JPH10147721A - Resin composition for molding material and molding material obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can give a molding material which is satisfactory in the wettability of the filler with the resin and interfacial adhesion and can give a molding not suffering from whitening by mixing a specified polymer with a radical-polymerizable polycarboxy compound and a radial-polymerizable monomer. SOLUTION: A radical-polymerizable compound having a functional group reactive with an acid anhydride is reacted with an aliphatic or alicyclic unsubstituted polybasic acid anhydride or a 2C or lower substituent-substituted polybasic acid anhydride derivative at 80-130 deg.C in the presence of an esterification catalyst and a polymerization inhibitor to obtain a radical polymerizable carboxyl compound (B) having at least two carboxyl groups in the molecule and having a molecular weight of 300-5,000 and an acid value of 50mg/KOH/g. A polymer (A), such as an unsaturated polyester, a urethane acrylate or a polyester acrylate, having an acid value of 30mgKOH/g or below is mixed with 0.1-10wt.% component B and 10-90wt.% radical-polymerizable monomer (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to mechanical parts, building materials,
Resin molded products used in a wide range of fields, such as pipes, bathtubs, sinks, and other domestic facilities, containers, film sheets, printed wiring boards, and other electronic and electrical fields. The present invention relates to a resin composition which is a material used in the production of a resin composition, and particularly to a resin composition for a molding material which has good wettability and interfacial adhesion between a resin and an inorganic filler and does not cause whitening after molding. And a molding material using the composition.

[0002]

2. Description of the Related Art Unsaturated polyesters, urethane acrylates, polyester acrylates, vinyl esters, and the like are used when an oligomer having a radically polymerizable unsaturated group is mixed with a radically polymerizable monomer to produce a resin molded product. It is used as a resin for molding materials. It is also known that a polymer of methyl methacrylate and a monomer are mixed and used as a resin for a molding material as a so-called acrylic syrup.

[0003] These resins for molding materials are often compounded with inorganic fillers as bulking agents or as modifiers of various properties. Examples of the inorganic filler include those having various compositions and shapes such as aluminum hydroxide, calcium carbonate, zinc oxide, kaolin clay, and mica.In general, the inorganic filler wets with the resin in the molding material. Properties and interfacial adhesion are poor, so immediately after mixing the resin and the inorganic filler, even if the inorganic filler is uniformly dispersed,
If it takes time for the resin to cure, the inorganic filler may settle to the bottom of the molding die.

[0004] When the inorganic filler settles at the bottom of the mold, the resulting molded article has a partial variation in properties such as strength.
In particular, there is a problem that the water resistance and boiling resistance characteristics are significantly reduced. In other words, when exposed to harsh conditions such as boiling in an alkaline aqueous solution, the inorganic filler and the resin cause interfacial delamination, water penetrates into this interface and whitens, not only significantly impairing the product appearance, This causes inconveniences such as reduced strength and generation of mold.

[0005] From such a viewpoint, Japanese Patent Application Laid-Open No. 8-12762 is disclosed.
In No. 9, the epoxy vinyl ester resin itself is reacted with a polybasic anhydride having a long-chain alkyl group or a long-chain alkenyl group to improve the hot water resistance of the cured resin by using the resin as a molding material resin. Attempts have been made.

[0006] However, the present inventors have disclosed in Japanese Unexamined Patent Publication No.
When the resin composition disclosed in Japanese Patent No. 127629 was manufactured and subjected to an experiment for resistance to boiling with alkaline water, slight whitening was observed, and it is considered that there is still room for improvement in the resistance to boiling with alkaline water.

[0007]

Accordingly, the present invention provides a molding composition which is excellent in wettability with an inorganic filler and interfacial adhesion, and which does not cause inconvenience such as whitening even when boiling in an alkaline aqueous solution after molding and curing. An object was to provide a resin composition for a material.

[0008]

The resin composition for a molding material of the present invention comprises a polymer (A) having an acid value of 30 mg KOH / g or less and two or more polymers per molecule having an acid value of 50 mg KOH / g or more. The radical polymerizable polycarboxyl compound having a carboxyl group (B) and the radical polymerizable monomer (C) have the greatest characteristics.

The polymer (A) has an acid value of 30 mgKOH / g
The following embodiments, which are radical polymerizable oligomers (A1) that can be increased in molecular weight by radical polymerization, and those that are thermoplastic polymers (A2) having an acid value of 30 mgKOH / g or less, are preferred embodiments of the present invention. It is a form. Further, as the polymer (A), a radical polymerizable oligomer (A1) and a thermoplastic polymer (A
It may include both 2). The “polymer (A)” in the present invention includes, as described above, an oligomer having a radically polymerizable unsaturated group, that is, a radically polymerizable oligomer together with a polymer (polymer) that has already been polymerized. Is also included.

The radically polymerizable oligomer (A1) is preferably exemplified by one or more polymers selected from the group consisting of unsaturated polyesters, urethane acrylates, polyester acrylates and vinyl esters. Further, a so-called acrylic syrup type in which the thermoplastic polymer (A2) is a polymer containing polymethyl methacrylate as a main component and part or all of the radically polymerizable monomer (C) is methyl methacrylate is also preferable.

When the acid value of the radically polymerizable polycarboxyl compound (B) [hereinafter simply referred to as polycarboxyl compound (B)] is 70 mgKOH / g or more, the effect of improving the wettability with the inorganic filler and the interfacial adhesion is improved. Becomes even more pronounced. Furthermore, in order to exhibit this improvement effect,
Polycarboxyl compound (B) in resin composition for molding material
Is recommended to be 0.1 to 10% by weight.

The polycarboxyl compound (B) is reacted with a radical polymerizable compound having a functional group capable of reacting with an acid anhydride group with an aliphatic or alicyclic polybasic acid anhydride or a derivative thereof. A preferred embodiment is obtained. At this time, a derivative which is not substituted as an aliphatic or alicyclic polybasic acid anhydride, or is substituted by a substituent having 2 or less carbon atoms,
It is preferable to use a vinyl ester resin as a radical polymerizable compound having a functional group capable of reacting with an acid anhydride group. The present invention also includes a molding material containing the resin composition for a molding material and an inorganic filler.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has an acid value of 30 mg KOH.
/ G or less of a polymer (A), a resin for a molding material having a monomer (C) capable of participating in radical polymerization as a main component, and an acid value of 50 mgKOH / g or more and two or more per molecule. The most important point is that a radical polymerizable polycarboxyl compound (B) having a carboxyl group is blended into a resin composition for a molding material. Acid value is 30mgKO
H / g or less of the polymer (A) includes a radical polymerizable oligomer (A
1) or the thermoplastic polymer (A2) or (A
There is a combination type of 1) and (A2).

According to the technique disclosed in JP-A-8-127629, the polymer itself in the resin for molding material is modified with an acid anhydride having a long-chain alkyl group or a long-chain alkenyl group. Then, the polymer (A) itself is set to have a small acid value, and a radical polymerizable compound having a large acid value and having two or more carboxyl groups is separately added, so that the inorganic filler and the polymer (A) can be cured. This is a technical idea of improving the wettability and interfacial adhesion with a resin, and is clearly distinguished from the prior art. When we try to improve wettability by introducing carboxyl groups into the polymer itself in the resin for molding materials as in the prior art, we have to improve the wettability and interfacial adhesion in view of the water resistance after molding and curing. It is considered that a sufficient amount of a carboxyl group could not be introduced into the polymer main chain to achieve the effect. Therefore, improvement of water resistance due to the effect of improving wettability and interfacial adhesion,
It is difficult to balance with the deterioration of water resistance due to the introduction of a carboxyl group.

However, in the present invention, a polycarboxyl compound having a concentrated carboxyl group is added separately from the polymer (A), and the inorganic filler and the polymer (A) are added.
It only needs to be added in an amount necessary to enhance the wettability with the resin, so that the inconvenience of deterioration of the water resistance of the molded article due to the introduction of the carboxyl group cannot occur. Since the polycarboxyl compound surrounds the inorganic filler with the action of the carboxyl group, the wettability between the molding resin and the inorganic filler is remarkably improved, and since the polycarboxyl compound has radical polymerizability, the polymer is not polymerized at the time of molding. (A) and / or
Alternatively, it does not polymerize with the radical polymerizable monomer (C) to deteriorate the water resistance of the molded article.

Hereinafter, embodiments of the present invention will be described in detail. First, in the present invention, a known resin used for producing a resin molded product (including a molded product of a composite material such as FRP) as a resin for a molding material is used.
It can be used without particular limitation as long as it is not more than gKOH / g. Therefore, as the polymer (A) used in the present invention, a radical polymerizable oligomer (A) which can be polymerized to a high molecular weight by radical polymerization having an acid value of 30 mgKOH / g or less is used.
1) or a thermoplastic polymer (A2) having an acid value of 30 mg KOH / g or less, or a combination type in which (A1) and (A2) are used in combination. In the present invention, since the polycarboxyl compound (B) described below is an essential component, the carboxyl group does not need to be present in the polymer (A), and the water resistance and the like may be deteriorated. (A)
Was determined to be 30 mgKOH / g or less. The acid value of the polymer (A) is determined by performing a titration with KOH.

The radically polymerizable oligomer (A1) is a resin which can be increased in molecular weight by radical polymerization at the time of molding, that is, a resin having one or more unsaturated double bonds in the molecule and starting thermal polymerization of an organic peroxide or the like. A polymer having a molecular weight of an oligomer level that can be cured by forming a three-dimensional network by copolymerizing with the radical polymerizable monomer (C1) by an agent or a photopolymerization initiator, and satisfies the acid value condition. Anything that can be used in the present invention. Molecular weight 50
A range of about 0 to 10,000 is preferable in that both the handleability and the performance after curing are compatible.

Specific examples include unsaturated polyesters, urethane acrylates, polyester acrylates, vinyl esters and the like. One of these, or two or more oligomers having good compatibility can be used in combination.

As the polymer (A), a thermoplastic polymer (A
In the case of using 2), the thermoplastic polymer (A2) itself is already a polymer and does not polymerize any more. However, a radical polymerizable monomer such as a thermal polymerization initiator such as an organic peroxide or a photopolymerization initiator is used. The monomer (C) is polymerized and cured. It is well known that a combination of a polymer having polymethyl methacrylate (PMMA) as a main component and a methyl methacrylate (MMA) monomer, which is called an acrylic syrup, is part or all of a radical polymerizable monomer (C). Therefore, it is preferably used because a molded article excellent in various properties such as water resistance and transparency can be manufactured. The thermoplastic polymer (A2) can be used without particular limitation as long as the acid value is 30 mgKOH / g or less. Specifically, in addition to PMMA, poly (meth) acrylates, polystyrene, polyethylene, polybutadiene, Polyvinyl acetate,
Examples thereof include thermoplastic polymers such as saturated polyesters and the like, and mixtures thereof.

The radical polymerizable monomer (C) is a radical polymerizable monomer, and is appropriately selected according to the type of the polymer (A) in consideration of compatibility, use, and required characteristics.
Those having a molecular weight of 400 or less are preferred. Specifically, styrene, α-methylstyrene, α-chlorostyrene, vinyl toluene, divinylbenzene, diallyl phthalate,
Aromatic vinyl monomers such as diallylbenzene phosphonate; vinyl ester monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate;
Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [2- (meth) acryloyl (Meth) acrylic monomers such as [oxyethyl] triazine; triallyl cyanurate; and one or more of these can be used.

The amount of the radical polymerizable monomer (C) to be used is not particularly limited, and can be appropriately set in consideration of the viscosity when mixed with the polymer (A) and used as a resin for a molding material. Is 10 to 10% of the radical polymerizable oligomer (A1).
It may be used in the range of 90% by weight, preferably in the range of 20 to 80% by weight. Moreover, it is good to use it in 30-90 weight% with respect to a thermoplastic polymer (A2), Preferably it is 50-80 weight%.

Incidentally, as the polymer (A), a radical polymerizable oligomer (A1) and a thermoplastic polymer (A2) can be used in combination. Radical polymerizable oligomer (A
In order to prevent the volume shrinkage due to the curing of 1), it is effective to use the thermoplastic polymer (A2) in combination. (A1) and (A
The amount ratio of 2) can be appropriately determined according to the application. Further, instead of or in addition to the thermoplastic polymer (A2), three-dimensional polystyrene or the like generally used as a low-shrinking agent may be used.

The resin composition of the present invention has an acid value of 50 mgK together with the polymer (A) and the radical polymerizable monomer (C).
Radical polymerizable polycarboxyl compound having at least OH / g and having two or more carboxyl groups in one molecule (B)
Is an essential component. The acid value of the compound (B) is 50 mgK
If it is less than OH / g, the effect of improving the wettability and interfacial adhesion between the inorganic filler and the polymer (A) is not exhibited. A more preferred acid value is 70 mgKOH / g or more. Any compound that satisfies the acid value condition and has two or more carboxyl groups in one molecule and is capable of radical polymerization can be used without limitation as the polycarboxyl compound (B).

After the polycarboxyl compound (B) is mixed with the polymer (A), at the stage where the molding material hardens, the polymer (A) and the inorganic filler are surrounded so as to surround the inorganic filler. The increased wettability does not cause the disadvantage that the inorganic filler settles to the bottom of the mold before curing is completed. Further, since the compound (B) is capable of radical polymerization, the radical polymerizable oligomer (A) in the polymer (A)
1) to copolymerize with the radical polymerizable monomer (C),
The interfacial adhesion between the cured polymer (A) and the inorganic filler is maintained at a high level. Therefore, the water resistance of the obtained molded product,
Characteristics such as chemical resistance and boiling resistance are remarkably improved.

As the polycarboxyl compound (B),
Those having a molecular weight of 300 to 5000 and having two or more carboxyl groups in one molecule are preferable. The preferred upper limit of the carboxyl group is about 10 per molecule. As such a polycarboxyl compound (B), a polycarboxyl compound (B) in which a carboxyl group is introduced by reacting a hydroxyl group in a vinyl ester resin with a polybasic acid anhydride can be preferably used. In addition, for example, instead of a diol when synthesizing an unsaturated polyester, a polyol in which a part of a triol or more is used, a compound obtained by reacting an acid anhydride with an introduced hydroxyl group, or a hydroxyl group-containing monomer such as hydroxymethacrylate is oligomerized. hand,
Further, it is also possible to use a compound in which a double bond is introduced and a hydroxyl group in the oligomer is reacted with an acid anhydride.

The vinyl ester is also called an epoxy acrylate, and is a radical polymerizable oligomer obtained by reacting an unsaturated monobasic acid with an epoxy resin to introduce a radical polymerizable double bond. Examples of the starting material epoxy resin include bisphenol A epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and other bisphenol epoxy resins; phenol novolak epoxy resin, cresol novolak epoxy resin, Novolak epoxy resins such as bisphenol A novolak epoxy resin; biphenyl epoxy resins; alicyclic epoxy resins; polyfunctional glycidylamine resins such as tetraglycidylaminodiphenylmethane; polyfunctional glycidyl ether resins such as tetraphenylglycidyl ether ethane;
A reaction product of a polyhydric phenol compound obtained by a condensation reaction of a phenol such as phenol, o-cresol, m-cresol or a naphthol with an aromatic aldehyde having a phenolic hydroxyl group and epichlorohydrin; phenols and divinylbenzene or divinylbenzene Reaction products of polyhydric phenols obtained by addition reaction with a diolefin compound such as cyclopentadiene and epichlorohydrin; those obtained by epoxidizing a ring-opening polymer of 4-vinylcyclohexene-1-oxide with a peracid; Can be

The unsaturated monobasic acid to be reacted with the epoxy resin is defined as one carboxyl group and one or more (meth)
Monobasic acid having an acryloyl group, specifically, acrylic acid, methacrylic acid, a polyfunctional (meth) acrylate having one hydroxyl group and two or more (meth) acryloyl groups in one molecule, Examples thereof include a carboxyl group-containing polyfunctional (meth) acrylate which is a reaction product of a dibasic acid anhydride. Further, a part of the unsaturated monobasic acid can be replaced with a polybasic acid such as a long-chain dicarboxylic acid.

The reaction between the epoxy resin and the unsaturated monobasic acid is carried out according to a known method, and usually, the carboxyl group in the unsaturated monobasic acid is 0.9 to 1.0 equivalent to 1 chemical equivalent of the epoxy group in the epoxy resin. 1.1 Raw materials are charged so as to have a chemical equivalent, and as an esterification catalyst, for example, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, or an imidazole compound such as 2-ethyl-4-methylimidazole Using a phosphorus compound such as triphenylphosphine, a metal organic acid or inorganic salt or a chelate compound, in the presence or absence of a diluent, in the presence of a polymerization inhibitor such as hydroquinone or oxygen, at 80 to 130 ° C. By performing the above, a vinyl ester resin is obtained.

By reacting a hydroxyl group in the vinyl ester resin with a polybasic anhydride, a polycarboxyl compound (B) having a carboxyl group introduced therein can be obtained. As the polybasic acid anhydride, an aliphatic dibasic acid anhydride or an alicyclic dibasic acid anhydride is preferable because the effect of improving wettability and interfacial adhesion is large. The polybasic acid anhydride is preferably unsubstituted or substituted by a substituent having 2 or less carbon atoms. An acid anhydride having a long-chain alkyl group or a long-chain alkenyl group as a substituent is not preferred in the present invention because the effect of improving wettability and interfacial adhesion is not exhibited. It is presumed that this is because when the polycarboxyl compound (B) surrounds the inorganic filler, an acid anhydride having a long-chain alkyl group or long-chain alkenyl group as a substituent cannot be well surrounded by steric hindrance.

Specific examples of preferred polybasic anhydrides include aliphatic dibasic anhydrides such as succinic anhydride, glutaric anhydride, and maleic anhydride; and alicyclic rings such as tetrahydrophthalic anhydride and hexahydrophthalic anhydride. It is a dibasic acid anhydride of the formula, and one or more of these can be used.

The amount of the polybasic acid anhydride to be used is suitably 0.1 to 1.1 chemical equivalents with respect to 1 chemical equivalent of the hydroxyl group in the vinyl ester resin, and the acid value is 50 mgKOH / g or more.
Preferably, the reaction is performed so as to be 70 mgKOH / g or more. The reaction conditions are 50 to 13 in the presence or absence of a polymerization inhibitor such as hydroquinone or oxygen in the presence or absence of a diluent.
Perform at 0 ° C. At this time, if necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, or a metal salt such as lithium chloride may be added as a catalyst.

The resin composition for a molding material of the present invention comprises the above-mentioned polymer (A), polycarboxyl compound (B) and radically polymerizable monomer (C) as essential components. It can be obtained by kneading by a known method. The polycarboxyl compound (B) is preferably used in a range of 0.1 to 10% by weight in the resin composition. When the amount is less than 0.1% by weight, the effect of adding the compound (B) is hardly exhibited, and when the amount exceeds 10% by weight,
The water resistance and chemical resistance of the obtained molded product may deteriorate. The more preferred amount of the compound (B) used is 0.5 to 5
% By weight.

The molding material of the present invention contains the above-mentioned resin composition for a molding material, but when actually used as a molding material, an inorganic filler is blended from the viewpoint of obtaining a volume increasing effect and a reinforcing effect. It is recommended that As inorganic fillers, aluminum hydroxide, calcium carbonate, barium sulfate, alumina, metal powder, kaolin clay, talc,
Known inorganic fillers such as milled fiber, silica sand, river sand, diatomaceous earth, mica powder, gypsum, asbestos powder, carbon black, glass powder, glass spheres and the like can be used. The inorganic filler may be a resin composition 10 for a molding material depending on the use of the molded article.
It is preferable to use 30 to 600 parts by weight with respect to 0 parts by weight. Among the inorganic fillers, the effect of improving the wettability and interfacial adhesion in the present invention is remarkably observed when aluminum hydroxide is used.

Glass fiber, carbon fiber, metal fiber,
A fiber-reinforced composite material (FRP) may be formed by compounding and molding a reinforcing material such as an inorganic fiber such as a ceramic fiber or an organic fiber such as an aramid fiber or a polyester fiber.

When molding and curing the molding material of the present invention, a curing catalyst (polymerization initiator) or a curing accelerator may be mixed with the curing catalyst. As the curing catalyst, methyl ethyl keto-on peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, t-butyl peroxy benzoate, lauroyl peroxide and the like Organic peroxides and azo compounds such as 2,2′-azobisisobutyronitrile and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile are used as curing accelerators, such as cobalt naphthenate and Representative examples include cobalt octenoate and the like and tertiary amines. The curing catalyst is preferably used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the molding material resin (A).

A releasing agent, a lubricant, a plasticizer, an antioxidant,
UV absorbers, flame retardants, polymerization inhibitors, thickeners, pigments, and other known additives may be used depending on the application.

The resin composition for a molding material and the molding material of the present invention may be cast molding, compression molding, extrusion molding, injection molding, etc.
The molded article is processed into a molded article by a known molding means depending on the use of the molded article, and the molding / curing method is not particularly limited.

[0038]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention. The parts and percentages in the examples are on a weight basis.

Synthesis Example 1 <Resin for molding material ｛Polymer (A)
Of styrene oxide and radical polymerizable monomer (C): Synthesis of the same as in the following｝> propylene oxide adduct of bisphenol A (BP
X-11: 365 parts of a hydroxyl value 317 manufactured by ADEKA CORPORATION and 116 parts of fumaric acid were reacted at 200 ° C. for 15 hours, and it was confirmed that the acid value of the reaction product became 15. 481 parts of styrene was added to the reaction product to obtain an unsaturated polyester resin having a styrene content of 50%.

Synthesis Example 2 <Synthesis of resin for molding material> Bisphenol A type epoxy resin (Araldite GY-
250: Ciba-Geigy: Epoxy equivalent 185) 37
0 parts and 172 parts of methacrylic acid were reacted at 110 ° C. for 8 hours, and it was confirmed that the acid value of the reaction product was 4.0. 232 parts of styrene was added to the reaction product, and the styrene content was 30%.
To obtain a vinyl ester resin.

Synthesis Example 3 <Synthesis of resin for molding material> To a mixture of 65 parts of methyl methacrylate and 5 parts of trimerolpropane trimethacrylate, 30 parts of polymethyl methacrylate was added at 50 ° C. over 2 hours. An acrylic syrup was obtained.

Synthesis Example 4 <Synthesis of Radical-Polymerizable Polycarboxyl Compound> To 818 parts of bisphenol A-epichlorohydrin type epoxy resin (Araldite 6071: Ciba Geigy Co., Ltd .; epoxy equivalent: 465), 151 parts of methacrylic acid and 415 parts of styrene were added. . Then hydroquinone 0.21
And 3.18 parts of triethylamine.
For 5 hours, it was confirmed that the acid value of the reaction product was 4.7, and a styrene solution (a) containing 70% of a vinyl ester resin was obtained. To 395 parts of this styrene solution (a),
100 parts of succinic anhydride was added and reacted at 100 ° C. for 4.5 hours. After confirming that the acid value became 118, a styrene solution of the radically polymerizable polycarboxyl compound (B-1) was obtained.

Synthesis Example 5 <Synthesis of Radical-Polymerizable Polycarboxyl Compound> To 395 parts of the styrene solution (a) obtained in Synthesis Example 4, 152 parts of tetrahydrophthalic anhydride was added and reacted at 100 ° C. for 4.5 hours. , The acid value was confirmed to be 107, and the radically polymerizable polycarboxyl compound (B-2)
To obtain a styrene solution.

Synthesis Example 6 <Synthesis of Radical-Polymerizable Polycarboxyl Compound> 329 parts of a phenol novolak type epoxy resin having about 5 epoxy groups in one molecule (EPPN-201: Nippon Kayaku Co., Ltd .: epoxy equivalent: 187) , Methacrylic acid 1
51 parts and 206 parts of styrene were added. Next, 0.10 part of hydroquinone and 1.58 part of triethylamine were added and reacted at 115 ° C. for 6 hours, and the acid value of the reaction product was 4.8.
Was confirmed, and a styrene solution (b) containing 70% of a vinyl ester resin was obtained. This styrene solution (b)
To 390 parts, 57 parts of succinic anhydride was added and reacted at 100 ° C. for 4.5 hours. After confirming that the acid value became 76, the radically polymerizable polycarboxyl compound (B-3) was obtained.
To obtain a styrene solution.

Synthesis Example 7 <Synthesis of Radical-Polymerizable Polycarboxyl Compound> Dimer acid (Versa Dime 288, manufactured by Henkel Hakusui):
396 parts of bisphenol A-epichlorohydrin type epoxy resin (Araldite GY-250:
Ciba Geigy: Epoxy equivalent 185) 514 parts,
441 parts of styrene, 0.29 parts of hydroquinone and 3.38 parts of triethylamine were added and reacted at 115 ° C. for 3 hours. When the acid value of the reaction product reached 0.9, 119 parts of methacrylic acid was added. At 115 ° C. for 7 hours. It was confirmed that the acid value of the reaction product was 1.9, and a styrene solution (c) containing 70% of a vinyl ester resin was obtained. To 529 parts of this styrene solution (c), 154 parts of hexahydrophthalic anhydride were added and reacted at 100 ° C. for 4.5 hours. When the acid value reached 83, it was confirmed that the radical polymerizable polycarboxyl compound (B- A styrene solution of 4) was obtained.

Synthesis Example 8 <Synthesis of Comparative Polycarboxyl Compound> To 130 parts of hydroxypropyl acrylate, 100 parts of succinic anhydride was added and reacted at 110 ° C. for 2 hours to confirm that the acid value was 244. And the compound (B-5) were obtained.

Synthesis Example 9 <Synthesis of Polycarboxyl Compound for Reference Example> Dodecenyl succinic anhydride (substituted for a long-chain alkenyl group) was replaced with 395 parts of a styrene solution (a) containing 70% of the vinyl ester resin obtained in Synthesis Example 4. Acid anhydride as a group) 2
66 parts were added, the mixture was reacted at 100 ° C. for 4.5 hours, and it was confirmed that the acid value became 90. Thus, a styrene solution of the polycarboxyl compound (B-7) was obtained.

Examples 1 to 6, Comparative Examples 1 to 4 and Reference Example 1 The resin for molding material obtained in the above synthesis example and polycarboxyl compounds (B-1) to (B-5) and (B-7) Dimer acid having no radical polymerizability as a compound (B-6) (Versa Dime 288: manufactured by Henkel Hakusui Co., Ltd .: acid value 19)
7) with an inorganic filler (aluminum hydroxide: C-303)
E: manufactured by Sumitomo Chemical Co., Ltd.) in accordance with the composition shown in Table 1 to obtain a molding material. Each obtained molding material 10
To 0 parts, 1 part of an initiator t-butyl peroxybenzoate was added, and after stirring and defoaming, poured into a mold of a casting plate,
The resin was cured by heating at 100 ° C. for 30 minutes in a hot-air circulation drying oven to obtain a casting plate having a thickness of 3 mm.

The obtained casting plate was immersed in a 10% by weight aqueous solution of sodium hydroxide at 80 ° C. for 1 hour, and the whitening state of the casting plate surface after immersion was evaluated according to the following criteria. The results are shown in Table 1. ：: No whitening, no change before immersion ○: Slightly whitened, but almost no change before immersion △: Slightly whitened ×: Completely whitened

[0050]

[Table 1]

[0051]

The present invention is configured as described above.
Since the compound (B) having a concentrated carboxyl group was contained in the resin composition for a molding material separately from the resin for a molding material comprising the polymer (A) and the radical polymerizable monomer (C). When an inorganic filler is compounded and used as a molding material, the inorganic filler and the resin have excellent wettability and interfacial adhesion. The resulting molded article had significantly improved boiling resistance in an alkaline aqueous solution. The resin composition for a molding material of the present invention, even when used as a molding material without using an inorganic filler, has excellent adhesiveness (which is a necessary property for a laminate or the like) and excellent water resistance and strength. Molded articles can be manufactured.

Claims (5)

[Claims] 1. A polymer (A) having an acid value of 30 mg KOH / g or less, a radical polymerizable polycarboxyl compound (B) having an acid value of 50 mg KOH / g or more and having two or more carboxyl groups in one molecule, A resin composition for a molding material, comprising a radically polymerizable monomer (C). 2. The radical polymerizable polycarboxyl compound (B) has an acid value of 70 mg KOH / g or more.
3. The resin composition for a molding material according to item 1. 3. The resin composition for a molding material according to claim 1, wherein the content of the radically polymerizable polycarboxyl compound (B) is 0.1 to 10% by weight. 4. A radically polymerizable polycarboxyl compound (B) comprising a radically polymerizable compound having a functional group capable of reacting with an acid anhydride group, wherein the radically polymerizable polycarboxyl compound (B) is an unsubstituted aliphatic or alicyclic polybasic acid anhydride. The resin composition for a molding material according to any one of claims 1 to 3, which is obtained by reacting a product or a derivative of the polybasic anhydride substituted with a substituent having 2 or less carbon atoms. 5. A molding material comprising the resin composition for a molding material according to claim 1 and an inorganic filler.