JP2012097248A - Curable resin composition for thermoforming film, and thermoforming film made by laminating the resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoforming film and a laminated product thereof equipped with surface hardness, not causing cracks on the film surface when molded into a deep-drawn shape molding, and excellent in chemical resistance so that the surface of the acrylic film remains free from roughening even when the molding attached with e.g. lotion or hand cream used for sunscreening is exposed as it is for long hours under a high temperature.SOLUTION: This curable resin composition for a thermoforming film contains a vinylic polymer (A) having a carboxy group and a hydroxy group, the acid value of its solid content is 15-150 mg-KOH/g and the hydroxyl value of its solid content is 2-80 mg-KOH/g, and its glass transition temperature is 70-140°C and a polyisocyanate compound (B), where the content of the polyisocyanate compound (B) is one reacting with the 2-80 mg-KOH/g hydroxyl value of the solid content of the vinylic polymer (A). The thermoforming resin film is obtained by laminating the curable resin composition in a thickness of 1-20 μm on one side the thermoforming film as the outermost layer.

Description

  The present invention relates to a curable resin composition for a thermoforming film, a thermoforming film formed by coating the composition, and uses thereof.

  As a method for imparting design properties to a molded product at a low cost, there are thermoforming methods such as an insert molding method and an in-mold molding method. In the insert molding method, a film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated by printing or the like is previously formed into a three-dimensional shape by vacuum forming or the like, and an unnecessary film or sheet portion is removed. Then, it is transferred into an injection mold, and a molded product integrated by injection molding of a resin as a base material is obtained. On the other hand, the in-mold molding method is a method in which a film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated for printing or the like is placed in an injection mold, subjected to vacuum molding, and then in the same mold. In this way, an integrated molded product is obtained by injection molding a resin as a base material.

  As a molded product using an acrylic resin film having excellent surface hardness and heat resistance that can be used for insert molding or in-mold molding (hereinafter referred to as an acrylic resin film molded product), a rubber-containing polymer having a specific composition, An acrylic resin film molded article obtained by mixing a thermoplastic polymer having a specific composition at a specific ratio has been proposed (see, for example, Patent Documents 1 and 2). Such an acrylic resin film molded product not only imparts decorativeness to the molded product, but also has a function as an alternative material for clear coating.

  These acrylic resin film molded articles have excellent characteristics as a skin material for vehicle interiors, but have a problem of low resistance to liquid agents, for example, sunscreen lotions. Has been proposed (see, for example, Patent Documents 3 and 4). However, in the photocurable resin composition, in order to ensure processability at the time of thermoforming, a new process occurs because curing by light irradiation must be performed after thermoforming, and uniform light irradiation of a three-dimensional molded product There exists such a subject (refer patent document 3). The thermosetting resin composition loses its thermoplasticity when cured, and has a problem of cracking during thermoforming (see Patent Document 4).

JP-A-8-323934 Japanese Patent Laid-Open No. 11-147237 JP 2005-163003 A JP 2008-265062 A

  The present invention has chemical resistance, for example, a lotion used to prevent sunburn, and the surface of the acrylic resin film does not become rough even if it is exposed to a high temperature for a long time with the hand cream attached, and it is molded into a deep-drawn molded product. It is an object of the present invention to provide a thermoforming film having no surface cracking and having a surface hardness, and a laminate molded product thereof.

  As a result of intensive studies, the present inventors have found that a vinyl polymer (A) having a carboxyl group and a hydroxyl group and having a specific solid content acid value and glass transition temperature and a specific ratio of a polyisocyanate compound (B). When the curable resin composition was laminated on a thermoforming film, it was found that a laminated film having excellent chemical resistance and excellent thermoformability and surface hardness could be formed, and the present invention was completed. That is, the above object is achieved by the following present invention.

“1” a vinyl polymer (A) having a carboxyl group and a hydroxyl group, having a solid content acid value of 15 to 150 mg KOH / g and a glass transition temperature of 70 to 140 ° C. as a resin, and a polyisocyanate compound (B And the content of the polyisocyanate compound (B) is a content that reacts with the solid content hydroxyl value of 2 to 80 mgKOH / g of the vinyl polymer (A). Resin composition.
“2” Thermoforming resin film having a curable resin composition layer according to “1” having a thickness of 1 to 20 μm as an outermost layer on one surface of the thermoforming film.
“3” The thermoforming film according to “2”, wherein the curable resin layer of the thermoforming film has a pencil hardness (measured based on JIS K5400) of HB or higher.
[4] The thermoforming film as described in [2] or [3], wherein the outermost layer of the thermoforming film is 15 μm thick, and the elongation under a tensile condition of 150 ° C. and 500 mm / min is 100% or more.
“5” The thermoforming film according to any one of “2” to “4”, which has a pattern layer on a surface opposite to the curable resin composition layer.
“6” The thermoforming film according to any one of “2” to “5”, wherein the thermoforming film is for in-mold molding or insert molding.
It is a manufacturing method of the said film for thermoforming, Comprising: The manufacturing method of the film for thermoforming in any one of "2"-"6" which forms a curable resin layer by the printing method or the coating method.
A laminated body obtained by laminating the thermoforming film according to any one of the above “2” to “6” on a base material so that a surface opposite to the curable resin composition layer is in contact therewith.
The thermoforming film according to any one of the above “2” to “6” is laminated on a base material by an in-mold molding method or an insert molding method so that the surface opposite to the curable resin layer is in contact with the film. Laminated body.

  If the curable resin composition of the present invention is laminated on a thermoforming film, a thermoforming film excellent in chemical resistance, thermoformability, and surface hardness and a laminate product thereof can be obtained. If the film for thermoforming of the present invention and its laminated molded product are used for automobile interior members, insert molding and in-mold molding excellent in chemical resistance and surface hardness are possible in existing processes.

As the curable resin composition, it is preferable from the viewpoint of chemical resistance and thermoformability to use a thermosetting resin having a small curing shrinkage and capable of uniform crosslinking. In a non-uniform cured film, the weakest part is attacked by chemicals, and stress is concentrated in the non-uniform part even in thermoforming during heating and breaks. In addition, chemical resistance and thermoformability are in a trade-off relationship. If the curable resin is cured, chemical resistance is improved by increasing the crosslinking density, but thermoplasticity is lost and thermoformability is reduced. For this reason, it is desirable to form a cured film that is cross-linked at a maximum temperature of about 80 ° C. inside the automobile and is thermoplastic at a thermoforming temperature of about 150 ° C. In the present invention, it has been found that the cohesive strength of the carboxyl group expresses such characteristics, and it has a carboxyl group and a hydroxyl group based on the solid content acid value and the optimum value of the solid content hydroxyl value related to crosslinking, and has a solid content acid value of 15 A vinyl polymer (A) having a glass transition temperature of 70 to 140 ° C. and a polyisocyanate compound (B), which is a resin of ˜150 mg KOH / g, and a solid content hydroxyl value of 2 to 80 mg KOH / g of the vinyl polymer (A) A curable resin composition characterized by containing at a reacting ratio realized excellent chemical resistance, thermoformability and surface hardness.

  Examples of the resin containing a carboxyl group and a hydroxyl group include an acrylic type and a polyester type. In the case of an acrylic type, based on a polymerizable vinyl monomer containing a carboxyl group and a hydroxyl group, other common resins are used. It can be obtained by copolymerizing polymerizable polymerizable vinyl monomers. These resins may be used alone or in combination of two or more.

The solid content acid value is preferably 15 to 150 mg KOH / g resin, more preferably a resin having a solid content acid value of 20 to 100 mg KOH / g. If the solid content acid value of the resin is less than 15 mgKOH / g, the resulting cured film has insufficient chemical resistance and thermoformability. If the resin content exceeds 150 mgKOH / g resin, the resin viscosity increases and handling is difficult. It becomes difficult.
Here, the solid content acid value is a numerical value calculated from the formula shown below.
Solid content acid value = KOHmg / total amount of resin without solvent KOHmg: mole number of carboxyl group-containing vinyl monomer and / or derivative thereof × 56100 × N (N: carboxyl group-containing vinyl monomer and / or derivative thereof) Number of carboxyl groups in it)

  Moreover, the solid content acid value of this resin can also be calculated | required by the measuring method of JISK1557-5.

  Examples of the polymerizable vinyl monomer containing a carboxyl group include a hydroxyl group-containing polymerizable vinyl monomer such as methacrylic acid, acrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid or hydroxyethyl methacrylate. And a half ester acid obtained by reacting an acid anhydride such as maleic anhydride and itaconic anhydride. These may be used alone or in combination of two or more. Other acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, trimellitic anhydride, methylenetricyclohexeric carboxyl anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, hymic anhydride, succinic anhydride , And anhydrous het acid.

  The solid content hydroxyl value is preferably 2 mg KOH / g resin or more, but is not limited to this, and the solid content hydroxyl value involved in crosslinking is important.

Here, the solid content hydroxyl value is a numerical value calculated from the formula shown below.
Solid content hydroxyl value = KOH mg / total amount of resin not containing KOH mg: mol number of hydroxyl group-containing vinyl monomer and / or derivative thereof × 56100 × N (N: hydroxyl group-containing vinyl monomer and / or derivative thereof Number of hydroxyl groups

  Moreover, the hydroxyl value of this resin can also be calculated | required by the measuring method of JISK1557-1.

  Examples of the polymerizable vinyl monomer containing a hydroxyl group include hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 1,4-butanediol monomethacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 1 , 4-butanediol monoacrylate and the like. Further, the C1-C18 alkyl alcohol forming the acrylic ester may be any alcohol having a linear, branched, or cyclic alkyl group. These may be used alone or in combination of two or more.

  Other copolymerizable polymerizable vinyl monomers include, for example, methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid- t-butyl, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, adamantyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, Isopropyl acrylate, acrylate-n-butyl, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, acrylic Adamantyl acid, dodecyl acrylate, isobornyl acrylate, glycidyl methacrylate, glycidyl acrylate, allyl methacrylate, allyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, phenyl methacrylate, acrylic Acid phenyl, α-methylstyrene, p-vinyltoluene, methacrylamide, acrylamide, N, N-dimethylmethacrylamide, N, N-dimethylacrylamide, acrylic acid-2,2,6,6-tetramethyl-4-piperidyl , Ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl Aliphatic vinyl ether compounds such as nyl ether, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, trimethoxysilylpropyl methacrylate, maleic anhydride, itaconic anhydride, maleic esters, fumaric esters , Styrene, acrylonitrile, methacrylonitrile, 2-hydroxyethyl crotonic acid, 2-hydroxypropyl crotonic acid, 3-hydroxypropyl crotonic acid, 3-hydroxybutyl crotonic acid, 4-hydroxybutyl crotonic acid, 5-hydroxypentyl crotonic acid Allyl group-containing compounds such as 6-hydroxyhexyl crotonic acid, allyl alcohol, allyl glycidyl ether, alkyl crotonates such as methyl crotonate, ethyl crotonate, propyl crotonate, vinyl acetate Aliphatic carboxylic acid vinyl esters such as vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl stearate, and cycloaliphatic carboxyl such as vinyl cyclohexanecarboxylate Examples thereof include vinyl acid esters, vinyl benzoates, vinyl cinnamates, and aromatic carboxylic acid vinyl esters such as vinyl tert-butyl benzoate. These may be used alone or in combination of two or more.

  Other copolymerizable vinyl monomers are not essential components, and are appropriately selected and used as necessary according to the base material, purpose of use, etc. in designing a cured film.

  There is no restriction | limiting in particular about the method of superposing | polymerizing or copolymerizing a polymerizable vinyl type monomer etc., A well-known method, for example, solution polymerization in an organic solvent, etc. can be used. The polymerization method is not particularly limited, and for example, any of radical polymerization, cationic polymerization, and anionic polymerization can be used. Among these, radical polymerization is preferable from an industrial viewpoint. Examples of the polymerization initiator used in radical polymerization include t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyneodecanate, t-butyl peroxypivalate, t-hexyl peroxy-2- Organic peroxides such as ethyl hexanoate and methyl ethyl ketone peroxide, or 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile) (AIBN), Preferred examples include azo initiators such as 2,2′-azobis (2-methylbutyronitrile). Of course, it is not limited to these. These radical polymerization initiators may be used alone or in combination of two or more.

  The reaction temperature during radical polymerization is generally preferably 60 to 150 ° C. If this temperature is less than 60 ° C., the radical polymerization initiator is difficult to decompose and the reaction does not proceed easily. If it exceeds 150 ° C., even if the radical polymerization initiator is decomposed by heat to generate radicals, The lifetime is short and the growth reaction is difficult to proceed effectively. The polymerization time depends on the polymerization temperature and other conditions and cannot be determined in general, but generally about 2 to 6 hours is sufficient.

  Examples of the hydroxyl group-containing resin include those modified by addition reaction of a compound capable of addition reaction with a hydroxyl group. Examples of the compound capable of undergoing an addition reaction with a hydroxyl group include lactone compounds and alkylene oxides, with lactone compounds being preferred. Examples of the lactone compound include β-methyl-δ-valerolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, γ-caprolactone, ε-caprolactone, β-propiolactone, γ-butyrolactone, γ -Nonanoic lactone, (delta) -dodecanolactone, etc. are mentioned. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like. These compounds capable of undergoing an addition reaction with a hydroxyl group may be used singly or in combination of two or more.

  When the resin containing a carboxyl group and a hydroxyl group is a polyester resin, a polybasic acid and a polyhydric alcohol are reacted. Examples of the polybasic acid include phthalic anhydride and tetrahydrophthalic anhydride. Acid, isophthalic acid, maleic anhydride, fumaric acid, trimellitic anhydride, methylenetricyclohexanic carboxylic anhydride, pyromellitic anhydride, itaconic acid, adipic acid, sebacic acid, azelaic acid, hexahydrophthalic anhydride, hymic anhydride , Succinic anhydride, het anhydride, and the like. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, butylene glycol, hexanediol, trimethylolethane, Ji trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol and the like. Further, the polyester resin may be modified with a monobasic acid, a fatty acid, an oil component, or the like. Furthermore, the introduction of hydroxyl groups in the polyester-based resin can be easily performed using, for example, a polyhydric alcohol having three or more hydroxyl groups in one molecule.

The glass transition temperature of the resin containing a carboxyl group and a hydroxyl group is preferably 70 to 140 ° C, more preferably a resin having a glass transition temperature of 80 to 120 ° C. When the glass transition point of the resin is less than 70 ° C., the resulting cured film has insufficient chemical resistance at high temperatures, and when it exceeds 140 ° C., the softening point of the cured film becomes high, and thermoformability. Decreases.
The glass transition temperature is a value described in “Polymer Hand Book (J. Brandrup, Interscience, 1989)” (MMA: 105 ° C., BA: −54 ° C., ST: 100 ° C., HEMA: 55 ° C. , MAA; 130 ° C., BMA; 20 ° C.) was calculated using the Fox formula, but not including the initiator.

  The mass average molecular weight is preferably 2000 to 30000, particularly preferably 3000 to 20000. A mass average molecular weight of less than 2000 is not preferable because the entanglement of the resin is small, and a mass average molecular weight of 30000 or more is not preferable because of high viscosity.

(Polyisocyanate compound (B))
The polyisocyanate compound (B) is characterized in that it is contained in a proportion that reacts with the solid content hydroxyl value of 2 to 80 mgKOH / g of the vinyl polymer (A). The reaction here means that the hydroxyl group of the resin and the isocyanate group of the polyisocyanate compound (B) are reacted and crosslinked in an equivalent amount. The solid hydroxyl value involved in this crosslinking is preferably 2 to 80 mg KOH / g resin, and more preferably the polyisocyanate compound (B) is blended at a solid content hydroxyl value of 10 to 70 mg KOH / g.

  When the content ratio of the polyisocyanate compound (B) is such that the solid content hydroxyl value is less than 2 mgKOH / g, the resulting cured film has insufficient chemical resistance, and when it exceeds 80 mgKOH / g resin, The structure becomes too dense and the thermoformability is reduced.

Examples of the polyisocyanate compound include aliphatic and aromatic compounds. Specific examples of the aliphatic polyfunctional isocyanate include hexamethylene diisocyanate, dicyclohexylmethane 4,4′-isocyanate, 2,2,4-trimethyl-1,6-diisocyanate, and isophorone diisocyanate. Examples of the aromatic polyfunctional isocyanate include 2,4-tolylene diisocyanate, 2,6 tolylene diisocyanate, difinylmethane-4,4′-diisocyanate, xylene diisocyanate, and polymethylene-polyphenylel-polyisocyanate. Preferred compounds include hexamethylene diisocyanate and xylene diisocyanate.
The structure includes monomer, burette type, adduct type, and isocyanurate type. Among these, a burette type and an adduct type are preferable.

  As the usage-amount of a polyisocyanate compound (B), it is preferable that an isocyanate group is 0.1 equivalent or more and 2 equivalent or less with respect to the hydroxyl group of the said (A) component. If it is less than 0.1 times, the remaining hydroxyl groups are excessive, which is not preferable. If it exceeds 2 times, there is an isocyanate group which remains partially unreacted, which is not preferable.

(Curing catalyst)
A curing reaction catalyst can be used in the curable resin composition of the present invention.
Examples of the curing reaction catalyst include tin compounds and zinc compounds. Examples of the tin compound include tin halides such as tin chloride and tin bromide, and organic tin compounds such as dibutyltin diacetate and dibutyltin dilaurate. Examples of the zinc compound include zinc chloride and zinc bromide. Examples include zinc salts of organic acids such as zinc halide, zinc octylate, and zinc laurate. One kind of tin compound or zinc compound as a curing reaction catalyst may be used, or two or more kinds may be used in combination, or may be used in combination with another curing reaction catalyst.

(Curable resin layer)
The curable resin layer is obtained by curing a curable resin.
The thickness of the curable resin layer laminated on one surface of the thermoforming film needs to be 1 to 20 μm. When the thickness of the curable resin layer is 1 μm or more, chemical resistance when a laminated body is obtained can be exhibited. Since the chemical resistance of the part stretched by 200% or more may be required by thermoforming, it is more preferably 3 μm or more. If the thickness of the curable resin layer is 20 μm or less, insert molding or in-mold molding can be performed, and thermoforming into a deep drawing shape is possible, but from the viewpoint of cost, it is more preferably 15 μm or less. The thickness of the curable resin layer was calculated from the difference in thickness with and without coating, and the film thickness was measured according to JIS B 7503.

(Coating film for thermoforming)
In the thermoforming coating film of the present invention, the curable resin layer is preferably formed on the thermoformed film with a thickness of 1 to 20 μm, and the pencil hardness (measured based on JIS K5400) is preferably HB or more. . If the pencil hardness is high, the scratch resistance is improved, so that it can be suitably used for various vehicle members such as a door waist garnish, a front control panel, a power window switch panel, and an airbag cover. It is very useful industrially from the viewpoint of expanding applications.

It is preferable that the curable resin layer on the thermoforming film has a thickness of 15 μm and an elongation under a tensile condition of 150 ° C. and 500 mm / min is 100% or more. If the tensile elongation is 100% or more, deep drawing thermoforming can be performed. As tensile conditions, a 10 × 100 mm sample is visually checked for elongation until cracks occur in the film at a chuck interval of 50 mm, a tensile speed of 500 mm / min, and a tensile constant temperature layer temperature of 150 ° C. The film for thermoforming is preferably 100% or more in elongation until a 10 × 100 mm sample which is the above-mentioned tensile condition is 50 mm between chucks, a pulling speed is 500 mm / min, and a constant temperature isothermal layer temperature is 150 ° C. For example, a thermoplastic resin film of a polymethacrylate resin, a polycarbonate resin, or a polyethylene terephthalate resin can be mentioned, and a methacrylate resin is particularly preferable. The thickness of the thermoforming film is preferably 20 to 300 μm. By setting the thickness of the thermoforming film to 300 μm or less, the film can be wound around a paper tube or the like, and continuous production is facilitated. By making the thickness of the film for thermoforming 20 μm or more, a sense of depth can be more sufficiently imparted to the resulting laminate along with the protective properties of the film. The thickness of the thermoforming film is more preferably 30 μm or more, and particularly preferably 50 μm or more. The upper limit is more preferably 200 μm or less, and particularly preferably 150 μm or less.
The curable resin composition of the present invention may contain an organic solvent, a color pigment, and / or various additives as necessary, for example, an ultraviolet absorber, a light stabilizer, an antioxidant, a surfactant, a leveling agent, A foaming agent, rheology adjusting agents such as polyethylene wax, polyamide wax, and internally crosslinked resin fine particles can be blended.

  The organic solvent of the curable resin composition of the present invention is not particularly limited as long as each component can be dissolved, but is preferably selected so that the organic solvent does not remain after baking. . For example, aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform and carbon tetrachloride, methanol, ethanol Alcohols such as n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, ethers such as dibutyl ether, tetrahydrofuran and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and n acetate And esters such as -propyl and n-butyl acetate. Further, a solvent obtained by adding a soluble amount of water to these organic solvents and mixing them may be used as the solvent. These solvents may be used alone or in combination of two or more. After coating, in order to make the curable resin layer have a sufficient crosslinking density, it is preferably left still for several hours to several days in an atmosphere of 30 to 80 ° C. Usually, when spray coating is performed on a molded product, a large-scale coating booth is required, and productivity is poor due to poor coating efficiency. On the other hand, since the laminate of the present invention is a coating process on the film, the coating efficiency is good, the line speed is fast, and in-mold molding or insert molding is the same size as the injection molding, Industrial value is high in terms of productivity and small space.

(Method for forming curable resin layer)
The coating layer is preferably formed by a printing method or a coating method. In this case, the curable resin layer is prepared by dissolving or dispersing the raw material to be the coating layer in a solvent to prepare a paint, applying it to one side of the thermoformed film, and performing heat drying for removing the solvent. Is formed. This method is preferable because the adhesion between the curable resin layer and the thermoformed film is improved.

  Examples of the printing method include known printing methods such as gravure printing, screen printing, and offset printing.

  Coating methods include flow coating, spray coating, bar coating, gravure coating, gravure reverse coating, kiss reverse coating, micro gravure coating, roll coating, blade coating, rod coating, and roll doctor. Known coating methods such as a coating method, an air knife coating method, a comma roll coating method, a reverse roll coating method, a transfer roll coating method, a kiss roll coating method, a curtain coating method, a die coating method, and a dipping coating method may be mentioned. Particularly preferred is a vacuum die coater. The vacuum die coater can reduce the coating liquid retention and increase the air gap.

(2 mixed supply)
The two-component mixed supply system is preferably a two-component mixed supply system that mixes immediately before coating rather than a system that stores and supplies the mixed solution in a tank. By mixing immediately before coating, it is possible to improve the pot life problem of the two-component coating liquid. Furthermore, by combining with a die coater with less coating liquid retention, it is possible to greatly improve the pot life problem of the two-liquid coating liquid.

<Pattern layer>
In the thermoforming film of the present invention, a pattern layer may be formed in order to impart design properties to various substrates. In this case, it is preferable to form the pattern layer on the surface of the thermoforming film opposite to the surface on which the curable resin layer is provided. Moreover, at the time of manufacture of a laminated body, it is preferable from the point of protection of a decorating surface and provision of a high-class feeling to arrange | position a pattern layer to the adhesive surface with a base material. The pattern layer is preferably formed by a printing method or a vapor deposition method.

(Print layer)
The printed layer becomes a pattern or characters on the surface of the laminate obtained by insert or in-mold molding. Examples of the print pattern include a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, full face, and the like.

  As binders for the printing layer, polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose Examples of the resin include ester resins, alkyd resins, and chlorinated polyolefin resins.

Examples of the method for forming the printing layer include known printing methods such as offset printing, gravure rotary printing, and screen printing; known coating methods such as roll coating and spray coating; and flexographic printing. The thickness of the printing layer may be appropriately determined as necessary, and is usually about 0.5 to 30 μm.
The number of missing prints in the print layer is preferably 10 pieces / m ² or less from the viewpoints of design properties and decorating properties. By setting the number of printing omissions to 10 pieces / m 2 or less, the appearance of the laminate using the thermoforming acrylic resin film becomes better. The number of missing prints in the print layer is more preferably 5 pieces / m ² or less, and particularly preferably 1 piece / m ² or less.

(Deposition layer)
The vapor deposition layer is formed of at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or an alloy or compound thereof. The Examples of the method for forming the vapor deposition layer include vacuum vapor deposition, sputtering, ion plating, and plating.

<Other layers>
(Adhesive layer)
The acrylic resin film for thermoforming of the present invention may be provided with an adhesive layer as necessary. The adhesive layer is preferably formed on the surface opposite to the surface on which the curable resin layer is provided.

(Thermoplastic resin layer)
The direction in which the thermoforming film is laminated on the thermoplastic resin layer is preferably laminated so that the surface opposite to the surface on which the curable resin layer is provided is in contact with the thermoplastic resin layer. The thermoplastic resin layer is preferably made of a material having compatibility with the base material for the purpose of improving the adhesion with the base material. More preferably, the thermoplastic resin layer is made of the same material as the base material. As the thermoplastic resin layer, a known thermoplastic resin film or sheet can be used. For example, acrylic resin; ABS resin (acrylonitrile-butadiene-styrene copolymer); AS resin (acrylonitrile-styrene copolymer); Vinyl resin; Polyolefin resin such as polyethylene, polypropylene, polybutene, polymethylpentene; Polyolefin copolymer such as ethylene-vinyl acetate copolymer or saponified product thereof, ethylene- (meth) acrylate copolymer; polyethylene Polyester resins such as terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate; polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon; Resin; Fibrin derivatives such as cellulose acetate and nitrocellulose; Fluorine resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer; or two selected from these Three or more kinds of copolymers or mixtures, composites, laminates and the like can be mentioned.

  If necessary, the thermoplastic resin layer may contain general compounding agents such as stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, foaming agents, fillers, antibacterial agents, and antifungal agents. An agent, a release agent, an antistatic agent, a colorant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a flame retardant, and the like may be blended.

  Examples of a method for obtaining a laminated film or sheet include known methods such as thermal lamination, dry lamination, wet lamination, and hot melt lamination. Moreover, the acrylic resin film for thermoforming and the thermoplastic resin layer can be laminated by extrusion lamination.

  If necessary, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, anchor, primer treatment, etc. on one surface of the thermoforming film, the surface of the thermoplastic resin layer of the laminated film or sheet The surface treatment may be performed. These treatments improve adhesion between the thermoforming film and the curable resin layer or pattern layer, between the thermoplastic resin layer and the pattern layer, between the thermoforming film and the thermoplastic resin layer, etc. Let

<Laminated body>
The laminate of the present invention is obtained by laminating a thermoforming film, the laminated film or a sheet on a substrate. At this time, it is preferable to laminate | stack so that the surface on the opposite side to the surface in which the curable resin layer is provided may contact | connect a base material. Examples of the material of the base material include: resin; wood board such as wood veneer, wood plywood, particle board, medium density fiber board (MDF); water quality board such as wood fiber board; metal such as iron and aluminum.

  The type of resin is not particularly limited. For example, polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefinic thermoplastic elastomer; polystyrene resin, ABS resin (acrylonitrile-butadiene-styrene) Copolymer), AS resin (acrylonitrile-styrene copolymer), acrylic resin, urethane resin, unsaturated polyester resin, epoxy resin, and other general-purpose thermoplastic or thermosetting resins; polyphenylene oxide / polystyrene resin, polycarbonate General-purpose engineering resins such as resin, polyacetal, polycarbonate-modified polyphenylene ether, polyethylene terephthalate; polysulfone, polyphenylene sulfide, polyphenylene Super engineering resins such as oxides, polyetherimides, polyimides, liquid crystalline polyesters, polyallyl-based heat-resistant resins, etc .; reinforcing materials such as glass fibers or inorganic fillers (talc, calcium carbonate, silica, mica, etc.), modifiers such as rubber components A composite resin to which is added or various modified resins.

  Among these, as the material for the base material, a material that can be melt-bonded to a thermoforming film, a laminated film or a sheet thereof is preferable. For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or a resin containing these as main components can be given. In terms of adhesiveness, an ABS resin, an AS resin, a polycarbonate resin, a vinyl chloride resin, or a resin containing these as a main component is preferable, and an ABS resin, a polycarbonate resin, or a resin containing these as a main component is more preferable. Even if it is a resin that is not heat-sealed, such as a polyolefin-based resin, by providing an adhesive layer, it is possible to bond one selected from the group consisting of a film for thermoforming, a laminated film or a sheet thereof and a base material at the time of molding. Is possible.

  As a method for producing the laminate of the present invention, a known method such as thermal lamination can be used in the case of a two-dimensional laminate and when the substrate can be heat-sealed. For example, for wood substrates such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), water quality boards such as wood fiber board, metals such as iron and aluminum, etc. It is possible to bond them through an adhesive layer.

  In the case of a three-dimensional laminate, a known method such as an insert molding method or an in-mold molding method can be used.

  The in-mold molding method is a method of heating an acrylic resin film for thermoforming, or a laminated film or sheet thereof, and then vacuum-forming in a mold having a vacuuming function, and then a resin to be a base material in the same mold Is a method of obtaining a laminate in which an acrylic resin film for thermoforming, or a laminated film or sheet thereof and a substrate are integrated. The in-mold molding method is preferable from the viewpoints of workability and economy because the film molding and injection molding can be performed in one step.

  The heating temperature during the in-mold molding is preferably equal to or higher than the temperature at which the thermoforming acrylic resin film or sheet is softened. Specifically, it may be appropriately set depending on the thermal properties of the film or the shape of the laminate, and is usually 70 ° C. or higher. On the other hand, if the temperature is too high, the surface appearance tends to deteriorate or the releasability tends to deteriorate. This may be set as appropriate depending on the thermal properties of the film or the shape of the laminate, and is usually 170 ° C. or lower. Furthermore, from the viewpoint of energy efficiency, it is preferable that the preheating temperature during vacuum forming is low.

  When a three-dimensional shape is imparted to the film by vacuum forming, the curable resin composition for a thermoforming film of the present invention and the thermoforming film obtained by laminating this composition are rich in elongation at high temperatures, Very advantageous.

  Examples of the laminate obtained by the present invention include automotive parts (for example, parts such as bodies, bumpers, spoilers, mirrors, wheels, interior materials, etc., and various materials), motorcycle parts, road materials. (For example, traffic signs, soundproof walls, etc.), tunnel materials (for example, side walls, etc.), railway vehicles, furniture, musical instruments, home appliances, building materials, containers, office supplies, sports equipment, toys and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, these do not limit this invention at all. In the following description, “part” or “%” represents “part by weight” and “% by weight”, respectively, unless otherwise specified.

Measurement and evaluation in Examples and Comparative Examples were performed using the following conditions and methods.
(1) Polymerization conversion rate The obtained acrylic polymer (A) latex was dried in a hot air dryer at 120 ° C. for 1 hour to determine the amount of solid components, and polymerized by 100 × solid component amount / charged monomer. Conversion (%) was calculated.

(2) Gel content rate of acrylic resin composition The gel content rate in the acrylic resin composition is obtained by multiplying the gel content rate (%) of the acrylic polymer (A) by the blending ratio of the acrylic polymer (A). Calculated.
The gel content of the acrylic polymer (A) was determined by collecting a predetermined amount of the dry resin powder of the acrylic polymer (A) on a 100-mesh wire net, immersing it in methyl ethyl ketone for 48 hours, and drying it under reduced pressure to remove the methyl ethyl ketone. Thereafter, the constant weight was read and calculated according to the following formula (1).
Gel content of acrylic polymer (A) (%)
= (Weight after re-drying / weight of sample collected) × 100 (1)
The gel content (%) in the acrylic resin composition is obtained by multiplying the gel content (%) of the acrylic polymer (A) by the blending ratio of the acrylic polymer (A), from the following formula (2). Calculated.
Gel content in acrylic resin composition (%)
= (Gel content of acrylic polymer (A) (%) × (ratio of acrylic polymer (A))) (2)

(3) Glass transition temperature The values (MMA: 105 ° C., BA: −54 ° C., ST: 100 ° C.) described in “Polymer Hand Book (J. Brandrup, Interscience, 1989)” Fox), but not including the polyfunctional monomer, initiator, and surfactant.

(4) Graft rate 1 g of the dry resin powder of the acrylic polymer (A) is dispersed and dissolved in 50 ml of methyl ethyl ketone (MEK), and the insoluble content and the soluble content are separated with a centrifugal separator (30,000 rpm × 2 Hrs). The insoluble matter was sufficiently dried by vacuum drying, and the weight was measured as the rubber / graft content.
Graft rate (%)
= ((Weight of rubber / graft-weight of crosslinked acrylic polymer (A-1)) / weight of crosslinked acrylic polymer (A-1)) × 100

(5) Weight average particle diameter of the acrylic polymer (A) The temperature was 23 ° C. ± 2 ° C. and the humidity was obtained by diluting the obtained acrylic polymer (A) latex to a solid content concentration of 0.02%. The weight average particle diameter was determined from the light transmittance at a wavelength of 546 nm using a spectrophotometer (manufactured by HITACHI, Spectrophotometer U-2000) at 50% ± 5%.

(6) Reduced viscosity Methyl ethyl ketone (MEK) soluble content was measured at 30 ° C using a 0.3% N, N'-dimethylformamide solution. The unit is dl / g.

(7) Solid content of resin Calculated by the following formula from the monomer composition of the acid value resin.
Solid content acid value = KOHmg / total amount of resin without solvent KOHmg: mole number of carboxyl group-containing vinyl monomer and / or derivative thereof × 56100 × N (N: carboxyl group-containing vinyl monomer and / or derivative thereof) Number of carboxyl groups in it)

(8) Solid content of resin It was calculated from the following formula from the monomer composition of the hydroxyl value resin.
Solid content hydroxyl value = KOH mg / total amount of resin not containing KOH mg: mol number of hydroxyl group-containing vinyl monomer and / or derivative thereof × 56100 × N (N: hydroxyl group-containing vinyl monomer and / or derivative thereof Number of hydroxyl groups

(9) Mass average molecular weight of resin HLC8220GPC (manufactured by Tosoh Corporation), using three linked TSKgel Super H5000, H4000, H3000 (Tosoh Corporation) as GPC columns, and THF (with stabilizer) as solvent ) And measured in terms of polystyrene. Other conditions are measurement temperature: INLET OVEN 40 ° C., sample amount: 10 μl, liquid amount: 0.6 ml / min, detector: RI.

(10) Tensile elongation%
Autograph AGS10KNG (manufactured by Shimadzu Corporation), TERMOSATATIC CHAMBER is model: TCRI-200SP (manufactured by Shimadzu Corporation), sample size is 10 × 100 mm, chuck is 50 mm, pulling speed is 500 mm / min, A tensile test was performed under the condition of a tension thermostatic temperature of 150 ° C., and the elongation until cracks occurred in the film was measured.

(11) Chemical resistance Each of the following chemicals was dropped onto the curable resin layer before and after the following vacuum molding, and left on an oven at 80 ° C. for 1 hour, and then the chemicals on the surface were wiped and evaluated. After vacuum forming, the most stretched R part was evaluated.
Evaluation ○: Lifting is not generated and gloss is maintained ×: Lifting is generated and glossless chemicals (i) VW liquid: Octyl Methoxycinnamate / Octocryline / Homosalate / DEET mixed solvent (ii) Copatone: Copatone SPF50
(Iii) Nibea: Nivea SPF47

(12) Thickness of the cured resin layer
The thickness of the curable resin layer was calculated from the thickness difference with and without coating, and the film thickness was measured according to JIS B 7503.

(13) Pencil hardness
According to JIS K5400, the pencil hardness of the surface of the curable resin layer was measured.

(14) Vacuum forming was performed using a thermoforming film in which a curable resin layer was laminated.
Specifically, vacuum forming was performed with a Y-101 type vacuum forming machine (trade name, manufactured by Sanwa Kogyo Co., Ltd.) having a vacuum drawing function.
The shape of the mold is a box shape having a length of 95 mm, a width of 50 mm, and a depth of 5 mm, and a corner corner R connecting the bottom surface and the side surface of the mold is about 10.

  Vacuum forming of a thermoforming film laminated with a curable resin layer is performed under the conditions of a heater set temperature of about 340 ° C., a heating time of 15 seconds, and a distance between the heater and the film of 15 mm, and the curable resin layer does not contact the mold. Vacuum forming was performed in the direction.

  The state of the side portion of the R portion of the obtained vacuum formed body or the vicinity of the corner of the edge portion was observed and evaluated as follows.

(Evaluation)
○: No crack
×: Cracking occurred in the curable resin layer

(Method for producing crosslinked acrylic polymer (D): P-1)
200 parts by weight of water and OSA were added in the amounts shown in Table 1 into an 8 liter polymerization vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, monomer supply tube, and reflux condenser, and the inside of the vessel was sufficiently filled with nitrogen gas. After the substitution to make it substantially free of oxygen, the internal temperature was set to 40 ° C., 5 parts by weight of the mixture (d-1-1) shown in Table 1 was added all at once, and after stirring for 10 minutes, the following substance sodium Formaldehyde sulfoxylate 0.11 part by weight Ferrous sulfate dihydrate 0.004 part by weight Ethylenediaminetetraacetic acid-2-sodium 0.001 part by weight was charged, and the mixture (d-1-2) shown in Table 1 was prepared. After continuously adding and polymerizing at a rate of 10 parts by weight / hour, the polymerization was continued for another 0.5 hours, and the mixture (d-1-3) shown in Table 1 was added at 12.7 parts by weight / hour. After continuously adding and polymerizing at a ratio, 1 more After continuing the polymerization for 0 hour, the polymerization conversion rate is set to 98% or more, the internal temperature is set to 60 ° C., and the mixture (d-2-1) shown in Table 1 is continuously added at a rate of 16.7 parts by weight / hour. Then, the polymerization was further continued for 1.0 hour, and then the polymerization conversion rate was set to 98% or more to terminate the polymerization, thereby obtaining an acrylic polymer (D) latex. The obtained latex was salted out with calcium chloride, washed with water and dried to obtain a dry powder (P-1) of acrylic polymerization (D).

Each abbreviation in Table 1 represents the following substance.
OSA; dioctyl sodium sulfosuccinate BA; butyl acrylate MMA; methyl methacrylate
ST; Styrene CHP; Cumene hydroperoxide AMA; Allyl methacrylate tDM; Tertiary decyl mercaptan

(Method for producing thermoplastic film)
After blending the dry powder of P-1 obtained as an acrylic polymer (D) and a methacrylic resin (trade name: Sumipex EX-A manufactured by Sumitomo Chemical Co., Ltd.) at a ratio of 40 parts by weight / 60 parts by weight, , 1 part of UV absorber: TINUVIN234 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and antioxidant: AO60 (manufactured by ADEKA Co., Ltd.) with respect to 100 parts by weight of the total of acrylic polymer (D) and methacrylic resin Was blended at a blending ratio of 0.4 part, extruded at 240 ° C. setting in a vent-type extruder, pelletized, and further formed into a film with a T-die extruder at 230 ° C. extruder and 240 ° C. die (thickness). 125 μm).

(Production method of polymer (A) component: A-1 to A-8)
In a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe and a dropping funnel, the components (a) in Table 2 were charged, and the temperature was raised to 105 ° C. while introducing nitrogen gas. The mixture of components a) was dropped from the dropping funnel at a constant rate over 5 hours. Next, the mixed solution of the component (c) was dropped at a constant rate over 1 hour. Then, after stirring at 105 degreeC for 2 hours continuously, it cooled to 50 degreeC. After cooling, component (D) in Table 2 was added and stirred to synthesize polymer (A). Table 2 shows the solid content concentration of the obtained polymers (A-1 to 8), the number average molecular weight measured by GPC, the glass transition temperature obtained by calculation, and the solid content acid value and solid content hydroxyl value obtained by calculation. It was shown to.

(In the table, the amounts of the components (a) to (d) are parts by weight)

Takenate D-110N
(Mitsui Chemicals Co., Ltd. polyisocyanate NCO% = 11.5% solid content% = 75%).

(Examples 1-4 and Comparative Examples 1-5)
The obtained thermoplastic acrylic film is used as a thermoforming film, and the coating agent having a concentration of 35% is prepared by blending the components (A), (B) and (C) of Table 3 on one side. Coating was performed using a bar coater according to the conditions. No. No. 16 bar coater, 8 μm thick. No. 24 bar coater, 15 μm thick The thickness was 25 μm with a 50 bar coater. After coating, after setting at room temperature for 2 minutes, it was dried with an 80 ° C. dryer for 5 minutes and then cured with a 50 ° C. dryer for 7 days. Then, pencil hardness and chemical resistance were performed on the curable resin layer side, vacuum moldability was evaluated using the curable resin layer as the outermost surface, and a tensile test was performed by cutting into 10 × 100 mm strips. The results are shown in Table 3.

  A polyisocyanate compound (B) having a hydroxyl group, the content of the polyisocyanate compound (B) having a specific solid content acid value and glass transition temperature, and the specific solid content hydroxyl value (B) ) -Containing cured resin layers are excellent in vacuum moldability, chemical resistance, pencil hardness, and 150 ° C. tensile elongation.

Claims (9)

  Containing a vinyl polymer (A) having a carboxyl group and a hydroxyl group, a solid content acid value of 15 to 150 mgKOH / g and a glass transition temperature of 70 to 140 ° C., and a polyisocyanate compound (B), A curable resin composition for a film for thermoforming, characterized in that the content of the isocyanate compound (B) reacts with a solid content hydroxyl value of 2 to 80 mgKOH / g of the vinyl polymer (A). A thermoforming resin film having the curable resin layer according to claim 1 having a thickness of 1 to 20 µm as an outermost layer on one surface of the thermoforming film.   The thermoforming film according to claim 2, wherein the curable resin layer of the thermoforming film has a pencil hardness (measured based on JIS K5400) of HB or higher.   4. The thermoforming film according to claim 2, wherein the outermost layer of the thermoforming film has a thickness of 15 μm and an elongation under a tensile condition of 150 ° C. and 500 mm / min is 100% or more.   The film for thermoforming according to any one of claims 2 to 4, further comprising a pattern layer on a surface opposite to the curable resin layer.   The thermoforming film according to claim 2, wherein the thermoforming film is for in-mold molding or insert molding.   It is a manufacturing method of the said film for thermoforming, Comprising: The manufacturing method of the film for thermoforming in any one of Claims 2-6 which forms a curable resin layer by the printing method or the coating method.   The laminated body formed by laminating | stacking the film for thermoforming in any one of the said Claims 2-6 on a base material so that the surface on the opposite side to the curable resin layer may contact | connect. A laminate formed by laminating the thermoforming film according to any one of claims 2 to 6 on a substrate by an in-mold molding method or an insert molding method so that a surface opposite to the curable resin layer is in contact with the film. .