JPH10218951A - Preparation of crosslinked resin particle, crosslinked resin particle obtained thereby and thermoplastic resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce crosslinked resin particles easily without limitation by the type of the monomer used by uniformly mixing a polymer having radical- reactive groups in the molecule with a vinyl monomer and a crosslinkable monomer having at least two radical-reactive groups in the molecule, emulsifying the mixture in an aqueous medium in the presence of an emulsifier and polymerizing the emulsion in the presence of a radical polymerization initiator. SOLUTION: The polymer (A) having radical reactive groups in the molecule has desirably a number-average molecular weight of 250-1,000,000, and its radical reactive groups are selected among allyl, vinyl, etc., though not particularly limited. It is exemplified by an allyl-terminated polyisobutylene. The vinyl monomer (B) used is exemplified by methyl methacrylate. The crosslinking monomer (C) is exemplified by allyl methacrylate. The solvent component (D) which dissolves three components A, B and C is exemplified by hexane. The emulsifier (E) is exemplified by sodium laurylsulfate, and the polymerization initiator used is exemplified by benzoyl peroxide. The aqueous medium used is e.g. methanol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing crosslinked resin particles, crosslinked resin particles obtained therefrom, and a thermoplastic resin composition containing the same. More specifically, for example, a method for easily producing crosslinked resin particles useful as, for example, an impact resistance improver, without being limited by the type of monomer used, the crosslinked resin particles obtained by the method, and the crosslinking The present invention relates to a thermoplastic resin composition containing resin particles.

[0002]

2. Description of the Related Art Crosslinked resin particles containing a rubber component are generally useful as an impact resistance improver for imparting impact resistance to various resins, and various types have conventionally been proposed. As the impact resistance improver, for example, a product obtained by graft copolymerizing a vinyl monomer with a polybutadiene rubber having a low glass transition temperature (hereinafter, referred to as Tg) is well known.

[0003] The crosslinked resin particles are preferably used as an impact resistance improver because, when mixed with various resins, the dispersed particle size can be controlled in advance, and deformation of the particles such as flattening and orientation can be prevented. It is based on the ability to maintain the form.

[0004] The crosslinked resin particles as described above are generally produced by emulsion polymerization. Such emulsion polymerization is suitable for producing, for example, monodispersed crosslinked resin particles having a particle diameter of about 0.1 to 0.5 μm, which is considered as a method for producing an impact resistance improver. It can be said that this is a very advantageous feature.

However, only monomers capable of emulsion polymerization can be used in such emulsion polymerization. There is a problem that there is a limit.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and includes, for example, monomers which cannot be emulsion-polymerized, without being limited by the types of monomers used. Even in such a case, an object of the present invention is to provide a method capable of easily obtaining crosslinked resin particles.

[0007]

The present invention comprises: (A) a polymer having a radical reactive group in the molecule and having a number average molecular weight of 250 to 1,000,000, (B) a vinyl monomer and (C) ) A crosslinkable monomer having two or more radically reactive groups in a molecule is uniformly mixed, the obtained mixture is emulsified in an aqueous medium in the presence of an emulsifier, and polymerized with a radical polymerization initiator. A method for producing crosslinked resin particles, crosslinked resin particles obtained by the above method, crosslinked graft copolymer particles obtained by graft copolymerizing a vinyl monomer to the crosslinked resin particles obtained by the above method, The present invention relates to a thermoplastic resin composition containing the crosslinked resin particles and a thermoplastic resin, and a thermoplastic resin composition containing the crosslinked graft copolymer particles and a thermoplastic resin.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing crosslinked resin particles of the present invention is as follows:
As described above, (A) a polymer having a radical reactive group in a molecule and having a number average molecular weight of 250 to 1,000,000 (hereinafter, referred to as component (A)), (B) a vinyl monomer (hereinafter, referred to as a component) , (B) component) and (C) a crosslinkable monomer having two or more radically reactive groups in the molecule (hereinafter, referred to as a (B) component).
(Referred to as component (C)), and the resulting mixture is emulsified in an aqueous medium in the presence of an emulsifier and polymerized with a radical polymerization initiator.

As described above, the production method of the present invention comprises the steps of uniformly mixing the components (A), (B) and (C) and, if necessary, a solvent component described later to obtain a mixture;
In the presence of an emulsifier, a step of emulsifying the obtained mixture in an aqueous medium, and a step of performing a polymerization reaction with a radical polymerization initiator, containing a polymer having a radical reactive group in the molecule. The greatest feature is that the mixture is emulsified in an aqueous medium and a polymerization reaction is carried out with a radical polymerization initiator.

In the present invention, component (A) and component (B)
The component and the component (C) are mixed to prepare a uniform mixture.

The component (A) may be any polymer that can be dissolved in the component (B) and / or the solvent component described below at room temperature, and is not particularly limited. In order to reduce the cost, it is possible to reduce the cost by using the emulsion polymerization method.In consideration of economics, it is usually a polymer obtained by polymerizing a monomer that is not capable of emulsion polymerization. preferable. Such polymers include, for example, olefin (co) polymers, polysiloxanes, polyethers, polyesters, polyamides,
Polyurethane, polycarbonate and the like having a main chain skeleton are preferable, and among these, when the obtained crosslinked resin particles are used as an impact resistance improving agent, polyisobutylene, An ethylene-based copolymer such as an ethylene-α-olefin copolymer or an ethylene-vinyl ester copolymer, at least one polymer selected from polypropylene glycol, polytetramethylene glycol, polydimethylsiloxane, and polysulfide is used as a main chain bone. A rated one is more preferred.

The radical reactive group contained in the component (A) is not particularly limited, but from the viewpoint of reactivity and cost, allyl, vinyl, isopropenyl, allyloxy, acryloyl, methacryloyl, and mercapto groups It is preferably at least one radical reactive group selected from

The number average molecular weight of the component (A) is 250 or more, preferably 300 or more, more preferably 500 or more, considering that the characteristics of the component (A) are sufficiently exhibited. In order to eliminate the possibility that the dispersibility of component (A) of
Or less, preferably 100,000 or less, more preferably 30,000 or less.

Specific examples of the component (A) include, for example, allyl-terminated polyisobutylene (manufactured by Kaneka Chemical Industry Co., Ltd.) and Nissan polybutene N product (Nippon Yushi Co., Ltd.)
Nippon Petrochemical Co., Ltd.), Idemitsu Polybutene (Idemitsu Petrochemical Co., Ltd.), JSR butyl rubber (Nippon Synthetic Rubber Co., Ltd.), JSR EPDM (Nippon Synthetic Rubber Co., Ltd.) ), Thiokol LP (manufactured by Toray Thiokol Co., Ltd.), vinyl-modified silicone oil (manufactured by Nippon Unicar Co., Ltd.), vinyl-modified polysiloxane (manufactured by Chisso Co., Ltd.), Zeospan (manufactured by Zeon Corporation), allyl Terminal polypropylene glycol (manufactured by Kanegafuchi Chemical Industry Co., Ltd.), Fundalon (manufactured by Mitsubishi Chemical Corporation), Kaliflex TR (manufactured by Shell Japan Co., Ltd.), etc., may be used alone or in combination of two or more. They can be used in combination.

The component (B) is not particularly limited as long as it is a radical polymerizable vinyl monomer, and examples thereof include, but are not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl. Acrylates such as acrylate and n-octyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate; styrene, α-methylstyrene, p-methylstyrene, vinyl Aromatic alkenyl compounds such as toluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; non-conjugated diene compounds such as butadiene and isoprene; Alkenyl, is a halogen-containing unsaturated compounds such as vinylidene chloride. These may be used alone or in admixture of two or more. Among these, from the viewpoint of availability, at least one selected from acrylates, methacrylates, aromatic alkenyl compounds, and vinyl cyanide compounds.
Species are preferred, and methyl methacrylate, n-butyl acrylate, styrene and acrylonitrile are more preferred.

The ratio of the component (A) to the component (B) (component (A) / component (B) (weight ratio)) is 1/100 in order to sufficiently exhibit the characteristics of the component (A). It is desirable that the ratio is 99 or more, preferably 5/95 or more.
It is desirably 1 or less, preferably 95/5 or less.

The component (C) is not particularly limited as long as it is a crosslinkable monomer having two or more radically reactive groups in the molecule. The radical reactive group in the molecule is
They may be the same or different.

The radical reactive group contained in the component (C) is not particularly limited. However, from the viewpoint of reactivity and cost, allyl, vinyl, isopropenyl, allyloxy, acryloyl, methacryloyl, and mercapto groups are preferred. It is preferably at least one kind of radical reactive group selected from the group consisting of: allyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, triglycol, Allyl cyanurate and triallyl isocyanurate are particularly preferred.

The amount of the component (C) is at least 0.01 part by weight, preferably 0.05 part by weight, based on 100 parts by weight of the component (B), in order to eliminate the possibility that the crosslinked resin particles are hardly obtained. It is desirable that the amount is not less than parts by weight, and even though there is no change in the properties of the crosslinked resin particles, in order to eliminate the possibility that the cost is increased and the economic efficiency is reduced,
It is desirable that the amount is 30 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the component (B).

Further, in the present invention, in addition to the above components (A), (B) and (C), components (A),
For the purpose of further improving the dispersibility during emulsification of the mixture obtained by uniformly mixing the components (B) and (C), a solvent component may be added as necessary.

As the solvent component, component (A)
It is sufficient that all of the components (B) and (C) can be dissolved. Depending on the combination of the components (A), (B) and (C) used, hexane, heptane and octane are usually used. Aliphatic compounds such as benzene, xylene and toluene; halogen-containing compounds such as methyl chloride, methylene chloride and chloroform can be suitably used.

The amount of the solvent component depends on the amount of the component (A),
In order to sufficiently exhibit the effect of improving the dispersibility of the mixture of the components (B) and (C), the amount is preferably at least 5 parts by weight, more preferably at least 10 parts by weight, based on 100 parts by weight of the mixture. In order to eliminate the possibility that the crosslinked resin particles are hardly obtained, the amount is preferably 500 parts by weight or less, more preferably 100 parts by weight or less based on 100 parts by weight of the mixture.

The method of mixing the above-mentioned components (A), (B), (C) and, if necessary, the solvent component is not particularly limited. For example, sufficient stirring is carried out so as to obtain a uniform mixture. I just need.

Next, the obtained mixture is emulsified in an aqueous medium in the presence of an emulsifier.

As the emulsifier, those generally used in emulsion polymerization can be used, and there is no particular limitation. From the viewpoint of industrial availability, examples of the emulsifier include anionic salts such as alkyl sulfates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, fatty acid salts, alkyl phosphates and alkyl sulfosuccinates. Emulsifiers; cationic emulsifiers such as alkylamine salts, quaternary ammonium salts, alkyl betaines, and amine oxides; polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, oxyethylene-oxypropylene block copolymers, sorbitan fatty acid esters, It is preferable to use a nonionic emulsifier such as glycerin fatty acid ester and polyoxyethylene fatty acid ester. Among these, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium stearate, potassium oleate, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene nonyl phenyl ether are particularly preferred from the viewpoint of easy availability. More preferred.

In order to sufficiently emulsify the mixture in an aqueous medium, the amount of the emulsifier is preferably at least 0.1 part by weight, preferably at least 0.3 part by weight, per 100 parts by weight of the mixture. In order to suppress emulsion polymerization, which is a side reaction, the amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the mixture.

The aqueous medium used in the present invention is, for example, water or a mixed solvent of water and a water-soluble organic solvent. As the water-soluble organic solvent, for example, methanol, ethanol, ethylene glycol, glycerin, tetrahydrofuran, dimethylformamide, dioxane and the like can be used. Further, the aqueous medium may contain a water-soluble electrolyte such as an inorganic salt.

The amount of the aqueous medium is 50 parts by weight or more, preferably 1 part by weight, per 100 parts by weight of the mixture in order to eliminate the possibility that the stability of the emulsion after emulsification is deteriorated.
It is preferable that the amount is not less than 00 parts by weight, and in order to reduce the production efficiency and the risk of lowering the economy, 1000 parts by weight or less with respect to 100 parts by weight of the mixture,
Preferably, it is 500 parts by weight or less.

The method of emulsifying the mixture is not particularly limited, but from the viewpoint of simplicity, a method involving stirring using a homomixer, a method using a high-pressure homogenizer, a method involving passing through a porous membrane, and the like are preferable. The temperature, time, and the like for emulsification may be appropriately adjusted according to the type of each component.

Next, the mixture emulsified as described above is polymerized with a radical polymerization initiator.

As the radical polymerization initiator, those generally used for emulsion polymerization or suspension polymerization can be used, and there is no particular limitation. From the viewpoint of availability, examples of the radical polymerization initiator include benzoyl peroxide, cumene hydroperoxide, t-butylperoxyisobutyrate, di-t-butyl peroxide, dicumyl peroxide, t-cumyl peroxide, Organic peroxides such as -butyl hydroperoxide; 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-isobutyrovaleronitrile, 2,2'-azobis (2-methylbutyi It is preferable to use organic azo compounds such as Ronitrile); and persulfates such as potassium persulfate and sodium persulfate. In addition to these, it is also possible to use a redox initiator in which an oxidizing agent and a reducing agent are combined.

The amount of the radical polymerization initiator is not particularly limited, but is usually 0.1 to 100 parts by weight of the mixture.
It is preferably about 01 to 10 parts by weight.

The radical polymerization initiator may be added to a mixture of the components (A), (B) and (C) or may be added to an aqueous medium. It may be added inside. When an oil-soluble radical polymerization initiator is used, it is preferable to use it by adding it to a mixture of the components (A), (B) and (C). If you use it,
It is preferable to use it by adding it to an aqueous medium or an emulsion after emulsification. Further, the temperature, time, and the like at the time of the polymerization may be appropriately adjusted according to the type of each component.

Thus, the average particle size of the crosslinked resin particles in the emulsion obtained by the production method of the present invention is in the range of 0.05 to 10 μm, preferably 0.1 to 3 μm from the viewpoint of the stability of the emulsion. Is preferred.

The crosslinked resin particles may be used as they are as an aqueous emulsion (latex), or may be used as a powder composed of the crosslinked resin particles by salting out, coagulating and separating.

The crosslinked resin particles (latex) of the present invention thus obtained can be suitably used, for example, as paints, adhesives, coating agents and the like.

The crosslinked graft copolymer particles of the present invention can be obtained by graft copolymerizing a vinyl monomer to the crosslinked resin particles obtained by the production method of the present invention.

The vinyl monomer used in the graft copolymerization may be any vinyl monomer capable of emulsion polymerization, and is not particularly limited.

Examples of the vinyl monomer include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate and glycidyl acrylate; methyl methacrylate; Methacrylates such as ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate;
Styrene, α-methylstyrene, p-methylstyrene,
Aromatic alkenyl compounds such as vinyl toluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; non-conjugated diene compounds such as butadiene and isoprene; and halogen-containing unsaturated compounds such as vinyl chloride and vinylidene chloride. Can be used alone or in combination of two or more. Among these, methyl methacrylate and n are preferred from the viewpoints of availability and compatibility with, for example, a thermoplastic resin described later.
-Butyl acrylate, styrene and acrylonitrile are more preferred.

The ratio of the crosslinked resin particles to the vinyl monomer (crosslinked resin particles / vinyl monomer (weight ratio)) is determined by comparing the obtained crosslinked graft copolymer particles with the thermoplastic resin described later. Is preferably at least 1/99, more preferably at least 5/95, in order to sufficiently exhibit the effect of improving the compatibility of the resin, and 99/95 or more, in order to sufficiently exhibit the effect of improving the impact resistance. 1 or less, preferably 95/5
It is desirable that:

In the present invention, the method for obtaining the crosslinked graft copolymer particles is not particularly limited, and a method of copolymerizing in one step or in multiple steps by a usual radical polymerization technique can be adopted. Examples of the radical polymerization initiator used at this time include, for example, those exemplified when obtaining the crosslinked resin particles, and the temperature, time, and the like at the time of copolymerization are determined by using the crosslinked resin particles and the vinyl-based resin. What is necessary is just to adjust suitably according to the kind of a monomer, etc.

The average particle diameter of the thus obtained crosslinked graft copolymer particles is determined from the viewpoint of the stability of the emulsion.
It is preferably in the range of 0.05 to 10 μm, especially 0.1 to 3 μm.

Further, the crosslinked resin particles obtained by the production method of the present invention or the crosslinked graft copolymer particles obtained by graft copolymerizing a vinyl monomer to the crosslinked resin particles as described above, and the thermoplastic resin are used to obtain the present invention. The thermoplastic resin composition of the invention is obtained.

The thermoplastic resin is not particularly limited, but from the viewpoint of industrial availability, for example, polymethyl methacrylate resin, polyvinyl chloride resin, polyethylene resin, polypropylene resin, polycarbonate resin, etc. Resins, polyester resins, mixtures of polycarbonate resins and polyester resins, for example, at least one vinyl monomer selected from the group consisting of aromatic alkenyl compounds, vinyl cyanide compounds and (meth) acrylates Homopolymer or copolymer obtained by polymerizing 70 to 100% by weight of another vinyl monomer copolymerizable therewith with 0 to 30% by weight, polystyrene-based resin, polyphenylene ether-based resin, polystyrene-based Mixture of resin and polyphenylene ether resin, cyclic olefin Combined resins, and polyamide resins are preferably exemplified.

The ratio of the above-mentioned crosslinked resin particles or crosslinked graft copolymer particles to the thermoplastic resin (crosslinked resin particles or crosslinked graft copolymer particles / thermoplastic resin (weight ratio)) can be used to improve the impact resistance. Is preferably at least 1/99, more preferably at least 3/97, in order to sufficiently express the heat resistance. / 3
0 or less, preferably 50/50 or less.

The thermoplastic resin composition may further contain, if necessary, a stabilizer, a plasticizer, a lubricant, a flame retardant,
Additives such as pigments and fillers can be blended. Specific examples of the additive include stabilizers such as triphenyl phosphite; lubricants such as polyethylene wax and polypropylene wax; phosphate-based flame retardants such as triphenyl phosphate and tricresyl phosphate; decabromobiphenyl and decabromobiphenyl. Brominated flame retardants such as ether; flame retardants such as antimony trioxide; pigments such as titanium oxide, zinc sulfide and zinc oxide; fillers such as glass fiber, asbestos, wollastonite, mica, and talc.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited. For example, using a device such as a Banbury mixer, a roll mill, or a twin-screw extruder,
A method of mechanically mixing and, for example, shaping into pellets can be used. For example, pellets extruded and shaped as described above can be molded in a wide temperature range. For such molding, a usual injection molding machine, blow molding machine, extrusion molding machine, or the like can be used.

The crosslinked resin particles obtained by the method of the present invention and the crosslinked graft copolymer particles obtained by graft copolymerizing a vinyl monomer with the crosslinked resin particles are themselves used as impact-resistant resins. Can be used,
For example, impact resistance improver, processability improver, compatibilizer, matting agent, heat resistance improver, liquid crystal cell spacer, film spacer, pressure sensitive stilt, cosmetic lubricant, standard particles,
It can be suitably used as a resin for a toner, a carrier for a polymer catalyst, a column filler, a carrier for a diagnostic agent, and the like.

The thermoplastic resin composition of the present invention containing the above-mentioned crosslinked resin particles or crosslinked graft copolymer particles and a thermoplastic resin is particularly excellent in impact resistance and is applicable to various molding methods. Thus, a good molded product can be provided.

[0050]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Nisseki polybutene HV-3000 (manufactured by Nippon Petrochemical Co., Ltd., number average molecular weight 3000) was 60 parts by weight as the component (A), 40 parts by weight of n-butyl acrylate as the component (B), and (C) ) 1 part by weight of allyl methacrylate as a component and 0.5 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator, and 1.4 parts by weight of sodium lauryl sulfate as an emulsifier are dissolved. The mixture was added to 200 parts by weight of water, and the mixture was preliminarily dispersed at 30,000 rpm with a homomixer.
The mixture was emulsified and dispersed with a high-pressure homogenizer at a pressure of 700 kg / cm ² to obtain a mixed solution. This mixed solution was transferred to a separable flask equipped with a condenser, a nitrogen gas inlet tube and a stirring blade, and was rotated at 200 rpm under a nitrogen gas stream.
Then, the mixture was heated at 70 ° C. for 5 hours while stirring and mixing at m to obtain a crosslinked resin particle latex. The conversion was 99%.

The gel content of the obtained crosslinked resin particles and the polyisobutylene content in the gel (hereinafter referred to as PIB content in the gel) were measured according to the following methods. Table 1 shows the results together with the average particle size.

(Gel Content) The crosslinked resin particles were immersed in toluene for 8 hours with stirring at room temperature,
The mixture was centrifuged for 0 minutes, and the weight fraction of the toluene-insoluble component was measured.

(PIB content in gel) The FTIR spectrum of the toluene-insoluble portion of the crosslinked resin particles was 1370 c
The weight fraction of the polyisobutylene component was calculated from the ratio of the strength at m ^-1 to the strength at 1730 cm ^-1 .

Next, the latex was collected so that the solid content in the crosslinked resin particle latex was 70 parts by weight.
Put in a separable flask equipped with a condenser, a nitrogen gas inlet tube, a dropping funnel and a stirring blade, 260 parts by weight of water, 0.001 parts by weight of ferrous sulfate, 0.004 parts by weight of disodium ethylenediaminetetraacetate and formaldehyde 0.1 part by weight of sodium sulfoxylate is added,
70 ° C. while stirring at 200 rpm under nitrogen gas flow
Heated. Next, 30 parts by weight of methyl methacrylate and 0.06 parts by weight of cumene hydroperoxide were put into a dropping funnel and dropped into the latex over 2 hours. Thereafter, the mixture was further stirred at 70 ° C. for 1 hour to obtain a crosslinked graft copolymer. A particle latex was obtained. The conversion was 99%. To the obtained crosslinked graft copolymer particle latex, 200 parts by weight of a 1.5% by weight aqueous solution of calcium chloride was dropped, coagulated, separated, washed, dried at 40 ° C. for 15 hours, and crosslinked graft copolymer particles. (Hereinafter, referred to as S-1) was obtained.

The grafting efficiency of the obtained S-1 was examined according to the following method. Table 1 shows the results together with the average particle size.

(Graft Efficiency) The gel content of the crosslinked graft copolymer particles was measured in the same manner as the gel content of the crosslinked resin particles, and the graft copolymerization with the charged vinyl monomer for graft copolymerization (methyl methacrylate) was carried out. The ratio of the increase in the amount of the toluene-insoluble component due to was calculated.

Next, 16 parts by weight of S-1 was blended as an impact resistance improver with 84 parts by weight of a methacrylic resin (PARAPET G1000, manufactured by Kuraray Co., Ltd.) as a thermoplastic resin, and a vented twin-screw extruder was used. (32 mm, L / D = 2
Using 5.5), the mixture was extruded and kneaded at a set temperature of 230 ° C. to form pellets. The obtained pellets were dried at 80 ° C. for 15 hours, and then injection-molded at a set temperature of 230 ° C. to obtain 120 mm × 12 mm.
A flat sample of 0 mm × 3 mm (thickness) for evaluating physical properties was obtained.

The haze and Gardner impact of the obtained flat plate samples were examined according to the following methods. Table 1 shows the results.

(Haze) Measured according to the method described in ASTM D1003.

(Gardner Impact) ASTM D3
The measurement was performed at 23 ° C. and 0 ° C. using a 700 g weight according to the method described in 029-GB.

Example 2 In Example 1, Nisseki polybutene H was used as the component (A).
Crosslinked resin particles in the same manner as in Example 1 except that an allyl group-terminated polyisobutylene (a polymer having a number average molecular weight of 10400 produced by the method described in JP-B-7-53768) was used instead of V-3000. , Crosslinked graft copolymer particles (hereinafter, referred to as S-2) and flat plate samples.

The physical properties of the obtained crosslinked resin particles, S-2, and the flat plate sample were measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 The procedure of Example 1 was repeated except that S-1 was replaced by a commercially available acrylic impact modifier (Kaneace FM-21, manufactured by Kaneka Chemical Co., Ltd.). Similarly, a flat plate sample was prepared, and its physical properties were measured. Table 1 shows the results.
Shown in

The abbreviations in Table 1 indicate the following.

HV-3000: Nisseki polybutene HV-3
000 Al-PIB: allyl group-terminated polyisobutylene BA: n-butyl acrylate AlMA: allyl methacrylate MMA: methyl methacrylate PMMA: methacrylic resin (parapet G1000) S-1: crosslinked graft copolymer obtained in Example 1 of the present invention Combined particles S-2: Crosslinked graft copolymer particles obtained in Example 2 of the present invention FM-21: Kaneace FM-21

[0067]

[Table 1]

From the results shown in Table 1, according to the production method of the present invention, good crosslinked resin particles were obtained using the component (A) containing a monomer which was difficult to handle in conventional emulsion polymerization. It is understood that it can be obtained. Further, by mixing the crosslinked graft copolymer particles obtained by using the crosslinked resin particles obtained by the production method of the present invention with a thermoplastic resin, the haze is small,
The large Gardner impact indicates that a thermoplastic resin composition having improved impact resistance can be obtained without impairing the inherent transparency of the thermoplastic resin.

Example 3 70 parts by weight of allyl-terminated polyisobutylene (a polymer having a number average molecular weight of 10400 produced by the method described in JP-B-7-53768) as the component (A), and styrene as the component (B) 30 parts by weight, 1 part by weight of allyl methacrylate as the component (C) and 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator were mixed, and sodium lauryl sulfate 1 was used as an emulsifier. The above mixture was added to 200 parts by weight of water in which 0.4 parts by weight had been dissolved, preliminarily dispersed at 30,000 rpm using a homomixer, and then 700 kPa using a high-pressure homogenizer.
The mixture was emulsified and dispersed at a pressure of g / cm ² to obtain a mixed solution. This mixed solution was transferred to a separable flask equipped with a condenser, a nitrogen gas inlet tube and a stirring blade, and heated at 70 ° C. for 5 hours while stirring and mixing at 200 rpm under a nitrogen gas stream to obtain a crosslinked resin particle latex. . The conversion was 99%.

The gel content of the obtained crosslinked resin particles and the PIB content in the gel were measured in the same manner as in Example 1. Table 2 shows the results together with the average particle size.

Next, 200 parts by weight of a 1.5% by weight aqueous solution of calcium chloride was dropped into the latex of the crosslinked resin particles, coagulated, separated, washed, and dried at 40 ° C. for 15 hours to obtain the crosslinked resin particles (hereinafter referred to as “crosslinked resin particles”). , S-3).

Next, a cyclic polyolefin (Apel 6013, manufactured by Mitsui Petrochemical Industries, Ltd.) as a thermoplastic resin
100 parts by weight of S-32 as impact modifier
0 parts by weight and a vented twin-screw extruder (32 mm, L
/D=25.5), and was extruded and kneaded at a set temperature of 260 ° C. to form pellets. The obtained pellet is placed at 80 ° C for 15 minutes.
After drying for an hour, injection molding at a set temperature of 260 ° C, 120m
A flat sample for physical property evaluation having a size of mx 120 mm and a thickness of 1 mm or 3 mm was obtained.

The haze of the obtained flat plate sample (thickness 1 mm) was examined in the same manner as in Example 1, and the Izod impact strength of the flat plate sample (thickness 3 mm) was examined according to the following method. Table 2 shows the results.

(Izod impact strength) ASTM D25
According to the method described in 6-56, the sample with the V notch was measured at 23 ° C.

Comparative Example 2 In Example 3, commercial ethylene-
Flat plate samples were prepared in the same manner as in Example 3 except that propylene copolymer rubber (Tuffmer P0680, manufactured by Mitsui Petrochemical Industries, Ltd.) was used, and the physical properties were measured. Table 2 shows the results.

The abbreviations in Table 2 indicate the following.

Al-PIB: Allyl group-terminated polyisobutylene St: Styrene AlMA: Allyl methacrylate COC: Cyclic polyolefin (Apel 6013) S-3: Crosslinked resin particles obtained in Example 3 of the present invention EPR: Tuffmer P0680

[0078]

[Table 2]

From the results shown in Table 2, according to the production method of the present invention, good crosslinked resin particles were obtained using the component (A) containing a monomer which was difficult to handle in conventional emulsion polymerization. It is understood that it can be obtained. Furthermore, by mixing the crosslinked resin particles obtained by the production method of the present invention with a thermoplastic resin, the haze is small and the Izod impact strength is large,
It can be seen that a thermoplastic resin composition having improved impact resistance can be obtained without impairing the inherent transparency of the thermoplastic resin.

[0080]

According to the production method of the present invention, there is no limitation on the type of the monomer to be used, and for example, a crosslinked resin having a monomer as a structural unit which has been difficult to use in conventional emulsion polymerization. The particles can be easily manufactured, and their industrial value is very large.

Further, the crosslinked resin particles and crosslinked graft copolymer particles of the present invention are particularly useful, for example, as impact modifiers and the like, and are particularly excellent in compositions having these and various thermoplastic resins. A molded article exhibiting impact properties can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 283/12 C08F 283/12 C08L 55/00 C08L 55/00

Claims (10)

[Claims] 1. A polymer having (A) a radical reactive group in the molecule and having a number average molecular weight of 250 to 1,000,000, (B) a vinyl monomer and (C) two or more in the molecule. Crosslinkable resin particles characterized by uniformly mixing a crosslinkable monomer having a radical reactive group, emulsifying the obtained mixture in an aqueous medium in the presence of an emulsifier, and polymerizing with a radical polymerization initiator. Recipe. 2. A polymer having a main chain skeleton of at least one polymer selected from polyisobutylene, ethylene copolymer, polypropylene glycol, polytetramethylene glycol, polydimethylsiloxane and polysulfide. The method for producing crosslinked resin particles according to claim 1, wherein 3. The radical reactive group of the polymer (A) is at least one radical reactive group selected from an allyl group, a vinyl group, an isopropenyl group, an allyloxy group, an acryloyl group, a methacryloyl group and a mercapto group. The method for producing crosslinked resin particles according to claim 1 or 2, wherein 4. The at least one vinyl monomer (B) selected from acrylates, methacrylates, aromatic alkenyl compounds and vinyl cyanide compounds.
4. The method for producing crosslinked resin particles according to claim 1, which is a kind of vinyl monomer. 5. The radical reactive group of the crosslinking monomer (C) is at least one radical selected from an allyl group, a vinyl group, an isopropenyl group, an allyloxy group, an acryloyl group, a methacryloyl group and a mercapto group. 5. The method for producing crosslinked resin particles according to claim 1, which is a reactive group. 6. The process for producing crosslinked resin particles according to claim 1, wherein the average particle size is 0.05 to 10 μm. 7. Crosslinked resin particles obtained by the method according to claim 1, 2, 3, 4, 5, or 6. 8. Crosslinked graft copolymer particles obtained by graft copolymerizing a vinyl monomer onto the crosslinked resin particles obtained by the method according to claim 1, 2, 3, 4, 5, or 6. 9. A thermoplastic resin composition comprising the crosslinked resin particles according to claim 7 and a thermoplastic resin. 10. A thermoplastic resin composition comprising the crosslinked graft copolymer particles according to claim 8 and a thermoplastic resin.