JP2003170538A - Coated film and its laminating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored film showing outstanding workability and finishing characteristics. <P>SOLUTION: This coated film is structured of at least two different kinds of resin film, the top layer film (I) being formed of a crosslinkable resin coating material (A) and the bottom layer film (II) being formed of a thermoplastic resin (B). In addition, the formed film (II) is itself substantially lacking in viscosity and shows a modulus in tensile elongation at break of 50 to 1,000%. Also the coated film laminating method is provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel coated film and a laminating method.

BACKGROUND ART Conventionally, cross-linkable resin paints such as melamine curable resin paints, isocyanate curable resin paints and oxidation curable resin paints have been used for metal plates (steel plate, aluminum plate, iron plate, etc.), wood, Inorganic materials other than the above metals (concrete, ceramics, glass, etc.), plastics (polyvinyl chloride, polyethylene terephthalate, polyethylene, nylon, etc.) and other base materials, depending on the properties of each base material, anticorrosion, design, The base material is directly coated to impart functions such as durability, weather resistance, and scratch resistance. In order to paint directly on such a substrate, it is necessary to select the most suitable coating method, which is troublesome, in general it is not possible to maintain a uniform coating film thickness, the coating tends to cause coating defects, From the point of environmental pollution because it consumes more paint than necessary, it is difficult to safely manage the work environment and safety and hygiene of painting, and it is difficult to collect the painted film. There was a problem that it was not preferable.

Further, in general, paints are used according to the purpose of painting such as coating means, coating film performance, and designability, and as a matter of course, there are many kinds of products and many useless paints are produced. There is a demand in the field for product integration and effective use of paints.

[0003]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems, the uppermost layer is a film layer formed from a cross-linkable resin coating material that has been conventionally used. , And the lowermost layer is formed of a thermoplastic film layer which is substantially tack-free in itself and has a specific elongation, that is, a coating film of a multi-layer coating by casting has all of the conventional problems. The inventors have found that it is a solution and have completed the present invention.

That is, the present invention is a film obtained by laminating one or more kinds of resin films, wherein the uppermost layer film (I) is formed of a crosslinkable resin coating material (A) and the lowermost layer film ( II) is formed of a thermoplastic resin (B), and is formed into a film (I
I) is the tensile elongation at break (length 30 mm, width 10 mm, thickness 0.050 mm, and a tensile speed of 20 at -10 ° C).
Coating film (hereinafter, abbreviated as "first invention") characterized in that it is in the range of 50 to 1000% (value measured at 0 mm / min), 2. thermoplastic resin (B) The coating film according to item 1 above, which is formed of an aqueous urethane resin emulsion, 3. The activity of the aqueous urethane resin emulsion, which is capable of reacting with a polyisocyanate compound and an isocyanate group of the polyisocyanate compound. The above-mentioned 1 characterized in that a hydrophilic group-containing isocyanate-terminated prepolymer is produced by reacting with a hydrogen-containing compound, which is then dispersed in water and further chain-extended with amines. Or the coated film according to any one of the items 1 to 3 above, wherein the film (II) layer of the coated film is a film. A method for laminating a coated film, which comprises thermocompression-bonding the surface of the substrate so that it faces the surface of the substrate (hereinafter, this is abbreviated as "second invention"); The coated film according to any one of 3 above is simultaneously prepared so that the film (II) layer of the coated film is formed on the surface of the plastic base material. The present invention relates to a method for laminating a coated film, which is characterized by molding (hereinafter, this is abbreviated as "third invention").

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION First invention: The first invention is a film obtained by laminating two or more kinds of resin films, wherein the uppermost layer film (I) is formed of a crosslinkable resin coating material (A), And the lowermost layer film (II) is thermoplastic resin (B)
The film (II) formed and formed by the above method has a tensile elongation at break (value measured at a tensile speed of 20 mm / min at −10 ° C. for a sample having a length of 30 mm, a width of 10 mm and a thickness of 0.050 mm) of 50 to 50%. The coated film is characterized by being in the range of 1000%.

Top layer film (I) used in the first invention
Is a film constituting the uppermost layer of the multilayer film which is the coated film of the present invention, and a film obtained by using a conventionally known crosslinkable resin coating material (A) can be used.

As the crosslinkable resin coating material (A), for example,
Amino curable resin coating, isocyanate curable resin coating, acid epoxy curable resin coating, hydrolyzable silane curable resin coating, hydroxyl group epoxy group curable resin coating, hydrazine curable resin coating, oxidation polymerization type curable resin coating, Examples thereof include a light (heat) radical polymerization type resin coating material, a light (heat) cationic polymerization type resin coating material, and a curable resin coating material which is a combination of two or more kinds thereof.

The cross-linkable resin coating material (A) contains, if necessary, additives conventionally used in the coating material, for example, color pigments,
Extender pigment, metallic pigment, colored pearl pigment, fluidity regulator, cissing inhibitor, anti-sagging agent, ultraviolet absorber,
Antioxidants, UV stabilizers, matting agents, polishes, preservatives, curing accelerators, curing catalysts, anti-scratch agents, defoamers,
A solvent or the like can be used without particular limitation.

The form of the crosslinkable resin paint (A) is a powder paint using a crosslinkable resin, a solventless paint using a liquid resin of a crosslinkable resin (a crosslinkable or non-crosslinkable resin is radically polymerizable). Solvent-free paints that dissolve or disperse in monomers), water-based paints that dissolve or disperse a crosslinkable resin in water, and organic solvent-type paints that dissolve or disperse a crosslinkable resin in an organic solvent (also non-aqueous dispersion paints) It may be in any form such as (including).

The dry film thickness of the film (I) is 1 μm to 2
A range of 00 μm, particularly 20 μm to 80 μm is preferable.
When it is less than 1 μm, the weather resistance, solvent resistance and sharpness are deteriorated, while when it exceeds 200 μm, the coating film becomes brittle, which is not preferable.

The film (I) formed from the crosslinkable resin coating material (A) is obtained by reacting some or all of the functional groups contained in the crosslinkable resin. The degree of cross-linking of the film (I) depends on, for example, the gel fraction as described below.
It is preferably in the range of 0 to 100% by weight.

Gel fraction: The free film was peeled off, placed in a 300 mesh stainless steel mesh container and extracted with an acetone solvent in a Soxhlet extractor at a reflux temperature for 2 hours, and then the gel fraction was calculated according to the following formula. Was calculated.

Gel fraction (%) = (weight after extraction / weight of sample before extraction) × 100 amino-curable resin paint: As the paint , for example, an acrylic resin having a crosslinkable functional group such as a hydroxyl group is used. A composition comprising a base resin such as a resin, a vinyl resin or a polyester resin and an amino resin as a cross-linking agent can be given.

As the acrylic resin and the vinyl resin, a carboxyl group-containing polymerizable monomer (which can be used if necessary, especially when used as an aqueous paint),
10 to 200 mgKOH / g, which is obtained by copolymerizing a hydroxyl group-containing polymerizable monomer and another polymerizable monomer,
Those having a hydroxyl value within the range of 25 to 70 mgKOH / g can be preferably used.

The carboxyl group-containing polymerizable monomer is a compound having a carboxyl group and a polymerizable unsaturated bond in one molecule, and examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid and crotonic acid. . The hydroxyl group-containing polymerizable monomer is a compound having a hydroxyl group and a polymerizable unsaturated bond in one molecule, and examples thereof include 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth).
Number of carbon atoms of (meth) acrylic acid such as acrylate
Examples include 8 hydroxyalkyl esters.
The other polymerizable monomer is a compound having a polymerizable unsaturated bond in one molecule, which is copolymerizable with the carboxyl group-containing polymerizable monomer and the hydroxyl group-containing polymerizable monomer, such as methyl ( (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylic, lauryl (meth) acrylate, stearyl (meth) acrylate, alkyl or cycloalkyl ester of (meth) acrylic acid having 1 to 24 carbon atoms such as decyl acrylate; (meth) acrylamide, N
-Methyl (meth) acrylamide, N-ethyl (meth)
Functionalized (meth) acrylamides such as acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl acrylamide; glycidyl group-containing vinyl monovalent such as glycidyl (meth) acrylate, glycidyl (meth) acrylamide, allyl glycidyl ether Polymer: styrene, vinyltoluene, vinyl propionate, α-methylstyrene, vinyl acetate,
Examples thereof include vinyl monomers such as (meth) acrylonitrile, vinyl propionate, vinyl pivalate, and veova monomer (shell chemical product). The acrylic resin or vinyl resin may generally have a number average molecular weight within the range of 5,000 to 40,000.

Examples of the polyester resin include polyester resins obtained by subjecting a polyhydric alcohol and a polybasic acid to an esterification reaction.

The polyhydric alcohol is a compound having two or more alcoholic hydroxyl groups in one molecule, and examples thereof include ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol and 2,2.
-Dimethylpropanediol, glycerin, trimethylolpropane, pentaerythritol and the like. A polybasic acid is a compound having two or more carboxyl groups in one molecule, and includes, for example, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, adipic acid, sebacic acid, tricarboxylic acid and tricarboxylic acid. Examples thereof include meritic acid, pyromellitic acid, and their anhydrides. Furthermore, in the esterification reaction of these polyhydric alcohol and polybasic acid, a monohydric alcohol or a monoepoxy compound having a glycidyl group is used as a part of the alcohol component and / or a part of the acid component, if necessary. As the base, a monobasic acid such as benzoic acid or t-butylbenzoic acid can be used. The polyester resin also includes a polyester resin modified with an oil component such as castor oil, tung oil, safflower oil, soybean oil, linseed oil, tall oil, and coconut oil, or a fatty acid thereof. These polyester resins can generally have a number average molecular weight within the range of 500 to 10,000.

The polyester resin is 10 to 200 mg KO
It can have a hydroxyl value in the range of H / g, preferably 25-70 mg KOH / g.

The amino resin cross-linking agent reacts with the base resin by heating to form a three-dimensional cured coating film. Examples of such amino resins include melamine, benzoguanamine,
Examples thereof include those obtained by condensation or co-condensation of urea, dicyandiamide and the like with formaldehyde, and those obtained by modifying these with alcohols having 1 to 8 carbon atoms, carboxyl group-containing amino resins and the like can also be used. These amino resins generally use about 0.5 to about 2 equivalents of formaldehyde for 1 equivalent of amino groups, using a pH adjusting agent (for example, ammonia, sodium hydroxide, amines), in an alkaline or acidic manner. It can be produced by reacting by a method known per se.

When the amino-curable resin coating composition is used as an organic solvent system, it can be obtained by dissolving or dispersing the above resin in an organic solvent. As an organic solvent,
For example, hydrocarbon solvents such as heptane, toluene, xylene, octane, and mineral spirits, ethyl acetate, n-butyl acetate, isobutyl acetate, methyl cellosolve acetate, ester solvents such as butyl carbitol acetate, methyl ethyl ketone, methyl isobutyl ketone,
Ketone solvents such as diisobutyl ketone, methanol, ethanol, isopropanol, n-butanol, sec
-Alcoholic solvents such as butanol, isobutanol,
An ether solvent such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. can be used.

When used as an aqueous solution, an acid group is introduced by an acid monomer (usually 5 to 300 mgK).
OH / g, preferably an acid value within the range of 100 mgKOH / g) Acrylic resin or polyester resin obtained by neutralizing with a neutralizing agent is obtained by dissolving or dispersing in water.

Examples of the neutralizing agent include ammonia or amines such as triethylamine, monoethanolamine, diethanolamine, triethanolamine and dimethylaminoethanol, or basic substances such as alkali metal hydroxides such as sodium hydroxide. Neutralize using
After that, in order to obtain an appropriate solid content, water and, if necessary, an organic solvent compatible with water are added, and the mixture is diluted with water.

Further, in addition to the above, the aqueous acrylic resin is prepared by using, for example, an ionic or nonionic low-molecular or high-molecular surface-active substance, a water-soluble resin, etc. as a dispersion stabilizer, and the above-mentioned polymerizable monomer. Can be produced by emulsion polymerization in an aqueous medium by a method known per se.

The mixing ratio of the amino resin (solid content conversion) is
Approximately 10 to 2 per 100 parts by weight of hydroxyl group-containing resin solid
The amount is 00 parts by weight, preferably 20 to 100 parts by weight. Isocyanate-curable resin paint: The paint includes, for example, a base resin having a crosslinkable functional group such as a hydroxyl group similar to the above, such as an acrylic resin, a vinyl resin, or a polyester resin, and a (block) poly as a crosslinker. A composition comprising an isocyanate compound may be mentioned.

The polyisocyanate compound may be a free isocyanate compound or a blocked isocyanate compound. As the polyisocyanate compound having a free isocyanate group,
Aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate, cycloaliphatic diisocyanates such as xylene diisocyanate or isophorone diisocyanate, organic diisocyanates such as tolylene diisocyanate and 4,4′-diphenylmethane diisocyanate Diisocyanate itself, or excess amount of each of these organic diisocyanates and polyhydric alcohol,
Low molecular weight polyester resin or adduct with water, etc., or polymers of each organic diisocyanate listed above,
Further, there are isocyanate and burette compounds, and typical examples of commercially available products thereof are "Barnock D-750, -800, DN-950, -970 or 15-455" (above, Dainippon Ink and Chemicals). Industry Co., Ltd.
Product), "Dismodule L, N, HL, or N
3390 "(product of Bayer, West Germany)," Takenate D-102, -202, -110 or -123.
N "(a product of Takeda Pharmaceutical Company Limited)," Coronate EH,
L, HL or 203 "(product of Nippon Polyurethane Industry Co., Ltd.) or" Duranate 24A-90CX "
(Asahi Kasei Co., Ltd. product) and the like. Examples of the polyisocyanate compound having a blocked isocyanate group include those obtained by blocking the polyisocyanate compound having a free isocyanate group with a known blocking agent such as oxime, phenol, alcohol, lactam, malonic acid ester, and mercaptan. To be Examples of typical commercial products of these are "Barnock D-550" (manufactured by Dainippon Ink and Chemicals, Inc.),
"Takenate B-815-N" (product of Takeda Pharmaceutical Co., Ltd.), "Aditol VXL-80" (product of Hoechst, West Germany) or "Coronate 2507" [product of Nippon Polyurethane Industry Co., Ltd.] and the like can be mentioned. .

The above-mentioned (block) polyisocyanate compound cross-linking agent may be added in such a proportion that the coating film is hardened and has sufficient performance, but the weight ratio of the hydroxyl group-containing resin / cross-linking agent is 80/20. The range of 50/50 is preferable.

The paint can be used as an organic solvent-based paint obtained by dissolving or dispersing the above resin in the above organic solvent. In addition, an acid group was introduced by an acid monomer (usually 5-300 mgKOH /
g, preferably an acid value within the range of 100 mg KOH / g)
It can be used as an aqueous paint obtained by dissolving or dispersing a resin obtained by neutralizing the acid group of an acrylic resin or a polyester resin with the above-mentioned neutralizing agent in water.

Acid-epoxy curable resin paint: Examples of the paint include a composition comprising an epoxy resin substrate and a polycarboxylic acid compound as a crosslinking agent.

The epoxy resin is, for example, a conventionally known epoxy resin having at least one epoxy group in one molecule [for example, a radical polymerizable monomer containing an epoxy group (for example, (3,4-epoxy A homo-radical polymer of cyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, etc., the monomer and another radical-polymerizable monomer (for example, an alkyl or cycloalkyl ester of (meth) acrylic acid having 1 to 24 carbon atoms, Copolymer with styrene, etc., Epolide GT300 (trade name, trifunctional alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.), Epolide GT40
0 (manufactured by Daicel Chemical Industries, Ltd., trade name, tetrafunctional alicyclic epoxy resin), EHPE (Daicel Chemical Industries, Ltd.)
Company name, trifunctional alicyclic epoxy resin, bisphenol type epoxy resin, novolac type epoxy resin, ε
-Caprolactam-modified bisphenol type epoxy resin,
Polyvinyl cyclohexene diepoxide, etc.] is modified with a polycarboxylic acid.

Examples of the polycarboxylic acid include polycarboxylic acid resins (acrylic resins, polyester resins, etc.), polycarboxylic acid compounds (eg adipic acid, sebacic acid, phthalic acid, etc.) and the like.

The epoxy resin has a number average molecular weight of about 500.
The range of ˜20,000, particularly 700 to 10,000 is preferable. Further, it is preferable to have an average of two or more epoxy groups in one molecule.

The acid-epoxy curable resin coating material is used as an organic solvent-based coating material by dissolving or dispersing it in the above-mentioned organic solvent, and as an aqueous coating material in which a carboxyl group is neutralized with the above-mentioned neutralizing agent and dispersed in water. can do.

Further, the following hydrolyzable silane compound and resin can be blended and used in the coating material, if necessary.

Hydrolyzable silane-curable resin paint: As the paint , a compound containing a hydrolyzable silane group and / or a hydroxysilane group has at least two hydrolyzable silane groups or hydroxysilane groups in one molecule, or It is a coating material containing a silane compound containing at least one hydrolyzable silane group and a hydroxysilane group. Examples of the silane compound include dialkoxysilanes such as dimethoxydimethylsilane and dimethoxydiethylsilane; trialkoxysilanes such as trimethoxymethylsilane and trimethoxyethylsilane; tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane; vinyl. Vinylsilanes such as triethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and 2-styrylethyltrimethoxysilane; β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Epoxysilanes such as glycidoxypropylmethyldiethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, methyltrichlorosilane , Other silanes such as dimethyldichlorosilane, trimethylchlorosilane, condensates of these silane compounds, and radical (co) polymers of vinylsilanes.

The hydrolyzable silane-curable resin coating material is dissolved or dispersed in the above-mentioned organic solvent as an organic solvent-based coating material, or as it is or by introducing a carboxyl group into a copolymer (the above-mentioned carboxyl group-containing unsaturated monomer). Of the above-mentioned) and the introduced carboxyl groups are neutralized with the above-mentioned neutralizing agent and can be used as an aqueous paint in which they are dispersed in water.

Hydroxyl epoxy group curable resin coating: The coating includes a resin having a hydroxyl group and an epoxy group-containing functional group having a structure in which an epoxy group is directly bonded to an alicyclic skeleton and / or a bridged alicyclic skeleton. It is a coating material containing an epoxy resin having an average of 2 or more, preferably 3 or more per molecule as a curable resin component.

Examples of the resin having a hydroxyl group include base resins such as acrylic resin, vinyl resin and polyester resin having a crosslinkable functional group such as hydroxyl group described in the above amino-curable resin coating, and also include alkanolamines. Examples thereof include a hydroxyl group introduced by (1), a ring-opened product of caprolactone introduced in an epoxide compound, and a secondary hydroxyl group in an epoxy resin (bisphenol-epichlorohydrin reaction product, etc.).

The content of hydroxyl group is 20 to 20 in terms of hydroxyl group equivalent.
It is preferably in the range of 5,000, particularly in the range of 100 to 1,000, and particularly preferably in the range of 200 to 1,000 in terms of the primary hydroxyl group equivalent. The resin having a hydroxyl group can have a cationic group. This cationic group makes it possible to make it aqueous. This cationic group can be formed, for example, by reacting an epoxy group with a cationizing agent (such as an amine compound).

The epoxy group-containing functional group in the epoxy resin component comprises an alicyclic skeleton and / or a bridged alicyclic skeleton and an epoxy group, and the alicyclic skeleton has 4 to 10 members,
Preferably, it contains a 5- or 6-membered saturated carbocyclic ring or a condensed ring in which two or more of the rings are condensed, and the bridged alicyclic skeleton is a carbon constituting the monocyclic or polycyclic ring. A straight-chain or branched-chain C1-6 (preferably C1-4) alkylene group between two atoms [for example, -CH2-, -CH2C
H2-, -CH (CH3)-, -CH2 (CH3) CH2-,
-C (CH3) 2-, -CH (C2H5) CH2-, etc.] bridges (endmethylene, endoethylene, etc.) are contained. Epoxy equivalent is usually 100-
It can be in the range of 2,000, preferably 150-500, more preferably 150-250, and
The number average molecular weight is usually 400 to 100,000, preferably 700 to 50,000, more preferably 700 to 3
Suitably it is in the range of 0000. The epoxy resin [component (B)] having two or more such epoxy group-containing functional groups in one molecule is described in, for example, JP-B-56-80.
16, JP-A-57-47365, JP-A-6-
No. 0-166675, JP-A-63-221121, JP-A-63-234028, and the like, which are known per se, can be used.

Hydrazine curable resin coating material: As the coating material , a hydrazide group (-CO-NH-NH2) is contained in one molecule.
Is a paint which forms a crosslinked structure by the reaction of a polyhydrazide compound containing two or more of) and a carbonyl group-containing compound.

Typical examples of polyhydrazide compounds include dihydrazides such as carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, eicoic acid diacid. Aromatic polyhydrazides such as C2-40 aliphatic carboxylic acid dihydrazide such as dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, pyromellitic acid dihydrazide, pyromellitic acid trihydrazide, pyromellitic acid tetrahydrazide,
And maleic acid dihydrazide, fumaric acid dihydrazide,
Monoolefinically unsaturated dihydrazides such as itaconic acid dihydrazide, bissemicarbazide, polyacrylic acid polyhydrazide, and other polyhydrazides such as 1,3-bis (hydrazide / carboethyl) -5-isopropylhydantoin.

The compounding ratio of the polyhydrazide compound is 0. 1 with respect to the carbonyl group of the carbonyl group-containing compound.
It is in the range of 1 to 2 equivalents, preferably 0.2 to 1 equivalents.

As the carbonyl group-containing compound, a polymer of the following carbonyl group-containing unsaturated monomer or a copolymer of the above-mentioned other unsaturated monomer capable of radical polymerization reaction can be used.

The carbonyl group-containing unsaturated monomer is a monomer having at least one keto group or aldehyde group and one radically polymerizable double bond in one molecule, that is, a polymerizable mono-olefinically unsaturated aldehyde. Compounds and keto compounds. As typical specific examples, for example, diacetone (meth) acrylamide, acrolein, formyl styrene, (meth) acrylamide pivalin aldehyde, diacetone (meth) acrylate,
Acetonyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate acetyl acetate, vinyl alkyl ketone, etc. are mentioned. Among these, diacetone (meth) acrylamide is preferable.

Oxidative polymerization type curable resin coating material: The coating material is a coating material containing an unsaturated fatty acid which is conventionally crosslinked by air oxidation polymerization as a curing component. The iodine value of the paint is preferably in the range of 35 to 90. The iodine value is JIS
It is measured by the method of K-0070. If the iodine value is less than 30, the oxidative polymerization ability will be insufficient and the curability will be poor. On the other hand, when the iodine value exceeds 100, the storage stability of the paint is deteriorated.

As the unsaturated fatty acid, any natural or synthetic unsaturated fatty acid can be used, and examples thereof include tung oil, linseed oil, castor oil, dehydrated castor oil, safflower oil, tall oil, soybean oil and coconut oil. The unsaturated fatty acid obtained is mentioned. The above fatty acids may be used alone or in combination of two or more.

Examples of the type of coating material using the unsaturated fatty acid include alkyd resins and epoxy-modified alkyd resins.

As the alkyd resin, for example, the above drying oil or semi-drying oil is mixed with at least one polyhydric alcohol at 200 to 250 ° C. for 10 to 1 while being well stirred.
It is obtained by holding 00 minutes. If necessary, a low molecular weight alkyd resin obtained by subsequently adding a polybasic acid, a polyhydric alcohol and the like and then reacting at 200 to 250 ° C. may be used.

Polyhydric alcohols that can be used include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol or polypropylene glycol having a number average molecular weight of 150 to 6000, monoalkyl ethers thereof, neopentyl glycol. , Diethyl propane diol, ethyl butyl propane diol, cyclohexane dimethanol, butylene glycol, pentane diol, hexane diol, hydrogenated bisphenol A, ethylene glycol adduct of bisphenol A, trimethylol propane, trimethylol ethane, glycerin, pentaerythritol, etc. Can be mentioned.

As the polybasic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic anhydride, succinic acid, adipic acid, sebacic acid,
Examples thereof include monovalent and polyvalent carboxylic acids such as benzoic acid, alkylbenzoic acid, maleic anhydride, itaconic anhydride and fumaric acid. These may be used alone or in a mixture of several kinds at any ratio.

The epoxy-modified alkyd resin is obtained from an epoxy resin and a fatty acid by a conventionally known method. For example, an epoxy resin and a fatty acid are mixed in a suitable solvent (for example, toluene, xylene, etc.) with a condensation catalyst under an inert gas (for example, nitrogen gas etc.) atmosphere, if necessary, at 150 to 2
The reaction can be carried out at 50 ° C. until the desired acid value is reached. As the epoxy resin, for example, “Epicoat 82
8 "," Epicote 1001 "," Epicote 100
2 "," Epicote 1004 "," Epicote 100
7 "and" Epicoat 1009 "(both made by Shell Co., bisphenol A type epoxy resin);" Epotote YD-128 "," Epotote YD-011 "," Epotote YD-012 "," Epotote YD-014 ",
"Epototo YD-017" and "Epototo YD-
019 "(manufactured by Tohto Kasei Co., bisphenol A type epoxy resin);" Epototo ST-5700 "(manufactured by Tohto Kasei Co., Ltd.
Commercially available epoxy resins such as hydrogenated bisphenol A type epoxy resin) and "Epototo YDF-2004" (bisphenol F type epoxy resin manufactured by Toto Kasei Co., Ltd.) can be used. The epoxy resins may be used alone or in combination of two or more.

It is also possible to use an epoxy-modified epoxy ester resin obtained by reacting the above-mentioned epoxy ester resin with an ethylenically unsaturated monomer. The ethylenically unsaturated monomer, styrene, (meth) acrylic acid, unsaturated carboxylic acid such as maleic anhydride and itaconic acid,
(Meth) acrylic acid esters, as well as mixtures thereof. It is essential that at least one of the acrylic monomers contains a carboxylic acid group,
One or more acrylic monomers are mixed with styrene for use.

The oxidative polymerization type curable resin coating is an organic solvent type,
It does not matter whether the form is solvent-free or water-based.

The desiccant which can be used is not particularly limited. Aliphatic carboxylic acids such as oleic acid, alicyclic carboxylic acids such as naphthenic acid as a carrier cobalt salts, manganese salts, zirconium salts, calcium salts, metal salts such as lead salts, lead salts and the like anionic emulsifiers Examples thereof include cation emulsifiers, nonionic emulsifiers and the like that have been hydrated, and tertiary amines such as dimethylaniline, diethylaniline and dimethylparatoluidine. These can be used alone or in combination.

There is no particular limitation on the amount added, but
A range of 003 to 0.5% by weight is preferable. If the amount is less than 0.003% by weight (metal content), the effect is not recognized, and 0.5
If it is used in an amount of more than wt% (metal content), there is a drawback such as poor water resistance. A more preferable amount used is in the range of 0.05 to 0.4% by weight (metal content).

Light (heat) radical polymerization type resin coating material: As the coating material, an ultraviolet polymerization initiator, a peroxidation catalyst, and a photosensitizing dye are optionally mixed with an unsaturated resin which causes a radical polymerization reaction by light or heat. You can use what you have done.

Examples of the unsaturated resin include urethane resin, acrylic resin, alkyd resin, polyester resin,
It is a resin in which a radically polymerizable unsaturated group is introduced into a resin such as silicone resin, fluororesin, spirane resin, polyether resin, or epoxy resin. Examples of the radically polymerizable unsaturated group include a vinyl group, a (meth) acryloyl group, a styryl group and a group derived from maleic acid.

Typical examples of unsaturated resins include urethane resin acrylate, acrylic resin acrylate,
Examples thereof include acrylic resin malate, alkyd resin acrylate, polyester resin acrylate, polyester resin malate, fluororesin acrylate, spirane resin acrylate, polyether resin acrylate, and epoxy resin acrylate.

As the UV polymerization initiator, conventionally known ones can be used.

Specifically, for example, 4-phenoxydichloroacetophenone, 4-ter-butyl-dichloroacetophenone, 4-ter-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane. -1-on, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyphenoxy) -phenyl (2
-Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4
Acetophenone-based compounds such as-(methylthio) phenyl] -2-morpholinepropane-1, thioxanthone,
Thioxanthone compounds such as 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and 2,4-dichlorothioxanthone, benzoin compounds such as benzoin and benzoin methyl ether, and dimethylbenzyl ketal. , And acylphosphine oxide. Among these, acetophenone compounds are preferable.

The mixing ratio of the above-mentioned ultraviolet polymerization initiator is
About 0.1 parts by weight per 100 parts by weight of total unsaturated resin
It is preferable to mix 10 to 10 parts by weight.

Further, a photopolymerization accelerator can be added in order to accelerate the photocrosslinking reaction by the above-mentioned ultraviolet polymerization initiator. Specifically, for example, triethylamine,
Examples include tertiary amines such as triethanolamine and 2-dimethylaminoethanol, alkylphosphines such as triphenylphosphine, and thiols such as β-thioglycol.

As the photosensitizer, conventionally known photosensitizing dyes can be used. Examples of this include thioxanthene-based, xanthene-based, ketone-based, thiopyrylium salt-based, base styryl-based, merocyanine-based,
3-substituted coumarin type, 3.4-substituted coumarin type, cyanine type, acridine type, thiazine type, phenothiazine type,
Anthracene type, Coronene type, Benz anthracene type,
Examples thereof include perylene-based, merocyanine-based, ketocoumarin-based, fumarine-based, and borate-based dyes. These can be used alone or in combination of two or more. Examples of the borate-based photosensitizing dye include, for example, JP-A
JP-A-5-241338, JP-A-7-5685 and JP-A-7-2254
Those described in Japanese Patent Publication No. 74 etc. can be mentioned.

As the irradiation source of the light rays, those which have been conventionally used, for example, electron beam, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, Examples thereof include a light source obtained by each light source such as a fluorescent lamp, a tungsten lamp, and sunlight. As the heat ray, for example, a semiconductor laser (830
nm), YAG laser (1.06 μm), infrared rays and the like.

Photo (heat) cationic polymerization type resin coating material: As the coating material, a cationic photo-polymerizable compound is irradiated with light under a cationic photo-polymerization initiator or a photo-sensitizer to give a high degree of crosslinking or polymerization reaction. It is a paint that becomes molecular weight.

As the light (heat) cationically polymerizable compound,
For example, epoxy compounds, styrenes, vinyl compounds,
Vinyl ethers, spiro orthoesters, bicyclo orthoesters, spiro orthocarbonates, cyclic ethers, lactones, oxazolines, aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams, alkoxysilanes Examples thereof include compounds and aryldialdehydes.

Examples of the epoxy compound include conventionally known aromatic epoxy compounds, alicyclic epoxy compounds and aliphatic epoxy compounds.

Examples of aromatic epoxy compounds include monofunctional epoxy compounds such as phenyl glycidyl ether, and polyglycidyl ethers of polyhydric phenols having at least one aromatic ring or alkylene oxide adducts thereof. Glycidyl ethers produced by the reaction of a bisphenol compound such as bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S or an adduct of an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide) of a bisphenol compound with epichlorohydrin , Novolac type epoxy resins (eg, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated phenol novolac) Epoxy resin, etc.), etc. trisphenolmethane triglycidyl ether.

Examples of the alicyclic epoxy compound include 4-vinylcyclohexene monoepoxide, norbornene monoepoxide, limonene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4- Epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexanone-meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, BHP
E-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin (softening point 71 ° C.), etc. may be mentioned.

Examples of the aliphatic epoxy compound include:
1,4-butanediol diglycidyl ether, 1,6
-Hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, propylene glycol monoglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Neopentyl glycol monoglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether,
Examples thereof include trimethylolpropane monoglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, allyl glycidyl ether, and 2-ethylhexyl glycidyl ether.

Examples of styrenes include styrene, α-methylstyrene, p-methylstyrene, p-chloromethylstyrene and the like. As the vinyl compound, N-
Examples thereof include vinylcarbazole and N-vinylpyrrolidone.

Examples of vinyl ethers include n-
(Or iso-, t-) butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, Propylene glycol divinyl ether, propylene glycol monovinyl ether, neopentyl glycol divinyl glycol, neopentyl glycol monovinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, diglycero Trivinyl ether, sorbitol tetravinyl ether, cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, 2,2-bis (4-cyclohexanol) propane divinyl ether, 2,2-bis (4-cyclohexanol) trifluoropropane di Alkyl vinyl ethers such as vinyl ether, alkenyl vinyl ethers such as allyl vinyl ether, ethynyl vinyl ether, alkynyl vinyl ethers such as 1-methyl-2-propenyl vinyl ether, 4-
Vinyl ether styrene, hydroquinone divinyl ether, phenyl vinyl ether, p-methoxyphenyl vinyl ether, bisphenol A divinyl ether,
Aryl vinyl ethers such as tetrabromobisphenol A divinyl ether, bisphenol F divinyl ether, phenoxyethylene vinyl ether, p-bromophenoxyethylene vinyl ether, 1,4-benzenedimethanol divinyl ether, Nm-chlorophenyldiethanolamine divinyl ether, m-phenylene Examples thereof include aralkyl divinyl ethers such as bis (ethylene glycol) divinyl ether, urethane polyvinyl ether (for example, VECtomer 2010 manufactured by ALLIED-SIGNAL), and the like.

The spiro orthoesters include
4,6-trioxaspiro (4,4) nonane, 2-methyl-1,4,6-trioxaspiro (4,4) nonane,
1,4,6-trioxaspiro (4,5) decane and the like are bicycloorthoesters such as 1-phenyl-4-ethyl-2,6,7-trioxabicyclo (2,2).
2,2) octane, 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo (2,2,2) octane and the like are spiro orthocarbonates.
Examples include cyclic ethers such as 1,5,7,11-tetraoxaspiro (5,5) undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro (5,5) undecane. To be

Examples of the cyclic ethers include oxetanes such as oxetane and phenyloxetane, tetrahydrofurans such as tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrobilanes such as tetrahydrobilane and 3-propyltetrahydrobilane, trimethylene oxide and s-trioxane. And so on. Examples of lactones include β-propiolactone and γ-
Butyl lactone, δ-caprolactone, δ-valerolactone and the like can be mentioned. Examples of the oxazolines include oxazoline, 2-phenyloxazoline, 2-decyloxazoline and the like.

Examples of aziridines include aziridine and N-
Examples include ethyl aziridine. Examples of cyclosiloxanes include hexamethyltrisiloxane, octamethylcyclotetrasiloxane, and triphenyltrimethylcyclotrisiloxane. As the ketals, 1,3-dioxolane, 1,3-dioxane,
2,2-Dimethyl-1,3-dioxane, 2-phenyl-1,3-dioxane, 2,2-dioctyl-1,3-
Examples include dioxolane. Cyclic acid anhydrides include phthalic anhydride, maleic anhydride, succinic anhydride, and the like, lactams include β-propiolactam,
Examples include γ-butyrolactam and δ-caprolactam. Examples of aryldialdehydes include 1,2-benzenedicarboxaldehyde and 1,2-naphthalenedialdehyde.

The photosensitizer is preferably used in the range of 0.01 to 10 parts by weight, and more preferably in the range of 0.1 to 5 parts by weight, based on 100 parts by weight of these photocationically polymerizable compounds. If the amount of the photosensitizer is less than 0.01 parts by weight, the curability is lowered, while if it exceeds 10 parts by weight, the cost is increased and the coating performance such as water resistance is deteriorated, which is not preferable.

As the cationic photopolymerization initiator, known ones can be used. As an initiator,
For example, an aryl diazonium salt, an aryl iodonium salt, an aryl sulfonium salt, etc. are mentioned as a preferable thing. Specifically, as the trade name, for example, Syracure UVI-6970, Syracure UVI-697
4, Syracure UVI-6990, Syracure UV
I-6950 (above, product name of Union Carbide, USA), Irgacure 261 (Ciba Specialty
Chemicals, trade name), SP-150, SP-17
0 (above, Asahi Denka Kogyo KK, trade name), CG-2
4-61 (trade name, manufactured by Ciba Specialty Chemicals), DAICAT-II (trade name, manufactured by Daicel Chemical Industries, Ltd.), CI-2734, CI-2758, CI-28
55 (above, Nippon Soda Co., Ltd. product name), PI-2074
(Rhone Poulenc Company, trade name, pentafluorophenyl borate toluyl cumyl iodonium salt), FFC5
09 (manufactured by 3M, trade name), BBI102 (manufactured by Midori Kagaku, trade name) and the like.

The cationic photopolymerizing agent is preferably used in the range of 0.01 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight, per 100 parts by weight of these cationic photopolymerizable compounds. Photocationic polymerization initiator is 0.0
If it is less than 1 part by weight, the curability is lowered, while if it is more than 20 parts by weight, the cost becomes high and the coating performance such as water resistance is deteriorated, which is not preferable.

The light source used for the active energy rays is, for example, without particular limitation, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp lamp, carbon arc lamp, xenon lamp, metal halide lamp, tungsten lamp, etc. and argon. Laser (488 nm), YAG-SHG laser (5
32 nm) and a UV laser (351 to 364 nm) with a laser having an oscillation line can also be used. Examples of heat rays include semiconductor lasers (830 nm), YAG lasers (1.06 μm), and infrared rays.

In the first invention, the uppermost film (I)
Between the bottom layer film (II) and the
Conventionally known plastic films (which may be transparent or opaque, various synthetic resin films such as polyethylene terephthalate, polyimide, polyamide, acrylic, polycarbonate, polypropylene, polyvinyl chloride, ABS, etc.), metal films (aluminum, metal vapor deposition films, etc.) ) Or adhesive (adhesive) layer (natural rubber, acrylic resin, ethylene / vinyl acetate copolymer, polyurethane, polyester, silicone rubber, fluororubber, polyvinyl butyral, etc.), printing layer (polyamide resin, chlorinated rubber) , Urethane resin, epoxy resin, acrylic resin, polyester resin,
Silicone resin, vinyl chloride, vinyl chloride / vinyl acetate copolymer and the like as a resin component, and a colorant and an organic solvent mixed), a crosslinked or non-crosslinkable resin colored coating layer (for example, the above-mentioned crosslinkable resin coating material) (A), polyamide resin, chlorinated rubber, urethane resin, epoxy resin, acrylic resin, polyester resin, silicone resin, vinyl chloride,
A non-crosslinking resin component such as a vinyl chloride / vinyl acetate copolymer containing a coloring agent such as a coloring pigment, a metallic pigment or a pearl pigment can be used. Other layers such as) can be provided. These layers can be used in an appropriate combination.

Between the uppermost layer film (I) and the lowermost layer film (II), one kind of intermediate layer such as the non-crosslinkable resin colored coating film and the crosslinkable resin colored coating film layer may be provided, if necessary. Alternatively, a laminate of two or more kinds will be described below.

The intermediate layer is, for example, a colored coating formed by a non-crosslinked or crosslinked colored base coating material containing at least one kind of coloring pigment selected from metallic pigments, (colored) pearl pigments, coloring pigments and the like. A first clear coating film layer formed by a film layer or a non-crosslinked or crosslinked first clear coating material (the uppermost layer film (I) is laminated on the surface of the first clear coating film layer as a second clear coating film layer). The first clear coating film layer is a layer provided below the uppermost film (I).

The coated sheet containing the intermediate layer can be produced by a conventionally known method, for example, after coating a base material with a coating material for forming the first layer, the first layer is uncrosslinked (the intermediate layer is not crosslinked). By the method of coating the paint forming the second layer on the coating surface of the cross-linking type (not dried) and then simultaneously cross-linking both coatings (drying when the intermediate layer is the non-cross-linking type), the so-called 2 coat 1 bake method. Also, after coating the base material with the paint forming the first layer, the coating film is cross-linked (dry if the intermediate layer is a non-cross-linked type)
After the coating, a coating for forming the second layer is applied to the surface of the crosslinked coating film, and then the coating film of the second layer is crosslinked, that is, a so-called two-coat / two-bake system, and similarly 3
A multilayer film of the intermediate layer and the uppermost layer film (I) can be formed by the coat 1 bake system and the 3 coat 2 bake system.

As a concrete example of the production of the coated sheet containing the above intermediate layer, for example, in the case of a two-coat one-bake system, a colored base paint is applied to a release paper such as a release-treated polyethylene terephthalate sheet. After that, if necessary, preliminary drying and setting are performed, and then a clear coating material of the crosslinkable resin coating material (A) that forms the uppermost layer film (I) on the surface of the coating film that has not been crosslinked (undried). A thermoplastic resin that forms the lowermost layer film (II) on the surface of the colored base film layer after coating, then simultaneously crosslinking both coating films (drying if the colored base paint is non-crosslinked) and then peeling off the release paper ( It is obtained by coating with an aqueous urethane resin emulsion) and drying. In addition to the above, after the clear paint of the crosslinkable resin paint (A) forming the uppermost layer film (I) is applied to the release paper, predrying and setting are carried out if necessary, and then the colored base paint is applied. , A thermoplastic resin (water-based urethane resin emulsion) that is crosslinked (if the colored base coating is non-crosslinked, dried) and then, if necessary, the release paper is peeled off to form the lowermost layer film (II) on the colored base film layer surface. ) Is applied and dried.

Further, after the colored base coating material is applied to the surface of the lowermost layer film (II), if necessary, preliminary drying and setting are performed, and then the uncrosslinked (undried) coating film surface of the coating film is coated with the uppermost layer film. It is also possible to apply a clear paint of the crosslinkable resin paint (A) forming (I), and then to simultaneously crosslink both paint films (if the colored base paint is non-crosslinked, dry).

As a specific example of the production of the coated sheet containing the above-mentioned intermediate layer, taking a two-coat two-bake system as an example, a release paper such as a release-treated polyethylene terephthalate sheet is coated with a colored base coating material and then the coated base coating is applied. A clear coating of the crosslinkable resin coating (A) forming the uppermost layer film (I) is applied to the surface of the crosslinked (dry) coating film obtained by crosslinking (crosslinking type) or drying (non-crosslinking type) the film, and then After the coating film of the crosslinkable resin coating material (A) is crosslinked, and then the release paper is peeled off, a thermoplastic resin (aqueous urethane resin emulsion) for forming the lowermost layer film (II) is applied to the surface of the colored base film layer and dried. It is obtained by performing. In addition to the above, the release paper is coated with the clear coating of the crosslinkable resin coating material (A) for forming the uppermost layer film (I), and after cross-linking, the colored base coating material is applied to cross-link (the color base coating material is not (Crosslinked products are dried), and then the release paper is peeled off if necessary, then the thermoplastic resin (aqueous urethane resin emulsion) that forms the lowermost layer film (II) is applied to the colored base film layer surface and dried. It is obtained by

Further, after coating the surface of the lowermost layer film (II) with a colored base paint, the coating film is crosslinked (crosslinked type) or dried (non-crosslinked type) to form a topmost layer on the surface of the crosslinked (dry) coating film. It is also possible to apply a clear paint of the crosslinkable resin paint (A) forming the film (I) and then crosslink the coating film of the crosslinkable resin paint (A).

When a layer provided as necessary between the uppermost layer film (I) and the lowermost layer film (II) is used, the thickness thereof is not particularly limited, but the total thickness of one layer or multiple layers is used. The film thickness is 10 to 100 μm, especially 2
It is preferably in the range of 0 to 80 μm.

Bottom layer film (II) used in the first invention
Is formed of a thermoplastic resin (B), and the formed film (II) has a tensile elongation at break (length of 30 mm,
A value measured at a pulling speed of 200 mm / min at -10 ° C with a sample having a width of 10 mm and a thickness of 0.050 mm) 50 to 1
It is in the range of 000%.

The tensile elongation at break is 200 mm in length and 1 in width.
0 mm, 0.050 mm thick sample (isolated film)-
It is a value when measured at a measuring temperature of 10 ° C. and a tensile speed of 200 mm / min. As the measuring machine, for example, a universal tensile tester with a thermostat (Shimadzu Corporation Autograph SD type) can be used for measurement.

In this specification, the tensile elongation at break is
[(Length of sample at break (mm) -length of original sample (mm)) / length of original sample (mm)] x 100 (%) is shown.

When the tensile elongation at break of the film (II) is less than 50%, the conformability to a cubic curved surface is poor and the workability of sticking is poor. It has the drawback of being inferior in sex. Further, it is preferable that the lowermost layer film (II) has substantially no tackiness at room temperature (20 ° C.). Specifically, the glass transition temperature is preferably -40 ° C to 80 ° C, particularly preferably -20 ° C to 40 ° C. When the glass transition temperature is lower than -40 ° C, the tackiness becomes high and the handling becomes difficult, while when the glass transition temperature exceeds 80 ° C, the elongation is lowered and the workability is deteriorated, which is not preferable.

As the film (II), any film formed of a conventionally known thermoplastic resin can be used without particular limitation as long as it satisfies the above-mentioned conditions, but it is particularly formed of an aqueous urethane resin emulsion. It is preferable to use a water-based epoxy resin in the water-based urethane resin emulsion because it is non-polluting, safe, and hygienic because it uses water as a solvent. It is preferable to use the one formed from the compounded one from the viewpoint of forming a coating film excellent in water resistance.

What is particularly useful as the water-based urethane resin emulsion is one that can be produced by various methods. As a general method for preparing the water-based urethane resin emulsion, a compound having an ionic functional group (reactive polar group) is partially added during the urethanization reaction,
A so-called hydrophilic group-containing isocyanate-terminated prepolymer obtained by copolymerization is dispersed in water, and then,
It is known to extend the chain with amines.

The above-mentioned hydrophilic group-containing isocyanate-terminated prepolymer to be used is such that it is produced from a conventionally known polyisocyanate compound and an active hydrogen-containing compound capable of reacting with an isocyanate group.

Examples of the polyisocyanate compound include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and isophorone diisocyanate; Alicyclic diisocyanates such as 4,4'-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, Aromatic diisocyanates such as polyphenylmethane diisocyanate (hereinafter referred to as “polymeric MDI”); and similar compounds such as isocyanurates and burettes thereof, and these may be used alone or in combination of two or more. Can be used.

The compound containing active hydrogen capable of reacting with the above-mentioned isocyanate group used in the production of the isocyanate-terminated prepolymer has an average molecular weight of 3
00-10,000, preferably 500-5,000
Within the range of so-called high molecular weight compounds and molecular weight of 3
It is classified into a so-called low molecular weight compound of 00 or less.

Of these, polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyesteramide polyols, polythioether polyols and the like are particularly representative as the high molecular weight compound.

Examples of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol and 1,6. -Hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, molecular weight 300-600
Within the range of 0, polyethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A or hydroquinone, or alkylene thereof. Various glycol components such as oxide adducts, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4- Cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-
Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid,
Biphenyldicarboxylic acid or 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, or anhydrides or ester-forming derivatives of various dicarboxylic acids thereof; p-hydroxybenzoic acid or p- (2-hydroxy) (Ethoxy) benzoic acid, or polyesters obtained by dehydration condensation reaction with various acid components such as ester-forming derivatives of various hydroxycarboxylic acids thereof, and ε-caprolactone,
Polyesters obtained by a ring-opening polymerization reaction of various cyclic ester compounds, or copolyesters thereof are particularly representative.

As the polyether, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, trimethylene glycol, 1,
3-butanediol, 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpereropan, sorbitol, sucrose, aconit sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, 1 of various compounds having at least 2 active hydrogen atoms, such as hydroxyphthalic acid or 1,2,3-propanetrithiol
One or two or more kinds of various monomers, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran or cyclohexylene, as an initiator are used by a conventional method. The addition-polymerized form is particularly typical.

As the polycarbonate polyol,
Compounds obtained by reacting various glycols such as 1,4-butanediol, 1,6-hexanediol or diethylene glycol with diphenyl carbonate or phosgene are particularly representative.

On the other hand, a low molecular weight compound has a molecular weight of 30.
A compound having 0 or less and having at least 2 or more active hydrogens in a molecule is referred to, and only typical ones among them are used as a raw material of a polyester polyol. , Various glycol components; various polyhydroxy compounds such as glycerin, trimethylolethane, trimethylolpropane, sorbitol or pentaerythritol; or ethylenediamine, 1,6-hexamethylenediamine,
Piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine,
Various amine compounds such as 1,2-propanediamine, hydrazine, diethylenetriamine or triethylenetetramine.

A method of introducing a hydrophilic group into the isocyanate-terminated prepolymer containing a hydrophilic group is to have at least one or more active hydrogens in the molecule and to have a carboxyl group, a sulfonic acid group, a sulfonate group or ethylene. Examples thereof include a method of copolymerizing at least one kind of hydrophilic group-containing compound having an oxide repeating unit at the time of producing the prepolymer.

Specific examples of such hydrophilic group-containing compounds include only 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, and the like.
Various sulfonic acid-containing compounds such as sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-4,6-disulfonic acid and 2,4-diaminotoluene-5-sulfonic acid, or those And various polyester polyols obtained by copolymerizing them; 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2 , 6-dioxybenzoic acid, 3,4-diaminobenzoic acid, various carboxylic acid-containing compounds, or various derivatives thereof, and further a polyester polyol obtained by copolymerizing them; or at least 30% by weight or more of repeating units of ethylene oxide,
In addition, various nonionic group-containing compounds such as polyethylene-polyalkylene copolymer having at least one or more active hydrogens in the polymer and having a molecular weight of 300 to 10,000 or copolymerizing them. The obtained polyester polyether polyol and the like are particularly representative, and these may be used alone or in combination of two or more kinds. In the present invention, particularly preferable hydrophilic group-containing compounds are carboxyl group-containing compounds; or Examples thereof include derivatives thereof and polyester polyols obtained by copolymerizing them.

The hydrophilic group content in the isocyanate-terminated prepolymer containing a hydrophilic group is such that, in the case of a hydrophilic group such as a carboxyl group, a sulfonic acid group or a sulfonate group, the solid content of the polyurethane resin finally obtained is 100.
At least 0.01 equivalent or more per part, preferably,
The range of 0.01 to 0.2 equivalent is suitable, and
In the case of the nonionic group-containing compound, it is appropriate that the content of the non-ionic group-containing compound is at least 3% by weight, preferably 5 to 30% by weight, based on the solid content of the finally obtained polyurethane resin.

The hydrophilic group-containing isocyanate-terminated prepolymer is produced by a conventionally known method. For example, as described above, various polyisocyanate compounds and active hydrogen-containing compounds (including hydrophilic group-containing compounds) are included. The equivalent ratio of the isocyanate group and the active water group is 1.1: 1 to 3:
1, preferably at a ratio of 1.2: 1 to 2: 1 at 20 to 120 ° C., preferably 30 to 100 ° C.
It is carried out according to a method such as reacting with.

As typical examples of the polyamine chain extender, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4 '. -Dicyclohexylmethanediamine, 3,
Various diamines such as 3′-dimethyl-4,4′-dicyclohexylmethanediamine or 1,4-cyclohexanediamine; various polyamines such as diethylenetriamine, dipropylenetriamine or triethylenetetramine; hydrazines; or acid hydrazide It is a matter of course that they may be used alone or in combination of two or more kinds.

The polyamine chain extender is used by dissolving it in water as a dispersion medium, which is necessary for obtaining an aqueous urethane resin emulsion, and the amount of the polyamine chain extender used in the hydrophilic group-containing isocyanate-terminated prepolymer is It is suitable that the equivalent ratio to the isocyanate group is 0: 1 to 1: 1 and preferably 0.6: 1 to 0.98: 1.

The amount of water to be used may be a minimum amount enough to form an O / W type water dispersion after mixing the prepolymer and the water phase, and is 1 with respect to the solid content of the polyurethane resin.
It is suitable to be in the range of from 0 to 1,000% by weight.

When the hydrophilic group of the isocyanate-terminated prepolymer having a hydrophilic group is a carboxyl group, various tertiary amines such as trimethylamine or triethylamine are used as a neutralizing agent necessary for neutralizing the carboxyl group. , To the carboxyl group in an equivalent ratio of 0.
Within the range of 5: 1 to 1.5: 1, preferably 1: 1 to
The range of 1.3: 1 is suitable, and it is necessary to incorporate such a ratio in the aqueous solution of the above polyamine chain extender.

Such a neutralizing agent can be added in advance to the hydrophilic group-containing isocyanate-terminated prepolymer, but since these tertiary amines are also strong catalysts for the urethanization reaction, they do not undergo side reactions. It is easy to cause
It is not preferable because the prepolymer tends to be colored.

The aqueous urethane resin emulsion is usually
Before the chain extension reaction with amines is completed, or after the chain extension reaction is completed, the process is transferred to the next solvent removal step.

As the aqueous urethane resin emulsion,
Examples of product names include Superflex 410, same-left 420, same-left 600, same-left 150, same-left 126, same-left 107M, and Superflex E-2500 (above, product name of Dai-ichi Kogyo Seiyaku Co., Ltd.).

As the water-based epoxy resin to be used by blending with the water-based urethane resin emulsion, the film (II)
Is not particularly limited as long as the above conditions are satisfied, specific examples include Tenacor EX-611 and EX.
-612, EX-614, EX-614B, EX-51
2, EX-521, EX-421, EX-313, EX
-314, EX-810, EX-811, EX-85
0, EX-851, EX-821, EX-830, EX
-832, EX-841, EX-861, EX-91
1, EX-941, EX-920 (all above, manufactured by Nagase Chemtech Co., Ltd., trade name) and other polyfunctional aqueous epoxy resins; Tenacor EX-145, EX-171 (all above, manufactured by Nagase Chemtech Co., Ltd., A monofunctional aqueous epoxy resin such as (trade name); and the like. The blending amount is the resin solid content 1 of the aqueous urethane resin emulsion.
1 to 50 parts by weight, preferably 2 to 4 with respect to 00 parts by weight
It is in the range of 0 parts by weight.

If necessary, an auxiliary compounding agent may be contained in the aqueous urethane resin emulsion. Examples of the auxiliary compounding agents include dyes, pigments, inorganic fillers, organic modifiers, stabilizers, plasticizers, surfactants, defoamers, cross-linking agents,
Other additives may be mentioned. Examples of dyes include direct dyes, acid dyes, basic dyes, reactive dyes, and metal complex dyes. As the pigment, carbon black,
Titanium oxide, chromium oxide, zinc oxide, iron oxide, mica,
Inorganic pigments such as navy blue and coupling azo type, condensed azo type anthraquinone type, perylene type, quinacridone type,
Examples include organic pigments such as thioindigo type, dioxazine type and phthalocyanine type. As an inorganic filler,
Examples include calcium carbonate, silica, talc, glass fiber, potassium titanate whiskers and the like. Examples of the organic modifier include fluororesin powder, acrylic resin powder, silicone resin powder, polyamide resin powder, urethane resin powder and the like. As stabilizers, hindered phenols, hydrazines, phosphorus, benzophenones,
Examples thereof include benzotriazole type, oxalic acid anilide type and hindered amine type. These stabilizers are additives for improving weather resistance and preventing heat deterioration.

Examples of the plasticizer include dibutyl phthalate and dioctyl phthalate. Examples of the surfactant (foam stabilizer, etc.) include silicone foam stabilizers such as siloxane oxyalkylene block copolymers. Examples of the defoaming agent include silicone-based defoaming agents. Amino resin as cross-linking agent [methylolation and / or alkoxylation (methyl to butyl)
Urea, melamine, etc.], epoxy compound [bisphenol A type glycidyl ether, hydrogenated bisphenol A type glycidyl ether, ethylene glycol to polyethylene glycol glycidyl ether, glycerin, trimethylolpropane, sorbitol and other glycidyl ether glycerin, trimethylolpropane, Glycidyl ether of alkylene oxide (having 2 to 3 carbon atoms) added to sorbitol, etc.], polyethylene urea compound (diphenylmethane-bis-4,4'-
N, N'-ethylene urea, etc., a blocked isocyanate system (for example, 1 mol of trimethylolpropane and hexamethylene diisocyanate, isophorone diisocyanate, or an adduct synthesized from 3 mol of toluene diisocyanate; water-modified hexamethylene diisocyanate, isophorone diisocyanate) And hexamethylene diisocyanate trimer, etc. masked with phenol, methylethylketoxime, ε-caprolactam, etc.), aqueous polyisocyanate system (for example, reaction of polyoxyalkylene [C2-4] polyol with polyisocyanate) Thing). Other additives include flame retardants,
Examples include thixotropic agents, antistatic agents, bactericides, and the like.

The amount of the auxiliary compounding agent added is on a weight basis with respect to the weight solid content of the resin composition, the dye is usually 0 to 50%, preferably 0 to 20%, the pigment, the inorganic filler and the organic modifier are Usually 0 to 170%, preferably 0 to 150%, stabilizer is usually 0 to 20%, preferably 0 to 10%, plasticizer is usually 0 to 100%, preferably 0 to 50%, surfactant is usually 0 to 20%, preferably 0 to 10%, the antifoaming agent and other additives are usually 0 to 20%, preferably 0 to
10%, crosslinking agent is usually 0 to 50%, preferably 0 to 40
%. These auxiliary compounding agents may be mixed by ordinary stirring alone, or may be obtained by dispersion mixing using a dispersion mixing device (ball mill, kneader, sand grinder, roll mill, flat stone mill, etc.). The order of mixing may be any order.

The thickness of the aqueous urethane resin emulsion can be variously changed, but is usually 5 to 500 μm, preferably 10 to 250 μm. Examples of the coating method include spray coating, brush coating, iron coating, roll coating, flow coating and dipping method knife coater, gravure coater, screen printing, and revers roll coater. Drying is from room temperature to warming (for example, 40 to 270 ° C. for 10 seconds to 60 seconds).
Minutes).

The coated film of the present invention is formed by laminating the film (II) side with a laminating agent on films of various plastics such as PVC, acryl and polycarbonate, steel plates, plate materials (hereinafter referred to as adherends). By combining, weather resistance, light resistance, moisture resistance, heat resistance, stain resistance, water repellency, boiling water resistance, etc. are given to the surface of the adherend, and interior building materials, exterior building materials, ornaments, for packaging, It is a functional film that can be used in a wide range of applications such as protective films, guides, signs, markings, and storage.

The coated film of the present invention has a textured surface when a fine uneven pattern (hereinafter referred to as "texture") is formed on the surface of the layer by embossing or rubbing under moist heat conditions. As for the formation, the texture as described above may be formed.

The method for producing the coated film of the present invention can be produced without any particular limitation. Specifically, for example, a release-treated polyethylene terephthalate sheet (release paper) is coated with a crosslinkable resin coating material (A), and after crosslinking, the release paper is peeled off if necessary, and then thermoplastic resin is coated on one side. It can be obtained by coating a resin (water-based urethane resin emulsion), drying, and peeling the release paper if it is not peeled off.

Second invention: The present invention is characterized in that the above-mentioned coated film is thermocompression-bonded to the surface of the substrate so that the film (II) layer of the coated film faces the surface of the substrate. Is a method for laminating coated films. This method can be laminated by a conventionally known method except that the coated film of the present invention is used as a film.

Third invention: In the present invention, the above coated film and a raw material for the plastic substrate are used so that the film (II) layer of the coated film is formed on the surface of the plastic substrate. Is a simultaneous molding process. This method can be laminated by a conventionally known method except that the coated film of the present invention is used as a film.

Molding processing (in-mold method) will be described below as a typical example of the coated film of the present invention.

The molding method is a method of simultaneously molding the coated film and the plastic material so that the film (II) layer surface of the coated film is in contact with the outer surface of the plastic molded product.

In the molding method, the coated film and the plastic material are molded at the same time, and the molding method is preferably injection molding.

The injection molding method is carried out by injecting and filling a heated and melted plastic material into a coating film provided in a mold, cooling it, and then taking out the plastic material from the mold as a molded product. The coating film provided in the mold is preferably installed so that the film (I) layer of the coating film contacts the inner surface of the mold and the film (II) layer contacts the plastic surface. The heat-melted plastic material is injected into the coating film provided in the mold, but in this case, the molten plastic material is filled between the mold surface and the coating film surface so that the coating film is not filled. The film (II) is filled in the surface direction.

The size of the coated film may be a part of the inner surface of the die or the entire size of the die. That is, by changing the size of the coated film, the coated film can be formed on part or all of the surface of the plastic molded product.

As the plastic material, any material known from the conventional ones can be used without particular limitation. Specifically, for example, polyethylene, polypropylene, polyisobutylene, polybutadiene, polystyrene, polychloroprene, polyvinyl chloride, polyvinyl acetate, nylon,
Acrylic resin, polycarbonate, cellulose, polyethylene terephthalate, polyacetal, AS resin, A
Examples thereof include BS resins and glass fiber reinforced resins obtained by mixing these with glass fibers.

If desired, known additives such as colorants, fillers, plasticizers and heat stabilizers can be added to the plastic material.

The molding processing temperature may be set to a temperature suitable for the types of the coating film and the plastic material.

The molding process may be carried out, for example, by simultaneously molding the coating film and the plastic material so that the film (II) layer surface of the uncrosslinked coating film is in contact with the outer surface of the plastic molded product. It is also possible to crosslink the film.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples. "Parts" and "%" in Examples and Comparative Examples are based on weight. Further, the present invention is not limited to the embodiments.

Example 1 A release-treated polyethylene terephthalate sheet (release paper) having a film thickness of 150 μm and a dry film of Retan PG-80 metallic (trade name, isocyanate-curable acrylic resin paint manufactured by Kansai Paint Co., Ltd.) Paint to a thickness of 10 μm 8
Dry at 0 ° C. for 20 minutes, and then retan PG-
80 Quartz Z (trade name, clear, manufactured by Kansai Paint Co., Ltd.) is applied to a dry film thickness of 20 μm, and the temperature is 2 at 80 ° C.
After drying for 0 minutes, the release paper was peeled off to produce a metallic-tone colored film (corresponding to the film layer (I) of the present invention).

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was coated on the metallic coating film surface of the obtained colored film with a knife coater and dried at 100 ° C. for 10 minutes to form a film. A urethane coating having a thickness of 50 μm (corresponding to the film (II) of the present invention) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

The coating film of Example 1 obtained above was applied to the inner surface of an injection mold capable of being molded into a bumper for automobiles so that the clear layer of the colored sheet was in contact with the inner surface of the mold. Installed, and then press-injected into the film (II) layer surface of the coated film by heating and melting polypropylene at about 230 ° C. with an injection molding machine, cooling the mold, and taking out from the mold Was manufactured.

The polypropylene molded product thus obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling and cracks on both the curved surface and the flat surface.

The polypropylene molded article was immersed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the volatile oil resistance of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the portion where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 2 1 mol of urethane diacrylate (polyester diol "phthalic anhydride / neopentyl glycol") was reacted with 2 mol of hexamethylene diisocyanate on the above-mentioned release paper to obtain a terminal isocyanate. -To-group containing polyester, and further 2 per 1 mol of the polyester containing terminal isocyanate group.
-75 parts by weight of an average molecular weight of about 3000 oligomer obtained by reacting 2 mol of hydroxyethyl acrylate, 10 parts by weight of methyl methacrylate, 10 parts of butyl acrylate
5 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 acetophenone initiator, and 4 parts by weight of 2,4-dimethylthioxanthone thioxanthone initiator. Screened] to a film thickness of 10 microns and 500
Ultraviolet rays were irradiated under the condition of mj / cm 2 to obtain a clear coating film (corresponding to the film layer (I) of the present invention).

Next, Acrylic # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied to the surface of the obtained clear coating film by spray coating so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes. To obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Super Flex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of the colored coating film with a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface. there were.

The polypropylene molded product was immersed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the volatile oil resistance of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 3 Bisphenol A type epoxy resin having an epoxy equivalent of 950 [trade name "Epicoat 1004", Shell Chemical Co., Ltd.]
Made] 1900 parts dissolved in 993 parts butyl cellosolve,
Then 210 parts of diethanolamine at 80 to 100 ° C
After dropping at 100 ° C. for 2 hours, the resin (A- having a solid content of 68%, a primary hydroxyl group equivalent of 528, and an amine value of 53 (A-
1) was obtained. 110 parts of this resin (A-1) (solid content 75
Part), EHPE3150 (trade name, manufactured by Daicel Chemical Industries, Ltd., having a cyclohexane skeleton using 4-vinylcyclohexene-1-oxide, epoxy resin, epoxy equivalent 175 to 195) as a curing agent (component B))
31% of 80% butyl cellosolve solution (solid content 25 parts)
Was blended to obtain a mixture (AB).

On the other hand, 14.8 parts of the above resin (A-1)
4.4 parts of 0% formic acid aqueous solution was added, and 15 parts of deionized water was added while stirring. Furthermore, 20 parts of titanium white, 1 part of carbon black, and 4 parts of CUREZOL C11Z (manufactured by Shikoku Kasei Co., Ltd.) were added, and the mixture was dispersed in a ball mill for 24 hours.
Pigment paste with a solid content of 50% (P
-1) was obtained.

To 141 parts of the above mixture (AB), 10% was added.
12.0 parts of a formic acid aqueous solution was added, and deionized water was added while stirring to obtain 333 parts of emulsion having a solid content of 30%.

The above-mentioned release paper was coated with the emulsion and dried at 140 ° C. for 20 minutes to obtain a 20 μm clear coating film (corresponding to the film layer (I) of the present invention).

Next, Acrylic # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied to the surface of the obtained clear coating film by spray coating so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes. To obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of the colored coating film with a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained was free from defects such as wrinkles, blisters, bubbles, reduced gloss, peeling and cracks on both the curved surface and the flat surface and had a good appearance. there were.

The polypropylene molded article was immersed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded article was immersed in gasoline for 5 hours and then left at room temperature for 2 hours so as to evaluate the resistance to volatile oil, and evaluated. As a result, wrinkles, blisters and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 4 300 parts of flaxseed oil was added to a clean container in which nitrogen gas was refluxed.
250 parts of soybean oil, 20.5 parts of D-glycerin, 78.1 parts of pentaerythritol and 0.05 part of lithium hydroxide were charged and stirred, and then the mixture was kept at 250 ° C. for 1 hour, then 200
The mixture was cooled to ℃, charged with 50 parts of pentaerythritol and 300 parts of phthalic anhydride, heated to 230 ° C., reacted for 4 to 5 hours until the acid value reached 30, then cooled to 150 ° C. and added 27 parts of phthalic anhydride. After stirring for 2 hours, 465 parts of n-butyl cellosolve and 75 parts of triethylamine were added and well stirred to obtain a viscous resin liquid having a nonvolatile content of 65%.

The release liner described above is coated with the resin solution, and
It was dried at 0 ° C. for 20 minutes to obtain a 20 μm clear coating film (corresponding to the film layer (I) of the present invention).

Then, Aclick # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied to the surface of the obtained clear coating film by spray coating so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes. To obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of the colored coating film with a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface. there were.

The polypropylene molded product was immersed in water at 40 ° C. for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the volatile oil resistance of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 5 Soflex 1630 Clear- (Kansai Paint Co., Ltd.,
A product name, melamine-curable acrylic resin-based clear) is applied to the above-mentioned release paper with the resin solution and dried at 80 ° C. for 20 minutes to obtain a 20 μm clear coating (corresponding to the film layer (I) of the present invention). It was

Next, Acrylic # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied to the surface of the obtained clear coating film by spray coating so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes. To obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of the colored coating film with a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface. there were.

The polypropylene molded product was immersed in water at 40 ° C. for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded article was dipped in gasoline for 5 hours and then allowed to stand at room temperature for 2 hours so as to evaluate the resistance to volatile oil. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 6 KINO # 400 clear (Kansai Paint Co., Ltd., trade name, acid epoxy curing type acrylic resin clear) was coated with the resin solution on the above-mentioned release paper and dried at 80 ° C. for 20 minutes. 20 μm clear coating (the film layer (I) of the present invention)
Equivalent to) was obtained.

A click # on the surface of the clear coating obtained.
2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied by spray coating so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes to obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of this colored coating film with a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained was free of defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface and had a good appearance. there were. After immersing the polypropylene molded product in 40 ° C. water for 20 days, the presence of defects such as peeling of the coating film-attached portion, blistering, and deterioration of gloss was examined. there were.

In order to evaluate the resistance to volatilized oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 7 85 parts of toluene was charged into a clean container in which nitrogen gas was refluxed and heated to 110 ° C., then 10 parts of styrene, 20 parts of methyl methacrylate and 65 parts of isobutyl methacrylate.
Part, γ-methacryloxypropyltrimethoxysilane 5
A solution in which 2 parts of a polymerization initiator 2,2-azobis (2-methylbutyronitrile) was dissolved in 1 part of the mixed solution was added dropwise over about 3 hours. After completion of dropping, the mixture was allowed to stand at 110 ° C. for 2 hours, 15 parts of toluene was added to terminate the reaction, and the mixture was cooled to obtain a viscous hydrolyzable silane-curable acrylic resin solution having a nonvolatile content of 50%.

The glass transition temperature of this resin solution by DSC measurement was 64 ° C., and the weight average molecular weight by GPC (gel permeation chromatography) was 16000.

100 parts of the obtained resin solution was added to Neostan U
-100 (organic tin compound manufactured by Nitto Kasei Co., Ltd.)
A solution prepared by mixing 01 parts was coated on the above-mentioned release paper with a knife coater and dried at 80 ° C. for 20 minutes to obtain a clear coating film (corresponding to the film layer (I) of the present invention) having a film thickness of 20 μm.

Next, Acrylic # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied to the surface of the clear film thus obtained by spray coating so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes. To obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of the colored coating film using a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface. there were.

The polypropylene molded product was immersed in water at 40 ° C. for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

In order to evaluate the resistance to volatilized oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and then allowed to stand at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 8 242 parts of deionized water, Newcol 7 in a clean container
07SF (Daiichi Kogyo Seiyaku Co., Ltd., trade name, solid content 30)
%) 2.4 parts was added, and the atmosphere was replaced with nitrogen, and the temperature was maintained at 80 ° C. Immediately before dropping the pre-emulsion having the following composition, 0.7 part of ammonium sulfate was added, and the pre-emulsion was dropped over 3 hours. Deionized water 352 parts Diacetone acrylamide 33 parts Acrylic acid 3.3 parts Styrene 134 parts Methyl methacrylate 255 parts 2-Ethylhexyl acrylate 147 parts n-Butyl acrylate 98 parts Newcol 707SF 64.5 parts Ammonium persulfate From 30 minutes after the end of 1.3 parts of the dropwise addition, a solution of 0.7 parts of ammonium persulfate in 7 parts of deionized water was added dropwise for 30 minutes,
Further, the temperature was kept at 80 ° C. for 2 hours to obtain a hydrazine-curable acrylic emulsion having a nonvolatile content of 51%.

To this hydrazine-curable acrylic emulsion solution, adipic acid dihydrazide as a cross-linking agent was adjusted to pH 8-9 with aqueous ammonia, and then a solution prepared by mixing 0.3 equivalent of a hydrazide group with 1 equivalent of a carbonyl group was used. Coated on the above-mentioned release paper with a taper and dried at 80 ° C. for 10 minutes to obtain a clear coating film having a thickness of 20 μm (corresponding to the film layer (I) of the present invention).

Then, Aclick # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied to the surface of the obtained clear coating film by spray coating so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes. To obtain a colored coating film.

An aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of this colored coating film with a knife coater and dried at 100 ° C. for 10 minutes to form a urethane coating film with a thickness of 50 μm ( (Corresponding to the film (II) of the present invention) was formed. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface and the flat surface. there were.

The polypropylene molded article was immersed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

In order to evaluate the resistance to volatilized oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 9 85 parts of toluene was charged into a clean container in which nitrogen gas was refluxed and heated to 110 ° C., and then 20 parts of styrene, 20 parts of methyl methacrylate and 30 parts of n-butyl methacrylate.
Part, 30 parts of glycidyl methacrylate and 4 parts of a polymerization initiator 2,2-azobis (2-methylbutyronitrile) were added dropwise over about 3 hours. After the dropping is completed,
The mixture was left standing at 110 ° C for 5 hours, charged with 15 parts of acrylic acid, 0.05 part of hydroquinone monomethyl ether and 0.2 part of tetraethylammonium bromide, reacted at 110 ° C for 5 hours while blowing air, and the acid value became almost 0. After confirming that, 35 parts of toluene was added to terminate the reaction, and the mixture was cooled to obtain a viscous radical-curable acrylic resin solution having a nonvolatile content of 50%.

The glass transition temperature of this resin solution by DSC measurement was 37 ° C., the number average molecular weight by GPC (gel permeation chromatography) was 5,000, and the average number of unsaturated groups contained in one molecule was 9.0. was.

Then, 100 parts of the obtained resin solution was mixed with 2 parts of "Irgacure 184" (a photo radical polymerization initiator manufactured by Ciba Specialty Chemicals Co., Ltd.) and the solution was coated on the above-mentioned release paper with a knife coater. , 1000 mj
It was irradiated with ultraviolet rays under the condition of / cm 2 to obtain a clear coating film (corresponding to the film layer (I) of the present invention) having a film thickness of 30 μm. Retin PG-80 metallic (trade name, manufactured by Kansai Paint Co., Ltd., isocyanate-curable acrylic resin coating) was applied by spray coating on the surface of the obtained clear coating film to a thickness of 20 μm, and dried at 80 ° C. for 10 minutes. To obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of the colored coating film with a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface. there were.

The polypropylene molded product was immersed in water at 40 ° C. for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the volatile oil resistance of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 10 100 parts of the above radical-curable acrylic resin solution was mixed with 2 parts of "perbutyl Z" (NOF Corporation, trade name, peroxide).
The above-mentioned release paper was coated with a knife coater on the above-mentioned release paper and dried at 120 ° C. for 10 minutes to obtain a clear coating having a thickness of 30 μm (corresponding to the film layer (I) of the present invention).

On the surface of the obtained clear coating film, PG-
80 metallic (manufactured by Kansai Paint Co., Ltd., trade name, isocyanate-curable acrylic resin paint) was spray-coated to a thickness of 20 μm, and dried at 80 ° C. for 10 minutes to obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of this colored coating film with a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface. there were.

[0209] The polypropylene molded product was immersed in water at 40 ° C for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the volatile oil resistance of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 11 To a clean container in which nitrogen gas was refluxed, 85 parts of toluene was charged and heated to 110 ° C., then, 40 parts of 3.4-epoxycyclohexylmethyl acrylate, methyl methacrylate.
A solution of 2 parts of 2,2-azobis (2-methylbutyronitrile), a polymerization initiator, in a mixed solution of 20 parts of n-butyl methacrylate and 40 parts of n-butyl methacrylate was added dropwise over about 3 hours.
After the completion of dropping, leave at 110 ° C. for 2 hours to remove toluene by adding 15
Then, the reaction was terminated by cooling, and the mixture was cooled to obtain a viscous cation-curable acrylic resin solution having a nonvolatile content of 50%.

The glass transition temperature of this resin solution measured by DSC was 34 ° C., the number average molecular weight measured by GPC (gel permeation chromatography) was 8000, and the number of epoxy groups in one molecule was 17.6.

A solution prepared by mixing 0.5 part of "Cyracure UVI-6990" (manufactured by Union Carbide Co., Ltd., a photocation radical polymerization initiator) with 100 parts of the obtained resin solution was prepared using a knife coater and the release paper described above. Painted on 1000
UV irradiation under the condition of mj / cm2 gives a film thickness of 30 μm
To obtain a clear coating (corresponding to the film layer (I) of the present invention).

Aclick on the surface of the obtained clear film #
2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied by spray coating so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes to obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of this colored coating film with a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface. there were.

[0218] The polypropylene molded product was washed with water at 40 ° C for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the resistance to volatile oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 12 A solution prepared by mixing 100 parts of the above-mentioned cationically curable acrylic resin solution with 2 parts of "SAN-AID SI-80L" (NOF CORPORATION, trade name, peroxide) was separated with a knife coater as described above. Paint on a pattern paper and dry at 110 ° C for 10 minutes to obtain a film thickness of 2
A clear coating of 0 μm (corresponding to the film layer (I) of the present invention) was obtained.

Next, Acrylic # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied by spray coating on the surface of the obtained clear coating film so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes. To obtain a colored coating film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of the colored coating film with a knife coater, and 10
It was dried at 0 ° C. for 10 minutes to form a urethane coating (corresponding to the film (II) of the present invention) having a film thickness of 50 μm. Then, the release paper was peeled off.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface. there were.

[0225] The polypropylene molded article was immersed in water at 40 ° C for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

In order to evaluate the resistance to volatilized oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 13 The release paper described above was coated with Retan PG-80 metallic (manufactured by Kansai Paint Co., Ltd., trade name, isocyanate-curable acrylic resin paint) so that the dry film thickness would be 10 μm.
Dry at 20 ° C. for 20 minutes, and then retan PG-8
0 Quartz Z base agent (Kansai Paint Co., Ltd., trade name, clear) 100 parts and Duranate MF-K60X 50 parts (Asahi Kasei Co., Ltd., trade name, block isocyanate) mixed solution to a dry film thickness of 20 μm And paint at 80 ℃ for 1
After drying for 0 minutes, the release paper was peeled off to produce a metallic colored film.

Next, an aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) was applied to the surface of the metallic coating film of the obtained colored film with a knife coater and dried at 100 ° C. for 10 minutes to form a film. A urethane coating having a thickness of 50 μm (corresponding to the film (II) of the present invention) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

The coating film of Example 1 obtained above was applied to the inner surface of an injection mold capable of being molded into a bumper for automobiles so that the clear layer of the colored sheet was in contact with the inner surface of the mold. Installed, and then press-injected into the film (II) layer surface of the coated film by heating and melting polypropylene at about 230 ° C. with an injection molding machine, cooling the mold, and taking out from the mold Was manufactured. Then, in order to cure the clear film layer of the molded product, it was heated at 120 ° C. for 30 minutes. (The clear film layer is the film layer (I) of the present invention.
The obtained polypropylene molded product has wrinkles, blisters, bubbles, reduced gloss, and peeling on both the curved surface portion and the flat surface portion.
The appearance was good without defects such as cracks.

The polypropylene molded product was placed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

In order to evaluate the volatile oil resistance of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Example 14 A release-treated polyethylene terephthalate sheet (release paper) having a film thickness of 150 μm and a dry film of retan PG-80 metallic (trade name, isocyanate-curable acrylic resin coating manufactured by Kansai Paint Co., Ltd.) Paint to a thickness of 10 μm 8
Dry at 0 ° C. for 20 minutes, and then retan PG-
80 Quartz Z (trade name, clear, manufactured by Kansai Paint Co., Ltd.) is applied to a dry film thickness of 20 μm, and the temperature is 2 at 80 ° C.
After drying for 0 minutes, the release paper was peeled off to produce a metallic-tone colored film (corresponding to the film layer (I) of the present invention).

Then, the following aqueous urethane resin emulsion (a) was coated on the surface of the metallic coating film of the obtained colored film with a knife coater and dried at 100 ° C. for 10 minutes to obtain a urethane coating film having a thickness of 50 μm (the film of the present invention (II )
Equivalent to) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 210% at 0 ° C.

The coating film of Example 1 obtained above was applied to the inner surface of an injection mold capable of being molded into a bumper for automobiles so that the clear layer of the colored sheet was in contact with the inner surface of the mold. Installed, and then press-injected into the film (II) layer surface of the coated film by heating and melting polypropylene at about 230 ° C. with an injection molding machine, cooling the mold, and taking out from the mold Was manufactured.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded article was placed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

In order to evaluate the volatile oil resistance of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Aqueous urethane resin emulsion (a): polyester polyol (butylene adipate, molecular weight 2)
000) 350 parts, trimethylol propane 10.1
Part, polyethylene glycol 35 parts (molecular weight 600),
PO (propylene oxide) / EO (ethylene oxide) random copolymer polyether polyol 35 parts (PO / EO = 30/70, molecular weight 3400) and 1,4-butanediol 78.3 parts methyl methyl ketone 400 parts Then, 310 parts of isophorone diisocyanate was added at a system temperature of 50 ° C. afterwards,
Dibutyltin dilaurate (0.05 parts) was added, and the system temperature was gradually raised to 75 ° C. At the stage of reacting at 75 ° C for 60 minutes, dibutyltin dilaurate 0.05 was added.
Parts were added. Then, continue the reaction at 75 ° C / 200
After a lapse of minutes, the system was cooled to the system temperature of 50 ° C. Fifty
Free isocyanate of urethane prepolymer after cooling to ℃
The todo group was 2.0% (based on solid content).

Next, at an internal temperature of 45 ° C., 80 parts of polyoxyetherene allylphenol ether type nonionic surfactant (HLB = 15), which is an ethylene oxide adduct of distyrenated phenol, was added. And mixed for 10 minutes. After that, the contents in the system were heated to 300 using a homomixer.
The mixture was stirred at 0 rpm at high speed, 1300 parts of distilled water was gradually added thereto, and then emulsification was carried out at a system temperature of 30 ° C. for 20 minutes.

After cooling the system temperature to 20 ° C., an aqueous solution of ethylenediamine in which 10.5 parts of ethylenediamine was dissolved in 130 parts of distilled water was added.

The system temperature was controlled at 20 to 25 ° C., and stirring was continued for 60 minutes using a homomixer at 3000 rpm.

Next, the solvent used, methyl ethyl ketone, was recovered under reduced pressure (water bath 40 ° C.) to obtain an aqueous urethane resin emulsion (a).

Example 15 A release-treated polyethylene terephthalate sheet (release paper) having a film thickness of 150 μm and a dry film of retan PG-80 metallic (trade name, isocyanate-curable acrylic resin coating manufactured by Kansai Paint Co., Ltd.) Paint to a thickness of 10 μm 8
Dry at 0 ° C. for 20 minutes, and then retan PG-
80 Quartz Z (trade name, clear, manufactured by Kansai Paint Co., Ltd.) is applied to a dry film thickness of 20 μm, and the temperature is 2 at 80 ° C.
After drying for 0 minutes, the release paper was peeled off to produce a metallic-tone colored film (corresponding to the film layer (I) of the present invention).

Next, the following aqueous urethane resin emulsion (b) was applied to the surface of the metallic coating film of the obtained colored film with a knife coater and dried at 100 ° C. for 10 minutes to obtain a urethane coating having a thickness of 50 μm (the film of the present invention (II )
Equivalent to) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 180% at ° C.

The coating film of Example 1 obtained above was applied to the inner surface of an injection mold capable of being molded into a bumper for automobiles so that the clear layer of the colored sheet was in contact with the inner surface of the mold. Installed, and then press-injected into the film (II) layer surface of the coated film by heating and melting polypropylene at about 230 ° C. with an injection molding machine, cooling the mold, and taking out from the mold Was manufactured.

The polypropylene molded product thus obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface portion and the flat surface portion.

[0250] The polypropylene molded product was washed with water at 40 ° C for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

In order to evaluate the resistance to volatilized oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and allowed to stand at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. , Low gloss, peeling,
The appearance was good without defects such as cracks.

Aqueous urethane resin emulsion (b): Polycarbonate polyol (polycarbonate of 1,6 hexane, molecular weight 2000) 255 parts to 7.0 parts trimethylolpropane and 1,4-butanedio- 57.0 parts of methyl ethyl ketone and then 290 parts of methyl ethyl ketone were added and dissolved.

Next, 260 parts of isophorone diisocyanate and 0.01 part of dibutyltin dilaurate were added thereto at a system temperature of 50 ° C., and the mixture was gradually heated to a system temperature of 75 ° C.
Was reacted for 180 minutes to obtain a urethane prepolymer containing 5.0% of free isocyanate groups (based on solid content). Then, to this, dimethylolpropionic acid 26.5
Parts and 120 parts of methyl ethyl ketone, 0.07 part of dibutyltin dilaurate was added, and 9.9 parts of triethylamine was further added. When this was gradually heated and the system temperature was cooled to 50 ° C., a urethane prepolymer containing 1.99% of free isocyanate groups (based on solid content) and a carboxyl group was obtained.

Next, 9.9 parts of triethylamine was added thereto at an internal temperature of 50 ° C. to neutralize the remaining carboxyl groups. Then, 900 parts of distilled water was gradually added, the mixture was stirred at 3000 rpm using a homomixer, and the emulsification operation was carried out at a system internal temperature of 25 ° C. for 20 minutes.

Next, 7.8 parts of ethylenediamine was added to 8 parts of distilled water.
An ethylenediamine aqueous solution dissolved in 0 part of the system has a temperature of 25
The mixture was added at 0 ° C, and mixed by stirring at 25 ° C for 60 minutes.

Thereafter, the solvent used, methyl ethyl ketone, was recovered under reduced pressure (water bath 40 ° C.) to obtain an aqueous urethane resin emulsion (b).

Comparative Example 1 In Example 1, Retan PG-80 metallic (manufactured by Kansai Paint Co., Ltd., trade name, isocyanate-curable acrylic resin paint) was applied to a dry film thickness of 10 μm.
Acrylic # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) 20 μm is used to form a clear coating film by drying at 0 ° C for 20 minutes.
A multilayer coating film of Example 1 was obtained in the same manner as in Example 1 except that the non-crosslinking clear coating film was formed by spray coating at 80 ° C. for 10 minutes.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling and cracks on both the curved surface and the flat surface. there were.

The polypropylene molded article was placed in 40 ° C. tap water for 2 minutes.
After soaking for 0 days, the part to which the coating film was applied was peeled off, and defects such as blistering and deterioration of gloss were observed, which was bad.

In order to evaluate the resistance to volatilized oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and then allowed to stand at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters and gloss were observed on the part where the coating film was applied. Defects such as deterioration were observed, and the resistance to volatile oil was poor.

Comparative Example 2 Acrylic # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied by spray coating to a thickness of 20 μm on a soft polyvinyl chloride film, and dried at 80 ° C. for 10 minutes. To form a non-crosslinkable clear coating film, and then apply Retan PG-80 metallic (trade name, isocyanate-curable acrylic resin coating manufactured by Kansai Paint Co., Ltd.) to a dry film thickness of 10 μm.
A laminated coating film of Comparative Example 2 was obtained by drying at 20 ° C. for 20 minutes to form a clear coating film.

As a result of molding in the same manner as in Example 1, the polypropylene molded product obtained was bad in that defects such as wrinkles, decrease in gloss and cracks were observed in both the curved surface portion and the flat surface portion. After immersing the polypropylene molded article in 40 ° C. water for 20 days, peeling off of the portion to which the coating film was attached,
As a result of checking the presence of abnormalities such as blisters and deterioration of gloss,
All were good with no abnormalities.

Further, in order to evaluate the volatile oiliness of the polypropylene molded product, a portion having a good appearance was selected, dipped in gasoline for 5 hours, and allowed to stand for 2 hours at room temperature for evaluation. As a result, a coating film was applied. Wrinkles, blisters,
There were no defects such as foam, deterioration of gloss, peeling, and cracks, which were good.

Example 16 In place of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) in Example 1, tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. A colored film (film layer (I)) and a urethane coating ((polyfunctional water-based epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name) were mixed in the same manner as in Example 1 except that 5 parts by weight of 611 was used. Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded product was immersed in water at 40 ° C. for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

In order to evaluate the resistance to volatilized oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 17 In place of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) in Example 1, tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. 810 (bifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name) 5 parts by weight was used in the same manner as in Example 1 except that a colored film (film layer (I)) and a urethane coating ( Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was manufactured in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface portion and the flat surface portion.

[0274] The polypropylene molded product was immersed in water at 40 ° C for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded article was evaluated for volatile oil resistance by immersing it in gasoline for 5 hours and then allowing it to stand at room temperature for 2 hours, and it was evaluated that wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 18 In place of the aqueous urethane resin emulsion (Superflex 410, Dai-Ichi Kogyo Seiyaku Co., Ltd., trade name) in Example 2, tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. A clear coating (film layer (I)) and a colored coating film were prepared in the same manner as in Example 2 except that 5 parts by weight of 521 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd.) was blended. And a urethane coating (Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was manufactured in the same manner as in Example 1.

The polypropylene molded product thus obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface portion and the flat surface portion.

[0280] The polypropylene molded product was immersed in water at 40 ° C for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the volatile oil resistance of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 19 In place of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) in Example 3, tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. 811 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name) was used in the same manner as in Example 3 except that 5 parts by weight was blended. And a urethane coating (Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The polypropylene molded product thus obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling and cracks on both the curved surface and the flat surface.

The polypropylene molded article was placed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded article was dipped in gasoline for 5 hours and allowed to stand at room temperature for 2 hours for evaluation so as to evaluate the resistance to volatilized oil. As a result, wrinkles, blisters and bubbles were observed on the portion where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 20 In place of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) in Example 4, tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. 850 (polyfunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name) 5 parts by weight were used in the same manner as in Example 4 except that a clear coating (film layer (I)) and a colored coating film were used. And a urethane coating (Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded article was placed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded article was evaluated for volatile oil resistance by immersing it in gasoline for 5 hours and then allowing it to stand at room temperature for 2 hours, and it was evaluated that wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 21 In place of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) in Example 5, tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. 810 (bifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name) 5 parts by weight were used in the same manner as in Example 5 except that a clear coating (film layer (I)) and a colored coating film were used. And a urethane coating (Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded article was produced in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded article was placed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded article was evaluated for volatile oil resistance by immersing it in gasoline for 5 hours and then allowing it to stand for 2 hours at room temperature. The results showed that wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 22 In Example 6, instead of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name), tenacol EX- was added per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. A clear coating (film layer (I)) and a colored coating film were prepared in the same manner as in Example 6 except that 5 parts by weight of 851 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd.) was used. And a urethane coating (Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded product was immersed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded product was evaluated for volatile oil resistance by dipping it in gasoline for 5 hours and then allowing it to stand at room temperature for 2 hours. As a result, it was observed that wrinkles, blisters and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 23 In place of the aqueous urethane resin emulsion (Superflex 410, Daiichi Kogyo Seiyaku Co., Ltd., trade name) in Example 7, tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. A clear coating (film layer (I)), a colored coating film was prepared in the same manner as in Example 7 except that 5 parts by weight of 861 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd.) was used. And a urethane coating (Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The polypropylene molded product thus obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded product was immersed in water at 40 ° C. for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the volatile oil resistance of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 24 In Example 8, instead of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name), tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. A clear coating (film layer (I)), a colored coating film was prepared in the same manner as in Example 8 except that 5 parts by weight of 920 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd.) was used. And a urethane coating (Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded product was washed with water at 40 ° C. for 2 times.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the resistance to volatilized oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 25 In place of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) in Example 9, tenacol EX- was added per 100 parts by weight of the aqueous urethane resin emulsion solid content. A clear coating (film layer (I)) and a colored coating film were prepared in the same manner as in Example 9 except that 5 parts by weight of 313 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd.) was used. And a urethane coating (Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The polypropylene molded product thus obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded article was immersed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the volatile oil resistance of the polypropylene molded product, the polypropylene molded product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 26 In Example 10, instead of the aqueous urethane resin emulsion (Superflex 410, Daiichi Kogyo Seiyaku Co., Ltd., trade name), tenacol EX- was added per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. Example 10 except that 5 parts by weight of 814 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name) was blended.
A clear coating (film layer (I)), a colored coating film and a urethane coating (film (II)) were formed in the same manner as in.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was manufactured in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded product was washed with water at 40 ° C. for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

The polypropylene molded product was evaluated for volatile oil resistance by immersing it in gasoline for 5 hours and then allowing it to stand at room temperature for 2 hours. As a result, it was observed that wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 27 In place of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name) in Example 11, tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. Example 1 except that 15 parts by weight of 313 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name) was blended.
In the same manner as in 1, a clear film (film layer (I)),
A colored coating film and a urethane coating (film (II)) were formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded product was placed in 40 ° C. tap water for 2 minutes.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

The polypropylene molded product was evaluated for volatile oil resistance by immersing it in gasoline for 5 hours and then allowing it to stand at room temperature for 2 hours. As a result, it was observed that wrinkles, blisters and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 28 In Example 12, instead of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name), tenacol EX- was used per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. Example 1 except that 10 parts by weight of 512 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name) was blended
In the same manner as in 2, a clear coating (film layer (I)),
A colored coating film and a urethane coating (film (II)) were formed.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was manufactured in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded product was immersed in water at 40 ° C. for 2 times.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded article was dipped in gasoline for 5 hours and then allowed to stand at room temperature for 2 hours for evaluation so as to evaluate the resistance to volatile oil. As a result, wrinkles, blisters and bubbles were observed on the portion where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 29 In Example 13, instead of the aqueous urethane resin emulsion (Superflex 410, Daiichi Kogyo Seiyaku Co., Ltd., trade name), tenacol EX- was added per 100 parts by weight of the solid content of the aqueous urethane resin emulsion. Example 1 except that 15 parts by weight of 612 (multifunctional aqueous epoxy resin, manufactured by Nagase Chemtec Co., Ltd., trade name) was blended.
A colored film (film layer (I)) and a urethane coating (film (II)) were formed in the same manner as in 3.

The tensile elongation at break of the urethane coating is -10.
It was 170% at 0 ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, and cracks on both the curved surface portion and the flat surface portion.

[0346] The polypropylene molded product was immersed in water at 40 ° C for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, in order to evaluate the resistance to volatile oil of the polypropylene molded product, it was immersed in gasoline for 5 hours and then left at room temperature for 2 hours for evaluation. As a result, wrinkles, blisters, and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 30 In place of the aqueous urethane resin emulsion (a) in Example 14, tenacol EX-31 was added per 100 parts by weight of the solid content of the aqueous urethane resin emulsion (a).
4 (polyfunctional water-based epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name) was used in the same manner as in Example 14 except that a colored film (film layer (I)) and urethane coating ( Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 210% at 0 ° C.

A polypropylene molded product was manufactured in the same manner as in Example 1.

The polypropylene molded product thus obtained had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling, and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded product was immersed in water at 40 ° C. for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded article was evaluated for volatile oil resistance by dipping it in gasoline for 5 hours and then allowing it to stand at room temperature for 2 hours. As a result, it was observed that wrinkles, blisters and bubbles were observed on the portion where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

Example 31 In Example 15, instead of the aqueous urethane resin emulsion (Superflex 410, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name), 100 parts by weight of the aqueous urethane resin emulsion (b) solid content was added. Tenacor EX-85
A colored film (film layer (I)) and a urethane coating ((polyfunctional water-based epoxy resin, manufactured by Nagase Chemtech Co., Ltd., trade name)) were blended in the same manner as in Example 15 except that 25 parts by weight were used. Film (II)) was formed.

The tensile elongation at break of the urethane coating is -10.
It was 180% at ° C.

A polypropylene molded product was produced in the same manner as in Example 1.

The obtained polypropylene molded product had a good appearance with no defects such as wrinkles, blisters, bubbles, reduced gloss, peeling and cracks on both the curved surface portion and the flat surface portion.

The polypropylene molded product was immersed in water at 40 ° C. for 2 hours.
After soaking for 0 day, the presence of defects such as peeling, blistering, and lowering of gloss on the part to which the coating film was applied was examined.

Further, the polypropylene molded article was dipped in gasoline for 5 hours and then allowed to stand at room temperature for 2 hours for evaluation so as to evaluate the resistance to volatile oil. As a result, wrinkles, blisters and bubbles were observed on the part where the coating film was applied. The appearance was good with no defects such as deterioration in gloss, peeling and cracks.

EFFECTS OF THE INVENTION In the film of the present invention, the thermosetting coating layer is used as the surface layer, while the urethane resin layer is used as the attachment surface to furniture, vehicles or buildings. At the time of this attachment, the film (II) layer has excellent flexibility and elongation, so that defects such as wrinkles due to the attachment of the film do not occur, so that the finished appearance is excellent. Further, when an external object such as pebbles or sand hits the surface of the applied coating film, the surface of the film (I) has a high hardness and the film (II) absorbs the energy from the impact from the surface. Therefore, even though the surface hardness is high, there is an effect that the performance of the film having excellent durability can be maintained for a long period of time without causing defects such as cracking and peeling of the coating film. Further, since a cross-linked coating film is formed on the surface layer, it exhibits excellent chemical resistance, stain resistance and abrasion resistance.

Further, since it is not necessary to directly coat the base material with the crosslinkable resin coating material such as the conventional melamine curable resin coating material, isocyanate curable resin coating material, and oxidation curable resin coating material, it is possible to apply the coating means in advance. A suitable method can be selected depending on the coating purpose such as coating film performance and design. It is possible to prevent coating defects from occurring due to painting, to prevent the paint required for painting from being consumed more than necessary, and to safely manage the work environment and safety and hygiene of painting. Further, it is easy to collect the applied coating film, which is preferable from the viewpoint of environmental pollution.

Molding process (10
(0% or more), the film has excellent elongation, tension, and bending force, so that a molded product having an excellent finished appearance without deterioration of gloss, cracks, or peeling can be obtained.

INDUSTRIAL APPLICABILITY The coated film of the present invention is a film of various plastics such as PVC, acrylic and polycarbonate,
Film (II) on steel plates, plate materials, etc. (hereinafter referred to as adherends)
By laminating the surface side with a laminating agent,
Weather resistance, light resistance, moisture resistance, heat resistance, stain resistance, water repellency,
Adds functions such as boiling water resistance to the surface of the adherend, interior building materials,
It is a functional film that can be used in a wide range of applications such as exterior building materials, ornaments, packaging, protective films, guides, signs, markings, and storage.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor, Akagi             Seki, 4-17-1, Higashi-Hachiman, Hiratsuka City, Kanagawa Prefecture             West Paint Co., Ltd. (72) Inventor Osamu Isozaki             Seki, 4-17-1, Higashi-Hachiman, Hiratsuka City, Kanagawa Prefecture             West Paint Co., Ltd. F term (reference) 4F100 AK01A AK01B AK51B AK53B                       AL05B BA02 BA07 BA15                       CC00A EJ05A GB90 JB05B                       JB16B JK08B JL01 JM01B                       YY00B                 4J002 CD01X CD02X CD03X CD04X                       CD05X CK02W GH01 HA07                 4J034 BA02 BA03 CA03 CA11 CA14                       CA15 CA16 CA24 CB03 CB04                       CC01 CC26 CC52 CE03 DA01                       DA05 DB03 DC02 DF01 DF02                       DG00 DG20 DH00 DR01 HA06                       HA07 HC12 HD00 QA05 QB04                       QB05 QC05 RA07 SA01 SA02                       SB04 SB05 SC04

Claims (5)

[Claims] 1. A film formed by laminating two or more kinds of resin films, wherein the uppermost layer film (I) is formed of a crosslinkable resin coating material (A), and the lowermost layer film (II).
Is formed of a thermoplastic resin (B), and the formed film (II) is substantially tack-free and has a tensile elongation at break (length 30 mm, width 10 mm, thickness 0.05 mm).
The value of the above sample measured at a tensile speed of 200 mm / min at −10 ° C.) is in the range of 50 to 1000%. 2. The coated film according to claim 1, wherein the thermoplastic resin (B) is an aqueous urethane resin emulsion or a mixture of the aqueous urethane resin emulsion and an aqueous epoxy resin. 3. An aqueous urethane resin emulsion is prepared by reacting a polyisocyanate compound with an active hydrogen-containing compound capable of reacting with an isocyanate group of the polyisocyanate compound to produce a hydrophilic group-containing isocyanate-terminated prepolymer, Disperse things in water,
Further, the coated film according to claim 1 or 2, wherein the chain is extended with an amine. 4. The coated film according to any one of claims 1 to 3 is applied to the surface of the base material so that the film (II) layer of the coated film faces the surface of the plastic base material. A method for laminating a coated film, which comprises thermocompression bonding. 5. The coated film according to claim 1, wherein the film (II) layer of the coated film is formed on the surface of a plastic substrate. A method for laminating a coated film, which comprises simultaneously molding a raw material of a plastic substrate.