JP2004148507A - Colored film, its manufacturing method and lamination method using the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored film excellent in processability and finish properties. <P>SOLUTION: The colored film is manufactured by successively laminating layers (I)-(IV). The layer (I) comprises a releasable layer provided if necessary and a bonding layer formed of a pressure-sensitive adhesive or an adhesive. The layer (II) is a clear layer formed from an aqueous urethane resin dispersion (A) and substantially has no tackiness in itself, and the tensile elongation at break thereof is 50-1,000%. The layer (III) is a colored layer formed of the aqueous urethane resin dispersion (A) and a colorant (B) and substantially having no tackiness itself and the tensile elongation at break thereof is 50-1,000%. The layer (IV) is a clear layer formed of a crosslinkable resin coating (C). The tensile elongation at break is a value obtained when a sample with a length of 30 mm, a width of 10 mm and a thickness of 0.05 mm is measured at -10°C at a tensile speed of 200 mm/min. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
The present invention relates to a novel colored film and a laminating method.
2. Description of the Related Art Conventionally, crosslinkable 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, Base materials such as inorganic materials (concrete, ceramic, glass, etc.) and plastics (polyvinyl chloride, polyethylene terephthalate, polyethylene, nylon, etc.) other than the above metals, have anticorrosion properties, design properties, A substrate is directly coated to impart functions such as durability, weather resistance, and scratch resistance. In order to apply directly to such a substrate, it is necessary to select the optimal coating method, it is troublesome, generally, it is not possible to maintain a uniform coating film thickness, it is easy to cause coating defects due to coating, From the point of consumption of unnecessary paints, difficulties in safeguarding the work environment and safety and health of painting, and difficulties in collecting painted coatings and environmental pollution. However, there is a problem that it is not preferable.
Also, in general, paints are used for coating purposes such as coating means, coating film performance, and design, so naturally there are many varieties and many wasteful paints are produced. There is a need in the art for effective use of paints.
[0002]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific coloring layer is formed on the surface of a bonding agent layer formed of an adhesive or an adhesive. The present inventors have found that a colored film formed by sequentially laminating a clear layer formed of a crosslinkable resin paint solves all the conventional problems, and have completed the present invention.
[0003]
Thus, according to the present invention, a release layer provided as needed, a bonding agent layer (I) formed of an adhesive or an adhesive, and an aqueous urethane resin dispersion (A) are formed and formed. The layer itself is substantially non-tacky and has a tensile elongation at break (measured at a tensile speed of 200 mm / min at −10 ° C. for a sample having a length of 30 mm, a width of 10 mm and a thickness of 0.05 mm) of 50. Formed from the clear layer (II), the aqueous urethane resin dispersion (A) and the colorant (B) in the range of 〜1000%, and the formed layer itself is substantially tack-free and tensile break A colored layer (III) having an elongation percentage (a value measured at a tensile speed of 200 mm / min at −10 ° C. of a sample having a length of 30 mm, a width of 10 mm and a thickness of 0.05 mm at −10 ° C.) of 50 to 1000%; Resin coating Colored film, characterized in clear layer formed in (C) (IV) that formed by sequentially laminating is provided.
[0004]
According to the present invention, the colored film is bonded by heat and / or pressure such that the bonding agent layer (I) of the colored film faces the surface of the adherend. Is provided.
[0005]
Further, the aqueous urethane resin dispersion (A) is coated on the surface of a bonding film having a release layer provided as required and a bonding agent layer (I) formed of a pressure-sensitive adhesive or an adhesive, and the clear film is applied. A layer (II) is formed, and then an aqueous colorant containing the aqueous urethane resin dispersion (A) and the colorant (B) is applied to form a colored layer (III). (C) is applied and a clear layer (IV) is sequentially laminated to provide a method for producing a colored film.
[0006]
Hereinafter, the constituent requirements of the present invention will be described.
[0007]
The present invention provides a release layer provided as necessary, a bonding agent layer (I) formed of an adhesive or an adhesive, an aqueous urethane resin dispersion (A), and a formed layer, It has substantially no tackiness itself, and has a tensile elongation at break (value of a sample having a length of 30 mm, a width of 10 mm, and a thickness of 0.05 mm, measured at a tensile speed of 200 mm / min at −10 ° C.) of 50 to 1000%. The clear layer (II), the aqueous urethane resin dispersion (A) and the colorant (B) are formed in the range described above, and the formed layer itself is substantially tack-free and has a tensile elongation at break ( A colored layer (III) having a length of 30 mm, a width of 10 mm, and a thickness of 0.05 mm measured at −10 ° C. at a tensile speed of 200 mm / min) in the range of 50 to 1000%; Formed in C) Clear layer that is formed by sequentially laminating (IV) relates to a colored film characterized.
[0008]
The release layer provided as necessary can be used for facilitating storage (stacking, winding, etc.) and handling of the colored film. Specifically, it does not remain on the attached colored film. As such a layer, there is no particular limitation as long as the pressure-sensitive adhesive or the adhesive can be easily peeled off, and it is conventionally known, for example, a plastic sheet such as a polyethylene terephthalate sheet, paper, cloth, or a plastic sheet. Those treated with a mold agent (silicon, wax, fluorine, etc.) can be generally used. The thickness of the release layer is preferably in the range of about 10 to 1000 μm, preferably about 20 to 500 μm.
[0009]
The bonding agent layer (I) formed of an adhesive or an adhesive is a bonding agent for attaching the colored film of the present invention to an adherend. Examples of such an adhesive include a bisphenol type epoxy resin, a resol type epoxy resin, an acrylic resin, an aminoplast resin, a polyester resin, a urethane resin, a polysiloxane resin, and an (iso) butylene resin containing a curing agent. Thermosetting or thermoplastic adhesives and pressure-sensitive adhesives containing one or more resins selected from vinyl acetate resin, vinyl chloride resin, vinyl chloride / vinyl acetate copolymer, synthetic rubber, natural rubber, etc. And so on. Furthermore, 2,4,6-trimercapto-S-triazine, 2-dibutylamino-4,6-dimercapto-S-triazine, 2,4,6-trimercapto-S-triazine-monodium salt, Triazinethiol compounds such as 2,4,6-trimercapto-S-triazine-trisium salt can also be used as the adhesive. These bonding agents can be used as a pressure-sensitive adhesive, a heat-sensitive adhesive, or a curing type adhesive, depending on the type.
[0010]
The thickness of the bonding agent layer (I) is preferably in the range of usually 1 to 100 μm, particularly preferably 5 to 50 μm.
[0011]
The clear layer (II) is formed of the aqueous urethane resin dispersion (A), and the formed layer is substantially free from tackiness itself, and has a tensile elongation at break (length of 30 mm, width of 10 mm, thickness of 0 mm). (Measured at a tensile speed of 200 mm / min at −10 ° C. for a 0.05 mm sample) is in the range of 50 to 1000%.
[0012]
The tensile elongation at break is a value obtained by measuring a sample (isolated film) having a length of 200 mm, a width of 10 mm, and a thickness of 0.050 mm at a measurement temperature of -10 ° C at a tensile speed of 200 mm / min. As the measuring instrument, for example, measurement can be performed using a universal tensile tester equipped with a thermostat (Shimadzu Corporation, Autograph SD type).
[0013]
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)] × 100 ( %).
When the tensile elongation at break of the film (II) is less than 50%, the ability to follow a cubic curved surface is poor, and the sticking workability is inferior. There are drawbacks.
[0014]
Further, it is preferable that the clear layer (II) has substantially no tackiness at normal temperature (20 ° C.). Specifically, the glass transition temperature is preferably in the range of -40 ° C to 80 ° C, particularly preferably in the range of -20 ° C to 40 ° C. If the glass transition temperature is lower than −40 ° C., the tackiness increases and handling becomes difficult. On the other hand, if the glass transition temperature exceeds 80 ° C., the elongation decreases and the workability and the like are undesirably low.
[0015]
The clear layer (II) is formed of the aqueous urethane resin dispersion (A), and any conventionally known one can be used as long as it has the above-mentioned coating film properties.
[0016]
Particularly useful as the aqueous urethane resin dispersion (A) are those which can be produced by various methods. As a general method for preparing the aqueous urethane resin dispersion liquid (A), a compound having an ionic functional group (reactive polar group) is partially copolymerized at the time of a urethane-forming reaction. A method is known in which a so-called hydrophilic group-containing isocyanate-terminated prepolymer is dispersed in water and then chain-extended with amines.
[0017]
The hydrophilic group-containing isocyanate-terminated prepolymer to be used is one produced from a conventionally known polyisocyanate compound and an active hydrogen-containing compound capable of reacting with an isocyanate group.
[0018]
Examples of the polyisocyanate compound include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate; Alicyclic diisocyanates such as' -methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane Aromatic diisocyanates such as diisocyanate (hereinafter referred to as polymeric MDI); and similar compounds such as isocyanurates and burettes thereof, and these can be used alone or in combination of two or more. .
[0019]
As the compound containing an active hydrogen capable of reacting with the above-mentioned isocyanate group, which is used in the production of the isocyanate-terminated prepolymer, an average molecular weight of 300 to 10,000, preferably 500 to 5,000, that is, a so-called high-molecular compound is used. It is classified into a molecular weight compound and a so-called low molecular weight compound having a molecular weight of 300 or less.
[0020]
Among them, as the high molecular weight compounds, polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyesteramide polyols and polythioether polyols are particularly representative.
[0021]
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, polyethylene glycol having a molecular weight of 300 to 6,000, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, Various glycol components such as 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A or hydroquinone, or an alkylene oxide adduct thereof; 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 a mixture thereof Various anhydrides or ester-forming derivatives of various dicarboxylic acids; various kinds of such as p-hydroxybenzoic acid or p- (2-hydroxyethoxy) benzoic acid, or ester-forming derivatives of these various hydroxycarboxylic acids. PO obtained by a dehydration condensation reaction with an acid component In addition to esters, .epsilon.-caprolactone such as, polyesters obtained by ring-opening polymerization of various cyclic ester compound, or the like thereof copolymerized polyesters are particularly representative.
[0022]
Examples of the polyether include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, and trimethylol. Ethane, trimethylolpropane, sorbitol, sucrose, aconit sugar, trimellitic acid, hemicellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid or 1,2,3-propane One or more of various compounds having at least two active hydrogen atoms, such as trithiol, may be used as an initiator with ethylene oxide, propylene oxide, Alkylene oxide, styrene oxide, epichlorohydrin, such as tetrahydrofuran or cyclohexylene, also using various one or more monomers in a usual manner, of the form obtained by addition polymerization, particularly representative.
[0023]
As the polycarbonate polyol, a compound obtained by reacting various glycols such as 1,4-butanediol, 1,6-hexanediol or diethylene glycol with diphenyl carbonate or phosgene is particularly typical. is there.
[0024]
On the other hand, a low molecular weight compound refers to a compound having a molecular weight of 300 or less and having at least two or more active hydrogens in a molecule, and among these, only typical compounds are exemplified. Various glycol components used as a raw material of the polyester polyol; 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, 1,2-propanediamine , Hydra Emissions, such as diethylenetriamine or triethylenetetramine, various amine compounds.
[0025]
As a method for introducing a hydrophilic group into the hydrophilic group-containing isocyanate-terminated prepolymer, a method having at least one active hydrogen in a molecule and repeating a carboxyl group, a sulfonic acid group, a sulfonate group, or ethylene oxide is preferred. A method in which at least one or more of the hydrophilic group-containing compounds having a unit is copolymerized during the production of a prepolymer.
[0026]
Only typical examples of such a hydrophilic group-containing compound include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, and 1,3. -Various sulfonic acid-containing compounds such as phenylenediamine-4,6-disulfonic acid and 2,4-diaminotoluene-5-sulfonic acid, or various derivatives thereof, and obtained by copolymerizing them. Polyester polyols: 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4-diaminobenzoic acid Such as various carboxylic acid-containing compounds, or various derivatives thereof, and further, A polyester polyol obtained by copolymerization; or having at least 30% by weight or more of ethylene oxide repeating units and having at least one active hydrogen in the polymer, and having a molecular weight of 300 to 10,000. And non-ionic group-containing compounds such as polyethylene-polyalkylene copolymers, and polyester polyether polyols obtained by copolymerizing them, and the like. Although it may be used in combination, particularly preferred hydrophilic group-containing compounds in the present invention include carboxyl group-containing compounds; or derivatives thereof, or polyester polyols obtained by copolymerizing them.
[0027]
The content of the hydrophilic group in the hydrophilic group-containing isocyanate-terminated prepolymer is, in the case of a hydrophilic group such as a carboxyl group, a sulfonic acid group or a sulfonate group, at least per 100 parts of solid content of the finally obtained polyurethane resin. It is suitably at least 0.01 equivalent, preferably within the range of 0.01 to 0.2 equivalent, and in the case of a nonionic group-containing compound, at least 3 equivalents per solid content of the finally obtained polyurethane resin. % Or more, preferably within a range of 5 to 30% by weight.
[0028]
The hydrophilic group-containing isocyanate-terminated prepolymer is produced by a conventionally known method. For example, as described above, various polyisocyanate compounds and an active hydrogen-containing compound (including a hydrophilic group-containing compound) are converted into an isocyanate group. At 20 to 120 ° C., preferably 30 to 30: 1 at a ratio such that the equivalent ratio to the active water group becomes 1.1: 1 to 3: 1, preferably 1.2: 1 to 2: 1. The reaction is performed according to a method such as reaction at 100 ° C.
[0029]
Particularly typical examples of the polyamine-based chain extender include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, and 4,4′-dicyclohexylmethane. Diamines such as diamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine or 1,4-cyclohexanediamine; various polyamines such as diethylenetriamine, dipropylenetriamine or triethylenetetramine; hydrazines Or acid hydrazides; or water, which may be used alone or in combination of two or more.
[0030]
The polyamine-based chain extender is used by dissolving in water as a dispersion medium, which is necessary to obtain an aqueous urethane resin dispersion, and the amount of the polyamine chain extender is the isocyanate in the hydrophilic group-containing isocyanate-terminated prepolymer. It is appropriate that the equivalent ratio to the group is in the range of 0: 1 to 1: 1 and preferably in the range of 0.6: 1 to 0.98: 1.
[0031]
The amount of water to be used may be a minimum amount that becomes an O / W type aqueous dispersion after mixing the prepolymer and the aqueous phase, and is 100 to 1, based on the solid content of the polyurethane resin. 000% by weight is appropriate.
[0032]
When the hydrophilic group of the hydrophilic group-containing isocyanate-terminated prepolymer is a carboxyl group, various tertiary amines such as trimethylamine or triethylamine are used as neutralizing agents necessary for neutralizing the carboxyl group. The equivalent ratio is preferably in the range of 0.5: 1 to 1.5: 1, and more preferably in the range of 1: 1 to 1.3: 1. It is necessary to incorporate the polyamine chain extender into the aqueous solution.
[0033]
Such a neutralizing agent can be added in advance to the hydrophilic group-containing isocyanate-terminated prepolymer, but these tertiary amines are liable to cause side reactions because they are also strong catalysts for the urethane reaction. In addition, it is not preferable because the prepolymer tends to be colored.
[0034]
The aqueous urethane resin dispersion (A) is usually transferred to the next solvent removal step before or after the chain extension reaction with amines is completed.
[0035]
Examples of the aqueous urethane resin dispersion (A) include trade names such as Superflex 410, 420 on the left, 600 on the left, 150 on the left, 126 on the left, 107M on the left, and Superflex E-2500 (Daiichi Kogyo Seiyaku Co., Ltd.) Product name).
[0036]
The aqueous urethane resin dispersion (A) may contain an auxiliary compounding agent as necessary. Examples of the auxiliary compounding agent include an inorganic filler, an organic modifier, a stabilizer, a plasticizer, a surfactant, an antifoaming agent, a crosslinking agent, and other additives.
[0037]
Examples of the inorganic filler include calcium carbonate, silica, talc, glass fiber, and potassium titanate whisker. Examples of the organic modifier include a fluorine resin-based powder, an acrylic resin-based powder, a silicone resin-based powder, a polyamide resin-based powder, and a urethane resin-based powder. Examples of the stabilizer include hindered phenols, hydrazines, phosphorus, benzophenones, benzotriazoles, oxalic acid anilides, and hindered amines. These stabilizers are additives for improving weather resistance and preventing heat deterioration.
[0038]
Examples of the plasticizer include dibutyl phthalate and dioctyl phthalate. Examples of the surfactant (such as a foam stabilizer) include a silicone-based foam stabilizer such as a siloxaneoxyalkylene block copolymer. Examples of the antifoaming agent include silicone-based ones such as dimethylsiloxane-based ones. Examples of the crosslinking agent include amino resins [methylolated and / or alkoxylated (methyl-butyl) urea, melamine, etc.], epoxy compounds [bisphenol A-type glycidyl ether, hydrogenated bisphenol A-type glycidyl ether, ethylene glycol-polyethylene glycol glycidyl] Glycidyl ethers such as ether, glycerin, trimethylolpropane, and sorbitol; glycidyl ethers obtained by adding alkylene oxides (2 to 3 carbon atoms) to glycerin, trimethylolpropane, sorbitol, etc.], polyethylene urea compounds (diphenylmethane-bis-4) , 4'-N, N'-ethylene urea), blocked isocyanates (for example, 1 mol of trimethylolpropane, hexamethylene diisocyanate, isophorone Isocyanate or adduct synthesized from 3 moles of toluene diisocyanate; water-modified hexamethylene diisocyanate, block isocyanate obtained by masking a trimerized product of isophorone diisocyanate and hexamethylene diisocyanate with phenol, methyl ethyl ketoxime, ε-caprolactam, etc.) And aqueous polyisocyanates (e.g., a reaction product of a polyoxyalkylene [C2-4] polyol and a polyisocyanate). Other additives include flame retardants, thixotropic agents, antistatic agents, bactericides and the like.
[0039]
The amount of the auxiliary compounding agent is based on the weight solid content of the resin composition. The inorganic filler and the organic modifier are usually 0 to 170%, preferably 0 to 150%, and the stabilizer is usually 0 to 20%. %, Preferably 0 to 10%, the plasticizer is usually 0 to 100%, preferably 0 to 50%, the surfactant is usually 0 to 20%, preferably 0 to 10%, an antifoaming agent and other additives. The amount of the agent is usually 0 to 20%, preferably 0 to 10%, and the amount of the crosslinking agent is usually 0 to 50%, preferably 0 to 40%. These auxiliary compounding agents may be mixed only by ordinary stirring, or may be obtained by dispersing and mixing using a dispersion mixing apparatus (ball mill, kneader, sand grinder, roll mill, flat stone mill, etc.). The order of mixing may be any order.
[0040]
The aqueous urethane resin dispersion (A) may contain a coloring agent such as a dye or a pigment, if necessary, to such an extent that the base is not completely hidden.
[0041]
The thickness of the aqueous urethane resin dispersion (A) can be variously changed, but is usually 5 to 500 μm, preferably 10 to 250 μm. Coating methods include spray coating, brush coating, iron coating, roll coating, flow coating and dipping methods such as knife coating, gravure coating, screen printing, and reverse roll coating. Drying can be performed at room temperature or warming (for example, at 40 to 270 ° C. for 10 seconds to 60 minutes).
[0042]
The colored layer (III) is formed of the aqueous urethane resin dispersion (A) and the aqueous colorant containing the colorant (B), and the formed colored layer (III) has a tensile elongation at break (length of 30 mm). , 10 mm in width and 0.050 mm in thickness, measured at −10 ° C. at a tensile speed of 200 mm / min) in the range of 50 to 1000%.
[0043]
When the tensile elongation at break of the colored layer (III) is less than 50%, the ability to adhere to a cubic curved surface is poor, and the sticking workability is inferior. There is a disadvantage that it is inferior.
[0044]
Further, it is preferable that the coloring layer (III) has substantially no tackiness at normal temperature (20 ° C.). Specifically, the glass transition temperature is preferably in the range of -40 ° C to 80 ° C, particularly preferably in the range of -20 ° C to 40 ° C. If the glass transition temperature is lower than −40 ° C., the tackiness increases and handling becomes difficult. On the other hand, if the glass transition temperature exceeds 80 ° C., the elongation decreases and the workability and the like are undesirably low.
[0045]
The coloring layer (III) is formed of the above-mentioned aqueous coloring agent, and a conventionally known coloring layer can be used as long as the coloring layer has the above-mentioned physical properties of the coating film.
[0046]
As the colorant (B), dyes such as direct dyes, acid dyes, basic dyes, reactive dyes and metal complex dyes: carbon black, titanium oxide, chromium oxide, zinc oxide, iron oxide, mica, navy blue, etc. And organic pigments such as coupling azo type, condensed azo type anthraquinone type, perylene type, quinacridone type, thioindigo type, dioxazine type and phthalocyanine type, metallic pigments and pearl pigments. The dye is usually in the range of 1 to 50 parts by weight, preferably 2 to 20 parts by weight, and the pigment is usually in the range of 1 to 200 parts by weight, preferably 2 to 150 parts by weight, based on 100 parts by weight (solid content) of the resin.
[0047]
If necessary, the same auxiliary compounding agent as described above can be contained in the aqueous urethane resin dispersion (A).
[0048]
The colorant (B) may be mixed only by ordinary stirring, or may be obtained by dispersing and mixing using a dispersion mixing apparatus (such as a ball mill, a kneader, a sand grinder, a roll mill, and a flat stone mill). The order of mixing may be any order.
[0049]
Although the thickness of the colored layer (III) can be variously changed, it is usually 5 to 500 μm, preferably 10 to 250 μm. The method of applying the aqueous colorant is spray coating, brush coating, iron coating, roll coating, flow coating and dipping method knife coater, gravure coater, screen print, reverse roll coater, etc. There is. Drying can be performed at room temperature or warming (for example, at 40 to 270 ° C. for 10 seconds to 60 minutes).
[0050]
The clear layer (III) is a layer constituting the uppermost layer of the colored film of the present invention, and is a layer obtained by using a conventionally known crosslinkable resin paint (C).
[0051]
Examples of the crosslinkable resin paint (C) include amino-curable resin paint, isocyanate-curable resin paint, acid-epoxy-curable resin paint, hydrolyzable silane-curable resin paint, hydroxyl-epoxy-curable resin paint, and hydrazine-curable. Examples include a curable resin coating, an oxidation polymerization type curable resin coating, a photo (thermal) radical polymerization type resin coating, a photo (thermal) cationic polymerization type resin coating, and a curable resin coating obtained by combining two or more of these.
[0052]
The crosslinkable resin paint (C) may contain additives conventionally added to the paint as required, for example, coloring pigments, extender pigments, metallic pigments, coloring pearl pigments, fluidity regulators, cissing inhibitors, anti-dripping Use of inhibitors, ultraviolet absorbers, antioxidants, ultraviolet stabilizers, matting agents, polishes, preservatives, curing accelerators, curing catalysts, abrasion inhibitors, defoamers, solvents, etc. without any particular restrictions Can be.
[0053]
The form of the crosslinkable resin paint (C) is a powder paint using a crosslinkable resin, a solventless paint using a liquid resin of the crosslinkable resin (a crosslinkable or noncrosslinkable resin is dissolved in a radical polymerizable monomer). Or a dispersed non-solvent paint), an aqueous paint in which a crosslinkable resin is dissolved or dispersed in water, and an organic solvent paint in which a crosslinkable resin is dissolved or dispersed in an organic solvent (including non-aqueous dispersion paint) Any of these forms may be used.
[0054]
The cured film thickness of the clear layer (III) is preferably in the range of 1 μm to 200 μm, particularly preferably in the range of 20 μm to 80 μm. If the thickness is less than 1 μm, weather resistance, solvent resistance and sharpness decrease, while if it exceeds 200 μm, the colored film becomes brittle, which is not preferable.
[0055]
The clear layer (III) formed by the crosslinkable resin paint (C) is obtained by reacting some or all of the functional groups contained in the crosslinkable resin. In addition, the degree of crosslinking of the clear layer (III) is preferably, for example, a gel fraction described below in the range of 50 to 100% by weight.
[0056]
Gel fraction: The free film was peeled off, placed in a 300-mesh stainless steel mesh container, and extracted with a Soxhlet extractor at reflux temperature for 2 hours using an acetone solvent, and the gel fraction was calculated according to the following equation. Done.
[0057]
Gel fraction (%) = (weight after extraction / weight of sample before extraction) × 100
Amino curable resin paint:
Examples of the paint include a composition comprising a base resin having a crosslinkable functional group such as a hydroxyl group, such as an acrylic resin, a vinyl resin, or a polyester resin, and an amino resin as a crosslinker.
[0058]
Examples of the acrylic resin and the vinyl resin include a carboxyl group-containing polymerizable monomer (which can be used as needed, particularly when used as an aqueous paint), a hydroxyl group-containing polymerizable monomer, and other polymerizable monomers. What has a hydroxyl value in the range of 10-200 mgKOH / g, preferably 25-70 mgKOH / g, obtained by copolymerizing the monomer, can be used.
[0059]
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. For example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and other (meth) acrylic acid Examples thereof include hydroxyalkyl esters having 1 to 8 carbon atoms. The other polymerizable monomer is a compound having a polymerizable unsaturated bond in one molecule, which can be copolymerized with the carboxyl group-containing polymerizable monomer and the hydroxyl group-containing polymerizable monomer. (Meth) such as (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and decyl acrylate Alkyl or cycloalkyl ester of acrylic acid having 1 to 24 carbon atoms; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, diacetoneacrylamide, N-methylol (meth) acrylamide, Government officials such as N-butoxymethylacrylamide (Meth) acrylamide; glycidyl (meth) acrylate, glycidyl (meth) acrylamide, glycidyl group-containing vinyl monomers such as allyl glycidyl ether; styrene, vinyl toluene, vinyl propionate, α-methylstyrene, vinyl acetate, ) Vinyl monomers such as acrylonitrile, vinyl propionate, vinyl pivalate, and beova monomer (shell chemical products). The acrylic or vinyl resin can generally have a number average molecular weight in the range of 5,000 to 40,000.
[0060]
Examples of the polyester resin include a polyester resin obtained by subjecting a polyhydric alcohol and a polybasic acid to an esterification reaction.
[0061]
Polyhydric alcohols are compounds having two or more alcoholic hydroxyl groups in one molecule, and include, for example, ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, 2,2-dimethylpropanediol, glycerin, and trimethylolpropane. And pentaerythritol. A polybasic acid is a compound having two or more carboxyl groups in one molecule. For example, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, adipic acid, sebacic acid, Examples include melitic acid, pyromellitic acid, and anhydrides thereof. Further, in the esterification reaction of these polyhydric alcohols and polybasic acids, if necessary, monohydric alcohols and monoepoxy compounds having a glycidyl group are used as a part of the alcohol component, and / or a part of the acid component is used. And monobasic acids such as benzoic acid and t-butylbenzoic acid. The polyester resin also includes polyester components modified with oil components such as castor oil, tung oil, safflower oil, soybean oil, linseed oil, tall oil, and coconut oil, or fatty acids thereof. These polyester resins can generally have a number average molecular weight in the range of 500-10000.
[0062]
The polyester resin can have a hydroxyl value in the range of 10-200 mgKOH / g, preferably 25-70 mgKOH / g.
[0063]
The amino resin crosslinking agent reacts with the base resin by heating to form a three-dimensional cured coating. Examples of such amino resins include those obtained by condensation or co-condensation of melamine, benzoguanamine, urea, dicyandiamide, and the like with formaldehyde, and those obtained by modifying these with alcohols having 1 to 8 carbon atoms or carboxyl groups. Amino resin containing etc. can also be used. These amino resins are usually prepared by adding about 0.5 to about 2 equivalents of formaldehyde to 1 equivalent of an amino group using a pH adjuster (e.g., ammonia, sodium hydroxide, amines) under alkaline or acidic conditions. It can be produced by reacting by a method known per se.
[0064]
When the amino-curable resin coating is used as an organic solvent, the resin is obtained by dissolving or dispersing the above resin in an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as heptane, toluene, xylene, octane, and mineral spirits; ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl cellosolve acetate, and butyl carbitol acetate; and methyl ethyl ketone. Ketone solvents such as methyl isobutyl ketone and diisobutyl ketone, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, sec-butanol and isobutanol, n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether solvents such as ether can be used.
[0065]
When used as an aqueous solution, an acrylic resin or polyester resin having an acid group introduced therein by an acid monomer (usually having an acid value in the range of 5 to 300 mgKOH / g, preferably 100 mgKOH / g) is neutralized with a neutralizing agent. It is obtained by dissolving or dispersing the hydrated resin in water.
[0066]
As the neutralizing agent, for example, ammonia or a basic substance such as amines such as triethylamine, monoethanolamine, diethanolamine, triethanolamine, and dimethylaminoethanol or hydroxides of alkali metals such as sodium hydroxide are used. Then, water and, if necessary, an organic solvent compatible with water are added to obtain an appropriate solid content, followed by dilution with water.
[0067]
Further, in addition to the above, the aqueous acrylic resin is, for example, an ionic or nonionic low-molecular or high-molecular surfactant, a water-soluble resin or the like as a dispersion stabilizer, the above-mentioned polymerizable monomer in an aqueous medium It can be produced by emulsion polymerization in a manner known per se.
[0068]
The mixing ratio (in terms of solid content) of the amino resin is in the range of about 10 to 200 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the hydroxyl group-containing resin solids.
[0069]
Isocyanate curable resin paint:
As the paint, for example, a composition comprising a base resin such as an acrylic resin, a vinyl resin, or a polyester resin having a crosslinkable functional group such as a hydroxyl group and a (block) polyisocyanate compound as a crosslinker Is raised.
[0070]
The polyisocyanate compound may be a free isocyanate compound or a blocked isocyanate compound. Examples of the polyisocyanate compound having a free isocyanate group include aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate, cycloaliphatic diisocyanates such as xylene diisocyanate or isophorone diisocyanate, tolylene diisocyanate or 4,4 '. Organic diisocyanates themselves such as aromatic diisocyanates such as diphenylmethane diisocyanate, or an adduct of an excess of each of these organic diisocyanates with a polyhydric alcohol, a low molecular weight polyester resin or water, or each of the organic diisocyanates listed above And further, isocyanate / bipellet products, and typical examples of commercially available products include "Varnock D" 750, -800, DN-950, -970 or 15-455 "(products of Dainippon Ink and Chemicals, Inc.)," Dismodule L, N, HL, or N3390 "(manufactured by Bayer AG, West Germany), "Takenate D-102, -202, -110 or -123N" (product of Takeda Pharmaceutical Co., Ltd.), "Coronate EH, L, HL or 203" (product of Nippon Polyurethane Industry Co., Ltd.) or "Duranate 24A-90CX" (Products of Asahi Kasei Corporation). Examples of the polyisocyanate compound having a blocked isocyanate group include those obtained by blocking a polyisocyanate compound having a free isocyanate group with a known blocking agent such as oxime, phenol, alcohol, lactam, malonate, and mercaptan. Can be Examples of these typical commercial products include "Barnock D-550" (product of Dainippon Ink and Chemicals, Inc.), "Takenate B-815-N" (product of Takeda Pharmaceutical Co., Ltd.), and "Aditol VXL". -80 "(a product of Hoechst AG, West Germany) or" Coronate 2507 "(a product of Nippon Polyurethane Industry Co., Ltd.)," Turanate 17B60PX "," Turanate TPA-B80X "," Turanate MF-B60X "," Turanate MF-K60X "," Turanate E402 ". -B80T "(a product of Asahi Kasei Corporation).
[0071]
The mixing ratio of the (block) polyisocyanate compound crosslinking agent may be such that the coating film is cured and has sufficient performance, but the ratio of the hydroxyl group-containing resin / crosslinking agent is 80/20 to 50 / by weight. A range of 50 is good.
[0072]
The paint can be used as an organic solvent-based paint obtained by dissolving or dispersing the above resin in the above organic solvent. Further, a resin in which an acid group is introduced by an acid monomer (usually an acid value within a range of 5 to 300 mg KOH / g, preferably 100 mg KOH / g) is used. It can be used as an aqueous coating obtained by dissolving or dispersing in water.
[0073]
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.
[0074]
As the epoxy resin, 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-epoxycyclohexylmethyl ( (Meth) acrylate), glycidyl (meth) acrylate, etc.), and a radical polymerizable monomer (eg, alkyl or cycloalkyl ester of (meth) acrylic acid having 1 to 24 carbon atoms, styrene, etc.) Eporide GT300 (trade name, manufactured by Daicel Chemical Industries, Ltd., trifunctional alicyclic epoxy resin), Eporide GT400 (trade name, manufactured by Daicel Chemical Industries, Ltd., trade name, tetrafunctional alicyclic) Epoxy resin), EHPE (manufactured by Daicel Chemical Industries, Ltd., trade name, trifunctional alicyclic epoxy) Resin), bisphenol epoxy resins, novolak epoxy resins, .epsilon.-caprolactam-modified bisphenol epoxy resins, polyvinyl cyclohexene diepoxide etc.] made modified with polycarboxylic acids to.
[0075]
Examples of the polycarboxylic acid include a polycarboxylic acid resin (eg, an acrylic resin and a polyester resin) and a polycarboxylic acid compound (eg, adipic acid, sebacic acid, and phthalic acid).
[0076]
The epoxy resin preferably has a number average molecular weight of about 500 to 20,000, particularly 700 to 10,000. Further, it is preferable that one molecule has an average of two or more epoxy groups.
[0077]
The acid-epoxy curable resin coating may be dissolved or dispersed in the above-mentioned organic solvent to be used as an organic solvent-based coating, or a water-dispersed aqueous coating obtained by neutralizing a carboxyl group with the above-described neutralizing agent. it can.
[0078]
In addition, the following hydrolyzable silane compound or resin can be blended and used with the paint as needed.
[0079]
Hydrolyzable silane curable resin paint:
As the paint, the compound containing a hydrolyzable silane group and / or a hydroxysilane group contains at least two hydrolyzable silane groups or hydroxysilane groups in one molecule, or at least one or more hydrolyzable silane groups and hydroxy groups. It is a paint containing a silane compound containing a silane 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) ethyltrimethoxy Epoxysilanes such as silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane; γ-mercaptopropyltrimethoxysilane, γ- Other silanes such as rucaptopropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, condensates of these silane compounds, and vinylsilanes Radical (co) polymer and the like.
[0080]
The hydrolyzable silane-curable resin coating is dissolved or dispersed in the above-mentioned organic solvent to form an organic solvent-based coating, or a carboxyl group is introduced as it is or in a copolymer (the above-mentioned carboxyl group-containing unsaturated monomer was used. The resulting carboxyl groups can be neutralized with the above-described neutralizing agent and used as a water-dispersed aqueous paint.
[0081]
Hydroxyl epoxy group curable resin paint:
As the coating material, an average of two or more, preferably three, epoxy group-containing functional groups having a structure in which an epoxy group is directly bonded to a resin having a hydroxyl group and an alicyclic skeleton and / or a bridged alicyclic skeleton is preferable. It is a paint containing the epoxy resin having the above as a curable resin component.
[0082]
As the resin having a hydroxyl group, for example, having a crosslinkable functional group such as a hydroxyl group described in the amino-curable resin coating, acrylic resin, vinyl resin, other than a base resin such as a polyester resin, for example, introduced by alkanolamine And a hydroxyl-opened product of caprolactone introduced into an epoxide compound, and a secondary hydroxyl group in an epoxy resin (a bisphenol-epichlorohydrin reaction product or the like).
[0083]
The content of the hydroxyl group is preferably in the range of 20 to 5,000, particularly 100 to 1,000 in terms of the hydroxyl equivalent, and particularly preferably the primary hydroxyl equivalent is in the range of 200 to 1,000. The resin having a hydroxyl group can have a cationic group. The cationic group enables aqueous conversion. This cationic group can be formed by, for example, a reaction between an epoxy group and a cationizing agent (such as an amine compound).
[0084]
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 5 to 6 members. It contains a saturated carbocyclic ring or a condensed ring obtained by condensing two or more such rings, and the bridged alicyclic skeleton has a straight chain between two carbon atoms constituting the above monocyclic or polycyclic ring. A chain or branched C1-6 (preferably C1-4) alkylene group [for example, -CH₂-, -CH₂CH₂-, -CH (CH₃)-, -CH₂  (CH₃) CH₂-, -C (CH₃)₂-, -CH (C₂H₅) CH₂-Etc.) (endmethylene, endethylene, etc.). The epoxy equivalent can usually be in the range of 100 to 2,000, preferably 150 to 500, more preferably 150 to 250, and the number average molecular weight is usually 400 to 100,000, preferably 700 to 50. Suitably, it is in the range of 3,000, more preferably 700 to 30,000. Such epoxy resins having two or more epoxy group-containing functional groups in one molecule [component (B)] are described in, for example, JP-B-56-8016, JP-A-57-47365, and JP-A-60-47605. No. 166675, JP-A-63-221121, JP-A-63-234028, and the like, and those known per se can be used.
[0085]
Hydrazine curable resin paint:
As the paint, a hydrazide group (—CO—NH—NH₂    ) Is a coating material which forms a crosslinked structure by reacting a polyhydrazide compound containing two or more compounds with a carbonyl group-containing compound.
[0086]
Representative specific examples of polyhydrazide compounds include, for example, dihydrazide such as carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, eicoic acid dihydrazide, and the like. C2-40 aliphatic carboxylic acid dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, pyromellitic dihydrazide, aromatic polyhydrazide such as trihydrazide pyromellitic acid, tetrahydrazide pyromellitic acid, and maleic dihydrazide, Monoolefinically unsaturated dihydrazides such as fumaric dihydrazide and itaconic dihydrazide, bissemicarbazide, polyacrylic polyhydrazide, 1,3-bis (hydr) Raj / Karuboechiru) -5 and other polyhydrazides such as isopropyl hydantoin and the like.
[0087]
The compounding ratio of the polyhydrazide compound is in the range of 0.1 to 2 equivalents, preferably 0.2 to 1 equivalent, relative to the carbonyl group of the carbonyl group-containing compound.
[0088]
As the carbonyl group-containing compound, a polymer of the following carbonyl group-containing unsaturated monomer or, if necessary, a copolymer with the above-mentioned other unsaturated monomer capable of undergoing a radical polymerization reaction can be used.
[0089]
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 monoolefinically unsaturated aldehyde compound and a keto group. Compound. Representative examples include, for example, diacetone (meth) acrylamide, acrolein, formylstyrene, (meth) acrylamide pivalinaldehyde, diacetone (meth) acrylate, acetonyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Acetyl acetate, vinyl alkyl ketone and the like can be mentioned. Of these, diacetone (meth) acrylamide is preferred.
[0090]
Oxidation polymerization type curable resin paint:
As the paint, a paint containing an unsaturated fatty acid which is conventionally crosslinked by air oxidation polymerization as a curing component is used. The iodine value of the paint is preferably in the range of 35 to 90. The iodine value is measured according to the method of JIS K-0070. If the iodine value is less than 30, the oxidative polymerization ability becomes insufficient and the curability deteriorates. Conversely, if the iodine value exceeds 100, the storage stability of the paint will deteriorate.
[0091]
As the unsaturated fatty acid, any of natural or synthetic unsaturated fatty acids can be used, and examples thereof include those obtained from tung oil, linseed oil, castor oil, dehydrated castor oil, safflower oil, tall oil, soybean oil, and coconut oil. And saturated fatty acids. One or more of the above fatty acids may be used at the same time.
[0092]
Examples of the type of paint using the unsaturated fatty acid include alkyd resins and epoxy-modified alkyd resins.
[0093]
The alkyd resin is obtained, for example, by holding the above-mentioned drying oil or semi-dry oil with at least one or more polyhydric alcohols at 200 to 250 ° C for 10 to 100 minutes with good stirring. If necessary, a low molecular weight alkyd resin obtained by adding a polybasic acid, a polyhydric alcohol or the like and then reacting at 200 to 250 ° C. may be used.
[0094]
Examples of 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, and monoalkyl ethers such as neopentyl glycol and diethyl propane. Examples thereof include diol, ethylbutylpropanediol, cyclohexanedimethanol, butylene glycol, pentanediol, hexanediol, hydrogenated bisphenol A, an ethylene glycol adduct of bisphenol A, trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol.
[0095]
Examples of polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic anhydride, succinic acid, adipic acid, sebacic acid, benzoic acid, alkylbenzoic acid, maleic anhydride, and itaconic anhydride. And monocarboxylic and polycarboxylic acids such as fumaric acid. One or more of these can be mixed and used in an arbitrary ratio.
[0096]
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 placed in a suitable solvent (e.g., toluene, xylene, etc.) at 150 to 250 [deg.] C. under an inert gas (e.g., nitrogen gas, etc.) atmosphere as necessary using a condensation catalyst. , Until the desired acid value is reached. Examples of the epoxy resin include “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, “Epicoat 1007”, and “Epicoat 1009” (all bisphenol A epoxy resins manufactured by Shell); “Epotote YD-128”, “Epotote YD-011”, “Epotote YD-012”, “Epotote YD-014”, “Epotote YD-017” and “Epotote YD-019” (manufactured by Toto Kasei Co., Ltd., bisphenol A type Epoxy resin); commercially available epoxy resins such as "Epototo ST-5700" (manufactured by Toto Kasei Co., hydrogenated bisphenol A epoxy resin) and "Epotote YDF-2004" (Toto Kasei Co., Ltd., bisphenol F epoxy resin) Can be used. One or more of the above epoxy resins may be used simultaneously.
[0097]
Those obtained by reacting the above-mentioned epoxy ester resin with an ethylenically unsaturated monomer to obtain an acrylic-modified epoxy ester resin can also be used. Ethylenically unsaturated monomers include styrene, unsaturated carboxylic acids such as (meth) acrylic acid, maleic anhydride and itaconic acid, (meth) acrylic esters, and mixtures thereof. It is essential that at least one of the above acrylic monomers contains a carboxylic acid group, and one or more acrylic monomers are used as a mixture with styrene.
[0098]
The oxidative polymerization type curable resin paint may be in any of an organic solvent-based, solvent-free, and water-based form.
[0099]
The drying agent that can be used is not particularly limited. For example, an aliphatic carboxylic acid such as oleic acid, a metal soap such as a cobalt salt, a manganese salt, a zirconium salt, a calcium salt, an iron salt, and a lead salt using an alicyclic carboxylic acid such as naphthenic acid as a carrier, or the compound is an anionic emulsifier. And tertiary amines such as dimethylaniline, diethylaniline, dimethylparatoluidine, etc., which are made aqueous by adding a cationic emulsifier, a nonionic emulsifier, or the like. These can be used alone or in combination.
[0100]
The amount of addition is not particularly limited, but is preferably in the range of 0.003 to 0.5% by weight. When the content is less than 0.003% by weight (metal content), the effect is not recognized. When the content is more than 0.5% by weight (metal content), there are disadvantages such as deterioration of water resistance. A more preferred amount is in the range of 0.05 to 0.4% by weight (metal content).
[0101]
Light (heat) radical polymerization type resin paint:
As the paint, there can be used a mixture of an unsaturated resin which undergoes a radical polymerization reaction by light or heat and, if necessary, a UV polymerization initiator, a peroxide catalyst and a photosensitizing dye.
As the unsaturated resin, for example, a resin having a radical polymerizable unsaturated group introduced into a resin such as a urethane resin, an acrylic resin, an alkyd resin, a polyester resin, a silicone resin, a fluororesin, a spirane resin, a polyether resin, and an epoxy resin. It is. Examples of the radical polymerizable unsaturated group include a vinyl group, a (meth) acryloyl group, a styryl group, and a group derived from maleic acid.
Representative examples of the unsaturated resin include, for example, urethane resin acrylate, acrylic resin acrylate, acrylic resin malate, alkyd resin acrylate, polyester resin acrylate, polyester resin malate, fluororesin acrylate, spirane resin acrylate, polyether resin acrylate, epoxy resin Acrylate and the like.
[0102]
As the ultraviolet polymerization initiator, a conventionally known one can be used.
[0103]
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 Acetophenone compounds such as -hydroxyphenoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinepropane-1 , Thioxanthone, 2-chlorothioxanthone, 2- Thioxanthone compounds such as tylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone and 2,4-dichlorothioxanthone; benzoin compounds such as benzoin and benzoinmethyl ether; dimethylbenzylketal and acylophosphine oxide. Can be Of these, acetophenone compounds are preferred.
[0104]
It is generally preferable that about 0.1 to 10 parts by weight of the above-mentioned ultraviolet polymerization initiator is blended with respect to 100 parts by weight of the total amount of the unsaturated resin.
[0105]
Further, a photopolymerization accelerator can be blended in order to accelerate the photocrosslinking reaction by the above-mentioned ultraviolet polymerization initiator. Specifically, for example, tertiary amines such as triethylamine, triethanolamine and 2-dimethylaminoethanol, alkylphosphines such as triphenylphosphine, and thiols such as β-thioglycol. No.
As the photosensitizer, a conventionally known photosensitizing dye can be used. Examples thereof include thioxanthenes, xanthenes, ketones, thiopyrylium salts, basestyryl, merocyanines, 3-substituted coumarins, 3.4-substituted coumarins, cyanines, acridines, and thiazines. And phenothiazine, anthracene, coronene, benzanthracene, perylene, merocyanine, ketocoumarin, fumaline, and borate dyes. These can be used alone or in combination of two or more. Examples of the borate-based photosensitizing dye include those described in JP-A-5-241338, JP-A-7-5685, and JP-A-7-225474.
[0106]
Further, as a light irradiation source, those 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, fluorescent lamp, A light source obtained from each light source such as a tungsten lamp and sunlight can be used. Examples of the heat ray include a semiconductor laser (830 nm), a YAG laser (1.06 μm), and infrared rays.
[0107]
Light (heat) cationic polymerization type resin paint:
The coating material is a coating material in which a cationic photopolymerizable compound is irradiated with light under a cationic photopolymerization initiator and a photosensitizer to increase the molecular weight by a crosslinking or polymerization reaction.
[0108]
Examples of the photo (thermal) cationic polymerizable compound include epoxy compounds, styrenes, vinyl compounds, vinyl ethers, spiro ortho esters, bicyclo ortho esters, spiro ortho carbonates, cyclic ethers, lactones, oxazolines. , Aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams, alkoxysilane compounds, aryl dialdehydes and the like.
[0109]
Examples of the epoxy compound include conventionally known aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.
[0110]
Examples of the aromatic epoxy compound include a monofunctional epoxy compound such as phenylglycidyl ether and a polyglycidyl ether of a polyhydric phenol having at least one aromatic ring or an alkylene oxide adduct thereof, such as bisphenol A. Glycidyl ethers and novolak type produced by reacting bisphenol compounds such as tetrabromobisphenol A, bisphenol F and bisphenol S or alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of bisphenol compounds with epichlorohydrin Epoxy resins (for example, phenol novolak epoxy resin, cresol novolak epoxy resin, brominated phenol novolak epoxy resin Etc.), etc. trisphenolmethane triglycidyl ether.
[0111]
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-epoxy) Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, BHPE-3150 (Daicel Chemical Industries, Ltd. stock) And alicyclic epoxy resin (softening point 71 ° C.) and the like.
[0112]
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, and propylene glycol monoglycol. Glycidyl 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, trimethylolpropane mono Glycidyl ether, trimethylolpropane triglycidide Ether, diglycerol triglycidyl ether, sorbitol tetra glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether.
[0113]
Examples of the styrenes include styrene, α-methylstyrene, p-methylstyrene, p-chloromethylstyrene, and the like. Examples of the vinyl compound include N-vinylcarbazole and N-vinylpyrrolidone.
[0114]
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, and triethylene glycol divinyl ether. Vinyl 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 , Trimethylol Pro Trivinyl ether, diglycerol 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 ) Alkyl vinyl ethers such as trifluoropropane divinyl ether, alkenyl vinyl ethers such as allyl vinyl ether, alkynyl vinyl ethers such as ethynyl vinyl ether, 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 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.
[0115]
Examples of spiro ortho esters include 1,4,6-trioxaspiro (4,4) nonane, 2-methyl-1,4,6-trioxaspiro (4,4) nonane, 1,4,6-trio Xaspiro (4,5) decane and the like are bicycloorthoesters such as 1-phenyl-4-ethyl-2,6,7-trioxabicyclo (2,2,2) octane and 1-ethyl-4- Hydroxymethyl-2,6,7-trioxabicyclo (2,2,2) octane and the like, as spiroorthocarbonates, 1,5,7,11-tetraoxaspiro (5,5) undecane, 3,3 Cyclic ethers such as 9-dibenzyl-1,5,7,11-tetraoxaspiro (5,5) undecane;
[0116]
Examples of the cyclic ethers include oxetanes such as oxetane and phenyloxetane; tetrahydrofurans such as tetrahydrofuran and 2-methyltetrahydrofuran; tetrahydrobilanes such as tetrahydrosilane and 3-propyltetrahydrosilane; trimethylene oxide; and s-trioxane. Can be Examples of the lactones include β-propiolactone, γ-butyllactone, δ-caprolactone, δ-valerolactone, and the like. Examples of oxazolines include oxazoline, 2-phenyloxazoline, 2-decyloxazoline and the like.
[0117]
Examples of the aziridine include aziridine and N-ethylaziridine. Examples of cyclosiloxanes include hexamethyltrisiloxane, octamethylcyclotetrasiloxane, and triphenyltrimethylcyclotrisiloxane. Examples of ketals include 1,3-dioxolan, 1,3-dioxane, 2,2-dimethyl-1,3-dioxane, 2-phenyl-1,3-dioxane, and 2,2-dioctyl-1,3-dioxane. Oxolan and the like. The cyclic acid anhydrides include phthalic anhydride, maleic anhydride, succinic anhydride and the like, and the lactams include β-propiolactam, γ-butyrolactam, δ-caprolactam and the like. Examples of the aryl dialdehydes include 1,2-benzenedicarboxaldehyde, 1,2-naphthalenedialdehyde, and the like.
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 the photocationic polymerizable compound. When the amount of the photosensitizer is less than 0.01 part by weight, the curability is reduced. On the other hand, when the amount is more than 10 parts by weight, the cost is increased and the coating properties such as water resistance are deteriorated.
[0118]
As the photocationic polymerization initiator, conventionally known ones can be used. Preferred initiators include, for example, aryldiazonium salts, aryliodonium salts, arylsulfonium salts and the like. Specifically, as the trade names, for example, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-6950 (all trade names, manufactured by Union Carbide Co., USA), Irgacure 261 (Ciba Specialty Chemicals) SP-150, SP-170 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), CG-24-61 (trade name, manufactured by Ciba Specialty Chemicals), DAICAT-II (trade name) CI-2834, CI-2758, CI-2855 (product name, manufactured by Nippon Soda Co., Ltd.), PI-2074 (product name, manufactured by Rhone Poulin Co., trade name, pentafluorophenyl borate toluyl) Cumyliodonium salt), FFC509 (manufactured by 3M, trade name), BI102 (Midori Chemical Co., Ltd., trade name) and the like.
[0119]
The photo-cationic polymerization agent is used in an amount of preferably 0.01 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the photo-cationic polymerizable compound. If the amount of the cationic photopolymerization initiator is less than 0.01 part by weight, the curability is reduced. On the other hand, if the amount is more than 20 parts by weight, the cost is increased and the coating properties such as water resistance are undesirably reduced.
[0120]
Examples of the light source used for the active energy ray include, but are not particularly limited to, ultrahigh pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, tungsten lamps, and the like, and argon lasers (488 nm). ), YAG-SHG laser (532 nm), and UV laser (351-364 nm) having an oscillation line can also be used. Examples of the heat ray include a semiconductor laser (830 nm), a YAG laser (1.06 μm), and infrared rays.
[0121]
The colored film of the present invention is obtained by bonding the bonding agent (I) surface side to films of various plastics including PVC, acrylic, and polycarbonate, steel plates, plate materials, and the like (hereinafter, referred to as adherends) to obtain weather resistance, By imparting functions such as light resistance, moisture resistance, heat resistance, stain resistance, water repellency, and boiling water resistance to the adherend surface, interior building materials, exterior building materials, decorative articles, packaging, protective films, guidance, notices, It is a functional film that can be used for a wide range of applications such as black tape for marking, storage, automobile sash, side garnish, emblem, design stripe, and door molding.
[0122]
In the case of forming a fine uneven pattern (hereinafter referred to as “texture”) on the surface of the layer by embossing or kneading under moist heat conditions, the colored film of the present invention also has the above texture. Such a grain may be formed.
[0123]
The method for producing a colored film of the present invention can be produced without any particular limitation. Specifically, for example, an aqueous resin urethane dispersion is applied to the surface (adhesive layer surface) of an adhesive film having a bonding agent layer (I) on one surface of a polypropylene sheet (release paper), and then dried to clear. After forming a layer (II) and then applying an aqueous colorant, drying is performed to form a colored layer (III), and then a crosslinkable resin paint (C) is applied, and then the applied coating film is cured. A clear layer (IV) can be formed. The curing conditions for the clear layer (IV) can be set as appropriate depending on the type of the paint.
[0124]
The colored film of the present invention can be bonded by heat or by pressure or by applying heat so that the bonding agent layer (I) of the colored film faces the surface of the adherend.
[0125]
Further, in the present invention, the colored film can be bonded to the surface of the adherend having a three-dimensional surface while being molded by heating. Molding by heating can be performed using a molding machine such as a mold or vacuum molding. These moldings can be performed by a conventionally known method.
[0126]
As the molding temperature, an appropriate temperature may be set according to the types of the colored film and the plastic material.
[0127]
In the molding process, for example, it is also possible to cross-link the colored film before the uncrosslinked colored film is formed so that the bonding agent (I) layer surface is in contact with the outer surface of the plastic molded product. is there.
[0128]
The present invention will be described in detail below with reference to examples. In the Examples and Comparative Examples, "parts" and "%" are based on weight. Further, the present invention is not limited to the embodiments.
[0129]
Example 1
Adhesive film: 50 parts by weight of SK Dyne A-1310 (manufactured by Soken Kagaku Co., Ltd., trade name, acrylic resin-based pressure-sensitive adhesive) on the surface of a 50 μm-thick polypropylene film (release paper) A mixed solution containing 10 parts by weight of a -5A curing agent was applied, and dried at 80 ° C. for 2 minutes to form an adhesive layer having a thickness of about 25 μm to obtain an adhesive film.
[0130]
Adhesive film: An adhesive film in which an acrylic resin-based pressure-sensitive adhesive layer of 30 μm is laminated on a 50 μm-thick polypropylene film (release paper).
[0131]
An aqueous urethane resin emulsion (Superflex 410, Daiichi Kogyo Seiyaku Co., Ltd., trade name) is applied on the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film with a knife coater, dried at 100 ° C. for 1 minute, and dried to a thickness of 50 μm. A resin layer was formed.
[0132]
Next, the following aqueous colorant (a) was applied to the surface of the obtained urethane resin layer by a knife coater and dried at 100 ° C. for 1 minute to form a urethane resin colored layer having a thickness of 30 μm.
[0133]
Further, on the surface of the urethane resin coloring layer, a urethane PG-80 clear (clear main agent / urethane PG80 curing agent = 100/25) (trade name, manufactured by Kansai Paint Co., Ltd., isocyanate-curable acrylic resin paint) is dried. The film was coated to a thickness of 30 μm and cured by heating at 140 ° C. for 1 minute to produce a metallic colored film.
[0134]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0135]
After the release paper of the obtained colored film is peeled off, it is stretched with a squeegee on a side mirror made of polypropylene for automobiles while being pressed and adhered and trimmed to obtain a metallic-colored polypropylene molded product (maximum elongation 200 times). Manufactured.
[0136]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0137]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0138]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then allowed to stand at room temperature for 2 hours. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0139]
Aqueous colorant (a): Aqueous urethane resin emulsion (Superflex 410, Daiichi Kogyo Seiyaku Co., Ltd., trade name) in 100 parts (solid content), aluminum flake aqueous paste ("Alpaste 7679NS") (Toyo Aluminum Co., Ltd., trade name, aluminum flake paste) 10 parts, "Laponite RD" 2 parts, "Dispalon AQ-600" 3 parts, high acid value acrylic resin (acid value 100 mg KOH / g, number average) 20 parts (solid content) obtained by mixing and dispersing 2 parts in deionized water (molecular weight: 70000) and stirring and mixing.
[0140]
Example 2
On the surface of the urethane resin colored layer used in Example 1, 2 moles of hexamethylene diisocyanate was reacted with 1 mole of urethane diacrylate (polyester diol "phthalic anhydride / neopentyl glycol"). 75 parts by weight of an average molecular weight of about 3000 oligomers obtained by reacting 2 mol of 2-hydroxyethyl acrylate with respect to 1 mol of the terminal isocyanate group-containing polyester thus obtained, 10 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, 5 parts by weight of an acetophenone-based initiator of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, 2,4 -4 parts by weight of a thioxanthone-based initiator of dimethylthioxanthone] so that the film thickness becomes 10 microns. - by irradiating ultraviolet rays to obtain a clear coating under conditions of screen printing to 500 mj / cm @ 2.
[0141]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0142]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0143]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0144]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0145]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then allowed to stand at room temperature for 2 hours. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0146]
Example 3
300 parts of linseed oil, 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 into a clean container in which nitrogen gas was refluxed, and heated to 250 ° C. while stirring. After holding for 1 hour, the mixture was cooled to 200 ° C, 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, and then cooled to 150 ° C. After adding 27 parts of phthalic anhydride and stirring for 2 hours, 465 parts of n-butyl cellosolve and 75 parts of triethylamine were added and stirred well to obtain a viscous resin liquid having a nonvolatile content of 65%.
[0147]
The resin solution described above was applied to the surface of the urethane resin colored layer used in Example 1, and dried at 80 ° C. for 20 minutes to obtain a clear coating of 20 μm.
[0148]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0149]
After the release paper of the obtained colored film is peeled off, it is stretched with a squeegee on a side mirror made of polypropylene for automobiles while being pressed and adhered and trimmed to obtain a metallic-colored polypropylene molded product (maximum elongation 200 times). Manufactured.
[0150]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0151]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0152]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then allowed to stand at room temperature for 2 hours. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0153]
Example 4
On the surface of the urethane resin colored layer used in Example 1, Soflex 1630 Clear (Kansai Paint Co., Ltd., trade name, melamine-curable acrylic resin-based clear) was applied to the above-mentioned release paper, and the resin solution was applied. And dried at 80 ° C. for 20 minutes to obtain a 20 μm clear coating.
[0154]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0155]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0156]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0157]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0158]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0159]
Example 5
On the surface of the urethane resin colored layer used in Example 1, KINO # 400 clear (Kansai Paint Co., Ltd., trade name, acid epoxy-curable acrylic resin-based clear) was coated with the resin solution on the release paper described above. Then, it was dried at 80 ° C. for 20 minutes to obtain a clear coating of 20 μm.
[0160]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0161]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0162]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0163]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0164]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0165]
Example 6
After 85 parts of toluene was charged into a clean container in which a nitrogen gas was refluxed and heated to 110 ° C., 10 parts of styrene, 20 parts of methyl methacrylate, 65 parts of isobutyl methacrylate, γ-methacryloxypropyl trimethoxysilane A solution in which 2 parts of a polymerization initiator 2,2-azobis (2-methylbutyronitrile) was dissolved in 5 parts of a mixed solution was added dropwise over about 3 hours. After completion of the dropwise addition, the mixture was left 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 measured by DSC was 64 ° C., and the weight-average molecular weight measured by GPC (gel permeation chromatography → gel permeation chromatography) was 16,000.
[0166]
A solution in which 0.01 part of Neostan U-100 (manufactured by Nitto Kasei Co., Ltd., organic tin compound) was mixed with 100 parts of the obtained resin solution was coated on the surface of the urethane colored film similar to that obtained in Example 1, It was coated with a knife coater and dried at 80 ° C. for 20 minutes to obtain a 20 μm-thick clear film).
[0167]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0168]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0169]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0170]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0171]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0172]
Example 7
To a clean container, 242 parts of deionized water and 2.4 parts of Newcol 707SF (Daiichi Kogyo Seiyaku Co., Ltd., trade name, solid content: 30%) are added, and the mixture is kept at 80 ° C. after purging with nitrogen. Immediately before dropping a pre-emulsion having the following composition, 0.7 parts of ammonium sulfate was added, and the pre-emulsion was dropped over 3 hours.
352 parts of deionized water
33 parts of diacetone acrylamide
Acrylic acid 3.3 parts
Styrene 134 parts
255 parts of methyl methacrylate
147 parts of 2-ethylhexyl acrylate
98 parts of n-butyl acrylate
Newcol 707SF 64.5 parts
1.3 parts of ammonium persulfate
From 30 minutes after the completion of the dropwise addition, a solution prepared by dissolving 7 parts of ammonium persulfate in 7 parts of deionized water was added dropwise for 30 minutes and kept at 80 ° C. for 2 hours to obtain a hydrazine-curable acrylic emulsion having a nonvolatile content of 51%. Obtained.
To this hydrazine-curable acrylic emulsion solution, adipic dihydrazide as a cross-linking agent was adjusted to pH 8 to 9 with aqueous ammonia, and a solution obtained by mixing 0.3 equivalent of hydrazide group with respect to 1 equivalent of carbonyl group was mixed with a knife coater. The same urethane colored film as that obtained in Example 1 was coated on the surface and dried at 80 ° C. for 10 minutes to obtain a clear film having a thickness of 20 μm.
[0173]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0174]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0175]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0176]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0177]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0178]
Example 8
After 85 parts of toluene was charged into a clean container in which nitrogen gas was refluxed and heated to 110 ° C., 20 parts of styrene, 20 parts of methyl methacrylate, 30 parts of n-butyl methacrylate and 30 parts of glycidyl methacrylate 30 were used. Of a polymerization initiator and 4 parts of a polymerization initiator 2,2-azobis (2-methylbutyronitrile) were added dropwise over about 3 hours. After completion of the dropwise addition, the mixture was allowed to stand at 110 ° C. for 5 hours, charged with 15 parts of acrylic acid, 0.05 parts of hydroquinone monomethyl ether and 0.2 parts of tetraethylammonium bromide, and reacted at 110 ° C. for 5 hours while blowing air thereinto. After confirming that the value was almost 0, 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 the resin solution measured by DSC was 37 ° C., the number average molecular weight measured by GPC (gel permeation chromatography → gel permeation chromatography?) Was 5,000, and the average number of unsaturated groups contained in one molecule. Was 9.0.
Next, a solution obtained by mixing 2 parts of “Irgacure 184” (a photo-radical polymerization initiator manufactured by Ciba Specialty Chemicals Co., Ltd.) with 100 parts of the obtained resin solution was applied to the urethane used in Example 1 using a knife coater. The surface of the colored film was coated and irradiated with ultraviolet light under the condition of 1000 mj / cm 2 to obtain a clear film (thickness: 30 μm).
[0179]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0180]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0181]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0182]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0183]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0184]
Example 9
A solution obtained by mixing 2 parts of "Perbutyl Z" (trade name, peroxide, manufactured by NOF CORPORATION) with 100 parts of the above-described radical-curable acrylic resin solution was obtained in the same manner as that obtained in Example 1 using a knife coater. The surface of the urethane colored film was coated and dried at 120 ° C. for 10 minutes to obtain a clear film having a thickness of 30 μm.
[0185]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0186]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0187]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0188]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0189]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0190]
Example 10
85 parts of toluene was charged into a clean container in which a nitrogen gas was refluxed, heated to 110 ° C., and then 3.4 parts of epoxycyclohexylmethyl acrylate, 20 parts of methyl methacrylate, and n-butyl methacrylate were added. A solution in which 2 parts of a polymerization initiator 2,2-azobis (2-methylbutyronitrile) was dissolved in 40 parts of a mixed solution was dropped over about 3 hours. After completion of the dropwise addition, the mixture was left 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 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 8,000, and the number of epoxy groups in one molecule was 17.6.
A solution in which 0.5 part of “Siracure UVI-6990” (manufactured by Union Carbide Co., Ltd., photocationic radical polymerization initiator) was mixed with 100 parts of the obtained resin solution was obtained in Example 1 with a knife coater. The same urethane-colored coating was coated on the surface and irradiated with ultraviolet light at 1000 mj / cm 2 to obtain a 30 μm-thick clear coating.
[0191]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0192]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0193]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0194]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0195]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0196]
Example 11
A solution obtained by mixing 2 parts of "San-Aid SI-80L" (trade name, peroxide, manufactured by NOF CORPORATION) with 100 parts of the above-mentioned cation-curable acrylic resin solution is the same as that obtained in Example 1 with a knife coater. The surface of the urethane colored film was coated and dried at 110 ° C. for 10 minutes to obtain a clear film having a thickness of 20 μm.
[0197]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0198]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0199]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0200]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0201]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0202]
Example 12
On the surface of the urethane colored film used in Example 1, 100 parts of urethane PG-80 quartz Z base (Kansai Paint Co., Ltd., trade name, clear) and 50 parts of Duranate MF-K60X (Asahi Kasei, trade name) , Block isocyanate) was applied to a dry film thickness of 20 μm and dried at 80 ° C. for 10 minutes to produce a colored film.
[0203]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0204]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0205]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0206]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0207]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0208]
Example 13
A coating was formed in the same manner as in Example 1 except that the following aqueous urethane resin emulsion (a) was used in place of the aqueous urethane resin emulsion used for the clear and colored paints.
[0209]
The tensile elongation at break of the urethane resin layer and the urethane resin colored layer was 170% at -10 ° C.
[0210]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0211]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0212]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0213]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0214]
Aqueous urethane resin emulsion (a):
350 parts of polyester polyol (butylene adipate, molecular weight 2000), 10.1 parts of trimethylolpropane, 35 parts of polyethylene glycol (molecular weight 600), random copolymer of PO (propylene oxide) / EO (ethylene oxide) After adding and dissolving 35 parts of terpolyol (PO / EO = 30/70, molecular weight 3400) and 78.3 parts of 1,4-butanediol in 400 parts of methyl ethyl ketone, 310 parts of isophorone diisocyanate is heated to a system temperature of 50 parts. C. was added. Thereafter, 0.05 parts of dibutyltin dilaurate was added, and the system was gradually heated to a system temperature of 75 ° C. At the stage where the reaction was carried out at 75 ° C. for 60 minutes, 0.05 part of dibutyltin dilaurate was further added. Thereafter, the reaction was continued and the system was cooled when 75 ° C./200 minutes had elapsed, and the internal temperature of the system was set to 50 ° C. After cooling to 50 ° C., the free isocyanate groups of the urethane prepolymer were 2.0% (based on solids).
Next, at a system temperature of 45 ° C., 80 parts of a polyoxyetherene allylphenol ether type nonionic surfactant (HLB = 15), which is an ethylene oxide adduct of distyrenated phenol, was added, and 10 parts were added. Mix for minutes. Thereafter, the contents in the system were stirred at a high speed of 3000 rpm using a homomixer, and 1300 parts of distilled water was gradually added thereto, and thereafter, emulsification was performed at a system temperature of 30 ° C. for 20 minutes.
After further cooling the system temperature to 20 ° C., an ethylenediamine aqueous solution in which 10.5 parts of ethylenediamine was dissolved in 130 parts of distilled water was added.
The temperature in the system was controlled at 20 to 25 ° C, and stirring was continued at 3000 rpm for 60 minutes using a homomixer.
Next, the solvent used, methyl ethyl ketone, was recovered under reduced pressure (water bath 40 ° C.) using an evaporator to obtain an aqueous urethane resin emulsion (a).
[0215]
Example 14
A coating film was formed in the same manner as in Example 1 except that the following aqueous urethane resin emulsion (b) was used instead of the aqueous urethane resin emulsion used for the clear and coloring paints.
The tensile elongation at break of the urethane coating was 170% at -10 ° C.
[0216]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0219]
The obtained molded polypropylene product had good appearance without any defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like in both the curved surface portion and the flat surface portion.
[0218]
After immersing the molded polypropylene product in water at 40 ° C. for 20 days, the colored film was peeled off, the blisters were observed, and the gloss was reduced. Was.
[0219]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate. The wrinkles, blisters, bubbles, and gloss reduction were observed at the portion where the colored film was attached. The appearance was good without defects such as peeling and cracking.
[0220]
Aqueous urethane resin emulsion (b):
To 255 parts of polycarbonate (polycarbonate of 1,6 hexane, molecular weight: 2,000), 7.0 parts of trimethylolpropane and 57.0 parts of 1,4-butanediol were added, and then methyl ethyl ketone was added. 290 parts 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 and reacted at a system temperature of 75 ° C. for 180 minutes to form free isocyanate groups of 5 parts. A urethane prepolymer containing 0.0% (based on solid content) was obtained. Next, 26.5 parts of dimethylolpropionic acid and 120 parts of methyl ethyl ketone were added thereto, then 0.07 part of dibutyltin dilaurate was added, and 9.9 parts of triethylamine was further added. This was gradually heated, and the system temperature was cooled to 50 ° C. to obtain a urethane prepolymer containing 1.99% of free isocyanate groups (based on solid content) and carboxyl groups.
Next, 9.9 parts of triethylamine was added thereto at a system temperature of 50 ° C. to neutralize the remaining carboxyl groups. Thereafter, 900 parts of distilled water was gradually added, and the mixture was stirred at 3000 rpm using a homomixer, and emulsification was performed at a system temperature of 25 ° C for 20 minutes.
Next, an ethylenediamine aqueous solution in which 7.8 parts of ethylenediamine was dissolved in 80 parts of distilled water was added at a system temperature of 25 ° C, and the mixture was stirred and mixed at 25 ° C for 60 minutes.
Thereafter, the solvent used, methyl ethyl ketone, was recovered under reduced pressure (water bath 40 ° C.) using an evaporator to obtain an aqueous urethane resin emulsion (b).
[0221]
Comparative Example 1
In Example 1, a urethane 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 and dried at 80 ° C. for 20 minutes to clear. Acrylic # 2000 Clear- (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) is applied by spray coating to a thickness of 20 μm, and dried at 80 ° C. for 10 minutes to be non-crosslinkable. A laminated coating of Example 1 was obtained in the same manner as in Example 1 except that a clear coating film was formed.
[0222]
As a result of sticking in the same manner as in Example 1, the obtained polypropylene molded product had a good appearance without defects such as wrinkles, blisters, bubbles, gloss reduction, peeling, cracks and the like on both the curved surface portion and the flat surface portion.
[0223]
After the polypropylene molded article was immersed in water at 40 ° C. for 20 days, defects such as peeling, blistering, and reduction in gloss were observed on the portion where the colored film was adhered.
[0224]
In order to evaluate the volatile oil resistance of the polypropylene molded product, the product was immersed in gasoline for 5 hours and then left at room temperature for 2 hours to evaluate the product. And the oil resistance was poor.
[0225]
Comparative Example 2
Acrylic # 2000 metallic (Kansai Paint Co., Ltd., trade name, acrylic lacquer paint) was applied to a soft polyvinyl chloride film having the same adhesive as in Example 1 by spray coating so as to have a thickness of 20 μm. Dry for 10 minutes to form a non-crosslinkable clear coating film, and then apply a urethane PG-80 metallic (manufactured by Kansai Paint Co., Ltd., trade name, isocyanate-curable acrylic resin paint) to a dry film thickness of 10 μm. Then, drying was performed at 80 ° C. for 20 minutes to form a clear coating film, thereby obtaining a multilayer coating film of Comparative Example 2.
[0226]
After the release paper of the obtained colored film is peeled off, the film is stretched by using a squeegee on a side mirror made of an automobile for automobiles, and then adhered and trimmed to obtain a metallic polypropylene molded product (maximum elongation 200 times). Manufactured.
[0227]
The obtained molded polypropylene product had defects such as a decrease in gloss and cracks in both the curved surface portion and the flat surface portion, and the film was poor in workability in sticking.
[0228]
After the polypropylene molded product was immersed in water at 40 ° C. for 20 days, the portion where the colored film was adhered was peeled off, and the presence or absence of defects such as blisters and gloss reduction was examined. Met.
[0229]
Also, as to evaluate the volatile oil property of the polypropylene molded product, a portion having a good appearance was selected, immersed in gasoline for 5 hours, and then left at room temperature for 2 hours to evaluate. It was good without defects such as blisters, bubbles, gloss reduction, peeling, cracks and the like.
[0230]
In the colored film of the present invention, the thermosetting coating layer is used as a surface layer, while the urethane resin layer is used as a mounting surface for furniture, vehicles or buildings. In this attachment, the layers (II) and (III) have excellent flexibility and elongation, so that defects such as wrinkles due to attachment of the film do not occur, so that the finished appearance is excellent. Further, when an external object such as pebbles or sand collides with the surface of the attached colored film, the surface (IV) has a high hardness and absorbs energy due to impact from the surface in (II) and (III). Therefore, 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 despite the high surface hardness. In addition, since the surface layer is formed with a crosslinked coating film, it exhibits excellent performance in chemical resistance, stain resistance, and abrasion resistance.
[0231]
In addition, since it is not necessary to apply a cross-linkable resin paint such as a conventional melamine-curable resin paint, an isocyanate-curable resin paint, or an oxidatively-curable resin paint to the base material directly, it is not necessary to apply the coating means, coating film in advance. A suitable method can be selected depending on the purpose of coating such as performance and design. It is possible to safely perform the work environment and safety and health management of the coating, because the coating does not easily cause coating defects and the coating required for the coating is not consumed more than necessary. Further, it is easy to collect the coated film, which is preferable from the viewpoint of environmental pollution.
[0232]
Even in a molding process (100% or more) requiring a high elongation, the film has excellent elongation, tension, and bending force, so that a molded product excellent in finished appearance without gloss reduction, cracking, or peeling can be obtained.
[0233]
Furthermore, since the aqueous urethane resin dispersion is used as the clear layer (II) formed on the surface of the bonding agent layer (I), the aqueous layer is intermingled with each other at the interface between the bonding agent layer (I) and the clear layer (II). There is no danger of a mixed layer being formed or the components forming one layer permeating into the other layer, so that the functions of these layers are effectively exhibited without being impeded. effective.

Claims (4)

An optional release layer, a bonding agent layer (I) formed of an adhesive or an adhesive, an aqueous urethane resin dispersion (A), and the formed layer itself is substantially Has no tackiness and has a tensile elongation at break (a value measured at a tensile speed of 200 mm / min at −10 ° C. for a sample having a length of 30 mm, a width of 10 mm, and a thickness of 0.05 mm) in the range of 50 to 1000%. The clear layer (II), the aqueous urethane resin dispersion (A) and the colorant (B) are formed, and the formed layer is substantially tack-free per se, and has a tensile elongation at break (length of 30 mm, A colored layer (III) having a width of 10 to 10% in a sample having a width of 10 mm and a thickness of 0.05 mm measured at −10 ° C. at a tensile speed of 200 mm / min) and a crosslinkable resin paint (C) Chestnut Colored film characterized by comprising sequentially laminated over layer (IV). The aqueous urethane resin dispersion (A) is reacted with a polyisocyanate compound and 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. Is dispersed in water and further chain-extended with an amine. 3. A method for bonding a colored film according to claim 1 or 2, wherein the colored film is bonded by heat and / or pressure such that the bonding agent layer (I) of the colored film faces the surface of the adherend. Attachment method. Aqueous urethane emulsion (A) is applied to the surface of a bonding film of a bonding film having a releasing layer provided as necessary and a bonding agent layer (I) formed of an adhesive or an adhesive, and a clear layer is formed. (II) is formed, and then an aqueous colorant containing the aqueous urethane emulsion (A) and the colorant (B) is applied to form a colored layer (III), and further, a crosslinkable resin paint (C) And a clear layer (IV) is sequentially laminated thereon.