JPH06248188A - In-mold coating resin compositions and method for in-mold coating - Google Patents

Abstract

PURPOSE:To obtain the subject resin compositions which have good adherence to each other and can maintain sufficient adhesion even after having been subjected to changes in the environment, such as repeated cooling and heating, and to provide the title method wherein this compositions are used. CONSTITUTION:One of a thermosetting molding material and a thermosetting coating material comprises a thermosetting resin composition containing a thermosetting resin and at least one of unsaturated silane, unsaturated titanate and unsaturated aluminum coupling agents, and the other comprises a thermosetting resin composition containing a thermosetting resin and at least one of unsaturated silane, unsaturated titanate and unsaturated aluminum coupling agents, and unsaturated mercaptan, unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid and unsaturated glycidyl compounds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition used in an in-mold coating molding method for forming a coating layer on a molding material in a molding die, and more particularly to the adhesion between the molding material and the coating layer. The present invention relates to a thermosetting resin composition that enables to obtain a coated molded article having excellent properties, and an in-mold coating molding method using the thermosetting resin composition.

[0002]

2. Description of the Related Art Recently, molded articles made of thermosetting material have
It is very widely used in industrial parts as a substitute for metal parts. Above all, a sheet molding compound (hereinafter abbreviated as SMC) or a bulk molding compound (hereinafter abbreviated as BMC) is generally used.

However, in a molded product obtained by molding SMC or BMC by heating and pressing in a molding die, surface defects such as pores, microcracks, sink marks or undulations tend to occur on the surface. When such surface defects are present, it is difficult to form a sufficient coating film even if the molded product is coated by a usual method.

Therefore, a so-called in-mold coating molding method has been proposed as a method for concealing the above-mentioned surface defects. For example, Japanese Examined Patent Publication No. 4-33252 discloses a method of forming a coating layer on the surface of a molded article by injecting a coating material at an injection pressure higher than the molding pressure and curing it during compression molding.

[0005]

However, the coating film coated by the in-mold coating molding has a drawback that the adhesion to the molding material is poor.

The present invention remedies the above drawbacks,
A thermosetting resin composition for in-mold coating molding which has good adhesion in the in-mold coating molding method and can maintain sufficient adhesion even after being subjected to environmental changes such as repeated cold and heat, and the same An object is to provide a coating molding method.

[0007]

The invention according to claim 1 is a thermosetting method used in an in-mold coating molding method for forming a coating layer by coating a thermosetting coating material on a molding material in a die. Resin composition, wherein one of the thermosetting molding material and the thermosetting coating material is a thermosetting resin, an unsaturated silane coupling agent, an unsaturated titanate-based coupling agent,
And a thermosetting resin composition containing at least one of an unsaturated aluminum-based coupling agent, and the other is a thermosetting resin and an unsaturated silane coupling agent,
Unsaturated titanate-based coupling agent, unsaturated aluminum-based coupling agent, unsaturated alcohol, unsaturated mercaptan, unsaturated carboxylic acid (including salt and anhydride), unsaturated sulfonic acid (including salt and anhydride), A thermosetting resin composition for in-mold coating molding, which is a thermosetting resin composition containing at least one of unsaturated phosphoric acid (including salt and anhydride) and an unsaturated glycidyl compound. It is a composition.

The invention according to claim 2 is a thermosetting resin composition used in an in-mold coating molding method for molding a coating layer by coating a thermosetting molding material on a thermosetting molding material in a mold. One of the thermosetting molding material and the thermosetting coating material is a thermosetting resin, an unsaturated silane coupling agent, an unsaturated titanate coupling agent, and an unsaturated aluminum coupling agent. Is a thermosetting resin composition containing at least one of the above, and the other is at least one of a thermosetting resin, polyisocyanate, polyol, polymercaptan, and an epoxy compound having a plurality of glycidyl groups. A thermosetting resin composition for in-mold coating molding, which is a thermosetting resin composition containing a seed.

Further, in the invention described in claim 3, in the in-mold coating molding method, the molding material and the coating material are:
The thermosetting molding material and the thermosetting coating material according to claim 1 or 2 are used. Hereinafter, the details of the configuration of each invention described in claims 1 to 3 (hereinafter, "the present invention" means each invention described in claims 1 to 3) will be described.

As the thermosetting resin in the thermosetting resin composition used as the molding material in the present invention, a three-dimensional network structure is formed by cleavage addition reaction of unsaturated bond using a heat decomposable radical catalyst. An unsaturated polyester resin having a reactive unsaturated bond in the molecule, an epoxy acrylate (vinyl ester) resin, a urethane acrylate resin or the like that can be used is used. These resins may be used alone or as a mixture of plural kinds.

Similarly, as the thermosetting resin in the thermosetting resin composition used as the coating material in the present invention, unsaturated polyester resin, epoxy acrylate (vinyl ester) resin, urethane acrylate resin and the like are used. These resins may be used alone or as a mixture of plural kinds.

The above-mentioned unsaturated polyester resin is usually produced by a known and commonly used method, usually an organic polyol, an aliphatic unsaturated polycarboxylic acid, and, if necessary, an aliphatic saturated polycarboxylic acid and / or an aromatic polycarboxylic acid. Manufactured from.

On the other hand, the above-mentioned epoxy acrylate (vinyl ester) resin is usually produced by a known and conventional method from an epoxy resin and a monocarboxylic acid having a reactive unsaturated bond such as (meth) acrylic acid. It is a thing.

The urethane acrylate resin is usually obtained by reacting an organic polyol such as an alkylene diol, an alkylene diol ester, an alkylene diol ether, a polyether polyol or a polyester polyol with an organic polyisocyanate, and further reacting with a hydroxyalkyl (meth) acrylate. It is manufactured by doing so.

Here, examples of the organic polyol used in the unsaturated polyester resin include diols, triols, tetraols and mixtures thereof, and they are mainly divided into aliphatic polyols and aromatic polyols, of which aliphatic ones are used. Typical polyols include ethylene glycol, propylene glycol,
Dipropylene glycol, butylene glycol, triethylene glycol, neopentyl glycol, dibromoneopentyl glycol, hexamethylene glycol,
There are trimethylene glycol, trimethylolpropane, glycerin, pentaerythrite diallyl ether, hydrogenated bisphenol A, etc., and typical aromatic polyols are bisphenol A or bisphenol S, or bisphenol A or bisphenol S thereof with ethylene oxide. Polyoxyalkylene bisphenol A obtained by adding an aliphatic oxirane compound such as propylene oxide or butylene oxide in the range of 1 to 20 on average in one molecule.
Alternatively, there is polyoxyalkylene bisphenol S or the like.

As the aliphatic unsaturated polycarboxylic acid used in the unsaturated polyester resin, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid and the like are used. As the aliphatic saturated polycarboxylic acid used for the unsaturated polyester resin, sebacic acid, adipic acid, (anhydrous) succinic acid and the like are used.

As the aromatic polycarboxylic acid used in the unsaturated polyester resin, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride and the like are used.

As the epoxy resin used for the epoxy acrylate (vinyl ester) resin, a bisphenol A type epoxy resin produced from epichlorohydrin and bisphenol A, epichlorohydrin and brominated bisphenol A are also produced by a known and conventional method. Brominated bisphenol A type epoxy resin produced, phenol novolac or novolac type epoxy resin produced by glycidyl etherification of orthocresol novolak, tetraglycidyl metaxylenediamine, tetraglycidyl 1 obtained by reacting various amines with epichlorohydrin .3-bisaminomethylcyclohexane, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl m- aminophenol, diglycidyl aniline, glycidyl amine compounds such as diglycidyl ortho-toluidine is used.

As the polyol used for the urethane acrylate resin, alkylene diols such as ethylene glycol, propylene glycol,
Diethylene glycol, diisopropylene glycol,
Polyethylene glycol, polypropylene glycol,
Polyoxymethylene, polyethylene oxide, polypropylene oxide, etc. as polyether polyols such as hydroxyalkyl ethers of butanediol, polyesters with hydroxyl groups at both ends manufactured by the above-mentioned organic polyols and polycarboxylic acids as polyester polyols. A polyol or the like is used.

As the polyisocyanate used in the urethane acrylate resin, tolylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate and the like are used.

The hydroxyalkyl (meth) acrylate used in the urethane acrylate resin is usually hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate or the like, and the hydroxyl group is usually It is bonded to the beta carbon of the alkyl group.
Alkyl groups can usually contain up to 8 carbon atoms.

The unsaturated silane coupling agent used in the present invention means a silane coupling agent having a reactive unsaturated bond, and generally has an alkoxyl group,
Known and conventional ones are used. Specifically, N- (3-
Acryloxy-2-hydroxypropyl) 3-aminopropyltriethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropenyltrimethoxy There are silane, 2-methacryloxyethyldimethyl [3-trimethoxysilylpropyl] ammonium chloride, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, trimethoxyvinylsilane, etc., and (meth) acryloyl group Those having are preferably used.

The unsaturated titanate coupling agent used in the present invention means a titanate coupling agent having a reactive unsaturated bond, and known and commonly used ones are used. For example, a (meth) acrylic acid derivative such as isopropyl trioctanoyl titanate and isopropyl isostearoyl diacrylic titanate, tetra (2.
Those having an allyl group such as 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate are used.

The unsaturated aluminum-based coupling agent used in the present invention means an aluminum-based coupling agent having a reactive unsaturated bond, specifically, ethyl acetoacetate aluminum diisopropylate, alkyl. Acetoacetate aluminum diisopropylate or the like is used.

The unsaturated alcohol used in the invention of claim 1 means a compound having a reactive unsaturated bond and a hydroxyl group, and any known and commonly used one can be used. That is, for example, allyl alcohol, 3 butene 1 ol, 3 butene 2 ol, 2 methyl 3 butene 1 ol, 3 methyl 2
Butene 1 ol, 3 Methyl 3 butene 1 ol, 1 Pentene 3 ol, 3 Pentene 2 ol, 4 Pentene 1 ol, 4 Pentene 2 ol, 1 Hexene 3 ol, 2 Hexene 1 ol, 4 Hexene 1 ol, 5 Hexene 1 ol 2 hydroxyethyl acrylate, 2 hydroxyethyl methacrylate, 2 hydroxypropyl acrylate, 2 hydroxypropyl methacrylate, 3 chloro 2
Hydroxypropyl methacrylate, 2hydroxy 1 acryloxy 3 methacryloxypropane, tetramethylolmethane triacrylate, 3-methyl-1-butyne-
There are 3-alls.

The unsaturated mercaptan used in the invention of claim 1 means a compound having a reactive unsaturated bond and a mercapto group, and any one produced by a known and commonly used method is used. For example, a method produced by reacting an acetylene compound and hydrogen sulfide, a method produced by reacting a halogenated alkene with an alkali hydrosulfide, and the like are known. Specifically, allyl thio alcohol, 2 methyl 2 propene 1 thiol, 1,1,
1 trifluoro 4 mercapto 4 (2 thienyl) but 3 ene 4 one and the like.

The above-mentioned unsaturated carboxylic acid means a compound having a carboxyl group and a reactive unsaturated bond, and an easily hydrated compound such as unsaturated carboxylic acid anhydride or unsaturated carboxylic acid metal salt, or water. It means a compound that can be ion-exchanged with a molecule or the like to form a carboxyl group.

As the compound having a carboxyl group and a reactive unsaturated bond, any conventionally known compound can be used. For example, acrylic acid, methacrylic acid, fumaric acid,
Examples thereof include maleic acid, itaconic acid, phthalic acid monohydroxyethyl acrylate, succinic acid monohydroxyethyl acrylate, phthalic acid monohydroxyethyl methacrylate, and succinic acid monohydroxyethyl methacrylate.

As the unsaturated carboxylic acid anhydride, any conventionally known one can be used. Examples include maleic anhydride and itaconic anhydride. As the unsaturated carboxylic acid metal salt, any conventionally known one can be used.
For example, specifically, metal (meth) acrylates of lithium, sodium, potassium, magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, copper, silver, zinc and aluminum,
Maleate, itaconic acid, etc. are mentioned.

The above-mentioned unsaturated sulfonic acid is a sulfone which is easily hydrated or ion-exchanged with a water molecule or the like such as a compound having a SOOH group and a reactive unsaturated bond, or a salt or an anhydride thereof. It means a compound that can be an acid group.

As the compound having a SOOH group and a reactive unsaturated bond, any conventionally known compound can be used. For example, there are para-styrene sulfonic acid, beta-styrene sulfonic acid, allyl sulfonic acid, 2 acrylamido 2-methylpropane sulfonic acid and the like.

As the above-mentioned unsaturated sulfonic acid metal salt, any conventionally known one can be used. For example, potassium parastyrene sulfonate, sodium parastyrene sulfonate, sodium beta styrene sulfonate, sodium allyl sulfonate, and sodium acrylamido 2-methylpropane sulfonate.

As the above-mentioned unsaturated sulfonic acid anhydride, any conventionally known one can be used. For example, there is allyl sulfonic anhydride. The above-mentioned unsaturated phosphoric acid is a phosphoric acid group which is easily hydrated or ion-exchanged with a water molecule or the like such as a compound having a POOH group and a reactive unsaturated bond and its metal salt or anhydride. Means a compound that can be

As the compound having the POOH group and the reactive unsaturated bond, the following compounds are used. For example, mono (2-acryloyloxyethyl) dihydrogen phosphate, mono (2-methacryloyloxyethyl) dihydrogen phosphate, di (2-acryloyloxyethyl) monohydrogen phosphate, di (2-methacryloyloxyethyl) mono Hydrogen phosphate, mono {5 carbonyloxy (2-acryloyloxyethyl) pentane} dihydrogen phosphate, mono {5 carbonyloxy (2
-Methacryloyloxyethyl) pentane} dihydrogen phosphate, di {5-carbonyloxy (2-
Acryloyloxyethyl) pentane} monohydrogen phosphate, di {5-carbonyloxy (2-acryloyloxyciethyl) pentane} monohydrogen phosphate, and the like.

The above-mentioned unsaturated phosphoric acid metal salt is
Known and conventional ones are used. For example, there are mono (2-acryloyloxyethyl) disodium phosphate, mono (2-methacryloyloxyethyl) dipotassium phosphate, and the like. As the unsaturated phosphoric acid anhydride, known and commonly used ones are used. For example, Mono (2
-Acryloyloxyethyl) dihydrogen phosphate anhydrous and the like.

The unsaturated glycidyl compound used in the invention described in claim 1 means a compound having a glycidyl group and a reactive unsaturated bond, and any compound produced by a known and commonly used method is used. For example, a method is known in which an unsaturated acid or an unsaturated alcohol is reacted with epichlorohydrin to remove hydrochloric acid. Specific examples include acrylates such as glycidyl acrylate and glycidyl methacrylate, and allyl compounds such as allyl glycidyl ether.

Further, as the molding material, an unsaturated silane coupling agent, a titanate coupling agent, an aluminum coupling agent, an unsaturated alcohol, an unsaturated mercaptan, an unsaturated carboxylic acid, an unsaturated sulfonic acid, an unsaturated phosphoric acid are used. When an unsaturated glycidyl compound is used, its amount is, as its sum, 0.1 to 70% by weight of the total resin component (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin) of the molding material. % Is preferred, more preferably 0.5
Is about 20% by weight. If the amount used is less than 0.1%, it is difficult to obtain a sufficient effect of improving the adhesion to the coating, and conversely 70
%, The viscosity of the composition becomes too low.
It tends to be difficult to form MC or BMC (solid state).

When an unsaturated alcohol, unsaturated mercaptan, unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid or unsaturated glycidyl compound is used for the coating material, the amount thereof is the sum thereof. 0.1 to 90% by weight, and more preferably 0.5 to 30% by weight, of the total resin content (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin) of the coating material is preferable. . If the amount used is 0.1% or less, it is difficult to obtain a sufficient effect of improving the adhesion to the molding material, and if it is 90% or more, the water resistance of the coating tends to deteriorate.

When an unsaturated silane coupling agent, an unsaturated titanate-based coupling agent, or an unsaturated aluminum-based coupling agent is used as the coating material, the amount thereof is, as its sum, the total resin content of the coating material. Of the (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin), 0.1 to 80% by weight is preferable, and 0.5 is more preferable.
~ 25% by weight. When the amount used is 0.1% or less, it is difficult to obtain a sufficient effect of improving the adhesiveness with the molding material. On the contrary, when the amount is 80% or more, the alcohol produced by hydrolysis easily remains in the coating film even after molding. Therefore, the hardness of the coating is likely to decrease.

As the epoxy compound having a plurality of glycidyl groups in the molecule (hereinafter, may be simply referred to as “epoxy”) used in the invention of claim 2, known and commonly used compounds are used. That is, a bisphenol A type epoxy resin produced from epichlorohydrin and bisphenol A, a brominated bisphenol A type epoxy resin produced from epichlorohydrin and brominated bisphenol A, a novolac type produced by converting phenol novolac or orthocresol novolak into glycidyl ether. Epoxy resin, obtained by reacting various amines with epichlorohydrin, tetraglycidyl metaxylenediamine, tetraglycidyl 1.3-bisaminomethylcyclohexane, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol,
Glycidyl amine compounds such as triglycidyl-m-aminophenol, diglycidyl aniline and diglycidyl orthotoluidine are used.

The polyisocyanate used in the invention of claim 2 means a compound having a plurality of isocyanate groups in the molecule, and known and commonly used ones are used. Specifically, namely, tolylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate,
Polymethylene polyphenyl diisocyanate, metaphenylene diisocyanate, 4,4 'diphenylmethane diisocyanate, 3,3' dichlorodiphenyl 4,4 '
Diisocyanate, meta-xylene diisocyanate, etc. can be used.

The polyol used in the invention of claim 2 is
Means a compound having a plurality of hydroxyl groups in the molecule, known and commonly used compounds are used, and specific examples include diols, triols, tetraols and mixtures thereof, but mainly in aliphatic polyols and aromatic polyols. Of these, typical ones of the aliphatic polyols include ethylene glycol, propylene glycol,
Dipropylene glycol, butylene glycol, triethylene glycol, neopentyl glycol, dibromoneopentyl glycol, hexamethylene glycol,
There are trimethylene glycol, trimethylolpropane, glycerin, pentaerythrite diallyl ether, hydrogenated bisphenol A, etc., and typical aromatic polyols are bisphenol A or bisphenol S, or bisphenol A or bisphenol S thereof with ethylene oxide. Polyoxyalkylene bisphenol A obtained by adding an aliphatic oxirane compound such as propylene oxide or butylene oxide in the range of 1 to 20 on average in one molecule.
Alternatively, there is polyoxyalkylene bisphenol S or the like.

The polymercaptan used in the invention of claim 2 means a compound having a plurality of mercapto groups in the molecule, and known and conventional ones are used. For example, 1,2-propanedithiol, 1,3-propanedithiol, 1,
4 butanedithiol, 1,6 hexanedithiol, 1,
10 Decanedithiol, 2,3 mercapto-1-propanol, di (2-mercaptoethyl) ether, pentaerythritol tetra (mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate) and the like.

When epoxy, polyisocyanate, polyol, or polymercaptan is used as the molding material, the total amount thereof is the total resin component (thermosetting resin, copolymerizable monomer, thermosetting resin) of the molding material. The total amount of the plastic resin) is preferably 0.1 to 20% by weight, more preferably 1 to 12% by weight. The amount used is 0.1%
In the following cases, it is difficult to obtain a sufficient effect of improving the adhesiveness with the coating film, and conversely, in the case of 20% or more, it is difficult to form SMC or BMC (solid state) because the viscosity of the composition becomes too low. Tend to be next door.

When epoxy, polyisocyanate, polyol, or polymercaptan is used for the coating material, the total amount thereof is the total resin component (thermosetting resin, copolymerizable monomer, heat-resistant monomer) of the coating material. The total amount of the plastic resin) is preferably 0.1 to 20% by weight, more preferably 1 to 12% by weight. The amount used is 0.1%
In the following cases, it is difficult to obtain a sufficient effect of improving the adhesiveness with the molding material, and conversely, in the case of 20% or more, the water resistance of the coating tends to deteriorate.

In the molding material and the coating material used in the present invention, polyvinyl acetate, polymethyl (meth) acrylate, polyethylene, ethylene vinyl acetate copolymer, vinyl acetate-styrene copolymer, polybutadiene are used as a low-shrinking agent. Thermoplastic resins such as saturated polyesters, saturated polyethers, etc. can be used in appropriate amounts as necessary.

Further, to the molding material and the coating material used in the present invention, an appropriate amount of inorganic filler can be added depending on the purpose and application. As usable inorganic fillers,
There are the following. That is, elemental minerals such as sulfur, graphite and diamond, sulfide minerals such as pyrite, halogenated minerals such as rock salt and potassium rock salt, carbonate minerals such as calcium carbonate, phosphate minerals such as cyanite, vanadium such as carnotite. Sulfate minerals, barite (barium sulfate), gypsum (calcium sulfate) and other sulfate minerals, borax and other borate minerals, perovskite and other titanate minerals, mica, talc (talc) and leaf wax. Silicate minerals such as stones, kaolin, quartz and feldspar, metals such as titanium oxide, corundum (aluminum oxide) and aluminum hydroxide (water)
Natural or artificial minerals centered on oxides, glass products such as (hollow) glass spheres, and the like, processed, purified or processed products thereof, and mixtures thereof are used.

The amount of the filler used in the molding material is 0 to 300 with respect to 100 parts by weight of the resin component (total amount of thermosetting resin, thermoplastic resin and copolymerizable monomer).
It is preferably added in parts by weight. If the amount added exceeds 300 parts, it will be difficult to uniformly disperse the filler in the resin and the monomer, and the viscosity will become too high, so that the fluidity in the mold will deteriorate and dimensional stability will be obtained. Becomes difficult.

The amount of the above filler used for the coating material is 0 to 150 with respect to 100 parts by weight of the resin component (total amount of thermosetting resin, thermoplastic resin and copolymerizable monomer).
It is preferably added in parts by weight. If the amount added exceeds 150 parts, the viscosity becomes too high and the flow in the mold deteriorates, making it difficult to spread it over the entire surface of the molding material.

Various reinforcing fibers, that is, glass fibers, carbon fibers and the like can be added to the molding material and the coating material as a reinforcing agent, if necessary.

Further, if necessary, the molding material and the coating material may include copolymerizable monomers such as styrene, alphamethylstyrene, divinylbenzene, vinyltoluene, diallylphthalate, various acrylate monomers, and various methacrylate monomers. Known initiators such as ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, alkyl peresters, percarbonates and peroxyketals, known initiators such as dimethylaniline and cobalt naphthenate Curing accelerators, polymerization inhibitors such as parabenzoquinone, carbon black and titanium oxide, iron oxide, cyanine pigments, aluminum flakes, nickel powder, gold powder, silver powder and other pigments, azo dyes and anthraquinone pigments,
Indigoid-based, stilbene-based dyes, conductivity-imparting agents such as carbon black, emulsifiers, metal soaps such as zinc stearate, aliphatic phosphates, release agents such as lecithin, etc. Can be added.

The molding material used in the present invention is a molding material having the form of SMC or BMC by a conventionally known method using the above-mentioned compounded material.

Specifically, for example, a styrene solution of an unsaturated polyester resin (styrene concentration 40 to 70%) 50 to
With respect to 99 parts by weight, 0 to 30 parts of a styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, or polyvinyl acetate (styrene concentration 30 to 80%), unsaturated alcohol, unsaturated mercaptan, unsaturated carboxylic acid, 1 to 20 parts of unsaturated sulfonic acid and unsaturated phosphoric acid are added to make 100 parts, 100 to 300 parts of filler powder such as calcium carbonate and aluminum hydroxide, 0.1 to 3 parts of thickening agent such as magnesium oxide, A solid molding material prepared by adding 0.1 to 5 parts of an organic peroxide as an initiator and thoroughly kneading, and impregnating 1 to 200 parts of reinforcing fibers such as glass fibers with a kneading machine or an impregnating machine. However, since they are excellent in moldability, handleability, and physical properties of molded products, they are preferably used.

The coating material used in the present invention is kneaded into a liquid coating material using the above-mentioned compounded material by a conventionally known method.

Specifically, for example, 60 to 99 parts of a styrene solution of an epoxy acrylate resin or a urethane acrylate resin (styrene concentration 40 to 70%) is added to a thermoplastic resin such as polymethyl methacrylate, polystyrene or polyvinyl acetate. 0-30 parts polystyrene solution (styrene concentration 30-80%), unsaturated silane coupling agent, unsaturated titanate coupling agent, unsaturated aluminum coupling agent, unsaturated alcohol, unsaturated mercaptan, unsaturated carvone Acid, unsaturated sulfonic acid, 1 to 20 parts of unsaturated phosphoric acid is added to make 100 parts, and 10 to 150 parts of filler powder such as calcium carbonate and barium sulfate.
A mixture of 0.1 to 3 parts of an internal release agent such as zinc stearate and 0.1 to 5 parts of an organic peroxide as an initiator and well kneaded has excellent moldability, handleability, and physical properties of the molded product. Therefore, it is preferably used.

The molding material and coating material thus obtained can be used for conventionally known in-mold coating molding. For example, the SMC is put in a molding die heated to 130 to 160 ° C. and the pressure is set to 40 to 120 kg / cm ^{2 at} a pressure of 30.
After pressing for 5 seconds to 5 minutes, the mold is opened slightly to inject the coating material, and then 5 to 120 kg / cm ² , 130 to
Spreading the coating material over the entire surface of the molded SMC by reheating and repressurizing at 160 ° C. for 30 seconds to 5 minutes,
There is a method of curing to form a film.

Further, it is disclosed in Japanese Patent Publication No. 4-33252.
So that SMC at 130-160 ° C, 40-120k
g / cm²After pressure molding for several tens of seconds to several minutes, the pressure is adjusted to 10
~ 30 kg / cm²Use a high-pressure injection machine with the pressure reduced to
100-300 kg / cm ²High pressure of coating material in the mold
And inject again into 30 to 100 kg / cm²Increase pressure to cover
There is also a method of spreading and hardening the material,
The coating material and the molding material which are the features of the present invention are used in the coating method.
If a covering material is used, it is easy to improve the adhesion between the film and the molding material.
A good coating can be formed.

[0058]

According to the thermosetting resin composition of the invention described in claim 1, one of the thermosetting resin compositions constituting the molding material and the coating material is provided with an unsaturated silane coupling agent or an unsaturated titanate-based coupling agent. Agent, or unsaturated aluminum-based coupling agent is contained, and on the other hand, unsaturated silane coupling agent, unsaturated titanate-based coupling agent, unsaturated aluminum-based coupling agent, unsaturated alcohol, unsaturated Mercaptan, unsaturated carboxylic acid,
It contains an unsaturated sulfonic acid, an unsaturated phosphoric acid, or an unsaturated glycidyl compound.

When an unsaturated silane coupling agent, an unsaturated titanate coupling agent or an unsaturated aluminum coupling agent is contained in the molding material,
At the time of pressure molding, these reactive unsaturated bonds undergo a copolymerization reaction with the thermosetting resin composition, and the alkoxyl groups are hydrolyzed to give SiOH groups, TiOH groups, or AlOH groups on the surface. This is an unsaturated silane coupling agent contained in the coating material and copolymerized at the time of molding, an unsaturated titanate coupling agent, an unsaturated aluminum coupling agent, an unsaturated alcohol, an unsaturated mercaptan, an unsaturated carboxylic acid, SiOH group, TiOOH group, AlOH group in or formed of unsaturated sulfonic acid, unsaturated phosphoric acid or unsaturated glycidyl compound,
OH group, SH group, COOH group, SOOH group, POOH
It has a function of reacting with a group or a glycidyl group to form a chemical bond as shown in the following formula, and by this chemical bond, the adhesion between the molding material and the coating film can be improved.

[0060]

[Chemical 1]

[0061]

[Chemical 2]

[0062]

[Chemical 3]

[0063]

[Chemical 4]

[0064]

[Chemical 5]

[0065]

[Chemical 6]

In the above chemical reaction formulas (formula 1 to formula 6),
The substituent R has the following meaning. (R ^{1 to} R ⁹ , R ¹³ to
^{R 15, R 21 ~R 23,} R 37 ~R 39, R 49 ~R 51, R
^{53 ~ 55, R 71 ~ 73} , R 82 ~R 84, R 94 ~R 96: unsaturated silane coupling agent residue ^{R 10 ~R 12, R 18 ~R} 20, R 24 ~R 32, R 42 ~ R ⁴⁴ , R
^{57 to} R ⁵⁹ , R ^{61 to} R ⁶³ , R ^{75 to} R ⁷⁷ , R ^{86 to} R ⁸⁸ , R ⁹⁸
To R ^100: unsaturated titanate coupling agent residue ^{R 16 ~ 17, R 33 ~R} 36, R 40 ~R 41, R 45 ~R 48, R 65
To R ⁶⁶ , R ^{68 to} R ⁶⁹ , R ^{79 to} R ⁸⁰ , R ^{90 to} R ⁹¹ , R
¹⁰² to R ^103: Unsaturated aluminum coupling agent residue ^{R 52, R 60, R 67} : an unsaturated alcohol residues ^{R 56, R 64, R 70} : unsaturated mercaptan residue R ^74, R ^78, R ⁸¹ : Unsaturated carboxylic acid residue R ⁸⁵ , R ⁸⁹ , R ⁹² : unsaturated sulfonic acid residue R ⁹⁷ , R ¹⁰¹ , R ¹⁰⁴ : unsaturated phosphoric acid residue)

[0067]

[Chemical 7]

In the above chemical reaction formula (Formula 7), the substituent R has the following meaning. ^{(R 3, R 7, R} 11: an unsaturated glycidyl compound residue R ⁴ to R ^6: unsaturated silane coupling agent residue R ⁸ to R ^10: unsaturated titanate coupling agent residue R ¹² to R ¹³ : Unsaturated aluminum coupling agent residue)

When an unsaturated alcohol, an unsaturated mercaptan, an unsaturated carboxylic acid, an unsaturated sulfonic acid, an unsaturated phosphoric acid or an unsaturated glycidyl compound is contained in the molding material, these are not pressed during the pressure molding. The reactive unsaturated bond of causes a copolymerization reaction with the thermosetting resin composition,
OH group, SH group, COOH group, SOOH group, PO on the surface
OH group or glycidyl group is released. This is because the unsaturated silane coupling agent, unsaturated titanate-based coupling agent, or unsaturated aluminum-based coupling agent that is contained in the coating material and copolymerizes at the time of molding has an alkoxyl group (which most coupling agents have). It has a function of reacting with a SiOH group, a TiOH group, or an AlOH group generated by hydrolysis to form a chemical bond as shown in the following formula,
This chemical bond can improve the adhesion between the molding material and the coating.

[0070]

[Chemical 8]

[0071]

[Chemical 9]

In the above chemical reaction formulas (formula 8 and formula 9),
And the substituent R has the following meaning. (R⁷²~ R⁷⁴, R
⁷⁶~ R⁷⁸, R¹⁰⁶~ R¹⁰⁸, R¹¹⁰~ R¹¹²,
R¹²⁸ ~ R¹³⁰ , R¹³⁹~ R¹⁴¹, R¹⁵⁰~ R
¹⁵²: Unsaturated silane coupling agent residue R⁸⁰~ R⁸², R⁸⁴~ R⁸⁶, R¹¹⁴~ R¹¹⁶, R
¹¹⁸~ R¹²⁰, R¹³² ~ R¹³⁴ , R¹⁴³~ R
¹⁴⁵, R¹⁵⁴~ R¹⁵⁶: Unsaturated titanate cup
Pulling agent residue R⁸⁸~ R⁸⁹, R⁹¹~ R⁹², R¹²²
~ R¹²³, R¹²⁵~ R¹²⁶, R¹³⁶~ R¹³⁷,
R¹⁴⁷~ R¹⁴⁸, R¹⁵⁸~ R¹⁵⁹: Unsaturated aluminum type
Residue of pulling agent R¹⁰⁵, R¹¹³, R¹²¹: Unsaturated Al
Cole residue R¹⁰⁹, R¹¹⁷, R¹²⁴: Unsaturated mercaptan residue R¹²⁷, R¹³¹, R¹³⁵: Unsaturated carboxylic acid residue R¹³⁴, R¹³⁸, R¹⁴²: Unsaturated sulfonic acid residue R¹⁴⁹, R¹⁵³, R¹⁵⁷: Unsaturated phosphate residue)

[0073]

[Chemical 10]

In the above chemical reaction formula (Formula 10), the substituent R has the following meaning. (R ¹⁹ , R ²³ , R ²⁶ : unsaturated glycidyl compound residue R ^{16 to} R ¹⁸ : unsaturated silane coupling agent residue R ^{20 to} R ²² : unsaturated titanate coupling agent residue R ^{24 to} R ²⁵ : Unsaturated aluminum coupling agent residue)

In the thermosetting resin composition of the second aspect of the present invention, one of the thermosetting resin composition constituting the molding material and the coating material contains epoxy, polyisocyanate, polyol or polymercaptan. On the other hand, an unsaturated silane coupling agent, an unsaturated titanate coupling agent, or an unsaturated aluminum coupling agent is contained in the other.

When the molding material contains epoxy, polyisocyanate, polyol, or polymercaptan, these compounds release glycidyl groups, isocyanate groups, hydroxyl groups, and mercapto groups on the surface of the molding material during pressure molding. This is because the alkoxyl group (which most coupling agents have) is hydrolyzed from unsaturated silane coupling agents, unsaturated titanate coupling agents, or aluminum coupling agents that are contained in the coating material and copolymerize during molding. Is removed and SiOH appears on the surface
A strong cured resin layer at the interface between the molding material and the coating material by reacting with the base, the TiOH group, and the AlOH group as shown in the following formula (It is presumed that they intrude into each other's crosslinked structure and are entangled with each other) It has a function of forming a resin, which improves the adhesion between the molding material and the coating.

[0077]

[Chemical 11]

[0078]

[Chemical 12]

[0079]

[Chemical 13]

[0080]

[Chemical 14] In the above chemical reaction formulas (Formula 11 to Formula 14), the substituent R
Has the following meaning: ^{(R 2 ~R 4, R 6} ~R 8, R 10 ~R 12, R 14 ~R 16:
Unsaturated silane coupling agent residue ^{R 18 ~R 20, R 22 ~R} 24, R 26 ~R 28, R 30 ~R 32: unsaturated titanate coupling agent residue ^{R 34, R 35, R 37} , R ³⁸ , R ⁴⁰ , R ⁴¹ , R ⁴³ , R ⁴⁴ : Unsaturated aluminum coupling agent residue R ¹ , R ¹⁷ , R ³³ : Epoxy residue R ⁵ , R ²¹ , R ³⁶ : Polyisocyanate residue R ⁹ , R ²⁵ , R ³⁹ : Polyol residue R ¹³ , R ²⁹ , R ⁴² : Polymercaptan residue)

When an unsaturated silane coupling agent, an unsaturated titanate type coupling agent or an unsaturated aluminum type coupling agent is used as the molding material, these reactive unsaturated bonds are not formed during pressure molding. It undergoes a copolymerization reaction with the thermosetting resin composition, and the alkoxyl group is hydrolyzed to expose a SiOH group, a TiOH group, or an AlOH group on the surface. This is the glycidyl group, isocyanate group, OH of the epoxy, polyisocyanate, polyol, or polymercaptan contained in the coating material.
It has the function of forming a cured resin layer such as IPN at the interface between the molding material and the coating material by reacting with the base and the mercapto group as in the following formula, thereby improving the adhesion between the molding material and the coating. can do.

[0082]

[Chemical 15]

[0083]

[Chemical 16]

[0084]

[Chemical 17]

[0085]

[Chemical 18]

In the above chemical reaction formulas (Formulas 15 to 18), the substituent R has the following meaning. (R ^{45 to} R ⁴⁷ , R ^{49 to} R ⁵¹ , R ^{53 to} R ⁵⁵ , R ^{57 to} R ⁵⁹ :
Unsaturated silane coupling agent residues R ^{61 to} R ⁶³ , R ^{65 to} R ⁶⁷ , R ^{69 to} R ⁷¹ , R ^{73 to} R ⁷⁵ : Unsaturated titanate coupling agent residues R ^{77 to} R ⁷⁸ , R ⁸⁰ to R ⁸¹ , R ^{83 to} R ⁸⁴ , R ^{86 to} R ⁸⁷ : Unsaturated aluminum coupling agent residue R ⁴⁸ , R ⁶⁴ , R ⁷⁹ : Epoxy residue, R ⁵² , R ⁶⁸ , R ⁸² :
Polyisocyanate residue R ⁵⁶ , R ⁷² , R ⁸⁵ : Polyol residue, R ⁶⁰ , R ⁷⁶ ,
R ⁸⁸ : polymercaptan residue)

[0087]

EXAMPLES Examples of the present invention will be described below. [Preparation of Materials] The following materials were used as compounding materials.

1. Unsaturated polyester resin liquid 5 mol of isophthalic acid, 5 mol of maleic acid and 10 mol of propylene glycol were condensed by a conventionally known method to obtain an unsaturated polyester resin (molecular weight: about 1000). This was dissolved in styrene monomer to obtain an unsaturated polyester resin liquid. (Styrene content about 40% by weight, UP, UP
Abbreviated)

2. Polystyrene-based low-shrinking agent resin solution (polystyrene resin approximately 30 wt%, styrene monomer approximately 70 wt%
%, Hereinafter abbreviated as LPA) 3.3 Methacryloxypropyltrimethoxysilane (manufactured by Toray Dow Corning Silicone Co., Ltd., hereinafter M
(Abbreviated as PTMS)

4. 4. Vinyltrimethoxysilane (manufactured by Toray Dow Corning Silicone Co., Ltd., hereinafter abbreviated as VTMS) 5. Isopropyl isostearoyl diacrylic titanate (KR-11: Ajinomoto Co., Inc., abbreviated as TC hereinafter)

6. Alkyl acetoacetate aluminum diisopropylate (Planeact AL-M: Ajinomoto Co., Inc., existing chemical substance number 9-2000, hereinafter, A
Abbreviated as LC) 7.2 hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as HEMA)

8. Allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AA) 9. Allyl thioalcohol (manufactured by Wako Pure Chemical Industries,
Hereinafter referred to as ATA) 10. Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.,
(Abbreviated as MA) 11. Maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AMA) 12. Allyl sulfonic acid (Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as ASA)

13. 14. Parastyrene sulfonate potassium (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as SSA) 14. Mono (2-acryloyloxyethyl) dihydrogen phosphate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AEHP)

15. Epoxy resin 1 (XAC5020,
15. Bisphenol A type epoxy resin, manufactured by Ciba-Geigy Co., Ltd., hereinafter abbreviated as EP1) 16. Epoxy resin 2 (EPN1139, phenol novolac type epoxy resin, manufactured by Nippon Ciba-Geigy Co., Ltd., hereinafter abbreviated as EP2) 17. Tolylene diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as TDI)

18. Hexamethylene diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as HDI) 19. Propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as PPG) 20. Bisphenol A (Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as BPA) 21.1,2 Propanedithiol (Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as PDT)

22.1,6 Hexanedithiol (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as HDT) 23. Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as GMA) 24. Allyl glycidyl ether (Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AG)

25. Calcium carbonate powder (NS-10
0: Nitto Koka Kogyo Co., Ltd., hereinafter abbreviated as charcoal) 26. Curing agent (Kayabutyl B: Kayaku Akzo, tertiary butyl peroxobenzoate content 98 wt%)

27. Thickener (magnesium oxide powder, Kyowamag 150: Kyowa Chemical Industry Co., Ltd.) 28. Glass fiber (Roving made by Asahi Fiber Glass Co., Ltd .: ER4630LBD166W cut into a length of 25 mm, hereinafter abbreviated as GF)

[Manufacture of molding material] Of these materials,
Mixing ingredients other than glass fiber according to the following recipe,
After sufficiently stirring, the glass fiber was impregnated with an SMC impregnation device to obtain SMC.

[Production of Coating Material] The above-mentioned compounded materials were mixed and sufficiently kneaded according to the following compounding table to obtain a coating material.

[Molding] The SMC and the coating material thus obtained were molded as follows. 150 upper mold
Approximately 700 g of the above SMC was charged in a die of a square plate of 30 cm × 30 cm in which the lower die was heated to 150 ° C. and 100 kg / (which corresponds to a thickness of about 4 mm).
After pressure molding at a pressure of cm ² for 100 seconds, the mold is slightly opened, 10 ml of the above coating material is injected, the mold is closed again, and the mold is reheated and repressurized at 80 kg / cm ² for 120 seconds to mold. The coating material was spread over the entire surface of the SMC and cured to form a film. After that, the mold was opened and the mold was removed to obtain a molded product whose surface was covered with a film having a thickness of about 100 μm.

[Evaluation] On the surface of the molded product thus obtained, a straight line reaching 11 substrates at 2 mm intervals was drawn on the surface of the molded product, and further 11 straight lines were drawn perpendicular thereto. An adhesive tape (Cellotape manufactured by Sekisui Chemical Co., Ltd.) was attached to the eye-shaped portion and then peeled off, and the number of remaining squares of the squares was examined (cross-grid adhesion test).

From the obtained molded product, 10 cm × 10
cm test piece is cut out, and in a programmable oven, 80 ° C for 5 hours → 23 ° C for 1 hour → -30 ° C for 5 hours → 2
Repeat the cold heat repeated test of 3 ℃ for 1 hour → 80 ℃ →
The cycle was repeated continuously. A cross-cut adhesion test was performed on the test piece after the completion of the cold heat repetition test. The following table shows the adhesion data obtained in the above manner and after the repeated heat and cold test.

Example I series Examples and comparative examples of the invention of claim 1 are shown below. (Examples I-1 to 59) According to Tables 1 to 6, the molding material and the coating material were blended, and molding and evaluation were performed by the above-mentioned method. The results are shown in Tables 1-6. The adhesiveness was good both in the initial stage and after the cold and heat repeated test.

Comparative Examples I-1 to 30 According to Tables 7 to 9,
The molding material and the coating material were blended, and molding and evaluation were performed by the above-mentioned method. The results are shown in Tables 7-9. The adhesiveness was good in the initial stage, but was poor after the cold heat repeating test.

(Comparative Example I-31) According to Table 9, the molding material and the coating material were blended, and molding and evaluation were carried out by the above-mentioned method. The results are shown in Table 9. The adhesiveness was poor both in the initial stage and after the cold and heat repeated test.

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

[Table 3]

[0110]

[Table 4]

[0111]

[Table 5]

[0112]

[Table 6]

[0113]

[Table 7]

[0114]

[Table 8]

[0115]

[Table 9]

Example II series Examples and comparative examples of the invention of claim 2 are shown below. (Examples II-1 to 24) According to Tables 10 to 12, the molding material and the coating material were blended, and molding and evaluation were performed by the above-mentioned method. The results are shown in Tables 10-12. Adhesion is
It was good both in the initial stage and after the thermal cycling test.

Comparative Examples II-1 to 16 According to Tables 13 and 14, the molding material and the coating material were blended, and molding and evaluation were carried out by the above-mentioned method. The results are shown in Tables 13 and 14. The adhesiveness was good in the initial stage, but was poor after the cold heat repeating test.

[0118]

[Table 10]

[0119]

[Table 11]

[0120]

[Table 12]

[0121]

[Table 13]

[0122]

[Table 14]

UP: Unsaturated polyester resin liquid LPA: Polystyrene type low-shrinking agent resin liquid MPTMS: 3 Methacryloxypropyltrimethoxysilane VTMS: Vinyltrimethoxysilane TC: Isopropylisostearoyldiacryl titanate

ALC: Alkyl acetoacetate aluminum diisopropylate HEMA: 2 Hydroxyethyl methacrylate AA: Allyl alcohol ATA: Allyl thioalcohol

MA: Methacrylic acid AMA: Maleic anhydride ASA: Allylsulfonic acid SSA: Potassium parastyrene sulfonate

AEHP: mono (2-acryloyloxyethyl) dihydrogen phosphate EP1: epoxy resin 1 EP2: epoxy resin 2 TDI: tolylene diisocyanate

HDI: hexamethylene diisocyanate PPG: propylene glycol BPA: bisphenol A PDT: 1,2 propanedithiol HDT: 1,6 hexanedithiol

GMA: Glycidyl Methacrylate AG: Allyl Glycidyl Ether Carbon Char: Calcium Carbonate Powder GF: Glass Fiber

[0129]

According to the invention of claim 1, the unsaturated silane coupling agent and the unsaturated aluminum-based cup contained in either of the two thermosetting resin compositions of the molding material and the coating material. Ring agents, unsaturated titanate coupling agents, unsaturated alcohols, unsaturated mercaptans, unsaturated carboxylic acids, unsaturated sulfonic acids, unsaturated phosphoric acids, unsaturated glycidyl compounds are reactive unsaturated bonds during pressure molding. Undergoes a copolymerization reaction with the thermosetting resin composition, and a SiOH group, a TiOH group, an AlOH group, a hydroxyl group, a mercapto group, a carboxyl group, a SOOH group, a POOH group,
Alternatively, the glycidyl group is introduced. This is an unsaturated silane coupling agent copolymerized in the other thermosetting resin composition, an unsaturated aluminum coupling agent, an SiOH group of an unsaturated titanate coupling agent, a TiOH group,
It has the function of reacting with AlOH groups to form chemical bonds,
By this chemical bond, the adhesiveness between the molding material and the coating can be improved, and sufficient adhesiveness can be maintained even after severe environmental changes such as repeated cold and heat.

According to the invention of claim 2, an unsaturated silane coupling agent or an unsaturated titanate-based coupling agent contained in either of the two thermosetting resin compositions of the molding material and the coating material. Alternatively, the unsaturated aluminum-based coupling agent causes a reactive unsaturated bond to undergo a copolymerization reaction with the thermosetting resin composition during pressure molding, resulting in SiOH on the surface.
Groups, TiOH groups, or AlOH groups. This is the epoxy contained in the other thermosetting resin composition,
Polyisocyanate, polyol, glycidyl group of polymercaptan, isocyanate group, hydroxyl group, having a function of reacting with a mercapto group to form a strong cured resin layer at the interface between the molding material and the coating material, and by this,
The adhesiveness between the molding material and the coating can be improved, and sufficient adhesiveness can be maintained even after severe environmental changes such as repeated cold and heat.

Claims (3)

[Claims] 1. A thermosetting resin composition for use in an in-mold coating molding method, comprising coating a thermosetting coating material on a thermosetting molding material in a mold to form a coating layer. One of the curable molding material and the thermosetting coating material,
A thermosetting resin composition, containing at least one of an unsaturated silane coupling agent, an unsaturated titanate-based coupling agent, and an unsaturated aluminum-based coupling agent, and the other is A thermosetting resin,
Unsaturated silane coupling agent, unsaturated titanate coupling agent, unsaturated aluminum coupling agent, unsaturated alcohol, unsaturated mercaptan, unsaturated carboxylic acid (including salt and anhydride), unsaturated sulfonic acid (salt , An anhydride), an unsaturated phosphoric acid (including a salt and an anhydride), and an unsaturated glycidyl compound, which is a thermosetting resin composition containing at least one kind. Thermosetting resin composition for molding. 2. A thermosetting resin composition for use in an in-mold coating molding method, which comprises coating a thermosetting coating material on a thermosetting molding material in a mold to form a coating layer. One of the curable molding material and the thermosetting coating material,
A thermosetting resin composition, containing at least one of an unsaturated silane coupling agent, an unsaturated titanate-based coupling agent, and an unsaturated aluminum-based coupling agent, and the other is A thermosetting resin,
Polyisocyanate, polyol, polymercaptan,
And a thermosetting resin composition containing at least one of epoxy compounds having a plurality of glycidyl groups, a thermosetting resin composition for in-mold coating molding. 3. A method of injecting a coating material made of a thermosetting resin composition into a mold to coat the molding material when molding a molding material made of the thermosetting resin composition in a mold, An in-mold coating molding method, wherein the thermosetting molding material and the thermosetting coating material according to claim 1 or 2 are used as the curable molding material and the thermosetting coating material.