JPH0356586B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and useful mold coating composition, the purpose of which is to hide surface defects such as pores and sink marks in thermosetting plastic molded products, particularly fiber reinforced plastic (FRP) molded products. An object of the present invention is to provide a one-component mold inner coating composition. Parts molded from thermosetting materials are popular due to their light weight, high strength, and excellent corrosion resistance.
Recently, its use has been rapidly expanding as an alternative to metal parts such as iron and aluminum. Among these, the most commonly used materials are molding materials that use unsaturated polyester resin as the thermosetting resin and glass fiber as the reinforcing fiber.
Generally, it is called sheet molding compound (SMC) or bulk molding compound (BMC). SMC and BMC are molded in heated molds, but there are many surface defects such as pores and sink marks on the surface of the molded products. Pores are found throughout the molded part;
It is believed that this is mainly caused by air trapped in the molding compound or insufficient dispersion of the molding compound. If pores exist on the surface of the molded product, the finish will lack smoothness when painted, and the durability of the paint film will decrease, and in extreme cases, blisters and cracks will occur in the paint film. This is because the solvent from the paint gets trapped in the pores and evaporates, putting pressure on the paint film. In addition, some molded products have auxiliary agents (so-called ribs) or punched-out protrusions (so-called bosses) that protrude downward from the lower side of a relatively thin cross section due to the need for strength. In molded parts having such a shape, depressions (so-called sink marks) occur on the upper surfaces of the reaction sides of the ribs and bosses. Such sink marks are a result of non-uniform curing shrinkage caused by the complex shape of the molded product, so even if a molding material with a low shrinkage rate is used, an improvement is recognized, but there is no fundamental improvement measure. It has not become possible. Molded articles with such surface defects are difficult to obtain with an acceptable and acceptable appearance using conventional painting methods. Therefore, in general, the molded SMC or BMC product is taken out of the mold, the surface defects are filled with a sealant, and after the sealant has hardened, the surface is polished with sand to make it smooth, and an undercoat is applied. After that, the intended main painting is done. Therefore, the current situation is that there are many processes and product productivity is low, which ultimately leads to an increase in product prices. This is one of the reasons why it is impossible to do so now. Therefore, a so-called in-mold coating method is known as a measure to overcome such problems. This coating method involves putting SMC, BMC, etc. into a mold, heating and pressurizing it, and curing it sufficiently, then opening the mold slightly and injecting the coating composition, and then repressing and heating. It consists of spreading the coating composition onto the surface of the substrate and then curing the coating composition. According to this method, the molded material is molded in one operation in the mold.
By sealing the surface of SMC or BMC molded products and then applying the main coating outside the mold, products with high surface smoothness can be manufactured with good productivity. By the way, as an in-mold coating composition conventionally used in such a method, there is a two-component urethane coating composition as described in Japanese Patent Publication No. 13273/1983. In this case, the two types of liquid must be mixed immediately before use, and the viscosity increases over time after mixing, so there is a limit to the usable time. Furthermore, when using only an unsaturated polyester resin as this type of coating composition, it can be a one-component type, but it has the drawback of poor adhesion to SMC or BMC substrates. However, as a result of intensive research by the present inventors to eliminate the various drawbacks of conventional coating compositions as described above, a coating composition consisting of a specific epoxy-modified polyester resin, a vinyl ester polyurethane resin, and an inorganic filler has been developed. , discovered that it has excellent adhesion to SMC and BMC substrates and the paint used for main coating (so-called top coat), and can be used as a one-component type, and completed the present invention. I've reached it. That is, the present invention contains an epoxy-modified polyester (A) having an average of 1.8 or more double bonds, a vinyl ester polyurethane (B), an α,β-unsaturated monomer (C), and an inorganic filler (D). An in-mold coating composition is provided. The epoxy-modified polyester having an average of 1.8 or more double bonds (hereinafter simply referred to as epoxy-modified polyester) (A) used in the present invention is a saturated and/or unsaturated polyester having at least one carboxyl group at the end, It is obtained by reacting an epoxy group-containing compound having and/or not having a double bond, and has an average of 1.8 or more double bonds, and usually the epoxy-modified polyester (A) is β-unsaturated monomer (C)
It is used as an epoxy-modified polyester resin. The saturated or unsaturated polyester having at least one carboxyl group at the end used here is produced by polycondensation of dibasic acid and glycol, and in some cases, linseed oil resin acid,
Manufactured using a combination of monocarboxylic acids such as soybean oil fatty acids, tung oil fatty acids, and bran oil fatty acids, or trifunctional or higher functional polycarboxylic acids such as trimellitic acid and pyromellitic acid, and having an acid value of usually 25 to 130, preferably 30.
~110 polyesters. Examples of the dibasic acids used here include α,β-unsaturated dibasic acids, aromatic saturated dibasic acids, aliphatic saturated dibasic acids, alicyclic saturated dibasic acids, and their acid anhydrides. , each acting alone or in combination. Examples of α,β-unsaturated dibasic acids and their acid anhydrides include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid, and esters thereof; Examples of acids and their acid anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and esters thereof. Examples of alicyclic saturated dibasic acids and their acid anhydrides include succinic acid, adipic acid, sebacic acid, hexahydrophthalic anhydride, and esters thereof. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butadiol, 1,4-butanediol, neopentyl glycol, triethylene glycol, 1,5-
pentanediol, 1,6-hexanediol,
Bisphenol A, hydrogenated bisphenol A,
Examples include 2,2-di(-4-hydroxypropoxyphenyl)-propane, which can be used alone or in combination, but oxides such as ethylene oxide and propylene oxide can also be used. Furthermore, polycondensates such as polyethylene terephthalate can also be used as part of the glycol and acid components. The epoxy group-containing compound having and/or not having a double bond capable of reacting with the terminal carboxyl group of the above-mentioned saturated and unsaturated polyesters may include, if necessary, a halogen atom, a hydroxyl group,
There are aliphatic, alicyclic, aromatic and heterocyclic compounds which may have an ether group etc. as a substituent, and among them, glycidyls are preferred, such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, fluoride, etc. enyl glycidyl ether; saturated fatty acid glycidyl ester obtained from an alkyl monocarboxylic acid and epichlorohydrin (for example, Cardiura E manufactured by Siel Kagaku Co., Ltd.); and the like. Epoxy modified polyester (A) used in the present invention
The production is carried out according to commonly used methods. In other words, acids and glycols, which are raw materials for polyester, are usually heated to 180~
After performing a polycondensation reaction at 230°C with heating and stirring until a predetermined acid value is reached, a polymerization inhibitor such as hydroquinone is added, and the temperature is heated to 80-150°C, preferably 100-100°C.
The mixture is cooled to 130°C, and then an epoxy group-containing compound is added dropwise to react with the terminal carboxyl group of the polyester to obtain an epoxy-modified polyester.
The amount of the epoxy group-containing compound added to the polyester for epoxy modification is usually 5 to 40% by weight, preferably 5 to 30% by weight.
Adjust so that the content is % by weight. If the content of the epoxy group-containing compound is less than 5% by weight, the adhesion of the resulting in-mold coating composition to the SMC or BMC substrate will be poor, and if it exceeds 40% by weight, the physical properties of the coating such as weather resistance and water resistance will deteriorate. This is not preferable because there is no cost advantage. Pinyl ester polyurethane (B) used in the present invention
is diisocyanate and hydroxyl group terminal (meta)
The following general formula obtained by addition reaction of acrylic ester and hydroxyl group-terminated saturated polyester and/or polyether diol (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a residue derived from a polyether diol, and X is a residue derived from a diisocyanate, or a hydroxyl group-terminated saturated polyester and/or a polyether diol and a diisocyanate. If necessary, the vinyl ester polyurethane (B) can be dissolved in an α,β-unsaturated monomer (C) and used as a vinyl ester polyurethane resin. As the diisocyanate used in the production of the vinyl ester polyurethane (B), any known diisocyanate can be used, such as tetramethylene diisocyanate, hexamethylene diisocyanate,
1,4-cyclohexane diisocyanate, 1,
Examples include 3-cyclohexane diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and naphthalene diisocyanate. Examples of hydroxyl group-terminated (meth)acrylic acid esters include those obtained by reacting (meth)acrylic acid with alkylene oxides such as ethylene oxide and propylene oxide by known methods. For example, β
-Hydroxyethyl (meth)acrylate, β-
Examples include hydroxypropyl (meth)acrylate, polyoxyethylene (2) acrylate, polyoxypropylene (3) methacrylate, and the like. The hydroxyl group-terminated saturated polyester is produced by polycondensation of an aliphatic polybasic acid and its acid anhydride and/or an aromatic polybasic acid and its acid anhydride, and glycol, and has a hydroxyl group value. 20 to 500. As the polyether diol, known polyether diols used in the production of polyurethane can be used, such as polypropylene glycol,
Examples include polyethylene glycol and polytetramethylene glycol. The vinyl ester polyurethane used in the present invention is usually obtained by adding one molecule of hydroxyl-terminated (meth)acrylic ester to a diisocyanate to obtain a monoisocyanate compound, and then adding the hydroxyl-terminated saturated polyester and/or polyether diol to the monoisocyanate. Isocyanate prepolymers with a molecular weight of 500 to 5000 are prepared by further addition to a compound, sometimes by reacting a hydroxyl-terminated saturated polyester and/or polyether diol with a diisocyanate compound to add an isocyanate group to the end. It may be produced by reacting the residual isocyanate with a hydroxyl-terminated (meth)acrylic ester, and the order of the reaction is not particularly limited. The reaction ratio of diisocyanate, hydroxyl-terminated (meth)acrylic ester, and hydroxyl-terminated saturated polyester and/or polyether diol when producing vinyl ester polyurethane is as follows:
Although it varies depending on the manufacturing method, it is usually a calculated reaction chemical equivalent ratio. As the α,β-unsaturated monomer (C), styrene,
Styrenic compounds such as vinyltoluene, α-methylstyrene, and chlorcutylene; acrylic compounds such as methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, trimethylolpropane triacrylate, and their esters; and triallyl cyanurate and diallyl phthalate. Examples include vinyl monomers or vinyl oligomers that can be crosslinked with unsaturated polyesters such as allyl compounds, and are used alone or in combination, but styrene is generally used. The ratio of epoxy-modified polyester (A), vinyl ester polyurethane (B), and α,β-unsaturated monomer (C) is usually (A+C)/(B) 5/100 by weight.
~100/5, (A)/(C) is 40/60 ~ 75/25, and (A
If +C)/(B) is less than 5/100 or greater than 100/5, it is not preferable because the adhesion to SMC or BMC substrates and water resistance are poor. By adding the inorganic filler (D) used in the present invention, the heat generation during curing of the coating composition and the curing shrinkage rate of the coating film are reduced, and as a result, the adhesion to the substrate is improved. can be improved. It may also be added for the purpose of controlling the viscosity of the coating composition. The inorganic fillers used are usually SMC,
Any of those used in BMC can be used, such as calcium carbonate, clay, talc, barium sulfate, aluminum hydroxide, zinc stearate,
Examples include hollow ceramic, hollow glass, and hollow graphite spheres, among which calcium carbonate,
Clay, talc, and aluminum hydroxide are preferred, but carbon black powder and metal powders such as nickel and zinc may also be used for the purpose of imparting conductivity to the molded product. The amount of inorganic filler (D) used is usually 10 to 300 parts by weight per 100 parts by weight of the epoxy-modified polyester (A), vinyl ester polyurethane (B), and α,β-unsaturated monomer (C). Parts by weight range. If the inorganic filler is less than 10 parts by weight, the curing shrinkage of the mold coating composition will be large, the adhesion to the SMC and BMC substrate will decrease, and the viscosity required for the mold coating will not be obtained.
If it exceeds 300 parts by weight, the physical properties of the coating such as weather resistance and water resistance will deteriorate, which is not preferable. The epoxy-modified polyester (A), vinyl ester polyurethane (B), α,β-unsaturated monomer (C), and inorganic filler (D) can be mixed using a conventional stirrer. Generally, epoxy-modified polyester resin obtained by dissolving epoxy-modified polyester (A) in α,β-unsaturated monomer (C) and vinyl ester polyurethane (B) are mixed with α,β-unsaturated monomer (C). Quantity (C)
The vinyl ester polyurethane resin obtained by dissolving the resin, the inorganic filler (D), and further α,
The β-unsaturated monomer (C) is mixed using a hand mixer, homomixer, or the like. The viscosity of the in-mold coating composition of the present invention thus obtained is usually 20 to 3500 poise, preferably 100 to 3500 poise.
Prepared and used in the 500 poise range. Furthermore, the in-mold coating composition of the present invention may contain known curing agents such as ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, alkyl peresters, percarbonates, and peroxyketals. ,
Known curing accelerators such as dimethylaniline and cobalt naphthenate, thermoplastic resins such as polyvinyl acetate, polymethyl (meth)acrylate, polyethylene, polystyrene, ethylene-vinyl acetate copolymer, vinyl acetate-styrene copolymer, polybutadiene , saturated polyesters, saturated polyethers, and other known low-shrinkage agents, metal soaps such as zinc stearate, aliphatic phosphates, lecithin, and other known mold release agents, organic pigments, inorganic pigments, etc. Pigments and the like can be added depending on the use and purpose. The one-component mold coating composition of the present invention thus obtained is generally used for mold coating in the same manner as conventionally known one-component mold coating compositions. For example 135
SMC, BMC in a mold heated to ~150℃
After putting molding material such as and pressure molding at a pressure of 60 to 120 kg/cm ² and fully curing, the mold was slightly opened and the in-mold coating composition was injected.
There is a method of spreading and curing the in-mold coating composition over the entire surface of a molded and hardened substrate such as SMC or BMC by repressing and reheating at 100 Kg/cm ² and 135 to 150°C. The present invention will be explained in more detail with reference to Examples below. It should be noted that all figures in the example and percentages are based on weight. Reference Example 1 (Manufacture of epoxy-modified polyester resin) 415 g of isophthalic acid, 775 g of 2 moles of ethylene oxide adduct of bisphenol A, and 260 g of neopentyl glycol were reacted with stirring at 215°C in an inert gas atmosphere until the acid value reached 5. After that, 150℃
187g of neopentyl glycol and 441g of maleic anhydride were charged, and the temperature was raised to 210℃ again.
The reaction took 8 hours to reach an acid value of 58, yielding 1957 g of unsaturated polyester. Hydroquinone 4.7 in this
After cooling to 130℃ and adding 0.2g of lithium chloride, 284g of glycidyl methacrylate was added dropwise over 30 minutes, and then the reaction was continued at 120℃ for 40 minutes to determine the glycidyl methacrylate content. A 13% modified polyester was obtained. This was diluted with 1,480 g of styrene monomer to obtain 3,721 g of glycidyl methacrylate-modified polyester resin (A-1) having an acid value of 4 and a viscosity of 4 poise. Reference Example 2 (See the example in Reference Example 1) 392 g of maleic anhydride, propylene glycol
258 g was subjected to a polycondensation reaction with heating and stirring at 200 to 210° C. in an inert gas atmosphere to obtain 589 g of unsaturated polyester having an acid value of 88. Then hydroquinone 0.5
g was added, cooled to 120°C, and 229 g of Cardilla E (manufactured by Ciel Chemical Co., Ltd.) was added dropwise over 3 hours.
After that, the reaction was continued for 2 hours to determine the content of Cardilla E.
A 28% modified polyester was obtained. This was diluted with 500 g of styrene monomer to obtain Cardiura E modified polyester resin (A-D) with an acid value of 8 and a viscosity of 2.5 poise.
1318g was obtained. Reference Example 3 (See the example in Reference Example 1) Phthalic anhydride 592g, propylene glycol 258g
was reacted with stirring at 215° C. in an inert gas atmosphere to obtain 789 g of a saturated polyester having an acid value of 84. Then add 0.48g of hydroquinone,
Cool to 120℃ and add 135g of allyl glycidyl ether.
was added dropwise over 2 hours, and the reaction was continued for 3 hours to obtain a modified polyester containing 15% allyl glycidyl ether. Add this to styrene monomer
Allyl glycidyl ether modified polyester resin (A-
3) Obtained 1570g. Reference Example 4 (Refer to the example in Reference Example 1) 332 g of isophthalic acid, neopentyl glycol
395g was heated and stirred in an inert gas atmosphere at 220°C to react until the acid value reached 8, then cooled to 150°C, 232g of fumaric acid was added, and the temperature was raised to 205°C again to reach an acid value of 31.
815 g of unsaturated polyester was obtained. Next, 0.6 g of hydroquinone was added, the mixture was cooled to 130° C., 68 g of phenyl glycidyl ether was added, and the reaction was continued for 2 hours to obtain a modified polyester having a phenyl glycidyl ether content of 8%. This was diluted with 600 g of styrene monomer to obtain 1483 g of phenyl glycidyl ether modified polyester resin (A-4) having an acid value of 2 and a viscosity of 3.8 poise. Reference Examples 5 to 12 (See the example in Reference Example 1) 392 g of maleic anhydride, propylene glycol
258 g was subjected to a polycondensation reaction while heating and stirring at 200 to 210° C. in an inert gas atmosphere to obtain 589 g of unsaturated polyester having an acid value of 25 to 286. Next, 0.5 g of hydroquinone was added, cooled to 120 ° C., 37 to 426 g of glycidyl methacrylate was added dropwise over 30 minutes to 3 hours, and the reaction was continued for 2 to 5 hours.
A modified polyester with a glycidyl methacrylate content of 5.9 to 42% was obtained. This was diluted with 196 to 900 g of styrene monomer to produce glycidyl methacrylate modified polyester resins (A-5) to (A-5).
12). In addition, the acid value of the unsaturated polyester, the amount of glycidyl methacrylate added, its dropping time and reaction time after dropping, the glycidyl methacrylate content in the modified polyester, the oxidation, viscosity and yield of the modified polyester resin are shown in Table 1. show.

[Table] Reference example 13 (Production of vinyl ester polyurethane) 382g of diethylene glycol and phthalic anhydride
444g was reacted at 215°C in an inert gas atmosphere to a hydroxyl value of 80, and after cooling to 60°C, 192g of 2,4-tolylene diisocyanate was added and reacted at 60°C for 8 hours, followed by β-hydroxyethyl methacrylate. 145g, added 0.6g of hydroquinone,
The reaction was further carried out for 8 hours to obtain 1111 g of vinyl ester polyurethane (B-1). This vinyl ester polyurethane (B-1) was a pale yellow viscous liquid with a hydroxyl value of 2 and no unreacted isocyanate remaining. Reference Example 14 (Refer to the example in Reference Example 13) Add 0.6 g of hydroquinone to 222 g of isophorone diisocyanate, and heat to 60°C while stirring.
-130g of hydroxyethyl methacrylate in 1
The mixture was added dropwise over a period of time, and the reaction was continued for an additional 2 hours. Then polypropylene glycol with a molecular weight of 400 [Dainippon Ink Chemical Co., Ltd. Hyprox DP-400]
200 g was added and the reaction was carried out for 8 hours while maintaining the temperature at 60°C to obtain 552 g of vinyl ester polyurethane (B-2) having a hydroxyl value of 3. No unreacted isocyanate remained. Reference Example 15 (Refer to the example in Reference Example 13) The hydroxyl value of 652 g of tetrabromobisphenol A and 202 g of sebacic acid was determined at 215°C in an inert gas atmosphere.
It reacted up to 300. On the other hand, 0.6 g of hydroquinone was added to 761 g of 2,4-tolylene diisocyanate, and 507 g of β-hydroxyethyl acrylate was added dropwise over 2 hours while stirring at 60°C.
After that, the reaction was carried out for 5 hours, and the above hydroxyl value was increased to 300.
The entire amount of saturated polyester was added thereto, and the mixture was reacted at 80° C. for 8 hours to obtain 2086 g of vinyl ester polyurethane (B-3) having a hydroxyl value of 2. No unreacted isocyanate remained. Reference Example 16 (Refer to the example in Reference Example 13) The hydroxyl value of 652 g of tetrabromobisphenol A and 586 g of dimer acid was determined at 215°C in an inert gas atmosphere.
400 to obtain a saturated polyester. On the other hand, 0.6 g of hydroquinone was added to 1491 g of 2,4-tolylene diisocyanate, and β-hydroxyethyl acrylate 994 was heated and stirred at 60°C.
g was added dropwise over 3 hours, and then reacted for 8 hours.Furthermore, the entire amount of the above saturated polyester with a hydroxyl value of 400 was added, and the reaction was carried out at 80°C for 8 hours to achieve a hydroxyl value of 3.
3687g of vinyl ester polyurethane (B-4)
I got it. No unreacted isocyanate remained. Reference Examples 17-19 (Refer to the example in Reference Example 13) The hydroxyl value of 845 g of 1,4-butylene glycol and 1168 g of adipic acid was determined at 215°C in an inert gas atmosphere.
30 to 200 to obtain a saturated polyester.
On the other hand, 2,4-tolylene diisocyanate 446~
Add 0.6 g of hydroquinone to 3107 g, and dropwise add 186 to 1243 g of β-hydroxyethyl acrylate over 1 to 4 hours while heating and stirring at 60°C.
After that, the reaction was carried out for 4 to 6 hours, and the above hydroxyl value was 30.
Add saturated polyester total amount of ~200, 80~90
It was made to react at ℃ for 8 hours to obtain vinyl ester polyurethanes (B-5) to (B-7) having a hydroxyl value of 2 to 3. No unreacted isocyanate remained. In addition, the hydroxyl value of the saturated polyester, the amount of 2,4-tolylene diisocyanate added, the amount of β-hydroxyethyl acrylate added, the dropping time and reaction time after dropping, the reaction temperature after adding the saturated polyester, and the amount of vinyl ester polyurethane added. The hydroxyl value and yield are shown in Table 2.

[Table] Reference Example 20 (See the example in Reference Example 13) Vinyl ester polyurethanes (B-2) and (B-7) obtained in Reference Example 14 and Reference Example 19 were blended in equal weight to obtain a polyurethane with a hydroxyl value of 3. Vinyl ester polyurethane (B-8) was obtained. Reference example 21 (Production of unsaturated polyester resin) 392 g of maleic anhydride, propylene glycol
258 g of the polyester was polycondensed with stirring at 200 to 210° C. in an inert gas atmosphere to obtain 589 g of unsaturated polyester having an acid value of 114. Next is hydroquinone 0.8
g and diluted with 500 g of styrene monomer to obtain 1090 g of an unsaturated polyester resin (A-6') having an acid value of 62 and a viscosity of 3.0 poise. Reference example 22 (Manufacture of saturated polyester resin) 845 g of 1,4-butylene glycol and 1168 g of adipic acid were heated at 215°C in an inert gas atmosphere to reduce the hydroxyl value.
Saturated polyester (B-6') by reacting up to 56
Obtained 1725g. Examples 1 to 27 and Comparative Examples 1 to 7 One-component mold coating compositions were prepared by blending the resins obtained in Reference Examples 1 to 22 and other components in the raw material compositions shown in Tables 3 to 5. I got it. The change in viscosity of these in-mold coating compositions at 25°C over the course of a day was measured, and the storage stability was checked based on the increase in viscosity, and all showed stability for one month or more. SMC made of isophthalic acid-based unsaturated polyester resin was placed in a ribbed flat plate mold of 350 mm x 350 mm, and pressure molded for 2 minutes at a mold temperature of 135 to 140°C and a pressure of 60 kg/cm ² . Next, the mold was slightly opened and 20 g of the in-mold coating composition obtained in Examples 1 to 27 or Comparative Examples 1 to 7 was automatically injected with a cylinder, and then the mold was closed and the mold was further heated under the same conditions for 2 minutes. A ribbed FRP plate coated by pressure molding was obtained, and the smoothness of its surface was evaluated (visually), and the following adhesion test was conducted. The results are shown in Tables 3 to 5.
Shown in the table. Adhesion test: Conduct a grid adhesion test in accordance with JIS K-5400 (general coating film test). (1) First adhesion - FRP with ribs coated in the mold
Adhesion of flat plate surface. (2) Second adhesion - FRP with ribs coated in the mold
Adhesion of the painted FRP flat plate surface obtained by applying aminoalkyd melamine baking paint to the flat plate and providing a top coat layer. (3) Third adhesion Adhesion of the coated FRP plate surface after being left at -60℃ and 100%RH for 400 hours.

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Claims (1)

[Claims] 1 Epoxy-modified polyester (A) and vinyl ester polyurethane having an average of 1.8 or more double bonds
1. An in-mold coating composition comprising (B), an α,β-unsaturated monomer (C), and an inorganic filler (D).