JP2014189746A - Urethane resin composition, primer, laminate and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane resin composition having high refractivity usable for optical purposes, excellent film-forming property and excellent adhesiveness to various substrates and to an overcoat layer or the like.SOLUTION: The urethane resin composition comprises a urethane resin (A) obtained by allowing a polyisocyanate (a2) to react with a polyol (a1) comprising a polyol (a1-1) expressed by general formula (1) and at least one polyol selected from the group consisting of an aromatic polyester polyol (a1-2) and a polyether polyol (a1-3) prepared by adding alkylene oxide to bisphenol.

Description

  The present invention relates to a urethane resin composition and a primer that can be used in the manufacture of image display devices such as liquid crystal televisions and touch panels.

  As urethane resin compositions, solvent-based urethane resin compositions, water-based urethane resin compositions, and solvent-free urethane resin compositions are conventionally known, such as molding materials such as films and sheets, adhesives, coating agents, etc. It is used for various purposes.

  In recent years, application of urethane resin compositions to films or sheets for optical applications has been studied. Specific examples of the optical application include applications such as a liquid crystal display and a touch panel. A display device such as a liquid crystal display is usually formed by laminating a number of optical films each having a function. As such an optical film, an antireflection film, a retardation film, a prism lens sheet, or the like is used.

  Examples of urethane resin compositions that can be used in the production of such optical films include polyesters obtained by reacting an acid component containing a specific proportion of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid with a glycol component. Water-based polyester polyurethane resins obtained by reacting polyols and polyisocyanates, containing pendant carboxyl groups in an amount of 0.5 to 6% by weight, and neutralizing the carboxyl groups with ammonia or the like are known (for example, (See Patent Document 1).

  However, the aqueous polyester polyurethane resin composition cannot form a film having a high refractive index of about 1.55 to 1.65, which is a level usable for optical applications, and supports the optical film. Interference fringes may occur due to the difference in refractive index from the polyethylene terephthalate base material. Moreover, since the said water-based polyester polyurethane resin composition may be a little inferior in the film forming property, there existed a case where a smooth film could not be formed.

By the way, in the said optical use, the optical film provided with the desired optical characteristic may be obtained by laminating | stacking several layers provided with various functions on the surface of a base material. As the base material, base materials of various materials have been studied along with diversification of products. For example, a polyethylene terephthalate base material that is generally difficult to adhere is known.
However, since a normal urethane resin composition may not have a level of adhesion that can be used for optical applications with respect to the polyethylene terephthalate base material, when the final product is used for a long time, a polyethylene terephthalate group In some cases, peeling from the material may occur.

  In addition, when an optical member is produced by further laminating a topcoat layer or the like having a different property from the olefin base material, it has excellent adhesion to both the polyethylene terephthalate base material and the topcoat layer. While it is required that a layer can be formed, it is sometimes difficult to make them compatible with the conventional urethane resin composition.

JP-A-61-36314

  The problem to be solved by the present invention is a urethane resin composition having a high refractive index of a level that can be used for optical applications, excellent film forming properties, and excellent adhesion to various substrates and topcoat layers. Is to provide things.

  The present inventors, as the polyol used for the production of the urethane resin, together with the polyol (a1-1) represented by the general formula (1), the polyoxypolyester in which an alkylene oxide is added to the aromatic polyester polyol (a1-2) and bisphenol. It has been found that the above problem can be solved by using a combination of one or more selected from the group consisting of ether polyols (a1-3).

  That is, the present invention is a group consisting of a polyol (a1-1) represented by the general formula (1), an aromatic polyester polyol (a1-2), and a polyether polyol (a1-3) in which an alkylene oxide is added to bisphenol. A urethane resin composition comprising a polyol (a1) containing one or more selected polyols and a urethane resin (A) obtained by reacting a polyisocyanate (a2). is there.

［前記一般式（１）中のＲ^１は、それぞれ独立して脂肪族構造または芳香族構造を有する基を表し、Ｒ^２は、それぞれ独立してアルキレン基を表す。］

[R ¹ in the general formula (1) independently represents a group having an aliphatic structure or an aromatic structure, and R ² independently represents an alkylene group. ]

  The urethane resin composition of the present invention can be used for the production of a film having a high refractive index comparable to that of a polyethylene terephthalate substrate, and is excellent in film-forming properties and adhesion. It can use suitably for manufacture of the optical film and lens used for manufacture of a display apparatus, a polarizing plate, etc.

  The urethane resin composition of the present invention comprises a polyol (a1-1) represented by the general formula (1), a polyether polyol (a1-3) in which an alkylene oxide is added to an aromatic polyester polyol (a1-2) and bisphenol. It contains a urethane resin (A) obtained by reacting a polyol (a1) containing at least one polyol selected from the group consisting of and a polyisocyanate (a2).

［前記一般式（１）中のＲ^１は、それぞれ独立して脂肪族構造または芳香族構造を有する官能基を表し、Ｒ^２は、それぞれ独立してアルキレン基を表す。］

[R ¹ in the general formula (1) independently represents a functional group having an aliphatic structure or an aromatic structure, and R ² each independently represents an alkylene group. ]

  As the urethane resin (A), a polyol (a1-1) represented by the general formula (1), an aromatic polyester polyol (a1-2), and a polyether polyol (a1-3) in which an alkylene oxide is added to bisphenol. A polyol (a1) containing one or more polyols selected from the group consisting of and a product obtained by reacting a polyisocyanate (a2) is used.

［前記一般式（１）中のＲ^１は、それぞれ独立して脂肪族構造または芳香族構造を有する基を表し、Ｒ^２は、それぞれ独立してアルキレン基を表す。］ As a polyol (a1-1) used for manufacture of the said urethane resin (A), the polyol shown by following General formula (1) is mentioned.

[R ¹ in the general formula (1) independently represents a group having an aliphatic structure or an aromatic structure, and R ² independently represents an alkylene group. ]

Examples of R ¹ in the general formula (1) include an aliphatic structure having an ethylene group, a propylene group, a butylene group, a cyclopentenyl group, a cyclohexyl group, and the like, and an aromatic structure having an aryl group. . Examples of R ² include an alkylene group having 1 to 5 carbon atoms, and specific examples include an alkylene group such as an ethylene group, a propylene group, and a butylene group.
Specific examples of the polyol (a1-1) include bisphenoxyethanol fluorene (R ¹ in the general formula (1) is an aryl group, and R ² is an ethylene group).

  The polyol (a1-1) can be used in the range of 5% by mass to 85% by mass with respect to the entire polyol (a1), and a film having a high refractive index at a level that can be used for optical applications. It is preferable when obtaining and it is more preferable that it is the range of 10 mass%-65 mass%.

  Moreover, as aromatic polyester polyol (a1-2) used for manufacture of the said urethane resin (A), the polyester polyol obtained by making polycarboxylic acid and a polyol react can be used.

  As the polycarboxylic acid, aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, and anhydrides thereof can be used.

  Examples of the polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 3-methyl-1,5-pentanediol.

  As said aromatic polyester polyol (a1-2), when giving the outstanding adhesiveness with respect to a base material, especially a polyethylene terephthalate base material, to the urethane resin composition of this invention, the number average molecular weight of 800-5,000. It is preferable to use those having a number average molecular weight in the range of 1,000 to 3,000.

  The aromatic polyester polyol (a1-2) is preferably used in a range of 5% by mass to 80% by mass with respect to the total amount of the polyol (a1), and is used in a range of 10% by mass to 65% by mass. It is preferable to do.

  Moreover, as polyether polyol (a1-3) used for manufacture of the said urethane resin (A), what added the alkylene oxide to bisphenol is used.

  The polyether polyol (a1-3) is a polyether polyol in which alkylene oxide is added to the hydroxyl group of bisphenol, and can be produced by adding alkylene oxide by a well-known and conventional method using the bisphenol as an initiator. it can.

Examples of the bisphenol include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, fluorinated bisphenol A, chlorinated bisphenol A, brominated bisphenol A, 4,4-bis (hydroxyphenyl) sulfide, and bis (4-hydroxyphenyl). ) methane, it may be used bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) amine, tricyclo [5,2,1,0 ^2,6] decane phenol. Among them, it is preferable to use bisphenol A in order to obtain a urethane resin composition that gives excellent adhesion to a substrate, particularly a polyethylene terephthalate substrate, and can form a coating film having a high refractive index.

  As the alkylene oxide that can be added to the hydroxyl group of the bisphenol, for example, ethylene oxide, propylene oxide and the like can be used, and it is preferable to use one or more selected from the group consisting of ethylene oxide and propylene oxide.

  The alkylene oxide is preferably added in an amount of 2 to 20 mol, more preferably 2 to 10 mol, with respect to one molecule of the bisphenol. It is preferable for forming a film or the like having excellent adhesion to a terephthalate substrate.

  The polyether polyol (a1-3) is preferably used in the range of 5% by mass to 80% by mass with respect to the entire polyol (a1), and is used in the range of 10% by mass to 65% by mass. Is preferred.

  In the present invention, any one or both of the aromatic polyester polyol (a1-2) and the polyether polyol (a1-3) can be used in combination as the polyol (a1).

  Examples of the urethane resin (A) include the polyol (a1-1) and the total of the aromatic polyester polyol (a1-2) and the polyether polyol (a1-3) [polyol (a1-1) / It is possible to use a urethane resin obtained by using the aromatic polyester polyol (a1-2) and the polyether polyol (a1-3)] (mass ratio) = 10/90 to 90/10. A film having a high refractive index of a level that can be used for optical applications can be formed, and it is preferable for obtaining a urethane resin composition excellent in film forming property, and is obtained in the range of 20/80 to 85/15. It is more preferable to use a urethane resin, and it is more preferable to use a urethane resin obtained by using the resin in the range of 40/60 to 70/30.

  As the polyol (a1), in addition to the polyol (a1-1), the aromatic polyester polyol (a1-2) and the polyether polyol (a1-3), other polyols may be used in combination as required. can do.

  As the other polyol, for example, when an aqueous medium (B) is used as a solvent for the urethane resin (A), a hydrophilic group is used from the viewpoint of imparting a hydrophilic group to the urethane resin (A). The polyol which has can be used.

  As the polyol having a hydrophilic group, for example, a polyol having an anionic group, a polyol having a cationic group, a polyol having a nonionic group can be used, and a polyol having an anionic group is preferably used. . Examples of the polyol having a hydrophilic group include a polyester polyol having a hydrophilic group obtained by reacting the above-described polyol having a low molecular weight hydrophilic group with various polycarboxylic acids such as adipic acid. It can also be used.

  Examples of the polyol having an anionic group include a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and 2,2-dimethylolvaleric acid; 5-sulfoisophthalic acid, Polyols having a sulfonic acid group such as sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used.

  The anionic groups are preferably partially or wholly neutralized with a basic compound or the like in order to exhibit good water dispersibility. The neutralization may be performed on the hydrophilic group of the polyol having the hydrophilic group, and the hydrophilic group after the urethane resin (A) is produced using the polyol having the hydrophilic group. You can go.

  Examples of basic compounds that can be used when neutralizing the anionic group include ammonia, triethylamine, morpholine, organic amines such as monoethanolamine and diethylethanolamine having a boiling point of 100 ° C. or higher, sodium hydroxide, water A metal hydroxide containing potassium oxide, lithium hydroxide or the like can be used. The basic compound is preferably used in the range of basic compound / anionic group = 0.2 to 3.0 (molar ratio) from the viewpoint of improving the dispersion stability of the obtained urethane resin composition. More preferably, it is used in the range of 0.6 to 1.5 (molar ratio).

  Further, as the polyol having a cationic group, for example, a polyol having a tertiary amino group can be used. Specifically, N-methyl-diethanolamine, a compound having two epoxies in one molecule, and 2 A polyol obtained by reacting with a secondary amine can be used.

  The cationic group is partially or entirely neutralized with an acidic compound such as formic acid, acetic acid, phosphoric acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, or dimethyl sulfate, diethyl sulfate, methyl It may be quaternized with a quaternizing agent such as chloride or ethyl chloride.

  The polyol having a cationic or anionic hydrophilic group is 0.1% by mass to 25% by mass with respect to the total amount of the polyol (a1) which is a raw material that can be used for the production of the urethane resin (A). Can be used in a range of

  Moreover, as the polyol having the nonionic group, polyalkylene glycol having a structural unit derived from ethylene oxide can be used.

  Examples of the polyisocyanate (a2) that reacts with the polyol (a1) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, Aliphatic or aliphatic cyclic structure-containing diisocyanates such as dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used alone or in combination of two or more. Above all, the use of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate has excellent adhesion to substrates, especially polyethylene terephthalate substrates, and urethane resin composition capable of forming a high refractive index coating film. It is preferable when obtaining a thing.

  The urethane resin (A) is produced, for example, by reacting the polyol (a1), the polyisocyanate (a2), and, if necessary, a chain extender in the absence of a solvent or in the presence of an organic solvent. Can do. When the organic solvent is used, it is preferable to remove the organic solvent by a method such as distillation as necessary when the urethane resin (A) is dispersed in the aqueous medium (B).

  Examples of the organic solvent that can be used in producing the urethane resin (A) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; Formamide, N-methylpyrrolidone and the like can be used alone or in combination of two or more.

  The reaction between the polyol (a1) and the polyisocyanate (a2) is, for example, such that the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is 0.8 to 2.5. It is preferable to carry out in the range, and it is more preferred to carry out in the range of 0.9 to 1.5.

  The chain extender that can be used when producing the urethane resin (A) is used for the purpose of increasing the molecular weight of the urethane resin (A) and improving the durability of the resulting laminate such as an image display device. be able to.

  As a chain extender that can be used when producing the urethane resin (A), polyamines, hydrazine compounds, other active hydrogen atom-containing compounds, and the like can be used.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like can be used.

  As the hydrazine compound, for example, hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine and the like can be used.

  Examples of the other active hydrogen-containing compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, neo Glycols such as pentyl glycol, saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone Such phenols, water and the like can be used.

  The chain extender is, for example, an isocyanate contained in a urethane prepolymer obtained by reacting the polyol (a1) with the polyisocyanate (a2) so that the equivalent of the amino group and active hydrogen atom-containing group of the chain extender It is preferable to use in the range which becomes 1.9 or less (equivalent ratio) with respect to the equivalent of group, and it is more preferable to use in the range of 0.3-1 (equivalent ratio).

  The chain extender can be used when the polyol (a1) and the polyisocyanate (a2) are reacted or after the reaction. Moreover, when the urethane resin (A) obtained above is dispersed in the aqueous medium (B) to make it aqueous, the chain extender can also be used.

  The urethane resin (A) obtained by the above method has a weight in the range of 10,000 to 200,000 for obtaining a urethane resin composition having excellent adhesion to a substrate, particularly a polyethylene terephthalate substrate. It is preferable to use those having an average molecular weight, and it is more preferable to use those having a weight average molecular weight in the range of 20,000 to 100,000.

  Moreover, when manufacturing the said urethane resin (A), in order to shorten reaction time with the said polyol (a1), the said polyisocyanate (a2), etc., a reaction catalyst can be used in combination.

  As the reaction catalyst, for example, a tertiary amine catalyst or an organometallic catalyst can be used. As the tertiary amine catalyst, for example, triethylenediamine, pentamethylenediethylenetriamine, triethylamine, N, N-dimethylethanolamine, ethylmorpholine and the like can be used. As the organometallic catalyst, for example, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, sodium bicarbonate and the like can be used.

  As the urethane resin (A) obtained by the above method, it is preferable to use a urethane resin having a hydrophilic group as described above, but the urethane resin (A) having no hydrophilic group is used. You can also In such a case, it is preferable to use a surfactant described later as one that can contribute to the dispersion of the urethane resin (A). Even when a urethane resin having a hydrophilic group is used as the urethane resin (A), a similar surfactant may be used as necessary from the viewpoint of further improving the water dispersion stability. Good.

  Examples of the surfactant include nonions such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Surfactant: Fatty acid salt such as sodium oleate, alkyl sulfate ester salt, alkyl benzene sulfonate, alkyl sulfosuccinate, naphthalene sulfonate, polyoxyethylene alkyl sulfate, alkane sulfonate sodium salt, alkyl diphenyl ether sulfonate Anionic surfactants such as sodium salts; cationic interfaces such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts It may be used sex agent. Among these, from the viewpoint of improving the dispersion stability of the urethane resin composition of the present invention, it is preferable to use an anionic or nonionic surfactant.

  When using the said surfactant, it is used in 0.5 mass%-5 mass% with respect to the whole quantity of a urethane resin (A) from a viewpoint of preventing the fall of the water resistance of a primer layer. preferable.

  Examples of the method of dispersing the urethane resin (A) obtained by the above method in the aqueous medium (B) include the following methods 1 and 2.

  [Method 1] When a urethane resin having a hydrophilic group is used as the urethane resin (A), a part or all of the hydrophilic group of the urethane resin obtained by the method is replaced with the basic resin as necessary. A method of obtaining an aqueous dispersion of a urethane resin (A) by mixing a mixture neutralized or quaternized with a compound or the like and an aqueous medium (B) and stirring.

  [Method 2] When a urethane resin having no hydrophilic group is used as the urethane resin (A), the urethane resin obtained by the method and a surfactant described later are mixed under stirring conditions. A method of obtaining an aqueous dispersion of a urethane resin (A) by emulsifying and dispersing by introducing an aqueous medium (B) or forcibly emulsifying and dispersing using an emulsifier or the like.

  When the urethane resin (A) is produced in the presence of an organic solvent, an aqueous dispersion of the urethane resin (A) is produced by the methods 1 and 2, and then the organic solvent is distilled as necessary. It is preferable to remove by such a method.

  Examples of the aqueous medium (B) that can be used as the solvent for the urethane resin (A) include water, organic solvents miscible with water, and mixtures thereof. Examples of organic solvents miscible with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols N-methyl-2-pyrrolidone and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  In any of the above methods 1 and 2, when the urethane resin (A) is dispersed in the aqueous medium (B), a machine such as a homogenizer can be used as necessary.

  The urethane resin composition obtained by the above method preferably contains the urethane resin (A) in a range of 5% by mass to 60% by mass with respect to the total amount of the urethane resin composition. It is more preferable to contain in the range of mass%. Moreover, it is preferable to use what the said aqueous medium (B) contains in the range of 35 mass%-85 mass% with respect to the whole quantity of the said urethane resin composition, In the range of 50 mass%-85 mass%. It is preferable to use what is contained.

  The urethane resin composition of the present invention comprises a film-forming aid, a crosslinking agent, a curing accelerator, a plasticizer, an antistatic agent, a wax, a light stabilizer, a flow regulator, a dye, a leveling agent, and a rheology control agent as necessary. Various additives such as ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments and extender pigments can be used.

  The cross-linking agent is preferably used for improving the heat and moisture resistance of a coating film or primer layer formed using the urethane resin composition, for example, a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound. And one or more selected from the group consisting of isocyanate compounds can be used. Especially, it is preferable to use a melamine compound and an epoxy compound.

  As the melamine compound, it is particularly preferable to use an alkylated methylol melamine resin.

  As the alkylated methylol melamine resin, for example, those obtained by reacting a methylolated melamine resin with a lower alcohol (alcohol having 1 to 6 carbon atoms) such as methyl alcohol or butyl alcohol can be used. Specifically, an imino group-containing alkylated methylol melamine resin, an amino group-containing alkylated methylol melamine resin, or the like can be used.

  Examples of the methylolated melamine resin include amino group-containing methylol-type melamine resins obtained by condensing melamine and formaldehyde, imino group-containing methylol-type melamine resins, trimethoxymethylol-type melamine resins, and hexamethoxymethylol-type melamine resins. It is preferable to use a trimethoxymethylol type melamine resin or a hexamethoxymethylol type melamine resin.

  The alkylated methylol melamine resin is preferably used in the range of 3% by mass to 50% by mass with respect to the mass of the urethane resin (A), and more preferably in the range of 3% by mass to 30% by mass. preferable.

  Examples of the epoxy compound that can be used for the crosslinking agent include bisphenol A epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexanediol glycidyl. Ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diamine glycidylamino) Methyl) cyclohexane and the like can be used.

  Among them, the epoxy compound preferably has an epoxy equivalent of 100 to 300 for imparting durability. Specifically, one or two of trimethylolpropane polyglycidyl ether or glycerin triglycidyl ether is used. It is more preferable to use more than one species, and it is more preferable to use trimethylolpropane triglycidyl ether or glycerin triglycidyl ether.

  Moreover, as the epoxy compound, an epoxy compound having a hydrolyzable silyl group can also be used.

  Examples of the epoxy compound having a hydrolyzable silyl group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxy. Propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like can be used.

The urethane resin composition can be suitably used for paints, adhesives and the like. Especially, it is preferable to use it for a coating material, and it is more preferable to use it as a primer.
The primer of this invention obtained by the said method can be used for manufacture of various laminated bodies including an image display apparatus.

  The laminate of the present invention has a primer layer formed using the primer on the surface of a substrate, and a photocurable layer formed using a photocurable resin composition on the surface of the primer layer. The laminated body which has is mentioned.

  First, the base material which comprises the laminated body of this invention is demonstrated.

  The laminate of the present invention is composed of at least a substrate, a primer layer, and a photocured layer.

  Examples of the base material layer include a polyester base, an acrylic base, a polycarbonate base, a polyolefin base, an acrylonitrile-butadiene-styrene base, a polystyrene base, a polyurethane base, an epoxy resin base, and a polyvinyl chloride base. And at least one plastic substrate selected from the group consisting of polyamide substrates, and when used in the production of the image display device, a polyester substrate, an acrylic substrate, a polycarbonate substrate, and a polyolefin. It is preferable to use at least one selected from the group consisting of base materials, more preferably polyester base materials, and use of base materials made of polyethylene terephthalate and polyethylene naphthalate having excellent light transmittance. Further preferred.

  The substrate may have any shape of a plate shape, a spherical shape, a film shape, and a sheet shape. The thickness of the substrate is preferably 10 μm to 200 μm.

  In addition, it is preferable to use a uniaxially or biaxially stretched base material in order to improve the strength and durability of the base material.

  Moreover, the primer layer which comprises the said laminated body can be formed by apply | coating the primer which consists of the said urethane resin composition to a part or all of the surface of the said base material, and then drying.

  Examples of the method for applying the primer to the substrate surface include a spray method, a curtain coater method, a flow coater method, a roll coater method, a gravure printing method, a brush coating method, and a dipping method.

  The primer is preferably applied before the substrate is stretched. It is preferable that the base material coated with the primer is then stretched as necessary to further improve the adhesion between the primer layer and the base material.

  As a method of drying the primer and forming the primer layer, for example, a method of curing for about 1 day to 10 days at room temperature may be used, but from the viewpoint of rapidly proceeding curing, a temperature of 50 ° C. to 250 ° C. A method of heating at a temperature for about 1 second to 600 seconds is preferable. Moreover, when using the plastic base material which is easy to deform | transform and discolor at comparatively high temperature, it is preferable to cure at comparatively low temperature of about 30 degreeC-100 degreeC.

  The primer layer preferably has a thickness of 20 nm to 10,000 nm in order to prevent deterioration of optical properties such as light transmittance of the substrate.

  The member in which the primer layer is laminated on the surface of the base material may be stored for a certain period in a state of being wound on a roll or the like.

  Moreover, the photocuring layer which comprises the said laminated body is a layer laminated | stacked on a part or all of the surface of the said primer layer, Comprising: It is a layer formed by hardening a photocurable resin composition.

  As the photocurable resin composition, for example, a composition containing a vinyl ester resin and a vinyl monomer can be used.

  As said vinyl ester resin, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, etc. can be used, for example.

  The polyester (meth) acrylate can be produced, for example, by reacting a polyol, a polycarboxylic acid, and a compound having a polymerizable unsaturated double bond.

  Examples of the polyol include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, dimethylolcyclohexane, 2,4,4-trimethyl-1,3-pentanediol, diethylene glycol, polyethylene glycol, and dipropylene glycol. Polypropylene glycol, polybutylene glycol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, and the like can be used.

  Examples of the polycarboxylic acid include o-phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic acid, tetrabromophthalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, 1,1. , 2-dodecanoic acid, itaconic acid, himitaic acid, het acid, and the like can be used.

  Moreover, as a compound which has the said polymerizable unsaturated double bond, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate etc. can be used, for example.

  Moreover, as an epoxy (meth) acrylate that can be used as the vinyl ester resin, those obtained by reacting various epoxy compounds with an unsaturated monobasic acid can be used.

  As the epoxy compound, for example, glycidyl ether such as low molecular weight glycol, bisphenol type epoxy compound, or novolak type epoxy compound can be used.

  Examples of the bisphenol type epoxy compound include compounds obtained by reaction of epichlorohydrin and bisphenol, compounds obtained by reaction of methyl epichlorohydrin and bisphenol, and reactions of alkylene oxide adducts of bisphenol and epichlorohydrin. Compounds and the like can be used.

  Examples of the unsaturated monobasic acid that can react with the epoxy compound include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethylmalate, monopropylmalate, monobutenemalate, sorbic acid, and mono (2- Ethylhexyl) malate or the like can be used.

  Moreover, as urethane (meth) acrylate which can be used as said vinyl ester resin, what is obtained by making polyisocyanate and the vinyl monomer which has a hydroxyl group react can be used.

  Examples of the polyisocyanate include 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4 ′. -Dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, adducts thereof and the like. Moreover, as said polyisocyanate, the urethane prepolymer which has an isocyanate group obtained by making the said polyisocyanate and various polyols react can be used.

  Examples of the (meth) acrylate containing a hydroxyl group capable of reacting with the polyisocyanate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like. can do.

  As the vinyl ester resin, it is preferable to use a resin having a weight average molecular weight of 500 to 20,000 in order to maintain ease of coating.

  Examples of vinyl monomers that can be used in combination with the vinyl ester resin include styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyltoluene, vinyl acetate, diarylphthalate, Triaryl cyanurate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate , Ethylene glycol monomethyl ester Ter (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (Meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono 2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) Acrylate, dipropylene glycol Monoethyl ether (meth) acrylate, dipropylene glycol monobutyl ether (meth) acrylate, dipropylene glycol monohexyl ether (meth) acrylate, dipropylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like can be used.

  It is preferable that the photocurable resin composition forming the photocurable layer contains the vinyl ester resin in a range of 10% by mass to 70% by mass with respect to the entire photocurable resin composition. Moreover, it is preferable that the said photocurable resin composition contains the said vinyl monomer in 20 mass%-80 mass% with respect to the whole said photocurable resin composition.

  It is preferable that the said photocurable resin composition contains the polymerization initiator which starts superposition | polymerization by light irradiation.

  Examples of the polymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2- Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) butanone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpionyl) ) Benzyl] phenyl} -2-methylpropan-1-one, benzoin, benzoin methyl ester Ter, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'- Tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium Bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propo Cithioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl- Acetoxy-ethoxy] ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] ethyl ester, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethyl Benzoyl-diphenyl-phosphine oxide or the like can be used.

  It is preferable that the said polymerization initiator is 0.1 mass%-10 mass% with respect to the whole quantity of the said photocurable resin composition.

  As a method of forming the photocured layer, the photocurable resin composition can be formed by applying and curing the photocurable resin composition on a part or the whole of the surface of the primer layer.

  Examples of a method for applying the photocurable resin composition to the surface of the primer layer include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.

Examples of the method of curing the photocurable resin composition include a method of irradiating light such as ultraviolet rays. The light irradiation is generally is preferably carried out in the energy range of ^{200mJ / cm 2 ~2,000mJ / cm 2} .

  The photocured layer preferably has a thickness of approximately 0.01 μm to 0.5 mm.

  Since the laminate of the present invention obtained by the above method does not cause interference fringes, it can be suitably used, for example, for the production of optical films and lenses, and for the production of image display devices such as touch panels. .

Hereinafter, the present invention will be described in more detail by way of examples.

Synthesis example 1
A four-necked flask was charged with 287 parts by mass of ethylene glycol, 481 parts by mass of neopentyl glycol, 635 parts by mass of terephthalic acid, 635 parts by mass of isophthalic acid, and 0.05 parts by mass of tetrabutyl titanate. By reacting for a period of time, polyester polyol (PES-1) [acid value 0.3, hydroxyl value 74.5] was obtained.

Synthesis example 2
A four-necked flask was charged with 305 parts by mass of ethylene glycol, 512 parts by mass of neopentyl glycol, 335 parts by mass of adipic acid, 888 parts by mass of isophthalic acid, and 0.05 parts by mass of tetrabutyl titanate. By reacting for a period of time, polyester polyol (PES-2) [acid value 0.2, hydroxyl value 111.9] was obtained.

<Preparation of urethane resin>
Synthesis example 3
149 parts by mass of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 150 parts by mass of the polyester polyol (PES-1) are mixed, dehydrated at 100 ° C. under reduced pressure, and cooled to 80 ° C. Then, 357 parts by mass of methyl ethyl ketone was added and sufficiently stirred, 26 parts by mass of 2,2-dimethylolpropionic acid was added, and 111 parts by mass of tolylene diisocyanate and 0.2 parts by mass of tin octylate were added at 75 ° C. The reaction was allowed for 8 hours.

  After confirming that the isocyanate content after reaction [mass ratio of isocyanate group with respect to the total amount of the reaction product] was 0.1% by mass or less, the reaction product was cooled to 50 ° C. and 20 parts by mass of triethylamine. The mixture was neutralized and 2000 parts by mass of water was added.

  Next, after removing methyl ethyl ketone at 40 ° C. to 60 ° C. under reduced pressure, water was added to adjust the concentration to obtain a urethane resin composition (PUD-1) having a nonvolatile content of 25% by mass.

Synthesis example 4
180 parts by mass of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 120 parts by mass of the polyester polyol (PES-2) were mixed, dehydrated at 100 ° C. under reduced pressure, and cooled to 80 ° C. Then, 11 parts by mass of 1,4-butanediol and 395 parts by mass of methyl ethyl ketone were added and sufficiently stirred, 26 parts by mass of 2,2-dimethylolpropionic acid was added, and 147 parts by mass of tolylene diisocyanate and tin octylate were added. .2 parts by mass was added and reacted at 75 ° C. for 8 hours.

  After confirming that the isocyanate content after reaction [mass ratio of isocyanate group with respect to the total amount of the reaction product] was 0.1% by mass or less, the reaction product was cooled to 50 ° C. and 20 parts by mass of triethylamine. The mixture was neutralized and 2000 parts by mass of water was added.

  Next, after removing methyl ethyl ketone at 40 ° C. to 60 ° C. under reduced pressure, water was added to adjust the concentration to obtain a urethane resin composition (PUD-2) having a nonvolatile content of 25% by mass.

Synthesis example 5
178 parts by mass of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 119 parts by mass of glycol (hydroxyl value = 168) obtained by adding 8 mol of propylene oxide to bisphenol A were mixed, and the mixture was mixed under reduced pressure. After dehydration at 0 ° C. and cooling to 80 ° C., 7.8 parts by mass of neopentyl glycol and 393 parts by mass of methyl ethyl ketone were added and stirred sufficiently, 30 parts by mass of 2,2-dimethylolpropionic acid was added, and 153 parts by weight of diisocyanate and 0.2 parts by weight of tin octylate were added and reacted at 75 ° C. for 8 hours.

  After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50 ° C., 23 parts by mass of triethylamine was added to neutralize, and 2000 parts by mass of water was added.

  Next, after removing methyl ethyl ketone at 40 ° C. to 60 ° C. under reduced pressure, water was added to adjust the concentration to obtain a urethane resin composition (PUD-3) having a nonvolatile content of 25% by mass.

Synthesis Example 6
210 parts by mass of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 90 parts by mass of glycol (hydroxyl value = 231) obtained by adding 3 mol of propylene oxide to bisphenol A were mixed, and 100 parts under reduced pressure were mixed. After dehydration at 80 ° C. and cooling to 80 ° C., 386 parts by mass of methyl ethyl ketone was added and stirred sufficiently, 24 parts by mass of 2,2-dimethylolpropionic acid was added, and then 148 parts by mass of hexamethylene diisocyanate and tin octylate were added in an amount of 0.1%. 2 parts by mass was added and reacted at 75 ° C. for 8 hours.

  After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50 ° C., neutralized by adding 18 parts by mass of triethylamine, and 2000 parts by mass of water was added.

  Next, after removing methyl ethyl ketone at 40 ° C. to 60 ° C. under reduced pressure, water was added to adjust the concentration to obtain a urethane resin composition (PUD-4) having a nonvolatile content of 25% by mass.

Synthesis example 7
195 parts by mass of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 105 parts by mass of glycol (hydroxyl value = 229) obtained by adding 6 mol of propylene oxide to bisphenol A were mixed at 100 ° C. under reduced pressure. After dehydration and cooling to 80 ° C., 389 parts by mass of methyl ethyl ketone was added and sufficiently stirred, 27 parts by mass of 2,2-dimethylolpropionic acid was added, and then 150 parts by mass of tolylene diisocyanate and 0.2 parts by mass of tin octylate. Part was added and reacted at 75 ° C for 8 hours.
After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50 ° C., neutralized by adding 20 parts by mass of triethylamine, and 2000 parts by mass of water was added.
Subsequently, after removing methyl ethyl ketone at 40-60 degreeC under pressure reduction, the urethane resin composition (PUD-5) of 25 mass% of non volatile matters was obtained by adding water and adjusting a density | concentration.

Synthesis example 8
150 parts by mass of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 150 parts by mass of the polyester polyol (PES-2), and glycol (hydroxyl value = 229) obtained by adding 6 mol of propylene oxide to bisphenol A ) 150 parts by mass, dehydrated at 100 ° C. under reduced pressure, cooled to 80 ° C., added 559 parts by mass of methyl ethyl ketone, sufficiently stirred, added 41 parts by mass of 2,2-dimethylolpropionic acid, 193 parts by mass of tolylene diisocyanate and 0.2 parts by mass of tin octylate were added and reacted at 75 ° C. for 8 hours.
After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50 ° C., added with 31 parts by mass of triethylamine, and neutralized with 2000 parts by mass of water.
Subsequently, after removing methyl ethyl ketone at 40-60 degreeC under pressure reduction, the urethane resin composition (PUD-6) of 25 mass% of non volatile matters was obtained by adding water and adjusting a density | concentration.

Comparative Synthesis Example 1
77 parts by mass of glycol (hydroxyl value = 325) obtained by adding 2 mol of propylene oxide to bisphenol A and 221 parts by mass of the polyester polyol (PES-2) are mixed, dehydrated at 100 ° C. under reduced pressure, and cooled to 80 ° C. Then, 357 parts by mass of methyl ethyl ketone was added and sufficiently stirred, 26 parts by mass of 2,2-dimethylolpropionic acid was added, and then 111 parts by mass of tolylene diisocyanate and 0.2 parts by mass of tin octylate were added at 75 ° C. The reaction was allowed for 8 hours.

  After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50 ° C., neutralized by adding 20 parts by mass of triethylamine, and 1600 parts by mass of water was added.

  Next, after removing methyl ethyl ketone at 40 ° C. to 60 ° C. under reduced pressure, water was added to adjust the concentration to obtain a urethane resin composition (PUD′-1) having a nonvolatile content of 25% by mass.

Comparative Synthesis Example 2
After 300 parts by mass of glycol added with 6 mol of ethylene oxide of bisphenol A was dehydrated at 100 ° C. under reduced pressure and cooled to 80 ° C., 6.3 parts by mass of neopentyl glycol and 398 parts by mass of methyl ethyl ketone were added and sufficiently stirred. 28 parts by mass of 2,2-dimethylolpropionic acid was added, and then 153 parts by mass of tolylene diisocyanate and 0.2 parts by mass of tin octylate were added and reacted at 75 ° C. for 8 hours.

  After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50 ° C., 21 parts by mass of triethylamine was added to neutralize, and 1700 parts by mass of water was added.

  Next, methyl ethyl ketone was removed at 40 ° C. to 60 ° C. under reduced pressure, and the concentration was adjusted by adding water to obtain a urethane resin composition (PUD′-2) having a nonvolatile content of 25% by mass.

<Preparation of photocurable resin composition>
Preparation Example 1
By mixing 50 parts by mass of Unidic V-4260 (manufactured by DIC Corporation, urethane acrylate resin), 50 parts by mass of tripropylene glycol diacrylate and 3 parts by mass of Irgacure 184 (photopolymerization initiator manufactured by BASF), light A curable resin composition (UV-1) was obtained.

Adjustment example 2
By mixing 50 parts by mass of Unidic V-5500 (manufactured by DIC Corporation, epoxy acrylate resin), 50 parts by mass of tripropylene glycol diacrylate and 3 parts by mass of Irgacure 184 (manufactured by BASF, photopolymerization initiator), A photocurable resin composition (UV-2) was obtained.

[Example 1]
By mixing 100 parts by mass of the urethane resin composition (PUD-1), 5 parts by mass of Becamine M-3 (manufactured by DIC Corporation, melamine crosslinking agent) and 185 parts by mass of ion-exchanged water, a primer (P- 1) was prepared.

  The primer (P-1) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

[Example 2]
The primer (P-1) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 3
By mixing 100 parts by mass of the urethane resin composition (PUD-1), 2 parts by mass of CR-5L (manufactured by DIC Corporation, epoxy crosslinking agent) and 168 parts by mass of ion-exchanged water, a primer (P-2) ) Was prepared.

  The primer (P-2) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 4
The primer (P-2) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 5
By mixing 100 parts by mass of the urethane resin composition (PUD-1), 4 parts by mass of Carbodilite V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide cross-linking agent) and 162 parts by mass of ion-exchanged water, a primer is mixed. (P-3) was prepared.

  The primer (P-3) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 6
The primer (P-3) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm micron, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface of the material.

The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 7
By mixing 100 parts by mass of the urethane resin composition (PUD-2), 5 parts by mass of Becamine M-3 (manufactured by DIC Corporation, melamine crosslinking agent), and 185 parts by mass of ion-exchanged water, a primer (P- 4) was prepared.

  The primer (P-4) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 8
The primer (P-4) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 9
By mixing 100 parts by mass of the urethane resin composition (PUD-3), 5 parts by mass of Becamine M-3 (manufactured by DIC Corporation, melamine crosslinking agent) and 185 parts by mass of ion-exchanged water, a primer (P- 5) was prepared.

  The primer (P-5) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 10
The primer (P-5) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 11
By mixing 100 parts by mass of the urethane resin composition (PUD-4), 5 parts by mass of Becamine M-3 (manufactured by DIC Corporation, melamine crosslinking agent) and 185 parts by mass of ion-exchanged water, a primer (P- 6) was prepared.

  The primer (P-6) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

Example 12
The primer (P-6) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.

The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.
Example 13
By mixing 100 parts by mass of the urethane resin composition (PUD-5), 5 parts by mass of Becamine M-3 (manufactured by DIC Corporation, melamine crosslinking agent) and 185 parts by mass of ion-exchanged water, a primer (P- 7) was prepared.
The primer (P-7) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.
The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.
Example 14
The primer (P-7) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.
The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.
Example 15
By mixing 100 parts by mass of the urethane resin composition (PUD-6), 5 parts by mass of Becamine M-3 (manufactured by DIC Corporation, melamine crosslinking agent) and 185 parts by mass of ion-exchanged water, a primer (P- 8) was prepared.
The primer (P-8) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.
The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.
Example 16
The primer (P-8) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and the substrate is heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface.
The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

[Comparative Example 1]
By mixing 100 parts by mass of the urethane resin composition (PUD′-1), 5 parts by mass of Becamine M-3 (manufactured by DIC Corporation, melamine crosslinking agent) and 185 parts by mass of ion-exchanged water, a primer (P -7) was prepared.

  The primer (P′-1) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and heated at 150 ° C. for 5 minutes, thereby A primer layer was formed on the surface of the material.

The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

[Comparative Example 2]
The primer (P′-1) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and heated at 150 ° C. for 5 minutes, thereby A primer layer was formed on the surface of the material.

The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

[Comparative Example 3]
By mixing 100 parts by mass of the urethane resin composition (PUD′-2), 5 parts by mass of Becamine M-3 (manufactured by DIC Corporation, melamine crosslinking agent) and 185 parts by mass of ion-exchanged water, a primer (P '-2) was prepared.

  The primer (P′-2) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and heated at 150 ° C. for 5 minutes, thereby A primer layer was formed on the surface of the material.

The photocurable resin composition (UV-1) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

[Comparative Example 4]
The primer (P′-2) is applied to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness when dried is about 1 μm, and heated at 150 ° C. for 5 minutes, thereby A primer layer was formed on the surface of the material.

The photocurable resin composition (UV-2) is applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface is irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source. Thus, a laminate having a primer layer on the surface of the base material and a photocured layer on the surface of the primer layer was obtained.

[Preparation of test plate]
On the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm, the primers (P-1) to (P-8), (P′-1) and (P′-1) and (P ′) so that the film thickness when dried is about 1 μm. -2) was applied and heated at 150 ° C. for 5 minutes to prepare a test plate made of a member in which a primer layer was laminated on the surface of the substrate.

[Adhesion between substrate and primer layer (initial) <Cellophane adhesive tape peeling test>]
A 24 mm wide adhesive tape made by Nichiban Co., Ltd. was applied to the surface of the primer layer constituting the test plate prepared by the above method.

  Next, the surface of the primer layer when the pressure-sensitive adhesive tape was pulled in a direction perpendicular to the primer layer and the pressure-sensitive adhesive tape was peeled off from the surface of the primer layer was visually evaluated according to the following evaluation criteria.

(Double-circle); The primer layer did not peel at all from the base-material surface which comprises a test board.
○: A part of the primer layer was peeled off from the surface of the base material constituting the test plate, but the peeled range was less than 10% with respect to the total area of the film constituting the test plate.
(Triangle | delta); The primer layer of the range of 10% or more and less than 50% with respect to the area of the primer layer which comprises a test board peeled from the base-material surface which comprises a test board.
X: The primer layer in the range of 50% or more with respect to the total area of the primer layer constituting the test plate was peeled off from the substrate surface constituting the test plate.

[Adhesion between primer layer and photocured layer (initial) <Cellophane adhesive tape peeling test>]
A 24 mm wide adhesive tape made by Nichiban Co., Ltd. was affixed to the surface of the photocured layer constituting the laminate obtained in Examples and Comparative Examples.

  Next, the surface state of the photocured layer when the pressure sensitive adhesive tape is pulled in a direction perpendicular to the photocured layer and the pressure sensitive adhesive tape is peeled off from the surface of the photocured layer is visually evaluated according to the following evaluation criteria. did.

(Double-circle): The photocuring layer did not peel at all from the base-material surface which comprises a laminated body.
○: A small part of the photocured layer was peeled off from the surface of the base material constituting the laminate, but the peeled area was less than 10% with respect to the total area of the photocured layer constituting the laminate. .
(Triangle | delta); The photocuring layer of the range of 10% or more and less than 50% with respect to the area of the photocuring layer which comprises a laminated body peeled from the base-material surface which comprises a laminated body.
X: The photocuring layer of the range of 50% or more with respect to the total area of the photocuring layer constituting the laminate was peeled from the surface of the base material constituting the laminate.

[Adhesion between primer layer and photocured layer (after durability test)]
The obtained laminate was put into a high-temperature humidity chamber having a temperature of 60 ° C. and a relative humidity of 90% for 50 hours. Thereafter, the laminate was taken out, and the adhesion between the primer layer and the photocured layer was evaluated in the same manner as the above [Adhesion between the primer layer and the photocured layer (initial) <cellophane adhesive tape peeling test>]. .

[Evaluation method of refractive index]
By applying the primers obtained in Examples and Comparative Examples to the surface of the polypropylene base so that the film thickness after drying is 100 μm, and then drying at room temperature for 24 hours, and then performing heat treatment at 150 ° C. for 5 minutes. A coating film was formed.
By dissolving the obtained coating film in N, N-dimethylformamide (DMF), a DMF solution of urethane resin in which the solid content of the urethane resin constituting the coating film is 10% by mass, urethane in which 20% by mass is formed. A DMF solution of resin and a DMF solution of 30% by mass urethane resin were prepared.
By measuring the refractive index of the DMF solution of the three types of urethane resins using a digital refractometer RX-5000 (manufactured by Atago Co., Ltd.), and linearly approximating the obtained measurement values, the solid content of the urethane resin Was calculated as the refractive index.
When the refractive index is in the range of 1.55 to 1.65, it is possible to prevent the occurrence of interference fringes when laminated with a polyethylene terephthalate base material (PET). It was evaluated as being particularly preferable for preventing the occurrence of interference fringes. On the other hand, when the refractive index was less than 1.55, it was evaluated that it could not be said to have a high refractive index at a level usable for optical applications.

[Evaluation method of film-forming property]
The primer layer is applied to the surface of the base material by applying the primer to the surface of the base material made of polyethylene terephthalate having a thickness of 125 μm so that the film thickness when dried is about 1 μm and heating at 150 ° C. for 5 minutes. Formed.
◯: When the surface of the primer layer was visually observed, it was transparent.
Δ: When the surface of the primer layer was visually observed, cracks were confirmed although it was transparent.
X: When the surface of the primer layer was visually observed, cracks to the extent that whitening occurred occurred, and a part of the primer layer was easily peeled off from the polyethylene terephthalate substrate.

Claims (6)

One or more selected from the group consisting of a polyol (a1-1) represented by the general formula (1), an aromatic polyester polyol (a1-2), and a polyether polyol (a1-3) in which an alkylene oxide is added to bisphenol. A urethane resin composition comprising a polyol (a1) containing a polyol and a urethane resin (A) obtained by reacting a polyisocyanate (a2).

[R ¹ in the general formula (1) independently represents a group having an aliphatic structure or an aromatic structure, and R ² independently represents an alkylene group. ] The urethane resin composition according to claim 1, further comprising an aqueous medium (B). A primer comprising the urethane resin composition according to claim 1. It has the primer layer formed using the primer of Claim 3 on the surface of a base material, and has the topcoat layer formed using the photocurable resin composition on the surface of the said primer layer. A featured laminate. The laminate according to claim 4, wherein the photocurable resin composition contains a resin having a polymerizable unsaturated double bond and a monomer having a polymerizable unsaturated double bond. An image display device comprising the laminate according to claim 4.