JPH05124053A - Thermosetting resin composition for inner-mold coat molding and coat molded product - Google Patents

Abstract

PURPOSE:To manufacture a thermosetting resin composition for inner-mold coat molding to be used for molding a base for inner-mold coat molding from which a coat molded product with a coated layer of good bonding properties and also manufacture a coat molded product for which said thermosetting resin composition for inner-mold coat molding is used for a base. CONSTITUTION:Unsaturated polyester resin liquid of 60 pts.wt., a polystyrene low shrinkage agent of 30 pts.wt., acrylamide of 10 pts.wt. and the like are mixed together and a thermosetting resin composition for inner-mold coat molding to be used for forming a base is manufactured.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermosetting resin composition for in-mold coating molding, which is used for forming a base material for in-mold coating molding for forming a coating layer on a substrate in a molding die. And a coated molded article using the thermosetting resin composition for in-mold coating molding as a substrate.

[0002]

2. Description of the Related Art Recently, molded articles made of thermosetting materials have been
It is widely used in industrial parts as a substitute for metal parts. Among them, 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 Patent Application Laid-Open No. 53-71167 discloses a method of forming a coating layer on a molded article by heating and pressurizing the SMC in the mold to semi-cure the SMC, then opening the mold and injecting a coating material. It is disclosed. On the other hand, JP-A-61-273
No. 921 discloses a method of forming a coating layer on the surface of a molded article by injecting a coating material at an injection pressure higher than the molding pressure and curing the same during compression molding.

[0004]

However, in the in-mold coating molding method described in the above-mentioned prior art, SM is used.
There is a problem that the adhesion between the base material made of C or BMC and the coating layer is not sufficient.

Therefore, an object of the present invention is to obtain a coated molded article having a good coating layer adhesion, which is used for forming a base material for in-mold coating molding. It is intended to provide a coated molded article using a thermosetting resin composition and a thermosetting resin composition for in-mold coating molding as a substrate.

[0006]

The invention of claim 1 of the present application is a thermosetting resin composition used for forming a base material for in-mold coating molding for forming a coating layer on a base material in a molding die. A thermosetting resin composition for in-mold coating molding, which comprises an unsaturated polyester resin as a main component and a compound having an acryloyl group or a methacryloyl group and a polar group in the molecule.

The invention of claim 2 of the present application is the composition of claim 1 further selected from at least one of acrylic acid ester of hydroxyalkene, methacrylic acid ester of hydroxyalkene, vinyl acrylate and vinyl methacrylate. A thermosetting resin composition for in-mold coating molding containing a polyfunctional monomer.

The invention of claim 3 of the present application is a thermosetting resin composition for in-mold coating molding, which comprises the composition of claim 1 further containing a compound having two or more acryloyl groups or methacryloyl groups. is there.

The invention of claim 4 of the present application is a thermosetting resin composition for in-mold coating, which comprises the composition of claim 1 and further a silane coupling agent having an acryloyl group or a methacryloyl group. ..

The invention of claim 5 of the present application relates to a thermosetting resin composition used for forming a base material for in-mold coating molding, wherein a coating layer is formed on a base material in a molding die. A thermosetting resin composition for in-mold coating molding, which comprises a saturated polyester resin as a main component and a compound having two or more acryloyl groups or methacryloyl groups and a polar group in the molecule.

The invention of claim 6 of the present application is a thermosetting resin composition for in-mold coating molding according to any one of claims 1 to 5, which is a coated molded article in which a coating layer is formed on a substrate. It is a coated molded product using the product as a substrate.

In addition to the above essential components, the thermosetting resin composition of the present invention may optionally contain a thermoplastic resin as a low-shrinking agent, a copolymerizable monomer, a reinforcing material and various additives.

For the sake of convenience, the resin component of the thermosetting resin contains a thermoplastic resin and a copolymerizable monomer in addition to the thermosetting resin containing an unsaturated polyester resin as a main component. The polar group in the compound having an acryloyl group or a methacryloyl group used in the present invention and a polar group (hereinafter referred to as a polar acrylic monomer) is specifically a carboxyl group, an alcoholic-OH group, or phenol. Properties --OH group, --OH group of phosphoric acid monoester or diester, --OH group of silanol, --OH of titanol
Group, --OH group such as --OH group of aluminic acid, --NH ₂ group,
Nitrogen-containing polar group such as (--NHCO--) group, (--SO _2- )
Group, Cl group, --Br group, --CN group and the like.

Examples of the polar acrylic monomer used in the present invention include unsaturated carboxylic acids such as (meth) acrylic acid and monohydroxyethyl (meth) acrylate phthalate, 2-hydroxyethyl (meth) acrylate,
Unsaturated alcohols such as 2-hydroxypropyl (meth) acrylate and allyl acrylate, unsaturated phenols such as isoeugenol, unsaturated phosphoric acid compounds such as mono (meth) acryloyloxy-2-hydroxyethyl phosphate, and isopropylisostearoyldiacryl. Titanate coupling agents such as titanates, aluminum coupling agents such as acetylalkoxyaluminum diisopropylate, amino group-containing monomers such as (meth) acrylamide, urethane acrylates such as —NH
CO group-containing monomer, acrylamido-2-methylpropanesulfonic acid, etc.-SO ₂ group-containing monomer, acryloyl chloride, etc. Cl group-containing monomer, acryloyl bromide, etc. --Br group-containing monomer, acrylonitrile etc.
Examples thereof include N group-containing monomers.

In the present invention, the compound containing an acryloyl group or a methacryloyl group and a polar group in the molecule is contained in the coating layer of the thermosetting resin composition used for the substrate as described later. It is for increasing the adhesiveness of the acryloyl group or methacryloyl group used in the present invention, and the amount of the compound having a polar group in the molecule, the total resin content (thermosetting resin, copolymerizable monomer, The total amount of the thermoplastic resin (hereinafter the same) is preferably contained in the range of 0.1 to 70% by weight.

The reason is that if the amount is less than 0.1% by weight, the effect of improving the adhesion to the coating layer tends to be insufficient, and conversely, if the amount exceeds 70% by weight. Since the viscosity of the thermosetting resin composition becomes too low, SMC
Alternatively, it tends to be difficult to form the BMC (solid state).

The polyfunctional monomer (hereinafter referred to as an alkenyl acrylic monomer) selected from at least one of acrylic acid ester of hydroxyalkene, methacrylic acid ester of hydroxyalkene, vinyl acrylate and vinyl methacrylate used in the present invention is It can be obtained by a known and commonly used method such as an esterification reaction of (meth) acrylic acid with a hydroxyalkene or a transesterification reaction.

As the hydroxyalkene, for example,
Lil alcohol (CH₂= CHCH ₂OH), 2− (A
Ryloxy) ethanol (CH₂= CHCH₂OCH₂
CH ₂OH), 2-methyl-2-propene-1-ol
[CH₂= CH (CH₃) CH₂OH], 3-butene
1-all (CH₂= CHCH₂CH₂OH) 3-bu
Ten-2-all [CH₂= CHCH (OH) C
H₃] 2-Methyl-3-butene-2-ol [CH₂
C (CH₃) (OH) CH = CH₂] 1-Penten-
3-all [CH₂= CHCH (OH) CH₂C
H₃] 2-Pentene-2-All [CH₃C (OH)
= CHCH₂CH₃] 4-Pentene-1-All (C
H₂= CHCH₂CH₂CH₂OH), 4-Pentene-
2-all [CH₂= CHCH₂CH (OH) C
H₃] 1-Hexen-3-all [CH₂= CHCH
(OH) CH₂CH₂CH₃], Cis-3-hexene-
1-all (CH₃CH = CHCH₂CH₂OH),
Lance-3-hexene-1-all (CH₃CH = CH
CH₂CH₂OH), trans-2-hexene-1-o
(CH₃CH₂CH₂CH = CHCH₂OH), 4
--Hexen-1-All (CH₃CH = CHCH₂CH
₂CH₂OH), 5-hexene-1-ol (CH₂=
CHCH ₂CH₂CH₂CH₂OH), 3-methyl-2
--Cyclohexene-1-ol (CH₃C₆H₈OH)
Etc.

In the present invention, the alkenyl acrylic monomer is contained in order to enhance the adhesiveness with the coating layer of the thermosetting resin composition used for the base material as described later, but it is used in the present invention. The amount of the alkenyl ecryl monomer to be contained is preferably in the range of 0.1 to 70% by weight of the total resin content.

The reason is that if the amount is less than 0.1% by weight, the effect of improving the adhesion to the coating layer tends to be insufficient, and conversely, if the amount exceeds 70% by weight. Since the viscosity of the thermosetting resin composition becomes too low, SMC
Alternatively, it tends to be difficult to form the BMC (solid state).

The compound having two or more acryloyl groups or methacryloyl groups (hereinafter referred to as a polyfunctional acrylic monomer) used in the present invention means a compound having a plurality of (meth) acryloyl groups in the molecule, It is obtained by esterifying a (meth) acrylic acid with a polyol. As a specific example, ethylene glycol (meth)
Acrylate, polyethylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
2,2-bis {4 [(meth) acryloxydiethoxy] phenyl} propane, 2,2-bis {4 [(meth)]
Examples thereof include acryloxy / polyethoxy] phenyl} propane, trimethylolpropane tri (meth) acrylate, and tetramethylolmethanetetra (meth) acrylate.

In the present invention, the polyfunctional acrylic monomer is contained for the purpose of enhancing the adhesiveness with the coating layer of the thermosetting resin composition used for the base material as described later. The amount of the polyfunctional acrylic monomer used is preferably in the range of 0.1 to 70% by weight of the total resin content.

The reason is that if it is less than 0.1% by weight, the effect of improving the adhesion to the coating layer tends to be insufficient, and conversely, if it is contained in excess of 70% by weight. Since the viscosity of the thermosetting resin composition becomes too low, SMC
Alternatively, it tends to be difficult to form the BMC (solid state).

The acryloyl group or the methacrylic group used in the present invention
Silane coupling agent having an acryloyl group (hereinafter,
Examples of acrylic silane coupling agents)
For example, N- (3-acryloxy-2-hydroxypropyi
) -3-Aminopropylethoxysilane [CH₂= C
HCOOCH₂CHOHCH₂NHCH₂CH₂CH ₂
Si (OCH₂CH₃)₃] 3-Acryloylpropionate
Rudimethylmethoxysilane [CH₂= CHCOOCH₂
CH₂Si (CH₃)₂(OCH₃)] 3-methacrylate
Roxypropylmethyldiethoxysilane [CH₂= CC
H₃COOCH ₂CH₂CH₂Si (CH₃) (OCH
₂CH₃)₂] 3-methacryloxypropenyl trime
Toxysilane [CH₂= CCH₃COOCH₂CH = C
HSi (OCH₃)₃2-methacryloxyethyl dimeth
Cyl (3-trimethoxysilylpropyl) ammonium
Chloride {CH₂= CCH₃COOCH₂CH₂CH
[N (CH₃)₂Cl] CH₂CH₂Si (OC
H₃)₃} 3-Methacryloxypropyltrimethoxy
Silane [CH₂= CCH₃COOCH₂CH₂CH₂S
i (OCH₃)₃] 3-methacryloxypropyl dime
Cylethoxysilane [CH₂= CCH₃COOCH₂C
H₂CH₂Si (CH₃)₂(OCH₂CH₃)] Etc.
Can be mentioned.

In the present invention, the reason why the acrylic silane coupling agent is contained is to enhance the adhesiveness with the coating layer of the thermosetting resin composition used for the substrate as described later. The amount of the acrylic silane coupling agent used in the invention is 0.01 to 2 based on the total resin content (the total amount of the thermosetting resin, the copolymerizable monomer, and the thermoplastic resin).
It is preferably contained in the range of 0% by weight. The reason is that when the amount is less than 0.01% by weight, the effect of improving the adhesion with the coating layer, the effect of improving the strength, and the effect of improving the hot water resistance tend to be insufficient, and conversely, when the amount exceeds 20% by weight. When contained, the liberated alcohol is likely to remain in the molded product, and as a result, the strength of the molded product tends to be low.

The polar group in the compound having two or more acryloyl groups or methacryloyl groups used in the present invention and a polar group in the molecule (hereinafter referred to as a polar group-containing polyfunctional acrylic monomer) is, for example, Examples thereof include --OH group of alcohol, --OH group of phosphoric acid, --NHCO group contained in urethane bond, peptide bond, urea bond and the like.

As a polar group, the --OH group of alcohol is separated.
As a polar group-containing polyfunctional acrylic monomer in the child
Is, for example, 2-hydroxy-1,3-dimethacryloxy
Cipropane {CH₂[OCOC (CH₃) = CH₂] C
H (OH) CH₂OCOC (CH₃) = CH₂}, 2-
Hydroxy-1-acryloxy-3-methacryloxyp
Lopin [CH₂(OCOCH = CH₂) CH (OH) C
H₂OCOC (CH₃) = CH₂], Tetramethylol
Methane triacrylate [HOCH₂C (CH ₂OCO
CH = CH₂)₃], Di (2-acryloyloxyethyl)
) Monoahydrodiene phosphate [(CH₂= C
HCOOCH₂CH₂O)₂POOH], di (2-meta
Cryloyloxyethyl) monohydrogenene phosphate
To {{CH₂= C (CH₃) COOCH₂CH₂O]
₂POOH} and the like.

Examples of the polar group-containing polyfunctional acrylic monomer having a --NHCO-- group as a polar group in the molecule include hydroxyalkyl (meth) acrylate adducts of organic polyisocyanates. As a specific example, for example, 2-hydroxyethyl methacrylate of hexamethylene diisocyanate [CH ₂ ═CCH ₃ CO
OCH ₂ CH ₂ OCONH (CH ₂ ) ₆ NHCOOCH
_{2 CH 2 OCOC (CH 3)} = CH 2 ], adduct of 2─ hydroxypropyl acrylate tolylene diisocyanate _{[CH 2 = CHCOOCH 2 CH (CH} 3) OC
ONHC ₆ H ₃ (CH ₃ ) NHCOOCH (CH ₃ ) C
H ₂ OCOCH = CH ₂ ] and the like, and any organic polyisocyanate and any hydroxyalkyl (meth)
A combination of acrylates is possible.

In the present invention, the polar group-containing polyfunctional acrylic monomer is contained in order to enhance the adhesiveness with the coating layer of the thermosetting resin composition used for the base material as described below. The amount of the polar group-containing polyfunctional acrylic monomer used in the present invention is preferably in the range of 0.1 to 70% by weight of the total resin content, and 1 to 50% by weight.
Is more preferable.

The reason is that if the amount is less than 0.1% by weight, the effect of improving the adhesion with the coating layer tends to be insufficient, and conversely, if the amount exceeds 70% by weight. Since the viscosity of the thermosetting resin composition becomes too low, SMC
Alternatively, it tends to be difficult to form the BMC (solid state).

The thermosetting resin contained in the thermoplastic resin composition for in-mold coating used in the present invention has a three-dimensional network structure in which a double bond is cleaved and added using a thermally decomposable radical catalyst. An unsaturated polyester resin having a reactive double bond in the molecule, a vinyl ester (epoxy acrylate) resin, a urethane acrylate resin, etc. capable of forming The thermosetting resin may be used alone or in combination of two or more.

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

On the other hand, the vinyl ester resin is also usually produced by a known and commonly used method from an epoxy resin and a monocarboxylic acid having a reactive double bond such as (meth) acrylic acid.

Further, the urethane acrylate resin is
Usually, it is produced by reacting an organic polyol such as an alkylene diol, an alkylene diol ester, an alkylene diol ether, a polyether polyol or a polyester polyol with an organic polyisocyanate and further reacting with a hydroxyalkyl (meth) acrylate. It is also possible to leave a free isocyanate group at a part of the terminal and combine this with the vinyl ester resin for use.

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

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

The aliphatic unsaturated polycarboxylic acid used for producing the unsaturated polyester resin is
(Anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid and the like, and as the aliphatic saturated polycarboxylic acid, sebacic acid, adipic acid, (anhydrous) succinic acid and the like, the aromatic polycarboxylic acid Examples thereof include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride and the like.

The epoxy resin used for producing the vinyl ester resin is also produced from bisphenol A type epoxy resin, epichlorohydrin and brominated bisphenol A produced from epichlorohydrin and bisphenol A by a known and conventional method. Brominated bisphenol A type epoxy resin, novolak type epoxy resin produced by glycidyl etherification of phenol novolac or orthocresol novolak, tetraglycidyl metaxylenediamine, tetraglycidyl 1,3 obtained by reacting various amines with epichlorohydrin -Bisaminomethylcyclohexane,
Examples thereof include glycidylamine compounds such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, and diglycidyl orthotoluidine.

Examples of the organic polyol used for producing the urethane acrylate resin include alkylene diols such as ethylene glycol, propylene glycol, diethylene glycol, diisopropylene glycol, polyethylene glycol, polypropylene glycol, butane diol, and other hydroxyalkyl ethers. Examples of the polyether polyol include polyoxymethylene, polyethylene oxide, polypropylene oxide, and the like, and examples of the polyester polyol include the above-described organic polyols and polyester polyols having hydroxyl groups at both ends, which are produced by polycarboxylic acid.

The organic polyisocyanate used for producing the urethane acrylate resin includes tolylene diisocyanate, isophorone diisocyanate,
Examples thereof include polymethylene polyphenyl diisocyanate.

Examples of the hydroxyalkyl (meth) acrylate used for producing the urethane acrylate resin include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate. The group is usually attached to the beta carbon of the alkyl group. Alkyl groups can usually contain up to 8 carbon atoms.

In the thermosetting resin composition for in-mold molding of the present invention, polyvinyl acetate, polymethyl (meth) acrylate, polyethylene, ethylene vinyl acetate copolymer, vinyl acetate-styrene copolymer is used as a low shrinking agent. Thermoplastic resins such as polymers, polybutadiene, saturated polyesters, saturated polyethers and the like can be used in appropriate amounts as needed.

Furthermore, an appropriate amount of an inorganic filler can be added to the thermosetting resin composition for in-mold coating molding of the present invention depending on the purpose and application. Examples of usable inorganic fillers are as follows.

That is, elemental minerals such as sulfur, graphite and diamond, sulfide minerals such as pyrite, halogenated minerals such as rock salt and potassium rock salt, carbonate minerals such as carbon calcium, phosphate minerals such as cyanite and carnotite. Etc., vanadate minerals, barite (barium sulfate), gypsum (calcium sulfate) and other sulfate minerals, borax and other borate minerals, perovskite and other titanate minerals, mica, talc (talc) , Silicate minerals such as pyrophyllite, kaolin, quartz, feldspar, metal oxides such as titanium oxide, corundum (aluminum oxide), aluminum hydroxide, glass products such as (hollow) glass spheres The natural or artificial minerals, processed or purified or processed products thereof, and mixtures thereof are used.

The amount of the filler added is 0 to 30 with respect to 100 parts by weight of the resin in the thermosetting resin composition.
It is preferably added in an amount of 0 parts by weight. If the added amount exceeds 300 parts by weight, it becomes difficult to uniformly disperse the filler in the resin and the monomer, and since the viscosity becomes high, the fluidity in the mold deteriorates and it becomes difficult to obtain dimensional stability. Tend. Further, in the thermosetting resin composition for in-mold coating molding of the present invention, various reinforcing fibers, that is, glass fiber, carbon fiber and the like can be added as an appropriate amount as a reinforcing material.

Further, in the thermosetting resin composition for in-mold coating of the present invention, if necessary, styrene, α-methylstyrene, divinylbenzene, vinyltoluene, diallylphthalate, various acrylate monomers, various methacrylates. An appropriate amount of a polymerizable monomer such as a monomer can be added.

Known polymerization initiators such as ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, alkyl peresters, percarbonates and peroxyketals, dimethylaniline and naphthene. Known curing accelerators such as cobalt acid, polymerization inhibitors such as parabenzoquinone, carbon black and titanium oxide, iron oxide, cyanine pigments, aluminum flakes, nickel powder, pigments such as gold powder and silver powder, azo dyes and anthraquinone pigments , Indigoid,
A suitable amount of a stilbene-based dye, a conductivity-imparting agent such as carbon black, an emulsifier, a metal soap such as zinc stearate, an aliphatic phosphate, a release agent such as lecithin, etc. may be added depending on the application and purpose. it can.

The coating layer forming composition used in combination with the in-mold thermosetting resin composition of the present invention is a thermosetting unsaturated polyester resin, vinyl ester resin, urethane acrylate resin or the like. Resin is used, and various fillers, additives and the like can be added if necessary.

The thermosetting resin composition for in-mold coating molding of the present invention obtained as described above is a thermosetting resin composition for in-mold coating molding having a form of SMC or BMC by a conventionally known method. And can be used as a conventionally known in-mold coating together with the composition for forming a coating layer.

For example, SMC is put in a molding die heated to 130 to 160 ° C., pressure molding is performed at a pressure of 40 to 120 kg / cm ² for 30 seconds to 5 minutes, and then the mold is slightly opened for coating. Injecting the layer-forming composition, then 5 to 120
By reheating and repressurizing at 130 to 160 ° C. for 30 seconds to 5 minutes at 130 kg / cm ² , the composition for forming a coating layer is spread over the entire surface of the molded SMC and cured to form a coating layer. be able to.

Further, as disclosed in Japanese Patent Laid-Open No. 61-273921, SMC at 130 to 160 ° C., 40 to 1
Coating layer forming composition at a high pressure of 100 to 300 / cm ² using a high pressure injection machine in a state where the pressure was reduced to 10 to 30 kg / cm ² after several tens of seconds to several minutes pressed at 20 kg / cm ² Is injected into the mold and again 30 to 100 kg / c
There is also a method of increasing the pressure to m ² to spread and harden the coating layer forming composition. By using the thermosetting resin composition for in-mold coating molding of the present invention in the above-described in-mold coating method, a coated molded article having good adhesion can be easily molded.

[0052]

The thermosetting resin composition for in-mold coating molding according to the invention of claim 1 of the present application contains an unsaturated polyester resin as a main component and contains a polar acrylic monomer. Undergoes a copolymerization reaction with an unsaturated polyester resin or the like to form a polar group on the surface of the copolymer resin. As a result, since the polarity of the surface of the copolymer resin is increased, hydrogen bonds between the base material using this thermosetting resin composition and the resin in the coating layer forming composition increase, This enhances the adhesion between the base material and the coating layer.

The thermosetting resin composition for in-mold coating molding according to the invention of claim 2 of the present application comprises an unsaturated polyester resin as a main component, and contains a polar acrylic monomer and an alkenyl acrylic monomer. At times, a polar acrylic monomer and an alkenyl acrylic monomer undergo a copolymerization reaction with an unsaturated polyester resin or the like to form a polar group on the surface of the copolymer resin.

The alkenyl acrylic monomer is (meth)
The double bond of the acryloyl group and the double bond of the polar acrylic monomer are easily copolymerized, and the double bond of the hydroxyalkene residue is copolymerized with the double bond of the unsaturated polyester resin. Since it is easy, it is easily copolymerized with both the unsaturated polyester resin and the polar acrylic monomer. Then, the double bonds in the copolymer resin are crosslinked to form a three-dimensional network structure. In addition, polar acrylic monomers that have not been copolymerized with unsaturated polyester resins and the like are copolymerized with alkenyl acrylics, and the double bonds in the copolymerized resins are crosslinked to form a three-dimensional network structure. ..

As a result, the polarity of the surface of these copolymer resins is increased, so that the hydrogen bond between the base material using this thermosetting resin and the resin in the coating layer forming composition. Increase, thereby improving the adhesion between the substrate and the coating layer.

Further, since the copolymer resin has a three-dimensional network structure, there is no fear that the water resistance will be lowered by absorbing water molecules and the water resistance will be excellent. Claim 3 of the present application
The thermosetting resin composition for in-mold coating molding of the invention of (1) contains an unsaturated polyester resin as a main component, and contains a polar acrylic monomer and a polyfunctional acrylic monomer in the resin component. The monomer and the polyfunctional acrylic monomer are copolymerized with the unsaturated polyester resin to form a polar group on the surface of the copolymer resin.

Since the polyfunctional acrylic monomer has a plurality of (meth) acryloyl groups, the remaining double bonds of the copolymerization reaction residue in the copolymer resin are crosslinked to form a three-dimensional network structure. In addition, the polyfunctional acrylic monomer is
Since the copolymerization reaction between the double bond of the (meth) acryloyl group and the double bond of the polar acrylic monomer is easy, the polar acrylic monomer that did not copolymerize with the unsaturated polyester resin is a polyfunctional acrylic monomer. Copolymerization reaction occurs with each other, and the double bond in the copolymer resin is crosslinked to form a three-dimensional network structure.

As a result, the polarity of the surface of these copolymer resins is increased, so that the hydrogen bond between the base material using this thermosetting resin and the resin in the composition for forming the coating layer. Increase, thereby improving the adhesion between the substrate and the coating layer.

Further, since the copolymer resin forms a three-dimensional network structure, there is no fear that water molecules will be absorbed to lower the hot water resistance and the hot water resistance is excellent. Claim 4 of the present application
The thermosetting resin composition for in-mold coating molding of the invention of (1) contains an unsaturated polyester resin as a main component, and contains a polar acrylic monomer and an acrylic silane coupling agent. The acrylic silane coupling agent copolymerizes with the unsaturated polyester resin to form a polar group on the surface of the copolymer resin.

Since the acrylic silane coupling agent has a silanol group, the silanol group of the residue in the copolymer resin forms a siloxane bond and crosslinks to form a three-dimensional network structure. Further, the acrylic silane coupling agent easily causes a copolymerization reaction between the double bond of the (meth) acryloyl group and the double bond of the polar acrylic monomer. For this reason, polar acrylic monomers that did not copolymerize with unsaturated polyester resins, etc., copolymerize with the acrylic silane coupling agent, and the silanol groups of the residues in the copolymerized resin form siloxane bonds. And cross-link 3
Form a dimensional meshwork.

As a result, the polarity of the surface of these copolymer resins is enhanced, so that the hydrogen bond between the base material using this thermosetting resin and the resin in the composition for forming the coating layer. Increase, thereby improving the adhesion between the substrate and the coating layer.

Further, since the copolymer resin has a three-dimensional network structure, it has excellent bending strength, and there is no fear of absorbing water molecules to lower the hot water resistance. There is.

The thermosetting resin composition for in-mold coating molding according to the invention of claim 5 of the present application contains an unsaturated polyester resin as a main component and contains a polar group-containing polyfunctional acrylic monomer, so that it is pressure-molded. At times, the polar group-containing polyfunctional acrylic monomer undergoes a copolymerization reaction with the unsaturated polyester resin to form a polar group on the surface of the copolymer resin.

Since the polar group-containing polyfunctional acrylic monomer has a plurality of (meth) acryloyl groups, the double bond in the copolymer resin is crosslinked to form a three-dimensional network structure.
In addition, the polar group-containing polyfunctional acrylic monomer that has not copolymerized with the unsaturated polyester resin or the like has a three-dimensional network structure in which double bonds in the resin are cross-linked even when the homopolymerization reaction occurs.

As a result, the polarities of the surfaces of these copolymer resins and homopolymer resins are increased, so that the base material using this thermosetting resin and the resin in the coating layer forming composition are Hydrogen bonds of the base material are increased, thereby improving the adhesion between the base material and the coating layer.

Further, since the copolymer resin and the homopolymer resin form a three-dimensional network structure, there is no fear of absorbing water molecules to lower the hot water resistance, and the hot water resistance is excellent. The coated molded article according to the invention of claim 6 of the present application, on a substrate,
Since the curable resin composition for in-mold coating molding according to any one of claims 1 to 5 is used, the coating layer is firmly adhered to the base material.

[0067]

Example 1 The following compositions were mixed and sufficiently stirred, and then glass fiber (Roving made by Asahi Fiber Glass Co., Ltd., trade name: “ER4630LBD166W” with a length of 2 was mixed with an SMC impregnating device.
It was impregnated with 60 parts by weight (cut into 5 mm) to obtain SMC as a thermosetting resin composition.

Composition Unsaturated polyester resin liquid [Isophthalic acid-based unsaturated polyester resin (molecular weight: about 1000): about 60% by weight and styrene monomer: about 40% by weight)] ... 65 parts by weight Polystyrene low-shrinking agent resin (polystyrene) Resin about 30
% By weight and about 70% by weight of styrene monomer)
30 parts by weight Acrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) …… 10 parts by weight Calcium carbonate powder (manufactured by Nitto Koka: brand name "NS-1"
00 ") ... 120 parts by weight Curing agent (t-butylperoxybenzoate content 98
%) ...... 1 part by weight Thickener [magnesium oxide powder (Kyowa Chemical Industry Co., Ltd .: trade name "Kyowamag 150")] ...... 1 part by weight Next, 100 parts by weight of the above unsaturated polyester resin liquid,
100 parts by weight of calcium carbonate and 1 part by weight of a curing agent (t-butylperoxybenzoate) were mixed and sufficiently stirred to obtain an in-mold coating composition.

Using the SMC and the in-mold coating composition prepared as described above, molding was carried out in the following manner. First, the upper mold and the lower mold were heated to 150 ° C., 30 cm × 3
Approximately 7 of the above SMC is placed in a 0 cm square flat plate mold.
00g charged (charged SMC is about 4m
had a thickness of m). Next, after pressure-molding at a pressure of 100 kg / cm ² for 100 seconds, the mold is opened slightly and 10 ml of the above composition for in-mold coating is injected, the mold is closed again, and 120 kg / cm ² for 120 seconds. Then, by reheating and repressurizing, the composition for in-mold coating was spread over the entire surface of the molded SMC and cured to form a coating layer. After that, the mold was opened and the mold was released to obtain a molded product whose surface was covered with a coating layer having a thickness of 100 μm.

On the surface of the molded article obtained as described above, on which the coating layer is formed, a straight line reaching the substrate of the molded article (the base material made of the thermosetting resin composition) with a cutter knife is 2 mm. 11 lines in parallel at intervals of
Eleven straight lines orthogonal to the straight line were similarly drawn to form a grid-like portion. Further, an adhesive tape (manufactured by Sekisui Chemical Co., Ltd., trade name: Sekisui Tape) was attached to the cross-shaped portion, and then the number of remaining squares of the cross was checked by peeling it off (hereinafter, referred to as a cross-contact test. I call it). As a result, the ratio of the mass in which the coating layer remained was 100 pieces / 1
It was 00. That is, in the cross-cut adhesion test,
No peeling of the coating layer was observed.

Comparative Example 1 An SMC was obtained in the same manner as in Example 1 except that the amount of unsaturated polyester resin liquid was 70 parts by weight and acrylamide was not used. Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 31 /
It was 100.

Comparative Example 2 Except that 10 parts by weight of acrylic methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used without using acrylamide,
An SMC was obtained in the same manner as in Example 1. Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 43.
The number was 100/100.

The mixing ratios of the thermosetting resin compositions of Example 1, Comparative Example 1 and Comparative Example 2 and the results of the cross-cut adhesion test are shown in Table 1 below (carbonic acid in the composition). Calcium 120 parts by weight, t-butyl peroxybenzoate, magnesium oxide 1 part by weight, glass fiber 6
Since 0 parts by weight is common to each example, the description in the table is omitted. same as below. ).

[0074]

[Table 1]

As is clear from the description of Example 1, Comparative Example 1 and Comparative Example 2 and Table 1, Comparative Example 1 and Comparative Example 2
In contrast, the cross-cut adhesion is considerably low, whereas in Example 1, the cross-cut adhesion is high and the coating layer is not peeled off at all, and the coating layer is firmly adhered to the thermosetting resin. I understand that

Example 2 9 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and allyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
SMC as in Example 1 except that 1 part by weight was used.
Got

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was conducted and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. Also, from this coated molded product, 10 cm × 10 cm
The test piece was cut out and immersed in hot water at 80 ° C. for 200 hours to examine whether or not the appearance changed (hereinafter referred to as a hot water resistance test). As a result, there is no change in the appearance of the test piece,
The hot water resistance was good.

Example 3 The amount of the unsaturated polyester resin liquid was set to 40 parts by weight, 25 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and further allyl methacrylate was used. SMC was obtained in the same manner as in Example 1 except that 5 parts by weight was used.

When a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer did not peel off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 4 S was the same as Example 1 except that 8 parts by weight of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and 2 parts by weight of allyl methacrylate was used.
I got MC.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 5 : Instead of acrylamide, 3 parts by weight of methacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) and 7 parts by weight of vinyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) were used. An SMC was obtained in the same manner as in Example 1.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 6 The amount of the unsaturated polyester resin liquid was 50 parts by weight, 7 parts by weight of methacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and further 13 parts by weight of allyl methacrylate. SMC was obtained in the same manner as in Example 1 except that was used.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was carried out and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Table 2 below shows the mixing ratios of the thermosetting resin compositions of Examples 2 to 6, the results of the cross-cut adhesion test, and the results of the hot water resistance test.

[0087]

[Table 2]

As is clear from the description of Examples 2 to 6 and Table 2, in Examples 2 to 6, both the cross-cut adhesion and the hot water resistance were high and the coating layer was not peeled at all. It can be seen that the coating layer is firmly adhered to the thermosetting resin.

Example 7 9 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of acrylamide, and 1 part by weight of diethylene glycol dimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) was used. An SMC was obtained in the same manner as in Example 1 except for the above.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 8 The amount of unsaturated polyester resin liquid was 64 parts by weight, 1 part by weight of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and diethylene glycol dimethacrylate (new SMC was obtained in the same manner as in Example 1 except that 5 parts by weight (Nakamura Chemical Co., Ltd.) was used.

When a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 9 Instead of acrylamide, 9.5 parts by weight of monoacryloxy-2-hydroxyethyldihydrodiene phosphate (manufactured by Nippon Kayaku Co., Ltd.) was used, and diethylene glycol dimethacrylate (Shin Nakamura Chemical Co., Ltd.) was used. Made)
As in Example 1, except that 0.5 parts by weight was used, S
I got MC.

When a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was conducted and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 10 The amount of unsaturated polyester resin liquid was 62 parts by weight, the amount of acrylamide was 5 parts by weight, and further 3 parts by weight of diethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used. An SMC was obtained in the same manner as in Example 1 except for the above.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 11 The amount of unsaturated polyester resin liquid was set to 57 parts by weight, 3 parts by weight of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and diethylene glycol dimethacrylate (Shin Nakamura) was used. SMC was obtained in the same manner as in Example 1 except that 10 parts by weight of Chemical Industry Co., Ltd.) was used.

When a coated molded product was obtained in the same manner as in Example 1 and evaluated by a cross-cut adhesion test, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 12 The amount of the unsaturated polyester resin liquid was set to 32 parts by weight, 32 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and diethylene glycol di Except that 6 parts by weight of methacrylate (Shin-Nakamura Chemical Co., Ltd.) was used,
An SMC was obtained in the same manner as in Example 1.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 13 The amount of unsaturated polyester resin liquid was set to 50 parts by weight, 18 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and further trimethylol was used. SMC was obtained in the same manner as in Example 1 except that 2 parts by weight of propane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 14 The amount of unsaturated polyester resin liquid was 25 parts by weight, 15 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) in place of acrylamide, and acrylic acid (Wako Pure Chemical Industries, Ltd.) (Manufactured by Kogyo Co., Ltd.) was used,
Further, SMC was obtained in the same manner as in Example 1 except that 30 parts by weight of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was carried out and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 15 The amount of unsaturated polyester resin liquid was 40 parts by weight, the amount of acrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) was 5 parts by weight, and monoacryloxy-2-hydroxyethyldihydro. SMC was obtained in the same manner as in Example 1 except that 5 parts by weight of diene phosphate (manufactured by Nippon Kayaku Co., Ltd.) and 20 parts by weight of trimethylolpropane triacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) were used. It was

When a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer did not peel off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

The mixing ratios of the thermosetting resin compositions of Examples 7 to 15, the results of the cross-cut adhesion test, and the results of the hot water resistance test are summarized in Table 3 below.

[0108]

[Table 3]

As is clear from the description of Examples 7 to 15 and Table 3, in Examples 7 to 15 all the cross-cut adhesion and hot water resistance were high and the coating layer was not peeled at all. It can be seen that the coating layer is firmly adhered to the thermosetting resin. Example 16 Instead of acrylamide, 9 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used, and further 1 part by weight of 3-methacryloxypropyltrimethoxysilane (manufactured by Chisso Corporation) was used. An SMC was obtained in the same manner as in Example 1 except for the above.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was carried out and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. The bending strength of this coated molded article was measured by the test method of JIS K6911 "General Test Method for Thermosetting Plastics" 5-17-3. The result is 1
It was 1.3 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. Example 17 The amount of unsaturated polyester resin liquid was 63 parts by weight, 2 parts by weight of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of acrylamide, and 3-methacryloxypropyltrimethoxysilane was further used. An SMC was obtained in the same manner as in Example 1 except that 5 parts by weight (manufactured by Chisso Corporation) was used.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. Further, bending strength was measured in the same manner as in Example 16. The result was 13.4 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. Example 18 The amount of unsaturated polyester resin liquid was set to 63 parts by weight, and monoacryloxy-2 was used instead of acrylamide.
-7 parts by weight of hydroxyethyl dihydrodiene phosphate (manufactured by Nippon Kayaku Co., Ltd.), and 3-methacryloxypropyltrimethoxysilane (manufactured by Chisso Co.)
As in Example 1, except that 0.5 parts by weight was used, S
I got MC.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. Further, bending strength was measured in the same manner as in Example 16. The result was 12.1 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. Example 19 An SMC was prepared in the same manner as in Example 1 except that the amount of the unsaturated polyester resin liquid was set to 57 parts by weight and 3 parts by weight of 3-methacryloxypropyltrimethoxysilane (manufactured by Chisso Corporation) was used. Obtained.

When a coated molded product was obtained in the same manner as in Example 1 and evaluated by a cross-cut adhesion test, the number of remaining masses in which the coating layer was not peeled off was 100/100. Further, bending strength was measured in the same manner as in Example 16. The result was 12.8 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. Example 20 The amount of unsaturated polyester resin liquid was set to 57 parts by weight, 3 parts by weight of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and 3-methacryloxypropyltrimethoxysilane ( SMC was obtained in the same manner as in Example 1 except that 10 parts by weight (manufactured by Chisso Corporation) was used.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was conducted and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. Further, bending strength was measured in the same manner as in Example 16. The result was 13.2 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. Example 21 The amount of unsaturated polyester resin liquid was set to 32 parts by weight, 32 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and further 3-methacryloxypropyl was used. Except that 6 parts by weight of trimethoxysilane (manufactured by Chisso Corporation) was used,
An SMC was obtained in the same manner as in Example 1.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. Further, bending strength was measured in the same manner as in Example 16. The result was 13.0 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. Example 22 The amount of unsaturated polyester resin liquid was set to 50 parts by weight, 18 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and further 3-methacryloxypropyl. Except for using 2 parts by weight of trimethoxysilane (manufactured by Chisso),
An SMC was obtained in the same manner as in Example 1.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was carried out and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. Further, bending strength was measured in the same manner as in Example 16. The result was 11.6 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. Example 23 The amount of unsaturated polyester resin liquid was 45 parts by weight, 15 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, acrylic acid (Wako Pure Chemical Industries, Ltd.) SMC was obtained in the same manner as in Example 1 except that 5 parts by weight of Kogyo Co., Ltd. and 5 parts by weight of 3-methacryloxypropyltrimethoxysilane (made by Chisso Co.) were used.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was conducted and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. Further, bending strength was measured in the same manner as in Example 16. The result was 13.0 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. Example 24 The amount of unsaturated polyester resin liquid was 50 parts by weight, the amount of acrylamide was 5 parts by weight, and 10 parts by weight of monoacryloxy-2-hydroxyethyldihydrodiene phosphate (manufactured by Nippon Kayaku Co., Ltd.). Using the department,
Example 1 was repeated except that 5 parts by weight of 3-methacryloxypropyltrimethoxysilane (manufactured by Chisso Corporation) was used.
SMC was obtained in the same manner as.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was conducted and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. Further, bending strength was measured in the same manner as in Example 16. The result was 12.7 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. Example 25 The amount of unsaturated polyester resin liquid was 35 parts by weight, 5 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and further 3-methacryloxypropyl was used. Except that 25 parts by weight of trimethoxysilane (manufactured by Chisso Corporation) was used,
An SMC was obtained in the same manner as in Example 1.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. Further, bending strength was measured in the same manner as in Example 16. The result was 12.7 Kg / mm ² .

A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good. The mixing ratios of the thermosetting resin compositions of Examples 16 to 25, the results of the cross-cut adhesion test, the measurement results of the bending strength, and the results of the hot water resistance test are collectively shown in Table 4 below.

[0130]

[Table 4]

As is clear from the description of Examples 16 to 25 and Table 4, in Examples 16 to 25, both the cross-cut adhesion and the hot water resistance were high and the coating layer was not peeled at all. The coating layer is firmly adhered to the thermosetting resin. Further, it is understood that the flexural strength is sufficiently high except for Example 25, and that Example 25 also has a strength that does not hinder practical use.

Example 26 The amount of unsaturated polyester resin liquid was set to 65 parts by weight, and instead of acrylamide, 2-hydroxy-1,
3-Dimethacryloxypropane (Shin-Nakamura Chemical Co., Ltd.)
SMC as in Example 1 except that 5 parts by weight was used
Got

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 27 The amount of unsaturated polyester resin liquid was set to 70 parts by weight, and instead of acrylamide, 2-hydroxy-1,
3-Dimethacryloxypropane (Shin-Nakamura Chemical Co., Ltd.)
SMC as in Example 1 except that 2 parts by weight was used
Got

When a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was conducted and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 28 An SMC was obtained in the same manner as in Example 1 except that 10 parts by weight of tetramethylolmethane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of acrylamide.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 29 The amount of the unsaturated polyester resin liquid was 70 parts by weight, and 2 parts by weight of di (methacryloyloxyethyl) monohydrodiene phosphate (manufactured by Nippon Kayaku Co., Ltd.) was used instead of acrylamide. An SMC was obtained in the same manner as in Example 1 except for the above.

Further, when a coated molded article was obtained in the same manner as in Example 1 and evaluated by a cross-cut adhesion test, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 30 The amount of unsaturated polyester resin liquid was 50 parts by weight, 15 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and further 2 SMC was obtained in the same manner as in Example 1 except that 5 parts by weight of hydroxy-1,3-dimethacryloxypropane (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 31 Example 1 was repeated except that the amount of the unsaturated polyester resin liquid was changed to 65 parts by weight and 5 parts by weight of a 2-hydroxyethyl methacrylate adduct of hexamethylene diisocyanate was used instead of acrylamide. Similarly, SMC was obtained.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was conducted and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

Example 32 The amount of the unsaturated polyester resin liquid was 50 parts by weight, 10 parts by weight of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of acrylamide, and further 2 SMC was obtained in the same manner as in Example 1 except that 15 parts by weight of hydroxy-1,3-dimethacryloxypropane (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.

Further, when a coated molded product was obtained in the same manner as in Example 1 and a cross-cut adhesion test was performed and evaluated, the number of remaining masses in which the coating layer was not peeled off was 100/100. A hot water resistance test was conducted in the same manner as in Example 2. As a result, the appearance did not change and the hot water resistance was good.

The mixing ratios of the thermosetting resin compositions of Examples 26 to 32, the results of the cross-cut adhesion test, and the results of the hot water resistance test are summarized in Table 5 below.

[0147]

[Table 5]

As is clear from the description of Examples 26 to 32 and Table 5, in Examples 26 to 32, both the cross-cut adhesion and the hot water resistance were high and the coating layer was not peeled at all. It can be seen that the coating layer is firmly adhered to the thermosetting resin.

[0149]

The thermosetting resin composition for in-mold coating molding according to the first aspect of the present invention is constituted as described above, so that the polar acrylic monomer is not mixed with the unsaturated polyester resin or the like during pressure molding. Polymerize to form a polar group on the surface,
Since hydrogen bonds between the base material using the thermosetting resin composition and the resin in the coating layer forming composition increase, the adhesion between the base material and the coating layer increases, and the coating layer and the heat Adhesion with a molded article substrate made of a curable resin composition is effectively enhanced.

The thermosetting resin composition for in-mold coating molding according to the second aspect of the present invention has the above-mentioned constitution.
A polar acrylic monomer and an alkenyl acrylic monomer undergo a copolymerization reaction with an unsaturated polyester resin or the like during pressure molding to form a polar group on the surface, and a base material and a coating layer forming composition using the thermosetting resin composition. Since the hydrogen bond between the resin inside increases, the adhesiveness between the base material and the coating layer increases, and the adhesiveness between the coating layer and the molded product base material made of the thermosetting resin composition is effectively increased. To be enhanced. The copolymer resin is 3
As it forms a three-dimensional mesh, it has excellent hot water resistance.

The thermosetting resin composition for in-mold coating molding according to the third aspect of the present invention has the above-mentioned constitution.
During pressure molding, polar acrylic monomer and polyfunctional acrylic monomer undergo copolymerization reaction with unsaturated polyester resin,
Adhesion between the base material and the coating layer is formed by forming a polar group on the surface and increasing hydrogen bonding between the base material using the thermosetting resin composition and the resin in the coating layer forming composition. And the adhesiveness between the coating layer and the molded article substrate made of the thermosetting resin composition is effectively enhanced. Moreover, since the copolymer resin forms a three-dimensional network, it has excellent hot water resistance.

Since the thermosetting resin composition for in-mold coating of the invention of claim 4 of the present application has the above-mentioned constitution,
During pressure molding, polar acrylic monomer and acrylic silane coupling agent undergo copolymerization reaction with unsaturated polyester resin, etc. to form polar groups on the surface, and base material and coating layer formation using the thermosetting resin composition. Since the hydrogen bond between the resin in the composition for use increases, the adhesiveness between the base material and the coating layer increases, and the adhesiveness between the coating layer and the molded product base material made of the thermosetting resin composition increases. Effectively enhanced. Moreover, since the copolymer resin forms a three-dimensional network, it has excellent bending strength and hot water resistance.

Since the thermosetting resin composition for in-mold coating of the invention of claim 5 of the present application has the constitution as described above,
A polar group-containing polyfunctional acrylic monomer copolymerizes with an unsaturated polyester resin or the like during pressure molding to form a polar group on the surface, and a base material and a coating layer forming composition using the thermosetting resin composition Since the hydrogen bond between the resin inside increases, the adhesiveness between the base material and the coating layer increases, and the adhesiveness between the coating layer and the molded product base material made of the thermosetting resin composition is effectively increased. To be enhanced. Moreover, since the copolymer resin forms a three-dimensional network, it has excellent hot water resistance.

The coated molded article according to claim 6 of the present application is a molded article with a coating layer in which the coating layer is firmly adhered to the base material because it has the above-mentioned constitution.

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Claims (6)

[Claims] 1. A thermosetting resin composition used for forming a base material for in-mold coating molding for forming a coating layer on a base material in a molding die, comprising an unsaturated polyester resin as a main component. A thermosetting resin composition for in-mold coating molding, comprising a compound having an acryloyl group or a methacryloyl group, and a polar group in the molecule. 2. The composition according to claim 1, further comprising a polyfunctional monomer selected from at least one of acrylic acid ester of hydroxyalkene, methacrylic acid ester of hydroxyalkene, vinyl acrylate and vinyl methacrylate. A thermosetting resin composition for in-mold coating molding, which comprises: 3. A thermosetting resin composition for in-mold coating molding, wherein the composition of claim 1 further contains a compound having two or more acryloyl groups or methacryloyl groups. 4. A thermosetting resin composition for in-mold coating molding, wherein the composition of claim 1 further contains a silane coupling agent having an acryloyl group or a methacryloyl group. 5. A thermosetting resin composition used for forming a base material for in-mold coating molding for forming a coating layer on a base material in a molding die, which comprises an unsaturated polyester resin as a main component. A thermosetting resin composition for in-mold coating molding, comprising a compound having two or more acryloyl groups or methacryloyl groups and a polar group in the molecule. 6. A coated molded article having a coating layer formed on a base material, wherein the thermosetting resin composition for in-mold coating molding according to claim 1 is used as a base material. A coated molded article characterized in that