JPH06271815A - Thermosetting 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 capable of providing a coated molding, excellent in adhesion of a coating layer and capable of maintaining sufficient adhesion even after receiving a severe environment such as repetitive cooling and heating according to a method for molding the in-mold coating. CONSTITUTION:This thermosetting resin composition for molding an in-mold coating is used in a method for molding the in-mold coating for coating the top surface of a substrate composed of a thermosetting molding material in a mold and molding a coating layer and comprises the thermosetting molding material and a thermosetting coating material. In the composition, either thereof is a thermosetting resin composition containing a thermosetting resin and an unsaturated amine and the other is a thermosetting resin composition containing the thermosetting resin and at least a thermosetting one of unsaturated isocyanates, unsaturated isothiocyanates and unsaturated glycidyl compounds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an in-mold coating and molding method for forming a coating layer by coating a thermosetting coating material on a substrate made of a thermosetting molding material in a molding die. A thermosetting resin composition for in-mold coating used as a thermosetting molding material and a thermosetting coating material, and in particular, it is possible to obtain a coated molded article having excellent adhesion between a base material made of a molding material and a coating layer. The present invention relates to a thermosetting resin composition 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, there is a problem that the coating film formed by the in-mold coating molding method does not have sufficient adhesion to the base material made of the molding material. An object of the present invention is to obtain a coated molded article having good adhesiveness of a coating layer and capable of maintaining sufficient adhesiveness even after undergoing an environmental change such as repeated cold and heat by an in-mold coating molding method. It is an object of the present invention to provide a thermosetting resin composition for in-mold coating molding, which enables the above, and an in-mold coating molding method using the same.

[0006]

According to a first aspect of the present invention, there is provided an in-mold coating for forming a coating layer by coating a thermosetting coating material on a substrate made of a thermosetting molding material in a die. A thermosetting resin composition used in a molding method, wherein one of the thermosetting molding material and the thermosetting coating material contains a thermosetting resin and an unsaturated amine. And the other is a thermosetting resin composition containing a thermosetting resin and at least one kind of an unsaturated isocyanate, an unsaturated isothiocyanate and an unsaturated glycidyl compound. It is a thermosetting resin composition for coating molding.

The details of the structure of each invention according to claims 1 and 2 will be described below. In the invention according to claim 1, as the thermosetting resin used for the thermosetting molding material, a three-dimensional network structure can be formed by subjecting a double bond to a cleavage addition reaction using a thermally decomposable radical catalyst. Unsaturated polyester resin having a reactive double bond in the molecule, epoxy acrylate (vinyl ester) resin, urethane acrylate resin and the like are used. These resins may be used alone or as a mixture of plural kinds.

As the thermosetting resin used for the coating material,
Similarly, unsaturated polyester resin, epoxy acrylate (vinyl ester) resin, urethane acrylate resin and the like are used in addition to the above polyisocyanate, polyamine and epoxy. 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 also prepared by a known and conventional method.
Usually, it is produced from an epoxy resin and a monocarboxylic acid having a reactive double bond such as (meth) acrylic acid.

Further, 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.

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

Examples of the aliphatic unsaturated polycarboxylic acid used for the unsaturated polyester resin include (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid and the like. The aliphatic saturated polycarboxylic acid used in the unsaturated polyester resin, sebacic acid, adipic acid,
(Anhydrous) succinic acid or the like is 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.

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

As the polyol used 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 having hydroxyl groups at both ends produced by the above-mentioned organic polyols and polycarboxylic acids as polyester polyols. 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 for the urethane acrylate resin is usually hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc., and the hydroxyl group is usually beta of an alkyl group. Bound to carbon. Alkyl groups can usually contain up to 8 carbon atoms.

The unsaturated amine used in the present invention means a compound having a reactive unsaturated bond and a --NH ₂ group.
As 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 those 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 isocyanate used in the present invention means a compound having a reactive unsaturated bond and an isocyanate group, and can be obtained by reacting an alkali metal isocyanic acid salt with an alkenyl halide by a known method. Specific examples include allyl isocyanate, 1-butene-3 isocyanate, 2-methylpropene-3-isocyanate and the like. It can also be synthesized by addition reaction of unsaturated alcohol and polyisocyanate.

The unsaturated isothiocyanate used in the present invention means a compound having a reactive unsaturated bond and an isothiocyanate group, which is obtained by reacting an isothiocyanic acid alkali metal salt with an alkenyl halide by a well-known method. To be Specific examples thereof include allyl isothiocyanate, 1-butene-3 isothiocyanate, and 2-methylpropene-3-isocyanate. It can also be synthesized by an addition reaction of an unsaturated alcohol and polyisothiocyanate.

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

When an unsaturated amine is used as the molding material, the total amount of the unsaturated amine is the total resin content (the total amount of the thermosetting resin, the copolymerizable monomer, and the thermoplastic resin) of the molding material. 0.1 to 70% by weight is preferable,
More preferably, it is 0.5 to 20% by weight. If the amount used is less than 0.1% by weight, it is difficult to obtain the effect of sufficiently improving the adhesion to the coating layer. On the other hand, if it exceeds 70% by weight, the viscosity of the composition becomes too low, resulting in SMC or B
It tends to be difficult to form MC (solid state).

Further, unsaturated isocyanate is used as a molding material,
When an unsaturated isothiocyanate or an unsaturated glycidyl compound is used, the total amount of the unsaturated isothiocyanate and the unsaturated glycidyl compound is 0 out of the total resin components (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin) of the molding material. 1 to 70% by weight
Is preferred, and more preferably 0.5 to 20% by weight. If the amount used is less than 0.1% by weight, it is difficult to obtain the effect of sufficiently improving the adhesiveness with the coating layer. On the contrary, if the amount used exceeds 70% by weight, the viscosity of the composition becomes too low, so that S
It tends to be difficult to form MC or BMC (solid state).

When an unsaturated amine is used as the coating material, the amount thereof is 0.1 to 0.1% of the total resin content (total amount of thermosetting resin, copolymerizable monomer, thermoplastic resin) of the coating material. 90 wt% is preferred, more preferably 0.5
~ 30% by weight. If the amount used is less than 0.1% by weight, it is difficult to obtain the effect of sufficiently improving the adhesion to the molding material, and if it exceeds 90% by weight, the water resistance of the coating layer tends to deteriorate. Have.

Further, the coating material is unsaturated isocyanate,
When using an unsaturated isothiocyanate or unsaturated glycidyl compound, as the amount thereof, as a total thereof,
0.1 to 90% by weight, and more preferably 0.5 to 30% by weight, of the total resin content (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin) of the coating material is preferable. .
If the amount used is less than 0.1% by weight, it is difficult to obtain the effect of sufficiently improving the adhesion to the molding material, and conversely 90% by weight
If it exceeds, there is a drawback that the water resistance of the coating layer tends to deteriorate.

Further, the molding material and the coating material used in the invention according to claim 1 include polyvinyl acetate, polymethyl (meth) acrylate, polyethylene, as a low-shrinking agent.
A thermoplastic resin such as ethylene vinyl acetate copolymer, vinyl acetate-styrene copolymer, polybutadiene, saturated polyesters, saturated polyethers, etc. can be used in an appropriate amount, if necessary.

An appropriate amount of inorganic filler can be added to the molding material and the coating material used in the invention described in claim 1 according to 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, vanadium such as carnotite. Salt 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 flake wax. Natural products such as stones, kaolin, quartz, silicate minerals such as feldspar, titanium oxide, metal (hydr) oxides such as corundum (aluminum oxide) aluminum hydroxide, glass products such as (hollow) glass spheres Artificial minerals or processing it,
Purified or processed products 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 becomes difficult to uniformly disperse the filler in the resin and the monomer, and since the viscosity becomes too high, the flow in the mold deteriorates and dimensional stability is obtained. Becomes difficult.

The amount of the above filler used for the coating material is 0 to 150 with respect to 100 parts by weight of the resin component (total amount of thermosetting resin, thermoplastic resin and copolymerizable monomer).
It is preferably added in parts by weight. If the addition amount exceeds 150 parts, the viscosity becomes too high, so that the fluidity in the mold becomes poor and it becomes difficult to spread the molding material over the entire target area. 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 material in appropriate amounts as necessary.

Further, the above molding material and coating material include
As required, copolymerizable monomers such as styrene, alphamethylstyrene, divinylbenzene, vinyltoluene, diallylphthalate, various acrylate monomers, various methacrylate monomers, ketone peroxides, diacyl peroxides, hydroperoxides , Known initiators such as dialkyl peroxides, alkyl peresters, percarbonates and peroxyketals, known curing accelerators such as dimethylaniline and cobalt naphthenate, polymerization inhibitors such as parabenzoquinone, carbon black And titanium oxide, iron oxide,
Cyanine pigment, aluminum flake, nickel powder, gold powder,
Pigments such as silver powder, azo dyes, anthraquinone dyes, indigoid dyes, stilbene dyes, conductivity imparting agents such as carbon black, emulsifiers, metallic soaps such as zinc stearate, aliphatic phosphates, lecithin release agents, etc. A mold agent or the like can be added in an appropriate amount depending on the use and purpose.

The molding material used in the invention of claim 1 is the SM compounded by the conventionally known method using the compounding material as described above.
It becomes a molding material having the form of C or BMC. Specifically, for example, when an unsaturated amine is used as the molding material, polymethylmethacrylate, polystyrene, or polymethylmethacrylate, polystyrene, or polypolymethacrylate is used with respect to 50 to 99 parts by weight of a styrene solution of an unsaturated polyester resin (styrene concentration 40 to 70%). Styrene solution of thermoplastic resin such as vinyl acetate (styrene concentration 30-
0 to 30 parts by weight, 1 to 20 parts by weight of unsaturated amine are added to make 100 parts by weight, and 100 to 300 parts by weight of filler powder such as calcium carbonate and aluminum hydroxide,
0.1 to 3 parts by weight of a thickener such as magnesium oxide and 0.1 to 5 parts by weight of an organic peroxide as an initiator are added and kneaded well, to 1 to 200 parts by weight of reinforcing fiber such as glass fiber, 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.

When an unsaturated isocyanate, an unsaturated isothiocyanate or an unsaturated glycidyl compound is used as the molding material, for example, a styrene solution of an unsaturated polyester resin (styrene concentration: 40 to 70% by weight) is used.
To 99 parts by weight, 0 to 30 parts by weight of a styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, polyvinyl acetate (styrene concentration 30 to 80% by weight), unsaturated isocyanate, unsaturated isothiocyanate or unsaturated 1 to 20 parts by weight of a saturated glycidyl compound is added to 100 parts by weight, 100 to 300 parts by weight of filler powder such as calcium carbonate and aluminum hydroxide, 0.1 to 3 parts by weight of a thickener such as magnesium oxide, an initiator 0.1 to 5 parts by weight of organic peroxide as a mixture is added and kneaded well, and 1 to 200 parts by weight of reinforcing fibers such as glass fibers are impregnated with a kneading machine or an impregnating machine to obtain a solid molding material. However, since they are excellent in moldability, handleability, and physical properties of molded products, they are preferably used.

The coating material used in the invention described in claim 1 is kneaded into a liquid coating material by a conventionally known method using the compounding material as described above.

Specifically, for example, when an unsaturated isocyanate, unsaturated isothiocyanate or unsaturated glycidyl compound is used as the coating material, a styrene solution of unsaturated polyester resin, epoxy acrylate resin or urethane acrylate resin (styrene concentration 40-70
% By weight) 60 to 99 parts by weight, 0 to 30 parts by weight of a styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, polyvinyl acetate (styrene concentration 30 to 80% by weight), unsaturated isocyanate, unsaturated Isothiocyanate or unsaturated glycidyl compounds 1-2
Add 0 parts by weight to make 100 parts by weight calcium carbonate,
10 to 150 parts by weight of filler powder such as barium sulfate, 0.1 to 3 parts by weight of internal release agent such as zinc stearate, and 0.1 to 5 parts by weight of organic peroxide as an initiator are added and kneaded well. These are excellent in moldability, handleability, and physical properties of molded products, and thus are preferably used.

When an unsaturated amine is used as the coating material, 60 to 99 parts by weight of a styrene solution of an unsaturated polyester resin, an epoxy acrylate resin or a urethane acrylate resin (styrene concentration 40 to 70% by weight) is used. , Polymethylmethacrylate, polystyrene,
Add 0 to 30 parts by weight of a styrene solution of thermoplastic resin such as polyvinyl acetate (styrene concentration 30 to 80% by weight) and 1 to 20 parts by weight of unsaturated amine to make 100 parts by weight, and fill with calcium carbonate, barium sulfate, etc. Material powder 10-150
1 part by weight, 0.1 to 3 parts by weight of an internal release agent such as zinc stearate, and 0.1 to 5 parts by weight of an organic peroxide as an initiator are added and kneaded well. It is suitable for use because of its excellent physical properties.

The invention described in claim 2 is characterized by using the molding material and the coating material of the invention described in claim 1 obtained in this way, but other steps are publicly known. In-mold coating methods can be used.

For example, SMC is put in a molding die heated to 130 to 160 ° C. and pressure-molded at a pressure of 40 to 120 kg / cm ² for 30 seconds to 5 minutes, and then the mold is slightly opened to cover the coating material. Injection, then 5-120 kg / cm ² ,
There is a method in which the coating material is spread over the entire surface of the molded SMC and cured by reheating and repressurizing at 130 to 160 ° C. for 30 seconds to 5 minutes to form a coating.

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

[0039]

In the thermosetting resin composition according to the first aspect of the present invention, one of the thermosetting resin compositions constituting the molding material and the coating material contains an unsaturated amine, and the other contains the unsaturated amine. Contains at least one kind of unsaturated isocyanate, unsaturated isothiocyanate and unsaturated glycidyl compound.

When an unsaturated amine is contained in the molding material, these compounds are copolymerized with the thermosetting resin at the time of pressure molding to expose --NH ₂ groups on the surface of the molding material. This is a chemical reaction by reacting with unsaturated isocyanate, unsaturated isothiocyanate, glycidyl group appearing on the surface from unsaturated glycidyl compound, isocyanate group and isothiocyanate group which are contained in the coating material and are copolymerized at the time of molding as shown in the following chemical formula. Since the bond is formed, the adhesion between the molding material and the coating layer can be improved.

[0041]

[Chemical 1]

In the chemical formula of the above chemical formula ¹ , R ¹ , R ³ ,
R ^5: an unsaturated amine residue, R ^2: an unsaturated isocyanate residue, R ^4: unsaturated isothiocyanate residue, R ^6: an unsaturated glycidyl compound residue.

Further, unsaturated isocyanate is used as a molding material,
When an unsaturated isothiocyanate or unsaturated glycidyl compound is used, these give an isocyanate group, an isothiocyanate group or a glycidyl group on the surface during pressure molding. This reacts with the --NH ₂ group of the unsaturated amine contained in the coating material and copolymerized at the time of molding to form a chemical bond as shown in the following chemical formula, thus improving the adhesion between the molding material and the coating. be able to.

[0044]

[Chemical 2]

In the chemical formula of the above chemical formula 2, R⁷: Unsaturated
Isocyanate residue, R⁹: Unsaturated isothiocyanate
Residue, R¹¹: Unsaturated glycidyl compound residue, R⁸,
R⁹, R ¹²: It is an unsaturated amine residue.

[0046]

EXAMPLES The present invention will be clarified by giving Examples and Comparative Examples of the present invention. In the following, parts are parts by weight unless otherwise specified.

[Preparation of Material] 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. 2. Polystyrene low-shrinking agent resin liquid (about 30% by weight of polystyrene resin, about 70% by weight of styrene monomer, hereinafter abbreviated as LPA). Methacrylamide (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter MA
Abbreviated) 4. Allylamine (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as AA) 5. Allyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.,
(Abbreviated as AI)

6.1-Butene-3-isocyanate (sum
(Kou Pure Chemical Industries, Ltd., hereinafter abbreviated as BI) 7. Allyl isothiocyanate (Wako Pure Chemical Industries, Ltd.
Below, abbreviated as AIT) 8. Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.
Below, abbreviated as GMA) 7. Allyl glycidyl ether (Wako Pure Chemical Industries, Ltd.,
Below, abbreviated as AG) 10. Calcium carbonate powder (NS-100: Nitto Powder Kako
Made by a business company, below, CaCO ₃Abbreviated)

11. Curing agent (Kayabutyl B: Kayaku Akzo, tertiary butyl peroxobenzoate content 98% by weight) 12. Thickener (magnesium oxide powder, Kyowamag 1)
50: Kyowa Chemical Industry Co., Ltd.) 13. Glass fiber (Roving made by Asahi Fiber Glass: ER4630LBD166W cut into a length of 25 mm, hereinafter abbreviated as GF)

[Manufacture of Molding Material] Of these materials,
Compounding materials other than glass fiber were mixed according to the following Tables 1 to 3 and sufficiently stirred, and then glass fiber was impregnated with an SMC impregnation device to obtain SMC.

[Production of Coating Material] The above-mentioned compounded materials were mixed according to the following Tables 1 to 3 and sufficiently kneaded to obtain a coating material.

[Molding] SMC obtained as described above
And the coating material were used and molded as follows.

The above S was placed in a 30 cm × 30 cm square flat plate mold in which the upper mold was heated to 150 ° C. and the lower mold was heated to 150 ° C.
After charging about 700 g of MC (which corresponds to a thickness of about 4 mm) and press-molding at a pressure of 100 kg / cm ² for 100 seconds, the mold was slightly opened to make the coating material 1 above.
Inject 0 ml, close the mold again, and use 1 at 80 kg / cm ² .
Molded SM by reheating and repressurizing for 20 seconds
The coating material was spread over the entire surface of C and cured to form a coating. After that, the mold is opened and demolded, and the surface has a thickness of about 10
A molded article coated with a 0 μm coating was obtained.

[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 lines perpendicular to it were drawn. 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 on which the coating was not peeled off was examined (cross-grid adhesion test).

From the obtained molded product, 10 cm × 10
A test piece of cm is cut out, and in a program-type oven, 80 cycles of 80 ° C. × 5 hours → 23 ° C. × 1 hour → −30 ° C. × 5 hours → 23 ° C. × 1 hour → repeated cooling / heating cycle is 1 cycle, and 10 cycles are consecutive. I went over again. A cross-cut adhesion test was also performed on the test piece after the completion of the cold heat repetition test.

Tables 1 to 3 below show the results of the adhesion obtained in the above manner and after the repeated heat and cold test. (Examples 1 to 14) According to the following Tables 1 to 3, a molding material and a coating material were blended, and molding and evaluation were performed by the above-mentioned method. The results are shown in Tables 1 and 2 below. The adhesion of the coating was good both in the initial stage and after the cold and heat repeated test.

(Comparative Examples 1 to 14) According to the following Tables 2 and 3, the molding material and the coating material were blended, and molding and evaluation were carried out by the above-mentioned method. The results are also shown in Tables 2 and 3 below. The adhesion was good at the beginning,
It was poor after the cold heat repeated test.

Comparative Example 15 A molding material and a coating material were blended according to Table 3 below, and molding and evaluation were carried out by the above-mentioned method. The results are also shown in Table 3 below. The adhesiveness was poor both in the initial stage and after the cold and heat repeated test.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

In Tables 1 to 3, the symbols used for the molding material and the coating material have the following meanings. UP: Unsaturated polyester resin liquid LPA: Polystyrene low-contraction agent resin liquid MA: Methacrylamide AA: Allylamine AI: Allyl isocyanate BI: 1-Butene-3-isocyanate AIT: Allyl isothiocyanate GMA: Glycidyl methacrylate AG: Allyl glycidyl ether CaCO ₃ : calcium carbonate powder GF: glass fiber

[0064]

As described above, in the invention described in claim 1, the unsaturated amine is blended in either the molding material or the coating material, and the reactive unsaturated bond is thermoset during pressure molding. and copolymerization reaction and sex resin composition, it gives to the group -NH ₂ to the surface. Therefore, it reacts with the unsaturated isocyanate, unsaturated isothiocyanate, or isocyanate group, isothiocyanate group, or glycidyl group of the unsaturated glycidyl compound contained in the other of the molding material and the coating material to form a chemical bond. Therefore, the adhesiveness between the molding material and the coating layer can be improved, and the sufficient adhesiveness can be maintained even after a severe environmental change such as repeated heat and cold.

When the thermosetting molding material and the coating material according to claim 1 are used as in the invention described in claim 2, the coating layer has excellent adhesion to the molded article substrate, and is repeatedly subjected to cold heat. It is possible to provide a coated molded article in which a coating layer having sufficient adhesion is formed even after such a severe environmental change.

Claims (2)

[Claims] 1. A thermosetting resin composition for use in an in-mold coating molding method, which comprises coating a thermosetting coating material on a base material made of a thermosetting molding material in a mold to form a coating layer. One of the thermosetting molding material and the thermosetting coating material is a thermosetting resin composition containing a thermosetting resin and an unsaturated amine, and the other is a thermosetting resin and a thermosetting resin. A thermosetting resin composition for in-mold coating molding, which is a thermosetting resin composition containing at least one of a saturated isocyanate, an unsaturated isothiocyanate and an unsaturated glycidyl compound. 2. A method of coating a coating material made of a thermosetting resin composition on a substrate made of the molding material in a mold when molding a molding material made of a thermosetting resin composition, An in-mold coating molding method, wherein the thermosetting molding material and the thermosetting coating material according to claim 1 are used as the thermosetting molding material and the thermosetting coating material, respectively.