JPH06271814A - Resin composition for molding in-mold coating and method for molding in-mold coating - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition for molding an in-mold coating, good in adhesion and capable of maintaining sufficient adhesion even after receiving an environmental change such as repetitive cooling and heating in a method for molding the in-mold coating and the method for molding the coating. CONSTITUTION:This thermosetting resin composition comprises a thermosetting molding material and a thermosetting coating material. In the composition, either thereof contains a thermosetting resin and at least one of unsaturated carboxylic acids (including salts and anhydrides), unsaturated sulfonic acids (including salts and anhydrides) and unsaturated phosphoric acids and the other contains the thermosetting resin and at least a thermssetting one of unsaturated amines, unsaturated glycidyl compounds, unsaturated alcohols and unsaturated mercaptans.

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 is to improve the above-mentioned drawbacks. 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 heat and cold. A thermosetting resin composition for use and a coating molding method using the same.

[0006]

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 and at least one of unsaturated carboxylic acids, unsaturated sulfonic acids, and unsaturated phosphoric acids A thermosetting resin composition containing a seed, and the other is a thermosetting resin containing a thermosetting resin and at least one of an unsaturated amine, an unsaturated glycidyl compound, an unsaturated alcohol, and an unsaturated mercaptan. A thermosetting resin composition for in-mold coating molding, which is a thermosetting resin composition.

Further, in the invention described in claim 2, in the in-mold coating molding method, the molding material and the coating material are:
Each of them is characterized by comprising the thermosetting molding material and the thermosetting coating material of the invention of claim 1. The details of the configuration of each invention will be described below.

In the present invention, as the thermosetting resin used for the molding material, a reaction in the molecule capable of forming a three-dimensional network structure by cleavage addition reaction of a double bond using a heat decomposable radical catalyst. Unsaturated polyester resin with epoxy double bond, epoxy acrylate (vinyl ester)
Resin, urethane acrylate resin, etc. are used. These resins may be used alone or as a mixture of plural kinds.

The thermosetting resin used for the coating material is
Similarly, unsaturated polyester resin, epoxy acrylate (vinyl ester) resin, urethane acrylate resin and the like are also 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 double 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.

Examples of the organic polyol used in the above unsaturated polyester resin include diols, triols, tetrols and mixtures thereof.
It is mainly divided into an aliphatic polyol and an aromatic polyol, and among these, representative ones as the aliphatic polyol include ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, triethylene glycol, neopentyl glycol, dibromneo. There are pentyl glycol, hexamethylene glycol, trimethylene glycol, trimethylolpropane, glycerin, pentaerythritol diallyl ether, hydrogenated bisphenol A, etc., and typical aromatic polyols are bisphenol A or bisphenol S or these. One molecule of bisphenol A or bisphenol S containing an aliphatic oxirane compound such as ethylene oxide, propylene oxide or butylene oxide There is a polyoxyalkylene bisphenol A or polyoxyalkylene bisphenol S or the like obtained by addition with an average 1-20 range.

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

The epoxy resin used for the epoxy acrylate (vinyl ester) resin is also a bisphenol A type epoxy resin produced from epichlorohydrin and bisphenol A, epichlorohydrin and brominated bisphenol A, which are also known and commonly used. 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-a Bruno phenol, diglycidyl aniline, glycidyl amine compounds such as diglycidyl ortho-toluidine is used.

As the polyol used in 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 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 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 carboxylic acids used in the present invention include compounds having a carboxyl group and a reactive unsaturated bond, and easily hydrated compounds such as unsaturated carboxylic acid anhydrides and unsaturated carboxylic acid metal salts, Or, it means an unsaturated compound having an atomic group (bond) capable of forming a carboxyl group by ion exchange with a water molecule 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 acids used in the present invention include compounds having a sulfonic acid group and a reactive unsaturated bond, and metal salts, anhydrides thereof, etc., which are easily hydrated, or water molecules, etc. It means an unsaturated compound having an atomic group (bond) that can be ion-exchanged to form a 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 present invention 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 ion-exchanged with a water molecule or the like. It means an unsaturated compound having an atomic group (bond) that can be a POOH group.

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 amine used in the present invention means one having a reactive unsaturated bond and a --NH ₂ group.
The -NH ₂ group, -NH ₂ group in the -NH ₂ group or a primary amide group of the amino group, and both can be used, for example, as having an amino group, allylamine, 2-amino 1, 1, 3 tricyano 1 propene and the like, and examples of those having a primary amide group include maleamide, fumaramide, acrylamide and methacrylamide.

The unsaturated glycidyl compound used in the present invention means a compound having a reactive unsaturated bond and a glycidyl group, and known and commonly used compounds are used. Specific examples include acrylates such as glycidyl acrylate and glycidyl methacrylate, and allyl compounds such as allyl glycidyl ether. Further, as a somewhat special one, there is known an epoxy resin, which is a compound having a plurality of glycidyl groups, in which a part of the glycidyl groups is esterified with (meth) acrylic acid.

The unsaturated alcohol used in the present invention means a compound having a reactive unsaturated bond and a hydroxyl group, and known and commonly used ones are used. Specifically, for example, allyl alcohol, 3 butene 1 ol, 3 butene 2
All, 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, 2 hydroxy 1 acryloxy 3 methacryloxypropane, tetra Examples include methylol methane triacrylate.

The unsaturated mercaptan used in the present invention means a compound having a reactive unsaturated bond and a mercapto group, and is synthesized by a known and commonly used method. 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 can be mentioned.

Further, as the molding material, unsaturated carboxylic acids,
When unsaturated sulfonic acids and unsaturated phosphoric acids are used, the amount thereof is 0, out of the total resin components (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin) of the molding material. 0.1 to 70% by weight is preferable, and 0.5 to 20% 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 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 an unsaturated alcohol, an unsaturated mercaptan, an unsaturated amine or an unsaturated glycidyl compound is used as the molding material, the amount thereof is the sum of the total resin components (thermosetting resin) of the molding material. , The total amount of the copolymerizable monomer and the thermoplastic resin) is preferably 0.1 to 70% by weight, and 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.

Further, the coating material contains unsaturated carboxylic acids,
When unsaturated sulfonic acids or unsaturated phosphoric acids are used, the total amount is the total resin content of the coating material (total amount of thermosetting resin, copolymerizable monomer, thermoplastic resin).
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.

When an unsaturated alcohol, an unsaturated mercaptan, an unsaturated amine, or an unsaturated glycidyl compound is used for the coating material, the amount thereof is the sum of the total resin components (thermosetting resin) of the coating material. , The total amount of the copolymerizable monomer and the thermoplastic resin) is preferably 0.1 to 90% by weight, and more preferably 0.5 to 30% 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 molding material, and if it is 90% 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 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. Tends to be difficult.

The amount of the filler used in 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, and it tends to be difficult to spread the molding material over the entire surface.

In addition, 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, in appropriate amounts.

Further, if necessary, the molding material and the coating material may be 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, when an unsaturated carboxylic acid, an unsaturated sulfonic acid, or an unsaturated phosphoric acid is used as a molding material, a styrene solution of an unsaturated polyester resin (styrene concentration 40 to 70%) 50 ~ 99 parts by weight of polymethylmethacrylate, polystyrene,
0 to 30 parts of a styrene solution of a thermoplastic resin such as polyvinyl acetate (styrene concentration 30 to 80%), unsaturated carboxylic acids, unsaturated sulfonic acids, or unsaturated phosphoric acids 1 to
Add 20 parts to 100 parts, 100 to 300 parts filler powder such as calcium carbonate, aluminum hydroxide, 0.1 to 3 parts thickener such as magnesium oxide, 0.1 parts organic peroxide as an initiator. ~ 5 parts are added and kneaded well, and 1 to 200 parts of reinforcing fibers such as glass fibers are impregnated with a kneading machine or an impregnating machine to obtain a solid molding material. It is excellently used and is therefore preferably used.

When an unsaturated alcohol, an unsaturated mercaptan, an unsaturated amine, or an unsaturated glycidyl compound is used as a molding material, for example, a styrene solution of an unsaturated polyester resin (styrene concentration 40 to 70%) 50
To 99 parts by weight, 0 to 30 parts by weight 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 amine,
Or adding 1 to 20 parts of unsaturated glycidyl compound to give 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.

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 an unsaturated alcohol, unsaturated mercaptan, unsaturated amine, or unsaturated glycidyl compound is used as the coating material, a styrene solution of epoxy acrylate resin or urethane acrylate resin (styrene concentration 40 ˜70%) 60 to 99 parts, styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, polyvinyl acetate (styrene concentration 30 to 80%) 0 to 30 parts, unsaturated alcohol, unsaturated mercaptan, 1 to 20 parts of unsaturated amine or unsaturated glycidyl compound 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.

For example, when unsaturated carboxylic acids, unsaturated sulfonic acids, or unsaturated phosphoric acids are used as the coating material, a styrene solution of epoxy acrylate resin or urethane acrylate resin (styrene concentration 40 to 7) is used.
0%) 60 to 99 parts, styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, polyvinyl acetate (styrene concentration 30 to 80%) 0 to 30
Parts, unsaturated carboxylic acid, unsaturated sulfonic acid, or unsaturated phosphoric acid 1 to 20 parts to make 100 parts, and 10 to 150 parts of filler powder such as calcium carbonate and barium sulfate, internal separation such as zinc stearate. Since 0.1 to 3 parts of the mold agent and 0.1 to 5 parts of the organic peroxide as the initiator are added and well kneaded, the moldability, handleability, and physical properties of the molded product are excellent.
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, as disclosed in Japanese Examined Patent Publication No. 4-33252, SMC at 130 to 160 ° C., 40 to 120 k
After pressure molding at g / cm ² for several tens of seconds to several minutes, the pressure is adjusted to 10
Injecting a coating material into the mold at high pressure of 100 to 300 / cm ² boosts again 30~100kg / cm ² by spreading curing the coating material by using a high-pressure injection machine in a state of reduced pressure of 30 kg / cm ² If the molding material and the coating material, which are the features of the present invention, are used in these in-mold coating methods, it is possible to easily form a coating having good adhesion between the coating and the molding material. it can.

[0051]

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 has an unsaturated carboxylic acid, an unsaturated sulfonic acid or an unsaturated carboxylic acid. Phosphoric acid is contained, and on the other side, unsaturated alcohol, unsaturated mercaptan, unsaturated amine and unsaturated glycidyl compound are contained.

When unsaturated carboxylic acids, unsaturated sulfonic acids, or unsaturated phosphoric acids are contained in the molding material, these reactive unsaturated bonds form a thermosetting resin composition during pressure molding. Copolymerization reaction causes C on the surface
The OOH group, the SOOH group, or the POOH group is emitted. This includes unsaturated alcohols, unsaturated mercaptans, unsaturated amines, hydroxyl groups of unsaturated glycidyl compounds, mercapto groups, -NH ₂ groups, which are contained in the coating material and copolymerize during molding.
It has a function of reacting with a glycidyl group to form a chemical bond as shown in the following formula, and this chemical bond can improve the adhesion between the molding material and the film.

[0053]

[Chemical 1]

[0054]

[Chemical 2]

In the above formulas (Formula 1 and Formula 2), the substituent R has the following meaning. (R ¹ , R ³ , R ¹³ , R ¹⁵ : unsaturated carboxylic acid residue, R ² ,
R ^6, R ^10: an unsaturated amine residue ^{R 4, R 8, R 12} : an unsaturated glycidyl compound residue ^{R 5, R 7, R 17} , R 19: an unsaturated sulfonic acid residue R ^9, R ^11, R ^21, R ^23: unsaturated phosphate residues ^{R 14, R 18, R 22} : an unsaturated alcohol residues ^{R 16, R 20, R 24} : unsaturated mercaptan residue)

When an unsaturated alcohol, an unsaturated mercaptan, an unsaturated amine, or an unsaturated glycidyl compound is contained in the molding material, the reactive unsaturated bond in the molding material during thermoforming is a thermosetting resin. A OH group, SH group, —NH ₂ group, or glycidyl group is exposed on the surface through a copolymerization reaction with the composition. This is an unsaturated carboxylic acid, unsaturated sulfonic acid, which is contained in the coating material and copolymerizes during molding,
Unsaturated phosphoric acid carboxyl group, SOOH group, POOH
It has a function of reacting with a group to form a chemical bond as shown in the following formula, and this chemical bond can improve the adhesion between the molding material and the coating.

[0057]

[Chemical 3]

[0058]

[Chemical 4]

In the above formulas (Formula 3 and Formula 4), the substituent R has the following meaning. (R ²⁵ , R ²⁹ , R ³³ : unsaturated amine residue R ²⁶ , R ²⁸ , R ³⁸ , R ⁴⁰ : unsaturated carboxylic acid residue R ²⁷ , R ³¹ , R ³⁵ : unsaturated glycidyl compound residue R ³⁰ , R ³² , R ⁴² , R ⁴⁴ : unsaturated sulfonic acid residue R ³⁴ , R ³⁶ , R ⁴⁶ , R ⁴⁸ : unsaturated phosphoric acid residue R ³⁷ , R ⁴¹ , R ⁴⁵ : unsaturated alcohol residue R ³⁹ , R ⁴³ , R ⁴⁷ : unsaturated mercaptan residue)

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

[0061]

EXAMPLES Examples of the present invention will be described below. [Preparation of materials] The following materials were used as compounding ingredients. 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 approximately 30 wt%, styrene motilene monomer approximately 70 wt%, hereinafter abbreviated as LPA) 3.2 Hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as HEMA) 4 ． Allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AA) 5. Allyl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AM) 6. Methacrylamide (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as MAD) 7. Allylamine (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter, A
(Abbreviated as AM)

8. Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as GMA) 9. Allyl glycidyl ether (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AG) 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. Allylsulfonic acid (Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as ASA) 13. Potassium parastyrene sulfonate (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. 16. Calcium carbonate powder (NS-100: manufactured by Nitto Koka Kogyo Co., Ltd., hereinafter abbreviated as carbon char) 16. Curing agent (Kayabutyl B: Kayaku Akzo Co., tertiary butyl peroxobenzoate content 98 wt%) 17. Thickener (magnesium oxide powder, Kyowamag 1)
50: Kyowa Chemical Industry Co., Ltd.) 18. 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 compounding materials were mixed and sufficiently kneaded in accordance with 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] Using a cutter knife, a straight line reaching 11 substrates at 2 mm intervals was drawn on the surface of the thus-obtained molded product, and further 11 straight lines were drawn orthogonally 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 data of the adhesion thus obtained in the initial stage and after the cold and heat repeated test are shown in the following table. (Examples 1 to 40) According to Tables 1 to 4, 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 to 4. The adhesiveness was good both in the initial stage and after the cold and heat repeated test.

(Comparative Examples 1 to 24) According to Tables 5 to 7, 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 5 to 7. The adhesiveness was good in the initial stage, but was poor after the cold heat repeating test.

(Comparative Example 25) According to Table 7, a molding material and a coating material were mixed, and molding and evaluation were carried out by the above-mentioned method. The results are shown in Table 7. The adhesiveness was poor both in the initial stage and after the cold and heat repeated test.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

[Table 5]

[0078]

[Table 6]

[0079]

[Table 7]

The meanings of the abbreviations used in Tables 1 to 7 are summarized below. UP: Unsaturated polyester resin liquid LPA: Polystyrene-based low-contraction agent resin liquid HEMA: 2-hydroxyethylmethacrylate AA: Allyl alcohol AM: Allyl mercaptan MAD: Methacrylamide AAM: Allylamine GMA: Glycidyl methacrylate AG: Allylglycidyl ether MA: Methacrylic acid AMA: Maleic anhydride ASA: Allyl sulfonic acid SSA: Potassium parastyrene sulfonate AEHP: Mono (2-acryloyloxyethyl) dihydrogen phosphate GF: Glass fiber

[0081]

Since the resin composition for in-mold coating molding of the present invention has the above-mentioned constitution, the unsaturated composition contained in either of the two thermosetting resin compositions of the molding material and the coating material. Alcohols, unsaturated mercaptans, unsaturated glycidyl compounds, and unsaturated amines have a reactive unsaturated bond that undergoes a copolymerization reaction with the thermosetting resin composition during heating / pressurizing, and has hydroxyl groups, mercapto groups, glycidyl on the surface. Group, or --NH ₂ group. This is an unsaturated carboxylic acid, unsaturated sulfonic acid, carboxyl group of unsaturated phosphoric acid, SOOH which are copolymerized in the other thermosetting resin composition.
It has a function of reacting with a group or POOH group to generate a chemical bond, and by this chemical bond, the adhesion between the molding material and the coating can be improved, and even after a severe environmental change such as repeated heat and cold. It is possible to maintain sufficient adhesion.

In the in-mold coating molding method of the present invention, the molding material and the coating material are subjected to in-mold coating molding by containing components capable of forming a chemical bond with each other. Therefore, during in-mold coating molding, a chemical bond is formed between the coating layer and the substrate,
It is possible to obtain a coated molded article having excellent adhesiveness between the coating layer and the molding material, and in particular, a coated molded article having an adhesiveness that can withstand a severe durability test such as a cold heat repetition test.

Claims (2)

[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 a thermosetting resin and at least one kind of unsaturated carboxylic acids, unsaturated sulfonic acids, and unsaturated phosphoric acids, and the other is a thermosetting resin and unsaturated. A thermosetting resin composition for molding in-mold coating, which is a thermosetting resin composition containing at least one of an amine, an unsaturated glycidyl compound, an unsaturated alcohol, and an unsaturated mercaptan. 2. When a molding material made of a thermosetting resin composition is heated and pressed in a mold to be molded, a coating material made of a thermosetting resin composition is injected into the mold to coat the molding material. In the method, a thermosetting molding material and a thermosetting coating material according to claim 1 are used as the thermosetting molding material and the thermosetting coating material, respectively.