslinked polymer particle (E-1) of the present invention. The obtained crosslinked polymer particles (E-1) were molded by hot press molding, and the molded product was evaluated by the above-described evaluation method. Table 1 shows the composition, physical properties, and evaluation results of (E-1).
FIG. 1 shows the GPC measurement result of (E-1).

E-2 to 12 In the polymerization method of the above (E-1), the type and amount of the component (C), the type and amount of the monomer component (D) in the graft polymerization, (E-1) Polymerization was performed by changing the presence or absence and addition amount of t-dodecyl mercaptan as a chain transfer agent for adjusting the molecular weight of the grafted thermoplastic polymer, the addition amount of the surfactant, etc. as shown in Table 2, and And crosslinked polymer particles (E-2 to 12) were obtained. The composition, physical properties and evaluation results of the obtained (E-2 to 12) were
The results are shown in Tables 1 and 2.

As shown in FIG. 1, the GP of the crosslinked particles (C-1)
In the C chart, one peak was detected in the polymer region exceeding the exclusion limit. The GPC chart of the crosslinked polymer (E-1) has two peaks, and the lower molecular weight peak detected in a normal region is attributed to the ungrafted thermoplastic polymer (AS resin), while being excluded. The peak detected in the polymer region exceeding the limit is AS crosslinked particles (C-1).
The resin is attributed to the grafted polymer.

[0055]

[Table 1]

[0056]

[Table 2]

As shown in Table 1, the crosslinked polymer particles of the present invention were excellent in slidability, the surface of the molded article was not easily damaged, and the surface appearance of the molded article was excellent. Comparative Example 1 is an example in which the amount of the crosslinkable monomer (A) used in the production of the crosslinked particles (C) is out of the range of the present invention, and is poor in slidability and scratch resistance of the molded product surface. . Comparative Example 2 is an example in which the amount of the monomer component (D) used in the graft polymerization is out of the range of the present invention, and the sliding property, the scratch resistance of the molded product surface, and the appearance of the molded product surface are inferior. . Comparative Example 3 is an example in which the amount of the (A) crosslinkable monomer used in the (D) monomer component used in the graft polymerization is outside the range of the present invention, and the molded article surface appearance is inferior. Comparative Example 4 is an example in which the graft ratio is low outside the range of the present invention, and the slidability, the scratch resistance of the molded product surface, and the appearance of the molded product surface are inferior. Comparative Example 5 is an example in which the amount of the crosslinked particles (C) used is small outside the range of the present invention, and the slidability and the scratch resistance of the molded product surface are poor.

[0058]

As described above, the crosslinked polymer particles of the present invention have a sliding property,
Excellent molded article surface scratch resistance and molded article surface appearance,
Applicable to a wide range of fields.

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[Procedure amendment]

[Submission Date] August 19, 1998 (1998.8.1)
9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Added

[Correction contents]

[Brief description of the drawings]

FIG. 1 shows a crosslinked particle C-1 and a crosslinked polymer E of the present invention.
It is a graph of the GPC measurement result of -1.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BN031 BN051 BN111 BN121 BN141 FD140 FD310 GC00 GL00 GN00 GQ00 4J011 PA54 PA65 PA69 PA70 PA74 PB06 PC02 PC06 4J026 AA16 AA17 AA18 AA19 AAA AAAAAAAAAAAAAAAAAAAAAA AA67 AA68 AA69 AA71 AA76 AC31 AC36 BA04 BA05 BA06 BA07 BA08 BA12 BA16 BA25 BA27 BA28 BA29 BA30 BA31 BA32 BA35 BA38 BA40 BA45 BA46 BA47 BA49 BA50 BB01 BB02 DA02 DA03 DA04 DA07 DA08 DA09 DA10 DA12 DA14 DA15 DB10 DB03 DB04 DB14 DB15 DB16 DB26 DB29 DB30 DB32 DB34 DB40 EA04 FA03 FA09 GA08 GA09

Claims (2)

[Claims] 1. A composition comprising: (A) 5 to 100% by weight of a crosslinkable monomer, and (B) at least one vinyl monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a methacrylate ester. If necessary, 95 to 0% by weight of a monomer component composed of another vinyl monomer copolymerizable therewith (provided that (A) + (B) = 100% by weight) is polymerized (C In the presence of 10 to 90 parts by weight of the crosslinked particles, 90 to 10 parts by weight of the (D) monomer component consisting of (A) / (B) = 0 to 2/100 to 98% by weight [provided that (C) + (D) = 100 parts by weight], and the graft ratio is 5% by weight or more. 2. The method for producing crosslinked polymer particles according to claim 1, wherein the crosslinked polymer particles are obtained by emulsion graft polymerization or suspension graft polymerization.