JP2010167662A - In-mold coated composition and in-mold coated molded form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an in-mold coated molded form which shows the high level of coating rigidity, resistance to marring and surface smoothness, and is almost free from warpage and/or inverted blister with outstanding appearance and the ability to shorten a molding cycle. <P>SOLUTION: This in-mold coated composition is used for manufacturing an in-mold coated molded form by injecting the former into a cavity, then semi-curing it by heat, and further, completely curing the in-mold coated or molded form by UV irradiation. In addition, the in-mold coated composition contains (A) at least one selected from the group consisting of an urethane oligomer with (meth)acryloyl group, an epoxy oligomer, a polyester oligomer, a polyether oligomer or an unsaturated polyester, (B) an unsaturated monomer which is copolymerizable with (A), (C) either one or both of an organic peroxide polymerization initiator or an azo polymerization initiator, and (D) a photopolymerization initiator. Besides, the mass ratio of (A) to (D) is (A)/(B)=20/80 to 80/20, (C)/ä(A)+(B)}=0.1/100 to 5/100 and (D)/ä(A)+(B)}=0.1/100 to 10/100. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an in-mold coating composition and an in-mold coating molded body. More specifically, it is obtained by molding a thermosetting plastic molding material or a thermoplastic molding material in a mold by an injection molding method, an injection compression molding method, an injection press molding method, a compression molding method or a reaction injection molding method. An in-mold coating composition is injected between the surface of the molded body and the cavity surface of the mold, and the in-mold coating composition is cured in the mold, so that the in-mold coating composition is formed on the surface of the plastic molded body. The present invention relates to an in-mold coated molded body obtained by a so-called in-mold coating molding method (also referred to as an IMC method or an in-mold coating method), which produces an integrally molded body having a close contact.

  For the purpose of improving the scratch resistance of the surface of plastics moldings used in automobiles, home appliances, building materials, etc., or improving the weather resistance and extending the product life, the surface of the moldings is coated. Application has been widely used. Spray coating is generally used as such a coating method, but in recent years, there has been a strong interest in environmental problems, and the release of harmful volatile organic compounds, so-called VOCs, from coating plants to the atmosphere is severely limited. In view of the growing trend and emphasis on employee health protection, there is an urgent need to develop technology to replace spray painting.

  In such a situation, after injecting the paint between the surface of the plastic molded body molded in the mold and the cavity surface of the mold, the paint is cured in the mold to form a coating film on the surface of the plastic molded body. An in-mold coating forming method for producing an intimate integral molded body has attracted attention.

  This in-mold coating molding method is exclusively used for surface modification of molded products with thermosetting resin molding materials such as SMC (Sheet Molding Compound) and BMC (Bulk Molding Compound), but injection molding of thermoplastic resin. Is not yet widely used. One of the major reasons is that the thermosetting in-mold coating is cured in the mold using the mold surface temperature and the surface temperature of the molded product. A high mold temperature and a long time are required for sufficient curing, and in the case of thermoplastic resin molding materials, the mold temperature is generally set low. Time is required, the molding cycle becomes long, and this is a fatal defect in productivity (for example, see Patent Documents 1 to 3).

  As a characteristic of the curing of the coating agent, a method of curing the coating agent by high-frequency induction heating is disclosed in order to cure the coated thermosetting coating agent after being injected into the mold ( For example, see Patent Document 4).

  In addition, for the purpose of preventing defects such as wrinkles and uneven color on the surface of the coating caused by defects during flow of the coating in the mold, the coating does not peel off or crack even if the mold is opened. There has been proposed a method in which a molded product coated at the stage of curing is taken out and then the coated molded product is reheated (see, for example, Patent Document 5).

  However, in the methods of Patent Documents 1 to 3, under a high mold temperature at which the coating material is sufficiently cured, the coating material partially starts to gel in the middle of flowing in the mold, or the viscosity of the coating material. The coating flow becomes uneven due to the increase in the thickness of the coating, wrinkles are generated on the coating surface, color unevenness, defects in the coating film, such as weld lines, and the coefficient of thermal expansion. Defects such as sleds and meat scum were generated as the water cooled. Therefore, it is necessary to maintain sufficient fluidity without gelation or viscosity increase until the entire surface to be coated with the coating agent is coated. However, for this purpose, the mold temperature is lowered or the gelation of the coating agent is slowed down, in other words, the curing reaction is lowered, the curing time becomes extremely long, and a problem arises in productivity, In some cases, the curing reaction up to the point where sufficient performance is exhibited may not proceed.

  In patent document 4, since a metal mold | die is heated or cooled between shaping | molding cycles, there existed a fault that a loss of energy and a shaping | molding cycle became long.

  Moreover, in patent document 5, since the covering molded product taken out from the metal mold is reheated at a temperature higher than the molding temperature, problems such as deformation and warping of the molded product are not preferable.

  Patent Document 6 comprises a urethane (meth) acrylate having a benzene skeleton content of 15 to 50% by weight and a (meth) acrylate having a benzene skeleton, and further contains a thermosetting catalyst and / or a photopolymerization initiator. A coating agent is disclosed.

  In Patent Document 6, the temperature is adjusted to 35 ° C., and a transparent substrate made of a methyl methacrylate copolymer is applied to a die having a chrome plating applied in advance to a thickness of 50 to 150 μm using a dispenser. Is pressure laminated from above the coated resin. Furthermore, it is said that the composition is cured from the direction on the substrate using a UV irradiator, and a molded product having excellent releasability from the mold, high refractive index and excellent resin adhesion is obtained. However, in this method, since the spray dust is scattered around the mold because the paint is applied to the mold, the working environment is bad, and it is necessary to cure the coating film so that the coating film is not broken even if the resin substrate is pressed in the mold. In addition, since UV irradiation is performed in the mold, there is a problem that a molding cycle becomes long. Moreover, since it is comprised from the urethane (meth) acrylate which has a benzene skeleton, and the (meth) acrylate which has a benzene skeleton, there exists a subject that a coating film turns yellow easily easily to ultraviolet rays, such as sunlight.

  In Patent Document 7, a synthetic resin skin material is placed on a mold surface of a mold, and after a resin base material is injection-molded on one surface side, a paint is applied between the other surface side of the skin material and the mold surface. An in-mold coating method in which a coating film is formed on the other surface side of the skin material by injecting and pressurizing is disclosed. According to this method, both surfaces of the skin material are formed from materials having excellent adhesion to the resin base material or the paint, respectively, so that the resin can be used even when using a paint having poor adhesion to the resin base material. A coating film having excellent adhesion can be formed on the surface of the substrate. However, although the adhesion of the skin material is mentioned, there is no suggestion about the functions such as the design property of the skin material.

  In Patent Document 8, a porous skin material is placed in a mold, a resin base material is integrally formed on the back surface of the skin material, and a gap is formed by opening the surface of the skin material and the mold surface. A method of forming a coating film on the surface of the skin material by injecting a thermosetting paint into the gap and heating it while applying pressure is disclosed. Patent Document 8 does not describe the mold temperature. However, in order to cure the thermosetting paint in a short time to such an extent that practical performance is exhibited in the mold, the mold temperature needs to be high. When the molded body is taken out of the mold after curing the paint in such a state, when the molded body is cooled to the room temperature, the porous uneven surface is brought to the surface by the thermal contraction of the molded substrate and the coating film. Appearance is not preferable in appearance.

Japanese Patent Laid-Open No. 5-301251 JP-A-7-112450 JP 2001-96573 A JP-A-5-318527 JP 2003-154545 A JP 2006-274194 A JP 2001-170964 A JP 2003-159724 A

  The object of the present invention is to solve the above-mentioned problems, that is, the hardness and scratch resistance of the coating film are improved and the glossiness is high, and the surface smoothness is excellent. An object of the present invention is to provide an in-mold coating composition capable of shortening the cycle and an in-mold coating composition covering the surface of the in-mold coating mold.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved with the following configuration, and have reached the present invention.

That is, according to the present invention, using any one of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
A step of clamping a mold composed of a fixed mold part and a movable mold part;
Molding the resin in the mold cavity;
Injecting the in-mold coating composition into the cavity;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold coated molded body coated with the in-mold coating composition from a mold, and a step of completely curing the in-mold coated molded body taken out of the mold by UV irradiation In the in-mold coating composition used for the molded body,
The in-mold coating composition is
(A) at least one selected from urethane oligomers having a (meth) acryloyl group, epoxy oligomers, polyester oligomers, polyether oligomers or unsaturated polyesters, and (B) unsaturated monomers copolymerizable with (A) ( C) one or both of an organic peroxide polymerization initiator and an azo polymerization initiator and (D) a photopolymerization initiator, and
The mass ratio of the component (A) and the component (B) is (A) / (B) = 20/80 to 80/20,
The mass ratio of the component (C) is (C) / {(A) + (B)} = 0.1 / 100 to 5/100,
The mass ratio of the component (D) is (D) / {(A) + (B)} = 0.1 / 100 to 10/100.
An in-mold coating composition is provided.

Also, according to the present invention, using any one of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
A step of clamping a mold composed of a fixed mold part and a movable mold part;
Molding the resin in the mold cavity;
Injecting the in-mold coating composition into the cavity;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold coated molded body coated with the in-mold coating composition from a mold, and a step of completely curing the in-mold coated molded body taken out of the mold by UV irradiation In the molded body,
An in-mold coating product is provided, wherein the in-mold coating composition is the above-mentioned in-mold coating composition.

Also, according to the present invention, using any one of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
Placing a skin material on one of the molds composed of a fixed mold part and a movable mold part, and integrally molding a molded resin base material on the back surface of the skin material;
Injecting an in-mold coating composition into the mold cavity;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
An in-mold coating product is provided, wherein the in-mold coating composition is the above-mentioned in-mold coating composition.

Also, according to the present invention, using any one of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
A mold comprising a first cavity for molding a resin base, a mold part having a second cavity for applying a larger in-mold coating than the first cavity, and a core mold part,
Forming a molded resin base material on the first cavity surface;
While the molded body is fixed to the core mold portion, the first cavity is replaced with the second cavity surface, and the in-mold coating composition is injected into the gap between the second cavity surface and the molded body. Process,
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
An in-mold coating product is provided, wherein the in-mold coating composition is the above-mentioned in-mold coating composition.

Also, according to the present invention, using any one of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
A mold comprising a first cavity for molding a resin base, a mold part having a second cavity for applying a larger in-mold coating than the first cavity, and a core mold part,
Disposing a skin material on the first cavity surface and integrally molding a molded resin base material on the back surface of the skin material;
While the molded body is fixed to the core mold portion, the first cavity is replaced with the second cavity surface, and the in-mold coating composition is injected into the gap between the second cavity surface and the molded body. Process,
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
An in-mold coating product is provided, wherein the in-mold coating composition is the above-mentioned in-mold coating composition.

Also, according to the present invention, using any one of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
Molding a molded resin base material with a molding die comprising a fixed mold part and a movable mold part;
Removing the molded body from the mold;
Placing the molded body in another coating mold consisting of a fixed mold part having a cavity larger than the molded body and a movable mold part, and clamping the mold;
Injecting an in-mold coating composition into a cavity between the coating mold and the molded body;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
An in-mold coating product is provided, wherein the in-mold coating composition is the above-mentioned in-mold coating composition.

Also, according to the present invention, using any one of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
Placing a skin material on one of the molding dies composed of a fixed mold part and a movable mold part, and integrally molding a molding resin base material on the back surface of the skin material;
Removing the molded body from the mold;
Placing the molded body in another coating mold consisting of a fixed mold part having a cavity larger than the molded body and a movable mold part, and clamping the mold;
Injecting an in-mold coating composition into a cavity between the coating mold and the molded body;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
An in-mold coating product is provided, wherein the in-mold coating composition is the above-mentioned in-mold coating composition.

  According to the present invention, the coating composition is injected between the skin side surface of the molded body of the thermosetting molding resin or the thermoplastic molding resin in which the skin material is integrated and the surface of the mold cavity. After the coating composition is semi-cured by heat so that it can be removed from the mold, the coated molded body is taken out from the mold and further irradiated with UV to completely cure the coating composition, and the hardness and scratch resistance of the coating film. It is possible to provide an in-mold coated molded body having improved properties, high glossiness, excellent surface smoothness, almost no warpage or sinking, excellent appearance, and capable of shortening the molding cycle.

It is the schematic of the apparatus of the 1st aspect of the injection molding method of a thermoplastic resin molding material. It is the schematic of the apparatus of the 2nd aspect of the injection molding method of a thermoplastic resin molding material. It is a figure which shows the magnitude | size of the warp of the in-mold coating molding.

  Hereinafter, the in-mold coated molded body of the present invention will be specifically described.

  The in-mold coated molded body according to the present invention comprises a molded body made of a thermosetting molding resin or a thermoplastic molding resin, and a coating of the in-mold coating composition formed on the surface thereof. It is preferable from the viewpoint of design that the skin is integrally molded with the molded body.

  As the thermosetting molding resin, conventionally known molding materials can be used. For example, unsaturated polyester resin, epoxy acrylate resin, SMC having phenol resin as a matrix, fiber reinforced plastic molding material called BMC, unsaturated polyester Examples thereof include resin, epoxy acrylate resin, RTM molding material using epoxy resin as a matrix, RIM molding material using dicyclopentadiene, urethane and the like.

  As the thermoplastic molding resin, conventionally known various molding materials can be used, for example, polycarbonate, polymethyl methacrylate, polystyrene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, ABS resin or these resins. An alloy material is mentioned.

  Such molding materials contain, for example, reinforcing materials such as glass fibers, carbon fibers and calcium carbonate whiskers, ultraviolet absorbers, antioxidants, mold release agents, pigments, etc., so as to satisfy the properties according to the application. can do.

  Next, the in-mold coating composition used in the present invention will be described.

The in-mold coating composition used in the present invention is:
(A) at least one selected from urethane oligomers having a (meth) acryloyl group, epoxy oligomers, polyester oligomers, polyether oligomers or unsaturated polyesters, and (B) unsaturated monomers copolymerizable with (A) ( C) one or both of an organic peroxide polymerization initiator and an azo polymerization initiator and (D) a photopolymerization initiator,
And the mass ratio of said (A) component and said (B) component is (A) / (B) = 20 / 80-80 / 20,
The mass ratio of the component (C) is (C) / {(A) + (B)} = 0.1 / 100 to 5/100,
The mass ratio of the component (D) is (D) / {(A) + (B)} = 0.1 / 100 to 10/100.
As an essential component, and if necessary, glass flakes, pearl pigments, inorganic particles such as calcium carbonate, talc, clay, colored pigments, diallyl phthalate oligomers, saturated polyester resins, polyvinyl acetate resins, polymethyl methacrylate resins, etc. It contains optional components such as a low shrinkage agent, a release agent, an ultraviolet absorber, an antioxidant, an antifoaming agent, an antistatic agent, a polymerization inhibitor and a curing accelerator.

(A) Component (A) The component (A) used in the in-mold coating composition used in the present invention is a urethane oligomer, epoxy oligomer, polyester oligomer, polyether oligomer or unsaturated compound having a (meth) acryloyl group. It is at least one selected from polyester resins.

(A-1) Oligomer having (meth) acryloyl group Examples of the oligomer having (meth) acryloyl group include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. Can be mentioned.

  The mass average molecular weight of these oligomers may vary depending on the type of the oligomer, but is generally about 300 to 30,000, preferably 500 to 10,000. The oligomer having the (meth) acryloyl group preferably has at least 2 to 8, preferably 2 to 6, (meth) acryloyl groups in one molecule.

(A-1-1) Urethane (meth) acrylate oligomer The urethane (meth) acrylate oligomer as an oligomer used in the present invention includes, for example, (1) an organic diisocyanate compound, (2) an organic polyol compound, and (3 ) Hydroxyalkyl (meth) acrylate is mixed in an existing ratio such that the NCO / OH ratio is, for example, 0.8 to 1.0, preferably 0.9 to 1.0. Can be manufactured. An oligomer having a large number of hydroxyl groups can be obtained by using excessive hydroxyl groups or using a large amount of hydroxyalkyl (meth) acrylate.

  Specifically, (1) an organic diisocyanate compound and (2) an organic polyol compound are reacted in the presence of a urethanization catalyst such as dibutyltin laurate to obtain an isocyanate-terminated polyurethane prepolymer. Subsequently, the urethane (meth) acrylate oligomer can be produced by reacting (3) hydroxyalkyl (meth) acrylate until almost the free isocyanate group is reacted. The ratio of (2) organic polyol compound and (3) hydroxyalkyl (meth) acrylate is, for example, about 0.1 to 0.5 mol for the former with respect to 1 mol of the latter.

  Examples of (1) organic diisocyanate compounds used in the above reaction include 1,2-diisocyanatoethane, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, hexamethylene diisocyanate, and lysine. Diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane 1,3-bis (isocyanatoethyl) cyclohexane, 1,3-bis (isocyanatomethyl) benzene, 1,3-bis (isocyanato-1-methylethyl) benzene, and the like can be used. These organic diisocyanate compounds can be used alone or as a mixture of two or more thereof.

  The organic polyol compound (2) used in the above reaction preferably includes, as the organic diol compound, for example, alkyl diol, polyether diol, polyester diol and the like.

Examples of the alkyl diol include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, and 1,5-pentane. Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 4,8-dihydroxy Typical examples include tricyclo [5.2.1.0 ^2,6 ] decane, 2,2-bis (4-hydroxycyclohexyl) propane and the like.

  The polyether diol as the organic diol compound can be synthesized, for example, by polymerization of aldehyde, alkylene oxide, glycol or the like by a known method. For example, polyether diol can be obtained by addition polymerization of formaldehyde, ethylene oxide, propylene oxide, tetramethylene oxide, epichlorohydrin or the like to alkyl diol under appropriate conditions.

  Examples of the polyester diol as the organic diol compound include esterification reaction products obtained by reacting saturated or unsaturated dicarboxylic acids and / or their acid anhydrides with excess alkyl diols, and alkyl diols. An esterification reaction product obtained by polymerizing hydroxycarboxylic acid and / or lactone which is an intramolecular ester thereof and / or lactide which is an intermolecular ester can be used. These organic polyol compounds can be used alone or in combination of two or more thereof.

  As said (3) hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. can be mentioned. In addition, the urethane (meth) acrylate oligomer as an oligomer used in the present invention is a compound having a (meth) acryloyl group and a hydroxyl group in one molecule and an organic diisocyanate compound, and the NCO / OH ratio is, for example, Even if it reacts in the ratio of 0.9-1.0 in presence of urethanization catalysts, such as dibutyltin dilaurate, it can manufacture.

  The urethane (meth) acrylate oligomer as an oligomer used in the present invention is preferably at least one of a urethane (meth) acrylate oligomer or an aliphatic urethane (meth) acrylate oligomer having an alicyclic structure, particularly preferably an alicyclic structure. It is useful from the surface of the weather resistance and reactivity of a coating film that it is a urethane (meth) acrylate oligomer which has.

(A-1-2) Polyester (meth) acrylate oligomer The polyester (meth) acrylate as an oligomer used in the present invention is produced, for example, by a reaction between a polyester polyol having a hydroxyl group at the terminal and an unsaturated carboxylic acid. be able to. Such a polyester polyol can be typically produced by esterifying a saturated or unsaturated dicarboxylic acid or an acid anhydride thereof with an excess amount of an alkylene diol. Typical examples of the dicarboxylic acid used include oxalic acid, succinic acid, adipic acid, phthalic acid, maleic acid and the like. Examples of alkylene diols that can be used include ethylene glycol, propylene glycol, butane diol, pentane diol, and the like. Here, as unsaturated carboxylic acid, acrylic acid, methacrylic acid, etc. can be mentioned as a typical thing, for example.

(A-1-3) Epoxy (meth) acrylate oligomer The epoxy (meth) acrylate oligomer as an oligomer used in the present invention includes, for example, an epoxy compound and an unsaturated carboxylic acid as described above as an epoxy group 1. A carboxyl group equivalent per equivalent is used, for example, at a ratio of 0.5 to 1.5, and is produced by an acid ring-opening addition reaction to an ordinary epoxy group. As an epoxy compound used here, bisphenol A type epoxy, phenolic novolak type epoxy, etc. can be mentioned suitably, for example.

(A-1-4) Polyether (meth) acrylate oligomer The polyether (meth) acrylate as an oligomer used in the present invention is, for example, a polyether polyol such as polyethylene glycol or polypropylene glycol, and the above-mentioned unsaturated. It can be produced by reaction with a carboxylic acid.

(A-2) Unsaturated polyester resin On the other hand, in the present invention, the unsaturated polyester resin used as the component (A) is, for example, a reaction between an organic polyol compound and an unsaturated carboxylic acid by a known method, Further, if necessary, it can be produced by reacting a saturated polycarboxylic acid. Typical examples of the organic polyol to be used include ethylene glycol, propylene glycol, triethylene glycol, trimethylolpropane, glycerin, bisphenol A, and the like. Moreover, as unsaturated polycarboxylic acid to be used, (anhydrous) maleic acid, (anhydrous) fumaric acid, (anhydrous) itaconic acid etc. can be mentioned as a typical thing, for example.

  As these (A) components, you may use together the said (meth) acryloyl group containing oligomer and unsaturated polyester resin.

(B) Component (B) The component (B) used in the present invention is an unsaturated monomer copolymerizable with the component (A).

  Examples of such unsaturated monomers include styrene, α-methylstyrene, chlorostyrene, vinyl toluene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, ethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic amide, 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylic acid, β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succine N-vinyl-2-pyrrolidone, N-vinylcaprolactam, ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, Representative examples include dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, triallyl isocyanurate, and the like.

  As the component (B), the unsaturated monomer may be used alone or as a mixture thereof. In particular, by including a monomer having one ethylenic double bond in one molecule and a monomer having two or more ethylenic double bonds, the hardness of the formed film is increased and scratches are less likely to occur. preferable. As the component (B), an aliphatic (meth) acrylate monomer such as tripropylene glycol diacrylate (TPGDA) and 1,6-hexanediol diacrylate (1,6-HDDA) or cyclohexyl methacrylate is used. At least one of (meth) acrylate monomer having a simple alicyclic structure, trimethylolpropane triacrylate (TMPT), particularly at least one of aliphatic (meth) acrylate monomer or (meth) acrylate monomer having alicyclic structure Including seeds is preferable from the viewpoint of weather resistance and reactivity of the coating film.

  The mass ratio of the component (A) and the component (B) depends on the types of compounds used as the component (A) and the component (B), but usually (A) / (B) = 20 / 80 to 80/20, and more preferably 33/67 to 67/33. Within this range, a cured coating film having good curing characteristics and a firmness can be obtained, the fluidity in the mold of the coating composition is good, and uniform coating can be obtained without mixing of bubbles.

(C) Component (C) Component (C) used in the present invention is a polymerization initiator used to generate free radicals and polymerize the components (A) and (B). One or both of an organic peroxide polymerization initiator and an azo polymerization initiator are used.

  Examples of the organic peroxide polymerization initiator include isobutyryl peroxide 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, di-3-methoxybutylperoxy Dicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-isopropylperoxydicarbonate, t-butylperoxybenzoate, t-butylperoxyisobutyrate Organic peroxides such as t-butylperoxy 2-ethylhexanoate, t-amylperoxy 2-ethylhexanoate, t-butylperoxyisopropyl carbonate, lauroyl peroxide, benzoyl peroxide It is mentioned as a thing.

  Examples of the azo polymerization initiator include 2,2′-azobis-isobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethyl). Valeronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 4,4′-azobis-4-cyanovaleric acid, dimethyl-2,2′-azobis (2-methylpropionate) 1,1′-azobis (1-acetoxy-1-phenylene) and the like. These may be used alone or in combination.

  The compounding quantity of one or both of an organic peroxide polymerization initiator and an azo polymerization initiator is 0.1-5 mass parts with respect to a total of 100 mass parts of said {(A) + (B)} component. Yes, and more preferably 0.5 to 3 parts by mass. When the blending amount of one or both of the organic peroxide polymerization initiator and the azo polymerization initiator as the component (C) is less than 0.1 parts by mass, the reaction of the components (A) and (B) does not proceed well. When the coated molded body is taken out from the mold due to poor curing, the coated film peels off and a satisfactory molded body cannot be obtained. Moreover, when it exceeds 5 mass parts, the pot life of a coating composition will become remarkably short, and it is unpreferable practically.

(D) About (D) component (D) component used by this invention is a photoinitiator used in order to superpose | polymerize the said (A) component and (B) component by UV irradiation. Such photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphos Typical examples include fin oxide, benzophenone and derivatives thereof. These may be used alone or in combination.

  (D) The compounding quantity of the photoinitiator of a component is 0.1-10 mass parts with respect to a total of 100 mass parts of said {(A) + (B)} component, More preferably, 1- It is suitable that it is 7 parts by mass. Even if UV irradiation is performed when the blending amount of the polymerization initiator of the component (D) is less than 0.1 parts by mass, the reaction of the component (A) and (B) does not proceed well, and the coating film is not sufficiently cured. It becomes. Moreover, when it exceeds 10 mass parts, yellowing and transparency of a cured coating film will be impaired.

(E) Other components The in-mold coating composition used in the present invention may further contain at least one of glass flakes and pearl pigments as necessary. Moreover, at least 1 sort (s) of the inorganic particle whose average particle diameters are 0.1 micrometer or more and 20 micrometers or less, such as a calcium carbonate in the range which does not affect the polymerization reaction of a photoinitiator, can be included. Preferred examples of such materials include calcium carbonate, talc, barium sulfate, aluminum hydroxide, and clay. These inorganic particles are blended for the purpose of dispersing shrinkage stress accompanying coating curing, improving adhesion to the molded body, and reducing the thermal expansion coefficient. Further, for the purpose of improving the scratch resistance of the coating surface, particles such as alumina and silica having an average particle diameter of 5 nm to 100 nm can also be included.

  The in-mold coating composition used in the present invention may further contain at least one coloring pigment as long as it does not affect the polymerization reaction of the photopolymerization initiator, if necessary. As the color pigment, various color pigments conventionally used for plastics and paints can be used.

  In the present invention, a release agent can be optionally used in combination in order to smoothly release the cured coating film from the mold. Release agents include, for example, stearic acid, hydroxystearic acid, zinc stearate, aluminum stearate, magnesium stearate, calcium stearate and other stearates, soybean oil lecithin, silicone oil, fatty acid ester, fatty acid alcohol dibasic acid Examples include esters. The compounding quantity of these mold release agents is 0.1-5 mass parts with respect to a total of 100 mass parts of said {(A) + (B)} component, Furthermore, 0.2-2 mass parts, for example. Preferably there is. Within this range, the effect of releasing from the mold is suitably exhibited.

  In the present invention, a modified resin can be blended for the purpose of improving adhesion to various base resin. Examples of the modified resin used for such a purpose include chlorinated polyolefin, maleic acid-modified polyolefin, acrylic oligomer, polyvinyl acetate, polymethyl methacrylate, and allyl ester oligomer.

  Various additions such as an antistatic agent, an antioxidant, a polymerization inhibitor, a curing accelerator, a pigment dispersant, an antifoaming agent, and a plasticizer are further added to the in-mold coating composition used in the present invention. You may mix | blend an agent etc.

  As the skin material used in the present invention, those generally used in insert molding can be appropriately used. As such a skin material, for example, a bark sheet obtained by slicing natural wood is bonded to a film-like support such as a metal thin plate, a resin thin plate, or a nonwoven fabric, and the surface of the bark sheet is subjected to a coating treatment. Can be mentioned. Examples of natural wood include cherry, red oak, kokutan, rosewood, mahogany, kaya, boxwood, wig, zelkova, teak, and ho. The adhesive between the natural wood and the support is not particularly limited. However, when injection molding a synthetic resin in the molten state in the subsequent process, a heat-resistant thermosetting type such as an epoxy or urethane type can withstand this heat. It is preferable to perform pressure and heat bonding using an adhesive. The method for coating the surface of natural wood is not particularly limited. For example, a coating process such as base polishing, wash coat, coloring dyeing, sealing, polishing, clear coat, etc. can be adopted. Paints that are used for normal woodworking, such as those based on urethane, alkyd, melamine, and unsaturated polyester, are used.

  Moreover, a printing film can be used. As such a printing film, for example, a pattern layer such as a picture, a logo, a pattern, or a character is formed on a base film by a normal forming method. As a base film, it is used as a base film of a normal insert material, and can mention plastic films, such as an acryl, a styrene, and a polycarbonate.

<Method for producing in-mold coated molded body>
Hereinafter, regarding the method for producing an in-mold coated molded body of the present invention, the configuration of a molding machine, a molding die and a coating composition injection device for carrying out the same will be specifically described with reference to the drawings. The range is not limited by such a specific molding machine, mold, and coating composition injection apparatus.

  FIG. 1 shows a first mode in the case of an injection molding method of a thermoplastic resin molding material. In FIG. 1, reference numeral 1 is a fixed plate of a mold clamping device of an injection molding machine, and 2 is a movable plate, each having a fixed mold part 3 and a movable mold part 4 which are molding members facing each other. The movable platen 2 is configured to be moved back and forth by the mold clamping cylinder 5. A cavity 6 having a required shape is formed at a fitting portion between the fixed mold part 3 and the movable mold part 4, and a molten or soft thermoplastic resin molding material is injected and filled in the cavity 6. It is then solidified. When the molten resin molding material is injected and filled, the resin molding material can be injected into the cavity 6 from an injection cylinder 7 having a screw through a nozzle 8 and a sprue 9.

  Further, in FIG. 1, the injection means for the in-mold coating composition includes an injector 10 having a shut-off pin 10A, a measuring cylinder 11 for supplying a predetermined amount of the in-mold coating composition to the injector 10, and an in-mold coating composition. Is supplied from the storage part 12 to the measuring cylinder 11. The measuring cylinder 11 is provided with a plunger regulator 11A for in-mold coating composition injection.

  At the time of molding, the mold clamping cylinder 5 is first operated to close the fixed mold part 3 and the movable mold part 4 and apply mold clamping pressure. This clamping pressure needs to be able to counter the injection pressure of the resin molding material. Usually, this injection pressure is a high pressure of 40 to 250 MPa at the nozzle 8 portion. In this process, the supply pump 13 operates to supply a necessary amount of the in-mold coating composition to the measuring cylinder 11.

  Next, the molten or softened resin molding material is injected from the injection cylinder 7 into the cavity 6 through the nozzle 8 and the sprue 9. When the resin molding material is solidified within the mold to withstand the injection pressure and flow pressure of the in-mold coating composition, the mold clamping pressure is reduced or larger than the desired cured film thickness described below. However, the movable mold part 4 is moved backward by a distance that does not cause the fitting between the fixed mold part 3 and the movable mold part 4 to be released, and preferably by 0.2 to 5 mm. Next, the shutoff pin 10A is operated to open the injection port of the injector 10. Next, the plunger regulator 11A for in-mold coating composition injection of the measuring cylinder 11 is operated, and a desired film is formed between the cavity 6, that is, the inner wall of the fixed mold portion 3 and the surface of the resin molded body to be coated in the mold. An in-mold coating composition is injected in an amount sufficient to obtain a cured coating of thickness, preferably 20-1,000 μm.

  After injecting the in-mold coating composition, the injection port is closed again with the shut-off pin 10A, and the clamping cylinder 5 is operated as necessary to perform the clamping operation, and the in-mold coating composition is expanded and molded in the mold. The body surface is coated, and the in-mold coating composition is semi-cured by heat to the extent that it can be demolded on the surface of the molded body of the cavity 6. Next, the mold clamping cylinder 5 is operated, the fixed mold part 3 and the movable mold part 4 are separated from each other, and the in-mold coated molded body coated with the in-mold coating composition is taken out from the mold.

  About the semi-curing of the coating of the in-mold coating composition by heat, from the surface temperature of the fixed mold part and the movable mold part, from the injection of the resin molding material into the mold until the injection of the in-mold coating composition The temperature varies depending on the time, the type of in-mold coating composition, the holding time in the mold after the in-mold coating composition is injected, etc., but for example, the surface temperature of the fixed mold part and the movable mold part 75 ° C., about 15 seconds from injection of the resin molding material into the mold to injection of the in-mold coating composition, and about 15 seconds of holding time in the mold after injection of the in-mold coating composition. .

Although not shown below, the mold-covered molded product taken out is irradiated with active energy rays such as ultraviolet rays by a UV irradiation machine such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or a carbon arc. The inner coating composition is completely cured to obtain an in-mold coated product. Although the ultraviolet irradiation conditions are not particularly limited, it is preferable to irradiate ultraviolet light having a wavelength of 150 to 450 nm in air or in an inert gas atmosphere such as nitrogen or argon. Dose of ultraviolet light varies due film thickness and the like, usually, preferably 50~2000mJ / cm ^2, particularly preferably 200~1200mJ / cm ^2. The atmosphere temperature in the case of UV irradiation is lower than the mold temperature when the in-mold coating composition is semi-cured so that it can be demolded. From the aspect, it is more preferable.

  FIG. 2 shows a second embodiment. Two mold parts, a first cavity 14 for molding a resin base material, a second cavity 15 for applying a larger in-mold coating than the first cavity, and a core mold part 16 are provided. An injector 10 having a shut-off pin 10A as a means for injecting the same in-mold coating composition as in FIG. 1 is attached to the second cavity.

  Although not shown, a metering cylinder for supplying a predetermined amount of the in-mold coating composition to the injector 10 and a supply pump for supplying the in-mold coating composition from its storage to the measuring cylinder 11 are provided. . The metering cylinder is provided with a plunger regulator for in-mold coating composition injection.

  Reference numeral 17 denotes a hydraulic device for sliding the core mold part, and 18 denotes a sliding base board. In FIG. 2, a clamping cylinder and an injection cylinder part for melting and injecting a resin molding material are not shown.

  At the time of molding, the cavity mold portion and the core mold portion are closed by a mold clamping cylinder, and a mold clamping pressure is applied. This clamping pressure needs to be able to counter the injection pressure of the resin molding material. Normally, this injection pressure is a high pressure of 40 to 250 MPa at the nozzle portion (not shown). In this process, the supply pump operates to supply a necessary amount of the in-mold coating composition to the metering cylinder.

  Next, the molten or softened resin molding material is injected from the injection cylinder into the first cavity through the nozzle. In the state shown in FIG. 2 (a), the cavity mold part and the core mold part are separated from each other as shown in FIG. 2 (c), the core mold part is slid to replace the first cavity 14 with the second cavity 15, and the cavity mold part and the core mold part are closed again as shown in FIG. 2 (d). Apply pressure. This mold clamping pressure must be able to counter the injection pressure of the in-mold coating composition. The injection pressure at this time is usually 7 to 30 MPa.

  Next, the shutoff pin 10A is operated to open the injection port of the injector 10. Next, the plunger regulator for in-mold coating composition injection of the measuring cylinder is operated, and a desired film thickness, preferably in the space between the inner wall of the second cavity 15 and the surface of the resin molded body to be coated in the mold, preferably Injects the in-mold coating composition in an amount sufficient to obtain a cured coating of 20 to 1,000 μm.

  After injecting the in-mold coating composition, the injection port is closed again with the shut-off pin 10A, the clamping cylinder is operated as necessary to perform the clamping operation, and pressure is applied to the in-mold coating composition in the mold, The in-mold coating composition is semi-cured by heat on the surface of the molded body of the cavity 15 until it can be demolded. Next, the mold clamping cylinder is operated, the cavity mold parts 14 and 15 and the core mold part 16 are separated from each other, and the in-mold coated molded body coated with the in-mold coating composition is taken out from the mold.

  In the following, UV irradiation is performed in the same manner as in the first embodiment, and the in-mold coating composition is completely cured to obtain an in-mold coated molded body.

  According to a third aspect, after forming a molded body using a molding die including a fixed mold part and a movable mold part provided with a mold clamping device, the molded body is taken out from the mold, After being placed in another coating mold consisting of a fixed mold part having a large cavity and a movable mold part, the movable mold part is operated to perform clamping. A space (cavity) corresponding to the coating film thickness is formed in the gap between the inner surface of the movable mold and the molded body, and the in-mold coating composition is injected into the cavity.

  In the molding, the second and third aspects have an advantage that the coating film thickness can be arbitrarily set regardless of the shape of the molded body.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, the scope of the present invention is not limited at all by these Examples and comparative examples.

<Synthesis of urethane oligomer>
Urethane oligomers can be prepared by polymerization by various known methods. As a synthesis example, the amount of (A) component shown in Table 1 is charged with 0.02 parts by mass of dibutyltin dilaurate per 100 parts by mass of the total amount of components (A) to (C) and kept at 40 ° C. However, after adding (B) component of the quantity shown in Table 1 and making it react for sufficient time, it is set to (C) component shown in Table 1 in 0.1 mass per 100 mass parts of total amounts of (A)-(C) component. What melt | dissolved the hydroquinone of the quantity used as 1 mass part was dripped, and also heat stirring was continued at 75 degreeC for sufficient time, and urethane oligomer UAC-1-UAC-4 was obtained.

<Examples 1-7 and Comparative Examples 1-7>
Using a mold having a cavity for obtaining a box-shaped resin molded body having a length of 300 mm, a width of 200 mm, a height of 10 mm, and a plate thickness of 2.5 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. . The mold cavity surface was carefully polished with # 8000 diamond paste. The mold temperature is set to 75 ° C for the fixed mold, 75 ° C for the movable mold, and the barrel temperature is heated to 220 ° C. First, heat-resistant ABS resin is heated and melted in the injection cylinder, and the mold is clamped to 3,500KN. It was injected into a mold clamped with pressure over about 1 second, cooled for 15 seconds, and the surface of the obtained molded body was solidified to such an extent that it could withstand the injection and flow pressure of the in-mold coating composition.

Next, after moving the movable mold about 1 mm apart, 18 cm ³ of each in-mold coating composition described in Table 2 was injected between the mold surface and the surface of the molded body over about 0.9 seconds. After completion of the injection, the mold clamping pressure was increased to 200 KN over 1 second and held for 15 seconds. The in-mold coating composition was semi-cured until it could be demolded, and then the coated molded product was taken out from the mold. Then, the in-mold coating composition is completely cured by irradiating 1,000 mJ / cm ² of ultraviolet rays from the coating surface side of the coated molded product in the air at an ambient temperature of 25 ° C. using a UV irradiator. Coated molded articles of Examples 1 to 7 were obtained.

  Hardness, gloss, and scratch resistance of the coating film of Examples 1-7 obtained by UV irradiation and in-mold coatings of Comparative Examples 1-7 not subjected to UV irradiation Property, adhesion between the substrate and the coating film, and the degree of warping were measured by the following test methods. The results are shown in Table 3.

[Hardness of coating film]
JIS K 5600-5-4: The pencil hardness of the coating film was measured according to scratch hardness (pencil method).

[Specular gloss]
JIS K 5600-4-7: According to the specular glossiness, it was measured at an incident angle of 60 degrees using a specular glossiness meter.

[Abrasion resistance]
Using a dyeing material friction fastness tester (model RT-200, with a flat test stand, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), apply a load of 13.7 KPa to a wear pad equipped with # 000 steel wool. 11 times, and the specular gloss was measured to determine the amount of change before and after the test.

[Adhesion between substrate and coating film]
According to JIS K 5600-5-6: Adhesion (cross-cut method), an initial coating adhesion test was performed. The adhesion of the coating film was evaluated on the basis of the following 0 to 5 based on the classification of the test results described in JIS K 5600-5-6.
<6-level evaluation>
0: The edges of the cut are completely smooth, and there is no peeling in any lattice eye.
1 ... Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected.
2 ... The coating is peeled along the edge of the cut and / or at the intersection. The cross-cut part is clearly affected by more than 5% but not more than 15%.
3 ... The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eye are partially or completely peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
4: The coating film has been partially or completely peeled along the edges of the cut, and / or some eyes have been partially or completely peeled off. The cross-cut portion is clearly affected by more than 35% but not more than 65%.
5: When the degree of peeling exceeds Category 4.

[Shape size of molded body]
As shown in FIG. 3, when the concave depth of the center part of the molded body not coated with the mold is (a) and the concave depth of the molded body coated with the mold is (b), the following (I The value calculated according to the formula was taken as the warp size of the in-mold coated molded body. However, the unit is mm.
Warp size of in-mold coated molded article = (b)-(a) (I) formula

<Examples 8 to 15 and Comparative Examples 8 to 10>
Using a mold having a cavity for obtaining a box-shaped resin molded body having a length of 300 mm, a width of 200 mm, a height of 10 mm, and a plate thickness of 2.5 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. . The mold cavity surface was carefully polished with # 8000 diamond paste. The mold temperature is set to 75 ° C for the fixed mold, 75 ° C for the movable mold, and the barrel temperature is heated to 220 ° C. First, heat-resistant ABS resin is heated and melted in the injection cylinder, and the mold is clamped to 3,500KN. It was injected into a mold clamped with pressure for about 1 second, cooled for 20 seconds, and the surface of the obtained molded body was solidified to such an extent that it could withstand the injection and flow pressure of the in-mold coating composition.

Next, after moving the movable mold about 1 mm apart, 18 cm ³ of each in-mold coating composition described in Table 4 was injected between the mold surface and the surface of the molded body over about 0.9 seconds. After completion of the injection, the mold clamping pressure was increased to 200 KN over 1 second and held for 20 seconds, and the in-mold coating composition was semi-cured until demolding was possible, and then the coated molded product was taken out from the mold. Thereafter, the in-mold coating composition was completely cured by irradiating 1,000 mJ / cm ² of ultraviolet rays from the coating surface side of the coated molded article in the air at an atmospheric temperature of 25 ° C. using a UV irradiator. .

  The hardness, gloss, scratch resistance, adhesion between the substrate and the coating film, and the degree of warping were measured by the above-described test methods. The results are shown in Table 5.

<Examples 16 to 17 and Comparative Examples 11 to 12>
Using a mold having a cavity for obtaining a box-shaped resin molded body having a length of 300 mm, a width of 200 mm, a height of 10 mm, and a plate thickness of 2.5 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. . The mold cavity surface and the core side surface were carefully polished with # 8000 diamond paste. The mold temperature is set to 75 ° C for the fixed mold, 75 ° C for the movable mold, the barrel temperature is heated to 280 ° C, and the polycarbonate resin is first heated and melted in the injection cylinder, and the mold clamping pressure is 3,500KN. It was injected into the mold clamped in step 1 for about 1 second, cooled for 15 seconds, and the surface of the obtained molded body was solidified to the extent that it could withstand the injection and flow pressure of the in-mold coating composition.

Next, after moving the movable mold about 1 mm apart, 4 cm ³ of each in-mold coating composition described in Table 6 was injected between the mold surface and the surface of the molded article over about 0.9 seconds. After completion of the injection, the mold clamping pressure was increased to 200 KN over 1 second and held for 15 seconds. The in-mold coating composition was semi-cured until it could be demolded, and then the coated molded product was taken out from the mold. Thereafter, the in-mold coating composition was completely cured by irradiating 1,000 mJ / cm ² of ultraviolet rays from the coating surface side of the coated molded article in the air at an atmospheric temperature of 25 ° C. using a UV irradiator. .

  Hardness, gloss, adhesion between substrate and coating film, and degree of warpage of in-mold coated product obtained by UV irradiation and in-mold coated product not subjected to UV irradiation as a comparison Was measured by the test method described above. Further, the scratch resistance was measured by the following method. The results are shown in Table 7.

[Abrasion resistance]
Using a dyeing material friction fastness tester (model RT-200, with a flat test stand, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), apply a load of 13.7 KPa to a wear pad equipped with # 000 steel wool. 11 times, the haze value was measured, and the amount of change before and after the test was determined.

<Examples 18 to 20 and Comparative Examples 13 to 15>
Using a mold having a cavity for obtaining a box-shaped resin molded body having a length of 300 mm, a width of 200 mm, a height of 10 mm, and a plate thickness of 2.5 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. . In Examples 18 to 20, in-mold coatings of Examples 18 to 20 were obtained under the same conditions as in Examples 1 to 7, except that the injection amount of the in-mold coating composition was set to 30 cm ³ .

  On the other hand, for Comparative Examples 13 to 15, the mold temperature was set to 100 ° C. for the fixed mold, 100 ° C. for the movable mold, and the barrel temperature was heated to 220 ° C. First, the heat-resistant ABS resin was placed in the injection cylinder. It is heated and melted and injected into a mold clamped at a clamping pressure of 3,500 KN for about 1 second, cooled for 20 seconds, and the surface of the resulting molded body is injected and flown with the in-mold coating composition. Solidified to the extent that it can withstand the pressure.

Next, after moving the movable mold about 1 mm apart, 30 cm ³ of each in-mold coating composition described in Table 8 was injected between the mold surface and the surface of the molded body over about 1 second. After completion of the injection, the mold clamping pressure is increased to 200 KN over 0.5 seconds and held for 20 seconds to cure the in-mold coating composition, and then the coated molded product is taken out from the mold, and the molds of Comparative Examples 13-15 are used. A coated molded body was obtained.

  The hardness, gloss, scratch resistance, adhesion between the substrate and the coating film, and the degree of warping were measured by the above-described test methods. The results are shown in Table 9.

<Examples 21 to 22 and Comparative Examples 16 to 17>
Using a mold having a cavity for obtaining a box-shaped resin molded body having a length of 200 mm, a width of 150 mm, a height of 10 mm, and a plate thickness of 2.5 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. . The mold temperature was set to 75 ° C. for the fixed mold, 75 ° C. for the movable mold, and a single plate of teak material sliced to a thickness of 0.3 mm was placed on the mold surface of the movable mold. The veneer was arranged such that the surface to be the design surface was opposed to the movable mold surface. A non-woven fabric is laminated on the back surface of the veneer via a urethane adhesive to form an adhesive layer. Next, the mold is clamped at a clamping pressure of 2,000 KN, the heat-resistant ABS resin is heated and melted in an injection cylinder heated to a barrel temperature of 220 ° C., injected into the mold for about 1 second, cooled for 20 seconds, The obtained molded body was solidified.

Next, after moving the movable mold about 1 mm apart, 18 cm ³ of each in-mold coating composition described in Table 10 was injected between the mold surface and the surface of the molded body over about 1.5 seconds. After completion of the injection, the mold clamping pressure was increased to 200 KN over 1 second and held for 20 seconds, and the in-mold coating composition was semi-cured until demolding was possible, and then the coated molded product was taken out from the mold. Thereafter, in the air using a UV irradiation machine from the coating surface side of the coated moldings, under conditions of ambient temperature 25 ° C., to completely cure the mold coating composition by irradiation with ultraviolet rays of 1,000 mJ / cm ^2, Coated molded articles of Examples 21 to 22 were obtained.

  Hardness, gloss, and scratch resistance of the coating films of the in-mold coatings of Examples 21 to 22 obtained by UV irradiation and the in-mold coatings of Comparative Examples 16 to 17 that were not irradiated by UV. And the adhesion between the substrate and the coating film and the degree of warping were measured by the above test methods. The results are shown in Table 11.

<Examples 23 to 24 and Comparative Examples 18 to 19>
A first cavity for obtaining a box-shaped resin molded body having a length of 200 mm, a width of 150 mm, a height of 10 mm, and a plate thickness of 2.5 mm, and a second cavity capable of applying an in-mold coating with a set film thickness of 50 μm In-mold coating was performed on the compact according to the embodiment shown in FIG. The mold cavity surface and the core side surface were carefully polished with # 8000 diamond paste. The mold temperature is set to 75 ° C. for the first and second cavity mold portions, 75 ° C. for the core mold portion, the barrel temperature is heated to 280 ° C., and the polycarbonate resin is first heated and melted in the injection cylinder. , Injection into a mold clamped at a mold clamping pressure of 500 KN over about 1 second, cooling for 30 seconds, and the surface of the resulting molded body can withstand the injection and flow pressure of the in-mold coating composition Solidified.

Next, the cavity mold part and the core mold part are separated, the core mold part is slid to replace the first cavity with the second cavity, the cavity mold part and the core mold part are closed again, and the mold is clamped at 1,000 KN Clamped with pressure. Thereafter, 1.9 cm ³ of the in-mold coating compositions of Examples 16 to 17 and Comparative Examples 11 to 12 shown in Table 6 were injected between the mold surface and the surface of the molded article over about 0.5 seconds. For 20 seconds. The injection pressure at this time was 7 MPa. After semi-curing until the in-mold coating composition became demoldable, the coated molded product was taken out from the mold. Thereafter, in Examples 23 to 24, an in-mold coating composition was irradiated by irradiating 1,000 mJ / cm ² of ultraviolet rays in the air at an atmospheric temperature of 25 ° C. from the coating film surface side of the coated molded article. The product was completely cured to obtain a coated molded product. Comparative examples 18-19 did not perform UV irradiation.

  Hardness, gloss, and abrasion resistance of the coating films of the in-mold coatings of Examples 23 to 24 obtained by UV irradiation and the in-mold coatings of Comparative Examples 18 to 19 that were not irradiated with UV. And the adhesion between the substrate and the coating film and the degree of warping were measured by the above test methods. The results are shown in Table 12.

<Examples 25-26 and Comparative Examples 20-21>
A first cavity for obtaining a box-shaped resin molded body having a length of 200 mm, a width of 150 mm, a height of 10 mm, and a plate thickness of 2.5 mm, and a second cavity capable of applying an in-mold coating with a set film thickness of 500 μm In-mold coating was performed on the compact according to the embodiment shown in FIG. The mold temperature is set to 75 ° C. for the first and second cavity mold parts, 75 ° C. for the core mold part, and a single plate of teak material sliced to a thickness of 0.3 mm is used as the mold surface of the first cavity. Arranged. The veneer was arranged so that the surface to be the design surface was opposed to the mold surface of the first cavity. A non-woven fabric is laminated on the back surface of the veneer via a urethane adhesive to form an adhesive layer. Next, the mold is clamped with a clamping pressure of 3,000 KN, the heat-resistant ABS resin is heated and melted in an injection cylinder heated to a barrel temperature of 220 ° C., injected into the mold for about 1 second, cooled for 30 seconds, The obtained molded body was solidified.

Next, the cavity mold part and the core mold part are separated, the core mold part is slid to replace the first cavity with the second cavity, the cavity mold part and the core mold part are closed again, and the mold is clamped at 1,000 KN Clamped with pressure. Thereafter, 18.5 cm ³ of the in-mold coating compositions of Examples 21 to 22 and Comparative Examples 16 to 17 described in Table 10 were injected between the mold surface and the surface of the molded article over about 1.5 seconds. For 20 seconds. The injection pressure at this time was 12 MPa. After semi-curing until the in-mold coating composition became demoldable, the coated molded product was taken out from the mold. Thereafter, Examples 25 to 26 were prepared by irradiating 1,000 mJ / cm ² of ultraviolet rays from the coating surface side of the coated molded article in the air at an atmospheric temperature of 25 ° C. using an UV irradiator. The product was completely cured to obtain a coated molded product. Comparative Examples 20-21 did not perform UV irradiation.

  Hardness, gloss, and scratch resistance of the coating films of the in-mold coatings of Examples 25 to 26 obtained by UV irradiation and the in-mold coatings of Comparative Examples 20 to 21 that were not irradiated by UV. And the adhesion between the substrate and the coating film and the degree of warping were measured by the above test methods. The results are shown in Table 13.

<Examples 27 to 28 and Comparative Examples 22 to 23>
First mold including a fixed mold part having a cavity and a movable mold part for obtaining a box-shaped resin molded body having a length of 200 mm, a width of 150 mm, a height of 10 mm, and a plate thickness of 2.5 mm, and the molded body A mold for a molded body according to the third embodiment, using a second coating mold comprising a fixed mold part and a movable mold part having a cavity that can be coated with a mold thickness of 500 μm larger than the mold. Inner coating was performed. The first mold temperature was set to 75 ° C. for the fixed mold part and 75 ° C. for the movable mold part, and a single plate of teak material sliced to a thickness of 0.3 mm was placed on the movable mold surface. The veneer was arranged such that the surface to be the design surface was opposed to the movable mold surface. A non-woven fabric is laminated on the back surface of the veneer via a urethane adhesive to form an adhesive layer. Next, the mold is clamped at a clamping pressure of 2,000 KN, the heat-resistant ABS resin is heated and melted in an injection cylinder heated to a barrel temperature of 220 ° C., injected into the mold over about 1 second, cooled for 30 seconds, The obtained molded body was solidified.

Next, the fixed mold and the movable mold were separated from each other, and the molded body was taken out from the mold. Next, after placing the molded body on the fixed mold of the second coating mold with the fixed mold part set at 75 ° C. and the movable mold part set at 75 ° C., the movable mold was closed and the mold clamping pressure was 500 KN The mold was clamped. Thereafter, 18.5 cm ³ of the in-mold coating compositions of Examples 21 to 22 and Comparative Examples 16 to 17 described in Table 10 were injected between the mold surface and the surface of the molded article over about 1.5 seconds. For 25 seconds. The injection pressure at this time was 12 MPa. After semi-curing until the in-mold coating composition became demoldable, the coated molded product was taken out from the mold. Thereafter, in Examples 27 to 28, an in-mold coating composition was irradiated by irradiating 1,000 mJ / cm ² of ultraviolet rays from the coating film surface side of the coated molded article in air at an atmospheric temperature of 25 ° C. The product was completely cured to obtain a coated molded product. In Comparative Examples 22 to 23, UV irradiation was not performed.

  Hardness, gloss, and abrasion resistance of the coating films of the in-mold coatings of Examples 27 to 28 obtained by UV irradiation and the in-mold coatings of Comparative Examples 22 to 23 not subjected to UV irradiation And the adhesion between the substrate and the coating film and the degree of warping were measured by the above test methods. The results are shown in Table 14.

DESCRIPTION OF SYMBOLS 1 Fixed platen 2 Movable platen 3 Fixed mold part 4 Movable mold part 5 Clamping cylinder 6 Cavity 7 Injection cylinder 8 Nozzle 9 Sprue 10 Injector 10A Shut-off pin 11 Measuring cylinder 11A Plunger regulator 12 Storage part 13 Supply pump 14 1st 1 cavity 15 second cavity 16 core mold part 17 hydraulic device 18 slide base board

Claims (9)

Using any of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
A step of clamping a mold composed of a fixed mold part and a movable mold part;
Molding the resin in the mold cavity;
Injecting the in-mold coating composition into the cavity;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold coated molded body coated with the in-mold coating composition from a mold, and a step of completely curing the in-mold coated molded body taken out of the mold by UV irradiation In the in-mold coating composition used for the molded body,
The in-mold coating composition is
(A) at least one selected from urethane oligomers having a (meth) acryloyl group, epoxy oligomers, polyester oligomers, polyether oligomers or unsaturated polyesters, and (B) unsaturated monomers copolymerizable with (A) ( C) one or both of an organic peroxide polymerization initiator and an azo polymerization initiator and (D) a photopolymerization initiator, and
The mass ratio of the component (A) and the component (B) is (A) / (B) = 20/80 to 80/20,
The mass ratio of the component (C) is (C) / {(A) + (B)} = 0.1 / 100 to 5/100,
The mass ratio of the component (D) is (D) / {(A) + (B)} = 0.1 / 100 to 10/100.
An in-mold coating composition characterized by   The in-mold coating composition according to claim 1, wherein the urethane oligomer having a (meth) acryloyl group as the component (A) is a urethane (meth) acrylate oligomer having an alicyclic structure.   The unsaturated monomer copolymerizable with the component (A) of the component (B) is at least one of an aliphatic (meth) acrylate monomer or a (meth) acrylate monomer having an alicyclic structure. The in-mold coating composition according to 2. Using any of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
A step of clamping a mold composed of a fixed mold part and a movable mold part;
Molding the resin in the mold cavity;
Injecting the in-mold coating composition into the cavity;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold coated molded body coated with the in-mold coating composition from a mold, and a step of completely curing the in-mold coated molded body taken out of the mold by UV irradiation In the molded body,
The in-mold coating composition, wherein the in-mold coating composition is the in-mold coating composition according to any one of claims 1 to 3. Using any of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
Placing a skin material on one of the molds composed of a fixed mold part and a movable mold part, and integrally molding a molded resin base material on the back surface of the skin material;
Injecting an in-mold coating composition into the mold cavity;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
The in-mold coating composition, wherein the in-mold coating composition is the in-mold coating composition according to any one of claims 1 to 3. Using any of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
A mold comprising a first cavity for molding a resin base, a mold part having a second cavity for applying a larger in-mold coating than the first cavity, and a core mold part,
Forming a molded resin base material on the first cavity surface;
While the molded body is fixed to the core mold portion, the first cavity is replaced with the second cavity surface, and the in-mold coating composition is injected into the gap between the second cavity surface and the molded body. Process,
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
The in-mold coating composition, wherein the in-mold coating composition is the in-mold coating composition according to any one of claims 1 to 3. Using any of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
A mold comprising a first cavity for molding a resin base, a mold part having a second cavity for applying a larger in-mold coating than the first cavity, and a core mold part,
Disposing a skin material on the first cavity surface and integrally molding a molded resin base material on the back surface of the skin material;
While the molded body is fixed to the core mold portion, the first cavity is replaced with the second cavity surface, and the in-mold coating composition is injected into the gap between the second cavity surface and the molded body. Process,
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
The in-mold coating composition, wherein the in-mold coating composition is the in-mold coating composition according to any one of claims 1 to 3. Using any of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
Molding a molded resin base material with a molding die comprising a fixed mold part and a movable mold part;
Removing the molded body from the mold;
Placing the molded body in another coating mold consisting of a fixed mold part having a cavity larger than the molded body and a movable mold part, and clamping the mold;
Injecting an in-mold coating composition into a cavity between the coating mold and the molded body;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
The in-mold coating composition, wherein the in-mold coating composition is the in-mold coating composition according to any one of claims 1 to 3. Using any of injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method,
Placing a skin material on one of the molding dies composed of a fixed mold part and a movable mold part, and integrally molding a molding resin base material on the back surface of the skin material;
Removing the molded body from the mold;
Placing the molded body in another coating mold consisting of a fixed mold part having a cavity larger than the molded body and a movable mold part, and clamping the mold;
Injecting an in-mold coating composition into a cavity between the coating mold and the molded body;
Semi-curing with heat so that the injected in-mold coating composition can be demolded;
In-mold coating produced by a step of taking out an in-mold molded body coated with the in-mold coating composition from a mold and a step of completely curing the in-mold coated body taken out of the mold by UV irradiation In the body,
The in-mold coating composition, wherein the in-mold coating composition is the in-mold coating composition according to any one of claims 1 to 3.