JP2011094125A - Composition for coating and laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for coating which is excellent not only in an early adhesive property but also especially in an adhesive property at high temperature and high humidity and an adhesive property after UV irradiation, and constitutes a laminate with very little change of a coated appearance due to time passage and to provide a laminated film provided with the laminate comprising the composition for coating. <P>SOLUTION: (1) The composition for coating contains an acrylic-urethane copolymer resin (A), an isocyanate compound (B), an oxazoline compound (C) and a carbodiimide compound (D). When the total content of (A) and (B) in the composition is made to be 100 pts.wt., contents of (A), (B), (C) and (D) meet relations as follows; (A): 40-70 pts.wt., (B): 30-60 pts.wt., (C): 20-40 pts.wt., and (D): 20-40 pts.wt. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a coating composition comprising a specific resin and a compound, and a laminated film in which a layer (composition layer) comprising the composition is laminated on a thermoplastic resin film. Specifically, optical adhesive films for displays, window glass for automobiles and buildings, easy adhesive films for hard coat films used for building materials such as doors and windows for system kitchens and unit baths, and various inks The present invention relates to an easy-adhesion film excellent in adhesiveness to clothing.

  Thermoplastic resin films, especially biaxially stretched polyester films, have excellent properties such as mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance. Widely used as a substrate film in applications. In particular, in recent years, the demand for various optical films including display materials related to flat panel displays is increasing.

  Above all, it is an excellent machine as a base film for hard coat films, antireflection films, prism lens films, lenticular lens films, light diffusion films, condensing films, etc. used in liquid crystal televisions, plasma display televisions, rear projection televisions, etc. Polyester films are used because of their physical properties, dimensional stability and transparency. When used for the above-described applications, for example, adhesion to a hard coat layer, adhesion to a prism lens layer, adhesion to a lenticular lens layer, adhesion to a light diffusion layer, and the like are required. In general, ultraviolet (UV) curable resins are often used for these layers, and adhesion to the layers is required. On the other hand, in general, the biaxially stretched polyester film surface has a high crystal orientation, so it has the disadvantage of poor adhesion to various paints such as hard coats, adhesives, inks, etc. The case is not an exception, for example, since the UV curable resin constituting the hard coat layer and the prism lens layer hardly adheres, the functional layer is peeled off from the base film during the processing step and actual use after the functional layer is formed. Problems occur. Therefore, methods for imparting easy adhesion to the polyester film surface by various methods have been studied conventionally. For example, a method of providing acrylic modified polyurethane as a primer layer on the film surface (Patent Document 1, Patent Document 2), Copolyester A method in which a resin and an isocyanate-based crosslinking agent are provided as a primer layer (Patent Document 3), a method in which a carbodiimide-based crosslinking agent is used as a primer layer as a primer layer (Patent Document 4), and an acrylic resin and epoxy, oxazoline, melamine, and isocyanate. A method of using one or more crosslinking agents as a primer layer has been proposed.

JP-A-6-346019 JP 2000-229394 A JP 2003-49135 A JP 2001-79994 A JP 2005-89622 A

  Regarding adhesion, for example, the method of providing acrylic modified polyurethane or copolymer polyester as a primer layer on the film surface is particularly wet heat when adhesion to UV curable resin is insufficient or a crosslinking agent is not used. Problems such as inability to obtain adhesiveness (moisture and heat resistance) after storage in the environment are likely to occur.

  In addition, in the method of providing a copolyester resin or acrylic resin and a crosslinking agent such as isocyanate, carbodiimide, or oxazoline as a primer layer, an improvement effect on moisture and heat resistance is recognized, but a UV curable resin, especially a prism lens layer is used. In many cases, the adhesiveness with the solvent-free UV curable resin constituting the resin is still insufficient.

  Furthermore, functional films having unique surface shapes such as a prism lens layer, a lenticular lens layer, and a light diffusion layer are often irradiated with UV from the base film side during the production to cure the solventless UV curable resin. . In particular, when providing a primer layer (easy-adhesive layer) on both sides, UV degradation of the easy-adhesive layer provided on the base film occurs due to UV irradiation during shaping curing on one side, and then provided on the opposite side. A major problem has occurred, such as failure to obtain adhesion of the laminate.

  In addition, hard coat films developed for various uses are widely used for building materials such as windows and doors of automobiles and buildings, system kitchens and unit baths, as well as displays. For example, when sticking an adhesive layer on the opposite side of the hard coat layer in an application where the hard coat film is attached to a window glass of an automobile, etc., when the adhesive layer is attached to the glass, the hard coat film is first temporarily applied by spraying water. However, it is necessary to take into account that hot air blows off the water and attaches the adhesive layer, and that hot water is directly applied to the film in application development to windows and doors of unit baths and system kitchens. For example, it is required that the adhesiveness does not decrease even when immersed in hot water (boiling resistance).

  However, with the above-described technique, sufficient boiling resistance cannot be obtained.

  Therefore, the object of the present invention is to eliminate the above-mentioned drawbacks, not only the initial adhesiveness, but also excellent in heat-and-moisture-resistant adhesiveness, boiling-resistant adhesiveness, adhesiveness after UV irradiation, and change in coating appearance over time. An object of the present invention is to provide a coating film having a very low coating composition and a laminated film in which a layer (composition layer) using the composition is laminated on a thermoplastic resin film.

The present invention has the following configuration. That is,
A coating composition containing an acrylic / urethane copolymer resin (A), an isocyanate compound (B), an oxazoline compound (C) and a carbodiimide compound (D),
Coating in which the content of (A), (B), (C) and (D) satisfies the following relationship when the total content of (A) and (B) in the composition is 100 parts by weight Composition.
(A): 40 to 70 parts by weight (B): 30 to 60 parts by weight (C): 20 to 40 parts by weight (D): 20 to 40 parts by weight.

  A laminated film provided with a layer (composition layer) using the coating composition of the present invention is not only for initial adhesiveness, but particularly for wet heat and boiling resistance, and adhesiveness after UV irradiation. And an effect that the change in coating appearance with time is extremely small.

  Hereinafter, the coating composition of the present invention and the laminated film using the same will be described in detail.

  The coating composition of the present invention must contain an acrylic / urethane copolymer resin (A), an isocyanate compound (B), an oxazoline compound (C), and a carbodiimide compound (D).

(1) Acrylic / urethane copolymer resin In the present invention, an acrylic / urethane copolymer is used from the viewpoints of adhesiveness and UV resistance (adhesiveness after UV irradiation). The acrylic / urethane copolymer resin (A) used in the coating composition of the present invention is not particularly limited as long as it is a resin in which an acrylic component and a urethane component are copolymerized. In particular, acrylic is a skin layer, and urethane is a core layer. An acrylic / urethane copolymer resin is preferred. At this time, it is preferable that the core layer is not completely encased by the skin layer but has a form in which the core layer is exposed. That is, when the core layer is completely encased by the skin layer, when the resin is applied and dried to form a film, the surface state has only acrylic characteristics, and the characteristics of the urethane derived from the core layer It becomes difficult to obtain the surface state possessed. On the other hand, the state in which the core layer is not encapsulated by the skin layer, that is, the state in which the core layer is separated is simply a mixture of acrylic and urethane. In order to selectively coordinate to the side, when the resin is applied and dried to form a film, the film has a surface state having only acrylic characteristics.

  For example, the acrylic / urethane copolymer resin having a core / skin structure is firstly subjected to first-stage emulsion polymerization using a monomer, an emulsifier, a polymerization initiator, and a water that form the core portion of the polymer resin. After the completion, it can be obtained by adding a monomer for forming the shell portion and a polymerization initiator and performing second-stage emulsion polymerization. At this time, since the copolymer resin to be produced has a two-layer structure, the emulsifier is not added in the second-stage emulsion polymerization, or even if added, the amount is such that a new core is not formed. It is effective to allow the polymerization to proceed on the surface of the copolymer resin core formed in (1). In particular, the core layer, which is a preferred embodiment of the present invention, is not completely encased by the skin layer, but the form in which the core layer is exposed is adjusted, for example, in the above-mentioned production method, with the amount of emulsifier charged during the second stage emulsion polymerization. Or a portion corresponding to the skin layer to be subjected to the second-stage emulsion polymerization is polymerized separately, and the second-stage emulsion polymerization is further performed on the core surface.

  The above-mentioned acrylic / urethane copolymer resin (A) is obtained by, for example, copolymerizing an acrylic monomer constituting acrylic in the presence of aqueous urethane, or by using aqueous urethane and aqueous acrylic, particularly aqueous acrylic having a crosslinkable functional group. It can be obtained by copolymerization or copolymerization of water-based urethane and water-based acrylic with the crosslinkable functional group of each resin.

  These water-based urethanes are functional groups that increase the affinity for water to ordinary urethane resins, for example, anionic functional groups such as carboxylic acid groups, sulfonic acid groups, sulfuric acid half ester bases, and cationic functional groups such as quaternary ammonium bases. The thing which introduce | transduced group can be illustrated. Further, among these functional groups, an anionic functional group is preferable from the viewpoint of dispersibility in water and ease of reaction control during synthesis, and a carboxylate group and a sulfonate group are more preferable. For example, the introduction of a carboxylic acid group may be performed by using a carboxylic acid group-containing polyhydroxy compound as one component of a polyhydroxy compound used as a raw material during urethane copolymerization, or by adding a hydroxyl group-containing carboxylic acid to the isocyanate group of a urethane having an unreacted isocyanate group. The reaction can be carried out by reacting the amino group-containing carboxylic acid, and then adding the reaction product to an alkaline aqueous solution with high-speed stirring and neutralizing.

  In addition, introduction of a sulfonate group or a sulfuric acid half ester base, for example, forms a prepolymer from a polyhydroxy compound, a polyisocyanate, and a chain extender, and an amino group or a hydroxyl group that can react with a terminal isocyanate group and a sulfonate group. Alternatively, a compound having a sulfuric acid half ester base in the molecule is added and reacted to finally obtain an aqueous urethane having a sulfonate group or a sulfuric acid half ester base in the molecule.

In that case, it is preferable to perform a production | generation reaction in an organic solvent, and then remove this organic solvent after adding water. As another method, a compound having a sulfonic acid group is used as one of raw materials to polymerize a urethane having a sulfonic acid group, and then the urethane is added to an alkaline aqueous solution with high-speed stirring, followed by neutralization. And a method of introducing a sulfonic acid alkali salt (for example, sulfonated sodium base) in the presence of an alkali into the primary or secondary amino group of the main chain or side chain of urethane. As the alkaline aqueous solution, it is preferable to use an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia, alkylamine, etc., particularly ammonia that does not leave the alkali in the coating film after coating and drying, amine that volatilizes under dry solid conditions, etc. preferable. The amount of a base such as a carboxylic acid base, a sulfonic acid base, or a sulfuric acid half ester base is preferably 0.5 × 10 ^{−4 to} 20 × 10 ⁻⁴ equivalent / g, and more preferably 1 × 10 ⁻⁴ to 10 × 10 ^−4. Equivalent / g is preferred. If the proportion of the base is too small, the affinity of urethane for water is insufficient, making it difficult to prepare an aqueous dispersion, and if it is too large, the original properties of urethane are impaired. Of course, the water-based urethane forms a stable aqueous dispersion or forms an aqueous solution by using a dispersion aid as required.

  Examples of the polyhydroxy compound used in the synthesis of urethane include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, poly Caprolactone, polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythritol, polycarbonate diol, glycerin, and the like can be used.

  In particular, in the present invention, those using polycaprolactone or polycarbonate diol are preferable as the polyhydroxy compound. In this case, the coating appearance is particularly excellent when applied on a film.

  Therefore, in the present invention, the acrylic / urethane copolymer resin (A) is preferably a resin using a polycaprolactone-based urethane component and / or a polycarbonate-based urethane component.

Examples of the polyisocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, an adduct of tolylene diisocyanate and trimethylol propane, an adduct of hexamethylene diisocyanate and trimethylol ethane, and the like.
Examples of the carboxylic acid group-containing polyhydroxy compound include dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid, trimellitic acid bis (ethylene glycol) ester, and the like. As the amino group-containing carboxylic acid, for example, β-aminopropionic acid, γ-aminobutyric acid, P-aminobenzoic acid and the like can be used. As the hydroxyl group-containing carboxylic acid, for example, 3-hydroxypropionic acid, γ-hydroxybutyric acid, P- (2-hydroxyethyl) benzoic acid, malic acid and the like can be used.

  Examples of the compound having an amino group or a hydroxyl group and a sulfone group that can react with a terminal isocyanate group include aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 2-amino-5-methylbenzene-2-sulfonic acid, and β-hydroxy. Sodium ethanesulfonate, a propane sultone of an aliphatic diprimary amine compound, a butane sultone addition product, and the like can be used, and a propane sultone adduct of an aliphatic primary amine compound is preferable.

  Furthermore, examples of the compound containing an amino group or a hydroxyl group capable of reacting with a terminal isocyanate group and a sulfuric acid half ester include aminoethanol sulfate, ethylenediamineethanol sulfate, aminobutanol sulfate, hydroxyethanol sulfate, γ-hydroxypropanol sulfate, α-hydroxy. Butanol sulfate or the like can be used.

  Polymerization of urethane using these compounds can be performed by a conventionally used method.

  Examples of the acrylic monomer used in the acrylic / urethane copolymer resin (A) used in the present invention include alkyl acrylate (the alkyl group is methyl, ethyl, n-propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl). , Cyclohexyl etc.), alkyl methacrylate (alkyl groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl etc.), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Hydroxy group-containing monomers such as 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-methylol Amide group-containing monomers such as rilamide, N-methylolmethacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, N-phenylacrylamide, N, N- Amino group-containing monomers such as diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate, glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, acrylic acid, methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) A monomer containing a carboxyl group such as a salt thereof or a salt thereof can be used.

  In the present invention, it is preferable to copolymerize a crosslinkable functional group, and it is particularly preferable to copolymerize N-methylolacrylamide in terms of improving the self-crosslinking property and the crosslinking density. The copolymerization ratio of N-methylolacrylamide is preferably from 0.5 to 5% by weight in terms of copolymerizability and the degree of crosslinking, and more preferably from 1 to 3% by weight in view of the coating appearance. When the amount is less than 0.5% by weight, for example, the moisture-resistant adhesion tends to be inferior, and when it exceeds 5% by weight, for example, the stability of the aqueous dispersion of the resin tends to be inferior, and the coating appearance tends to be poor.

  These acrylic monomers can also be used in combination with other types of monomers. Examples of other kinds of monomers include glycidyl group-containing monomers such as allyl glycidyl ether, sulfonic acid groups such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) or salts thereof. Monomers, monomers containing carboxyl groups such as crotonic acid, itaconic acid, maleic acid, fumaric acid and their salts (sodium salt, potassium salt, ammonium, etc.) or acid anhydrides such as maleic anhydride and itaconic anhydride Monomer containing functional groups, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoester, acrylonitrile , Methacrylonitrile, alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate, vinyl chloride, etc. can be used vinylpyrrolidone.

  Acrylic monomers are polymerized using one or more types, but when other types of monomers are used in combination, the proportion of acrylic monomers in all monomers may be 50% by weight or more, and even 70% by weight or more. preferable.

  The glass transition temperature (Tg) of the acrylic resin constituting the acrylic / urethane copolymer resin (A) is preferably 20 ° C. or higher, more preferably 40 ° C. or higher. When the glass transition temperature is 20 ° C. or higher, for example, it becomes difficult to block at room temperature, and whitening with time can be suppressed. Further, the ratio of “acrylic resin / urethane” in the acrylic / urethane copolymer resin (A) is preferably “10/90” to “70/30”, more preferably “20/80” to “weight ratio”. “50/50”. When the ratio of the acrylic resin is smaller than 10/90, a layer (composition layer) made of the coating composition is provided on the thermoplastic resin film to obtain a laminated film after UV deterioration of the composition layer. There is a tendency for the adhesiveness of the composition to deteriorate, and when it exceeds 70/30, since the ratio of the surface of the composition layer covered with acrylic increases, the initial adhesiveness tends to deteriorate. The weight ratio of acrylic resin / urethane can be set to a desired value by adjusting the blending amount of the raw materials at the time of production of the acrylic / urethane copolymer resin (A).

  As a method for producing the acrylic / urethane copolymer resin (A), for example, a small amount of a dispersant and a polymerization initiator are added to the aqueous dispersion of the aqueous urethane described above, and the acrylic monomer is stirred while maintaining a constant temperature. While gradually adding, then raise the temperature as necessary, continue the reaction for a certain period of time to complete the polymerization of the acrylic monomer, and obtain a water dispersion of acrylic-urethane copolymer resin, etc. It is not limited to this.

  The content of the acrylic / urethane copolymer resin (A) needs to be 40 to 70 parts by weight when the content of (A) and (B) in the coating composition is 100 parts by weight, More preferably, it is 50-60 weight part. When a layer (composition layer) using the coating composition of the present invention is provided on a thermoplastic resin film by using 40 to 70 parts by weight of the acrylic / urethane copolymer resin (A) to form a laminated film In addition to being able to impart good transparency, it is possible to impart adhesion to UV ink, which will be described later, and adhesion after UV irradiation.

(2) Isocyanate compound (B)
Examples of the isocyanate compound that can be used in the coating composition of the present invention include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, metaxylylene diisocyanate, hexamethylene-1,6-diisocyanate, 1,6- Diisocyanate hexane, adduct of tolylene diisocyanate and hexane triol, adduct of tolylene diisocyanate and trimethylol propane, polyol-modified diphenylmethane-4,4′-diisocyanate, carbodiimide-modified diphenylmethane-4,4′-diisocyanate, isophorone diisocyanate, 1 , 5-naphthalene diisocyanate, 3,3′-vitrylene-4,4 ′ diisocyanate, 3,3′dimethyldiphenylmethane-4,4′-diisocyanate, Metaphenylene diisocyanate or the like can be used. In particular, when a polymer-type isocyanate compound having a plurality of isocyanate groups is used at the terminal or side chain of a polymer such as a polyester resin or an acrylic resin, a layer formed by using the coating composition of the present invention (composition When the layer) is provided on a thermoplastic resin film to form a laminated film, the flexibility and toughness of the composition layer can be increased and it can be preferably used.

  Furthermore, in the case of using a coating composition, for example, a blocked isocyanate compound in which the isocyanate group is masked with a blocking agent or the like is preferably used from the viewpoint of easy reaction of the isocyanate group with the water and pot life of the coating agent. be able to. A typical example of the blocking agent is a system in which the blocking agent is volatilized by heating after coating and heat in the drying process, and an isocyanate group is exposed to cause a crosslinking reaction. The isocyanate group may be either a monofunctional type or a polyfunctional type, but a polyfunctional type block polyisocyanate compound can be suitably used in that the crosslinking density can be easily increased. Examples of low-molecular or high-molecular compounds having two or more blocked isocyanate groups include tolylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane 3-mole adduct, polyvinyl isocyanate, vinyl isocyanate copolymer, polyurethane-terminated diisocyanate. , A methyl ethyl ketone oxime block of tolylene diisocyanate, a sodium hyposulfite block of hexamethylene diisocyanate, a methyl ethyl ketone oxime block of a polyurethane-terminated diisocyanate, a phenol block of trimethylolpropane to a tolylene diisocyanate 3 mol adduct, and the like. it can.

  The content of the isocyanate compound (B) needs to be 30 to 60 parts by weight, more preferably 40 to 50, when the content of (A) and (B) in the coating composition is 100 parts by weight. Parts by weight. In addition to forming a tough composition layer by using 30 to 60 parts by weight of the isocyanate compound (B), a layer (composition layer) comprising the coating composition of the present invention is provided on the thermoplastic resin film. When the laminated film is used, the adhesion between the laminated film and the UV ink can be made better than when the acrylic / urethane copolymer resin (A) is used alone.

(3) Oxazoline compound (C)
The oxazoline compound that can be used in the coating composition of the present invention is not particularly limited as long as it has at least one oxazoline group or oxazine group per molecule, but an addition polymerizable oxazoline group-containing monomer alone. Polymerization or a polymer type polymerized with other monomers is preferred. By using a polymer type oxazoline compound, when a layer (composition layer) using the coating composition of the present invention is provided on a thermoplastic resin film to form a laminated film, the flexibility of the composition layer This is because the property, toughness, water resistance, and solvent resistance are enhanced.

  As addition-polymerizable oxazoline group-containing monomers, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline. These may be used alone or in a mixture of two or more. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. The other monomer is not limited as long as it is a monomer copolymerizable with an addition-polymerizable oxazoline group-containing monomer, such as alkyl acrylate, alkyl methacrylate (the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, (Meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group), acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.), unsaturated nitriles such as acrylonitrile, methacrylonitrile; acrylamide, methacrylamide, N-alkylacrylamide N-alkyl methacrylamide N, N-dialkylacrylamide, N, N-dialkylmethacrylate (as alkyl groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group) , Cyclohexyl groups, etc.), vinyl esters such as vinyl acetate, vinyl propionate, acrylic acid, methacrylic acid with polyalkylene oxide added to the ester moiety, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, etc. , Α-olefins such as ethylene and propylene, halogen-containing α and β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride, α and β-unsaturated aromatics such as styrene and α-methylstyrene Group monomers and the like, one or more of these It may be used monomers.

  The content of the oxazoline compound (C) needs to be 20 to 40 parts by weight when the content of (A) and (B) in the coating composition is 100 parts by weight. By using 20 to 40 parts by weight, when a layer (composition layer) using the coating composition of the present invention is provided on a thermoplastic resin film to form a laminated film, high moisture and heat resistance and boiling resistance An improvement in adhesiveness can be imparted to the laminated film.

(4) Carbodiimide compound (D)
The carbodiimide compound that can be used in the coating composition of the present invention is not particularly limited as long as it has at least one carbodiimide structure represented by the following general formula (1) per molecule. A polycarbodiimide compound having two or more in one molecule is particularly preferable in terms of thermal adhesiveness and boiling resistance. In particular, when a polymer-type isocyanate compound having a plurality of carbodiimide groups is used at the terminal or side chain of a polymer such as a polyester resin or an acrylic resin, a layer formed by using the coating composition of the present invention (composition When the layer) is provided on a thermoplastic resin film to form a laminated film, the flexibility and toughness of the composition layer can be increased and it can be preferably used.
-N = C = N- (1)
A known technique can be applied to the production of the polycarbodiimide compound, and it is generally obtained by polycondensation of a diisocyanate compound in the presence of a catalyst. As the diisocyanate compound that is a starting material of the polycarbodiimide compound, aromatic, aliphatic, and alicyclic diisocyanates can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane. Diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate and the like can be used. Furthermore, in order to improve the water solubility and water dispersibility of the polycarbodiimide compound within the range not losing the effect of the present invention, a surfactant is added, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, hydroxy A hydrophilic monomer such as an alkyl sulfonate may be added or used.

In the present invention, an isocyanate compound (B), an oxazoline compound (C), and a carbodiimide compound (D) are used. In addition to the compound, other compounds such as a melamine compound (E), an epoxy compound are used. , Aziridine compounds, amide epoxy compounds, titanate coupling agents such as titanium chelates, methylolated or alkylolated urea compounds, acrylamide compounds, and the like can be optionally used.
The content of the carbodiimide compound (D) needs to be 20 to 40 parts by weight when the contents of (A) and (B) in the coating composition are 100 parts by weight. By using 20 to 40 parts by weight, when a layer (composition layer) using the coating composition of the present invention is provided on a thermoplastic resin film to form a laminated film, a high moisture and heat resistant adhesive property is obtained. Can be granted. Further, when used in combination with the oxazoline compound (C), the laminated film is imparted with a heat and heat resistance higher than that of the oxazoline compound (C) or the carbodiimide compound (D) alone and extremely good boiling resistance that cannot be achieved by each of them. be able to.

(5) Melamine compound (E)
The coating composition of the present invention preferably further contains a melamine compound (E).

  The melamine compound used in the coating composition of the present invention is not particularly limited. However, methylol melamine derivatives obtained by condensing melamine and formaldehyde in terms of hydrophilization, methyl alcohol and ethyl alcohol as lower alcohols. And compounds obtained by etherification by dehydration condensation reaction of isopropyl alcohol and the like.

  Examples of methylolated melamine derivatives include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine.

  The content of the melamine compound (E) is preferably 10 to 30 parts by weight when the contents of (A) and (B) in the coating composition are 100 parts by weight. By using 10 to 30 parts by weight, when a layer (composition layer) using the coating composition of the present invention is provided on a thermoplastic resin film to form a laminated film, adhesion between the laminated film and the UV ink is achieved. The property can be made better.

(6) Organometallic compound (F)
The coating composition of the present invention preferably further contains an organometallic compound (F).

  The organometallic compound that can be used in the coating composition of the present invention contains a metal atom and generally undergoes an addition reaction such as an isocyanate group, a hydroxyl group, a carboxyl group, or an amino group, a polymerization reaction, or a crosslinking reaction. It is not particularly limited as long as it is a compound having a catalytic action to promote, but is preferably one in which the metal atom contained is selected from organometallic compounds consisting of tin, bismuth, zirconium, aluminum, titanium, iron and zinc, and further for coating In consideration of application to the composition, a chelate compound is preferable. In particular, tin-based compounds, zirconium-based compounds, and titanium-based compounds having a high reaction promoting effect are preferable.

  The organometallic compound (F) is preferably 0.3 to 1.0 part by weight when the content of (A) and (B) in the coating composition is 100 parts by weight. By using 0.3 to 1.0 part by weight, when a layer (composition layer) using the coating composition of the present invention is provided on a thermoplastic resin film, the degree of crosslinking of the composition layer is improved. Thus, it becomes possible to provide a stronger composition layer, and whitening with time can be significantly suppressed.

  Then, the laminated | multilayer film which uses the composition for coating mentioned above are demonstrated. The laminated film of the present invention is a laminated film obtained by providing a layer (composition layer) using the above-described coating composition on at least one surface of a thermoplastic resin film.

(7) Thermoplastic resin film The thermoplastic resin film used in the laminated film of the present invention is a general term for films made of a thermoplastic resin and melted or softened by heat, and is not particularly limited. . Examples of thermoplastic resins include polyester resins, polypropylene resins, polyolefin resins such as polyethylene films, polylactic acid resins, polycarbonate resins, acrylic resins such as polymethacrylate resins and polystyrene resins, polyamide resins such as nylon resins, polyvinyl chloride resins, A polyurethane resin, a fluororesin, a polyphenylene resin, etc. are mentioned. The thermoplastic resin used for the thermoplastic resin film may be a monopolymer or a copolymer. A plurality of resins may be used.

  Typical examples of thermoplastic resin films using these thermoplastic resins include polyester films, polyolefin films such as polypropylene films and polyethylene films, polylactic acid films, polycarbonate films, acrylic films such as polymethacrylate films and polystyrene films, and nylon. Examples thereof include polyamide films, polyvinyl chloride films, polyurethane films, fluorine-based films, polyphenylene sulfide films, and the like.

  Of these, polyester films, polypropylene films, polyamide films and the like are preferable in terms of mechanical properties, dimensional stability, transparency, and polyester films are particularly preferable in terms of mechanical strength and versatility.

  Therefore, in the present invention, the polyester resin constituting the polyester film particularly preferably used as the thermoplastic resin film will be described in detail below.

  First, polyester is a general term for polymers having an ester bond as a main bond chain, and includes ethylene terephthalate, propylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene-2,6-naphthalate. , One having at least one component selected from ethylene-α, β-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylate as a main component can be preferably used. These constituent components may be used alone or in combination of two or more. Among them, it is particularly preferable to use ethylene terephthalate in view of quality, economy and the like. That is, in the present invention, it is preferable to use polyethylene terephthalate as the thermoplastic resin used for the thermoplastic resin film. When heat or shrinkage stress acts on the thermoplastic resin film, polyethylene-2,6-naphthalate having excellent heat resistance and rigidity is particularly preferable. These polyesters may further contain a part of other dicarboxylic acid components and diol components, preferably 20 mol% or less.

  The intrinsic viscosity (measured in o-chlorophenol at 25 ° C.) of the above-mentioned polyester is preferably 0.4 to 1.2 dl / g, more preferably 0.5 to 0.8 dl / g. Is suitable for carrying out the present invention.

  The polyester film using the polyester is preferably biaxially oriented. A biaxially oriented polyester film is generally an unstretched polyester sheet or film that is stretched about 2.5 to 5 times in the longitudinal direction and in the width direction perpendicular to the longitudinal direction, and then subjected to heat treatment to produce crystals. The alignment is completed, and it indicates a biaxial alignment pattern by wide-angle X-ray diffraction. When the thermoplastic resin film is not biaxially oriented, it is not preferable because the thermal stability of the conductive film, particularly the dimensional stability and mechanical strength are insufficient or the flatness is poor.

  Further, in the thermoplastic resin film, various additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, a pigment, a dye, an organic or inorganic fine particle, a filler, Antistatic agents, nucleating agents, and the like may be added to such an extent that the characteristics are not deteriorated.

  The thickness of the thermoplastic resin film is not particularly limited and is appropriately selected depending on the application and type, but is preferably preferably 10 to 500 μm, more preferably 38 from the viewpoint of mechanical strength, handling properties, and the like. ˜250 μm, most preferably 75 to 150 μm. Further, the thermoplastic resin film may be a composite film obtained by coextrusion or a film obtained by bonding the obtained film by various methods.

(8) Method for forming composition layer In the present invention, the acrylic / urethane copolymer resin (A), the isocyanate compound (B), the oxazoline compound (C), the carbodiimide compound (D), and a solvent as necessary are used. A composition layer can be formed on a thermoplastic resin film by apply | coating the coating composition to contain on a thermoplastic resin film, and drying a solvent as needed.

  In the present invention, it is preferable to use an aqueous solvent (G) as a solvent. This is because the use of the aqueous solvent can suppress the rapid evaporation of the solvent in the drying step and can form a uniform composition layer, and is excellent in terms of environmental load.

  Here, the aqueous solvent (G) is water or water and alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, and glycols such as ethylene glycol, diethylene glycol and propylene glycol. The organic solvent that is soluble is mixed at an arbitrary ratio. This is because the use of the aqueous solvent can suppress the rapid evaporation of the solvent in the drying step and can form a uniform composition layer, and is excellent in terms of environmental load.

  As a method for applying the coating composition to the thermoplastic resin film, either an in-line coating method or an off-coating method can be used, but an in-line coating method is preferred.

  The in-line coating method is a method of applying in the process of manufacturing a thermoplastic resin film. Specifically, it refers to a method of coating at any stage from melt extrusion of a thermoplastic resin to biaxial stretching followed by heat treatment and winding up, and is usually substantially obtained after melt extrusion and rapid cooling. Unstretched (unoriented) thermoplastic resin film (A film) in an amorphous state, then uniaxially stretched (uniaxially oriented) thermoplastic resin film (B film) stretched in the longitudinal direction, or further stretched in the width direction It is applied to any film of biaxially stretched (biaxially oriented) thermoplastic resin film (C film) before heat treatment.

  In the present invention, the coating composition is applied to any one of the A film, B film, and C film before the crystal orientation is completed, and then the thermoplastic resin film is uniaxially or biaxially coated. It is preferable to employ a method of stretching the shaft and performing a heat treatment at a temperature higher than the boiling point of the solvent to complete the crystal orientation of the thermoplastic resin film and to provide a composition layer. According to such a method, the production of the thermoplastic resin film and the coating and drying of the coating composition (that is, the formation of the composition layer) can be performed at the same time. Moreover, it is easy to make the thickness of the composition layer thinner in order to perform stretching after coating.

  Especially, the method of apply | coating the composition for coating to the film (B film) uniaxially stretched to the longitudinal direction, and extending | stretching to the width direction after that and heat-processing is excellent. After applying to an unstretched film, the stretching process is less than once compared to the method of biaxial stretching, so it is difficult to cause defects or cracks in the composition layer due to stretching, and a composition layer excellent in transparency and smoothness This is because it can be formed.

  On the other hand, the off-line coating method is a film after the A film is stretched uniaxially or biaxially and subjected to heat treatment to complete the crystal orientation of the thermoplastic resin film, or the film forming process of the film on the A film. In this method, the coating composition is applied in a separate step.

  In the present invention, the composition layer is preferably provided by an in-line coating method from the various advantages described above.

  Therefore, the best method for forming a composition layer in the present invention is to form an aqueous coating composition using an aqueous solvent (G) by applying it on a thermoplastic resin film using an in-line coating method and drying it. It is a method to do. More preferably, the coating composition is in-line coated on the uniaxially stretched B film. Furthermore, the solid content concentration of the coating composition is preferably 5% by weight or less. By setting the solid content concentration to 5% or less, good coating properties can be imparted to the coating composition, and a laminated film provided with a transparent and uniform composition layer can be produced.

(9) Preparation method of coating composition using aqueous solvent (G) The coating composition using aqueous solvent (G) was water-dispersed or water-solubilized as necessary (A) to (D). The aqueous compound and the aqueous solvent (G) can be prepared by mixing and stirring in a desired solid content weight ratio in any order.

Subsequently, it can produce by mixing and stirring (E) or / and (F) to the said composition for a coating by the desired solid content weight ratio in arbitrary orders as needed.
The mixing and stirring methods can be performed by shaking the container by hand, using a magnetic stirrer or stirring blade, irradiating ultrasonic waves, vibrating and dispersing.
Further, if necessary, various additives such as lubricants, inorganic particles, organic particles, surfactants and antioxidants may be added to such an extent that the properties of the composition layer provided by the coating composition are not deteriorated. .

(10) Coating method The coating method of the coating composition on the thermoplastic resin film is a known coating method such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, or a blade coating method. Can be used.

(11) Method for Producing Laminate Film Next, the method for producing a laminate film of the present invention will be described with reference to a case where a polyethylene terephthalate (hereinafter abbreviated as PET) film is used as a thermoplastic resin film. It is not limited to. First, PET pellets are sufficiently vacuum-dried, then supplied to an extruder, melt extruded into a sheet at about 280 ° C., and cooled and solidified to produce an unstretched (unoriented) PET film (A film). This film is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially oriented PET film (B film). The coating composition of the present invention prepared at a predetermined concentration is applied to one side of the B film. At this time, surface treatment such as corona discharge treatment may be performed on the coated surface of the PET film before coating. By performing surface treatment such as corona discharge treatment, the wettability of the coating composition to the PET film can be improved, the coating composition can be prevented from being repelled, and a uniform coating thickness can be achieved.

  After the application, the edge of the PET film is held with a clip and guided to a heat treatment zone (preheating zone) of 80 to 130 ° C., and the solvent of the coating composition is dried. After drying, the film is stretched 1.1 to 5.0 times in the width direction. Subsequently, it is guided to a heat treatment zone (heat setting zone) at 160 to 240 ° C., and heat treatment is performed for 1 to 30 seconds to complete crystal orientation.

  In this heat treatment step (heat setting step), a relaxation treatment of 3 to 15% may be performed in the width direction or the longitudinal direction as necessary. The laminated film thus obtained is transparent and becomes a laminated film excellent in adhesiveness to UV ink, moisture and heat resistant adhesiveness, adhesiveness after UV irradiation, and whitening with time.

(Characteristic measurement method and effect evaluation method)
The characteristic measurement method and effect evaluation method in the present invention are as follows.

(1) Adhesion with UV ink (adhesion under normal conditions)
Under normal conditions, in order to evaluate the wide ink adhesion of the laminated film according to the present invention, various types of inks and paints were used. First, as a printing ink, an organic solvent paint type ultraviolet curable hard coating agent (ink A), a solventless ultraviolet curable resin (ink B), and two types of ultraviolet curable offset inks (inks C and D) were used. (The following four types of ink).

Ink A: Hard coating agent (adjusted with the following composition ratio)
Dipentaerythritol hexaacrylate: 70 parts by weight N-vinylpyrrolidone: 30 parts by weight 1-hydroxycyclohexyl phenyl ketone: 4 parts by weight

Ink B: Solventless transparent ultraviolet curable resin (adjusted with the following composition ratio)
-Sanyo Chemical Co., Ltd. "Sun Rad" RC-610: 60 parts by weight Mitsubishi Rayon Co., Ltd. "Diabeam" UR-6530: 20 parts by weight Nippon Kayaku Co., Ltd. DPHA: 20 parts by weight.

  Ink C: “Best Cure” 161 Black (T & K Toka Co., Ltd.).

  Ink D: HS ink (HS-OS) manufactured by Kuboi Ink Co., Ltd.

Here, the ink A was applied to the surface of the composition layer of the laminated film using a bar coater so that the film thickness after curing was 5 μm, and then irradiated using an ultraviolet lamp with an irradiation intensity of 120 W / cm. The hard coat layer was cured by UV irradiation at a distance (distance between the lamp and the ink surface) of 12 cm, a conveyor speed of 2 m / min, and an integrated intensity of about 550 mJ / cm ² . Adhesion evaluation was performed using the following cross-cut method.

<Cross cut method>
Put 100 crosscut of 1 mm ² to the cured film of the ultraviolet curable ink, paste Nichiban Co., Ltd. manufactured cellophane tape (registered trademark) thereon, using a rubber roller, is 3 shuttled load 19.6N After pressing, the film was peeled in the direction of 90 ° and evaluated by the number of remaining cured films, and the remaining number of 80 or more was considered good adhesion.

Ink B was applied to the composition layer surface of the laminated film so as to have a thickness of about 25 μm by the wire bar coating method, and then an ultraviolet ray lamp with an irradiation intensity of 120 W / cm was used, and the irradiation distance (of the lamp and the ink surface) Distance) was 12 cm, UV irradiation was carried out at a conveyor speed of 2 m / min and an integrated intensity of about 550 mJ / cm ² to cure the solvent-free transparent ultraviolet curable resin. In addition, adhesive evaluation was performed by the above-mentioned crosscut method.

For ink C, the ink was applied to the composition layer surface of the laminated film to a thickness of about 1.5 μm by a roll coating method. Then, using an ultraviolet lamp with an irradiation intensity of 120 W / cm, UV irradiation was performed at an irradiation distance (distance between the lamp and the ink surface) of 12 cm, a conveyor speed of 6 m / min, and an integrated intensity of about 200 mJ / cm ^2. Cured. In addition, adhesive evaluation was performed by the above-mentioned crosscut method.

  For ink D, the ink was applied to the surface of the composition layer of the laminated film to a thickness of about 1.5 μm by roll coating. Thereafter, it was allowed to stand and cure under normal conditions for 24 hours. In addition, adhesive evaluation was performed by the above-mentioned crosscut method.

(2) Moisture and heat resistance adhesiveness The ink A was applied to the composition layer surface of the laminated film and cured in the same manner as in the evaluation of (1) to obtain a moisture and heat resistance resistance evaluation sample. Next, the above-described cross-cut method was used for a sample which was allowed to stand at 70 ° C. and 90% relative humidity for 240 hours and then dried for 1 hour in a normal state (23 ° C. and relative humidity 65%). The adhesiveness was evaluated.

(3) Moist heat resistant adhesion after UV irradiation Before applying the ink A, the composition layer of the laminated film was irradiated with UV on the same conditions as the curing conditions after application, and then the ink A (1) In the same manner as in the above evaluation, the sample was applied and cured on the surface of the composition layer of the laminated film to obtain a sample for evaluating moisture and heat resistance after UV irradiation. Next, in the same manner as in the evaluation in (2), the cross-cut method described above was applied to a sample that was left for 240 hours at 70 ° C. and 90% relative humidity and then dried for one hour in a normal state (23 ° C. and 65% relative humidity). It was used to evaluate adhesion.

(4) Transparency Evaluation of transparency used haze and total light transmittance. For measurement of haze and total light transmittance, in a normal state (23 ° C., relative humidity 65%), the laminated film was left for 2 hours, and then a fully automatic direct reading haze computer “HGM-2DP” manufactured by Suga Test Instruments Co., Ltd. was used. I went. The average value measured three times was used as the haze value of the sample.

(5) Evaluation of whitening over time The laminated film was allowed to stand for 30 days under normal conditions (23 ° C., relative humidity 65%), and then the whitening over time of the laminated film was visually evaluated by comparison with that immediately after the production of the laminated film.

<Whitening evaluation over time>
：: No change ○: Slightly whitened △: Whitened ×: Whitening is remarkable Note that (◎) and (◯) were good in the whitening evaluation with time.

(6) Boiling-proof adhesiveness The said ink A was apply | coated and hardened to the composition layer surface of a laminated film similarly to evaluation of (1), and the boiling-proof adhesiveness evaluation sample was obtained. Next, boil-resistant adhesion evaluation samples were cut into a size of 10 cm × 10 cm, each was fixed to a clip and suspended, and then laminated in boiling water (100 ° C.) made of pure water prepared in a beaker. The whole film was immersed for 3 hours. Thereafter, a sample for evaluation of boiling resistance was taken out and dried in a normal state (23 ° C., relative humidity 65%) for 1 hour. After drying, the adhesion evaluation of the boiling resistance evaluation sample was performed by the cross-cut method described above. Of 100 crosscuts, the remaining number of hard coat films was 80 or more.

  The present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples.

Example 1
The coating composition was prepared as follows.

Acrylic / urethane copolymer resin (A):
Acrylic / urethane copolymer resin anionic water dispersion ("Sannaron" WG-353 (prototype) manufactured by Shannan Synthetic Chemical Co., Ltd.). The acrylic resin component / urethane resin component (polycarbonate) has a solid weight ratio of 12/23, and 2 parts by weight of triethylamine is used as an aqueous dispersion.

Isocyanate compound (B):
Polyisocyanate aqueous dispersion (“Burnock” DNW-500, manufactured by DIC Corporation).

Oxazoline compound (C):
Oxazoline-containing polymer aqueous dispersion (“Epocross” WS-500, manufactured by Nippon Shokubai Co., Ltd.).

Carbodiimide compound (D):
Carbodiimide aqueous crosslinking agent (Nisshinbo Chemical Co., Ltd. “Carbodilite” V-04).

Aqueous solvent (G):
Pure water.

  The above-mentioned (A) to (D) and (G) are in a solid content weight ratio such that (A) / (B) / (C) / (D) = 40/60/30/30 and solid The mixture was mixed and adjusted so that the partial concentration was the value described in the table.

  Next, PET pellets (intrinsic viscosity 0.63 dl / g) substantially free of particles were sufficiently dried in vacuum, then supplied to an extruder, melted at 285 ° C., extruded into a sheet form from a T-shaped die, It was wound around a mirror-casting drum having a surface temperature of 25 ° C. using an electric application casting method and cooled and solidified. This unstretched film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film (B film). This film was subjected to corona discharge treatment in air.

  Next, the aqueous coating composition was applied to the corona discharge treated surface of the uniaxially stretched film using a bar coat. After gripping both ends in the width direction of the uniaxially stretched film coated with the aqueous coating composition to the preheating zone with a clip and setting the ambient temperature to 75 ° C, the ambient temperature was subsequently set to 110 ° C using a radiation heater, and then The coating composition was dried at an atmospheric temperature of 90 ° C. to form a composition layer. Continuously stretched 3.5 times in the width direction in a heating zone (stretching zone) at 120 ° C, and then heat treated for 20 seconds in a heat treatment zone (heat setting zone) at 230 ° C to complete the crystal orientation. Got. In the obtained laminated film, the thickness of the PET film was 100 μm. The characteristics of the obtained laminated film are shown in the table. It was excellent in transparency such as haze and total light transmittance, and also excellent in adhesion to UV ink, moisture and heat resistance, boiling resistance, adhesion after UV irradiation, and whitening with time.

(Examples 2 to 8)
A laminated film was obtained in the same manner as in Example 1 except that the solid content weight ratio and solid content concentration of (A) to (D) were changed to the numerical values shown in the table. The characteristics of the obtained laminated film are shown in the table. It was excellent in transparency such as haze and total light transmittance, and also excellent in adhesion to UV ink, moisture and heat resistance, boiling resistance, adhesion after UV irradiation, and whitening with time.

Example 9
In addition to (A) to (D) described in Example 1, the following melamine compound (E) was used, and in terms of solid content weight ratio, (A) / (B) / (C) / (D) / A laminated film was obtained in the same manner as in Example 1 except that (E) was adjusted to be 40/60/30/30/10.

  Melamine compound (E): Melamine resin water sol (“WATERSOL” S-695 manufactured by DIC Corporation).

  The characteristics of the laminated film are shown in the table. It was excellent in transparency such as haze and total light transmittance, and also excellent in adhesion to UV ink, moisture and heat resistance, boiling resistance, adhesion after UV irradiation, and whitening with time.

(Examples 10 to 20)
A laminated film was obtained in the same manner as in Example 9 except that the solid content weight ratio and solid content concentration of (A) to (E) were changed to the numerical values shown in the table. The characteristics of the obtained laminated film are shown in the table. It was excellent in transparency such as haze and total light transmittance, and also excellent in adhesion to UV ink, moisture and heat resistance, boiling resistance, adhesion after UV irradiation, and whitening with time.

(Example 21)
In addition to (A) to (D) described in Example 1, the following organometallic compound (F) was used, and (A) / (B) / (C) / (D ) / (F) = 40/60/30/30 / 0.6 A laminated film was obtained in the same manner as in Example 1 except that adjustment was made.

  Organometallic compound (F): an organozirconium compound (“Orgachix” ZB-126, manufactured by Matsumoto Fine Chemical Co., Ltd.).

  The characteristics of the obtained laminated film are shown in the table. It was excellent in transparency such as haze and total light transmittance, and also excellent in adhesion to UV ink, moisture and heat resistance, boiling resistance, adhesion after UV irradiation, and whitening with time.

(Examples 22 to 31)
A laminated film was obtained in the same manner as in Example 21, except that the solid content weight ratio and the solid content concentration of (A) to (F) were changed to the numerical values shown in the table. The characteristics of the obtained laminated film are shown in the table. It was excellent in transparency such as haze and total light transmittance, and also excellent in adhesion to UV ink, moisture and heat resistance, boiling resistance, adhesion after UV irradiation, and whitening with time.

(Example 32)
In addition to (A) to (D) described in Example 1, the melamine compound (E) described in Example 9 and the organometallic compound (F) described in Example 21 were used. Example except that the weight ratio was adjusted to be (A) / (B) / (C) / (D) / (E) / (F) = 40/60/30/30/10 / 0.6 1 was used to obtain a laminated film.
The characteristics of the obtained laminated film are shown in the table. It was excellent in transparency such as haze and total light transmittance, and also excellent in adhesion to UV ink, moisture and heat resistance, boiling resistance, adhesion after UV irradiation, and whitening with time.

(Examples 33 to 42)
A laminated film was obtained in the same manner as in Example 32 except that the solid content weight ratio and solid content concentration of (A) to (F) were changed to the numerical values shown in the table. The characteristics of the obtained laminated film are shown in the table. It was excellent in transparency such as haze and total light transmittance, and also excellent in adhesion to UV ink, moisture and heat resistance, boiling resistance, adhesion after UV irradiation, and whitening with time.

(Comparative Examples 1-10)
A laminated film was obtained in the same manner as in Example 1 except that the solid content weight ratio and solid content concentration of (A) to (D) were adjusted to the numerical values described in the table. The characteristics of the obtained laminated film are shown in the table.
The laminated film of Comparative Example 1 is excellent in transparency such as haze and total light transmittance, but has poor performance in adhesion with UV ink, resistance to boiling, adhesion after UV irradiation, and whitening with time. Met.

  Moreover, although the laminated film of Comparative Example 2 was excellent in transparency such as haze and total light transmittance, the performance was inferior in adhesiveness with UV ink, wet heat resistance, and boiling resistance. .

  Moreover, although the laminated film of Comparative Example 3 is excellent in transparency such as haze and total light transmittance, adhesion with UV ink, wet heat resistance, boiling resistance, adhesion after UV irradiation, The performance was inferior in whitening over time.

  Further, the laminated film of Comparative Example 4 had high haze, and was inferior in performance with respect to adhesion with UV ink, wet heat resistance, boiling resistance, adhesion after UV irradiation, and whitening with time.

  In addition, the laminated film of Comparative Example 5 is excellent in transparency such as haze and total light transmittance, but has poor performance in terms of adhesion to UV ink, moisture and heat resistance, and boiling resistance. It was.

  Moreover, although the laminated film of Comparative Example 6 was excellent in transparency such as haze and total light transmittance, the performance was poor in adhesion to UV ink and whitening with time.

  Moreover, although the laminated film of Comparative Example 7 was excellent in transparency such as haze and total light transmittance, the performance was inferior in adhesiveness to UV ink, wet heat resistance, and boiling resistance. .

  Moreover, although the laminated film of Comparative Example 8 was excellent in transparency such as haze and total light transmittance, the performance was poor in adhesiveness with UV ink and whitening with time.

  Moreover, although the laminated film of Comparative Example 9 is excellent in transparency such as haze and total light transmittance, adhesion with UV ink, wet heat resistance, boiling resistance, adhesion after UV irradiation, The performance was inferior in whitening over time.

  Moreover, although the laminated film of Comparative Example 10 is excellent in transparency such as haze and total light transmittance, adhesion with UV ink, wet heat resistance, boiling resistance, adhesion after UV irradiation, The performance was inferior in whitening over time.

The present invention is not only for initial adhesiveness, but particularly for wet and heat resistant adhesiveness, boiling resistant adhesiveness, adhesiveness after UV irradiation, and for coating that constitutes a composition layer with very little change in coating appearance over time. The present invention relates to a laminated film obtained by laminating a composition and a composition layer using the composition, and includes an optical easy-adhesive film for display applications, window glass for automobiles and buildings, doors of system kitchens and unit baths, It can be used for an easy-adhesion film for a hard coat film used for building materials such as windows and the like, and an easy-adhesion film excellent in adhesiveness with various clothes such as ink.

Claims (6)

A coating composition containing an acrylic / urethane copolymer resin (A), an isocyanate compound (B), an oxazoline compound (C) and a carbodiimide compound (D),
Coating in which the content of (A), (B), (C) and (D) satisfies the following relationship when the total content of (A) and (B) in the composition is 100 parts by weight Composition.
(A): 40 to 70 parts by weight (B): 30 to 60 parts by weight (C): 20 to 40 parts by weight (D): 20 to 40 parts by weight A coating composition according to claim 1,
The composition further contains a melamine compound (E),
And the composition for coating whose content of (E) is 10-30 weight part when the sum total of content of (A) and (B) in this composition is 100 weight part. A coating composition according to claim 1 or 2,
The composition further contains an organometallic compound (F),
And the composition for coating whose content of (F) is 0.3-1.0 weight part when the sum total of content of (A) and (B) in this composition is 100 weight part. The coating composition according to any one of claims 1 to 3, wherein the acrylic / urethane copolymer resin (A) is a resin comprising a polycaprolactone urethane component and / or a polycarbonate urethane component. A laminated film comprising a layer (composition layer) formed by using the coating composition according to any one of claims 1 to 4 on at least one surface of a thermoplastic resin film. The laminated film according to claim 5, wherein the thermoplastic resin film is a polyethylene terephthalate film or a polyethylene-2,6-naphthalate film.