JP2742841B2 - Reactive resin particles, method for producing the same, and resin composition for heat molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel three-dimensional resin fine particle having a crosslinkable reactive group on the surface of the particle and a method for producing the same.

[0002] The present invention also relates to a thermosetting resin composition for heat molding, comprising the above-mentioned reactive resin fine particles, more specifically, a marble-like material having a high transparency such as a bathtub, a vanity table, and a kitchen counter. SMC (Sheet Molding Compound) used to manufacture molded products
And BMC (bulk molding compound),
Or other resin compositions such as premix materials.

[0003]

2. Description of the Related Art In general, SM used for pressure and heat molding is used.
For C and BMC, thermoplastic resins such as polymethyl methacrylate, polystyrene, polyethylene, polyvinyl acetate or copolymers of these are used to prevent the loss of surface gloss and the occurrence of cracks during molding due to curing shrinkage of the resin. Is added as a low-shrinkage agent in the form of granules or in a state of being dispersed or dissolved in a crosslinkable monomer.

[0004] By the addition of the thermoplastic resin, the thermoplastic resin phase-separates from the matrix due to rapid heat generation during the curing of the thermosetting resin, and fine pores are formed due to the remarkable thermal expansion of the thermoplastic resin. Cracks occur, and these phenomena cancel out the curing shrinkage of the thermosetting resin, and the shrinkage of the whole molded article is suppressed.

[0005]

However, when a thermoplastic resin is used as a low-shrinking agent to suppress shrinkage during curing as described above, it is inevitable that the thermoplastic resin undergoes phase separation and fine pores as described above. Or the occurrence of microcracks, resulting in the scattering of light at the interface between the thermoplastic resin, the fine pores and the microcracks and the matrix, and as a result, the crucial transparency of this type of molded article is impaired. Occurs. Also, for molded products that come into contact with or heat hot water, such as bathtubs and vanities,
At the interface between the thermoplastic resin and the matrix, the former peels from the latter and water penetrates into the fine pores, causing whitening and discoloration of the molded product, resulting in reduced durability of the molded product, such as heat resistance and water resistance. was there.

Conventionally, the following two types of three-dimensional resin fine particles obtained by polymerization of a polyfunctional monomer and a polymerizable monomer are known: i) α, β
-Synthesis of crosslinked fine particles from a polyfunctional monomer having at least two ethylenically unsaturated groups and a polymerizable monomer having an α, β-ethylenically unsaturated group, in which case a hydrophilic monomer or oligomer having active hydrogen is synthesized. To form fine particles comprising an ethylenically unsaturated group introduced into the particle surface by introducing active hydrogen into the particle surface and then reacting the active hydrogen with a monomer having an ethylenically unsaturated group at the terminal. JP-A-62-84113), ii) Vinyl polymerization capable of undergoing a polymerization reaction only with a polyfunctional monomer having at least two ethylenically unsaturated groups having different copolymerizabilities and one unsaturated group of the polyfunctional monomer. Obtained by emulsion polymerization of a crosslinking monomer and leaving at least one unsaturated group of the crosslinking monomer as it is (JP-A-62-2469).
No. 16).

However, the former fine particles are intended to be mixed with a solvent-based coating composition to form a coating film having excellent physical properties such as hardness, abrasion resistance, tensile strength and heat resistance. In addition, the latter fine particles are intended to fix functional polymers or foreign substances on the particle surface, and blend this with solvent-based coating compositions to provide coatings with excellent coating workability and storage stability. Therefore, none of these fine particles have been used as a low-contracting agent for SMC or BMC.

An object of the present invention is to provide novel three-dimensional resin fine particles which can be used in a resin composition as a low-shrinkage agent in view of the above-mentioned situation, and to provide a molding which is rich in transparency and excellent in durability. An object of the present invention is to provide a thermosetting resin composition for thermoforming that can obtain a product.

[0009]

The present invention has been completed by creating novel three-dimensional resin fine particles having a cross-linkable reactive group on the surface of the particles. It has been provided based on the finding that the above-mentioned problems can be solved by blending the fine particles as a low-shrinkage agent in a resin composition.

It should be noted that throughout the present specification, all percentages and parts are on a weight basis.

I) Reactive resin fine particles The reactive resin fine particles according to the present invention have a degree of crosslinking of 0.05.
A core particle made of a three-dimensional crosslinked resin in the range of 2.0 to 2.0 mmol / g, and a shell portion formed on the surface of the particle and having a radically polymerizable ethylenically unsaturated bond. , 1-mono substitution in the molecule and 1,
1-disubstituted radically polymerizable ethylenically unsaturated bond (a)
And 1,2-disubstituted 1,1,1,2
At least one of tri-substituted and 1,1,2,2-tetra-substituted radically polymerizable ethylenically unsaturated bonds (b);
And a polyfunctional monomer having at least one species
It is obtained by polymerizing a single or mixture of (A) and a single or mixture of non-aromatic radical polymerizable monomer (B).

In the reactive resin fine particles according to the present invention, the 1-mono-substituted or 1,1-di-substituted radically polymerizable ethylenically unsaturated bond (a) in the polyfunctional monomer (A) for forming the shell portion is used alone. It is a polymerizable ethylenically unsaturated bond. The 1,2-di-substituted, 1,1,2-tri-substituted or 1,1,2,2-tetra-substituted radically polymerizable ethylenically unsaturated bond (b) is substantially homopolymerized or the above ethylenically unsaturated bond. It is an ethylenically unsaturated bond which is not copolymerized with the bond (a). The non-aromatic radical polymerizable monomer (B) can be copolymerized with the above-mentioned ethylenically unsaturated bond (a) but is not substantially copolymerized with the ethylenically unsaturated bond (b). Is a polymerizable monomer having one.

Accordingly, the reactive resin fine particles according to the present invention are, in other words, a core particle composed of a three-dimensional crosslinked resin having a degree of crosslinking in the range of 0.05 to 2.0 mmol / g, A shell portion formed and having a radical polymerizable ethylenically unsaturated bond, the shell portion being an ethylenically unsaturated bond capable of being homopolymerized in a molecule.
(a) and substantially the homopolymerization also includes the ethylenically unsaturated bond described above.
A polyfunctional monomer (A) having at least one ethylenically unsaturated bond (b), which is not copolymerized with (a), alone or in a mixture with the ethylenically unsaturated bond (a). Is obtained by polymerizing a polymerizable monomer (B) having one ethylenically unsaturated bond which does not substantially copolymerize with the ethylenically unsaturated bond (b), alone or as a mixture.

The weight ratio between the core particles and the shell portion of the reactive resin fine particles is preferably core particle / shell portion = 10/9.
It is in the range of 0-99 / 1. When the weight ratio (core particle / shell portion, abbreviated as “C / S”) is less than 10/90, the durability of the molded article is reduced. Particle dispersibility decreases. Particularly preferred weight ratios are in the range of 40/60 to 80/20.

The preferred average particle size of the reactive resin fine particles is in the range of 0.01 to 5 μm. When the particle size is less than 0.01 μm, the dimensional stability of the molded product is poor, and when it exceeds 5 μm, the transparency and other appearance of the molded product are deteriorated. Particularly preferred average particle size is in the range of 0.05 to 2 μm.

The refractive index of the shell is preferably adjusted so that the difference between the refractive index of the resin in which the reactive resin fine particles are blended and the refractive index of the other compound is within 0.05.

Ii) Method for Producing Reactive Resin Fine Particles The method for producing reactive resin fine particles according to the present invention comprises preparing a core particle comprising a three-dimensional crosslinked resin having a degree of crosslinking in the range of 0.05 to 2.0 mmol / g. A first step of synthesizing, and at least one of a 1-monosubstituted or 1,1-disubstituted radically polymerizable ethylenically unsaturated bond (a) in the molecule;
2-disubstitution, 1,1,2-trisubstitution and 1,1,2,2
2-tetra-substituted radically polymerizable ethylenically unsaturated bond
at least one of (b)
A single or mixture of the polyfunctional monomer (A) having one and a single or mixture of the non-aromatic radical polymerizable monomer (B) are polymerized to form a radical polymerizable ethylenically unsaturated bond on the surface of the core particle. Having a second shell portion
Process.

Ii-a) First Step Synthesis of core particles composed of a three-dimensionally crosslinked resin is performed, for example, by the following steps.
A crosslinkable monomer having at least two copolymerizable ethylenically unsaturated bonds in a vinyl polymerizable monomer has a degree of crosslinking of 0.05 to 2.0 mmol / g, preferably 0.2 to 1.
It is carried out by emulsion polymerization using an amount of 0 mmol / g. The vinyl polymerizable monomer used here is not particularly limited, and the following are exemplified. (Meta)
Acrylates: for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, phenyl acrylate and the like. Polymerizable aromatic compounds; for example, styrene, α-methylstyrene, vinyl ketone, t-butylstyrene, parachlorostyrene, vinylnaphthalene and the like. Carboxyl group-containing monomers; for example, acrylic acid, methacrylic acid,
Crotonic acid, itaconic acid, maleic acid, fumaric acid and the like.
Hydroxyl group-containing monomers; for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, methallyl alcohol; Nitrogen-containing alkyl (meth) acrylates; for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl methacrylamide and the like. Polymerizable amide; for example, acrylamide, methacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide and the like. Polymerizable nitrile; for example, acrylonitrile, methacrylonitrile and the like. Vinyl halides; for example, vinyl chloride, vinyl bromide, vinyl fluoride.
α-olefins; for example, ethylene, propylene and the like. Vinyl compounds; for example, vinyl acetate, vinyl propionate and the like. Diene compounds; for example, butadiene, isoprene and the like.

The crosslinkable monomer is not particularly limited as long as it has two or more radically polymerizable ethylenically unsaturated bonds in the molecule, and examples thereof include the following. Polymerizable unsaturated monocarboxylic acid esters of polyhydric alcohols;
For example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol Diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6
-Hexanediol dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol acryloxy dimethacrylate, 1,1,1-trishydroxymethylethanediacrylate, 1,1,1-trishydroxymethylethanedimethacrylate, 1,1,1-trishydroxymethylethanetriacrylate, 1,1,1
-Trishydroxymethylethanetrimethacrylate,
1,1,1-trishydroxymethylpropane diacrylate, 1,1,1-trishydroxymethylpropane dimethacrylate. Polymerizable unsaturated alcohol esters of polybasic acids; for example, diallyl terephthalate, diallyl phthalate, triallyl trimellitate. Aromatic compounds substituted with two or more vinyl groups; for example, divinylbenzene. An addition compound of a monomer having an epoxy group-containing ethylenically unsaturated bond and a monomer having a carboxyl group-containing ethylenically unsaturated bond; for example, a reaction product of glycidyl acrylate or glycidyl methacrylate with acrylic acid or methacrylic acid.

When an emulsifier is used, it is used in an amount of 0.1 to 20 parts per 100 parts of the total amount of the above monomers.
Parts, preferably 2 to 10 parts. The type of the emulsifier is not particularly limited, and an anionic, cationic, amphoteric, nonionic surfactant, a reactive or non-reactive surfactant, or the like is appropriately used. Examples of the surfactant include the following. Anionic surfactants such as fatty acid soaps, higher alcohol sulfates, alkylbenzene sulfonates, dioctyl sulfosuccinates, and commercially available reactive anionic emulsifiers, "Latemul S-120A" and "Latemul S-180" manufactured by Kao Corporation. "Latemul S-180A": "New Frontier A229E" manufactured by Daiichi Kogyo Seiyaku, "Aqualon HS-10": "Eleminol JS-2" manufactured by Sanyo Kasei Co., Ltd., "Eleminol SSS": manufactured by Nippon Emulsifier "RA-1022",
“RA-1024”, “RA-421”, “RA-42”
3 "," Antox-MS-2N (7) ":" SX-1154 "," SX-1159 "," SX-11 "manufactured by Asahi Denka Co., Ltd.
63 ". Nonionic surfactants such as polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether, polyethylene glycol fatty acid ester, polypropylene glycol, polyethylene glycol ether, polyoxyethylene sorbitan fatty acid ester, and commercially available reactive nonionic emulsifiers;
"New Frontier N177" manufactured by Daiichi Kogyo Seiyaku
E "," AQUALON RN-20 ":" RMA-862 "," RA-951 "," RA-95 "manufactured by Nippon Emulsifier Co., Ltd.
3 "," RA-954 "," RA-955 "," RA-
957 "," RA-958 ":" SX-1 "manufactured by Asahi Denka Co., Ltd.
151 "," SX-1152 "," SX-1156 ",
"SX-1157". As commercially available reactive cationic emulsifiers, "Latemul K-180" manufactured by Kao Corporation, "RF-755" and "RF-756" manufactured by Nippon Emulsifier Co., Ltd.

Particularly preferred emulsifiers are reactive emulsifiers and polyester emulsifiers having an amphoteric ionic group (JP-A-56-1981).
No. 151727 and JP-A-56-34725).

The method for preparing the core particles is not limited to the above-mentioned methods, and conventional methods such as suspension polymerization, dispersion polymerization, and post-emulsification are used. Or a condensation reaction. Examples of combinations of functional groups for this reaction include carboxylic acid / amino group / epoxy group, hydroxyl group / amino group / isocyanate, carboxylic acid / hydroxyl group / melamine, amino group / active ester group and the like. .

The core particles may also include the above-mentioned polyfunctional monomer (A)
, The radical polymerizable monomer (B), and 1
At least one of mono-substituted and 1,1-disubstituted radically polymerizable ethylenically unsaturated bonds is at least 2
It can also be formed by emulsion polymerization of a mixture of the polyfunctional monomers (C) having the same.

The polymerization reaction in the first step is carried out in the presence of a radical polymerization initiator, if necessary. The type of the initiator is not particularly limited, and the following general initiators are used. Oily peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate. Aqueous peroxides; for example, potassium persulfate, ammonium persulfate. Oil-based azo compounds; for example, azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-
Dimethylvaleronitrile). Aqueous azo compounds; for example, anionic azobiscyanovaleric acid and cationic-2,2'-azobis (2-amidinopropane) hydrochloride.

Ii-b) Second Step The shell part is formed in the second step by adding the above-mentioned polyfunctional monomer (A) alone or a mixture thereof and the above-mentioned radical polymerizable monomer (B) to the aqueous dispersion of the core particles. It is carried out by dropping a monomer group consisting of a mixture and an initiator solution. As described above, the polyfunctional monomer (A) comprises at least one selected from the group consisting of 1-mono-substituted and 1,1-di-substituted radically polymerizable ethylenically unsaturated bonds (a) in the molecule, At least one selected from the group consisting of 1,2-di-substituted, 1,1,2-tri-substituted and 1,1,2,2-tetra-substituted radically polymerizable ethylenically unsaturated bonds (b), Has at least one. Suitable polyfunctional monomers (A) include, for example, acrylic or methacrylic ethylenically unsaturated bonds (a) and maleic or fumaric acid ethylenically unsaturated bonds (b)
Are used.

Particularly preferred polyfunctional monomers (A) are, for example, reaction products of maleic anhydride and 2-hydroxyethyl methacrylate, and reaction products of monobutyl maleate and glycidyl methacrylate.

As the non-aromatic radical polymerizable monomer (B), those exemplified as the vinyl polymerizable monomer used in the first step can be used. In particular, methyl acrylate, methyl methacrylate, ethyl acrylate, (Meth) acrylic monomers such as ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, and phenyl acrylate are preferably used.

In the reaction of the second step, the proportion of the polyfunctional monomer (A) in all the monomers for forming the shell is preferably in the range of 1 to 50%. If the ratio of the monomer (A) is less than 1%, the interface between the fine particles and the resin cannot be made sufficiently strong and the durability of the molded product is poor. On the other hand, if it exceeds 50%, the dimensional stability of the molded product decreases. . A particularly desirable ratio of the polyfunctional monomer (A) is in the range of 5 to 40%.

In the polymerization reaction of the second step, an emulsifier is optionally used. The amount and type of the emulsifier are as exemplified in the description of the first step.

[0030] The polymerization reaction in the second step is also usually carried out in the presence of a radical polymerization initiator. The type of the initiator is not particularly limited, and those exemplified in the description of the first step are appropriately used.

The reactive resin fine particles according to the present invention are classified into a monomer having at least one ethylenically unsaturated bond copolymerizable with the radically polymerizable ethylenically unsaturated bond (b) or a monomer group containing at least one kind thereof. 1-4
0 parts can be dispersed to form a dispersion.

Iii) Thermosetting resin composition for thermoforming The above reactive resin fine particles are mixed with a thermosetting resin as a low shrinkage agent and used to form a thermosetting resin composition for thermoforming. Can be

The thermosetting resin composition for thermoforming according to the present invention comprises a thermosetting resin, an inorganic filler and the above-mentioned reactive resin fine particles.

Examples of the thermosetting resin which is one of the components of the resin composition include an unsaturated polyester resin, a thermosetting acrylic resin or a vinyl ester resin.

Examples of the inorganic filler as another component are preferably a refractive index in the range of 1.46 to 1.60 and 1 to 300 μm, more preferably 20 to 10 μm.
Glass powder having an average particle size in the range of 0 μm, aluminum hydroxide (its refractive index is 1.57), silica powder , etc., which are used alone or in a mixture. As the inorganic filler, those which have been subjected to a surface treatment with a silane coupling agent are preferably used to impart a transparent marble-like appearance to the molded article and to improve the hot water resistance of the molded article. You. Particularly preferred inorganic fillers are glass powder, aluminum hydroxide and mixtures thereof having a refractive index in the above range. The reactive resin fine particles, which are another component of the resin composition, function as a low-shrinking agent, and have an average particle diameter of preferably 0.01 to 5 μm, more preferably 0.02 μm.
And its refractive index is preferably in the range of 1.46 to 1.60.

With respect to the refractive indices of the inorganic filler and the reactive resin fine particles, in order to obtain a transparent molded article from a resin composition containing a combination of the thermosetting resin, the inorganic filler and the reactive resin fine particles, these three components are required. Are made as close as possible to avoid scattering of light at the interface between the resin and the filler and at the interface between the resin and the reactive resin fine particles. Since the refractive index of the thermosetting resin is generally in the range of 1.48 to 1.57, the inorganic filler and the reactive resin particles have a refractive index of 1.46 to 1.60 close to the refractive index of the thermosetting resin. Those having a refractive index are preferred. If the refractive index is less than 1.46 or more than 1.60, light scattering becomes remarkable at the interface between the resin and the filler and the interface between the resin and the reactive resin fine particles, and the transparency of the molded product is reduced. . A particularly preferred refractive index of the inorganic filler and the reactive resin fine particles is ± 0.05 of the refractive index of the cured resin.

Next, each component of the resin composition according to the present invention and the molding method will be described in more detail.

A) Thermosetting Resin An unsaturated polyester resin which is one of thermosetting resins is
An unsaturated polyester prepolymer dissolved in an ethylenically unsaturated monomer, usually in the form of a syrup. Any known unsaturated polyester resin can be used. Unsaturated polyester prepolymers are those derived from the polycondensation of at least one polyhydric carboxylic acid, including ethylenically unsaturated polycarboxylic acids, with at least one diol. Examples of the ethylenically unsaturated polycarboxylic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride and the like, and used in combination with these. Examples of the polyvalent carboxylic acid include phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic anhydride,
Adipic acid, sebacic acid, succinic acid and the like can be mentioned.
Suitable examples of the diol component include ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, butanediol, neopentyl glycol, hydrogenated bisphenol A, 2,2
-Bis (4-oxyethoxyphenyl) propane, 2,
2-bis (4-oxypropoxyphenyl) propane and the like can be mentioned.

It is also possible to use a prepolymer of an unsaturated ester derived from a polycarboxylic acid and an ethylenically unsaturated alcohol, such as diallyl phthalate (DAP).

As the ethylenically unsaturated monomer, one or a combination of two or more liquid monomers capable of radical polymerization is used. Of course, the combination of monomers and polyester prepolymer used must be capable of forming a homogeneous solution. Suitable examples of the monomer include vinyl aromatics such as styrene, vinyltoluene, α-methylstyrene, and divinylbenzene; and ethylenically unsaturated ester monomers such as ethyl acrylate, methyl methacrylate, diallyl phthalate, and triallyl cyanuric acid. However, needless to say, the monomers are not limited to those exemplified.

The unsaturated polyester prepolymer and the ethylenically unsaturated monomer are generally between 70:30 and 45: 5.
5 and preferably in a weight ratio of 65:35 to 55:45. The monomer solution of the prepolymer desirably generally has a viscosity of 50 to 8000 cP (25 ° C.).

A thermosetting acrylic resin, which is another thermosetting resin, is obtained by copolymerizing an acrylic ester or a methacrylic ester with another monomer to form a carboxy group, an epoxy group, a hydroxy group, an amide group, an amino group, or the like. It has an ethylenic double bond such as a vinyl group, and is self-cured by a catalyst and cured by a crosslinking agent. Any known thermosetting acrylic resin is used.

A vinyl ester resin, which is another example of a thermosetting resin, is a resin having a vinyl group at the terminal of an ester main chain or an ether main chain, and is usually an epoxy resin having a bisphenol A skeleton, Epoxy acrylate produced by reaction with an unsaturated monobasic acid such as acrylic acid or methacrylic acid is diluted with a polymerizable monomer such as styrene.

B) Inorganic Filler The glass powder as one of the inorganic fillers has a refractive index of 1.46 from the viewpoint of a transparent marble-like appearance characteristic.
~ 1.60, preferably in the range of ± 0.05 of the refractive index of the cured resin, the average particle size is 1 ~ 300μ
Those in the range of m are desirable. Regarding the glass composition, those having a composition of borosilicate glass are preferable,
Particularly preferred is a glass having the following composition.

SiO ₂ ; 40 to 65%, B ₂ O ₃ ;
30%, alkali metal oxide; 2 to 25%, alkaline earth metal; oxide or ZnO; 5 to 30%, Al
₂ O ₃ ; 0 to 25%, TiO ₂ ; 0 to 10%, Zr
O _2; 0~10%.

Aluminum hydroxide, which is another example of the inorganic filler, has a particle size of 1 to 4 from the viewpoint of a transparent marble-like appearance characteristic similarly to the above glass powder.
Those having a range of 300 μm are desirable, and commercially available products such as Heidilite H-310 and H-32 manufactured by Showa Denko KK
0 or the like is used. Aluminum hydroxide is a substance that also serves as a flame retardant.

The inorganic filler surface-treated with a silane coupling agent is obtained by subjecting an inorganic powder such as the above glass powder or aluminum hydroxide to a surface treatment with any known silane coupling agent. It is. As the silane coupling agent, silanes having an ethylenically unsaturated double bond and a hydrolyzable group in the molecule are preferably used. Suitable examples thereof include vinyltriethoxysilane and vinyltris-β. -Methoxyethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like. The amount of these silane coupling agents used is usually in the range of 0.01 to 2 parts by weight per 100 parts by weight of inorganic powder such as glass powder or aluminum hydroxide.

C) Reactive Resin Fine Particles The reactive resin fine particles constituting the resin composition have a degree of crosslinking and an average particle diameter in the above-mentioned ranges. The refractive index of the shell portion is adjusted so that the difference between the refractive index of the resin in which the reactive resin fine particles are blended and the refractive index of the other blend is within 0.05. The preferred refractive index is in the range from 1.46 to 1.60.

D) Blending Composition The resin composition according to the present invention preferably contains 100 to 400 parts of an inorganic filler, 5 parts or more, and usually up to 30 parts of reactive resin fine particles with respect to 100 parts of a thermosetting resin. .

When the amount of the inorganic filler is less than 100 parts with respect to 100 parts of the thermosetting resin, the weight and texture of the molded product become poor, and a transparent marble-like texture cannot be obtained. Occurs and a molded article having excellent heat resistance cannot be obtained. Conversely, if the amount of the inorganic filler exceeds 400 parts, the fluidity required for molding cannot be obtained, the machinability will be poor, and both the moldability and the mechanical properties of the molded article will be reduced.

If the amount of the fine particles of the reactive resin is less than 5 parts per 100 parts of the thermosetting resin, the effect of reducing the shrinkage by the fine particles of the reactive resin is not sufficiently exerted, and cracks are easily generated. The reactive resin fine particles may be blended in such an amount that a required low shrinkage effect can be obtained. There is no particular problem if the amount exceeds 30 parts, but from the viewpoint of economy, 30 parts or less is appropriate. A particularly preferable mixing ratio is such that the inorganic filler is 150 to 350 parts per 100 parts of the thermosetting resin.
Parts, 10 to 20 parts of the reactive resin fine particles.

E) Other Compounding Components In the resin composition according to the present invention, in addition to the above-mentioned essential components, other compounding components conventionally used as needed in this type of thermosetting resin composition may optionally be added. Can be added. Such compounding agents include fiber reinforcing agents, coloring agents,
Examples include an internal release agent, a thickener, and a water-containing water retention agent. As a fiber reinforcing agent, the fiber length is 0.5 to 50 m
Glass fibers, aramid fibers, vinylon fibers, polyester fibers, polyimide fibers, etc. having a range of m are used. As the colorant, an organic or inorganic pigment or a toner using the same is used. As the internal release agent, metal soaps such as zinc stearate and calcium stearate and phosphate ester-based ones are generally used. As the thickener, oxides or hydroxides of alkaline earth metals such as magnesium oxide and calcium hydroxide are preferable.

As curing catalysts important for completing the curing of the thermosetting resin, benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide,
Acetyl peroxide, dicumyl peroxide,
Organic peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperbenzoate are used alone or in combination. The amount of the curing catalyst used may be a so-called catalytic amount, and is preferably in the range of 0.3 to 2.5% by weight per resin.

F) Molding Method The resin composition according to the present invention may be formed into a sheet, rice cake, column,
SMC and BMC thickened into pellets
It is used as a material for producing various molded products such as bathtubs, kitchen counters, vanities, bathroom panels, table tops and the like, which are highly transparent. The heat molding method of the resin composition includes a pressure heat molding method. The molding conditions are not particularly limited.
It is preferred to work at a temperature of 0 to 160 ° C. and a pressure of ^{20 to} 140 kg / cm ² gauge.

[0055]

Since the reactive resin fine particles according to the present invention have non-copolymerized ethylenically unsaturated bonds (b) remaining in the shell, they can be copolymerized with the ethylenically unsaturated bonds (b). When the fine particles are mixed with a monomer or a thermosetting resin having at least one ethylenically unsaturated group to form a monomer dispersion or a thermosetting resin composition, The bond (b) copolymerizes with the monomer or the ethylenically unsaturated group of the thermosetting resin, and the reactive resin fine particles chemically bond to the matrix, and the fine particles function as a low shrinkage agent. Therefore, the phenomenon that light is scattered at the interface between the reactive resin fine particles and the matrix to impair the transparency does not occur at all.

Further, by the chemical bonding between the reactive resin fine particles and the matrix as described above, the durability of the obtained molded article such as heat resistance and water resistance is greatly improved.

Thus, the use of the above-mentioned reactive resin fine particles surely suppresses the curing shrinkage of the resin, and provides a molded article which is rich in transparency and excellent in durability and dimensional stability.

[0058]

Next, (a) production of reactive resin fine particles,
The present invention will be described in more detail by giving specific examples of (b) production of a thermosetting resin molded article and (c) a quality test of the molded article.

(A) Production Example 1 of Reactive Resin Fine Particles (Amphoteric Polyester Emulsifier) In a glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube, a stirrer and a decanter, 134 parts of bishydroxyethyltaurine were added. , Neopentyl glycol 13
0 parts, 236 parts of azelaic acid, 186 parts of phthalic anhydride and 27 parts of xylene were charged, and the reaction solution was heated to reflux. Water generated by the reaction was removed by azeotropy with xylene. The temperature was raised to 190 ° C. over about 2 hours from the start of reflux, and stirring and dehydration were continued until the acid value corresponding to carboxylic acid reached 145.

Subsequently, the temperature was cooled to 140 ° C. and maintained at this temperature, and 314 parts of glycidyl versatate “Cadura E10” (manufactured by Shell) was added dropwise over 30 minutes, and then stirring was continued for 2 hours. The reaction was completed.

Thus, an acid value of 59 and a hydroxyl value of 90
And a polyester emulsifier having a zwitterionic group, comprising a polyester resin having an average molecular weight of 1054.

Production Example 2 (Polyfunctional monomer) 98 parts of maleic anhydride, 130 parts of 2-hydroxyethyl methacrylate, and 57 parts of toluene were placed in a glass reactor equipped with a thermometer, a reflux condenser, an air inlet tube and a stirrer. And 0.5 parts of p-methoxyphenol, respectively, and the mixture was heated to 110 ° C.,
After reacting for an hour, the reaction solution was cooled and the solvent was removed under reduced pressure.

Thus, a polyfunctional monomer (A) having a maleic acid-based ethylenically unsaturated bond and a methacrylic acid-based ethylenically unsaturated bond as two radically polymerizable ethylenically unsaturated bonds having different reactivities was obtained.

Production Example 3 (Polyfunctional monomer) In a glass reactor equipped with a thermometer, a reflux condenser, an air inlet tube and a stirrer, 172 parts of monobutyl maleate, 149 parts of glycidyl methacrylate and 0 parts of p-methoxyphenol were added. .5 parts each, and the mixture was heated to 160 ° C.
Then, the reaction was carried out for 1 hour under air bubbling, and then the reaction solution was cooled.

Thus, a polyfunctional monomer (A) having a maleic acid-based ethylenically unsaturated bond and a methacrylic acid-based ethylenically unsaturated bond as two radically polymerizable ethylenically unsaturated bonds having different reactivities was obtained.

Example 1 (Particles by Two-Step Emulsion Polymerization) In a glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube and a stirrer, 213 parts of deionized water and a reactive emulsifier "New Frontier A229E" were added. 5.5 parts (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were charged, and the mixture was heated to 81 to 85 ° C. while passing nitrogen gas. Then, a monomer mixture comprising 30 parts of styrene, 10 parts of n-butyl acrylate and 10 parts of neopentyl glycol dimethacrylate, 20 parts of deionized water, 1 part of azobiscyanovaleric acid and 0.64 parts of dimethylethanolamine. A half amount of the initiator aqueous solution was dropped from another dropping port over 30 minutes. Thus, crosslinked core particles were obtained in the first step.

Then, a monomer mixture comprising 15 parts of the polyfunctional monomer (A) obtained in Production Example 2, 17.5 parts of methyl methacrylate and 17.5 parts of n-butyl acrylate, and the remainder of the above aqueous initiator solution Half of the reaction solution was added dropwise from another dropping port over 30 minutes, and the reaction solution was aged for 1 hour and then cooled.

Thus, reactive resin fine particles (1) having an ethylenically unsaturated bond in the shell part and having an average particle size of 0.07 μm and C / S = 5/5 were obtained.

Example 2 (Particles by Two-Step Emulsion Polymerization) In a glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube and a stirrer, 215 parts of deionized water, obtained in Production Example 1 10 parts of an emulsifier and 1 part of dimethylethanolamine were charged, and the mixture was heated to 81 to 85 ° C. while passing a nitrogen gas. Then, a monomer mixture comprising 35 parts of methyl methacrylate, 15 parts of n-butyl acrylate, 15 parts of ethylene glycol dimethacrylate and 5 parts of the polyfunctional monomer (A) obtained in Production Example 2, 20 parts of deionized water, azobis 70% of an aqueous initiator solution consisting of 1 part of cyanovaleric acid and 0.64 part of dimethylethanolamine were dropped from separate dropping ports over 40 minutes. Thus, crosslinked core particles were obtained in the first step.

Next, a monomer mixture comprising 10 parts of the polyfunctional monomer (A) obtained in Production Example 2, 15 parts of methyl methacrylate and 5 parts of benzyl methacrylate, and the remaining 30% of the aqueous initiator solution described above were separately separated. The reaction solution was aged for 1 hour, and then cooled.

In this way, reactive resin fine particles (2) having an ethylenically unsaturated bond in the shell portion and having an average particle size of 0.11 μm and C / S = 7/3 were obtained.

Example 3 (Soap-free cation large particle size particles) A glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube and a stirrer was charged with 109 parts of deionized water, and the mixed solution was charged to 75 parts. The temperature was raised to ° C. Then, an aqueous solution consisting of 5 parts of methyl methacrylate, 0.5 part of initiator 2,2′-azobis (2-amidinopropane) hydrochloride “V-50” (manufactured by Wako Pure Chemical Industries, Ltd.) and 10 parts of deionized water was added. After reacting for 10 minutes, methyl methacrylate 40
, 20 parts of n-butyl acrylate and 20 parts of 1.6 hexanediol dimethacrylate were added dropwise over 50 minutes.

After aging for 20 minutes, 10 parts of the polyfunctional monomer (A) obtained in Production Example 3 and methyl methacrylate 1
0 parts of a monomer mixture was added dropwise over 10 minutes,
The reaction solution was aged for 1 hour and then cooled.

Thus, soap-free cation-reactive resin fine particles (3) having an ethylenically unsaturated bond in the shell portion and having an average particle size of 1.1 μm and a C / S = 8/2 were obtained.

Example 4 (Melamine Cross-Linked Particles by Post-Emulsification) A water-soluble acrylic resin “Cotax WE-804” (Toray) was placed in a glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube and a stirrer. Company, solid content 50%) 91
Parts, 100 parts of melamine resin "Uban 22" (manufactured by Mitsui Toatsu Chemicals, Inc., solid content 50%) and 1.4 parts of triethylamine were added, and 308 parts of deionized water was gradually added while sufficiently stirring the mixture. The mixture was emulsified. Then remove the solvent under reduced pressure while replenishing deionized water,
The reaction solution was kept at 60 ° C. for 1 week and cooled after the reaction. Thus, crosslinked core particles were obtained in the first step.

Then, the reaction solution was diluted with 8 while passing nitrogen gas through.
The temperature was raised to 1 to 85 ° C., a monomer mixture comprising 8 parts of the polyfunctional monomer (A) obtained in Production Example 2 and 2.5 parts of methyl methacrylate, 20 parts of deionized water, and azobiscyanovaleric acid An initiator aqueous solution consisting of 0.2 part and 0.13 part of dimethylethanolamine was dropped from each of the dropping ports over 15 minutes, and the reaction solution was aged for 1 hour and then cooled. Thus, the emulsion polymerization is performed in the second step, and the shell portion has an ethylenically unsaturated bond.
Reactive resin fine particles (4) having an average particle size of 0.12 μm and C / S = 9/1 were obtained.

Example 5 (Dispersion of Reactive Resin Fine Particles) 80 parts of styrene was charged into a stainless steel beaker, and the emulsified aqueous solution of the reactive resin fine particles (1) obtained in Example 1 was freeze-dried. 20 parts of the obtained powder was added with stirring with a diver to obtain a styrene dispersion of reactive resin fine particles (1). This was a good milky white particle dispersion having a viscosity of 95 poise.

Comparative Example 1 (Single-Layer Cross-Linked Particles) In a glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube and a stirrer, 215 parts of deionized water, the emulsifier 10 obtained in Production Example 1, Parts and 1 part of dimethylethanolamine, respectively, and while passing nitrogen gas,
The mixture was heated to 81-85 ° C.

Then, a mixed solution consisting of 60 parts of styrene and 40 parts of ethylene glycol dimethacrylate, and an aqueous initiator solution consisting of 20 parts of deionized water, 1 part of azobiscyanovaleric acid and 0.64 part of dimethylethanolamine were added, respectively. The reaction solution was dropped from another dropping port over 60 minutes, aged for 1 hour, and then cooled.

Thus, styrene-based single-layer crosslinked resin particles (5) having an average particle size of 0.06 μm were obtained. Comparative Example 2 (Particles without Reactive Group) In a glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube and a stirrer, 213 parts of deionized water and an emulsifier "Eleminol JS2" (Sanyo Chemical Co., Ltd.) 5.5 parts), and the mixture was heated to 81 to 85 ° C. while passing nitrogen gas through. Then 30 parts of styrene, n-
A monomer mixture comprising 10 parts of butyl acrylate and 10 parts of neopentyl glycol dimethacrylate;
20 parts of deionized water, 1 part of azobiscyanovaleric acid and half of an aqueous initiator solution consisting of 0.64 parts of dimethylethanolamine were each added to another 30 drops from another dropping port.
It was added dropwise over a period of minutes. Thus, crosslinked core particles were obtained in the first step.

Then, a monomer mixture consisting of 32.5 parts of methyl methacrylate and 17.5 parts of n-butyl acrylate and the remaining half of the above-mentioned aqueous initiator solution were added dropwise from separate dropping ports over 30 minutes. Reaction solution 1
After aging for a time, it was cooled.

Thus, the shell part has no ethylenically unsaturated bond, the average particle size is 0.06 μm, and C / S = 5/5
To obtain core / shell type crosslinked resin particles (6).

Comparative Example 3 (Single-Layer Cross-Linked Particle Having Reactive Group) A glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube, and a stirrer was charged with 215 parts of deionized water. 10 parts of the obtained emulsifier and 1 part of dimethylethanolamine were respectively charged, and the mixture was heated to 81 to 85 ° C. while passing nitrogen gas. Then, a monomer mixture comprising 40 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 10 parts of ethylene glycol dimethacrylate and 10 parts of the polyfunctional monomer (A) obtained in Production Example 2, 20 parts of deionized water, and azobis An initiator aqueous solution comprising 1 part of cyanovaleric acid and 0.64 part of dimethylethanolamine was added dropwise from separate dropping ports over 60 minutes, and the reaction solution was aged for 1 hour and then cooled.

Thus, single-layer crosslinked particles (7) having an ethylenically unsaturated bond and having an average particle size of 0.09 μm were obtained.

(B) Thermosetting resin composition and molded article Example 6 1,000 g of unsaturated polyester resin ("Yupika 7661" manufactured by Nippon Yupika Co., Ltd.) 2,500 g of glass powder treated with a silane coupling agent (refractive index 1.548, "M-27-S" manufactured by Nippon Ferro Co., Ltd. ・ 120 g of reactive resin particles (2) obtained in Example 2 (refractive index 1.53) ・ 10 g of magnesium oxide ・ 50 g of zinc stearate ・ Tasha Lebutyl peroctoate 10 g Chopped strand glass (length 13 mm) 150 g (total) 3,840 g i) The raw material having the above composition was put into a kneader having a content volume of 5 liters and kneaded for 10 minutes.

The kneaded product was taken out of the kneader, and this was firstly wrapped with a polyethylene film, and then wrapped with an aluminum-evaporated polyethylene terephthalate film and sealed. Place the double-packed kneaded material in a drying oven at 45 ° C
For 20 hours. Thus, a press-molding composition which was thickened and hardened was obtained.

Ii) After removing the packaging film from the composition, the composition was cut into an appropriate size, charged in a predetermined amount on a press molding die, and a mold clamping pressure of 60 kg / kg.
cm ² : Press-molded at a molding temperature of 130 ° C. for 5 minutes to obtain a molded article having the shape shown in FIG. This molded article had no cracks, sink marks, and warpage, and had excellent surface gloss and high transparency.

Example 7-1,000 g of unsaturated polyester resin ("Yupika 7661" manufactured by Nippon Yupika)-2,500 g of aluminum hydroxide (refractive index 1.567, "Heidilite H-320" manufactured by Showa Denko KK) -120 g of the reactive resin particles (2) obtained in Example 2 (refractive index: 1.53)-10 g of magnesium oxide-50 g of zinc stearate-10 g of tertiary butyl peroctoate- 150 g of chopped strand glass (length 13 mm) (Total) 3,840 g The raw material having the above composition was kneaded and aged in the same manner as in step i) of Example 6 to obtain a composition for press molding. This composition was press-molded in the same manner as in Step ii) of Example 6 to obtain a molded product.

This molded article was free from cracks, sink marks and warpage, had excellent surface gloss and transparency, but was slightly inferior in transparency to the molded article.

Example 8-1,000 g of unsaturated polyester resin ("Yupika 7520" manufactured by Nippon Yupika)-1,500 g of aluminum hydroxide (refractive index 1.567, "Heidilite H-320" manufactured by Showa Denko KK) -150 g of reactive resin particles (1) obtained in Example 1 (refractive index: 1.48)-10 g of magnesium oxide-50 g of zinc stearate-10 g of tertiary butyl peroctoate- 400 g of chopped strand glass (length 13 mm) (Total) 3,120 g i) The raw materials having the above composition except for 400 g of chopped strand glass were placed in a container having an internal volume of 5 liters, and stirred and mixed with a dissolver for 5 minutes to prepare a premix for SMC. The premix was poured out onto a polypropylene film and spread out so that the thickness of the premix was about 2 mm, to obtain a premix sheet. Next, this premix sheet was cut in half at the center to obtain two premix sheets. Place one premix sheet with the premix side up, sprinkle 400 g of chopped strand glass evenly on the premix side, and then premix another premix sheet on the same side They were overlapped so that the surface was facing down.
Thus, a sandwich sheet in which glass fibers were sandwiched between premix sheets was obtained.

The sandwich-like sheet was passed three times between two rolls of 4 mm apart to sufficiently impregnate the glass fiber into the premix. This sheet was packaged and sealed with an aluminum-deposited polyethylene terephthalate film, placed in a drying oven, and aged at 45 ° C. for 20 hours. Thus, a press-molding composition which was thickened and hardened was obtained.

Ii) After removing the packaging film from the composition, the composition is cut into a suitable size, the polypropylene films on both sides of the sheet are removed, and a predetermined amount is charged on a press molding die, and the mold clamping pressure is applied. 60kg / c
m ² : Press molding was performed at a molding temperature of 130 ° C. for 5 minutes to obtain a molded product having the shape shown in FIG.

This molded product had no cracks, sink marks, and warpage, had excellent surface gloss, and had almost the same transparency as the molded product.

Example 9 : 1,000 g of vinyl ester resin ("Lipoxy RP-30" manufactured by Showa Polymer Co., Ltd.) 2,500 g of glass powder treated with a silane coupling agent (refractive index: 1.548, "M-27-S""Reactive resin particles (1) 120 g (refractive index: 1.48)" obtained in Example 1-Zinc stearate 50 g-Tertiary butyl peroctoate 10 g-Chopped strand glass (length 13 mm) 150g (total) 3,830g i) The raw material having the above composition was charged into a kneader having an internal volume of 5 liters and kneaded for 10 minutes. The kneaded material removed from the kneader was used as it was as a composition for press molding.

Ii) This composition was treated in step ii) of Example 6.
Press molding was performed in the same manner as described above to obtain a molded product.

This molded product was free from cracks, sink marks and warpage, and had excellent surface gloss and transparency.

Example 10 1,000 g of unsaturated polyester resin ("Yupika 7660" manufactured by Nippon Yupika Co.) 300 g of trimethylolpropane trimethacrylate 300 g of aluminum hydroxide (refractive index 1.567, "Heidilite H- 320 "(manufactured by Showa Denko KK) ・ 250 g of reactive resin particles (3) obtained in Example 3 (refractive index: 1.49) ・ 50 g of zinc stearate ・ 15 g of tert-butyl peroctoate ・ Chopped strand glass (length) 13 mm) 250 g (total) 4,865 g The raw material having the above composition was kneaded in the same manner as in step i) of Example 9 to obtain a composition for press molding. This composition was press-molded in the same manner as in Step ii) of Example 6 to obtain a molded product.

The molded product had slight cracks at the corners, but had no warpage, and had excellent surface gloss and transparency.

Comparative Example 4-1,000 g of unsaturated polyester resin ("Yupika 7661" manufactured by Nippon Yupika Co., Ltd.)-2500 g of glass powder treated with a silane coupling agent (refractive index: 1.548, "M-27-S" Japan) 300g (polystyrene dissolved in styrene, "Polylite PB-956" manufactured by Dainippon Ink and Chemicals, Inc.)-Magnesium oxide 10g-Zinc stearate 50g-Tertiary butyl peroctoate 10g-Chopped Strand glass (length 13 mm) 150 g (total) 4,020 g The raw material having the above composition was kneaded and aged in the same manner as in step i) of Example 6 to obtain a composition for press molding. This composition was press-molded in the same manner as in Step ii) of Example 6 to obtain a molded product.

This molded article was free from cracks, sink marks, and warpage, and had excellent surface gloss.
It was opaque.

Comparative Example 5 : 1,000 g of unsaturated polyester resin ("Yupika 7661" manufactured by Nippon Yupika Co., Ltd.) 2,500 g of glass powder treated with a silane coupling agent (refractive index: 1.548, "M-27-S" Japan) Ferro Corporation)-Single- layer crosslinked particles (7) having an ethylenically unsaturated bond obtained in Comparative Example 3 (7) 120 g -magnesium oxide 10 g-zinc stearate 50 g-tertiary butyl peroctoate 10 g-chopped strand glass ( length 13 mm) 150 g (total) 3, 84 0 g of the material of the blend kneaded and aged in the same manner as in step i) of example 6, to obtain a press-molding composition. This composition was press-molded in the same manner as in Step ii) of Example 6 to obtain a molded product.

This molded article had the same level of transparency as the molded article, but cracks occurred and a glossy surface could not be obtained.

Comparative Example 6-1,000 g of unsaturated polyester resin ("Yupika 7661" manufactured by Nippon Yupika)-2,500 g of aluminum hydroxide (refractive index 1.567, "Heidilite H-320" manufactured by Showa Denko KK) -120 g (refractive index: 1.48) of the core / shell crosslinked resin particles (6) obtained in Comparative Example 2-10 g of magnesium oxide-50 g of zinc stearate-10 g of tertiary butyl peroctoate-10 g of chopped strand glass (length 13 mm) 150 g (total) 3,840 g The raw material having the above composition was kneaded and aged in the same manner as in step i) of Example 6 to obtain a press molding composition. This composition was press-molded in the same manner as in Step ii) of Example 6 to obtain a molded product.

This molded product had no cracks, sink marks, and warpage, and had almost the same surface gloss and transparency as the molded product, but had disadvantages in water resistance, heat resistance, and the like.

Comparative Example 7-1,000 g of unsaturated polyester resin ("Yupika 7520" manufactured by Nippon Yupika)-1,500 g of aluminum hydroxide (refractive index 1.567, "Heidilite H-320" manufactured by Showa Denko KK)・ Styrene single-layer crosslinked resin particles (5) obtained in Comparative Example 1 200 g 200 g magnesium oxide 10 g zinc stearate 50 g tert-butyl peroctoate 10 g chopped strand glass (length 13 mm) 400 g (total) 3 , 170 g The raw material having the above composition was treated in the same manner as in step i) of Example 8 to obtain a composition for press molding. This composition was press-molded in the same manner as in step ii) of Example 8 to obtain a molded product.

The molded article had no cracks, sink marks, and warpages, and had an excellent surface gloss.
It was opaque.

Comparative Example 8 : 1,000 g of unsaturated polyester resin ("Yupika 7661" manufactured by Nippon Yupika Co.) 2,500 g of glass powder treated with a silane coupling agent (refractive index: 1.548, "M-27-S" Nippon Ferro) -Magnesium oxide 10 g-Zinc stearate 50 g-Tertiary butyl peroctoate 10 g-Chopped strand glass (length 13 mm) 150 g (total) 3,720 g The raw materials having the above composition are the same as in step i) of Example 6. To obtain a press molding composition. This composition was press-molded in the same manner as in step ii) of Example 6,
A molded product was obtained.

This molded article had the same level of transparency as the molded article, but cracks occurred and a glossy surface could not be obtained.

Comparative Example 9 : 1,000 g of unsaturated polyester resin ("Yupika 7661" manufactured by Nippon Yupika) 2,500 g of aluminum hydroxide (refractive index: 1.567, "Heidilite H-320" manufactured by Showa Denko KK)・ Acrylic-styrene copolymer fine particles 120 g (refractive index 1.56, no surface functional group, “Nippe Micro Gel” manufactured by Nippon Paint Co., Ltd.) ・ Magnesium oxide 10 g ・ Zinc stearate 50 g ・ Tertiary butyl peroctoate 10 g ・ Chopped Strand glass (length 13 mm) 150 g (total) 3,840 g The raw material having the above composition was kneaded and aged in the same manner as in step i) of Example 6 to obtain a composition for press molding. This composition was press-molded in the same manner as in step ii) of Example 6,
A molded product was obtained.

This molded product had no cracks, sink marks, and warpages, and had almost the same surface gloss and transparency as the molded product, but had disadvantages in water resistance and heat resistance.

Comparative Example 10-1,000 g of unsaturated polyester resin ("Yupika 7520" manufactured by Nippon Yupika)-1,500 g of aluminum hydroxide (refractive index 1.567, "Heidilite H-320" manufactured by Showa Denko KK) -Acrylic-styrene copolymer fine particles 120 g (refractive index 1.56, no surface functional group, "Nippe Microgel" manufactured by Nippon Paint Co., Ltd.)-Liquid low-shrinking agent 300 g (styrene dissolved in polystyrene, "Yupika A-02") 10 g of magnesium oxide, 50 g of zinc stearate, 10 g of tertiary butyl peroctoate, 400 g of chopped strand glass (13 mm in length), 3,270 g (total) 3,270 g ) To obtain a composition for press molding. This composition was press-molded in the same manner as in step ii) of Example 8 to obtain a molded product.

This molded article had no cracks, sink marks or warpage, and had excellent surface gloss, but was entirely cloudy and opaque.

(C) Quality test 1 of molded article (transparency and moldability) A plate of 50 mm x 50 mm (5 mm in thickness) was cut out from each formed article and used as a test piece. Place this test piece on the white part of the opacity test paper certified by Japan Paint Inspection Association,
A colorimeter of a colorimeter (Minolta CR-A10 type) was brought into contact therewith, and the values of Lw, aw and bw were measured. Next, the test piece was transferred to the black portion of the test paper, and L
The values of b, ab and bb were measured. Two color differences △ Ewb,
The transparency was determined by the following equation. Here, ΔEwb indicates that the larger the value, the greater the transparency.

[0114]

(Equation 1)

Further, the moldability of each test piece was also visually examined.

Table 1 summarizes the results of these tests.

[0117]

[Table 1]

Moldability (presence or absence of cracks) Visual transparency ◎ No cracks ◎ Extremely high transparency ○ Very small cracks in corners ○ High transparency × Large cracks △ Translucent × Opaque As is clear from Table 1, each of the Examples It is recognized that the molded article has excellent moldability and transparency as compared with those of the comparative examples.

Test 2 (Water Resistance) A plate of 80 mm × 80 mm (5 mm thick) was cut out from each molded product and used as a test piece. Using the hot water test apparatus shown in FIG. 2, a continuous hot water test was performed in hot water at 97 ° C. for 200 hours. In FIG. 2, (1) is a constant temperature water tank, (2) is hot water,
(3) is a thermometer, (4) is a hot water exposure port, (5) is a test piece, and (6)
Indicates a vise, respectively.

The transparency ΔEwb was determined for each of the test pieces left at room temperature for 24 hours before the hot water treatment and after the completion of the hot water treatment in the same manner as in the above-described comparison of the transparency. Next, the rate of change of ΔEwb before and after the hot water treatment was determined, and the hot water resistance was determined from the degree of deterioration of the transparency. Further, a change in the surface state was visually observed.

Table 2 shows the results of this test.

[0122]

[Table 2]

Change rate of ΔEwb before and after hot water treatment Evaluation of hot water resistance ◎ Extremely good ○ Excellent × Poor As can be seen from Table 2, it is recognized that each molded article of the example has excellent hot water resistance as compared with that of the comparative example.

Test 3 (Heat Resistance) A 50 mm × 50 mm (5 mm thick) plate piece was cut out from each molded product and used as a test piece. The test specimen was heated in a drying oven at 200 ° C. for 10 minutes, then taken out of the drying oven and cooled at room temperature, and the degree of discoloration and change in transparency of the test specimen was visually observed.

Table 3 shows the results of this test.

[0126]

[Table 3]

Heat Resistance Judgment ◎ Extremely Excellent ○ Excellent × Defective As can be seen from Table 3, it is recognized that the molded articles of the examples have excellent heat resistance as compared with those of the comparative examples.

Test 4 (Cigarette Resistance) Cigarettes dried for 2 hours in a drying oven at 80 ° C. were used as cigarettes for cigarette resistance test. The ignited tobacco was placed on each molded article and left for 10 minutes. After burning, the ash was removed, and the ash was washed off with acetone. Then, the change in the state of the portion where the tobacco had been placed was visually observed.

Table 4 shows the test results.

[0130]

[Table 4]

Judgment of Cigarette Resistance ◎ Extremely Excellent ○ Excellent × Defective As is clear from Table 4, it is recognized that each molded article of the example has excellent cigarette resistance as compared with that of the comparative example.

[0132]

According to the reactive resin fine particles of the present invention, since the ethylenically unsaturated bond (b) remains in the shell portion without being copolymerized, the above-mentioned ethylenically unsaturated bond (b)
When the same fine particles are blended with a monomer or a thermosetting resin having at least one ethylenically unsaturated group that can be copolymerized with, to form a monomer dispersion or a thermosetting resin composition, The above ethylenically unsaturated bond
(b) is copolymerized with the ethylenically unsaturated group, and the reactive resin fine particles are chemically bonded to the matrix, and the fine particles function as a low shrinkage agent. Therefore, it is possible to completely prevent the phenomenon that light is scattered at the interface between the reactive resin fine particles and the matrix to impair transparency.

The chemical bonding between the reactive resin fine particles and the matrix as described above can greatly improve the durability, such as heat resistance and water resistance, of the obtained molded article.

Thus, by using the above-mentioned reactive resin fine particles of the present invention, it is possible to reliably suppress curing shrinkage of the resin, and to obtain a molded article which is rich in transparency and excellent in durability and dimensional stability.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a molded product according to a sixth embodiment of the present invention.

FIG. 2 is a vertical sectional view showing the structure of the hot water test apparatus.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/22 C08K 3/22 3/40 3/40 9/06 9/06 C08L 31/00 C08L 31/00 33/08 33 / 08 51/00 51/00 67/06 67/06 101/00 101/00 (72) Inventor Toru Nakatsuka 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Shuhei Yamoto Osaka 19-17 Ikedanakamachi, Neyagawa-shi, Japan Japan Paint Co., Ltd.

Claims (17)

(57) [Claims] 1. A crosslinking degree of 0.05 to 2.0 mmol / g
And a shell portion formed on the surface of the particle and having a radical polymerizable ethylenically unsaturated bond, the shell portion,
In the molecule, at least one of 1-mono-substituted and 1,1-di-substituted radically polymerizable ethylenically unsaturated bonds (a), and 1,2-di-substituted, 1,1,2-tri-substituted and 1-substituted ,
A polyfunctional monomer (A) having at least one of at least one of 1,2,2-tetra-substituted radically polymerizable ethylenically unsaturated bonds (b); Reactive resin fine particles obtained by polymerizing the radically polymerizable monomer (B) alone or in a mixture. 2. The method according to claim 1, wherein the core particles comprise a vinyl polymerizable monomer and a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated bonds in a degree of crosslinking of 0.05 to 2.0 mmol / g.
2. The fine particles according to claim 1, wherein the fine particles are formed by emulsion polymerization in such an amount. 3. The core particle comprises a polyfunctional monomer (A), a radically polymerizable monomer (B), and a 1-mono-substituted or 1,1-di-substituted radically polymerizable ethylenically unsaturated bond in the molecule. 2. Fine particles according to claim 1, which are formed by emulsion polymerization of a mixture of polyfunctional monomers (C) having at least two of at least one kind. 4. The polyfunctional monomer (A) comprises an acrylic or methacrylic ethylenically unsaturated bond (a) and a maleic or fumaric acid ethylenically unsaturated bond (b).
The fine particles according to any one of claims 1 to 3, which have the following. 5. The fine particles according to claim 1, wherein the proportion of the polyfunctional monomer (A) in all the monomers for forming the shell is in the range of 1 to 50%. 6. Fine particles according to claim 1, having an average particle size in the range of 0.01 to 5 μm. 7. The fine particles according to claim 1, wherein the weight ratio between the core particle and the shell part is in the range of core particle / shell part (C / S) = 10/90 to 99/1. 8. The reactive resin fine particles according to claim 1, wherein the reactive resin fine particles are radically polymerizable ethylenically unsaturated bonds.
A dispersion comprising 1 to 40 parts of a monomer having at least one ethylenically unsaturated bond copolymerizable with (b) or a group of monomers containing at least one such monomer. 9. The crosslinking degree is 0.05 to 2.0 mmol / g.
A first step of synthesizing a core particle composed of a three-dimensionally crosslinked resin in the range of 1-monosubstituted or 1,1-disubstituted radically polymerizable ethylenically unsaturated bond (a) in the molecule. A species and at least one of 1,2-disubstituted, 1,1,2-trisubstituted and 1,1,2,2-tetrasubstituted radically polymerizable ethylenically unsaturated bonds (b), respectively. Multifunctional monomer (A) having at least one
Or a mixture of a non-aromatic radical polymerizable monomer (B) alone or a mixture thereof to form a shell having a radical polymerizable ethylenically unsaturated bond on the surface of the core particle. And a process for producing reactive resin fine particles. 10. A thermosetting resin composition for thermoforming, comprising a thermosetting resin, an inorganic filler and a reactive resin fine particle according to one of claims 1 to 7. 11. The composition according to claim 10, wherein the thermosetting resin is an unsaturated polyester resin, a thermosetting acrylic resin or a vinyl ester resin. 12. The composition according to claim 10, wherein the inorganic filler is a glass powder having a refractive index in the range from 1.46 to 1.60. 13. The composition according to claim 10, wherein the inorganic filler is aluminum hydroxide. 14. The composition according to claim 10, wherein the inorganic filler is a mixture of glass powder having a refractive index in the range of 1.46 to 1.60 and aluminum hydroxide. 15. The composition according to claim 10, wherein the inorganic filler has been surface-treated with a silane coupling agent. 16. The reactive resin fine particles have a particle size of 0.01 to 5 μm.
A composition according to claim 10 having an average particle size in the range of 1.46 and a refractive index in the range of 1.46 to 1.60. 17. The composition according to claim 10, comprising 100 to 400 parts of an inorganic filler and 5 to 30 parts of reactive resin fine particles, based on 100 parts of the thermosetting resin.