JP2003192753A - Resin composition, molding material, and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition, and a molding material that give molded articles, by the high productivity press curing process, not only indispensable properties such as strength and water resistance, but also a good texture and gloss, and have a markedly improved workability, and the molded articles obtained from the resin composition and the molding material. <P>SOLUTION: The resin composition comprises (a) an unsaturated resin containing a carboxylic group, (c) a polymerizable unsaturated monomer, (d) an inorganic filler, and (e) a polymerization initiator. The unsaturated resin containing the carboxylic group is prepared by reacting at least part of the hydroxyl groups of an epoxy resin having unsaturated groups resulted from the reaction of the epoxy resin with an unsaturated monobasic acid. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition suitable for a bulk molding compound (BMC) or a sheet molding compound (SMC), which is used for obtaining a molded product excellent in texture and gloss by press hardening. The present invention relates to a molding material and a molded product obtained by using them.

[0002]

2. Description of the Related Art In recent years, molded articles used for housing members, particularly system kitchens, system baths, etc., are required to have a high-class feel. Artificial marble is a representative example of high-quality molded products. However, on the other hand, it retains a high-grade feeling, but is considerably inferior in terms of productivity as compared with a molded product obtained by press molding because of the number of steps and the like. Therefore, high-quality molding materials and molded products have been developed that can obtain an artificial marble-like appearance by press molding. In particular, as a means to increase the sense of depth,
In some cases, the transparency of the molded product may be improved, and measures have been taken to match the refractive indices of the material constituent components. For example, in Japanese Unexamined Patent Publication No. 2001-114998, by using a specific glycol in an unsaturated polyester resin used as a material, a refractive index close to that of a filler to be blended is obtained, and transparency and a feeling of depth are achieved. Is disclosed. However, although the molded product thus obtained is excellent in transparency and depth, it is inferior in glossiness of the molded product and lacks a high-grade feeling like artificial marble.

Further, as a method of adjusting the refractive index, there is a method of substituting a part of a resin to be used, for example, an unsaturated polyester resin with an unsaturated group-containing epoxy resin. In the resin, because it was impossible to thicken using a metal compound, or even if functional group modification, that is, by providing a carboxyl group in the skeleton and using it as a thickenable resin, compared to unsaturated polyester resin, In general, the molding materials obtained by using them alone have stickiness, and thus have a defect of poor workability and the like, because they generally have a small molecular weight or a narrow molecular weight distribution.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a molded product having not only essential properties such as strength and water resistance but also texture and luster, and a press-curing method excellent in productivity. The present invention provides a resin composition, a molding material, and a molded article obtained by using the resin composition, which are obtained by molding the resin composition and have significantly improved workability.

[0005]

In order to solve the above problems, the inventors of the present invention have conducted extensive studies on resin compositions and molding materials, and as a result, found that it is easy to obtain a refractive index close to that of inorganic fillers and the like. By using a carboxyl group-containing unsaturated resin and an unsaturated polyester resin obtained by reacting a compound capable of imparting a carboxyl group to at least a part of the hydroxyl groups of a saturated group-containing epoxy resin in a specific formulation, molding which has hitherto been unattainable The present invention has been completed based on the finding that a resin composition or a molding material, which not only enables both high glossiness and a feeling of depth of a product to be compatible, but also can greatly improve workability, can be obtained. .

That is, in the present invention, (a) an unsaturated polyester and (b) an epoxy group-containing epoxy resin obtained by reacting an epoxy resin with an unsaturated monobasic acid have a carboxyl group on at least a part of the hydroxyl groups. A resin composition containing a carboxyl group-containing unsaturated resin obtained by reacting an impartable compound, (c) a polymerizable unsaturated monomer, (d) an inorganic filler, and (e) a polymerization initiator, and molding thereof. The present invention relates to materials and molded articles obtained by curing them.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, at least a part of the hydroxyl groups of an unsaturated group-containing epoxy resin obtained by reacting an unsaturated polyester (b) with an unsaturated monobasic acid (b) is a carboxyl group. The carboxyl group-containing unsaturated resin obtained by reacting a compound capable of providing a group is usually dissolved as a thermosetting resin by using a polymerizable unsaturated monomer (c) and is used as a thermosetting resin. The use ratio of (a) and (b) is preferably (a) 10 to
95 parts by weight of (b) 5 to 90 parts by weight, more preferably (a) 20 to 90 parts by weight of (b) 10 to 80 parts by weight.
Parts by weight.

Unsaturated polyester (a) in the present invention
Means an addition reaction of a dibasic acid containing an α, β-unsaturated dibasic acid with a polyhydric alcohol, a monobasic acid, a monoalcohol, a dicyclopentadiene compound, if necessary, or a dehydration condensation reaction, etc. Is obtained by synthesizing by a known method, and preferably has a number average molecular weight of 400 to 50.
In the range of 00.

Examples of the α, β-unsaturated dibasic acid used for preparing the unsaturated polyester (a) include maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride. . Typical examples of the saturated dibasic acid are phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride and hexahydrophthalic acid. , Hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, tetrachlorophthalic acid, tetrachlorophthalic anhydride, succinic acid, malonic acid, glutaric Acid, adipic acid, sebacic acid, dimer acid, 1,12-dodecane diacid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3
Examples thereof include naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. The above dibasic acids may be used alone or in combination of two or more.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1 , 3-propanediol, 2-methyl-1,3
-Propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-
Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethylpropanediol ,
Addition products of dihydric phenols represented by 1,6-hexanediol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A and the like and alkylene oxides represented by propylene oxide or ethylene oxide, 1,2, 3,4-tetrahydroxybutane, glycerin, trimethylolpropane, pentaerythritol, 1,2-cyclohexaneglycol-
1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexane dimethanol, paraxylene glycol, bicyclohexyl-
4,4'-diol, 2,6-decalin glycol,
2,7-decalin glycol and the like can be mentioned.
The polyhydric alcohols may be used alone or in combination of two or more.

The unsaturated polyester (a) of the present invention includes
You may use a monobasic acid in the range which does not impair performance.
Examples of the monobasic acids include benzoic acid, sorbic acid, monomethylmalate and the like.

The unsaturated polyester (a) of the present invention includes
Monoalcohols may be used as long as the performance is not impaired. Examples of monoalcohols include 2-ethylhexanol, benzyl alcohol, cyclohexyl alcohol, and tert-butylcyclohexyl alcohol.

The unsaturated polyester (a) of the present invention includes
It is also possible to use a dicyclopentadiene-based compound within a range that does not impair the performance. The dicyclopentadiene compound can be introduced by various known methods and is not particularly limited, but representative ones include dicyclopentadiene and malein which are known as unsaturated polyester production methods. There is a method of introducing an acid addition product (sidedecanol monomaleate) into the polyester skeleton as a monobasic acid.

In the unsaturated polyester (a) of the present invention, an epoxy (meth) acrylate monomer is used within a range that does not impair the performance, and the unsaturated polyester (meth) is used.
It may be acrylate. As the epoxy (meth) acrylate monomer, for example, glycidyl acrylate, glycidyl methacrylate and the like are preferable.

A carboxyl group obtained by reacting a compound capable of imparting a carboxyl group with at least a part of the hydroxyl groups of the unsaturated group-containing epoxy resin obtained by reacting the (b) epoxy resin of the present invention with an unsaturated monobasic acid. The group-containing unsaturated resin is obtained by obtaining an unsaturated group-containing epoxy resin by a known method and then reacting at least a part thereof with a compound capable of imparting a carboxyl group.

The unsaturated group-containing epoxy resin is 1
An unsaturated group-containing resin obtained by reacting an epoxy resin having at least two epoxy groups in the molecule with an unsaturated monobasic acid to add an acid group of the unsaturated monobasic acid to the epoxy group is designated. And preferably di (meth) acrylate,
And / or tri (meth) acrylate. Further, it is obtained by reacting an epoxy resin having an average epoxy equivalent of the unsaturated group-containing epoxy resin preferably in the range of 100 to 500 with an unsaturated monobasic acid in the presence of an esterification catalyst. As the epoxy resin, the following compounds are typical examples.

As the epoxy resin having a terminal epoxy group, a reaction product of bisphenol A and epichlorohydrin, a reaction product of bisphenol F and epichlorohydrin, a reaction product of hydrogenated bisphenol A and epichlorohydrin, a reaction of cyclohexanedimethanol and epichlorohydrin. , A reaction product of norbornane dialcohol and epichlorohydrin, a reaction product of tetrabromobisphenol and epichlorohydrin, a reaction product of tricyclodecanedimethanol and epichlorohydrin, a reaction product of phenol novolac and epichlorohydrin, a reaction of cresol novolac and epichlorohydrin Thing, 1,6
A reaction product of naphthalenediol and epichlorohydrin,
Examples thereof include epoxy resins having a dicyclopentadiene skeleton, dicyclopentadiene alicyclic diepoxy adipate, alicyclic diepoxy carbonate, alicyclic diepoxy acetal, and alicyclic diepoxy carboxylate.

As the glycidyl ether type compound obtained by adding ethylene oxide and / or propylene oxide to the terminal hydroxyl group of a compound having two or more hydroxyl groups, for example, the oxide is added to a compound having two or more hydroxyl groups to form epichlorohydrin. Is obtained by reacting. Examples of compounds obtained by adding ethylene oxide and / or propylene oxide to a compound having two or more hydroxyl groups include bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct. , Cyclohexanedimethanol ethylene oxide adduct, cyclohexanedimethanol propylene oxide adduct, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, diphenylethylene oxide adduct, diphenylpropylene oxide adduct, etc. Can be mentioned. In the case of these adducts, the number of moles of ethylene oxide or propylene oxide added is particularly limited as long as the cured product refractive index of the mixture with the unsaturated monomer is in the range of 1.540 to 1.580. It is not something that will be done. However, as the number of added moles increases, the refractive index decreases.

A compound having two or more hydroxyl groups may be used for adjusting the epoxy elongation, and specific compounds include bisphenol A, hydrogenated bisphenol A, cyclohexanedimethanol, norbornane dialcohol, Tetrabromobisphenol A, tricyclodecane dimethanol, 1,6-naphthalene diol and the like can be mentioned.

The epoxy resin having the terminal epoxy group is such that the refractive index of the cured product of the resulting mixture of unsaturated resin and polymerizable unsaturated monomer is in the range of 1.540 to 1.580. , And may be used alone or in combination of two or more kinds.

Typical examples of the unsaturated monobasic acid used in preparing the unsaturated group-containing epoxy resin (b) include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, Monomethylmalate,
There are monopropylmalate, monobutylmalate, etc.,
Acrylic acid and methacrylic acid are particularly preferable.

These unsaturated monobasic acids may be used alone or in combination of two or more. The above-mentioned reaction between the epoxy resin and the unsaturated monobasic acid can be synthesized by a known method, but preferably 60 to 14
It is carried out with an esterification catalyst at a temperature of 0 ° C., particularly preferably 80 to 120 ° C. The amount of the epoxy resin and the unsaturated monobasic acid used is preferably 0.7 to 1.3 / 1, more preferably 0.8 to 1.2 / 1 in terms of the equivalent ratio of acid group / epoxy group.

As the esterification catalyst, known and commonly used compounds can be used as they are, but only typical ones among them are triethylamine, N, N-dimethylbenzylamine, 2-methylimidazole, N, N.
Various amines such as dimethylaniline or diazabicyclooctane; or diethylamine hydrochloride,
Tin, zinc, iron, chromium, vanadium, phosphorus-containing compounds, and the like.

The number average molecular weight of the unsaturated group-containing epoxy resin is preferably in the range of 500 to 3000. Within such a molecular weight range, it is easy to thicken with a metal compound, and the workability of the molding material is better,
Moreover, the kneading property with the inorganic filler and the impregnating property when using the reinforcing fiber are improved.

Carboxyl group-containing unsaturated compound obtained by reacting a compound capable of imparting a carboxyl group to at least a part of hydroxyl groups of the unsaturated group-containing epoxy resin obtained by reacting the epoxy resin of the present invention with an unsaturated monobasic acid In the resin (b), as a method of introducing a carboxyl group,
Although not particularly limited, it is preferable to obtain an acid anhydride by reacting a hydroxyl group generated by a reaction of an epoxy resin with an unsaturated monobasic acid, that is, a secondary hydroxyl group generated by a ring-opening reaction of an epoxy group. . This reaction is carried out by producing an unsaturated group-containing epoxy resin and then adding an acid anhydride to the unsaturated group-containing epoxy resin, or in a mixture of the unsaturated group-containing epoxy resin and the above polymerizable unsaturated monomer. It is obtained by adding an acid anhydride to.

Typical examples of the acid anhydride, which is a preferred compound capable of imparting a carboxyl group, include maleic anhydride, itaconic anhydride, and the like.
Examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, halogenated phthalic anhydride, trimellitic anhydride, and 2,3-naphthalenedicarboxylic anhydride. The above-mentioned acid anhydride is preferable as the compound capable of imparting a carboxyl group, but, for example, a compound having an isocyanate group and a carboxyl group, a compound having a silyl group and a carboxyl group, or the like can also be used.

The carboxyl group-containing unsaturated resin (b) used in the present invention preferably has an acid value derived from a carboxyl group introduced by a compound capable of imparting a carboxyl group within the range of 5 to 130. When the acid value is in such a range, it is easy to increase the viscosity with a metal compound, the workability of the molding material is more excellent, and it is also excellent in demolding from the mold during press molding, etc. Goods are obtained.

The polymerizable unsaturated monomer (c) used in the present invention is an unsaturated group obtained by reacting (a) unsaturated polyester and (b) epoxy resin with unsaturated monobasic acid. Examples thereof include a carboxyl group-containing unsaturated resin obtained by reacting a compound capable of imparting a carboxyl group to at least a part of hydroxyl groups of the contained epoxy resin, and an unsaturated monomer or unsaturated oligomer capable of undergoing a crosslinking reaction. As the polymerizable unsaturated monomer, a monomer having a vinyl group or an acryloyl group is preferable. Specific examples of the monomer having a vinyl group include:
Styrene, p-chlorostyrene, vinyltoluene, α-
Methyl styrene etc. are mentioned.

Specific examples of the monomer having an acryloyl group include methyl acrylate, ethyl acrylate,
N-Butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, acrylic acid 2
-Hydroxyethyl, 2-hydroxypropyl acrylate, β-ethoxyethyl acrylate, acrylic acid 2
-Cyanoethyl, cyclohexyl acrylate, diethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, methacrylic acid 2-hydroxyethyl, 2-hydroxypropyl methacrylate, p-t-butylcyclohexyl methacrylate, phenyl carbitol acrylate methacrylate, nonyl phenyl carbitol acrylate, noniphenoxy propyl acrylate, N-vinyl pyrrolidone, polycaprolactone acrylate, Acryloyloxyethyl phthalate, acryloyloxy succinate, dicyclopentenyl (meth) acrylate, dicyclopentenyl Shiechiru (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tris (2-hydroxyethyl) isocyanuric (meth) acrylate.

Polymerizable unsaturated monomer (c) in the present invention
As the compound, a compound having at least two polymerizable double bonds in one molecule can also be used for the purpose of improving impact resistance, hot water resistance, chemical resistance and the like of the obtained molded product. Examples of the compound having at least two polymerizable double bonds in one molecule, that is, the polyfunctional unsaturated monomer include a polyfunctional (meth) acrylic acid ester monomer, for example, ethylene glycol di (meth) acrylate, 1,2
-Propylene glycol di (meth) acrylate, 1,
3-butylene glycol di (meth) acrylate, 1,
4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-
Alkanediol di- (meth) acrylate such as hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate Acrylate, polyoxyalkylene-glycol di (meth) acrylate such as polyethylene glycol (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl phthalate , Triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl fumarate and the like,
These are used alone or in combination of two or more.

The above-mentioned polymerizable unsaturated monomer (c) may be used alone or in combination of two or more within a range that does not impair the performance of the obtained molded product. The amount is preferably 5 to 5 in the total of (a) unsaturated polyester and (b) carboxyl group-containing unsaturated resin.
It is 90% by weight, more preferably 10 to 80% by weight.

In the present invention, in order to obtain a deep feeling of a molded product obtained by curing, (a) an unsaturated polyester,
The refractive index of the cured product of the mixture of the (b) carboxyl group-containing unsaturated resin and the (c) polymerizable unsaturated monomer is preferably adjusted to that of the inorganic filler or the reinforcing fiber. Specifically, the cured product of a mixture of (a) unsaturated polyester, (b) carboxyl group-containing unsaturated resin, and (c) polymerizable unsaturated monomer has a refractive index of 1.540 to 1.580. It is preferably within the range. In particular, in order to maintain a minimum sense of depth, the refractive index of a cured product of a mixture of (a) unsaturated polyester, (b) carboxyl group-containing unsaturated resin, and (c) polymerizable unsaturated monomer, It is more preferable to adjust the difference in refractive index between the inorganic filler and the inorganic filler and the reinforcing fiber to be within 0.030.

The inorganic filler (d) used in the present invention includes aluminum hydroxide and glass powder in order to match the refractive index of the cured product of a mixture of a carboxyl group-containing unsaturated resin and a polymerizable unsaturated monomer. , Glass powder is preferable, and it can be widely used from those surface-treated with a surface-treating agent to untreated products. The average particle size of these is 0.1 to 1 in order to obtain the surface smoothness of the molded product.
It is preferably 00 μm.

In addition to the above-mentioned inorganic filler, it is also possible to use another inorganic filler within a range that maintains a feeling of depth. Specifically, calcium carbonate powder, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, aluminum oxide, kaolin, clay, alumina powder, silica sand, silica powder, talc, silica powder, shirasu balloon, glass balloon, glass beads, Examples thereof include organic balloons, mica, cellulose yarn, mica powder, cold water stone, marble dust, and crushed stone.

The above-mentioned inorganic fillers may be used alone or in combination of two or more as long as the performance is not impaired. The amount of the inorganic filler added is 50 to 40 with respect to 100 parts by weight of the total amount of the unsaturated resin and the polymerizable monomer.
It is possible to add 0 parts by weight, and in consideration of material production, moldability, appearance of the obtained molded product and the like, addition of 100 to 350 parts by weight is preferable.

The polymerization initiator (e) used in the present invention is not particularly limited, but it is preferable to use a known organic peroxide in consideration of the molding method, productivity and the like. As the organic peroxide to be blended, only typical ones are specifically mentioned, specifically, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl peroxybenzoate, t-butyl. Peroxy octoate, t-hexyl peroxy benzoate, t-hexyl peroxy octoate, t-butyl peroxy isopropyl carbonate, t-butyl peroxy 2-ethylhexanoate, t-amyl peroxy isopropyl carbonate, t- Amyl peroxy 2-ethylhexanoate,
t-amyl peroxy 3,5,5-trimethylhexanoate, t-amyl peroxybenzoate, 1,1-
Di-t-butylperoxycyclohexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy)-
Known examples include 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, benzoyl peroxide, cumene hydroperoxide and the like. These organic peroxides are appropriately selected according to the molding conditions such as molding method and temperature, the productivity, etc., and are used alone or in combination of two or more in some cases, usually (a) unsaturated polyester, It is used by blending 0.3 to 5 parts by weight based on 100 parts by weight of the total of (b) the carboxyl group-containing unsaturated resin and (c) the polymerizable unsaturated monomer.

Reinforcing fibers can be further used in combination with the resin composition of the present invention. The reinforcing fiber is not particularly limited in material, shape, etc., as long as it does not impair strength performance, appearance, etc., but examples include glass fiber, amide,
It is possible to use organic fibers such as aramid, vinylon, polyester, phenol, etc., carbon fibers, metal fibers, ceramic fibers, natural fibers or a combination thereof, and consider the performance and economical efficiency of the obtained molded product. In this case, glass fiber and organic fiber are preferable. Specific examples of the glass fiber include what is called a milled fiber, or glass roving cut into chopped strands. In this case, the glass length is from a short length of about 10 μm to a long length of about 2 inches. Can be widely used up to. The shape and length of the glass fiber are appropriately selected depending on the strength of the obtained molded product, performance such as smoothness, and at least one kind alone,
In some cases, it is possible to use two or more types in combination. In addition, a mat-shaped product or the like may be used as long as the performance of the present invention is not impaired. In the case of organic fibers, specifically, aramid, nylon, vinylon, polyester,
Examples thereof include phenolic resin, and the form thereof includes, but is not particularly limited to, a woven mat and the like. The amount of the reinforcing fiber used is a resin composition,
Alternatively, it is possible to add 2 to 50 parts by weight to the total amount of the molding material.

Further, the resin composition of the present invention may further contain a shrinkage reducing agent. Examples of the shrinkage reducing agent include polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene, polypropylene,
Poly-ε-caprolactam, saturated polyester, polyvinyl chloride, polybutadiene, styrene-acrylic acid copolymer, styrene-vinyl acetate copolymer, acrylonitrile-styrene copolymer, styrene-butadiene rubber, nitrile rubber and the like. Can be used alone or in combination of two or more. Further, a copolymer of monofunctional or polyfunctional unsaturated monomers, or a copolymer in which a polymerizable unsaturated group is partially left may be used.
The monomer that can be used at that time is not particularly limited as long as it contains a polymerizable unsaturated group, but styrene, p-chlorostyrene, vinyltoluene,
α-Methylstyrene, (meth) acrylic acid, alkyl esters of (meth) acrylic acid, maleic anhydride, maleic acid, fumaric acid, monofunctional alcohols, (meth) acrylic acid esters of polyfunctional alcohols and ether glycols, etc. Is mentioned. The above-mentioned copolymer as a low-shrinking agent can be appropriately selected and used alone or in combination of two or more kinds.
From the viewpoint of maintaining the appearance of the molded article such as surface smoothness, with respect to a total of 100 parts by weight of (a) unsaturated polyester, (b) carboxyl group-containing unsaturated resin, and (c) polymerizable unsaturated monomer, It can be used in a range of 60 parts by weight or less, and preferably 50 parts by weight or less. In addition, it is necessary to select the kind and the addition amount of the shrinkage reducing agent within a range that does not impair the effects of the present invention.

Further, the resin composition of the present invention may contain a polymerization inhibitor, an internal release agent, a thickener, a colorant and the like within a range that does not impair the performance.

Typical examples of the polymerization inhibitor include hydroquinones such as hydroquinone, pt-butylcatechol or mono-t-butylhydroquinone; hydroquinone monomethyl ether or di-t-butyl-p-cresol. Phenols such as: p
Quinones such as benzoquinone, naphthoquinone or p-toluquinone; di-t-butylhydroxytoluene,
Alternatively, there are 2,5-di-t-butyl-4-methylphenol, copper salts such as copper naphthenate, and the like. These are usually blended in an amount of 0.001 to 2 parts by weight based on 100 parts by weight of the total of (a) unsaturated polyester, (b) carboxyl group-containing unsaturated resin and (c) polymerizable unsaturated monomer. It

Examples of the internal release agent include aliphatic organic acids such as stearic acid, metal salts thereof such as zinc stearate and calcium stearate, wax-based and silicone-based agents. These may be used alone in two kinds. The above can be used in combination. These are appropriately selected depending on the molding conditions and the like, but metal salts having a melting point lower than the molding temperature are preferably used. The blending amount is 0.5 to 15 parts by weight based on 100 parts by weight of the total of (a) the unsaturated polyester, (b) the carboxyl group-containing unsaturated resin, and (c) the polymerizable unsaturated monomer. Preferably. With such a blending amount, the releasability is good, and the appearance and strength of the molded product are excellent.

Examples of the thickener include magnesium oxide, magnesium hydroxide, calcium oxide, potassium oxide, potassium hydroxide, zinc oxide, etc. From the viewpoint of thickening, magnesium oxide is preferably used. In addition, an isocyanate thickener can also be used depending on the case. As the compounding amount of the thickener, (a) unsaturated polyester, (b) carboxyl group-containing unsaturated resin and (c)
To 100 parts by weight in total with the polymerizable unsaturated monomer, 0.
It is preferably 2 to 10 parts by weight. With such a blending amount, the viscosity is improved, the molding material does not become too hard, and the workability and moldability of the composition and molding material are maintained.

The colorant is used when coloring a molded article, and includes titanium oxide, carbon black,
Examples include inorganic pigments such as red bean paste, organic pigments such as phthalocyanine blue, dyes and the like. The content of these colorants is usually 30 parts by weight based on 100 parts by weight of the total of (a) unsaturated polyester, (b) carboxyl group-containing unsaturated resin, and (c) polymerizable unsaturated monomer. Below the section. When the molded product to be obtained has a particularly deep feeling, the amount of the colorant is preferably as small as possible, and in some cases, it is better not to add it.

Further, various additives other than the above-mentioned additives can be added to the resin composition and the molding material in the present invention as long as the performance is not impaired. Examples of such an additive include a separation inhibitor for a low-shrinking agent, a so-called thinning agent or a viscosity reducing agent, and the addition amount thereof is,
Total 10 of (a) unsaturated polyester, (b) carboxyl group-containing unsaturated resin, and (c) polymerizable unsaturated monomer
It is preferably 0.1 to 10 parts by weight with respect to 0 parts by weight.

In the present invention, for example, by using the above resin composition or the like applied to two films with a uniform thickness,
A reinforcing material can be sandwiched and impregnated using an impregnation device to obtain a sheet-shaped molding material (SMC). On this occasion,
The film used is a polyethylene film,
Examples thereof include polypropylene film and polyethylene terephthalate film. This sheet-shaped molding material can be wound into a roll, or folded and packed in a dedicated container, and if necessary, aged (thickening promoting step) or the like. This aging is usually performed at a temperature of room temperature to 50 ° C. for about 1 to 3 days.

In the present invention, the block molding material (BM
C) is also possible. When the agglomerate molding material is blended, the various components described in detail above are mixed, but the mixing method, order, etc. are not particularly limited.

The resin composition and molding material in the present invention can be obtained by curing by heat compression molding, transfer molding, cold pressing and the like.

The heat compression molding conditions include a mold temperature of 40 to 200 in consideration of productivity, appearance of the obtained molded product and the like.
C., more preferably 80 to 160.degree. C., and the surface pressure is preferably 0.5 to 50 MPa, more preferably 1 to 30 MPa. In addition, it is preferable to use a mold surface that has been mirror-finished to obtain an excellent molding appearance.

The use of the molded article obtained in the present invention is not particularly limited, but representative examples include wall materials such as system kitchens and system baths, waterproof pans, and washroom pans. , Ceilings, aprons, bathtubs, counters, various types of housing equipment such as septic tanks, washbasins, building materials, pipes, tank products, manholes, concrete walls, construction parts and materials such as bridges, miscellaneous goods such as trays, aero parts, Sunroof, headlamp reflector,
Examples include vehicle members such as air intakes.

[0050]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, the unit of the formulation in the table indicates parts by weight.

<Production Example 1> (Carboxyl Group-Containing Unsaturated Resin Composition) 226 parts of a bisphenol A type epoxy resin having an epoxy equivalent of 300, 225 parts of a novolac type epoxy resin having an epoxy equivalent of 182 and 168 parts of methacrylic acid are reacted. To obtain epoxy methacrylate. Then, 63 parts of maleic anhydride as an acid anhydride is reacted therewith to obtain an unsaturated resin having a carboxyl group, and a styrene content of 40% by weight.
Resin Composition A of The acid value of the resin composition A was 40. <Production Example 2> (Unsaturated polyester resin composition) 490 parts of maleic anhydride and neopentyl glycol 2
08 parts, 122 parts of propylene glycol, and 425 parts of hydrogenated bisphenol A were subjected to a dehydration condensation reaction to obtain an unsaturated polyester, which was an unsaturated polyester resin composition B having a styrene content of 40% by weight. The acid value of the resin composition B was 16. <Production Example 3> (Unsaturated resin composition containing no carboxyl group) 620 parts of a bisphenol A type epoxy resin having an epoxy equivalent of 410 and 124 parts of methacrylic acid are reacted to obtain epoxy methacrylate, and a resin having a styrene content of 38% by weight. It was designated as Composition X. <Production Example 4> (Unsaturated polyester resin composition) 133 parts of isophthalic acid, 235 parts of maleic anhydride and 218 parts of neopentyl glycol, propylene glycol 9
Dehydration condensation reaction with 1 part to obtain unsaturated polyester,
An unsaturated polyester resin composition Y having a styrene content of 40% by weight was used. The acid value of the resin composition Y was 13. <Production Example 5> (Unsaturated polyester resin composition) 232 parts of fumaric acid, 84 parts of propylene glycol and 2 moles of bisphenol A ethylene oxide adduct 32
Unsaturated polyester was obtained by reacting with 5 parts to obtain an unsaturated polyester resin composition Z having a styrene content of 42% by weight. The acid value of the resin composition Z was 10.

<Examples 1 to 3, Comparative Examples 1 to 4> Production Example 1
Examples of the resin shown in Tables 1 to 2 using the resin, the shrinkage reducing agent, the inorganic filler, the pigment, the inhibitor, the polymerization initiator, the mold release agent, the thickener, and the glass fiber shown in The SMC having the compounding ratio of the comparative example was manufactured by a known manufacturing method. In this case, when a shrinkage reducing agent is used, a styrene monomer solution of polystyrene (styrene content 65%) or SGP-70C manufactured by Soken Chemical Industry Co., Ltd. is used as a filler, and aluminum hydroxide having an average particle diameter of 6 μm is used. , A phthalocyanine blue-based organic pigment as a pigment, toluhydroquinone (THQ) as an inhibitor, and t-butylperoxybenzoate (TBPB) as a polymerization initiator.
As a release agent, zinc stearate (Zn-St)
Was used as the thickener, and glass fiber was used as the fiber reinforcing material.

In the SMC, the thickening agent and the raw materials other than the glass fiber were sufficiently stirred, and then the thickening agent was added to the mixture, which was impregnated with the glass fiber using an SMC impregnating machine to obtain 45 SMC. It was aged for 24 hours in an atmosphere of ° C to obtain an SMC molding material. This SMC molding material was subjected to heat compression molding under conditions of 145 ° C. and 10 MPa for 8 minutes to obtain a molded product having a thickness of 5 mm. The moldability of this molded product,
Tables 1 and 2 show the results of observation and confirmation of smoothness, gloss, depth, and workability of materials.

Regarding the material workability, when the material sandwiched in the film is taken out before molding the SMC molding material obtained by aging, the material is not sticky.
~ ○, × when sticky. With respect to moldability, the case where problems such as defective release did not occur during molding was evaluated as ◯.
Regarding the gloss, the glossy ones were evaluated as ⊚ to ◯, the non-glossy ones as x, and the ones thought to be located between the ones with and without the ones as Δ. Regarding the smoothness, ∘ to ∘ when the surface had no unevenness, x when the unevenness due to the glass was visible, and Δ when the surface was considered to be in the middle. Regarding the sense of depth, the presence or absence of transparency was visually observed, and a good one was evaluated as ◯, and a poor one was evaluated as Δ.

In Examples 1 to 3, molding materials and moldings were obtained which were satisfactory in both appearance and workability of the materials, although there were slight differences in gloss and depth.

In Comparative Examples 1 to 4, it was shown that the results satisfying both appearance and workability were not obtained. Specifically, in Comparative Examples 2 and 4, the depth feeling of the molded product is fair, but the gloss or the workability of the material is inferior, and in Comparative Example 1, the material workability is good. However, the results showed that gloss, depth and workability of materials could not coexist, such as poor gloss and depth, and poor workability of the molding material in Comparative Example 3.

[0057]

[Table 1]

[0058]

[Table 2]

The refractive index of the cured product in Tables 1 & 2 is the numerical value of the cured product of the unsaturated resin composition AZ.

[0060]

EFFECTS OF THE INVENTION The resin composition and molding material of the present invention not only provide a molded article having a deep feeling and gloss, but also have good material workability without stickiness, which has been difficult until now. Can be achieved at the same time.
Moreover, in the case of a sheet-like material form such as SMC, continuous production is possible, and there is no problem in workability of the molding material.
It is an extremely useful composition, a molding material, and a molded product that can be obtained by press molding using a mold while maintaining the same productivity as before.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) C08K 7/02 C08K 7/02 C08L 63/10 C08L 63/10 67/06 67/06 F term (reference) 4F072 AA02 AA07 AB05 AB29 AD05 AD38 AE12 AE13 AF03 AF06 AG03 AK05 AK14 AL01 AL06 4J002 BC032 BQ001 DE078 DE146 DL006 DL007 FA047 FD016 FD202 FD338 GL00 4J011 PA07 PA15 PA07 PA15 PA07 PA15 PA29 PA65 PB04 CAB02 PB22 PB22 PB22 PB32 PB32 P01

Claims (7)

[Claims] 1. A compound capable of imparting a carboxyl group to at least part of the hydroxyl groups of an unsaturated group-containing epoxy resin obtained by reacting an unsaturated polyester (a) with an unsaturated monobasic acid (b). A carboxyl group-containing unsaturated resin obtained by reacting with, (c) a polymerizable unsaturated monomer,
A resin composition containing (d) an inorganic filler and (e) a polymerization initiator. 2. A cured product of a mixture of (a) unsaturated polyester, (b) carboxyl group-containing unsaturated resin, and (c) polymerizable unsaturated monomer has a refractive index of 1.540 to 1.58.
The resin composition according to claim 1, which is 0. 3. A compound capable of imparting a carboxyl group,
The resin composition according to claim 1 or 2, which is an anhydride of a polybasic acid. 4. The resin composition according to claim 1, wherein the inorganic filler is at least one selected from aluminum hydroxide and glass powder. 5. The method according to claim 1, further comprising a reinforcing fiber.
~ The molding material as described in any one of 4 above. 6. The molding material according to claim 1, further comprising a low-contracting agent and a thickening agent. 7. A molded product obtained by curing the resin composition or the molding material according to claim 1.