JPH06220145A - Resin composition for coating in mold - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition for coating in a mold, capable of forming irregular color-free and uniformly colored coating layers on thermosetting molding materials. CONSTITUTION:At least one of the combinations from among (1) a polyamine or unsaturated amine and a carboxyl group-containing resin, (2) the polyamine or unsaturated amine and a polycarboxylic acid, (3) the polyamine and an uuaturated carboxylic acid, and (4) an alkaline earth metal element or zinc oxide or hydroxide and the carboxyl group-containing resin is added to a thermosetting resin composition for coating in a mold to provide the resin composition thickened into a viscosity of 150-550 poises (25 deg.C).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an in-mold coating resin composition which is injected into a mold to form a coating layer on a thermosetting molding material which is in a semi-cured state in the mold.

[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.

In-mold coating resin compositions used in these molding methods are, for example, JP-A-1-1263.
No. 16 discloses an in-mold coating resin composition containing urethane acrylate and epoxy acrylate as main components.

[0006]

However, the coating film formed by the in-mold coating molding using such a usual in-mold coating resin composition may partially or badly cause the entire surface of the molded product to be colored. It has the drawback of unevenness.

Further, if a pigment can be dispersed in a high-viscosity resin composition to obtain a high-viscosity coating composition, the high viscosity of the coating composition increases the dispersion stability of the pigment in the composition, Although it is expected to prevent color unevenness due to aggregation and separation, it is very difficult to uniformly disperse the color pigment in a highly viscous resin liquid of 100 poise or more,
In most cases, the pigment dispersion is insufficient, which causes a difference in the concentration distribution of the coloring pigment, which causes color unevenness during coating molding, resulting in poor appearance of the molded product. In particular, when a plurality of types of color pigments are included, intense color unevenness occurs. Specifically, for example, when a red coating material and a white pigment are used to form a pink coating material, the molded article formed by coating has a pink portion, a reddish pink portion, and a whitish pink portion. It causes a poor appearance such as being divided into two parts.

The present invention has been made to solve the above-mentioned conventional drawbacks, and provides an in-mold coating resin composition capable of forming a coating layer having a uniform color tone without color unevenness in in-mold coating molding. The purpose is to do.

[0009]

The in-mold coating resin composition of the invention of claim 1 contains a polyamine or an unsaturated amine, a resin having a carboxyl group, and a coloring pigment, and has a thickening effect after compounding. It is characterized in that the viscosity is adjusted to 150 poise to 550 poise (25 ° C.).

The in-mold coating resin composition of the invention of claim 2 is
Polyamine or unsaturated amine, polycarboxylic acid,
The composition is characterized by containing a coloring pigment and having a viscosity adjusted to 150 poises to 550 poises (25 ° C.) by a thickening effect after compounding.

The in-mold coating resin composition of the third aspect of the invention is
It contains a polyamine, an unsaturated carboxylic acid, and a coloring pigment, and has a viscosity of 150 poise to 5 due to the thickening effect after compounding.
It is characterized by being adjusted to 50 poise (25 ° C).

The in-mold coating resin composition of the invention of claim 4 is
It contains an oxide or hydroxide of an alkaline earth metal element or zinc, a resin having a carboxyl group, and a coloring pigment, and has a viscosity of 150 poise due to the thickening effect after compounding.
It is characterized by being adjusted to 550 poise (25 ° C).

In the above, polyamine means a compound having two or more --NH ₂ groups in the molecule, and unsaturated amine means a compound having a reactive unsaturated bond and --NH ₂ group in the molecule. is doing. Also, polycarboxylic acid means a compound having a plurality of carboxyl groups in the molecule,
The unsaturated carboxylic acid means a compound having an ethylenically unsaturated bond and a carboxyl group.

The inventions of claims 1 to 4 will be described in detail below. In the in-mold coating resin composition of the inventions of claims 1 to 4, a thermosetting resin is used as a resin main component. For example, unsaturated polyester resin, epoxy acrylate resin, urethane acrylate resin and the like are used. These resins may be used alone or as a mixture of plural kinds. When the thermosetting resin as the resin main component has a carboxyl group, this thermosetting resin may be the resin having a carboxyl group in claims 1 and 4.

Here, as the urethane acrylate resin, a conventionally known and conventional one is used. That is, 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.

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

The above-mentioned epoxy acrylate resin can also be produced by a well-known and conventional method.
It is produced from an epoxy resin and a monocarboxylic acid having a reactive double bond such as (meth) acrylic acid.

As the resin having a carboxyl group in the inventions of claims 1 and 4, both a thermosetting resin having a carboxyl group and a thermoplastic resin having a carboxyl group can be used. Here, the carboxyl group is, in addition to the carboxyl group itself, one that can be easily hydrated to form a carboxyl group, that is, an acid anhydride, and a carboxylic acid metal salt that is easily ion-exchanged with water molecules to form a carboxyl group. including.

Examples of the thermosetting resin having a carboxyl group include a carboxyl group-terminated unsaturated polyester resin, a carboxyl group-containing epoxy acrylate resin, and a carboxyl group-containing urethane acrylate resin.

Here, the unsaturated polyester resin having a carboxyl group terminal refers to an unsaturated polyester resin in which at least one of the resin terminals has a carboxyl group, which is used in the raw material when synthesizing the unsaturated polyester resin. It can be easily obtained by synthesizing so that the number of carboxyl groups is equal to or larger than the number of hydroxyl groups.

The carboxyl group-containing epoxy acrylate resin is specifically obtained, for example, by reacting an epoxy acrylate resin with a polybasic acid anhydride.

The carboxyl group-containing urethane acrylate resin is, for example, a urethane resin having a hydroxyl group remaining so that the number of hydroxyl groups in the raw material at the time of synthesizing the urethane acrylate resin is equal to or larger than the number of isocyanate groups. It can be easily obtained by a method of synthesizing and further adding a polybasic acid anhydride or the like to the hydroxyl group.

As the thermoplastic resin having a carboxyl group, any conventionally known thermoplastic resin can be used.
For example, a saturated polyester having a carboxyl group at the terminal and various resins obtained by copolymerizing an unsaturated monomer containing an unsaturated carboxylic acid are used. As the saturated polyester having a carboxyl group at the terminal, specifically, when the polyol and polycarboxylic acid are polymerized to synthesize a resin, the number of hydroxyl groups and carboxyl groups in the raw material is almost equal or the amount of hydroxyl groups is large. There may be mentioned those which are compounded and synthesized so that Further, as the resin obtained by copolymerizing an unsaturated monomer containing an unsaturated carboxylic acid, specifically, for example, a carboxyl group obtained by mixing acrylic acid, methacrylic acid, etc. with a monomer such as methyl methacrylate, and polymerizing the mixture. Acrylic resin containing, a carboxyl group-containing polystyrene resin obtained by mixing and polymerizing the same unsaturated monomer and styrene as described above are used. Of course, a homopolymer of the above unsaturated monomer may be used.

[0024] The polyamine used in the invention of claims 1 to 3, but those having a plurality of -NH ₂ group in the molecule, wherein as the -NH ₂ group -NH ₂ group and primary amide of the amino group -NH ₂ group or the like in the group. For example, as those having a plurality of amino groups, melamine, ethylenediamine, diethylenetriamine, triethylenetetramine,
Tetraethylenepentamine, benzoguanamine, acetoguanamine, acryloguanamine, paramine, amidole, 1,3 diaminopropane, 1,4 diaminobutane,
1,5 diaminopentane, 1,6 diaminohexane,
1,7 diaminoheptane, 1,8 diaminooctane,
1,9 diaminononane, 1,10 diaminodecane, 1,
11 diaminoundecane, 1,12 diaminododecane,
There are 1,2 diamino 2-methylpropane and the like, and examples of those having a plurality of primary amide groups include adipamide, orthophthalamide, isophthalamide, terephthalamide and the like.

The unsaturated amine used in the inventions of claims 1 and 2 is, for example, an ethylenically unsaturated bond or --NH ₂
But are used those having a group, as the -NH ₂ group, -N during -NH ₂ group or a primary amide group of the amino group
H ₂ group, and the like. For example, as those having an amino group, allylamine, 2 amino 1,1,3 tricyano 1
There are propene and the like, and examples of those having a primary amide group include maleamide, fumaramide, acrylamide,
Methacrylamide and the like.

As the unsaturated carboxylic acid used in the invention of claim 3, a conventionally known one is used. That is, in addition to maleic acid, fumaric acid, itaconic acid, which are aliphatic unsaturated carboxylic acids as described above, acrylic acid, methacrylic acid, phthalic acid monohydroxyethyl acrylate, succinic acid monohydroxyethyl acrylate, etc. , Phthalic acid monohydroxyethyl methacrylate, succinic acid monohydroxyethyl methacrylate and the like are used.

As the polycarboxylic acid used in the invention of claim 2, an aliphatic unsaturated or saturated carboxylic acid, an aromatic carboxylic acid and the like can be used. As the aliphatic unsaturated carboxylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, etc. are used, as the aliphatic saturated carboxylic acid, sebacic acid, adipic acid, (anhydrous) succinic acid, etc. Group carboxylic acid (anhydrous)
Phthalic acid, isophthalic acid, terephthalic acid, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride and the like are used. These polycarboxylic acids can also be used as a raw material for the unsaturated polyester resin.

As the polyol used as a raw material for the unsaturated polyester resin and the urethane acrylate resin, conventionally known ones are used. They are,
Examples thereof include diols, triols, tetraols, and mixtures thereof, and they are mainly classified into aliphatic polyols and aromatic polyols. Among them, typical aliphatic polyols include ethylene glycol, propylene glycol, dipropylene glycol. , Butylene glycol, diethylene glycol, diisopropylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, butanediol,
Neopentyl glycol, dibromoneopentyl glycol, hexamethylene glycol, trimethylene glycol, trimethylolpropane, glycerin, pentaerythritol diallyl ether, hydrogenated bisphenol A
And typical aromatic polyols are bisphenol A or bisphenol S or bisphenol A or bisphenol S thereof.
In addition, there are polyoxyalkylene bisphenol A and polyoxyalkylene bisphenol S obtained by adding an aliphatic oxirane compound such as ethylene oxide, propylene oxide or butylene oxide in the range of 1 to 20 on average in one molecule.

As the polyol used as the raw material of the urethane acrylate resin, the above-mentioned polyols are used, and also polyethers such as polyoxymethylene, polyethylene oxide and polypropylene oxide,
A polyester polyol having hydroxyl groups at both ends, which is produced from the above-described organic polyol and polycarboxylic acid, may also be used.

The epoxy resin used in the above-mentioned epoxy acrylate resin can be produced by a known and conventional method. A bisphenol A type epoxy resin produced from epichlorohydrin and bisphenol A, a bromine produced from epichlorohydrin and brominated bisphenol A. Bisphenol A type epoxy resin, novolak type epoxy resin produced by glycidyl etherification of phenol novolac or orthocresol novolak, tetraglycidyl metaxylenediamine, tetraglycidyl 1.3-bis obtained by reacting various amines with epichlorohydrin Aminomethylcyclohexane, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-
Glycidyl amine compounds such as m-aminophenol, diglycidyl aniline and diglycidyl orthotoluidine are used.

As the polyisocyanate used as the raw material of the urethane acrylate resin, conventionally known polyisocyanates are used. For example, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, 3,3′-dichlorodiphenyl-4,4 ′ diisocyanate, metaphenylene diisocyanate, trimethylhexamethylene diisocyanate, metaxylene diisocyanate, etc. It is possible to use the isocyanurate obtained by condensing the polyisocyanate of.

The hydroxyalkyl (meth) acrylate used in the urethane acrylate resin is usually hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc., 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.

When the thermosetting resin having a carboxyl group and the polyamine are used in the invention of claim 1, the amount of the thermosetting resin having a carboxyl group to be used depends on the molecular weight of the resin used, the viscosity, and the composition of other compounding materials. The amount of the resin component (the total amount of the thermosetting resin, the copolymerizable monomer, and the thermoplastic resin) is preferably about 3 to 50% by weight, though it depends on the amount of the resin, the amount of the compound, and the like. If the amount of the thermosetting resin having a carboxyl group to be used is too small, the composition does not reach a sufficient viscosity, so that color unevenness due to pigment separation is likely to occur during in-mold flow, and if too large, the viscosity is too high. May become too high, resulting in poor fluidity in the mold.

When a thermosetting resin having a carboxyl group and a polyamine are used in the invention of claim 1, the amount of the polyamine used varies depending on the molecular weight of the resin used, the viscosity, the composition of other compounding materials, the compounding amount and the like. However, about 1 to 10% by weight is preferable with respect to the resin component (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin). When the amount of the polyamine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation is liable to occur during in-mold flow, and when it is too large, the viscosity becomes too high, In some cases, the fluidity inside may deteriorate.

When the thermosetting resin having a carboxyl group and the polyamine are used in the invention of claim 1, the ratio of the amount of the thermosetting resin having a carboxyl group to the polyamine used is the ratio of the carboxyl group to the --NH ₂ group. The (carboxyl group / -NH ₂ group) is preferably about 0.8 to 5. When the amount of the polyamine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation is liable to occur during in-mold flow, and when it is too large, the viscosity becomes too high, In some cases, the fluidity inside may deteriorate.

When a thermosetting resin having a carboxyl group and an unsaturated amine are used in the invention of claim 1, the amount of the thermosetting resin having a carboxyl group to be used is determined by the molecular weight of the resin used, the viscosity, and other compounding materials. Although it depends on the composition, the amount of the compound, and the like, it is preferably about 3 to 50% by weight of the resin component (the total amount of the thermosetting resin, the copolymerizable monomer, and the thermoplastic resin). If the amount of the thermosetting resin having a carboxyl group to be used is too small, the composition does not reach a sufficient viscosity, so that color unevenness due to pigment separation is likely to occur during in-mold flow, and if too large, the viscosity is too high. May become too high, resulting in poor fluidity in the mold.

When a thermosetting resin having a carboxyl group and an unsaturated amine are used in the invention of claim 1, the amount of the unsaturated amine (which is also a copolymerizable monomer) used is the molecular weight of the resin used, the viscosity, etc. The composition of the compounding material of
And as a resin component (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin) is 2 to
About 20% by weight is preferable. If the amount of the unsaturated amine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation during flow in the mold is likely to occur.
On the other hand, if the amount is too large, the viscosity may be too high and the fluidity in the mold may be deteriorated.

When a thermosetting resin having a carboxyl group and an unsaturated amine are used in the invention of claim 1, the ratio of the amounts of the thermosetting resin having a carboxyl group and the unsaturated amine is such that the carboxyl group and --NH ₂ As the ratio of groups, 0.8
About 5 is preferable. If the amount of the unsaturated amine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation during flow in the mold is likely to occur.
If the amount is too large, the viscosity becomes too high, and the fluidity in the mold may deteriorate.

When the thermoplastic resin having a carboxyl group and the polyamine are used in the invention of claim 1, the amount of the thermoplastic resin having a carboxyl group to be used may be the molecular weight of the resin to be used, the viscosity and the composition of other compounding materials. The amount of the resin component (the total amount of the thermosetting resin, the copolymerizable monomer, and the thermoplastic resin) is preferably about 2 to 20% by weight, though it varies depending on the compounding amount, the compounding amount and the like. If the amount of the thermoplastic resin having a carboxyl group to be used is too small, the composition does not reach a sufficient viscosity, so that color unevenness due to pigment separation during flow in the mold is likely to occur. It may become too high, resulting in poor fluidity in the mold.

When the thermoplastic resin having a carboxyl group and the polyamine are used in the invention of claim 1, the amount of the polyamine used varies depending on the molecular weight of the resin used, the viscosity, the composition of other compounding materials, the compounding amount and the like. The resin content (total amount of thermosetting resin, copolymerizable monomer, and thermoplastic resin) is preferably about 1 to 10% by weight. When the amount of the polyamine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation is liable to occur during in-mold flow, and when it is too large, the viscosity becomes too high, In some cases, the fluidity inside may deteriorate.

When the thermoplastic resin having a carboxyl group and the polyamine are used in the invention of claim 1, the ratio of the amount of the thermoplastic resin having a carboxyl group to the polyamine used is the ratio of the carboxyl group to the --NH ₂ group. 0.
It is preferably about 8 to 5.0. When the amount of the polyamine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation is liable to occur during in-mold flow, and when it is too large, the viscosity becomes too high, In some cases, the fluidity inside may deteriorate.

When the thermoplastic resin having a carboxyl group and the unsaturated amine are used in the invention of claim 1, the amount of the thermoplastic resin having a carboxyl group to be used may be the molecular weight of the resin to be used, the viscosity and the composition of other compounding materials. The amount of the resin component (the total amount of the thermosetting resin, the copolymerizable monomer, and the thermoplastic resin) is preferably about 2 to 20% by weight, though it varies depending on the compounding amount, the compounding amount and the like. If the amount of the unsaturated amine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation during flow in the mold is likely to occur, and if too large, the viscosity becomes too high. , The fluidity in the mold may deteriorate.

When the thermoplastic resin having a carboxyl group and the unsaturated amine are used in the invention of claim 1, the amount of the unsaturated amine (which is also a copolymerizable monomer) used is such as the molecular weight of the resin used, the viscosity and other factors. Composition of compounding materials,
And resin content (thermosetting resin,
The total amount of the copolymerizable monomer and the thermoplastic resin is preferably about 2 to 20% by weight. If the amount of the unsaturated amine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation during flow in the mold is likely to occur.
If the amount is too large, the viscosity becomes too high, and the fluidity in the mold may deteriorate.

When a thermoplastic resin having a carboxyl group and an unsaturated amine are used in the invention of claim 1,
The ratio of the amount of the thermoplastic resin having a carboxyl group to the unsaturated amine used is preferably about 0.8 to 5.0 as the ratio of the carboxyl group to the —NH ₂ group. If the amount of the unsaturated amine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation during flow in the mold is likely to occur, and if too large, the viscosity becomes too high. , The fluidity in the mold may deteriorate.

When the polyamine is used in the invention of claim 2, the amount of the polyamine used varies depending on the molecular weight of the resin used, the viscosity, the composition of other compounding materials, the compounding amount, etc., but the resin component (thermosetting resin , The total amount of the copolymerizable monomer and the thermoplastic resin) is preferably about 1 to 10% by weight. When the amount of the polyamine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation is liable to occur during in-mold flow, and when it is too large, the viscosity becomes too high, In some cases, the fluidity inside may deteriorate.

When the polyamine is used in the invention of claim 2, the amount of the polyamine used varies depending on the molecular weight of the resin used, the viscosity, the composition of other compounding materials, the compounding amount, etc., but the resin component (thermosetting resin , The total amount of the copolymerizable monomer and the thermoplastic resin) is preferably about 1 to 10% by weight. When the amount of the polyamine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation is liable to occur during in-mold flow, and when it is too large, the viscosity becomes too high, In some cases, the fluidity inside may deteriorate.

When a polyamine is used in the invention of claim 2, the ratio of the amounts of polycarboxylic acid and polyamine used is the ratio of the number of carboxyl groups to the number of --NH ₂ groups.
It is preferably about 0.8 to 1.2. If either one of the --NH ₂ group or the carboxyl group is excessive, the thickening reaction does not proceed sufficiently, the composition does not reach a sufficient viscosity, and color unevenness occurs due to pigment separation when flowing in the mold. It may be easier.

When an unsaturated amine is used in the invention of claim 2, the amount of the unsaturated amine (which is also a copolymerizable monomer) to be used is determined by the molecular weight and viscosity of the resin used, the composition of other compounding materials, and the compounding amount. 2 of resin component (total amount of thermosetting resin, copolymerizable monomer, thermoplastic resin)
It is preferably about 20% by weight. If the amount of the unsaturated amine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation during flow in the mold is likely to occur, and if too large, the viscosity becomes too high. , The fluidity in the mold may deteriorate.

When an unsaturated amine is used in the invention of claim 2, the amount of polycarboxylic acid used varies depending on the molecular weight of the resin used, the viscosity, the composition of other compounding materials, the compounding amount, etc. The total amount of the curable resin, the copolymerizable monomer, and the thermoplastic resin is preferably about 1 to 10% by weight.
When the amount of the polycarboxylic acid used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation during flow in the mold is likely to occur, and when too large, the viscosity becomes too high. , The fluidity in the mold may deteriorate.

When a polyamine is used in the invention of claim 2, the ratio of the amount of polycarboxylic acid to the amount of polyamine used is the ratio of the number of carboxyl groups to the number of --NH ₂ groups.
It is preferably about 0.8 to 1.2. If either the carboxyl group or the --NH ₂ group is excessive, the thickening reaction does not proceed sufficiently, the composition does not reach a sufficient viscosity, and color unevenness occurs due to pigment separation when flowing in the mold. It may be easier.

The amount of the polyamine used in the invention of claim 3 depends on the molecular weight of the resin used, the viscosity, the composition of other compounding materials,
And resin content (thermosetting resin,
1 to the total amount of the copolymerizable monomer and the thermoplastic resin)
About 10% by weight is preferable. When the amount of the polyamine used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation is liable to occur during in-mold flow, and when it is too large, the viscosity becomes too high, In some cases, the fluidity inside may deteriorate.

The amount of unsaturated carboxylic acid (which is also a copolymerizable monomer) used in the invention of claim 3 varies depending on the molecular weight of the resin used, the viscosity, the composition of other compounding materials, the compounding amount, etc. (Thermosetting resin, copolymerizable monomer,
It is preferably about 2 to 20% by weight of the total amount of the thermoplastic resin). When the amount of the unsaturated carboxylic acid used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation is liable to occur during in-mold flow, and when too large, the viscosity becomes too high. Therefore, the fluidity in the mold may deteriorate.

As for the ratio of the amount of unsaturated carboxylic acid and polyamine in the invention of claim 3, the ratio of the number of carboxyl groups and the number of --NH ₂ groups is preferably about 0.8 to 5.0. . Carboxyl group or -NH
_{If one of the two} groups is excessive, the thickening reaction may not proceed sufficiently, the composition may not reach a sufficient viscosity, and color unevenness due to pigment separation may easily occur during flow in the mold. is there.

In the invention of claim 4, when a thermosetting resin having a carboxyl group is used as the resin having a carboxyl group, the amount thereof is a resin component (the total amount of the thermosetting resin, the copolymerizable monomer and the thermoplastic resin. 1 to 40% by weight is preferable. If the amount of the carboxyl group-containing thermosetting resin used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation is likely to occur during in-mold flow, and if too large, the viscosity is too high. It may become too high, resulting in poor fluidity in the mold.

When a thermoplastic resin having a carboxyl group is used as the resin having a carboxyl group, the amount thereof is about 1 to 15% by weight of the resin component (total amount of thermosetting resin, copolymerizable monomer and thermoplastic resin). Is preferred.
If the amount of the carboxyl group-containing thermoplastic resin used is too small, the composition does not reach a sufficient viscosity, and thus color unevenness due to pigment separation tends to occur during in-mold flow, and if too large, the viscosity is high. If it becomes too much, the fluidity in the mold may deteriorate.

When both a thermosetting resin having a carboxyl group and a thermoplastic resin having a carboxyl group are used as the resin having a carboxyl group, the total amount thereof is about 1 to 30% by weight of the resin. preferable. If the amount of the carboxyl group-containing thermoplastic resin used is too small,
Since the composition does not reach a sufficient viscosity, color unevenness due to pigment separation is likely to occur when flowing in the mold, and if too much, the viscosity becomes too high and the fluidity in the mold may deteriorate. is there.

As the alkaline earth metal element or zinc oxide or hydroxide in the invention of claim 4,
The thing used as a thickener of SMC or BMC can be used. More preferably, magnesium oxide, magnesium hydroxide, zinc oxide, calcium oxide,
Calcium hydroxide or the like is used.

In the invention of claim 4, the amount of (hydr) oxide of alkaline earth metal or zinc varies depending on the molecular weight and viscosity of the resin used, the composition of other compounding materials, the compounding amount, etc. It is preferably about 0.1 to 2% by weight based on the total amount of the thermosetting resin, the thermoplastic resin and the copolymerizable monomer. When the amount of the alkaline earth metal or zinc (hydroxide) used is too small, the composition does not reach a sufficient viscosity, which causes color unevenness due to pigment separation during flow in the mold, and is too large. In this case, the viscosity may become too high, resulting in poor fluidity in the mold.

In addition, the resin composition for in-mold coating according to any one of claims 1 to 4 contains, as a low-shrinking agent, polyvinyl acetate, polymethyl (meth) acrylate, polyethylene, ethylene vinyl acetate copolymer, vinyl acetate-styrene copolymer. Thermoplastic resins such as polymers, polybutadiene, saturated polyesters, saturated polyethers, etc. can be used in suitable amounts as needed.

As the color pigments used in the inventions of claims 1 to 4, conventionally known pigments are used. For example, titanium oxide, benzine yellow, anthraquinone yellow, titanium yellow, Hansa yellow, molybdate orange,
Yellow lead, disazo yellow, benzine orange, quinacridone red, quinacridone magenta, naphthol violet, chrome green, phthalocyanine green, alkali blue, cobalt blue, phthalocyanine blue, iron oxide (red iron oxide), copper azo brown, aniline black, carbon black, iron Various known and commonly used ones such as black are used.

Among the above-mentioned color pigments, when color pigments such as titanium oxide, titanium yellow, quinacridone red, iron oxide and carbon black are used, the occurrence of color unevenness is particularly large during coating molding. When an in-mold coating resin composition is to be obtained using the color pigment of (1), the in-mold coating resin composition of the inventions of claims 1 to 4 is particularly effective.

The amount of the color pigment added is preferably 3 to 130 parts by weight based on 100 parts by weight of the resin component (total amount of thermosetting resin, thermoplastic resin and copolymerizable monomer). When the addition amount is 3 parts or less, it is difficult to obtain sufficient coloring power and hiding power in the obtained coating material, and when the addition amount is more than 130 parts, the viscosity becomes too high and the fluidity in the mold deteriorates, resulting in a molding material. It may be difficult to spread over the entire surface.

Further, an appropriate amount of an extender pigment, that is, an inorganic filler can be added to the in-mold coating resin composition according to the first to fourth aspects of the invention, depending on the purpose and application. Examples of usable inorganic fillers are as follows. That is,
Elemental minerals such as graphite and diamond, halogenated minerals such as rock salt and potassium rock salt, carbonate minerals such as calcium carbonate, phosphate minerals such as cyanite, vanadate minerals such as carnotite, barite (barium sulfate) ), Sulfate minerals such as gypsum (calcium sulfate), borate minerals such as borax, titanate minerals such as perovskite, mica,
Silicate minerals such as talc (talc), pyrophyllite, kaolin, quartz, and feldspar, metal oxides such as titanium oxide, corundum (aluminum oxide), and aluminum hydroxide,
Glass products such as (hollow) glass spheres, natural or artificial minerals such as glass spheres, processed or purified or processed minerals, and mixtures thereof are used.

The filler is added in an amount of 0 to 100 parts by weight, based on 100 parts by weight of the resin component (total amount of thermosetting resin, thermoplastic resin, and copolymerizable monomer), extender pigment and coloring pigment. It is preferable to add 3 to 150 parts by weight as the sum of the above. If the addition amount exceeds 150 parts, the viscosity becomes too high, so that the flow in the mold becomes poor and it may be difficult to spread the molding material over the entire surface.

Further, various reinforcing fibers, that is, glass fibers, carbon fibers and the like can be added to the in-mold coating resin composition of the inventions of claims 1 to 4 as a reinforcing agent, if necessary. Further, if necessary, 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, titanium oxide, iron oxide, cyanine pigments, aluminum flakes, nickel powder, gold powder, silver powder and other pigments, azo dyes, anthraquinone dyes, indigoid dyes, stilbene dyes, etc. with conductivity Agents, emulsifying agents, metal soaps such as zinc stearate, fatty acid salts, and the like release agents such as lecithin applications, may be added an appropriate amount depending on the purpose.

When these compositions are blended, of course, various blending materials may be mixed at once, but in order to disperse the pigment for a long time at a lower viscosity, polyamine, unsaturated amine Etc., the pigment is dispersed without adding only the amine component or the (hydr) oxide component, and then the amine component or the (hydr) oxide component is added, or
More preferably, the pigment is dispersed without containing the carboxylic acid component, and the carboxylic acid component is added later.

Further, it is necessary to increase the viscosity of the in-mold coating resin composition of the first to fourth aspects of the invention after kneading and dispersing the pigment. Kneading and pigment dispersion work is usually at room temperature to 5
It is performed in an environment of about 0 ° C. and within 20 minutes to 2 hours to prevent a thickening reaction.

The in-mold coating resin composition according to any one of claims 1 to 4 is usually left at room temperature or several tens of degrees Celsius for several hours to several days to be aged to be thickened to increase the viscosity. A composition. The viscosity is preferably adjusted to 10 to 120 poise at the time of blending, kneading and dispersing the pigment, and the viscosity after thickening needs to be increased to be in the range of 150 to 550 poise. Preferably 2
It is from 00 to 500 poise.

If the viscosity at the time of compounding, kneading and dispersing the pigment is too low, it is difficult to increase the viscosity to a sufficient viscosity after thickening, and the pigment and the filler tend to settle during the thickening. Have. Further, if the viscosity at the time of compounding, kneading, and dispersing the pigment is too high, it is difficult to uniformly disperse the pigment, and color unevenness is likely to occur during coating molding. Further, if the viscosity after thickening is too low, color unevenness is likely to occur during in-mold coating molding, and if the viscosity after thickening is too high, the fluidity in the mold deteriorates and the coating material is spread over the entire surface. It has the drawback of being difficult to do.

The in-mold coating resin composition of the invention of claim 1 can be obtained by using the above-mentioned various compounding materials.
Specifically, for example, a styrene solution of an unsaturated polyester resin, a carboxyl group-containing epoxy acrylate resin esterified with a dicarboxylic acid, and a carboxyl group-containing urethane acrylate resin (styrene concentration 40 to 70).
%) 60 to 100 parts with respect to 0 to 20 parts of a carboxyl group-containing thermoplastic resin such as a carboxyl group-containing acrylic resin or styrene-acrylic acid copolymer, styrene of a thermoplastic resin such as polymethylmethacrylate, polystyrene, or polyvinyl acetate. Solution (styrene concentration 30-80%) 0-3
Add 0 parts to make 100 parts, and 1 to 10 parts of polyamines such as melamine and ethylenediamine or 2 to 20 parts of unsaturated amines such as allylamine and methacrylamide, coloring pigments such as titanium oxide, iron oxide, carbon black and titanium yellow 5 To 100 parts, 100 to 200 parts of filler powder such as calcium carbonate and aluminum hydroxide, and 0.1 to 5 parts of organic peroxide as an initiator are added, kneaded and dispersed to prepare 1
A composition having a composition of 0 to 120 poise, and then aged at a temperature of room temperature to about 50 ° C. for several hours to several days to be aged to increase its viscosity to 200 poise to 500 poise is preferably used. To be

Similarly, the in-mold coating resin composition of the invention of claim 2 can be obtained by using the above-mentioned various compounding materials. Specifically, for example, unsaturated polyester resin,
Styrene solution of epoxy acrylate resin and urethane acrylate resin (styrene concentration 40-70%) 60-1
Add 0 to 30 parts of a styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, or polyvinyl acetate (styrene concentration 30 to 80%) to 00 parts to obtain 1 part.
00 parts, 1 to 10 parts of polyamine such as melamine and ethylenediamine or 2 to 20 parts of unsaturated amine such as allylamine and methacrylamide, 1 to 10 parts of polycarboxylic acid such as adipic acid, isophthalic acid and terephthalic acid, titanium oxide, Add 5 to 100 parts of a coloring pigment such as iron oxide, carbon black and titanium yellow, 100 to 200 parts of filler powder such as calcium carbonate and aluminum hydroxide, and 0.1 to 5 parts of organic peroxide as an initiator. After kneading and dispersing to form a composition of 10 to 120 poise, the composition is left to stand at room temperature to about 50 ° C. for several hours to several days to be aged, and the viscosity is increased to 200 poise to 500 poise. Is preferably used.

Similarly, the in-mold coating resin composition of the invention of claim 3 can be obtained by using the above-mentioned various compounding materials. Specifically, for example, unsaturated polyester resin,
Styrene solution of epoxy acrylate resin and urethane acrylate resin (styrene concentration 40-70%) 60-1
To 00 parts, 0 to 30 parts of a polystyrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, or polyvinyl acetate (styrene concentration 30 to 80%) is added to 100 parts to make polyamines 1 to 10 such as melamine and ethylenediamine. Parts, unsaturated carboxylic acids such as methacrylic acid 2
˜20 parts, color pigments such as titanium oxide, iron oxide, carbon black and titanium yellow 5 to 100 parts, filler powders such as calcium carbonate and aluminum hydroxide 100 to 20
After adding 0 part and 0.1 to 5 parts of an organic peroxide as an initiator and kneading and dispersing to form a composition of 50 to 120 poise, the composition is heated to room temperature to about 50 ° C. for several hours to several days. Those that are left to stand and aged to increase their viscosity from 200 poise to 500 poise are preferably used.

Similarly, the in-mold coating resin composition of the invention of claim 4 can be obtained by using the above-mentioned various compounding materials. Specifically, for example, unsaturated polyester resin,
Carboxyl group-containing epoxy acrylate resin esterified with dicarboxylic acid, styrene solution of carboxyl group-containing urethane acrylate resin (styrene concentration 40
To 70%) 60 to 100 parts by weight, and 0 to 20 parts by weight of a carboxyl group-containing thermoplastic resin such as a carboxyl group-containing acrylic resin and styrene-acrylic acid copolymer, and a thermoplastic resin such as polymethylmethacrylate, polystyrene and polyvinyl acetate. Styrene solution (styrene concentration 30-80%)
Add 0 to 30 parts to make 100 parts, 0.1 to 2 parts of (hydr) oxides such as magnesium oxide, color pigments 5 to 10 such as titanium oxide, iron oxide, carbon black and titanium yellow.
0 part, 100 to 200 parts of filler powder such as calcium carbonate, aluminum hydroxide and 0.1 to 5 parts of organic peroxide as an initiator were added, kneaded and dispersed to obtain a composition of 10 to 120 poise. After that, the mixture is left to stand at room temperature to about 50 ° C. for several hours to several days to be aged, and the viscosity thereof is increased to 200 poises to 500 poises.

Further, as the thermosetting resin composition used as the thermosetting molding material in the inventions of claims 1 to 4,
As the thermosetting resin, unsaturated polyester resin, epoxy acrylate (vinyl ester) resin, urethane acrylate resin, etc. are used, and various fillers,
Reinforcing agents, additives and the like can be added, and can be used as a thermosetting resin composition having a form such as SMC or BMC by a conventionally known method.

Specifically, for example, a styrene solution of an unsaturated polyester resin (styrene concentration 40 to 70%) 60 to
To 100 parts, add 0 to 30 parts of a styrene solution of a thermoplastic resin such as polymethylmethacrylate, polystyrene, or polyvinyl acetate (styrene concentration 30 to 80%) and add 1
100 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 part of an organic peroxide as an initiator.
Reinforcing fiber 1 such as glass fiber
~ 200 parts are impregnated with a kneader or impregnator,
A solid molding material is preferably used because it has excellent moldability, handleability, and physical properties of the molded product.

The in-mold coating resin composition and molding material thus obtained can be used for conventionally known in-mold coating molding. For example, after putting SMC in a molding die heated to 130 to 160 ° C. and performing pressure molding for several tens of seconds to several minutes, the mold is slightly opened to inject the resin composition for coating in the mold, and then several tens of seconds. There is a method of spreading the in-mold coating resin composition on the entire surface of the molded SMC by reheating and repressurizing for a few minutes to cure and form a film.

As disclosed in Japanese Examined Patent Publication No. 4-33252, SMC is heated and pressure molded for several tens of seconds to several minutes, and then 100-300 kg /
There is also a method of injecting the coating material into the mold at a high pressure of cm 2 to spread and cure the in-mold coating resin composition. These thermosetting resin compositions, which are the features of the present invention, are used in these in-mold coating molding methods. If used, it is possible to easily form a uniformly colored coating body without color unevenness.

[0078]

According to the in-mold coating resin composition of the invention of claim 1, after mixing, kneading and dispersing, 2R ₁ COOH + R ₂ (NH ₂ ) ₂ → R ₁ CO
ONHR ₂ NHOCOR ₁ (R ₁ : resin residue having a carboxyl group, R ₂ : polyamine residue)

R ₃ COOH + R ₄ NH ₂ → R ₃
OCONHR ₄ (R ₃ : a residue of a resin having a carboxyl group, R ₄ : an unsaturated amine residue) 2R ₅ COOH + R ₆ (NH ₂ ) ₂ → R ₅ COON
HR ₆ NHOCR ₇ (R ₅ : residue of resin having carboxyl group, R ₆ : polyamine residue)

Alternatively, a reaction of R ₇ COOH + R ₈ NH ₂ → R ₇ COONHR ₈ (R ₇ : a residue of a resin having a carboxyl group, R ₈ : an unsaturated amine residue) occurs to increase the molecular weight, The composition thickens.

The resin composition for in-mold coating of the invention of claim 2
After mixing, kneading, and dispersing, R₉(COOH)₂+ R_Ten(NH₂)₂→ HOCOR₉
COO (NHR_TenNHOCOR₉COO)_n-1NHR_Ten
NH ₂ (R₉: Polycarboxylic acid residue, R_Ten: Polyamine residue)

Alternatively, HOCOR ₁₁ COOH + 2R ₁₂ NH ₂ → R ₁₂ N
The reaction of HOCOR ₁₁ COONHR ₁₂ (R ₁₁ : polycarboxylic acid residue, R ₁₂ : unsaturated amine residue) occurs, the molecular weight increases, and the composition thickens.

In the resin composition for in-mold coating of the invention of claim 3, 2R ₁₃ COOH + R ₁₄ (NH ₂ ) ₂ → R ₁₃ COO is added after mixing, kneading and dispersing.
The reaction of NHR ₁₄ NHOCOR ₁₃ (R ₁₃ : unsaturated carboxylic acid residue, R ₁₄ : polyamine residue) occurs, the molecular weight increases, and the composition thickens.

In the resin composition for in-mold coating of the invention of claim 4, after compounding, kneading and dispersing, 2R ₁₅ COOH + MeO → R ₁₅ CO
OMeOCOR ₁₅ or 2R ₁₆ COOH + Me (0H) ₂ → R ₁₆ CO
OMeOCOR ₁₆ Me: alkaline earth metal or zinc R ₁₅ , R ₁₆ : thermosetting resin skeleton or thermoplastic resin skeleton, the molecular weight increases, and the composition thickens.

It takes several hours to several days for these reactions to proceed. Therefore, at the time of mixing the respective blended materials and dispersing the raw materials, the composition has a low viscosity and the pigment is well dispersed. After that, the viscosity increases in a few hours to a few days.
In the inventions of claims 1 to 4, the viscosity when used for in-mold coating molding after the thickening is 150 poises to 550 poises (25 poises).
℃) is adjusted. Since the viscosity when used for molding is 150 poise or more, it is possible to obtain a uniform film with no pigment separation when flowing in the mold and without color unevenness. Further, since the viscosity when used for molding is 550 poise or less, sufficient fluidity can be secured in the mold.

[0086]

Embodiments of the present invention will be described below. In addition, below, a part means a weight part.

[Production of resin composition for coating in mold] The following materials were used as compounding materials. 1) Unsaturated Polyester Resin Liquid Isophthalic acid (manufactured by Wako Pure Chemical Industries, Ltd.), maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), by a known and commonly used method. Then, unsaturated polyester resin was synthesized and dissolved in styrene. (Hereinafter, abbreviated as UP, molar ratio of isophthalic acid / maleic anhydride / propylene glycol = 6: 4: 10, average molecular weight of about 2000, average carboxyl group content of 1.0
Individual, styrene concentration in resin liquid is about 40% by weight)

2) Carboxyl Group-Containing Epoxy Acrylate Resin Solution A bisphenol A type epoxy resin is methacrylic acid esterified by a well-known method to obtain an epoxy acrylate resin, which is reacted with maleic anhydride to contain a carboxyl group. It was used as an epoxy acrylate resin and dissolved in styrene (hereinafter referred to as EAAc, average molecular weight of about 700, average carboxyl group content of 1.0, styrene concentration in resin solution of about 40% by weight).

3) Epoxy Acrylate Resin Liquid A bisphenol A type epoxy resin was methacrylic acid esterified by a known and conventional method to obtain an epoxy acrylate resin, which was dissolved in styrene (hereinafter referred to as EAc, average molecular weight about 600, carboxyl). Group content of about 0.
0, the styrene concentration in the resin liquid is about 40% by weight).

4) Urethane acrylate resin liquid polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.,
Using an average molecular weight of about 1000), tolylene diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) and 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), a urethane acrylate resin was synthesized by a known and conventional method to give styrene. Dissolved (hereinafter, abbreviated as UAc, average molecular weight about 1600, carboxyl group content about 0.0, styrene concentration in resin liquid about 40% by weight)

5) Carboxyl group-containing acrylic resin (a resin having an average molecular weight of about 10,000 by polymerizing 95 mol% of methyl methacrylate monomer and 5 mol% of methacrylic acid, hereinafter abbreviated as APMMA)

6) Hexamethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as HMA) 7) Melamine (Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as ME) 8) Adipic acid (Wako Pure Chemical Industries, Ltd.) Co., Ltd., AA
9) Isophthalic acid (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter, I)
PA) 10) Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter M)
(Abbreviated as A)

11) Phthalic acid monohydroxyethyl acrylate (Wako Pure Chemical Industries, Ltd., abbreviated as PMA) 12) Methacrylamide (Wako Pure Chemical Industries, Ltd., abbreviated as MAA) 13) Allylamine (Japanese Koujunyaku Kogyo Co., Ltd., hereinafter A
RA) 14) Magnesium oxide (Kyowa Chemical Industry Co., Ltd.) 15) Calcium oxide (Wako Pure Chemical Industries Ltd.)

16) Zinc oxide (Wako Pure Chemical Industries, Ltd.) 17) Magnesium hydroxide (Wako Pure Chemical Industries, Ltd.) 18) Zinc hydroxide (Wako Pure Chemical Industries, Ltd.) 19) Titanium oxide (Tai Pure) 900, DuPont) 20) Titanium Yellow (Yellow 9121, Dainichiseika)

21) Calcium carbonate (NS-100, manufactured by Nitto Koka Co., Ltd.) 22) Curing agent (Kayabutyl B, manufactured by Kayaku Akzo Co., Ltd.)

These were mixed according to the following formulation table (Tables 1 to 5), and at room temperature (25 ° C.), the total amount of the formulation was 500 g.
And 500 g of glass beads having a diameter of 5 mm were dispersed by a disperser (Dispermat, manufactured by Kansai Paint Co., Ltd.) for 30 minutes, and then the glass beads were filtered and left at room temperature for 1 day to obtain a resin composition for coating in a mold. .

Tables 1 to 5 show the viscosity immediately after filtration and the viscosity after thickening. The abbreviations shown in Tables 1 to 5 are summarized below. UP: Unsaturated polyester resin liquid AEAc: Carboxyl group-containing epoxy acrylate resin liquid EAc: Epoxy acrylate resin liquid UAc: Urethane acrylate resin liquid APMMA: Carboxyl group-containing acrylic resin HMA: Hexamethylenediamine ME: Melamine AA: Adipic acid IPA: Isophthalate Acid MA: Methacrylic acid PMA: Phthalic acid monohydroxyethyl acrylate MAA: Methacrylamide ARA: Allylamine

[Preparation of Thermosetting Molding Material] The following materials were used as the compounding materials. 1. 70 parts of unsaturated polyester resin liquid (hydrogenated bisphenol-based unsaturated polyester resin dissolved in about 40% by weight of styrene monomer)

2. Polystyrene low-shrinking agent resin (about 30% by weight of polystyrene resin dissolved in about 70% by weight of styrene monomer) 30 parts 3. 120 parts of calcium carbonate powder (NS-100: manufactured by Nitto Koka Co., Ltd.) 4. Curing agent (Kayabutyl B: Kayaku Akzo Co., tertiary butyl peroxobenzoate content 98% by weight)
1 copy

5. Thickener (magnesium oxide powder, Kyowamag 150: Kyowa Chemical Industry Co., Ltd.) 1 part 6. 6. Internal release agent (zinc stearate: manufactured by Sakai Chemical Industry Co., Ltd.) 3 parts The above materials are mixed and sufficiently stirred, and then by an SMC impregnating device. 60 parts of glass fiber (Roving made by Asahi Fiber Glass Co., Ltd .: ER4630LBD166W cut into a length of 25 mm) was impregnated with 60 parts to obtain SMC.

[Molding method] The SM thus obtained
The C and in-mold coating resin composition were molded as follows.

A mold for molding a molded product as shown in FIG. 1 was prepared. 150 ° C for the upper mold and 140 ° C for the lower mold
To about 3.4 Kg of SMC,
(This corresponds to a thickness of about 5 mm on the bottom surface and 3 mm on other parts.) After high-pressure molding for 100 seconds at a pressure of 100 kg / cm2, a high-pressure injection machine (Morel attached to the center of the mold without changing the molding pressure). 100 ml of the above resin composition coated in a mold, and reheated and repressed for 120 seconds to spread and cure the thermosetting resin composition coated in a mold on the surface of the molded SMC. To form a film. After that, the mold was opened and the mold was removed to obtain a coated molded product. The coating state and appearance of the molded product were evaluated in stages as follows and shown in Tables 1 to 5. Coating: Full surface coating ×: Partially uncoated Appearance ○: No color unevenness ×: Partial color unevenness × ×: Full surface color unevenness

(Examples 1 to 25) According to the following formulation tables (Tables 1 to 3), coating materials were produced by the above-mentioned method, and molded and evaluated. The results are shown in Tables 1 to 3. In all the examples, it was possible to obtain a coating body which was covered with a cream-colored, uniformly colored coating film without uneven color.

Examples 1 to 3 are examples according to the invention of claim 1, in which carboxy-containing UP and EAAc, which are thermosetting resins of the in-mold coating resin composition, are used as the carboxyl group-containing resin, and polyamines are used. This is an example of using together. Examples 4 and 5 are examples according to the invention of claim 2 and are examples containing a polyamine and a polycarboxylic acid.

Examples 6 and 7 are examples according to the invention of claim 3, which are examples containing a polyamine and an unsaturated carboxylic acid. Examples 8 and 9 are examples according to the invention of claim 2 and contain unsaturated amine and polycarboxylic acid.

Examples 10 and 11 are examples according to the invention of claim 1, and are examples in which a thermosetting resin having a carboxyl group and an unsaturated amine are used in combination. Examples 12-15
Is an embodiment according to the invention of claim 1, wherein a resin having no carboxyl group is used as the thermosetting resin component of the in-mold coating resin composition, and APM is used as the carboxyl group-containing resin.
This is an example using MA.

Example 17 is an example according to the inventions of claims 1 to 4, and an example in which the characteristic components of claims 1 to 4 are respectively contained. Thus, the inventions of claims 1 to 4 may contain the components of the inventions of other claims.

Examples 18 to 25 are examples according to the invention of claim 4, and in Examples 18 to 22, the thermosetting resin component of the in-mold coating resin composition contains a carboxyl group. Examples 23 to 25 are examples in which the thermosetting resin component of the in-mold coating resin composition does not contain a carboxyl group and APMMA is used as the carboxyl group-containing resin.

Comparative Example 1 In accordance with the following formulation table (Table 4),
An in-mold coating resin composition was produced. However, in this case, the color pigment was not uniformly dispersed, and a coating material having a uniform color tone was not obtained. Molding was carried out by the above method, but there was uneven color on the entire surface.

(Comparative Example 2) According to the following formulation table (Table 4),
The coating material was manufactured by the method described above, and molded and evaluated. The results are shown in Table 4. The obtained coating was coated on the entire surface, but in the standing surface and the handrail part,
There was uneven color that was divided into a yellowish part and a whitish part.

(Comparative Example 3) According to the following formulation table (Table 4),
The coating material was manufactured by the method described above, and molded and evaluated. The results are shown in Table 4. The obtained coated body was coated on the entire surface, but color irregularity such as unevenness of yellow shade occurred at the handrail part.

Comparative Example 4 In accordance with the following formulation table (Table 4),
An in-mold coating resin composition was produced. However, in this case, the color pigment was not uniformly dispersed, and a coating material having a uniform color tone was not obtained. Molding was carried out by the above-mentioned method, but the obtained covering body was covered only on the bottom surface portion and the subsequent standing surface portion, and was not covered on the handrail portion and the outer peripheral portion outside thereof. There was uneven color on the entire surface.

Comparative Example 5 In accordance with the following formulation table (Table 4),
The coating material was manufactured by the method described above, and molded and evaluated. The results are shown in Table 4. The obtained coated body was coated on the entire surface, but color irregularity such as unevenness of yellow shade occurred at the handrail part.

(Comparative Example 6) According to the following formulation table (Table 4),
The coating material was manufactured by the method described above, and molded and evaluated. The results are shown in Table 4. The obtained covering body was covered only on the bottom surface portion and the standing surface portion following it, and was not covered on the handrail portion and the outer peripheral portion thereof. The coated part had a uniform cream color over the entire surface, and no color unevenness occurred.

(Comparative Example 7) According to the following formulation table (Table 5),
An in-mold coating resin composition was produced. However, in this case, the color pigment was not uniformly dispersed, and a coating material having a uniform color tone was not obtained. Molding was carried out by the above method, but there was uneven color on the entire surface.

(Comparative Example 8) According to the following formulation table (Table 5),
The coating material was manufactured by the method described above, and molded and evaluated. The results are shown in Table 5. The obtained coating was coated on the entire surface, but in the standing surface and the handrail part,
There was uneven color that was divided into a yellowish part and a whitish part.

(Comparative Example 9) According to the following formulation table (Table 5),
The coating material was manufactured by the method described above, and molded and evaluated. The results are shown in Table 5. The obtained coated body was coated on the entire surface, but color irregularity such as unevenness of yellow shade occurred at the handrail part.

Comparative Example 10 An in-mold coating resin composition was produced according to the following formulation table (Table 5). However, in this case, the color pigment was not uniformly dispersed, and a coating material having a uniform color tone was not obtained. Molding was carried out by the above-mentioned method, but the obtained covering body was covered only on the bottom surface portion and the subsequent standing surface portion, and was not covered on the handrail portion and the outer peripheral portion outside thereof. There was uneven color on the entire surface.

Comparative Example 11 A coating material was produced by the above-mentioned method according to the following formulation table (Table 5), and was molded and evaluated. The results are shown in Table 5. The obtained coated body was coated on the entire surface, but color irregularity such as unevenness of yellow shade occurred at the handrail part.

Comparative Example 12 A coating material was produced by the above-mentioned method according to the following formulation table (Table 5), and molding and evaluation were performed. The results are shown in Table 5. The obtained covering body was covered only on the bottom surface portion and the standing surface portion following it, and was not covered on the handrail portion and the outer peripheral portion thereof. The coated part had a uniform cream color over the entire surface, and no color unevenness occurred.

[0121]

[Table 1]

[0122]

[Table 2]

[0123]

[Table 3]

[0124]

[Table 4]

[0125]

[Table 5]

[0126]

The in-mold coating resin composition according to claims 1 to 4 comprises:
The viscosity is increased to 150 poises to 550 poises by utilizing the reaction between a carboxyl group and -NH ₂ group or the reaction between a carboxyl group and an alkaline earth metal or (hydr) oxide of zinc. It takes 1 hour to several days for the reaction of the thickening to proceed. Therefore, at the time of mixing the blended materials and dispersing the raw materials, the viscosity of the composition is low, so that the pigment can be favorably dispersed. After dispersing the pigment in this way, the viscosity increases, and when used for in-mold coating molding, it becomes 150 poises to 550 poises. Viscosity 15
Since it is 0 poise or more, there is no pigment separation when flowing in the mold, and it is possible to obtain a uniform coating without color unevenness. Further, since the viscosity is 550 poise or less, sufficient fluidity can be ensured in the mold, so that the coating can be spread / formed on the entire surface of the molding material.

[Brief description of drawings]

FIG. 1 is a perspective view showing an external shape of a molded product molded in an example.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location B29K 105: 06

Claims (4)

[Claims] 1. An in-mold coating thermosetting which is injected to form a coating layer on a thermosetting molding material which is heated and pressed in the mold when it is in a semi-cured state in the mold. Resin composition, which contains a polyamine or unsaturated amine, a resin having a carboxyl group, and a coloring pigment, and has a viscosity adjusted to 150 poises to 550 poises (25 ° C.) by a thickening effect after compounding. An in-mold coating resin composition, characterized in that 2. An in-mold coating thermosetting which is injected to form a coating layer on a thermosetting molding material which is heated and pressed in the mold when the thermosetting molding material is in a semi-cured state in the mold. Resin composition, which comprises a polyamine or an unsaturated amine, a polycarboxylic acid, and
An in-mold coating resin composition containing a coloring pigment and having a viscosity adjusted to 150 poises to 550 poises (25 ° C.) by a thickening effect after compounding. 3. In-mold coating thermosetting which is injected to form a coating layer on a thermosetting molding material that is heated and pressed in the mold when it is in a semi-cured state in the mold. Resin composition, which contains a polyamine, an unsaturated carboxylic acid, and a coloring pigment, and has a viscosity of 150 poises due to the thickening effect after blending.
An in-mold coating resin composition, which is adjusted to 550 poise (25 ° C.). 4. An in-mold coating thermosetting which is injected to form a coating layer on a thermosetting molding material which is heated and pressed in the mold when the thermosetting molding material is in a semi-cured state in the mold. Resin composition containing an alkaline earth metal element or an oxide or hydroxide of zinc, a resin having a carboxyl group, and a coloring pigment, and having a viscosity of 150 poise due to a thickening effect after compounding. An in-mold coating resin composition, which is adjusted to ˜550 poise (25 ° C.).