JPH069751A - Resin composition for in-mold coating molding and process for in-mold coating molding - Google Patents

Abstract

PURPOSE:To obtain a coated molding good in adhesion of the coating layer in an in-mold coating molding process. CONSTITUTION:The resin composition for in-mold coating molding molding material and a thermosetting coating material one of which is a thermosetting resin composition comprising a thermosetting resin and an unsaturated isocyanate or an unsaturated isothiocyanate, and the other of which comprises a thermosetting resin and at least one member selected from among a compound containing a copolymerizable double bond and a hydroxyl group in the molecule, an unsaturated carboxylic acid, an unsaturated sulfonic acid, an unsaturated phosphoric acid and an unsaturated mercaptan.

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 mold, and in particular, adhesion between the molding material and the coating layer. TECHNICAL FIELD The present invention relates to a thermosetting resin composition that makes it possible 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 In recent years, molded products made of thermosetting molding materials have been widely used as industrial parts and the like as substitute members for metal parts and the like. As the thermosetting molding material, a sheet
Molding compound (hereinafter abbreviated as SMC)
Or bulk molding compound (hereinafter,
BMC is abbreviated). However, S
In the molded product obtained by heating and press-molding MC or BMC in a mold, 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 coating film having sufficient adhesion and surface properties 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 Patent Application Laid-Open No. 53-71167 discloses a method of forming a coating layer on a molded article by heating and pressurizing the SMC in the mold to semi-cure the SMC, then opening the mold and injecting the coating material. It is disclosed. On the other hand, JP-A-61-273
No. 921 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 during compression molding and curing the material.

[0004]

However, the in-mold coating molding method described in the above-mentioned prior art has a problem that the adhesion to the coating layer is not sufficient. An object of the present invention is to provide a resin composition for in-mold coating molding and a coating molding method using the same in the above-mentioned in-mold coating molding method, which makes it possible to obtain a coated molded article having good coating layer adhesion. To provide.

[0005]

The invention according to claim 1 is an in-mold coating in which a thermosetting coating material is coated on a substrate made of a thermosetting molding material in a die to form a coating layer. A thermosetting resin composition used in a molding method, wherein one of the thermosetting molding material and the thermosetting coating material is a thermosetting resin and an unsaturated isocyanate (reactive unsaturated bond and an isocyanate group. A compound having a thermosetting resin) or an unsaturated isothiocyanate (a compound having a reactive unsaturated bond and an isothiocyanate group), and the other is a thermosetting resin and a reactive non-reactive compound in the molecule. It is a thermosetting resin composition containing a compound having a saturated bond and a hydroxyl group, which is a thermosetting resin composition for in-mold coating molding.

As the compound having a reactive unsaturated bond and a hydroxyl group used in the invention described in claim 1, not only an unsaturated compound having an actual hydroxyl group such as unsaturated alcohol but also further hydrolyzed OH
An unsaturated compound or the like that has a group is also included.

Examples of the unsaturated compound having an OH group by hydrolysis include an unsaturated silane coupling agent, an unsaturated titanate coupling agent, and an unsaturated aluminum coupling agent. Usually, those having an alkoxyl group are used.

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. In the above, one of the thermosetting molding material and the thermosetting coating material is a thermosetting resin and a thermosetting resin composition containing unsaturated isocyanate or unsaturated isothiocyanate, and the other is An in-mold coating, which is a thermosetting resin composition containing a thermosetting resin and at least one of unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid, and unsaturated mercaptan. It is a thermosetting resin composition for molding.

According to the third aspect of the present invention, a molding material made of a thermosetting resin composition is heated and pressed in a mold, and a coating material made of the thermosetting resin composition is injected into the mold to form a molding material. In the molding method for coating, the thermosetting molding material and the thermosetting coating material according to claim 1 or 2 are used as the thermosetting molding material and the thermosetting coating material, respectively. Is.

The details of the structure of each of the inventions described in claims 1 to 3 (hereinafter, "the present invention" simply means each invention described in claims 1 to 3) will be described.

Unsaturated Isocyanate The unsaturated isocyanate used in the present invention is obtained by reacting an alkali metal isocyanic acid salt with an alkenyl halide by a known and commonly used method. Specific examples of unsaturated isocyanates include allyl isocyanate, 1-butene 3 isocyanate, 2 methyl propene 3
Isocyanate and the like can be mentioned. The unsaturated isocyanate can also be synthesized by an addition reaction of unsaturated alcohol and polyisocyanate.

Unsaturated Isothiocyanate The unsaturated isothiocyanate used in the present invention is produced by reacting an alkali metal salt of isothiocyanate with an alkenyl halide by a known method. Specific examples of unsaturated isothiocyanates include allyl isothiocyanate, 1
Butene 3 isothiocyanate, 2 methyl propene 3 isothiocyanate, etc. are mentioned. The unsaturated isothiocyanate can also be synthesized by an addition reaction of an unsaturated alcohol and polyisothiocyanate.

Unsaturated isocyanate and unsaturated isothio
Cyanate compounding amount In the present invention, the unsaturated isocyanate and / or
Alternatively, unsaturated isothiocyanate is blended with the thermosetting resin composition for forming the molding material or the coating layer.

When blended in a base material, that is, a thermosetting molding material, this blending ratio is the total resin content (thermosetting resin and the below-mentioned thermosetting resin composition constituting the thermosetting molding material. Total amount of copolymerizable monomer and thermoplastic resin)
Of these, 0.1 to 70% by weight is preferable. 0.
If it is less than 1% by weight, it is difficult to obtain the effect of improving the adhesiveness with the coating layer. On the contrary, if it is compounded in an amount of more than 70% by weight, the viscosity of the thermosetting resin composition becomes too low, resulting in SMC This is because it is difficult to form the BMC (that is, solid).

On the other hand, when blended in the coating layer, that is, the thermosetting coating material, this blending ratio is such that the total resin content (thermosetting resin, as well as the thermosetting resin, which will be described later) of the thermosetting resin composition constituting the thermosetting coating material. 0.1 to 90% by weight of the total amount of the copolymerizable monomer and the thermoplastic resin). 0.1
If the amount is less than 10% by weight, it is difficult to obtain the effect of improving the adhesion to the base material. On the contrary, if the amount is more than 90% by weight, the chemical resistance and water resistance of the coating layer are likely to deteriorate. Because it will be.

Other Unsaturated Components As the unsaturated alcohol used in the invention described in claim 1, any unsaturated alcohol having a reactive unsaturated bond and a hydroxyl group can be used.

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 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, 2 hydroxy 1 acryloxy 3 methacryloxypropane, tetramethylol methanetri Acrylate, 3 methyl-1-butyn-3-ol and the like can be mentioned.

When the unsaturated alcohol is blended in the coating material, the blending ratio is such that the total amount of the resin component (thermosetting resin, co-curable resin) of the thermosetting resin composition constituting the thermosetting coating material is The total amount of the polymerizable monomer and the thermoplastic resin) is preferably 0.1 to 90% by weight. This is because if it is less than 0.1% by weight, it is difficult to obtain the effect of improving the adhesiveness to the substrate, and if it exceeds 90% by weight, the water resistance of the coating layer tends to deteriorate.

On the other hand, when the unsaturated alcohol is blended in the molding material, the total amount of the resin components (the total amount of the thermosetting resin, the copolymerization monomer and the thermoplastic resin) in the thermosetting resin composition is 0. It is suitable to be blended in a ratio of 1 to 70% by weight. If it is less than 0.1% by weight, it is difficult to obtain the effect of improving the adhesion to the coating layer. On the contrary, if it exceeds 70% by weight, the viscosity of the thermosetting resin composition becomes too low, and the form of SMC or BMC (solid This is because it is difficult to set the condition.

The unsaturated silane coupling agent used in the invention of claim 1 means a silane coupling agent having a reactive unsaturated bond, and known and commonly used ones are used.
Specifically, N- (3-acryloxy-2-hydroxypropyl) 3-aminopropyltriethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldi Ethoxysilane, 3-methacryloxypropenyltrimethoxysilane, 2-methacryloxyethyldimethyl [3-trimethoxysilylpropyl] ammonium chloride, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, trimethoxyvinylsilane And the like, and those having a (meth) acryloyl group are preferably used.

The unsaturated titanate coupling agent used in the invention of claim 1 means a titanate coupling agent having a reactive unsaturated bond, for example, isopropyl trioctanoyl titanate, isopropyl isostearoyl diacryl titanate. (Meth) acrylic acid derivative such as tetra (2.2-diallyloxymethyl-
Those having an allyl group such as 1-butyl) bis (ditridecyl) phosphite titanate are used.

The unsaturated aluminum-based coupling agent used in the invention of claim 1 means an aluminum-based coupling agent having a reactive unsaturated bond, and specifically, for example, ethyl acetoacetate aluminum diisopropylate, Alkyl acetoacetate aluminum diisopropylate or the like is used.

When an unsaturated silane coupling agent, an unsaturated titanate-based coupling agent, or an unsaturated aluminum-based coupling agent is used as the molding material, the amount thereof should be the sum of the total resin components of the molding material. Of the (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin), 0.1 to 70% by weight is preferable, and 0.5 is more preferable.
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 silane coupling agent, a titanate-based coupling agent, or an aluminum-based coupling agent is used as the coating material, the amount thereof is the total resin component (thermosetting resin, co-curable resin) of the coating material. The total amount of the polymerizable monomer and the thermoplastic resin) is preferably 0.1 to 80% by weight, more preferably 0.5 to 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.

The unsaturated carboxylic acid used in the invention of claim 2 is 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. It means a compound that can be converted to a carboxyl group by ion exchange with water molecules or the like.

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 unsaturated sulfonic acid used in the invention of claim 2 is a compound having a SOOH group and a reactive unsaturated bond, or a salt or an anhydride thereof, which is easily hydrated, or a water molecule or the like. Means a compound that can be ion-exchanged with sulfonic acid group.

As the compound having the SOOH group and the 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 metal salt of unsaturated sulfonic acid, 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 unsaturated phosphoric acid used in the invention of claim 2 is a compound having a POOH group and a reactive unsaturated bond, or a metal salt or an anhydride thereof, which is easily hydrated or a water molecule. Means a compound that can be ion-exchanged with the like to form a phosphate group.

The following compounds are used as the compound having the POOH group and the reactive unsaturated bond. 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) pentanedihydrogen phosphate, mono {5 carbonyloxy (2-
Methacryloyloxyethyl) pentane} dihydrogen phosphate, di {5-carbonyloxy (2-acryloyloxyethyl) pentane} monohydrogen phosphate, di {5-carbonyloxy (2-acryloyloxyethyl) pentane} monohydrogen Phosphate, etc. are mentioned.

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 mercaptan used in the present invention means a compound having a mercapto group and a reactive unsaturated bond, and is synthesized by a known and commonly used method. That is, for example, a method produced by a reaction between an acetylene compound and hydrogen sulfide, a method produced by a reaction between a halogenated alkene and 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 can be mentioned.

When unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid, or unsaturated mercaptan is used as the molding material, its amount is the sum of the total resin components (thermosetting) of the molding material. Resin, copolymerizable monomer,
The total amount of the thermoplastic resin) is preferably 0.1 to 70% by weight, more preferably 0.5 to 20% by weight. If the amount used is 0.1% or less, it is difficult to obtain a sufficient effect of improving the adhesion to the coating film. On the contrary, if the amount is 70% or more, the viscosity of the composition becomes too low, so the form of SMC or BMC (solid It tends to be difficult.

When unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid or unsaturated mercaptan is used for the coating material, the amount thereof is the total resin component (thermosetting resin, copolymerization) of the coating material. Total amount of polymerizable monomers and thermoplastic resins)
0.1 to 90% by weight is preferable, and 0.5 to 30% by weight is more 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.

As the thermosetting resin used in the thermosetting resin composition constituting the thermosetting resin molding material and the coating layer, a three-dimensional reaction is carried out by cleavage reaction of double bonds using a heat decomposable radical catalyst. An unsaturated polyester resin having a reactive unsaturated bond in the molecule capable of forming a network structure, an epoxy acrylate (vinyl ester) resin, a urethane acrylate resin, or the like can be used. Each of these resins may be used alone or in combination of two or more.

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 epoxy acrylate resin is also
It is usually produced by a known and conventional method from an epoxy resin and a monocarboxylic acid having a reactive double bond such as (meth) acrylic acid.

The urethane acrylate resin is
Usually, it is produced 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 also possible to leave a free isocyanate group at a part of the terminal and combine it with the above epoxy acrylate resin for use.

Examples of the above-mentioned organic polyol used for the unsaturated polyester resin include diols, triols, tetrols and mixtures thereof, and they are mainly classified into aliphatic polyols and aromatic polyols. Typical examples of the aliphatic polyol include ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, triethylene glycol, neopentyl glycol, dibromoneopentyl glycol, hexamethylene glycol, trimethylene glycol, trimethylolpropane, There are glycerin, pentaerythritol diallyl ether, hydrogenated bisphenol A, and the like.

As a typical aromatic polyol, bisphenol A or bisphenol S, or an oxirane compound such as ethylene oxide, propylene oxide or butylene oxide is added to these bisphenol A or bisphenol S on average in one molecule. There are polyoxyalkylene bisphenol A, polyoxyalkylene bisphenol S and the like obtained by adding in the range of 1 to 20.

The aliphatic unsaturated carboxylic acid is (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, etc., and the aliphatic saturated carboxylic acid is sebacic acid, adipic acid, (anhydrous) succinic acid, etc. However, as the aromatic carboxylic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride and the like are used.

The epoxy resin used for the epoxy acrylate resin is a bisphenol A type epoxy resin produced from epichlorohydrin and bisphenol A, a bromine produced from epichlorohydrin and brominated bisphenol A, also by a known and conventional method. Bisphenol A type epoxy resin, novolak type epoxy resin produced by glycidyl etherification of phenol novolac or orthocresol novolak, tetraglycidyl metaxylenediamine, tetraglycidyl 1,3-bis obtained by reacting various amines with epichlorohydrin Aminomethylcyclohexane,
Glycidylamine compounds such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, and diglycidyl orthotoluidine are used.

Examples of the polyol used in the urethane acrylate resin include alkylene diols such as ethylene glycol, propylene glycol, diethylene glycol, diisopropylene glycol, polyethylene glycol, polypropylene glycol, and hydroxyalkyl ethers such as butanediol. As the polyether polyol, polyoxymethylene, polyethylene oxide, polypropylene oxide or the like is produced, and as the polyester polyol, the above-mentioned organic polyol and polycarboxylic acid are used.
A polyester polyol having hydroxyl groups at both ends is used.

As the polyisocyanate used for 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, etc. are used, and the hydroxyl group is usually bonded to the carbon at the beta position of the alkyl group. Alkyl groups can usually contain up to 8 carbon atoms.

The thermosetting resin composition of the present invention also contains
As a low shrinkage agent, polyvinyl acetate, polymethyl (meth)
Thermoplastic resins such as acrylate, polyethylene, ethylene vinyl acetate copolymer, vinyl acetate-styrene copolymer, polybutadiene, saturated polyesters, saturated polyethers, styrene, alphamethylstyrene, divinylbenzene, vinyltoluene, Copolymerizable monomers such as diallyl phthalate, various acrylate monomers, and various methacrylate monomers can be used in appropriate amounts as necessary.

Further, the thermosetting resin composition of the present invention may contain an appropriate amount of an inorganic filler depending on the purpose and application. Examples of usable inorganic fillers are as follows.

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 and carnotite. Such as vanadate minerals, barite (barium sulfate), gypsum (calcium sulfate) and other sulfate minerals, borax and other borate minerals, perovskite and other titanate minerals, mica, talc (talc) , Silicate minerals such as pyrophyllite, kaolin, quartz and feldspar, metal oxides such as titanium oxide, corundum (aluminum oxide) and aluminum hydroxide, glass products such as (hollow) glass spheres The natural or artificial minerals, processed or purified or processed products thereof, and mixtures thereof are used.

When the filler is used as a molding material, it is added in an amount of 0 to 300 parts by weight with respect to 100 parts by weight of the resin component (total amount of thermosetting resin, thermoplastic resin and copolymerizable monomer). Preferably. When the amount added exceeds 300 parts by weight, it becomes difficult to uniformly disperse the filler in the resin and the monomer, and the viscosity becomes too high, so the fluidity in the mold decreases and the dimensional stability Becomes worse.

The amount of the filler used in the coating material is 0 to 150 relative 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. Moreover, in the thermosetting resin composition of the present invention, as a reinforcing material,
Various reinforcing fibers, that is, glass fibers, carbon fibers and the like can be added in appropriate amounts as needed.

Further, in the thermosetting resin composition of the present invention, if necessary, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, alkyl peresters, percarbonates. , Known polymerization initiators such as peroxyketals, known curing accelerators such as dimethylaniline and cobalt naphthenate, polymerization inhibitors such as parabenzoquinone, carbon black, titanium oxide, iron oxide, cyanine pigments, aluminum flakes , Pigments such as nickel powder, gold powder, silver powder, azo dyes and anthraquinones, indigoids,
A suitable amount of a stilbene-based dye, a conductivity-imparting agent such as carbon black, an emulsifier, a metal soap such as zinc stearate, an aliphatic phosphate, a release agent such as lecithin, etc. may be added depending on the application and purpose. it can.

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 compounding material. Specifically, for example, an unsaturated compound such as an unsaturated alcohol or an unsaturated silane coupling agent having a hydroxyl group in the molding material, an unsaturated carboxylic acid, an unsaturated sulfonic acid, an unsaturated phosphoric acid, or an unsaturated compound. When using mercaptan (hereinafter, these compounds are referred to as unsaturated alcohol etc.), a styrene solution of unsaturated polyester resin (styrene concentration 4
0 to 70%) to 50 to 99 parts, a styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, polyvinyl acetate (styrene concentration 30 to 80%) 0
~ 30 parts, 1 to 20 parts of unsaturated alcohol and the like 10
0 parts, 100 to 300 parts of filler powder such as calcium carbonate and aluminum hydroxide, 0.1 to 3 parts of a thickener such as magnesium oxide, 0.1 to 0.1 parts of an organic peroxide as an initiator.
Add 5 parts, knead well, and reinforce fibers 1 to 1
A solid molding material obtained by impregnating 200 parts with a kneading machine or an impregnation machine is preferably used because it has excellent moldability, handleability, and physical properties of the molded product.

For example, when unsaturated isocyanate or unsaturated isothiocyanate is used as the molding material, polymethyl methacrylate is added to 50 to 99 parts of a styrene solution of unsaturated polyester resin (styrene concentration 40 to 70%). , Styrene solution of thermoplastic resin such as polystyrene, polyvinyl acetate (styrene concentration 30-80
%) 0 to 30 parts, unsaturated isocyanate or unsaturated isothiocyanate 1 to 20 parts to make 100 parts, and filler powder 10 such as calcium carbonate and aluminum hydroxide.
0-300 parts, thickeners such as magnesium oxide 0.1-3
Parts, 0.1 to 5 parts of an organic peroxide as an initiator, and well kneaded to 1 to 200 parts of reinforcing fibers such as glass fibers,
A solid molding material which is impregnated with a kneading machine or an impregnation machine is preferably used because it has excellent moldability, handleability, and physical properties of the molded product.

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, when unsaturated isocyanate or unsaturated isothiocyanate is used for the coating material, a styrene solution of an unsaturated polyester resin, an epoxy acrylate resin or a urethane acrylate resin (styrene concentration 40 to 70%) 60 to 99
To 30 parts by weight of a styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, polyvinyl acetate (styrene concentration 30 to 80%), unsaturated isocyanate or unsaturated isothiocyanate 1 to 20 parts by weight.
To 100 parts by weight, 10 to 150 parts by weight of filler powder such as calcium carbonate and barium sulfate, 0.1 to 3 parts by internal release agent such as zinc stearate, and organic peroxide as an initiator. A well-kneaded mixture containing 1 to 5 parts is preferably used because it has excellent moldability, handleability, and physical properties of the molded product.

For example, when unsaturated alcohol or the like is used as the coating material, a styrene solution of an unsaturated polyester resin, an epoxy acrylate resin or a urethane acrylate resin (styrene concentration 40 to 70%) 60 to 99.
To 30 parts, add 0 to 30 parts of a styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, or polyvinyl acetate (styrene concentration 30 to 80%), 1 to 20 parts of unsaturated alcohol, etc. to make 100 parts. 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.

Molding method The combination of the thermosetting resin compositions of the invention described in claims 1 and 2 is used in a conventionally known in-mold coating molding method. For example, SMC is put in a molding die heated to 130 to 160 ° C. and pressure is set to 40 to 120 kg / cm ² for 3 times.
After pressure molding for 0 seconds to 5 minutes, the mold is slightly opened to inject the thermosetting coating material, and then 5 to 120 kg / c.
The thermosetting coating material can be spread over the entire surface of the molded SMC and cured by reheating and repressurizing at m ² of 130 to 160 ° C. for 30 seconds to 5 minutes to form a coating layer. .

Further, as disclosed in JP-A-61-273921, SMC is controlled at 130 to 160 ° C. and 40 to 1 ° C.
The thermosetting coating material under high pressure of 100 to 300 / cm ² pressure using a high pressure injection machine while reducing the pressure to 10 to 30 kg / cm ² after several tens of seconds to several minutes pressed at 20 kg / cm ² Inject into the mold again 30 ~ 100kg / cm
There is also a method of increasing the pressure to ² to spread-harden the thermosetting coating material. By using the thermosetting resin composition of the present invention for the in-mold coating method as described above, it is possible to easily form a coated molded article having good adhesion, and thus the in-mold coating molding method of the present invention is constituted. It

[0060]

In the thermosetting resin composition according to the first and second aspects of the present invention, one of the thermosetting resin composition constituting the molding material and the coating layer contains unsaturated isocyanate or unsaturated isothiocyanate. Has been done. Therefore, when contained in the molding material side, the copolymerizable double bond of the unsaturated isocyanate or unsaturated isothiocyanate undergoes a copolymerization reaction with the thermosetting resin during pressure molding, and the isocyanate is formed on the surface of the molding material. Expose the group or isothiocyanate group.

First, the case where the unsaturated alcohol is contained will be described. The above-mentioned isocyanate group and isothiocyanate group react with the OH group of the unsaturated alcohol which is copolymerized at the time of molding, and each is represented by the following formula. Form chemical bonds. Therefore, the formation of the chemical bond enhances the adhesion between the coating layer and the molding material.

[0062]

[Chemical 1]

On the contrary, when the thermosetting resin composition constituting the molding material contains unsaturated alcohol, the reactive unsaturated bond of the unsaturated alcohol constitutes the molding material at the time of pressure molding. Copolymerization reaction with a thermosetting resin for
The hydroxyl group is exposed on the surface of the base material. This hydroxyl group is contained in the thermosetting coating material and reacts with the NCO group of the unsaturated isocyanate or unsaturated isothiocyanate which is copolymerized at the time of molding to form a chemical bond as shown by the following formula. Therefore, this chemical bond enhances the adhesion between the coating layer and the substrate.

[0064]

[Chemical 2]

Note that R ₁ and R ₂ in the above formulas (Formula 1 and Formula 2) are (including a portion) an atomic group having a reactive unsaturated bond such as a (meth) acryl group and a (meth) acryloyl group.
Represents

Next, the case where other unsaturated components are contained will be described. Other unsaturated components, namely unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid, unsaturated silane coupling agent, unsaturated titanate coupling agent, unsaturated aluminum coupling agent, or unsaturated mercaptan Is contained in the molding material, these reactive unsaturated bonds (typically a copolymerizable double bond) undergo a copolymerization reaction with the thermosetting resin composition during pressure molding, Carboxyl group, SO on the surface
OH group, POOH group, SiOH group, TiOH group, AlO
H group and SH group are generated. It has a function of reacting with an unsaturated isocyanate contained in the coating material and copolymerized at the time of molding, or an isocyanate group or an isothiocyanate group of unsaturated isothiocyanate to form a chemical bond as shown in the following formula. The bonding can improve the adhesion between the molding material and the coating.

[0067]

[Chemical 3]

[0068]

[Chemical 4]

[0069]

[Chemical 5]

In the above formulas (formula 3 to formula 5), the substituent R has the following meaning. (R ^1, R ^3: an unsaturated carboxylic acid residues ^{R 2, R 6, R 10} , R 16, R 24, R 31, R 36: unsaturated isocyanates residues ^{R 4, R 8, R 12} , R 20 , R ²⁸ , R ³⁴ , R ³⁸ : unsaturated isothiocyanate residue R ⁵ , R ⁷ : unsaturated sulfonic acid residue, R ⁹ , R ¹¹ : unsaturated phosphoric acid residue R ^{13 to} R ¹⁵ , R ¹⁷ to R ¹⁹ : Unsaturated silane coupling agent residue R ^{21 to} R ²³ , R ^{25 to} R ²⁷ : Unsaturated titanate coupling agent residue R ^{29 to} R ³¹ , R ^{32 to} R ³³ : Unsaturated aluminum coupling Agent residue R ³⁵ , R ³⁷ : unsaturated mercaptan residue)

Further, unsaturated isocyanate is used as a molding material,
Alternatively, in the case of containing isothiocyanate, a reactive unsaturated bond undergoes a copolymerization reaction with the thermosetting resin composition during pressure molding to give an isocyanate group or an isothiocyanate group on the surface, which is a coating material. SOOH
Group, POOH group, SiOH group, TiOH group, AlOH
It has a function of reacting with the base and the SH group to form a chemical bond as shown in the following formula, and by this chemical bond, the adhesive force between the molding material and the film can be improved.

[0072]

[Chemical 6]

[0073]

[Chemical 7]

[0074]

[Chemical 8]

In the above formulas (formula 6 to formula 8), the substituent R has the following meaning. (R ⁴⁰ , R ⁴² : unsaturated carboxylic acid residue R ³⁹ , R ⁴³ , R ⁴⁷ , R ⁵¹ , R ⁵⁹ , R ⁶⁷ , R ⁷³ : unsaturated isocyanate residue R ⁴¹ , R ⁴⁵ , R ⁴⁹ , R ⁵⁵ , R ⁶³ , R ⁷⁰ , R ⁷⁵ : unsaturated isothiocyanate residue R ⁴⁴ , R ⁴⁶ : unsaturated sulfonic acid residue, R ⁴⁸ , R ⁵⁰ : unsaturated phosphoric acid residue R ^{52 to} R ⁵⁴ , R ⁵⁶ to R ⁵⁸ : Unsaturated silane coupling agent residue R ^{60 to} R ⁶² , R ^{64 to} R ⁶⁶ : Unsaturated titanate coupling agent residue R ^{68 to} R ⁶⁹ , R ^{71 to} R ⁷² : Unsaturated aluminum coupling Agent residue R ⁷⁴ , R ⁷⁶ : unsaturated mercaptan residue)

According to the third aspect of the invention, as described above, since the molding material and the coating material contain the components capable of forming a chemical bond with each other to form the in-mold coating, the coating layer and the molding material are formed. It is possible to manufacture a molded product having improved adhesion.

[0077]

EXAMPLES Examples of the present invention will be described below. In the following, “parts” means parts by weight unless otherwise specified.

Preparation of Resin Liquid In the following examples, the unsaturated polyester resin liquid obtained by the following steps was used. That is, 5 mol of isophthalic acid, 5 mol of maleic acid and 10 mol of polypropylene glycol were condensed according to a conventionally known method to obtain an unsaturated polyester resin having a number average molecular weight of about 1,000.
The unsaturated polyester resin obtained was dissolved in a styrene monomer to obtain an unsaturated polyester resin liquid. The styrene content in this unsaturated polyester resin liquid was 40% by weight.

First, an example of using an unsaturated alcohol in the invention of claim 1 will be described. Example 1 As a thermosetting resin composition for constituting a molding material,
The following composition was prepared. Unsaturated polyester resin liquid: 60 parts Polystyrene-based low-shrinking agent (containing about 30% by weight of polystyrene resin and about 70% by weight of styrene): 30 parts Allyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.): 10 parts Calcium carbonate powder (Nitto Product name: NS-1
00) ... 120 parts Curing agent (t-butylperoxybenzoate) ... 1 part Thickener (magnesium oxide powder, manufactured by Kyowa Chemical Industry Co., Ltd., trade name: Kyowamag 150) ... 1 part

After thoroughly mixing the above compositions and stirring, S
60 parts of glass fibers (ER4630LBD166W manufactured by Asahi Fiber Glass Co., Ltd., cut into a length of 25 mm) were impregnated with an MC impregnating device to obtain SMC as a thermosetting resin composition. On the other hand, 100 parts of the above unsaturated polyester resin liquid, calcium carbonate powder (NS-100) 10
By thoroughly mixing 0 parts, 5 parts of 2 hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 part of a curing agent (t-butylperoxybenzoate), and stirring,
A thermosetting coating material was obtained.

Using the SMC and thermosetting coating material prepared as described above, a molded product was obtained by the following procedure. 30 cm x 30 with the upper mold heated to 150 ° C and the lower mold heated to 150 ° C
Approximately 700 g of the above SMC in a square flat plate mold of cm
I charged. The charged SMC had a thickness of about 4 mm. Then, at a pressure of 100 kg / cm ² , 1
It is molded by pressing for 00 seconds, then slightly opening the mold, injecting 10 ml of the thermosetting coating material, closing the mold again, and reheating and repressing at 80 kg / cm ² for 120 seconds. A thermosetting coating material was spread over the entire surface of the SMC and cured to form a coating layer. Next, the mold was removed to obtain a molded product whose surface was covered with a coating layer having a thickness of about 100 μm.

A straight line reaching the 11 bases (base) was drawn in parallel on the surface of the obtained molded product with a cutter knife at an interval of 2 mm, and 11 straight lines orthogonal to these straight lines were 2 mm. It was pulled at intervals to form a grid-like portion. Next, stick an adhesive tape (Sekisui Chemical Co., Ltd., trade name: Cellotape) on the grid pattern, and then remove it to remove the remaining number of grids, that is, the number of remaining coating layers that will not peel off. (Hereinafter, referred to as a cross-cut adhesion test). As a result, the ratio of the coating layer that did not peel off (hereinafter, abbreviated as "adhesion") was 100 pieces / 100 pieces.

From the obtained coated molded product, 10 cm ×
A test piece of 10 cm is cut out, and using a programmable oven, 80 ° C for 5 hours → 23 ° C for 1 hour → -30 ° C for 5 hours →
The cooling and heating repeated test was conducted continuously for 10 cycles with 1 hour at 23 ° C. as one cycle. When the above cross-cut adhesion test was performed on the test piece after the completion of the cooling and heating test, the adhesion was 100 pieces / 100 pieces.

Example 2 The amount of unsaturated polyester resin liquid used was 65 parts,
An SMC was prepared in the same manner as in Example 1 except that the amount of allyl isocyanate was 5 parts. Also,
A thermosetting coating material was obtained in the same manner as in Example 1 except that the amount of 2-hydroxyethyl methacrylate used was changed to 20 parts. Using the obtained SMC and thermosetting coating material, molding was carried out in the same manner as in Example 1 to obtain a coated molded article.

A cross-cut adhesion test was conducted on the obtained molded product in the same manner as in Example 1. As a result, the adhesion was 100 pieces /
It was 100. Further, when a cold heat test was conducted in the same manner as in Example 1, the adhesiveness after the cold heat test was 100 pieces / 10.
It was 0.

Example 3 An SMC was prepared in the same manner as in Example 1 except that the amount of unsaturated polyester resin liquid was 50 parts and the amount of allyl isocyanate was 20 parts. On the other hand, Example 1 except that 10 parts of allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 2 hydroxyethyl methacrylate.
A thermosetting coating material was obtained in the same manner as in.

The SMC and thermosetting coating material obtained as described above were molded in the same manner as in Example 1 to obtain a coated molded article. Regarding the obtained molded article with a coating layer, Example 1
When evaluated in the same manner as above, the initial adhesion is 100/100, and the adhesion after the thermal test is 100/1.
It was 00.

Example 4 An SMC was prepared in the same manner as in Example 1 except that 10 parts of allyl isothiocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of allyl isocyanate. On the other hand, used 2
A thermosetting coating material was obtained in the same manner as in Example 1 except that the amount of hydroxyethyl methacrylate was 10 parts.

The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1 to obtain a coated molded product. The obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesiveness was 100/100, and the adhesiveness after the cold heat test was 100/100.

Example 5 The same as Example 1 except that the amount of the unsaturated polyester resin liquid used in the thermosetting resin composition for molding material was 40 parts and the amount of allyl isocyanate was 30 parts. S
MC was produced. Further, a thermosetting coating material was obtained in the same manner as in Example 1 except that the amount of 2 hydroxyethyl methacrylate was 50 parts.

The resulting SMC and thermosetting coating material were
Molding was performed in the same manner as in Example 1 to obtain a coated molded product. Further, the obtained molded article with a coating layer was evaluated in the same manner as in Example 1, and the initial adhesion was 100 pieces / 10.
0 pieces, and adhesion after cooling / heating test is 100 pieces / 10
It was 0.

Example 6 The amount of the unsaturated polyester resin liquid used in the thermosetting resin composition for a molding material was 65 parts, and allyl isothiocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of allyl isocyanate.
SMC was used in the same manner as in Example 1 except that 5 parts of
Got On the other hand, a thermosetting coating material was obtained in the same manner as in Example 1 except that 5 parts of allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 2 hydroxyethyl methacrylate.

The SMC and thermosetting coating material were molded in the same manner as in Example 1 to obtain a coated molded product. The obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesiveness was 100/100 and the adhesiveness after the cold heat test was 100/100.

Example 7 S was carried out in the same manner as in Example 1 except that the amount of allyl isocyanate used in the thermosetting resin composition for a molding material was 5 parts and 5 parts of allyl isothiocyanate was further added.
MC was produced. On the other hand, a thermosetting coating material was obtained in the same manner as in Example 1 except that the amount of 2 hydroxyethyl methacrylate was 15 parts.

The SMC and thermosetting coating material obtained as described above were molded in the same manner as in Example 1 to obtain a coated molded article. The coated molded product thus obtained was evaluated in the same manner as in Example 1. As a result, the initial adhesion is 100 /
100 pieces, and the adhesion after the thermal test is 100 pieces /
It was 100.

Comparative Example 1 An SMC was prepared in the same manner as in Example 1. Further, a thermosetting coating material was obtained in the same manner as in Example 1 except that 2-hydroxyethyl methacrylate was not used. The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1, and the obtained molded product was evaluated in the same manner as in Example 1. As a result, the initial adhesion was 100/100, and the adhesion after the cold heat test was 71/100.

Comparative Example 2 An SMC was prepared in the same manner as in Example 4. On the other hand, a thermosetting coating material was obtained in the same manner as in Example 4 except that 2 hydroxyethyl methacrylate was not used. The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1, and the obtained molded product was evaluated in the same manner as in Example 1. As a result, the initial adhesion is 100 pieces / 1
The number was 00, and the adhesion after the cold heat test was 56/100.

Comparative Example 3 An SMC was prepared in the same manner as in Example 1 except that allyl isocyanate was not used in the thermosetting resin composition for the substrate and the amount of the unsaturated polyester resin liquid was 70 parts. It was made. On the other hand, the same thermosetting coating material as in Example 4 was prepared. The obtained SMC and thermosetting coating material were molded by the same method as in Example 1, and the obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesion was 100/100, and the adhesion after the cold heat test was 43/100.

Comparative Example 4 An SMC was prepared in the same manner as in Example 1 except that allyl isocyanate was not used and the amount of unsaturated polyester resin liquid was 70 parts. On the other hand, Example 3
A thermosetting coating material was obtained in the same manner as in. The obtained SMC
The thermosetting coating material was molded in the same manner as in Example 1, and the obtained molded product was evaluated in the same manner as in Example 1. As a result, the initial adhesion was 100/100, and the adhesion after the cold heat test was 34/100.

Comparative Example 5 Example 1 except that no allyl isocyanate was used and the amount of unsaturated polyester resin liquid was 70 parts.
An SMC was prepared in the same manner as in. On the other hand, Example 1 except that 2 hydroxyethyl methacrylate was not used.
A thermosetting coating material was obtained in the same manner as in. The obtained SMC
The thermosetting coating material was molded by the same method as in Example 1, and the obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesion was 31/100, and the adhesion after the cold heat test was 13/100.

The compositions of the thermosetting resin compositions for molding materials and the thermosetting coating materials for Examples 1 to 7 and Comparative Examples 1 to 5 and the evaluation of the adhesiveness in the cross-cut adhesion test are shown in Table 1 below. It shows in Table 2.

[0102]

[Table 1]

[0103]

[Table 2]

As is clear from Tables 1 and 2, in Examples 1 to 7, allyl isocyanate and / or allyl isothiocyanate was contained in the base material side and 2-hydroxyethyl methacrylate in the thermosetting coating material side. Further, it is understood that since allyl alcohol is contained, not only the initial adhesiveness but also the adhesiveness after the cooling / heating cycle is enhanced. Next, an example in which an unsaturated alcohol is contained on the substrate side and an unsaturated isocyanate and / or an unsaturated isothiocyanate is contained on the thermosetting coating material side will be described.

Example 8 As the thermosetting resin composition for forming the base material, the following composition was prepared. Unsaturated polyester resin liquid: 60 parts Polystyrene-based low-shrinking agent (containing about 30% by weight of polystyrene resin and about 70% by weight of styrene): 30 parts 2 Hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.): 10 parts Calcium carbonate powder (Nitto Koka Co., Ltd., trade name: NS-1
00) ... 120 parts Curing agent (t-butylperoxybenzoate) ... 1 part Thickener (magnesium oxide powder, Kyowa Chemical Industry Co., Ltd., trade name: Kyowamag 150) ... 1 part

After thoroughly mixing the above compositions and stirring, S
60 parts of glass fiber (manufactured by Asahi Fiber Glass Co., Ltd., ER4630LDA166W cut into a length of 25 mm) was impregnated with an MC impregnation device to obtain SMC as a thermosetting resin composition. On the other hand, 100 parts of the above unsaturated polyester resin liquid, calcium carbonate powder (NS-100) 10
A thermosetting coating material was obtained by sufficiently mixing 0 parts, 5 parts of allyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 part of a curing agent (t-butylperoxybenzoate) and stirring.

A coated molded article was molded in the same manner as in Example 1 using the SMC and thermosetting coating material prepared as described above. The obtained molded product was evaluated for initial adhesion by a cross-cut adhesion test in the same manner as in Example 1.
The number was 00/100. Further, when a cold heat test was conducted in the same manner as in Example 1, the adhesion after the cold heat test was 100.
The number was 100/100.

Example 9 Example 9 except that the amount of the unsaturated polyester resin liquid was 65 parts and 5 parts of allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 10 parts of 2 hydroxyethyl methacrylate. SMC was prepared in the same manner as in 8. In addition, Example 8
A thermosetting coating material identical to that was prepared.

The obtained SMC and thermosetting coating material were
Molding was carried out in the same manner as in Example 1 to obtain a coated molded product. When the obtained coated molded article was evaluated in the same manner as in Example 1, the initial adhesion was 100/100, and the adhesion after the cold heat test was 100/100.

Example 10 An SMC was prepared in the same manner as in Example 8. On the other hand, Example 8 except that the amount of allyl isocyanate was 20 parts.
A thermosetting coating material was prepared in the same manner as in. The obtained S
The MC and the thermosetting coating material were molded in the same manner as in Example 1, and the obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesion is 100/100
The adhesiveness after the cold heat test was 100 pieces / 100 pieces.

Example 11 An SMC was prepared in the same manner as in Example 8. On the other hand, a thermosetting coating material was obtained in the same manner as in Example 8 except that 5 parts of allyl isothiocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of allyl isocyanate. The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1, and the obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesiveness was 100/100, and the adhesiveness after the cold heat test was 100/100.

Example 12 Example 8 was repeated except that the amount of the unsaturated polyester resin liquid was changed to 65 parts and 5 parts of allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 10 parts of 2 hydroxyethyl methacrylate. Similarly, SMC was produced. On the other hand, Example 1
A thermosetting coating material was obtained in the same manner as in 1. SM obtained
C and the thermosetting coating material were molded in the same manner as in Example 1, and the obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesion is 100/100
The adhesiveness after the cold heat test was 100 pieces / 100 pieces.

Example 13 An SMC was prepared in the same manner as in Example 8. On the other hand, a thermosetting coating material was obtained in the same manner as in Example 11 except that the amount of allyl isothiocyanate used was 20 parts.
The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1, and the obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesiveness was 100/100, and the adhesiveness after the cold heat test was 100/100.

Example 14 An SMC was prepared in the same manner as in Example 8. On the other hand, a thermosetting coating material was obtained in the same manner as in Example 8 except that 5 parts of allyl isothiocyanate was used in addition to 5 parts of allyl isocyanate. The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1, and the obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesiveness was 100/100, and the adhesiveness after the cold heat test was 100/100.

Comparative Example 6 An SMC was prepared in the same manner as in Example 8. On the other hand, a thermosetting coating material was obtained in the same manner as in Example 8 except that allyl isocyanate was not used. The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1,
The obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesion was 100/100, and the adhesion after the cold heat test was 81/100.

Comparative Example 7 An SMC was prepared in the same manner as in Example 8 except that 2-hydroxyethyl methacrylate was not used and the amount of unsaturated polyester resin liquid was 70 parts.
On the other hand, a thermosetting coating material was obtained in the same manner as in Example 8.
The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1, and the obtained coated molded article was subjected to Example 1
It evaluated similarly to. As a result, the initial adhesion is 10
0 pieces / 100 pieces, and the adhesion after the heat and cold test is 35 pieces /
It was 100.

Comparative Example 8 An SMC was prepared in the same manner as in Example 1 except that 2-hydroxyethyl methacrylate was not used and the amount of unsaturated polyester resin liquid was 70 parts. Also, the same thermosetting coating material as in Example 11 was produced. The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1, and the obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesion was 100/100, and the adhesion after the cold heat test was 4
The number was 9/100.

Comparative Example 9 An SMC was produced in the same manner as in Example 8 except that 2-hydroxyethyl methacrylate was not used and the amount of unsaturated polyester resin liquid was 70 parts.
On the other hand, a thermosetting coating material was obtained in the same manner as in Example 8 except that allyl isocyanate and allyl isothiocyanate were not used. The obtained SMC and thermosetting coating material were molded in the same manner as in Example 1, and the obtained coated molded article was evaluated in the same manner as in Example 1. As a result, the initial adhesion was 31/100, and the adhesion after the cold heat test was 13/100. The compositions and adhesiveness evaluations of the thermosetting resin compositions for molding materials and thermosetting coating materials of Examples 8 to 14 and Comparative Examples 6 to 9 are shown in Tables 3 and 4 below.

[0119]

[Table 3]

[0120]

[Table 4]

As is clear from Tables 3 and 4, in Examples 8 to 14, 2-hydroxyethyl methacrylate or allyl alcohol was contained on the molding material side, and allyl isocyanate and / or on the thermosetting coating material side. Since allyl isothiocyanate is contained, it can be seen that not only the initial adhesiveness but also the adhesiveness after the thermal cycle is enhanced.

Next, examples of the invention of claim 1 using a hydroxyl group-containing unsaturated compound of an unsaturated alcohol or less and examples of the invention of claim 2 will be described.

Preparation of Materials The following materials were used as compounding ingredients. The following materials 1, 2, 9, 11, and 17 to 20 are the same as those in Example 1 above.
14 to 14 and Comparative Examples 1 to 9 are the same as those used. 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 liquid (polystyrene resin about 30 wt%, styrene monomer about 70 wt%, below, LP
(Abbreviated as A)

3.3 Methacryloxypropyltrimethoxysilane (manufactured by Toray Dow Corning Silicone Co., Ltd., hereinafter abbreviated as MPTMS) 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. Allyl thioalcohol (manufactured by Wako Pure Chemical Industries,
Hereinafter, abbreviated as ATA) 8.2 Methyl 2 propene 1 thiol (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as MPT) 9. Allyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AI)

10.1 Butene 3 Isocyanate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as BI) 11. Allyl isothiocyanate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AIT) 12. Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as MA) 13. Maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AMA)

14. Allylsulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as ASA) 15. 16. Potassium parastyrene sulfonate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as SSA) 16. Mono (2-acryloyloxyethyl) dihydrogen phosphate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AEHP) 17. Calcium carbonate powder (NS-100: manufactured by Nitto Koka Kogyo Co., Ltd., abbreviated as carbon charcoal)

18. Curing agent (Kayabutyl B: Kayaku Akzo Co., tertiary butyl peroxobenzoate content 98 wt%) 19. Thickener (magnesium oxide powder, Kyowamag 1)
50: manufactured by Kyowa Chemical Industry Co., Ltd.) 20. Glass fiber (Roving made by Asahi Fiber Glass Co., Ltd .: ER463
0LBD166W cut into a length of 25 mm.
(Abbreviated as GF)

Examples 15 to 46 According to Tables 5 to 7, the molding material and the coating material were blended, and molding and evaluation were carried out in the same manner as in Example 1 described above. The results are shown in Tables 5 to 7. The adhesion was good both at the initial stage and after the heat cycle test.

Comparative Examples 10 to 37 In accordance with Tables 8 to 10, the molding material and the coating material were blended,
Molding and evaluation were performed in the same manner as in Example 1 described above. The results are shown in Tables 8 to 10. The adhesion was good in the initial stage, but poor after the heat cycle test.

[0131]

[Table 5]

[0132]

[Table 6]

[0133]

[Table 7]

[0134]

[Table 8]

[0135]

[Table 9]

[0136]

[Table 10]

The abbreviations used in Tables 5 to 10 are summarized below. UP: Unsaturated polyester resin liquid LPA: Polystyrene-based low-shrinking agent resin liquid MPTMS: 3 Methacryloxypropyltrimethoxysilane VTMS: Vinyltrimethoxysilane TC: Isopropylisostearoyldiacrylic titanate ALC: Alkylacetoacetate aluminum diisopropylate ATA: Allyl thioalcohol MPT: 2 methyl 2 propene 1 thiol MAD: methacrylamide Am A: allyl amine AI: allyl isocyanate BI: 1 butene 3 isocyanate AIT: allyl isothiocyanate MA: methacrylic acid AMA: maleic anhydride ASA: allyl sulfonic acid SSA: para Potassium styrenesulfonate AEHP: Mono (2-acryloyloxyethyl) dihydrogen phosphate Carbon: Calcium Powder GF: Glass fibers

[0138]

According to the invention of claim 1, one of the two thermosetting resin compositions, the molding material and the coating material, contains unsaturated isocyanate or unsaturated isothiocyanate, and the other contains hydroxyl group. Since it contains an unsaturated compound having an isocyanate group or an isothiocyanate group or a hydroxyl group is exposed on the surface of the molding material during pressure molding, the isocyanate group and / or the isothiocyanate group or a hydroxyl group is a hydroxyl group or an unsaturated isocyanate. And / or reacts with the NCO group or NCS group of unsaturated isothiocyanate to form a chemical bond. As a result, the chemical bond makes it possible to provide a coated molded article having excellent adhesion between the coating layer and the substrate.

According to the second aspect of the invention, the unsaturated isocyanate or unsaturated isothiocyanate contained in either of the thermosetting resin compositions of the molding material and the coating material reacts during pressure molding. Reactive unsaturated bond undergoes a copolymerization reaction with the thermosetting resin composition to form an isocyanate group or an isothiocyanate group on the surface. This is the unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid, carboxyl group of unsaturated mercaptan, SOOH group, POOH group, SH which are copolymerized in the other thermosetting resin composition.
It has a function of reacting with a group to form a chemical bond, and this chemical bond can improve the adhesion between the molding material and the coating, and provides sufficient adhesion even after a harsh durability test such as a cold heat repetition test. Can maintain sex.

According to the third aspect of the present invention, the molding material and the coating material are subjected to in-mold coating molding by including components capable of forming chemical bonds with each other. Therefore, during in-mold coating molding,
A chemical bond is formed between the coating layer and the molding material, and it is possible to obtain a coated molded article with excellent adhesion between the coating layer and the molding material, and it can withstand severe durability tests such as cold and heat repeated tests. A coated molded article having the obtained adhesiveness can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08F 299/04 MSP 7442-4J B29K 105: 06

Claims (3)

[Claims] 1. A thermosetting resin composition used 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 is a thermosetting resin, a thermosetting resin composition containing an unsaturated isocyanate or unsaturated isothiocyanate, the other is a thermosetting resin, A thermosetting resin composition containing a compound having a reactive unsaturated bond and a hydroxyl group, which is a thermosetting resin composition for in-mold coating 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,
Thermosetting resin, a thermosetting resin composition containing an unsaturated isocyanate or unsaturated isothiocyanate, the other is a thermosetting resin, unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid, And a thermosetting resin composition containing at least one of unsaturated mercaptans, and a thermosetting resin composition for in-mold coating molding. 3. A molding method in which a molding material made of a thermosetting resin composition is heated and pressed in a mold and a coating material made of the thermosetting resin composition is injected into the mold to coat the molding material. 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.