JP6181435B2 - Laminated body and method for producing the same - Google Patents

Description

  The present invention relates to a laminate having a cyclic polyolefin resin coat layer and a method for producing the same.

  Polyolefin materials represented by polyethylene and polypropylene have a good balance of physical properties such as mechanical properties and electrical properties, and are inexpensive, so they are widely used in various fields such as electricity, electronics, automobiles and packaging, and in large quantities. It is used. However, since polyolefin has a low surface free energy, it has difficulty in paintability and adhesion. Among them, the cyclic polyolefin resin has different resin characteristics compared to a normal crystalline polyolefin resin because it is non-crystalline, and has different properties in terms of wettability and adhesion, making it more difficult to bond. Known as material.

  On the other hand, since the cyclic polyolefin resin has the characteristics of excellent solubility and dispersibility in a solvent, it can be dissolved in a medium such as a solvent or water as proposed in Patent Document 1, Patent Document 2, and the like. It can be dispersed and processed into a coating agent. Such a coating agent usually has excellent transparency.

  However, even when the cyclic polyolefin resin is a coating agent shown in Patent Document 1, Patent Document 2, etc., there is a problem in use as a coating agent because of poor coating properties and adhesion to the substrate. . Patent Document 3 proposes a coating agent for a cyclic polyolefin resin with improved adhesion to a substrate, but even with this technique, the adhesion is still insufficient and there is room for improvement.

In addition, the coating layer obtained by coating and drying the coating agent of the cyclic polyolefin resin is poor in the drying property of the medium, and a large amount of the medium tends to remain in the coating layer. Cracks may occur, which is a problem.
On the other hand, the applicant of this application has proposed a laminate obtained by coating a base material with an aqueous dispersion of a polyolefin resin in Patent Document 4. This laminate is excellent in heat sealability with polyolefin resin. However, Patent Document 4 did not describe a cyclic polyolefin resin substrate such as a cyclic polyolefin resin coat layer.

JP 05-43834 A Japanese Patent Laid-Open No. 04-202277 JP 2004-58339 A JP 2003-103734 A

  The present invention solves the above problems, and by providing a primer layer having a specific composition on the base material layer, the wettability of the cyclic polyolefin resin coating agent to various base materials and the various base materials of the cyclic polyolefin resin coating layer. It is an object of the present invention to provide a laminate that can improve the adhesion to the resin and that can also suppress cracking of the cyclic polyolefin resin coat layer in the use environment, and a preferred method for producing the laminate.

  As a result of intensive studies to solve the above problems, the present inventors have solved the above problems with a laminate in which an aqueous dispersion of a specific modified polyolefin resin is used as a primer and a cyclic polyolefin resin coat layer is coated thereon. The present invention has been found.

  That is, the gist of the present invention is as follows.

(1) A laminate in which a substrate layer / primer layer / cyclic polyolefin resin coat layer is laminated at least in this order, and the primer layer has an unsaturated carboxylic acid component content of 0.1 to 10% by mass. coating der obtained from an aqueous dispersion containing an acid-modified polyolefin resin is is,
In addition, when the adhesion of the cyclic polyolefin resin coat layer was evaluated according to JIS K5400-8.5 (cross cut test), the number of the cyclic polyolefin resin coat layer in the 100 square cut was not peeled. A laminate characterized by being a cocoon or more .
(2) The laminate according to (1), wherein the aqueous dispersion further contains a crosslinking agent.
(3) The laminate according to (2), wherein the crosslinking agent is at least one selected from the group consisting of a polyvalent oxazoline compound, a polyvalent carbodiimide compound, and a polyvalent hydrazide compound.
(4) The laminate according to any one of (1) to (3), wherein the aqueous dispersion further contains a polyurethane resin.
(5) The laminate according to any one of (1) to (4), wherein the primer layer has a thickness in the range of 0.01 to 5 μm.
(6) The laminate according to any one of (1) to (5), wherein the thickness of the cyclic polyolefin resin coat layer is in the range of 0.1 to 30 μm.
(7) The base material layer is at least one selected from the group consisting of a polyester resin base material, a polycarbonate resin base material, a polymethyl methacrylate resin, and a cyclic polyolefin resin (1) to (6), The laminated body in any one.
(8) The laminate according to any one of (1) to (7), which is an optical film having a total light transmittance of 80 to 97%.
( 9 ) a step of coating a base layer with an aqueous dispersion containing an acid-modified polyolefin resin having an unsaturated carboxylic acid component content of 0.1 to 10% by mass, and forming a primer layer; and a cyclic polyolefin resin And a step of forming a cyclic polyolefin resin coat layer by coating the primer layer with a coating agent containing a primer. (1) to ( 8 ) Method.

  The laminate of the present invention is excellent in adhesion of the cyclic polyolefin resin coat layer, and further has an effect of suppressing cracking of the cyclic polyolefin resin coat layer in the use environment. Further, in the production method of the present invention, when a laminate is produced, a coating agent of a cyclic polyolefin resin is coated on the base material layer. At this time, a primer layer having a specific composition is formed on the base material layer. The coatability of the coating agent is improved, and the adhesion of the coating layer obtained later is also improved. Thereby, it becomes possible to apply the obtained laminated body to various uses including an optical film.

  The present invention will be described in detail below.

  The base material layer in the laminate of the present invention is arbitrarily selected according to the use or purpose to be used. Examples of the material for the base material layer include materials such as metal, glass, resin, rubber, wood, synthetic paper, and paper. Examples of the resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polyethylene succinate resin, polyglycolic acid resin and polylactic acid resin. Polyester resin such as nylon 6, polyamide resin such as nylon 66 and nylon 46, polyolefin resin such as polypropylene resin and polyethylene resin, cyclic polyolefin resin such as cyclic olefin polymer (COP) and cyclic olefin copolymer (COC), polymethacrylic acid Acrylic resins such as methyl resin, cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose butyrate, cellulose Scan acetate propionate or cellulose ester resins such as cellulose acetate butyrate, polycarbonate resins, polyurethane resins, polyimide resins, polyarylate resins, such as ABS resin. These may be single or a plurality of composites. Among these, polyester resin, polycarbonate resin, polymethyl methacrylate resin, cyclic polyolefin resin, and cellulose ester resin are preferable from the viewpoint of adhesion to the primer layer and transparency. In the case of a polyester resin, a polyethylene terephthalate resin and a polyethylene naphthalate resin are preferable, and a polyethylene terephthalate resin is more preferable. In the case of a cellulose ester resin, cellulose triacetate is preferable.

  In addition, when using the laminated body of this invention for an optical film, it is preferable to select a base material layer from a transparent material, and as a total light transmittance of a base material layer, the range of 80 to 97% is preferable.

  Although it does not specifically limit as a form of a base material layer, A film, a molded object, a fiber, a textile fabric, a knitted fabric, a nonwoven fabric etc. are mentioned. Considering versatility, handleability, and optical characteristics, it is preferable to form a film having a thickness of 1 to 200 μm. Among these, a film made of a thermoplastic resin is preferable. In addition, as a film, an unstretched film or a stretched film may be sufficient, and a manufacturing method is not limited.

  The substrate layer may be subjected to surface activation treatment in advance. Examples of the surface activation treatment include corona discharge treatment, flame plasma treatment, atmospheric pressure plasma treatment, low pressure plasma treatment, ozone treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, chemical treatment, and solvent treatment. Corona discharge treatment is preferred from the balance of the adhesion effect.

  The primer layer in the laminate of the present invention is a coating film obtained from an aqueous dispersion containing an acid-modified polyolefin resin having an unsaturated carboxylic acid component content of 0.1 to 10% by mass. In this invention, the effect of this invention can be expressed by providing this primer layer between a base material layer and a cyclic polyolefin resin coat layer. The primer generally means an undercoat. In the present invention, the primer is an undercoat of the cyclic polyolefin resin coat layer.

  The olefin component that is the main component of the acid-modified polyolefin resin is not particularly limited, but an alkene having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene is preferable, Mixtures of these may be used. Among these, from the viewpoint of enhancing the adhesion to the cyclic polyolefin resin coat layer, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferable, ethylene and propylene are further preferable, and ethylene is most preferable.

  In the present invention, the acid-modified polyolefin resin is a polyolefin resin that has been acid-modified with an unsaturated carboxylic acid component. Examples of the unsaturated carboxylic acid component include acrylic acid, methacrylic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. Of these, acrylic acid, methacrylic acid, and (anhydrous) maleic acid are preferable from the viewpoint of adhesion and the effect of suppressing cracking of the cyclic polyolefin resin coating layer, and acrylic acid and (anhydrous) maleic acid are particularly preferable. Moreover, the unsaturated carboxylic acid component should just be copolymerized in acid-modified polyolefin resin, and the form is not specifically limited. Examples of the state of copolymerization include random copolymerization, block copolymerization, and graft copolymerization (graft modification). In addition, “(anhydrous) to acid” means “to acid or anhydrous to acid”. That is, (anhydrous) maleic acid means maleic acid or maleic anhydride.

  The content of the unsaturated carboxylic acid component in the acid-modified polyolefin resin needs to be 0.1 to 10% by mass, preferably 0.2 to 8% by mass, and 0.5 to 5% by mass. It is more preferable that it is 1-5 mass%, and it is especially preferable that it is 2-4 mass%. When the content of the unsaturated carboxylic acid component is less than 0.1% by mass, the adhesiveness is lowered or it is difficult to process into an aqueous dispersion. On the other hand, when the content exceeds 10% by mass There is a tendency that the adhesion, cracking suppressing effect of the cyclic polyolefin resin coat layer, and water resistance are lowered.

  The acid-modified polyolefin resin contains a (meth) acrylic acid ester component in order to improve the wettability when coating the cyclic polyolefin resin in order to obtain sufficient adhesion with the base material layer and the cyclic polyolefin resin coat layer. It is preferable. Examples of the (meth) acrylic acid ester component include an esterified product of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms, and (meth) acrylic acid and carbon number 1 from the viewpoint of easy availability. Esterified products with ˜20 alcohols are preferred. Specific examples of the (meth) acrylic acid ester component include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth ) Octyl acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Among these, from the viewpoint of easy availability and adhesiveness, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, octyl acrylate are more preferable, ethyl acrylate, More preferred is butyl acrylate, and particularly preferred is ethyl acrylate. ("(Meth) acrylic acid-" means "acrylic acid- or methacrylic acid-".

  The content of the (meth) acrylic acid ester component in the acid-modified polyolefin resin is preferably 0.1 to 25% by mass and more preferably 1 to 20% by mass from the viewpoint of adhesion and paintability. 2 to 18% by mass is more preferable, and 3 to 15% by mass is particularly preferable. When the content of the (meth) acrylic acid ester component is less than 0.1% by mass, the adhesion tends to decrease. When the content exceeds 25% by mass, the cracking suppressing effect and water resistance of the cyclic polyolefin resin coating layer are low. There is a tendency to decrease. Further, the (meth) acrylic acid ester component may be copolymerized in the acid-modified polyolefin resin, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and grafting. Examples thereof include copolymerization (graft modification).

  Specific examples of the acid-modified polyolefin resin include ethylene- (meth) acrylic acid esters such as ethylene-ethyl acrylate- (anhydrous) maleic acid copolymer and ethylene-butyl acrylate- (anhydrous) maleic acid copolymer- (Anhydrous) maleic acid copolymer, ethylene-propylene- (meth) acrylic acid ester- (anhydrous) maleic acid copolymer, ethylene-butene- (meth) acrylic acid ester- (anhydrous) maleic acid copolymer, propylene -Butene- (meth) acrylic acid ester- (anhydrous) maleic acid copolymer, ethylene-propylene-butene- (meth) acrylic acid ester- (anhydrous) maleic acid copolymer, ethylene-acrylic acid copolymer, ethylene -Methacrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene-propylene- (anhydrous) Inic acid copolymer, ethylene-butene- (anhydrous) maleic acid copolymer, propylene-butene- (anhydrous) maleic acid copolymer, ethylene-propylene-butene- (anhydrous) maleic acid copolymer, etc. Among them, ethylene- (meth) acrylic acid ester- (anhydrous) maleic acid copolymer is most preferable. The form of the copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like, but a random copolymer and a graft copolymer are preferable because they are easily available.

  The ethylene- (meth) acrylic acid ester- (anhydrous) maleic acid copolymer is described in, for example, British Patent No. 2911745, US Pat. No. 4,617,366 and US Pat. No. 4,644,044. By referring to these methods, those skilled in the art can easily produce them.

  The melt flow rate (MFR) at 190 ° C. and 2160 g load, which is a measure of the molecular weight of the acid-modified polyolefin resin, is in the range of 0.01 to 300 g / 10 min from the viewpoint of adhesion and cracking suppression effect of the cyclic polyolefin resin coating layer. It is preferably 0.1 to 200 g / 10 minutes, more preferably 0.5 to 100 g / 10 minutes, and particularly preferably 1 to 70 g / 10 minutes. When the melt flow rate exceeds 300 g / 10 min, the crack suppressing effect of the cyclic polyolefin resin coat layer tends to be reduced, and when it is less than 0.01 g / 10 min, the adhesiveness tends to decrease, There are restrictions on the manufacturing side when increasing the molecular weight.

  In the present invention, the acid-modified polyolefin resin needs to be used as an aqueous dispersion. Here, the aqueous dispersion containing the acid-modified polyolefin resin will be described. The acid-modified polyolefin resin in the present invention can be processed into an aqueous dispersion by dispersing it in an aqueous medium. As a dispersion method, a known dispersion method such as a self-emulsification method or a forced emulsification method may be employed.

  The aqueous dispersion containing the acid-modified polyolefin resin may be an anionic aqueous dispersion obtained by neutralizing the unsaturated carboxylic acid component of the acid-modified polyolefin resin with a basic compound in an aqueous medium. It is preferable from the viewpoint of adhesiveness.

  The aqueous medium used when the acid-modified polyolefin resin is dispersed in water is a medium composed of water or a liquid containing water, and includes a neutralizing agent that contributes to stabilizing the dispersion, a water-soluble organic solvent, and the like. Also good. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, Alcohols such as 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, and cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, and isophorone; tetrahydrofuran, dioxane, and the like Ethers: ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, acetic acid-sec-butyl, acetic acid-3-methoxybutyl, propio Esters such as methyl acid, ethyl propionate, diethyl carbonate, dimethyl carbonate; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, Glycol derivatives such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate; Butoxy-3-methyl butanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate and the like. In addition, you may use these organic solvents in mixture of 2 or more types. Among these, it is preferable to use a volatile water-soluble organic solvent having a boiling point of 140 ° C. or less because the remaining amount after forming the primer layer can be reduced. Specifically, ethanol, n-propanol, isopropanol, n-butanol and the like are preferable.

  The basic compound used to neutralize the unsaturated carboxylic acid component of the acid-modified polyolefin resin includes ammonia, triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine. , Isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N -Organic amines, such as methyl morpholine, N-ethyl morpholine, sodium hydroxide and potassium hydroxide, and alkali metals. In addition, you may use a basic compound in mixture of 2 or more types. Among these, it is preferable to use a volatile basic compound having a boiling point of 140 ° C. or less because the remaining amount after forming the primer layer can be reduced. Specifically, ammonia, triethylamine, N, N-dimethylethanolamine and the like are preferable.

  When the acid-modified polyolefin resin is dispersed in water, it is preferable that a non-volatile dispersion aid is not substantially added. The acid-modified polyolefin resin in the present invention does not exclude the use of a nonvolatile dispersion aid, but can be stably dispersed in an aqueous medium without using a nonvolatile dispersion aid. By using such an aqueous dispersion of an acid-modified polyolefin resin that does not substantially contain a nonvolatile dispersion aid, the primer layer in the present invention can be obtained without substantially containing a nonvolatile dispersion aid. it can. Therefore, it is preferable that the primer layer in the present invention contains substantially no non-volatile dispersion aid.

  Here, the “aqueous dispersion aid” is a drug or compound added for the purpose of promoting aqueous dispersion or stabilizing the aqueous dispersion in the production of the aqueous dispersion. Means that it does not have a boiling point at normal pressure or has a high boiling point (for example, 300 ° C. or higher) at normal pressure.

  “Substantially free of non-volatile dispersion aid” means that such aid is not used in the production of an aqueous dispersion containing an acid-modified polyolefin resin, and the primer layer in the resulting laminate has this aid. This means that no agent is contained. Therefore, it is particularly preferable that the content of such an aqueous dispersion aid is zero. However, the non-volatile component (solid content) in the aqueous dispersion containing the acid-modified polyolefin resin is within a range that does not impair the effects of the present invention. 3% by mass or less, preferably 1% by mass or less, and more preferably less than 0.5% by mass.

  Examples of the non-volatile dispersion aid in the present invention include an emulsifier described later, a compound having a protective colloid effect, a modified wax, an acid-modified compound having a high acid value, and a water-soluble polymer.

  Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like.

  Compounds having protective colloid action, modified waxes, acid-modified compounds with high acid value, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, modified starch, polyvinylpyrrolidone , Polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax, and other acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid-anhydride Maleic acid copolymer and its salt, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride A copolymer, a carboxyl group-containing polymer containing an unsaturated carboxylic acid content exceeding 10% by mass, such as a (meth) acrylic acid- (meth) acrylic acid ester copolymer, and a salt thereof, polyitaconic acid and a salt thereof, Examples thereof include water-soluble acrylic copolymers having amino groups, gelatin, gum arabic, and casein, and the like compounds generally used as fine particle dispersion stabilizers.

  The number average particle diameter of the acid-modified polyolefin resin in the aqueous dispersion containing the acid-modified polyolefin resin is preferably 0.5 μm or less from the viewpoint of adhesion and dispersion stability, and is in the range of 0.01 to 0.4 μm. It is more preferable that it is 0.02-0.3 micrometer, 0.03-0.2 micrometer is further more preferable, and 0.04-0.1 micrometer is the most preferable.

  The pH of the aqueous dispersion containing the acid-modified polyolefin resin is preferably in the range of pH 7 to 12, more preferably pH 8 to 11, from the viewpoint of dispersion stability.

  In the present invention, the aqueous dispersion containing the acid-modified polyolefin resin is formed of a material other than the crosslinking agent or the acid-modified polyolefin resin for the purpose of further improving the adhesion and cracking suppression effect of the cyclic polyolefin resin coating layer when the primer layer is formed. It preferably contains a resin (hereinafter referred to as “other resin”). The crosslinking agent and the other resin may be used alone or in combination.

  In the present invention, the crosslinking agent is a compound capable of forming a crosslinked structure of the acid-modified polyolefin resin by reacting with the acid-modified polyolefin resin. Specifically, a compound containing a plurality of functional groups capable of reacting with the functional group contained in the acid-modified polyolefin resin in the molecule is exemplified. More specifically, examples include polyvalent oxazoline compounds, polyvalent carbodiimide compounds, polyvalent hydrazide compounds, polyvalent melamine compounds, polyvalent isocyanate compounds, polyvalent urea compounds, polyvalent epoxy compounds, polyvalent amine compounds, These crosslinking agents may be used in combination. Among these crosslinking agents, a polyvalent oxazoline compound, a polyvalent carbodiimide compound, and a polyvalent hydrazide compound are preferable from the viewpoint of further improving the adhesion and the cracking suppressing effect of the cyclic polyolefin resin coat layer. The crosslinking agent may be a low molecular weight compound or a polymer type.

  In the present invention, the crosslinking agent is preferably used as an aqueous solution or an aqueous dispersion as described later. That is, the cross-linking agent is preferably water-soluble or water-dispersible. The method for processing the crosslinking agent into an aqueous solution or an aqueous dispersion is not particularly limited, and a known method can be employed.

  Examples of the aqueous solution or aqueous dispersion of the polyvalent oxazoline compound include “Epocross (registered trademark)” manufactured by Nippon Shokubai Co., Ltd., and examples of the aqueous solution or aqueous dispersion of the polyvalent carbodiimide compound include “ Carbodilite (registered trademark) ". In any case, commercially available products can be used.

  The crosslinking agent is preferably contained in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the acid-modified polyolefin resin in the aqueous dispersion containing the acid-modified polyolefin resin. The range of parts is more preferable, the range of 0.3 to 10 parts by mass is particularly preferable, and the range of 0.5 to 5 parts by mass is further preferable. When the crosslinking agent is out of the above range, the adhesion and the effect of suppressing cracking of the cyclic polyolefin resin coat layer may be deteriorated.

  Other resins include polyurethane resin, acrylic resin, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, acrylic silicon resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic copolymer, ethylene-aminoacrylamide copolymer , Ethylene-aminoacrylate copolymer, polyvinylidene chloride, styrene-maleic acid resin, styrene-aminoalkylmaleimide copolymer, styrene-butadiene resin, styrene elastomer, butadiene resin, acrylonitrile-butadiene resin, poly (meth) acrylonitrile Resin, (meth) acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, modified nylon resin, polyester resin, cellulose resin, phenol resin, silicone resin, epoxy resin, -Containing resin, polyethylene imine, and the like UV-curable resin. These can be used alone or in admixture of two or more. Among these, a polyurethane resin is preferable from the viewpoint of adhesion and suppression of cracking of the cyclic polyolefin resin coat layer. When these other resins are added, it is preferable to use those in which the aqueous dispersion or aqueous solution is used.

  The polyurethane resin is a polymer containing a urethane bond in the main chain, and is obtained, for example, by a reaction between a polyol compound and a polyisocyanate compound.

  The polyol compound constituting the polyurethane resin is not particularly limited. For example, water, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 1 , 3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,3-hexane Low molecular weight glycols such as diol, diethylene glycol, triethylene glycol, and dipropylene glycol; low molecular weight polyols such as trimethylolpropane, glycerin, and pentaerythritol; and polymers having ethylene oxide and propylene oxide units. Lumpur compounds, polyether diols, high molecular weight diols such as polyester diols, bisphenols such as bisphenol A, bisphenol F, etc. dimer diol was converted to a hydroxyl group a carboxyl group in the dimer acid.

  On the other hand, as the polyisocyanate compound, one kind or a mixture of two or more kinds of known aromatic, aliphatic and alicyclic diisocyanates can be used. Specific examples of the diisocyanates include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, Examples include lysine diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group, and adducts, biurets, and isocyanurates. Of these, isophorone diisocyanate is preferred as the isocyanate compound from the viewpoint of improving adhesion. As the diisocyanates, trifunctional or higher functional polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate may be used.

  The polyurethane resin in the present invention is preferably used as a solution or an aqueous dispersion. Therefore, the polyurethane resin is preferably water-soluble or water-dispersible. The polyurethane resin preferably has an anionic group from the viewpoint of dispersibility in an aqueous medium. An anionic group is a functional group that becomes an anion in an aqueous medium, and examples thereof include a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group. Among these, it is preferable to have a carboxyl group.

  In order to introduce an anionic group into the polyurethane resin, a polyol component having a carboxyl group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group or the like may be used. Examples of the polyol compound having a carboxyl group include 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, and 2,2-bis (hydroxypropyl). Propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2 -Hydroxyethyl) -3-carboxyl-propionamide and the like.

  In addition, the molecular weight of the polyurethane resin can be appropriately adjusted using a chain extender. Examples of such compounds include compounds having two or more active hydrogens such as amino groups and hydroxyl groups capable of reacting with isocyanate groups. For example, diamine compounds, dihydrazide compounds, and glycols can be used.

  Examples of the diamine compound include ethylenediamine, propylenediamine, hexamethylenediamine, triethyltetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, and the like. In addition, diamines having a hydroxyl group such as N-2-hydroxyethylethylenediamine and N-3-hydroxypropylethylenediamine, dimeramine amine obtained by converting the carboxyl group of dimer acid into an amino group, and the like are also included. Furthermore, diamine type amino acids such as glutamic acid, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid and diaminobenzenesulfonic acid are also included.

  Dihydrazide compounds include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacin dihydrazide, etc., saturated aliphatic dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, etc. And unsaturated dihydrazides such as itaconic acid dihydrazide and phthalic acid dihydrazide, carbonic acid dihydrazide, carbodihydrazide, and thiocarbodihydrazide.

  As glycols, they can be appropriately selected from the aforementioned polyols.

  As the polyurethane resin in the present invention, a polyether type polyurethane resin or a polyester type polyurethane resin is preferable from the viewpoint of improving adhesion and cracking suppressing effect of the cyclic polyolefin resin coat layer.

  When the polyurethane resin is used as an aqueous solution or an aqueous dispersion, a method for processing into an aqueous solution or an aqueous dispersion is not particularly limited, and a known method can be adopted.

  The addition amount of the other resin may be appropriately designed according to the purpose, but in the aqueous dispersion containing the acid-modified polyolefin resin, 0.1 to 300 mass with respect to 100 mass parts of the total amount of the acid-modified polyolefin resin. Part, preferably 3 to 200 parts by weight, and particularly preferably 5 to 100 parts by weight.

  Furthermore, various additives may be added to the aqueous dispersion containing the acid-modified polyolefin resin as long as the effects of the present invention are not impaired. Additives include inorganic fine particles, leveling agents, antifoaming agents, anti-waxing agents, pigment dispersants, UV absorbers, catalysts, photocatalysts, UV curing agents, wetting agents, penetrants, softeners, thickeners, dispersants. Water repellents, antistatic agents, anti-aging agents, vulcanization accelerators, silane coupling agents and other various agents, pigments or dyes, carbon black, carbon nanotubes, glass fibers and the like may be added. These may be used alone or in combination of two or more.

  Examples of inorganic fine particles include metal fine particles and metal oxides such as magnesium oxide, tin oxide, and titanium oxide, calcium carbonate, silica, barium sulfate, calcium silicate, zeolite, kaolinite, halloysite, magnesium carbonate, calcium sulfate, mica, Examples thereof include inorganic particles such as talc, pseudoboehmite, alumina, aluminum silicate, calcium silicate, magnesium silicate, zirconium oxide, zirconium hydroxide, cerium oxide, lanthanum oxide, and yttrium oxide. These may be used alone or in combination of two or more.

  The average particle diameter of the inorganic fine particles is preferably 0.0005 to 100 μm, more preferably 0.005 to 10 μm from the viewpoint of dispersion stability of the aqueous dispersion.

  The primer layer in the present invention is a coating film obtained by coating a base material layer with an aqueous dispersion containing the acid-modified polyolefin resin as described above. Specifically, it is obtained by coating at least a part of the base material layer with an aqueous dispersion containing an acid-modified polyolefin resin and then evaporating a part or all of the aqueous medium in the coated aqueous dispersion by drying. It is a coating film.

  As a method for coating and drying the aqueous dispersion, known methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc. After coating the base layer surface uniformly with the aqueous dispersion and setting it as necessary near room temperature, it is subjected to a drying treatment or a heat treatment for drying to vaporize part or all of the aqueous medium. A uniform coating film, that is, a primer layer can be formed in close contact with the surface of the base material layer. Although a drying temperature is not specifically limited, it can dry favorably in the range of 40-150 degreeC. In drying, it is preferable to vaporize all of the aqueous medium from the viewpoint of adhesion and suppression of cracking of the cyclic polyolefin resin coat layer.

  The thickness of the primer layer is preferably in the range of 0.01 to 5 μm, more preferably in the range of 0.05 to 4 μm, particularly preferably in the range of 0.1 to 3 μm, and still more preferably in the range of 0.2 to 2 μm. When the thickness is less than 0.01 μm, the wettability when the cyclic polyolefin resin is coated tends to be deteriorated, and when it exceeds 5 μm, the effect is not achieved and the cost is disadvantageous.

  The primer layer obtained by the method as described above usually has transparency.

  Next, the cyclic polyolefin resin coat layer in the present invention will be described. The cyclic polyolefin resin is a resin having a cyclic olefin component in the molecule, a polymer obtained by ring-opening polymerization of a cyclic olefin component, or a polymer obtained by copolymerizing a cyclic olefin component and an α-olefin component, These hydrides and the like can be mentioned. Specifically, a ring-opening polymer of a monomer having a norbornene structure, an addition polymer of a monomer having a norbornene structure, an addition copolymer of a monomer having a norbornene structure and an α-olefin, dicyclopentadiene Examples include addition copolymers of monomers and α-olefins, and hydrides thereof. In addition, the cyclic polyolefin resin may contain a polar group such as an unsaturated carboxylic acid or a derivative thereof as a copolymer component from the viewpoint of improving the ease of processing into a coating agent and improving adhesion.

  Examples of the cyclic polyolefin resin include JP-A-51-80400, JP-B-57-8815, JP-A-60-26024, JP-A-60-168708, JP-A-62-252406, JP-A-63-145324, JP-A-63-264626, JP-A-1-240517, JP-A-1-168725, JP-A-1-190726, JP-A-2-133413, JP-A-3-14882, JP-A-3-122137, JP-A-4-63807, JP-A-4-202277, JP-A-5-339327, JP-A-5-9223, JP-A-5-9223 No. 05-043834, JP-A-6-271628, JP-A-7-253315, JP-A-8-134794, JP 10-120768, JP-A-11-43566, JP-A-2000-26635, JP-A-2000-44869, JP-A-2001-98026, JP-A-2004-51949, JP-A-2004-2004. No. 156048, European Patent Application Publication (A) No. 203799, No. 407870, No. 283164, No. 156464, and the like.

  The molecular weight, melt flow rate (MFR), softening point, glass transition temperature, and other characteristics of the cyclic polyolefin resin may be appropriately designed in consideration of the intended performance.

  Commercially available products of cyclic polyolefin resin include “ARTON” (manufactured by JSR), “ZEONOR”, “ZEONEX” (manufactured by Nippon Zeon), “OPTOREZ” (manufactured by Hitachi Chemical Co., Ltd.), “APEL” (Mitsui Chemicals), “TOPAS” (Polyplastics) and the like.

  The cyclic polyolefin resin can be processed into a coating agent containing the cyclic polyolefin resin by dissolving or dispersing it in a medium composed of a solvent or, in some cases, water. A method for processing the cyclic polyolefin resin into a coating agent is not particularly limited, and a known method can be adopted.

  The coating agent containing the cyclic polyolefin resin in the present invention may contain components other than the cyclic polyolefin resin in the medium as long as the effects of the present invention are not impaired. As components other than cyclic polyolefin resin, resin components other than cyclic polyolefin resin, crosslinking agent component, basic compound, acidic compound, inorganic fine particles, leveling agent, antifoaming agent, anti-waxing agent, pigment dispersant, ultraviolet absorber, Various agents such as catalyst, photocatalyst, UV curing agent, wetting agent, penetrating agent, softener, thickener, dispersant, water repellent, antistatic agent, anti-aging agent, vulcanization accelerator, silane coupling agent, Examples thereof include pigments or dyes, carbon black, carbon nanotubes, and glass fibers. These may be used alone or in combination of two or more.

  The cyclic polyolefin resin coat layer in the present invention is a coat layer obtained by coating a cyclic polyolefin resin on the primer layer formed on the surface of the base material layer. As a method for coating the cyclic polyolefin resin, a method in which the cyclic polyolefin resin is melted and extrusion coated, or after coating a coating agent containing the cyclic polyolefin resin, a part or all of the medium in the coated coating agent is dried. The method of making it vaporize by is mentioned. In the present invention, the latter method, in which a coating agent containing a cyclic polyolefin resin is coated and then dried, is preferable from the viewpoints of workability and obtaining a thin coating layer.

  The coating agent containing a cyclic polyolefin resin is preferably either a solvent-based coating agent dissolved or dispersed in a solvent or an aqueous coating agent dissolved or dispersed in an aqueous medium.

  As a method for coating and drying a coating agent containing a cyclic polyolefin resin, known methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, Apply the aqueous dispersion uniformly on the primer layer provided on the surface of the base material layer by brushing, etc., set it near room temperature as necessary, and then perform drying treatment or heat treatment for drying. By providing, a part or all of the medium is vaporized, and a uniform coat layer, that is, a cyclic polyolefin resin coat layer can be formed in close contact with the primer layer on the surface of the base material layer. Although a drying temperature is not specifically limited, it can dry favorably in the range of 40-150 degreeC.

  The thickness of the cyclic polyolefin resin coat layer is preferably in the range of 0.1 to 30 μm, more preferably in the range of 0.5 to 20 μm, particularly preferably in the range of 1 to 10 μm, and most preferably in the range of 1 to 5 μm. When the thickness is less than 0.1 μm, the paintability may be deteriorated. When the thickness exceeds 30 μm, the adhesion with the primer layer is deteriorated or the coating layer tends to crack in the use environment. and so on.

  As described above, as a method for producing the laminate of the present invention, the base layer is coated with an aqueous dispersion containing an acid-modified polyolefin resin having an unsaturated carboxylic acid component content of 0.1 to 10% by mass. It is preferable to employ a method comprising a step of forming a primer layer and a step of forming a cyclic polyolefin resin coat layer by coating a coating agent containing a cyclic polyolefin resin on the primer layer.

  The laminate of the present invention is a laminate in which a base material layer / primer layer / cyclic polyolefin resin coat layer is laminated at least in this order, and other layers are laminated depending on the purpose of use or use. It doesn't matter. Further, in the present specification, the description “base layer / primer layer / cyclic polyolefin resin coat layer is laminated at least in this order” only means that the layers are laminated in such a relative positional relationship. It does not prevent another layer or surface treatment from entering between each layer.

  As a use which the laminated body of this invention uses, it can be used for various uses, such as an optical film, a packaging material, daily miscellaneous goods, a motor vehicle, an architecture, a solar cell. Especially, since the cyclic polyolefin resin coat layer in this invention has the characteristic which is excellent in transparency, it can be preferably used for an optical film. When used for an optical film, it is preferable to employ a transparent film as the substrate layer. Here, the optical film in the present invention is a film for industrial materials that requires transparency, and is mainly used on the outermost surface of a display device such as a liquid crystal display, a plasma display, and an organic EL display or the inside thereof. Including a polarizing plate protective film, a retardation film, an antireflection film, a brightness enhancement film, an optical compensation film for expanding the viewing angle, and the like.

  When the laminate of the present invention is used as an optical film, the total light transmittance measured according to JIS K7361 of the laminate is preferably in the range of 80 to 97%, more preferably in the range of 85 to 95%. A range of 90-94% is particularly preferred. If it is less than 80%, the optical film has a problem in transparency, and if it exceeds 97%, it is difficult to produce each constituent material.

  The laminate of the present invention is excellent in the adhesion of the cyclic polyolefin resin coat layer. The adhesion of the cyclic polyolefin resin coat layer is evaluated according to JIS K5400-8.5 (cross cut test). Specifically, in the cross cut test, first, 100 squares with a 1 mm interval are formed on the surface of the cyclic polyolefin resin coat layer. Next, a cellophane tape is affixed thereon, and the cellophane tape is peeled off. At this time, the number of hooks where the cyclic polyolefin resin coat layer was not peeled was counted and used as an index of adhesion. In the present invention, the number of wrinkles that have not peeled is preferably 70 mm or more, more preferably 80 mm or more, particularly preferably 90 mm or more, and further preferably 95 mm or more. The most preferable is 100 mm.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

1. Properties of modified polyolefin resin (1) Monomer composition
^It calculated | required from the <1> H-NMR analyzer (the JEOL company make, ECA500, 500MHz). Tetrachloroethane (d ₂ ) was used as a solvent and measurement was performed at 120 ° C.
(2) Melt flow rate (MFR)
According to the method described in JIS K7210: 1999, the measurement was performed at 190 ° C. under a load of 2160 g.

2. Characteristics of Coating Agent (1) Paintability In each example, the degree of repelling of the coating agent when the coating agent containing a cyclic polyolefin resin was coated was visually observed and evaluated according to the following index.
○: No repelling.
Δ: Partly repelled.
X: There was repelling on the entire surface.

3. Properties of Laminate (1) Adhesiveness of Cyclic Polyolefin Resin Coated Layer According to JIS K5400-8.5 (cross cut test), 100 mm mesh of 1 mm × 1 mm with a cutter knife is applied to the cyclic polyolefin resin coated layer side of the laminate. A cellophane tape (TF-12 manufactured by Nichiban Co., Ltd.) was applied thereon, and then the cellophane tape was peeled off, and the number of cells in which the cyclic polyolefin resin coat layer did not peel was examined in 100 mm. The test was carried out 5 times and evaluated with an average value of 5 times.
(2) Total light transmittance (%)
Using a turbidimeter (cloudiness meter) NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), light is incident from the cyclic polyolefin resin coat layer side of the laminate in accordance with K7361, and the total light in the laminate thickness direction The transmittance was measured. The test was carried out 5 times and evaluated with an average value of 5 times.
(3) Cracking of cyclic polyolefin resin coating layer 20 laminates (size: rectangle of 150 mm × 250 mm) immediately after production were placed in an incubator at 40 ° C. and allowed to stand for 30 days. Thereafter, the laminate was taken out and the state of the cyclic polyolefin resin coat layer was visually observed. The number of laminates in which cracks were confirmed even in part of the cyclic polyolefin resin coat layer was examined. The above was taken as the crack of the cyclic polyolefin resin coat layer in use environment.

  An aqueous dispersion of acid-modified polyolefin resin was produced by the following method.

<Production of aqueous dispersion of ethylene-ethyl acrylate-maleic anhydride copolymer>
The ethylene-ethyl acrylate-maleic anhydride copolymer PO1, PO2 based on the methods described in British Patent No. 2911745, US Pat. No. 4,617,366, and US Pat. No. 4,644,044. And PO3 were produced. The monomer composition and properties of PO1, PO2 and PO3 are shown in Table 1. Next, 100 g of PO1, PO2 or PO3 obtained above, 100 g of isopropanol, 5 g of 2-dimethylaminoethanol and 295 g of distilled water were charged into a 1 liter glass container equipped with a stirrer and a heater. When the stirring blade was rotated at a rotational speed of 300 rpm, the resin bottoms were not observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 120 minutes to be dispersed. Then, while stirring at a rotational speed of 300 rpm, when the heater was turned off and cooled to about 40 ° C., isopropanol was added to adjust the solid content concentration of the aqueous dispersion to 10% by mass, and 180 mesh The mixture was filtered under pressure with a stainless steel filter to obtain a milky white uniform aqueous PO1, PO2 or PO3 dispersion.

  Hereinafter, the aqueous dispersion of PO1 is indicated as “E-1”, the aqueous dispersion of PO2 as “E-2”, and the aqueous dispersion of PO3 as “E-3”. The number average particle size of PO1 in E-1 is 0.07 μm, the number average particle size of PO2 in E-2 is 0.07 μm, and the number average particle size of PO3 in E-3 Was 0.07 μm. In addition, the number average particle diameter of the aqueous dispersion containing the acid-modified polyolefin resin of the present invention is obtained by using a microtrack particle size distribution meter (manufactured by Nikkiso Co., Ltd., UPA150, MODEL No. 9340, dynamic light scattering method). The refractive index was determined as 1.50.

<Production of aqueous dispersion of ethylene-propylene-butene-maleic anhydride copolymer>
PO4 which is an ethylene-propylene-butene-maleic anhydride copolymer was produced based on the method described in International Publication No. 2004/104090. The monomer composition and characteristics of PO4 are shown in Table 1. Next, 75 g of PO4 obtained above, 150 g of tetrahydrofuran, 8 g of 2-dimethylaminoethanol, and 267 g of distilled water were charged into a 1 liter glass container equipped with a stirrer and a heater. When the stirring blade was rotated at a rotational speed of 300 rpm, the resin bottoms were not observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was maintained at 130 ° C. and further stirred for 120 minutes to be dispersed. Then, while stirring at a rotational speed of 300 rpm, when the heater was turned off and cooled to about 40 ° C., isopropanol was added to adjust the solid content concentration of the aqueous dispersion to 10% by mass, and 180 mesh The mixture was filtered under pressure with a stainless steel filter to obtain a milky white uniform aqueous dispersion of PO4. Hereinafter, the aqueous dispersion of PO4 is referred to as “E-4”. The number average particle diameter of PO4 in E-4 was 0.12 μm.

<Production of aqueous dispersion of ethylene- (meth) acrylic acid copolymer>
Ethylene-methacrylic acid copolymer (Mitsui / DuPont Polychemical Co., Ltd., Nucrel N0903HC, hereinafter referred to as N0903HC), ethylene-methacrylic acid copolymer (Mitsui / Dupont Polychemical Co., Ltd., Nucrel AN42115C, hereinafter referred to as AN42115C) ), Ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N1560, hereinafter referred to as N1560), ethylene-acrylic acid copolymer (manufactured by Dow Chemical Co., Ltd., Primacol 5990, hereinafter, 5990) These aqueous dispersions were produced by the following method. Table 1 shows the monomer composition and characteristics of N0903HC, AN42115C, N1560, and 5990.

(Production of aqueous dispersion of N0903HC and AN42115C)
A 1 liter glass container equipped with a stirrer and a heater was charged with 75 g of N0903HC or AN42115C, 175 g of n-propanol, 20 g of 2-dimethylaminoethanol, and 230 g of distilled water. When the stirring blade was rotated at a rotational speed of 300 rpm, the resin bottoms were not observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was maintained at 150 ° C. and further stirred for 120 minutes to be dispersed. Then, while stirring at a rotational speed of 300 rpm, when the heater was turned off and cooled to about 40 ° C., isopropanol was added to adjust the solid content concentration of the aqueous dispersion to 10% by mass, and 180 mesh The mixture was filtered under pressure with a stainless steel filter to obtain a milky white uniform aqueous dispersion of N0903HC or AN42115C. Hereinafter, the aqueous dispersion of N0903HC is indicated as “E-5”, and the aqueous dispersion of AN42115C is indicated as “E-6”. The number average particle size of N0903HC in E-5 was 0.18 μm, and the number average particle size of AN42115C in E-2 was 0.20 μm.

(Production of aqueous dispersion of N1560, 5990)
A 1 liter glass container equipped with a stirrer and a heater was charged with 75 g of N1560 or 5990, 50 g of isopropanol, 7 g of 2-dimethylaminoethanol, and 368 g of distilled water. When the stirring blade was rotated at a rotational speed of 300 rpm, the resin bottoms were not observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was maintained at 130 ° C. and further stirred for 120 minutes to be dispersed. Then, while stirring at a rotational speed of 300 rpm, when the heater was turned off and cooled to about 40 ° C., isopropanol was added to adjust the solid content concentration of the aqueous dispersion to 10% by mass, and 180 mesh The mixture was filtered under pressure with a stainless steel filter to obtain a milky white uniform aqueous dispersion of N1560 or 5990. Hereinafter, the aqueous dispersion of N1560 is referred to as “E-7”, and the aqueous dispersion of 5990 is referred to as “E-8”. The number average particle diameter of N1560 in E-7 was 0.05 μm, and the number average particle diameter of 5990 in E-7 was 0.04 μm.

  The characteristics of the acid-modified polyolefin resin used are shown in Table 1.

<Production of aqueous dispersion of polyurethane resin>
A reactor equipped with a stirrer, a thermometer, a nitrogen seal tube, and a condenser was charged with 345 g of polytetramethylene glycol having a number average molecular weight of 1970, 77.8 g of isophorone diisocyanate, and 0.03 g of dibutyltin dilaurate. Reacted for hours. Subsequently, after cooling this reaction liquid to 50 degreeC, 11.7g of 3-dimethylamino propanol, 8.85g of triethylamine, and 177g mass part of acetone were added, and it was made to react for 3 hours. Further, 175 g of acetone was added to the reaction liquid and cooled to 30 ° C., and a liquid mixture consisting of 13.4 g of isophorone diisocyanate, 1.07 g of monoethanolamine, 87.9 g of isopropanol and 1039 g of water was added and stirred at high speed for 10 minutes. In the meantime, isopropanol was added to adjust the solid content concentration of the aqueous dispersion to 10% by mass to obtain an aqueous dispersion of a polyether type polyurethane resin. Hereinafter, this aqueous dispersion is referred to as “U-1”.

<Manufacture of solvent-based coating agent for cyclic polyolefin resin>
6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 100 g of a 15% by weight cyclohexane solution of triethylaluminum as a polymerization catalyst, 50 g of triethylamine And 100 g of a 20% by mass cyclohexane solution of titanium tetrachloride were added to carry out ring-opening polymerization in cyclohexane, and the resulting ring-opening polymer was hydrogenated with a nickel catalyst to obtain a resin solution. This resin solution was coagulated in isopropyl alcohol and dried to obtain a powdered cyclic polyolefin resin. The number average molecular weight of this resin was 39,000, the hydrogenation rate was 99.7%, and the glass transition temperature was 142 ° C. Next, this cyclic polyolefin resin was dissolved in xylene to a concentration of 20% by weight, and an antioxidant (Irganockl 1010, manufactured by Ciba Geigy) was 0.025% by mass with respect to the resin, and a leveling agent (Florard FC-430, Sumitomo). 150 ppm of 3M) was added to the solution to obtain a cyclic polyolefin resin solvent-based coating agent. Hereinafter, this coating agent is indicated as “Y-1”.

<Manufacture of water-based coating agent for cyclic polyolefin resin>
The number average molecular weight is 19000, the mass average molecular weight is 44000, the glass transition temperature is 150 ° C., the hydrogenation rate is 99.9%, and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene (TCD) and tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (also referred to as DCP or dicyclopentadiene) 1 liter of toluene was added to 125 g of 85/15 TCD / DCP ring-opening copolymer hydrogenated product and dissolved. To 500 g of this TCD / DCP ring-opening copolymer hydrogenated product / toluene solution, 500 g of distilled water and 1.44 g of sodium dodecylbenzenesulfonate were added, and the mixture was stirred and mixed at a rotational speed of 10,000 rpm for 15 minutes using a homomixer. Subsequently, 0.72 g of carboxymethylcellulose was added and further stirred. This stirred liquid is distilled under reduced pressure with an evaporator, and the solid content concentration is adjusted to 20% by mass by distilling toluene and a part of water to obtain an aqueous coating agent that is an aqueous dispersion of a cyclic polyolefin resin. It was. Hereinafter, this aqueous coating agent is indicated as “Y-2”.

<Example 1>
Using E-1 as an aqueous dispersion containing an acid-modified polyolefin resin, using an optical polyethylene terephthalate resin film (thickness 100 μm, total light transmittance 92%, hereinafter referred to as “PET”) as a base material layer, Y-1 was used as a coating agent containing a cyclic polyolefin resin.

  An aqueous dispersion containing an acid-modified polyolefin resin was coated on one surface of the substrate layer so that the thickness of the coating film after drying was 1 μm, and dried at 100 ° C. for 1 minute to form a primer layer. . Next, a coating agent containing a cyclic polyolefin resin is coated on the surface of the primer layer of the base layer so that the thickness of the coating layer after drying is 10 μm, and dried at 100 ° C. for 3 minutes to form a cyclic polyolefin resin coat layer. A laminate was obtained.

<Examples 2 to 6, Comparative Examples 6 and 7>
A laminate was obtained in the same manner as in Example 1 except that the aqueous dispersion shown in Table 2 was used instead of E-1 as the aqueous dispersion containing the acid-modified polyolefin resin.

<Examples 7 and 8>
A laminate was obtained in the same manner as in Example 1 except that the thickness of the primer layer was changed to the thickness shown in Table 2.

<Example 9>
A laminate in the same manner as in Example 1 except that an optical polycarbonate resin film (thickness 100 μm, total light transmittance 90%, hereinafter referred to as “PC”) was used as the base layer instead of PET. Got.

<Example 10>
The same method as in Example 1 except that an optical polymethyl methacrylate resin film (thickness 125 μm, total light transmittance 93%, hereinafter referred to as “PMMA”) was used as the base layer instead of PET. A laminate was obtained.

<Example 11>
Laminated in the same manner as in Example 1 except that instead of PET, an optical cyclic olefin polymer film (thickness 125 μm, total light transmittance 92%, hereinafter referred to as “COP”) was used as the base material layer. Got the body.

<Example 12>
A laminate in the same manner as in Example 1, except that an optical cellulose triacetate film (thickness 80 μm, total light transmittance 93%, hereinafter referred to as “TAC”) was used as the base material layer instead of PET. Got.

<Examples 13 and 14>
A laminate was obtained in the same manner as in Example 1 except that the thickness of the cyclic polyolefin resin coat layer was changed to the thickness shown in Table 2.

<Example 15>
A laminate was obtained in the same manner as in Example 1 except that Y-2 was used instead of Y-1 as a coat layer containing a cyclic polyolefin resin.

<Example 16>
A laminate was obtained in the same manner as in Example 1 except that an aqueous dispersion prepared by the following method was used instead of E-1 as the aqueous dispersion containing the acid-modified polyolefin resin.

  Preparation of aqueous dispersion: 100 parts by mass of acid-modified polyolefin resin contained in E-1 was used as a cross-linking agent as a polyvalent oxazoline compound aqueous solution (manufactured by Nippon Shokubai Co., Ltd., Epocros WS700, aqueous solution of oxazoline group-containing acrylic resin, solid concentration 25 E-1 and WS700 were mixed so that the solid content of mass% (hereinafter referred to as “WS700”) was 5 parts by mass, and this was used as an aqueous dispersion containing an acid-modified polyolefin resin.

<Example 17>
In place of the polyvalent oxazoline compound aqueous solution, a polyvalent carbodiimide compound aqueous solution (manufactured by Nisshinbo Chemical Co., Ltd., carbodilite V-02-L2, an aqueous solution of a carbodiimide group-containing resin, solid content concentration 40% by mass, hereinafter abbreviated as “V02L2”) is used. A laminate was obtained in the same manner as in Example 16 except that.

<Example 18>
Lamination was carried out in the same manner as in Example 16 except that a polyhydric hydrazide compound aqueous solution (aqueous solution of adipic acid dihydrazide, solid content concentration 8 mass%, hereinafter abbreviated as “ADH”) was used instead of the polyvalent oxazoline compound aqueous solution. Got the body.

<Examples 19 to 22>
A laminate was obtained in the same manner as in Example 16 except that the base material layer shown in Table 2 was used instead of PET as the base material layer.

<Examples 23 and 24>
A laminate was obtained in the same manner as in Example 16 except that the thickness of the cyclic polyolefin resin coat layer was changed to the thickness shown in Table 2.

<Example 25>
A laminate was obtained in the same manner as in Example 16 except that Y-2 was used instead of Y-1 as a coat layer containing a cyclic polyolefin resin.

<Examples 26 and 27>
A laminate was obtained in the same manner as in Example 16 except that the thickness of the primer layer was changed to the thickness shown in Table 2.

<Example 28>
A laminate was obtained in the same manner as in Example 1 except that an aqueous dispersion prepared by the following method was used instead of E-1 as the aqueous dispersion containing the acid-modified polyolefin resin.

  Preparation of aqueous dispersion: E 100-part by mass of acid-modified polyolefin resin contained in E-1 so that the solid content of the aqueous dispersion U-1 of a polyether type polyurethane resin as a polyurethane resin is 10 parts by mass. -1 and U-1 were mixed to obtain an aqueous dispersion containing an acid-modified polyolefin resin.

<Examples 29 to 32>
A laminate was obtained in the same manner as in Example 28 except that the base material layer shown in Table 2 was used instead of PET as the base material layer.

<Examples 33 and 34>
A laminate was obtained in the same manner as in Example 28 except that the thickness of the cyclic polyolefin resin coat layer was changed to the thickness shown in Table 2.

<Example 35>
A laminate was obtained in the same manner as in Example 28 except that Y-2 was used instead of Y-1 as a coat layer containing a cyclic polyolefin resin.

<Examples 36 and 37>
A laminate was obtained in the same manner as in Example 28 except that the thickness of the primer layer was changed to the thickness shown in Table 2.

<Comparative Example 1>
PET was used as a base material layer, and Y-1 was used as a coating agent containing a cyclic polyolefin resin.

  Y-1 was coated on one surface of the base material layer so that the thickness of the coating film after drying was 10 μm, and dried at 100 ° C. for 3 minutes to form a cyclic polyolefin resin coating layer to obtain a laminate. It was. That is, the laminate does not have a primer layer.

<Comparative Examples 2-5>
A laminate was obtained in the same manner as in Comparative Example 1 except that the base material layer shown in Table 2 was used instead of PET as the base material layer. That is, the laminate does not have a primer layer. In Comparative Example 3 using PMMA, when a coating agent containing a cyclic polyolefin resin was coated, repelling occurred on the entire surface, and the cyclic polyolefin resin coating layer could not be formed. Therefore, the laminate was not evaluated.

<Comparative Example 8>
A laminate was obtained in the same manner as in Example 1 except that an aqueous dispersion prepared by the following method was used instead of E-1 as the aqueous dispersion containing the acid-modified polyolefin resin.

  Preparation of aqueous dispersion: E-8 and WS700 were mixed so that the solid content of WS700 as a crosslinking agent was 5 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin contained in E-8, and this was mixed with acid. An aqueous dispersion containing a modified polyolefin resin was obtained.

<Comparative Example 9>
A laminate was obtained in the same manner as in Example 1 except that an aqueous dispersion prepared by the following method was used instead of E-1 as the aqueous dispersion containing the acid-modified polyolefin resin.

  Preparation of aqueous dispersion: E-8 and U-1 are mixed so that the solid content of U-1 as polyurethane resin is 10 parts by mass with respect to 100 parts by mass of acid-modified polyolefin resin contained in E-8. This was made into the aqueous dispersion containing acid-modified polyolefin resin.

  The evaluation results of the laminates obtained in Examples 1 to 37 and Comparative Examples 1 to 9 are shown in Table 2.

  As the results of Examples 1 to 37, the primer layer is a coating film obtained from an aqueous dispersion containing an acid-modified polyolefin resin having an unsaturated carboxylic acid component content of 0.1 to 10% by mass. The body was excellent in the adhesion of the cyclic polyolefin resin coat layer and the crack suppression effect. Furthermore, the coatability of the cyclic polyolefin resin coating agent during the production of the laminate was also excellent. The laminate was transparent with optical film suitability.

  In Examples 16 to 37, the cross-linking agent and the polyurethane resin were added to the aqueous dispersion containing the acid-modified polyolefin resin, which resulted in better adhesion.

On the other hand, in the comparative example, it was inferior in the applicability | paintability and adhesiveness of the coating agent of cyclic polyolefin resin. From the results of Comparative Examples 8 and 9, when using an aqueous dispersion of an acid-modified polyolefin resin in which the content of the unsaturated carboxylic acid component does not satisfy the range defined in the present invention, a crosslinking agent or a polyurethane resin may be added. No performance improvement was confirmed.

Claims (9)

A base material layer / primer layer / cyclic polyolefin resin coat layer is a laminate obtained by laminating at least in this order, and the primer layer is an acid having an unsaturated carboxylic acid component content of 0.1 to 10% by mass. Ri coating der obtained from an aqueous dispersion containing modified polyolefin resin,
And, when the adhesion of the cyclic polyolefin resin coat layer was evaluated according to JIS K5400-8.5 (cross cut test), the number of the cyclic polyolefin resin coat layer in the 100 cut grid that was not peeled was A laminate having a thickness of 70 mm or more . The laminate according to claim 1, wherein the aqueous dispersion further contains a crosslinking agent. The laminate according to claim 2, wherein the crosslinking agent is at least one selected from the group consisting of a polyvalent oxazoline compound, a polyvalent carbodiimide compound, and a polyvalent hydrazide compound. The laminate according to any one of claims 1 to 3, wherein the aqueous dispersion further contains a polyurethane resin. The thickness of a primer layer is the range of 0.01-5 micrometers, The laminated body in any one of Claims 1-4 characterized by the above-mentioned. The laminate according to any one of claims 1 to 5, wherein the thickness of the cyclic polyolefin resin coat layer is in the range of 0.1 to 30 µm. The base material layer is at least one selected from the group consisting of a polyester resin base material, a polycarbonate resin base material, a polymethyl methacrylate resin, a cyclic polyolefin resin, and a cellulose ester resin. The laminated body of crab. The laminate according to any one of claims 1 to 7, which is an optical film having a total light transmittance of 80 to 97%. A step of coating a base layer with an aqueous dispersion containing an acid-modified polyolefin resin having an unsaturated carboxylic acid component content of 0.1 to 10% by mass, and forming a primer layer; and a cyclic polyolefin resin The method for producing a laminate according to any one of claims 1 to 8 , further comprising a step of coating the primer layer on the primer layer to form a cyclic polyolefin resin coat layer.