Curable composition

Abstract

To provide a curable resin composition that has high refractive index and exhibits antistatic property.SOLUTION: A curable composition, serving as a coating agent to be laminated on a substrate having a refractive index of 1.45 or more and 1.75 or less, comprises a compound (A) having an ammonium base and a compound (B) having a (meth)acryloyl group and at least one aromatic ring structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition.

[0002] Many displays are used in environments where external light such as sunlight or fluorescent lights enters. Therefore, in order to prevent reflections and backgrounds from appearing on the display surface, It has a prevention function. In addition to contamination of the display surface due to the adhesion of dust, etc., Anti-static properties are also required due to concerns about the internal effects of static electricity.

[0003] As a hard coat layer with antistatic properties, a cationic surfactant, quaternary ammonium hydroxide, is used. Compounds containing quaternary ammonium salts are preferably used (Patent Document 1). The hard coat layer contains an antistatic agent containing ammonium salt, which provides antistatic properties. However, this technology requires a high refractive index substrate surface such as polyester film. If a hard coat layer is directly applied, interference unevenness occurs due to external light reflection, and visibility is reduced. When the adhesive is stuck to the adherend, the condition of the adherend cannot be observed. Unexpected problems may occur. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-81266 Summary of the Invention [Problem to be solved by the invention]

[0005] In view of the above circumstances, the present inventors have determined that the cause of the interference unevenness is the difference in the refractive index between the substrate and the hard coat layer. It is assumed that the difference is large, and in order to increase the refractive index of the hard coat layer, a compound with a high refractive index is used. I paid attention to things.

[0006] By using the above high refractive index compounds, the refractive index is 1.45 or more and 1.75 or less. The refractive index of the hard coat layer applied to the substrate is in the ideal range of 1.52 to 1.8. 0 or less, which can effectively reduce interference unevenness caused by external light reflection. We were able to develop a new material.

[0007] The present invention provides a curable film having a high refractive index, which reduces interference unevenness and also has antistatic properties. The present invention aims to provide a sexual composition. [Means for solving the problem]

[0008] The present invention has the following aspects. That is, the above object of the present invention can be achieved by the following means [1] to

[14] . [1] A coating agent to be laminated on a substrate having a refractive index of 1.45 or more and 1.75 or less, A compound (A) having an ammonium salt group and at least one (meth)acryloyl group A curable composition comprising the compound (B) having the aromatic ring structure described above. [2] A compound (C) having a (meth)acryloyl group, which is different from the compound (B). The curable composition according to [1], [3] The ratio of the compound (A) is the solid ratio of the compound (A), the compound (B), and the compound (C). The total amount of the components is 0.5% by mass or more and 20% by mass or less, as described in [1] or [2] A curable composition comprising: [4] The ratio of the compound (B) is the solid ratio of the compound (A), the compound (B), and the compound (C). Any one of [1] to [3], which is 10 mass % or more and 80 mass % or less of the total amount of the components Item 1. The curable composition according to item 1. [5] The compound (C) has 3 to 10 (meth)acryloyl groups, The curable composition according to any one of [1] to [4]. [6] The compound (C) is a compound having a hydroxyl group, a carboxyl group, an amide group, or a sulfonic acid group. The curable polymer according to any one of [1] to [5], wherein the curable polymer contains one or more polar groups selected from the group consisting of: sexual composition. [7] A cured film obtained by curing the curable composition has a refractive index of 1.52 or more and 1.80 or less. A cured product obtained by curing the composition according to any one of [1] to [6] within the scope of the present invention. [8] The surface resistance of the cured film is 5.0×10 13 Any of [1] to [7] that is less than or equal to Ω A cured product obtained by curing the composition according to any one of claims 1 to 3. [9] The refractive index of the liquid of the compound (B) is 1.50 or more and 1.80 or less. [1] A cured product obtained by curing the composition according to any one of [8] to [8].

[10] The curable composition according to any one of [1] to [9], wherein the substrate is a film. Finished product.

[11] The substrate is polyester, silicon olefin, polyurethane, polycarbonate The curable composition according to any one of [1] to

[10] , wherein the curable composition is any one of the above.

[12] A substrate and a cured coating film provided on the surface of the substrate, wherein the cured coating film is A laminate comprising a cured product obtained by curing the composition according to any one of [1] to

[10] .

[13] The laminate according to

[12] , wherein a primer is laminated between the substrate and the hard coat layer. Layered body.

[14] The laminate according to

[13] , wherein the primer contains a polymer.

[15] A compound having an ammonium base on a substrate having a refractive index of 1.45 or more and 1.75 or less. Compound (A), a compound having a (meth)acryloyl group and at least one aromatic ring structure A laminate having a cured film containing (B). [Effects of the Invention]

[0009] According to the present invention, the high refractive index reduces interference unevenness and further provides antistatic properties. A curable composition can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0010] As used herein, the following terms have the following meanings: "(Meth)acrylic" is a general term for "acrylic" and "methacrylic." "(Meth)acryloyl" is a general term for "acryloyl" and "methacryloyl". be. "(Meth)acrylate" is a general term for "acrylate" and "methacrylate." be. "(Meth)acryloyl functional group number" refers to the number of functional groups contained in one molecule of (meth)acrylate. It means the number of (meth)acryloyl groups. The numerical ranges disclosed in this specification can be arbitrarily combined with the upper and lower limits to form new numerical ranges. It can be a range of values. The "~" symbol indicates a range of values, and includes the values before and after it as the lower and upper limits. This means:

[0011] The present invention will be described in detail below. <Compound (A)> The compound (A) used in the present invention is a copolymer having an ammonium salt group. The compound (A) may be, for example, a monomer having a polymerizable group containing an ammonium salt group. by copolymerization of the compound with other polymerizable groups (e.g., monomers, oligomers) Specific examples of the compound (A) having such an ammonium salt group include: The following (i) to (v) are included. (i) A monomer having a polymerizable group containing an ammonium salt group and a (meth)acrylic acid ester Copolymer with styrene (ii) an oligomer having a polymerizable group containing an ammonium salt group and (meth)acrylic acid Copolymer with ester (iii) Ammonium salt-containing (meth)acrylic acid esters and other (meth)acrylic acids Copolymers with esters and / or styrene monomers (iv) Ammonium salt group-containing (meth)acrylic acid esters and other (meth)acrylic acid esters Copolymers with styrene and / or styrene oligomers (v) Ammonium salt-containing (meth)acrylic acid esters and other (meth)acrylic acid esters Copolymers with esters and / or other (meth)acrylic acid ester oligomers

[0012] A compound with an ammonium base is a compound that has an ammonium group in the molecule. Examples of the amines include aliphatic amines, alicyclic amines, and aromatic amines. In addition, the compound having an ammonium salt group is preferably a polymer type ammonium salt. The ammonium salt group is preferably a compound having an ammonium group as a counter ion. It is preferable that the structure is incorporated into the main chain or side chain of the polymer, rather than Among polymers, in order to effectively impart antistatic properties, the concentration of ammonium base is high. It is preferable that the polymer is a (meth)acrylic polymer. For example, a polymerizable ammonium group or a precursor of an ammonium group such as an amine may be used. A copolymer having an ammonium base is obtained by polymerizing a monomer having an ammonium base with another monomer. Examples include:

[0013] Examples of the ammonium group or the precursor monomer of the ammonium group such as an amine include diamines, ... Compounds with ester bonds such as methylaminoethyl (meth)acrylate, diethyl and compounds having an amide bond such as dimethylaminoethyl (meth)acrylamide. Specifically, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminopropyl N,N-diethylaminobutyl (meth)acrylate, N,N-diethylaminobutyl (meth)acrylate, N,N-dihydroxyethylaminoethyl (meth)acrylate, (meth)acrylic acid N-methylol (meth)acrylamide, N,N-dimethyl (meth)acrylamide , N,N-dibutyl(meth)acrylamide, N,N-dioctyl(meth)acrylamide amide, N-monobutyl(meth)acrylamide, N-(2-hydroxyethyl)acrylamide Amido, N-(2-hydroxyethyl)methacrylamide (meth)acryloylmorpholine Acrylic compounds such as N-vinylformamide, N-vinylpyrrolidone, N-vinyl In particular, vinyl compounds such as N,N-dimethylaminoethylene and α-ε-caprolactam are used. Preferably, N,N-diacid (meth)acrylate and N-vinylformamide are used. The ammonium group of the alkylamino group-containing monomer may be, for example, a (meth)amino group of an amino alcohol. It can also be produced by the quaternization reaction of acrylic acid esters. Examples of the ammonium group of the ammonium group-containing monomer include N,N-dimethylaminoethyl methacrylate. Examples include quaternized acrylates with methyl chloride.

[0014] In the case of (meth)acrylic polymers, ammonium groups or amines The polymerizable monomer may contain a polymerizable monomer unit other than the precursor monomer of the hydroxyl group. Examples of the acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and propionate. Phenyl (meth)acrylate, Butyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate Acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tri Alkyl (meth)acrylates such as decyl (meth)acrylate; the amino alcohols (Meth)acrylic acid esters of 2-hydroxyethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc. Hydroxyalkyl (meth)acrylate; Cyclohexyl (meth)acrylate, Benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethoxyethyl Ethyl (meth)acrylate, Ethyl carbitol (meth)acrylate, Butoxyethyl (Meth)acrylate, cyanoethyl (meth)acrylate, glycidyl (meth)acrylate Examples of such acrylates include various (meth)acrylates, styrene, and methylstyrene. One of these may be used alone, or two or more may be used in combination. When a polymerizable monomer having a long-chain alkyl group is contained, it may segregate at the air interface of the cured film. This is a preferred embodiment because it can enhance the antistatic properties of the cured film. The polymerizable monomer having a chain alkyl group is preferably an alkyl group having 8 or more but less than 30 carbon atoms. alkyl(meth)acrylate, more preferably alkyl(meth)acrylate having 12 or more but less than 22 carbon atoms ) acrylates, such as lauryl (meth)acrylate, tridecyl (meth)acrylate, acrylate, and stearyl (meth)acrylate.

[0015] The proportion of ammonium base-containing monomer units in the copolymer having an ammonium base is preferably Preferably, it is 0.1 to 95% by mass, more preferably 0.2 to 90% by mass, and even more preferably 0.1 to 95% by mass. Preferably, the range is 0.5 to 80% by mass, and particularly preferably 1.0 to 70% by mass. The higher this ratio, the higher the antistatic properties, and the lower this ratio, the worse the appearance of the cured product layer after application. By using it in the above range, antistatic properties and appearance are well balanced. It becomes something.

[0016] The weight average molecular weight of the copolymer having an ammonium base is 800 or more and 120,000 or less. A value of 1,000 or less and 60,000 or less is preferable, and a value of 1,000 or more and 60,000 or less is more preferable.

[0017] The number average molecular weight of the copolymer having an ammonium salt group is 800 or more and 120,000 or less. is preferable, and 1,000 or more and 60,000 or less is more preferable.

[0018] Copolymers having ammonium salt groups can be produced by radical polymerization using the above raw material monomers. The radical polymerization reaction is carried out in an organic solvent in the presence of a radical polymerization initiator. It is preferable to carry out the process under the presence of

[0019] Examples of organic solvents used in radical polymerization reactions include acetone and methyl ethyl ketone. Ketone solvents such as (MEK); ethanol, methanol, isopropyl alcohol (IP A), alcoholic solvents such as isobutanol; ethylene glycol dimethyl ether, propanediol, etc. Ether solvents such as propylene glycol monomethyl ether; ethyl acetate, propylene glycol Esters such as glycerol monomethyl ether acetate and 2-ethoxyethyl acetate Solvent: Aromatic hydrocarbon solvents such as toluene can be used. Only one of these organic solvents can be used. Alternatively, two or more of them may be used in combination.

[0020] Examples of the radical polymerization initiator used in the radical polymerization reaction include benzoyl peroxide. organic peroxides such as di-t-butyl peroxide; 2,2'-azobisbutyronite 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( 4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds. The radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is in the range of 0.01 to 5% by mass based on the total amount of raw material monomers. It is preferable to use it in

[0021] In addition, during radical polymerization reactions, chain transfer is performed to control the weight average molecular weight of the polymer. Examples of chain transfer agents that can be used include butanethiol and octanethiol. thiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol cyclohexyl mercaptan, thiophenol, octyl thioglycolate, 2-methylpropional Octyl mercaptopropionate, Octyl 3-mercaptopropionate, Mercaptopropionate Pionic acid 2-ethylhexyl ester, thioglycolic acid 2-ethylhexyl, butyl- 3-Mercaptopropionate, Mercaptopropyltrimethoxysilane, Methyl-3- Mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol ol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1, 8-Dimercapto-3,6-dioxaoctane, Decanetrithiol, Dodecylmercapto Tan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1- Propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycol carboxylic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptoamic acid Examples of the compounds include thiol compounds such as 2-mercaptoethanesulfonic acid and 2-mercaptoethanesulfonic acid. Only one type may be used, or two or more types may be used in combination.

[0022] The amount of the chain transfer agent used is preferably 0.1 to 25% by mass based on the total amount of the raw material monomers. It is more preferably 0.5 to 20% by mass, and even more preferably 1.0 to 15% by mass. It's nice.

[0023] The reaction time of the radical polymerization reaction is preferably 1 hour or more and less than 20 hours, and more preferably 3 hours or more and less than 12 hours. The reaction temperature is preferably 40 to less than 120°C, more preferably 50 to less than 100°C. Full is more preferable.

[0024] The compound (A) having an ammonium base may be used alone or in combination of two or more. It may also be used.

[0025] In the curable composition of the present invention, by using the compound (A), As shown in the examples, a cured product having excellent antistatic properties can be obtained.

[0026] <Compound (B)> The compound (B) used in the present invention is used to increase the refractive index in order to reduce interference unevenness. The compound used is a compound having a (meth)acryloyl group and at least one aromatic ring structure. Compound (B) is a compound having an aromatic ring structure and a (meth)acryloyl group. The compound may be a monomer or a polymer. In this case, the aromatic ring structure may be the same as or different from the aromatic ring structure. The (meth)acryloyl group may be the same or different. It may have only one or two or more. Compound (B) with a high refractive index is preferred. The preferred refractive index of the liquid is 1. It is 50 or more and 1.80 or less, preferably 1.53 or more and 1.70 or less, and more preferably Preferably, it is 1.54 or more and 1.68 or less, and more preferably, it is 1.56 or more and 1.65 or less. do.

[0027] Examples of aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a phenyl ring. In the present invention, examples of the aromatic ring structure include a fluorene ring, a 1-fluorene ring, and the like. It is preferable that the aromatic ring structure has a phenoxybenzyl group or a biphenyl group. It is preferable to use a (meth)acrylate compound having the following structure. Specifically, acrylic acid ( methacrylic acid (CH2=C(CH3)-COOH) and bis(methacrylic acid) Phenoxyethanol fluorene, bis(4-glycidyloxyphenyl)fluorene, Obtained by esterification with phenoxybenzyl alcohol or biphenyl alcohol (Meth)acrylate compounds are exemplified.

[0028] The compound (B) used in the present invention is, for example, bisphenoxyethanol fluorene. Fluorene skeleton-containing (meth)acrylates such as phenyl diacrylate, ethoxylated o-phenyl Nylphenol acrylate, 2-phenylphenoxyethyl (meth)acrylate, Luoren epoxy (meth)acrylate, 3-phenoxybenzyl (meth)acrylate , biphenyl (meth)acrylate, EO modified orthophenylphenol (meth)acrylate (Meth)acrylate containing bisphenol A skeleton, such as bisphenol A dimethacrylate bisphenol A skeleton-containing epoxy compounds such as bisphenol A acrylate and bisphenol epoxy diacrylate Thio(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate Acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene Styrene glycol (meth)acrylate, 2-acryloyloxyethyl-2-hydroxy Ethyl phthalate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 1 -Naphthylmethyl (meth)acrylate, 2-naphthylmethyl (meth)acrylate, 4 ,4'-bisacryloxymethylbiphenyl, 4-methacryloyloxybenzophenone Among them, bisphenoxyethanol and 4-hydroxyphenyl methacrylate are Ethyl fluorene diacrylate, ethoxylated o-phenylphenol acrylate acrylate, 2-naphthyl methacrylate, and 3-phenoxybenzyl acrylate are preferred.

[0029] The compound (B) may be used alone or in combination of two or more.

[0030] <Compound (C)> The compound (C) used in the present invention is a compound having a (meth)acryloyl group. The (meth)acrylate is not particularly limited, and may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, or the like. ) acrylate, a mixture of one or more types of trifunctional or higher multifunctional (meth)acrylate, Any commercially available hardening resin material or any other material that does not impair the object of this embodiment may be used. Other components may be added as long as they are not added excessively. Among them, tri- or higher functional (meth)acrylates are preferred due to their excellent curing properties. A compound having 3 to 10 (meth)acryloyl groups is particularly preferred.

[0031] Monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, Acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Uryl (meth)acrylate, Stearyl (meth)acrylate, Morpholyl (meth)acrylate Acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth) Acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate (meth)acrylate, tricyclodecane (meth)acrylate, polyethylene glycol Cyclohexyl (meth)acrylate, tetrahydrofurfuryl dicyclopentanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl Allyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate acrylate, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethanol Mono(meth)acrylates such as hydroxyethyl (meth)acrylate and phenyl (meth)acrylate acrylate, adduct of phthalic anhydride and 2-hydroxyethyl (meth)acrylate, etc. Examples thereof include mono(meth)acrylate compounds.

[0032] The bifunctional polyfunctional (meth)acrylate is not particularly limited, but examples thereof include For example, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Acrylate, 1,6-Hexanediol Di(meth)acrylate, 1,9-Nonanedio di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, etc. Alkanediol di(meth)acrylate, bisphenol A modified with ethylene oxide Di(meth)acrylate, bisphenol F ethylene oxide modified di(meth)acrylate bisphenol-modified di(meth)acrylates such as polyethylene glycol di(meth)acrylate ) acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate ) acrylate, epoxy di(meth)acrylate, etc.

[0033] The trifunctional or higher polyfunctional (meth)acrylate is not particularly limited, but may be: For example, pentaerythritol tri(meth)acrylate, dipentaerythritol pentaerythritol Dipentaerythritol hexa(meth)acrylate, pentaerythritol hexa(meth)acrylate Erythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate Acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane Glycerin-containing polyfunctional ( meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate Acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate ethylene oxide-modified pentaerythritol tri(meth)acrylate, etc. Oxide-modified (meth)acrylate, ethylene oxide-modified tri(meth)acrylate isocyanurate acrylate, ε-caprolactone modified tris(acryloxyethyl) isocyanurate isocyanuric acid-modified tri(meth)acrylates such as pentaerythritol triacrylate, Lactic hexamethylene diisocyanate urethane prepolymer, pentaerythritol Triacrylate Toluene Diisocyanate Urethane Prepolymer, Dipentaerythritol Urethane such as hexamethylene diisocyanate urethane prepolymer (meth)acrylate and the like.

[0034] Among these, tri- or higher functional (meth)acrylates are preferred from the viewpoint of hardness. From the viewpoint of compatibility with the copolymer having an ammonium salt group, those containing a polar group are preferred. Examples of the polar group include a hydroxyl group, a carboxyl group, an amide group, and a sulfonic acid group. Among them, pentaerythritol tri(meth)acrylate, dipentaerythritol Hydroxyl-containing (meth)acrylates such as penta(meth)acrylate are preferred.

[0035] The curable composition may contain an active energy ray-curable compound other than (meth)acrylate. For example, styrene, vinyl halide, vinyl acetate, etc. Vinyl compounds, vinylidene halides, 1,3-butadiene, isoprene, chloroprene and other diene compounds.

[0036] The curable composition contains various polymers to adjust the hardness of the cured product. Examples of the material include acrylic polymers, polyesters, and polyurethanes.

[0037] The curable composition of the present invention generally contains an organic solvent. Examples of the organic solvent include: n-Hexane, n-Heptane, n-Octane, n-Decane, n-Dodecane, 2,3-Dimethyl cyclohexane, 2-methylheptane, 2-methylhexane, 3-methylhexane, Saturated hydrocarbon solvents such as hexane; aromatic solvents such as toluene and xylene; methyl ethyl Ketone solvents such as ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol Cholesterol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, propylene glycol mono Ether solvents such as methyl ether, anisole, and phenetole; ethyl acetate, butyl acetate ester solvents such as ethanol, isopropyl acetate, and ethylene glycol diacetate; dimethyl Amide solvents such as formamide, diethylformamide, and N-methylpyrrolidone; methyl Cellosolve solvents such as cellosolve, ethyl cellosolve, and butyl cellosolve; methanol, Alcoholic solvents such as ethanol, propanol, isopropanol, and butanol; Examples of the solvent include halogen-based solvents such as chloromethane and chloroform.

[0038] The proportions of the above components in the curable composition of the present invention are as follows: The proportion of compound (A) relative to the total amount of compound (A), compound (B) and compound (C) is: Usually, 0.5 to 20% by mass, preferably 2 to 10% by mass, more preferably 2 The compound (B) is usually 10 to 89% by mass, preferably is 20 to 78% by mass, more preferably 30 to 67% by mass, and the compound ( C) is preferably 10 to 89% by mass, more preferably 20 to 78% by mass, The amount of the compound (B) is more preferably 30 to 67% by mass. The proportion of the polymerization initiator used is usually 0.01 to 5% by mass. The organic solvent is used in an amount that results in a solid content concentration of about 5 to 95% by mass.

[0039] <Photopolymerization initiator> A photopolymerization initiator may be added to promote the curing of the curable composition. The molecular weight is preferably 1,000 or less. Nylketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, Naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, p ,p'-Bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone Pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloro dichloroacetophenone, pt-butyldichloroacetophenone, 2-chlorothioxanthone , 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxythioxanthone Cetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro- 4-phenoxyacetophenone, phenyl glyoxylate, α-hydroxyisobutyl Phenone, Dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2 -Methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morph Orino-1-propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone These photopolymerization initiators can be used alone or in combination of two or more. good. When a photopolymerization initiator is added, its content should be determined from the viewpoints of curing promotion and hardness of the cured film. Preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the curable composition The range is more preferably 8% by mass or less, and particularly preferably 5% by mass or less. There is no limit to the amount, but it is, for example, 0.01% or more.

[0040] <Leveling agent> To improve the appearance of the cured film, a leveling agent can be incorporated into the curable composition. Examples of the leveling agent include an acrylic leveling agent and a silicone leveling agent. These leveling agents can be used alone or in combination. More than one species may be used in combination. When a leveling agent is added, its content should be adjusted to the curable composition from the viewpoint of improving the appearance of the cured film. It is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably The content is preferably in the range of 5% by mass or less.

[0041] <Various additives> The curable composition may contain an antifouling agent, a plasticizer, a surfactant, Antioxidants, UV absorbers, light stabilizers, polymerization accelerators such as compounds containing thiol groups, etc. Various additives such as those listed above may also be added.

[0042] <Cured product> The curable composition of the present invention can be cured by applying it to a substrate and then irradiating it with active energy rays. The coating method includes, for example, a reverse coating method and a gravure coating method. , rod coating method, bar coating method, Mayer bar coating method, die coating method, spray coating method Examples of active energy rays include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. Examples of the radiation include light, but ultraviolet rays and electron beams are preferably used.

[0043] For example, when using ultraviolet light, the cumulative light intensity of irradiation is 20 to 5000 mJ / cm 2 The following is Preferably, 100 to 3000 mJ / cm2 is more preferable, and 200 to 2000 mJ / cm2 is more preferable. J / cm 2 The illuminance is more preferably 50 to 600 mW / cm. 2 below is preferred, and 75 to 450 mW / cm 2 Less than 100mW / 300mW is more preferable. cm 2 The following are more preferred: As the light source, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, Electron beams generated by electrodeless lamps, metal halide lamps, or scanning or curtain-type electron beam accelerating paths A linear high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a low-pressure mercury lamp, etc. can be used.

[0044] When curing is performed by electron beam irradiation, various electron beam irradiation devices can be used. The irradiation dose (Mrad) of the electron beam is preferably 0.5 or more and less than 20 Mrad. From the viewpoints of the curability of the active energy ray-curable composition, flexibility of the cured product, prevention of damage to the substrate, etc. Therefore, it is more preferably 1 or more and less than 15 Mrad.

[0045] <Haze> The coating film haze of the cured product obtained from the curable composition of the present invention is preferably 4.0 or less, more preferably The haze is preferably 3.0 or less, and more preferably 2.0 or less. tends to be better.

[0046] <Surface resistance value> The antistatic properties of the cured product obtained from the curable composition of the present invention were evaluated by the surface resistance value. The surface resistance is 5.0 x 10 13 Ω or less is preferable, 5.0×10 12 Ω or less is preferable 5.0 x 10 11 It is more preferable that the surface hardness of the coating film is within the above range. This can suppress the generation of static electricity and prevent dust from adhering during the process.

[0047] <Refractive index of cured film> The refractive index of the cured product obtained from the curable composition of the present invention is preferably 1.52 or more and 1.8 or less. 0 or less, more preferably 1.53 to 1.75, and even more preferably 1.55 to 1. 70 or less, and most preferably 1.57 to 1.68. , it is possible to prevent interference unevenness from occurring.

[0048] <Application> The composition of the present invention can provide a film that reduces interference unevenness and has antistatic properties. Therefore, it is suitable for use as an antistatic coating agent in flat panel displays, touch panels, etc. Optical products such as displays, DVDs and next-generation optical information media, automobile lamps, windows, etc. It has excellent antistatic properties and is suitable for the surface of various items such as (semi) transparent items and housings of electrical equipment. It can provide surface protection.

[0049] The cured product obtained from the curable composition of the present invention has a high refractive index and excellent antistatic properties, It is useful as a hard coat layer (high refractive index layer) for anti-reflection films, etc. In the use as a layer, there is no particular limitation on the thickness of the cured film made of the curable composition of the present invention. However, it is usually 0.1 to 20 μm, preferably 1 to 15 μm, and more preferably The range is preferably 2 to 10 μm, more preferably 3.5 to 8 μm. By using it in this range, anti-static properties are improved, interference unevenness is reduced, and haze is also optimized. value.

[0050] <Laminate> The laminate of the present invention (hereinafter also referred to as "the present laminate") comprises a base layer and one of the base layers. The laminate further comprises a substrate layer and a hard coat layer provided on the substrate surface. a primer layer provided between the hard coat layer and the substrate layer; a surface functional layer provided on the opposite surface and a surface opposite to the hard coat layer side of the substrate layer; and a back surface functional layer provided on the side surface of the substrate.

[0051] <Base material> The substrate may be a known resin having a refractive index of 1.45 or more and 1.75 or less. A substrate having a viscosity of 1.50 or more and 1.73 or less is preferred, and a resin substrate having a viscosity of 1.60 or less is more preferred. The resin substrate is preferably a single-layer substrate or a two-layer substrate. The substrate may have a multilayer structure as described above, and is not particularly limited. It is preferable to configure the film so that each layer has its own characteristics and achieve multi-function. The resin substrate preferably has transparency, smoothness, heat resistance, and excellent mechanical strength. Examples include polyester, cycloolefin, polycarbonate, polyvinyl chloride, Polyamide, polyimide, polyethersulfone, polysulfone, or polyurethane Examples of the thermoplastic resin include polyester, cycloolefin, polycarbonate, etc. In addition, considering transparency, moldability, and versatility, polyester is the most popular. The thickness of the substrate is preferably 10 μm or more and 300 μm or less. If the substrate is a plate, it must not exceed these thicknesses. The substrate may have a thickness of 1000 nm or less when a cured material layer is formed thereon. Therefore, in addition to physical treatments such as corona discharge treatment and oxidation treatment, anchor agents or ply A coating called a paint may be applied beforehand.

[0052] The polyester film may have a single layer structure or a multilayer structure. In this case, the surface layer and the inner layer, or both surface layers or each layer may be made of different polyester layers depending on the purpose. It is possible to make it multi-layered with two or more layers, and each layer can have its own characteristics, making it multi-functional. preferable.

[0053] The polyester used can be either homopolyester or copolymer polyester. In the case of homopolyester, aromatic dicarboxylic acid and aliphatic glycol are polycondensed. The aromatic dicarboxylic acid is preferably a dicarboxylic acid obtained by mixing terephthalic acid, 2,6 -naphthalenedicarboxylic acid, and the aliphatic glycols include ethylene glycol Examples of suitable olefins include olefin glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Typical examples of polyester include polyethylene terephthalate. The dicarboxylic acid components of the synthetic polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, hydroxycarboxylic acids (e.g. , p-hydroxybenzoic acid, etc.), and , ethylene glycol, diethylene glycol, propylene glycol, butanediol , 4-cyclohexanedimethanol, neopentyl glycol, etc. Examples include:

[0054] From the viewpoint of creating a film that can withstand various processing conditions, we have focused on mechanical strength and heat resistance (processing). It is preferable that the resin has high thermal dimensional stability, and in order to achieve this, the copolymer polyester component is small. Specifically, the proportion of copolymerized polymer in the polyester film is The proportion of monomers forming the diester is usually 10 mol % or less, preferably 5 mol % or less. It is more preferable that the amount of the hydroxyl group is in the range of 0.01 to 0.15, and more preferably in the range of 0.1 to 0.25, which is not generated as a by-product during homopolyester polymerization. The polyester contains 3 mol % or less of a diether component. In consideration of mechanical strength and heat resistance, the preferred form is terephthalic acid among the above compounds. Polyethylene terephthalate and polyethylene are polymerized from ethylene glycol. Films formed from naphthalate are preferred because of their ease of manufacture and surface protection. Considering the ease of handling for applications such as gypsum, Films are more preferred.

[0055] The polyester polymerization catalyst is not particularly limited, and any conventionally known compound may be used. For example, antimony compounds, titanium compounds, germanium compounds, manganese compounds compounds, aluminum compounds, magnesium compounds, calcium compounds, etc. Among these, antimony compounds are preferred because they are inexpensive, and titanium compounds and germanium compounds are also preferred. Nitride compounds have high catalytic activity and can be polymerized in small amounts, and do not remain in the film. This is preferable because the amount of metal used is small, which increases the transparency of the film. Since titanium compounds are expensive, titanium compounds are more preferably used.

[0056] In the case of polyesters that use titanium compounds, the titanium element content is usually 50 ppm or less. The range is preferably 1 to 20 ppm, more preferably 2 to 10 ppm. If the content of titanium compound is too high, the polyester may be melt-extruded. This may accelerate the deterioration of the ster and result in a film with a strong yellow tint. If the polymerization efficiency is too low, the cost will increase and a film with sufficient strength may not be obtained. In addition, when using polyester with a titanium compound, the melt extrusion process For the purpose of inhibiting deterioration, it is preferred to use a phosphorus compound to reduce the activity of the titanium compound. As the phosphorus compound, orthophosphoric acid is preferred in consideration of the productivity and thermal stability of polyester. The phosphorus content is preferably 1 to 300 parts per million based on the amount of polyester to be melt-extruded. pm or less, preferably 3 to 200 ppm or less, and more preferably 5 to 100 ppm or less If the content of phosphorus compounds is too high, it may cause gelation or foreign matter. If the content is too low, it may not be possible to sufficiently reduce the activity of the titanium compounds. This may result in a yellowish film.

[0057] The polyester layer contains a material that provides slipperiness, prevents scratches during each process, and has anti-blocking properties. For the purpose of improving the performance, particles may be blended. The type of particles is not particularly limited as long as they are particles that can provide lubricity. Examples of the inorganic fillers include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, Calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide inorganic particles such as titanium oxide, acrylic resin, styrene resin, urea resin, phenol Examples of the organic particles include those made of resin, epoxy resin, benzoguanamine resin, etc. During the ester manufacturing process, a part of the metal compounds such as catalysts is precipitated and finely dispersed to form precipitate particles. Among these, silica particles and carbonated powders are particularly effective in small amounts. Calcium particles are preferred.

[0058] The average particle size of the particles is usually 10 μm or less, preferably 0.01 to 5 μm, and more preferably Preferably, the average particle size is in the range of 0.01 to 3 μm. When the average particle size exceeds 10 μm, There is a concern that the film may have problems due to a decrease in transparency.

[0059] Furthermore, the particle content in the polyester layer is dependent on the average particle size, so it is difficult to generalize. Although it cannot be said that the content is always 5% by weight or less, it is preferably in the range of 0.0003 to 3% by weight. More preferably, the particle content is in the range of 0.0005 to 1% by weight. If it exceeds this limit, there may be concerns about problems such as particle shedding and a decrease in film transparency. If there are no particles or if there are only a few particles, the adhesive layer may not have sufficient slipperiness. It may be necessary to improve the slipperiness by adding particles inside.

[0060] The shape of the particles to be used is not particularly limited, and may be spherical, lumpy, rod-like, flat, or the like. There are no particular limitations on the hardness, specific gravity, color, etc. Two or more types of particles of this series may be used in combination as needed.

[0061] The method for adding particles to the polyester layer is not particularly limited, and any of the conventional methods can be used. Known methods can be used. For example, at any stage in the production of the polyester constituting each layer, However, it is preferable to add it after the esterification or transesterification reaction is completed. , it is good to add.

[0062] In addition to the above particles, the polyester film may contain a conventionally known ultraviolet absorber as needed. , antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, pigments, etc. may be added.

[0063] The thickness of the polyester film is not particularly limited as long as it can be formed into a film. Although it is not essential, it is usually 2 to 350 μm, preferably 5 to 200 μm, more preferably 100 to 250 μm. The most preferable range is 8 to 75 μm.

[0064] A specific example of film production will be described below, but the present invention is not limited to the following example. Generally, the resin is melted and formed into a sheet. For example, biaxially oriented polyester is used. When manufacturing sterilized film, polyester raw material is first melted and extruded from a die using an extruder. The molten sheet is extruded and cooled and solidified with a cooling roll to obtain an unstretched sheet. In order to improve the flatness of the sheet, it is preferable to increase the adhesion between the sheet and the rotating cooling drum. The electrostatic application adhesion method and the liquid application adhesion method are preferably used. The film is stretched in one direction using a roll or tenter type stretching machine. The stretching temperature is usually 70°C or higher. The temperature is 120°C or lower, preferably 80°C or higher and 110°C or lower, and the stretching ratio is usually 2.5 or higher. The stretching direction is then perpendicular to the first stretching direction. In the drawing direction, the temperature is usually 70 to 170° C., and the draw ratio is usually 2.5 to 7 times, preferably The stretching time is usually 3.0 to 6 times. One method is to obtain a biaxially oriented film by heat treating the film under tension or relaxation of 30% or less. In the above stretching, a method of performing stretching in one direction in two or more stages can be adopted. In this case, it is preferable to carry out the stretching so that the final stretching ratios in both directions are within the above ranges. I wish.

[0065] In addition, the polyester film that constitutes the laminated polyester film is manufactured at the same time. A biaxial stretching method can also be used. In the simultaneous biaxial stretching method, the unstretched sheet is stretched at a rate of usually 70°C. The temperature is controlled at 80 to 110°C. This method involves stretching and orienting the film simultaneously in the machine direction and the width direction. The stretching ratio is an area ratio of The ratio is usually 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times. Then, it is subsequently heated under tension or at a temperature of 180 to 270°C. The film is then heat-treated under a relaxation of 0% or less to obtain a stretched and oriented film. Regarding simultaneous biaxial stretching devices, screw type, pantograph type, linear drive type, etc. A conventionally known stretching method can be used.

[0066] Next, the formation of the adhesive layer that constitutes the laminated polyester film will be described. Examples of the forming method include coating, transfer, lamination, etc. Considering the ease of forming the layer, it is preferable to form it by coating.

[0067] Coating methods include in-line coating, which is carried out during the film manufacturing process. Alternatively, the coating may be applied by coating outside the system onto a film that has already been produced. It may be applied by in-coating, more preferably by in-line coating. It is something that is formed.

[0068] Specifically, in-line coating involves melt-extruding the resin that forms the film. This method involves coating at any stage from the time of stretching to heat setting and winding up. The term refers to an unstretched sheet obtained by melting and quenching, a uniaxially stretched film, and a biaxially stretched film before heat setting. Coating is applied to either axially stretched film or film after heat setting and before winding. Limited to the following: However, in the case of sequential biaxial stretching, the film is particularly stretched in the longitudinal direction (machine direction). The most effective method is to coat the uniaxially stretched film with the coating and then stretch it in the transverse direction. According to this method, film formation and adhesive layer formation can be performed simultaneously, which is advantageous in terms of manufacturing costs. In addition, since the film is stretched after coating, the thickness of the adhesive layer can be changed depending on the stretching ratio. This makes it easier to perform thin film coating than offline coating. It is possible to do so.

[0069] <Primer layer> The primer layer is designed to reduce interference unevenness caused by external light after the hard coat layer is formed, and This is provided to improve adhesion to the hard coat layer.

[0070] The metal oxide used to form the primer layer is mainly used to adjust the refractive index of the primer layer. In particular, the resin used in the primer layer has a low refractive index, so high refractive index It is preferable to use a metal oxide having a refractive index, and one having a refractive index of 1.7 or more is used. Specific examples of metal oxides include zirconium oxide, Titanium oxide, tin oxide, yttrium oxide, antimony oxide, indium oxide, zinc oxide, These include antimony tin oxide, indium tin oxide, etc., and these can be used alone. Among these, zirconium oxide and titanium oxide are particularly preferred. Zirconium oxide is more preferably used, and in particular, zirconium oxide is more preferably used from the viewpoint of weather resistance. can be.

[0071] Metal oxides are used in particle form because there is a concern that their adhesion may decrease depending on the type of use. It is preferable to use a cellulose acylate having an average particle size of 100 nm from the viewpoint of transparency. It is preferably 50 nm or less, more preferably 25 nm or less.

[0072] The components derived from the crosslinking agent in the primer layer are mixed with the hard coat layer provided on the primer layer. It is possible to improve the adhesion of the adhesive layer with only one type of crosslinking agent. The use of two or more crosslinking agents in combination can further improve the adhesion.

[0073] The crosslinking agent used to form the primer layer is an oxazoline compound, an epoxy compound, a methacrylate ... Lamin compounds, isocyanate compounds, carbodiimide compounds, silane coupling Among these crosslinking agents, compounds such as the following are preferred in terms of good adhesion: In particular, it is preferable to use an oxazoline compound or an epoxy compound, and more preferable Alternatively, an oxazoline compound and an epoxy compound may be used in combination.

[0074] An oxazoline compound is a compound that has an oxazoline group in the molecule, and in particular, A polymer containing an oxazoline group is preferred, and an addition-polymerizable oxazoline group-containing monomer alone or It can be prepared by polymerization with other monomers. is 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2- Vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2- Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2 -oxazoline, etc., and one or a mixture of two or more of these may be used. Among these, 2-isopropenyl-2-oxazoline is commercially available. The other monomer is copolymerized with the addition-polymerizable oxazoline group-containing monomer. There is no limitation as long as it is a possible monomer, for example, alkyl (meth)acrylate (with alkyl group Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups. (meth)acrylic acid groups such as butyl, t-butyl, 2-ethylhexyl, and cyclohexyl groups Acrylic acid esters; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, Styrene sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt) unsaturated carboxylic acids such as acrylonitrile, methacrylonitrile, tertiary amine salts, etc.; unsaturated nitriles such as (meth)acrylamide, N-alkyl (meth)acrylamides, N,N-dialkyl(meth)acrylamide (the alkyl group is methyl, butyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group unsaturated amides such as vinyl acetate, vinyl acetate, 2-ethylhexyl group, cyclohexyl group, etc.; Vinyl esters such as vinyl pionate; methyl vinyl ether, ethyl vinyl ether, etc. vinyl ethers; α-olefins such as ethylene and propylene; vinyl chloride, Halogen-containing α,β-unsaturated monomers such as vinylidene and vinyl fluoride; styrene, α-methyl Examples of the aromatic monomer include α,β-unsaturated aromatic monomers such as styrene and the like. Two or more kinds of monomers can be used.

[0075] An epoxy compound is a compound having an epoxy group in the molecule, such as epichlorohydrin. Hydrin and ethylene glycol, polyethylene glycol, glycerin, polyglycerin , condensation products of hydroxyl groups or amino groups of bisphenol A, etc., polyepoxy compounds, Diepoxy compounds, monoepoxy compounds, glycidylamine compounds, etc. Examples of the alkyl compounds include sorbitol polyglycidyl ether, polyglycerol polyglycerol, and the like. Diglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol Polyglycidyl ether, triglycidyl tris(2-hydroxyethyl) isocyanate Glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether Examples of the ester and diepoxy compounds include neopentyl glycol diglycidyl ether. 1,6-Hexanediol Diglycidyl Ether, Resorcinol Diglycidyl Ether , ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl Diglycidyl ether, polytetramethylene glycol diglycidyl ether, monoepoxy compound Examples of the glycidyl ether include allyl glycidyl ether and 2-ethylhexyl glycidyl ether. phenyl glycidyl ether, glycidylamine compounds such as N,N,N',N' -Tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidyl amine) aminocyclohexane, etc.

[0076] The melamine compound is a compound having a melamine structure, such as: Alkylolated melamine derivatives, alkylolated melamine derivatives reacted with alcohol Partially or completely etherified compounds and mixtures thereof can be used. The alcohols used for etherification include methyl alcohol, ethyl alcohol, Isopropyl alcohol, n-butanol, isobutanol, etc. are preferably used. The melamine compound may be either a monomer or a dimer or higher polymer. Furthermore, melamine may be partially co-condensed with urea or the like. A catalyst can also be used to increase the reactivity of the melamine compound. It is possible.

[0077] Isocyanate compounds are compounds that replace isocyanates or blocked isocyanates. It is a compound having an isocyanate derivative structure represented by the following formula: Examples of the isocyanate include tolylene diisocyanate, xylylene diisocyanate, and methylene diphenyl ether. diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, etc. Aromatic isocyanate, α,α,α',α'-tetramethylxylylene diisocyanate Aliphatic isocyanates with aromatic rings, such as methylene diisocyanate and propylene diisocyanate. isocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, Aliphatic isocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate methylcyclohexane diisocyanate, isophorone diisocyanate, methyl Bis(4-cyclohexyl isocyanate), isopropylidenedicyclohexyldiisocyanate Examples of the isocyanates include alicyclic isocyanates such as benzophenone, ... Biuret compounds, isocyanurates, uretdione compounds, carbodiimide modified compounds, etc. Polymers and derivatives thereof may also be mentioned. These may be used alone or in combination of two or more kinds. Among isocyanates, aromatic isocyanates are preferred to prevent yellowing due to ultraviolet rays. Aliphatic or alicyclic isocyanates are more preferred.

[0078] When used in the form of blocked isocyanate, the blocking agent is, for example, biphenyl. Sulfates, phenolic compounds such as phenol, cresol, and ethylphenol, Pyrene glycol monomethyl ether, ethylene glycol, benzyl alcohol, meth Alcoholic compounds such as alcohol and ethanol, dimethyl malonate, diethyl malonate, Active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, and acetylacetone, Mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, ε-caprolactone lactam compounds such as lactam and δ-valerolactam, diphenylaniline, aniline, Amine compounds such as ethyleneimine, acetanilide, acetic acid amide compounds, Formaldehyde, acetaldoxime, acetoneoxime, methyl ethyl ketone oxime oxime compounds such as cyclohexanone oxime and cyclohexanone oxime. Two or more types may be used in combination.

[0079] The isocyanate compound may be used alone or in the form of a mixture or bond with various polymers. It may be used as a compound. It is said that it improves the dispersibility and crosslinking property of isocyanate compounds. In this sense, it is preferable to use a mixture or combination of polyester resin and urethane resin. I wish.

[0080] Carbodiimide compounds are compounds that have a carbodiimide structure, and It is a compound that has one or more carbodiimide structures in it, but for better adhesion etc. Polycarbodiimide compounds having two or more of these groups in the molecule are more preferred.

[0081] Carbodiimide compounds can be synthesized by conventionally known techniques, and generally, The diisocyanate compound is not particularly limited. It is not intended to be used as a solvent, and either aromatic or aliphatic solvents can be used. Rylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate Phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate cyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclo hexyl diisocyanate, dicyclohexylmethane diisocyanate, etc. .

[0082] Furthermore, in order to improve the water solubility and water dispersibility of polycarbodiimide compounds, surfactants are used. Adding an agent, polyalkylene oxide, dialkylamino alcohol quaternary amine Hydrophilic monomers such as ammonium salts and hydroxyalkyl sulfonates can also be added. good.

[0083] These crosslinking agents are reacted during the drying process and film-forming process to improve the properties of the primer layer. The finished primer layer contains unreacted crosslinkers. It can be assumed that the reactants, the reacted compounds, or a mixture thereof are present.

[0084] Improved coating appearance of primer layer, hard coat layer is laminated on the primer coated surface Various polymers are used in combination to reduce interference unevenness when the material is coated, and to improve transparency and adhesion. It is preferable that

[0085] Specific examples of the polymer include polyester resin, acrylic resin, urethane resin, poly Polyvinyl (polyvinyl alcohol, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, etc.) , polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose Among these, the improvement of adhesion with the hard coat layer, From the viewpoint of improving the coating appearance, polyester resin, acrylic resin, and urethane resin are used. It is preferable that:

[0086] Polyester resins are mainly composed of polycarboxylic acids such as those shown below. and polyvalent hydroxy compounds. , terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldibenzoate carboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6-Naphthalenedicarboxylic acid, 2,7-Naphthalenedicarboxylic acid, 1,4-Cyclohexyl Xanedicarboxylic acid, 2-potassium sulfoterephthalate, 5-sodium sulfoisophthalate Acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid Trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride Monopotassium salts of benzoic acid, p-hydroxybenzoic acid, trimellitic acid and their esters As the polyhydroxy compound, ethylene glycol derivatives can be used. 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propane Hexanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5 -Pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-Xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene Glycol, triethylene glycol, polyethylene glycol, polypropylene glycol -al, polytetramethylene glycol, polytetramethylene oxide glycol, dimethyl Trimethylolpropionic acid, glycerin, trimethylolpropane, dimethylolethyl sulfonate sodium phosphate, potassium dimethylolpropionate, etc. One or more of the compounds are suitably selected from each of the above, and polyester is obtained by a conventional polycondensation reaction. A resin can be synthesized.

[0087] Acrylic resin is a type of polymer that contains carbon, such as acrylic and methacrylic monomers. These are polymers made from polymerizable monomers with -carbon double bonds. In addition, the polymer may be a copolymer of the polymer with other polymers (e.g., poly Also included are copolymers with ethylenediamine esters, polyurethanes, etc. For example, block copolymers, graphene copolymers, etc. Alternatively, a carbon copolymer may be used in a polyester solution or dispersion. - A polymer obtained by polymerizing a polymerizable monomer having a carbon double bond (in some cases, a polymer Similarly, carbon-carbon mixtures in polyurethane solutions and polyurethane dispersions are also included. A polymer (or sometimes a polymer) obtained by polymerizing a polymerizable monomer having a single double bond. Similarly, carbon-carbon dimers in other polymer solutions or dispersions are also included. Polymers (and sometimes polymer mixtures) obtained by polymerizing polymerizable monomers with bonds ) is also included. In order to further improve adhesion, it contains hydroxyl groups and amino groups. It is also possible to do this.

[0088] The polymerizable monomer having a carbon-carbon double bond is not particularly limited, but particularly, Typical compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Various carboxyl group-containing monomers such as fumaric acid, maleic acid, citraconic acid, and and their salts; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutyl hydroxy Various hydroxyl group-containing monomers such as monobutyl hydroxy itaconate, monobutyl hydroxy itaconate Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, (Meth)acrylic acid esters; (meth)acrylamide, diacetone acrylamide, N - various nitrogen-containing compounds such as methylol acrylamide or (meth)acrylonitrile, etc. Compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene Various styrene derivatives, various vinyl esters such as vinyl propionate; γ-methacrylate Various silicon-containing silanes such as hydroxypropyltrimethoxysilane, vinyltrimethoxysilane, etc. Polymerizable monomers; phosphorus-containing vinyl monomers; vinyl chloride, vinylidene chloride, and other vinyl halides; and various conjugated dienes such as butadiene.

[0089] Urethane resin is a polymer compound that has urethane bonds in its molecules. Polyurethane resin is made by the reaction of polyol and isocyanate. , polycarbonate polyols, polyester polyols, polyether polyols Polyolefin polyols and acrylic polyols are examples of such compounds. They may be used alone or in combination of two or more.

[0090] In addition, in forming the primer layer, the above-mentioned Particles other than metal oxides may be used in combination. The average particle size is preferably selected from the viewpoint of film transparency. The range is preferably 1.0 μm or less, more preferably 0.5 μm or less, and particularly preferably The particle size is in the range of 0.2 μm or less. Specific examples of particles include silica, alumina, kaolin, and carbon. Examples of suitable inorganic particles include calcium carbonate and organic particles.

[0091] Furthermore, the primer layer may contain antifoaming agents, coating improvers, thickeners, organic lubricants, etc., as needed. , antistatic agents, ultraviolet absorbers, antioxidants, foaming agents, dyes, pigments, etc. may also be contained.

[0092] Metal oxide as a percentage of the total non-volatile components in the primer liquid that forms the primer layer The content is usually in the range of 3 to 70% by weight, preferably in the range of 5 to 50% by weight, more preferably in the range of 10 to 150% by weight. Preferably, the range is 5 to 40% by weight, and particularly preferably, the range is 8 to 30% by weight. When the amount of metal oxide is 3% by weight or less, the refractive index of the primer layer is sufficiently high. If the amount exceeds 70% by weight, interference unevenness may not be reduced. In this case, the transparency of the primer layer may be deteriorated.

[0093] The ratio of two or more types to the total non-volatile components in the primer liquid that forms the primer layer is The crosslinking agent is usually in the range of 2 to 80% by weight, more preferably 4 to 60% by weight. The range is more preferably 10 to 40% by weight. If there is a concern that the adhesion to the hard coat layer may decrease, or if the coating appearance may be poor, When the hard coat layer is formed, the visibility may be poor due to interference unevenness after the hard coat layer is formed.

[0094] When an oxazoline compound is used as a crosslinking agent, the primer that forms the primer layer The content of oxazoline compounds in the liquid is usually between 1 and 5% of the total non-volatile components. 0% by weight or less, more preferably 1 to 30% by weight or less, and even more preferably 3 to 2 If the content is 1% by weight or less, the adhesion to the hard coat layer decreases. If the content exceeds 50% by weight, the refractive index of the coating layer will decrease, resulting in the risk of halo. Visibility may be poor due to interference unevenness after the hard coat layer is formed.

[0095] When an epoxy compound is used as a crosslinking agent, the primer liquid that forms the primer layer The content of epoxy compounds is usually 1 to 50% by weight as a percentage of the total non-volatile components. The range is preferably 3 to 30% by weight, more preferably 5 to 20% by weight. If the content is outside these ranges, the adhesion to the hard coat layer may be poor. There may be concerns that the coating may be weakened or the appearance of the coating may deteriorate.

[0096] The compound having a condensed polycyclic aromatic group that can be used in the primer layer is The proportion of polycyclic aromatic compounds is preferably in the range of 5 to 80% by weight, more preferably The content of the primer layer is preferably in the range of 10 to 60% by weight. The content of compounds having condensed polycyclic aromatic rings as a percentage of the total non-volatile components in the liquid is: Preferably, the range is 80% by weight or less, more preferably, the range is 5% by weight or more and 70% by weight or less, and The preferred range is 10 to 50% by weight. It becomes easier to adjust the refractive index of the coating layer, and it becomes easier to reduce interference unevenness after forming the hard coat layer. The proportion of the condensed polycyclic aromatic compound can be adjusted by, for example, dissolving the primer layer in a suitable solvent or warm water. The compound is dissolved and extracted, separated by chromatography, and its structure is analyzed by NMR and IR. By analyzing using GC-MS (gas chromatography mass spectrometry) and optical analysis, You can ask for it.

[0097] The components in the primer layer can be analyzed using, for example, TOF-SIMS, ESCA, fluorescent X-rays, etc. This can be done by analysis.

[0098] When applying a primer layer by in-line coating, the above-mentioned series of compounds are used. As an aqueous solution or dispersion, adjust the solids concentration to approximately 0.1 to 50% by weight. It is preferable to produce a laminated film in such a manner that the primer solution is applied to the film. In addition, a small amount of organic solvent is added to the primer liquid to improve its dispersibility in water and film-forming properties. The organic solvent may contain only one kind, or two or more kinds may be used as appropriate. That's fine.

[0099] The thickness of the primer layer is usually 0.04 to 0.20 μm, preferably 0.05 or more. The thickness is preferably 0.16 μm or less, and more preferably 0.07 to 0.13 μm. If the thickness is outside the above range, the visibility may be deteriorated due to interference unevenness after laminating the hard coat layer. This may be the case.

[0100] The method of forming a primer layer is reverse gravure coating, direct gravure coating, Conventional coating methods such as roll coating, die coating, bar coating, curtain coating, and spray coating are also available. A coating method can be used.

[0101] The drying and curing conditions for forming the primer layer are not particularly limited. For example, when a primer layer is provided by off-line coating, it is usually 80 or more. At 200°C or less for 3 to 40 seconds, preferably at 100 to 180°C for 3 to 40 seconds. It is advisable to carry out heat treatment as follows.

[0102] On the other hand, when applying a primer layer by in-line coating, the temperature is usually between 70 and 27°C. It is recommended to perform heat treatment at 0°C or below for 3 to 200 seconds.

[0103] In addition, whether it is offline coating or in-line coating, If necessary, heat treatment and irradiation with active energy rays such as ultraviolet rays may be used in combination. The surface may be previously subjected to a surface treatment such as a corona treatment or a plasma treatment.

[0104] <Surface functional layer> A surface functional layer can be provided on the hard coat layer to provide various additional functions. Surface functional layers include refractive index adjustment layers (anti-reflection layers, low-reflection layers, etc.), anti-fouling layers, etc. , an antistatic layer, an infrared absorbing layer, an ultraviolet absorbing layer, a color correction layer, and the like.

[0105] As a material used when forming a refractive index adjustment layer as a surface functional layer, In this case, conventionally known materials can be used, for example, acrylic resin or urethane. This is possible because resins generally have a low refractive index. In particular, fluorine atoms are incorporated into the resin. embedded compounds, such as fluororesins and compounds containing fluororesins in the main skeleton, Examples of inorganic materials include compounds containing perfluoroalkyl groups in the chain. Hollow silica particles and inorganic compounds containing fluorine atoms such as magnesium fluoride and calcium fluoride and hollow particles and nanoporous particles thereof.

[0106] Examples of the refractive index adjusting layer include a high refractive index layer, a low refractive index layer, and a laminate thereof. can be. As a material used when forming a refractive index adjustment layer as a surface functional layer, For example, benzene structure, bisphenol A structure, melamine structure, fluorene structure, Aromatic compounds such as benzene structures, and aromatic compounds that are considered to have high refractive indexes Phthalene, anthracene, phenanthrene, naphthacene, benz[a]anthracene, Benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, perylene structures condensed polycyclic aromatic compounds, zirconium oxide, titanium oxide, zinc oxide, tin oxide, oxide Antimony, yttrium oxide, indium oxide, cerium oxide, ATO (antimony Metal oxides such as ITO (indium tin oxide), titanium chelate, Metal-containing compounds such as metal chelate compounds, including zirconium chelate, sulfur-containing compounds compounds, compounds containing halogen elements, etc.

[0107] The anti-fouling layer improves the anti-fouling performance by imparting water and oil repellency to the hard coat layer. The materials used for the antifouling layer include silicone compounds, fluorinated Compounds containing a long chain alkyl group, and other known compounds can be used. However, for stronger antifouling properties, silicone compounds and fluorine compounds are preferred. From the viewpoint of preventing the antifouling layer from contaminating the surface it comes into contact with, it is recommended to use a material containing fluorine compounds or long-chain alkyl groups. Organic compounds are preferred.

[0108] Silicone compounds are compounds that have a silicone structure in the molecule, such as For example, alkyl silicones such as dimethyl silicone and diethyl silicone, and phenyl silicones Examples of silicones include phenyl silicone and methylphenyl silicone having a phenyl group. The amine may have various functional groups, such as an ether group, a hydroxyl group, Amino group, epoxy group, carboxylic acid group, halogen group such as fluorine, perfluoroalkyl group Examples of the functional group include hydrocarbon groups such as various alkyl groups and various aromatic groups. Silicones with hydroxyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms. The addition type (addition reaction between vinyl groups and hydrogen silane) is also common. It is also possible to use silicones of the type (where double bonds such as acryloyl groups are used). A method of introducing a bond and reacting at the double bond is also preferred.

[0109] In addition, silicone compounds include acrylic graft silicone and silicone graft silicone. Modified silicones such as acrylic, amino-modified silicone, and perfluoroalkyl-modified silicone It is also possible to use hardening type silicone resin, taking into consideration heat resistance and contamination. It is preferable to use the curing agent, and the curing type may be a condensation type, an addition type, or an active energy ray curing type. Any curing reaction type, such as a curing reaction type, can be used.

[0110] A fluorine compound is a compound that contains fluorine atoms. As the compound, an organic fluorine compound is preferably used, for example, a perfluoroalkyl group. fluorine-containing compounds, polymers of olefin compounds containing fluorine atoms, aromatic compounds such as fluorobenzene Aromatic fluorine compounds are also suitable. From the viewpoint of releasability, compounds having perfluoroalkyl groups are preferred. Further, the fluorine compound is preferably a long-chain alkyl compound as described below. Compounds containing

[0111] The compound having a perfluoroalkyl group is, for example, a perfluoroalkyl(meth) Acrylate, Perfluoroalkylmethyl (meth)acrylate, 2-Perfluoroa Alkylethyl (meth)acrylate, 3-perfluoroalkylpropyl (meth)acrylate acrylate, 3-perfluoroalkyl-1-methylpropyl(meth)acrylate, 3-perfluoroalkyl-1-methylpropyl(meth)acrylate Perfluoroalkyl groups such as fluoroalkyl-2-propenyl (meth)acrylate Contains (meth)acrylate and its polymer, perfluoroalkylmethyl vinyl ether, 2-Perfluoroalkylethyl vinyl ether, 3-perfluoropropyl vinyl ether ester, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoro perfluoroalkyl-containing vinyl ethers such as 2-(2-methyl-2-propenyl vinyl ether) Considering heat resistance and stain resistance, polymers are preferred. The polymer may be a polymer of a single compound or a polymer of multiple compounds. Therefore, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. The polymer may be a polymer with a compound containing such a long-chain alkyl compound.

[0112] The long-chain alkyl group-containing compound generally has 6 or more carbon atoms, preferably 8 or more carbon atoms, and more preferably Or a compound having 12 or more straight-chain or branched alkyl groups. Examples of the alkyl group include a hexyl group, an octyl group, a decyl group, a lauryl group, and an octadecyl group. Examples of compounds having an alkyl group include various long-chain alkyl groups. alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds Compounds, quaternary ammonium salts containing long-chain alkyl groups, etc. Considering heat resistance and contamination Therefore, a polymer compound is preferable. Therefore, it is more preferable that the polymer compound has a long-chain alkyl group on the side chain.

[0113] A polymer compound having a long-chain alkyl group on the side chain is a polymer having a reactive group and the reactive group is a polymer having a long-chain alkyl group on the side chain. The above reaction can be carried out by reacting a compound having a reactive group with a compound having a reactive alkyl group. Examples of the functional group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group. Examples of compounds having these reactive groups include polyvinyl alcohol, polyethylene Polyethyleneimine, polyethyleneamine, reactive group-containing polyester resin, reactive group-containing poly(meth)amine Among these, polypropylene is the most suitable in terms of stain resistance and ease of handling. Preferably it is vinyl alcohol.

[0114] The compound having an alkyl group capable of reacting with the reactive group is, for example, hexylisocyanate. Anate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, Isocyanates containing long-chain alkyl groups such as octadecyl isocyanate and behenyl isocyanate nate, hexyl chloride, octyl chloride, decyl chloride, lauryl chloride Acid chlorides containing long chain alkyl groups such as octadecyl chloride, behenyl chloride, etc. amines containing long-chain alkyl groups, and alcohols containing long-chain alkyl groups. Among these, isocyanates containing long-chain alkyl groups are preferred in consideration of releasability and ease of handling. Of these, octadecyl isocyanate is particularly preferred.

[0115] In addition, polymer compounds having long-chain alkyl groups in the side chains are also known as long-chain alkyl (meth)acrylates. Polymers of acrylates and copolymers of long-chain alkyl (meth)acrylates with other vinyl group-containing monomers The long-chain alkyl (meth)acrylate can also be obtained by, for example, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, Lauryl (meth)acrylate, Octadecyl (meth)acrylate, Behenyl (meth)acrylate acrylates and the like.

[0116] The content of the antifouling material in the surface functional layer for realizing the above-mentioned antifouling performance depends on the material used. It depends on the amount of silicon compound and fluorine compound, but it is usually 0 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more The upper limit may be 100% by mass. When the compound is used, it is usually at least 0.1% by mass, preferably at least 1% by mass, and more preferably The range is 3% by mass or more, and the upper limit may be 100% by mass. By using it in this manner, it is possible to obtain effective antifouling properties.

[0117] The antistatic agent used when forming the antistatic layer as the surface functional layer is the above-mentioned pro Various antistatic agents can be used in the primer layer. A double bond such as an acryloyl group is introduced into a compound having an ammonium group, and the double bond is reacted. A method in which

[0118] Metal oxides are used in particle form because there is a concern that their adhesion may decrease depending on the type of use. It is preferable to use an average particle size of 100 from the viewpoint of coating appearance. The thickness is preferably in the range of 50 nm or less, more preferably 50 nm or less, and even more preferably 25 nm or less.

[0119] The thickness of the surface functional layer is 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably Preferably 0.01 to 1 μm, more preferably 0.02 to 0.5 μm, and particularly preferably 0. By using it in the above range, the functionality of the surface functional layer can be developed. This makes it possible to achieve both the functionality of the hard coat layer and the current performance.

[0120] Regarding the formation of the surface functional layer, the above-mentioned series of compounds are dissolved or dispersed in a solvent, and then solidified. The liquid is adjusted to a concentration of approximately 0.1 to 80% by mass and coated onto the base film. It is particularly preferable to produce the laminate by in-line coating. In this case, it is more preferable that the composition is an aqueous solution or dispersion. For the purpose of improvement, a small amount of organic solvent may be contained in the liquid. Only one type may be used, or two or more types may be used as appropriate.

[0121] Examples of methods for forming the surface functional layer include gravure coating and reverse roll coating. , die coating, air doctor coating, blade coating, rod coating, bar coating, car Tencoat, knife coat, transfer roll coat, squeeze coat, impregnation coat, Conventional coating methods such as kiss coating, spray coating, calendar coating, and extrusion coating The method can be used.

[0122] <Back functional layer> The back functional layer is provided on the surface opposite to the hard coat layer of the substrate layer to impart various functions. The rear functional layer may include an adhesive layer, an antistatic layer, a refractive index adjusting layer, an antiblocking layer, and the like. Examples of such a layer include a coating layer. The adhesive layer is provided to bond the laminate to various adherends. The outermost surface of the substrate, especially the outermost surface opposite the hard coat layer, is subject to peeling electrification and frictional bands. This is provided to prevent the adhesion of dust and other foreign matter due to static electricity and the resulting defects. The layering is provided, for example, to improve the total light transmittance of the laminate. The back functional layer is formed by a known method. It can be formed by the method.

[0123] There are no particular restrictions on the drying and curing conditions when forming the surface functional layer or back functional layer on the substrate. Although it is not specified, in the case of coating method, the The drying temperature for the solvent such as water is usually 50 to 150°C, preferably 80 to 130°C. The drying time is preferably in the range of 90 to 120°C. The temperature is in the range of 3 to 200 seconds, preferably 5 to 120 seconds. In order to improve the strength of the functional layer, when it is performed in the film manufacturing process, it is usually 150 or more 270°C or less, preferably 170 to 230°C, more preferably 180 to 210°C The heat treatment process is carried out at a temperature of 100°C or less. The range is 3 to 200 seconds, preferably 5 to 120 seconds. [Example]

[0124] The present invention will be described in more detail below with reference to examples. The following examples are not intended to be limiting. The measurement and evaluation methods used in the present invention are as follows.

[0125] (1) Measurement method of average particle size A TEM (Hitachi High-Technologies Corporation H-7650, accelerating voltage 100 V) was used. The primer layer was observed using a microscope, and the average particle size of 10 randomly selected particles was taken as the average particle size. did.

[0126] (2) Evaluation method for coating appearance The appearance of the cured coating film prepared according to the example was visually inspected, and if there was no abnormality, it was rated A; If there were bumps on the film, it was rated B, and if there were many bumps on the coating, it was rated C.

[0127] (3) Method for measuring weight-average molecular weight and number-average molecular weight Equipment: Tosoh Corporation "HLC-8120GPC" Column: TSKgel SuperHZM-M*HZM-M*HZ manufactured by Tosoh Corporation 2000", Detector: Differential refractive index detector (RI detector / built-in), Solvent: tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: monodisperse polystyrene, Calibration method: Polystyrene equivalent.

[0128] (4) Evaluation method for interference unevenness The cured film prepared according to the example was visually inspected for interference unevenness under a three-wavelength fluorescent lamp. A indicates that no interference unevenness is visible, B indicates that thin and sparse interference unevenness is visible, and Those in which linear interference unevenness was confirmed were rated C, and those in which clear interference unevenness was confirmed were rated D.

[0129] (5) Transparency (haze) measurement method The cured film for measuring transparency (haze) was prepared according to the example. In accordance with the above, the haze meter (Nippon Denshoku Industries Co., Ltd. "NDH8000") was used to measure the substrate alone. (The present invention does not include a cured film layer formed by curing the active energy ray-curable resin composition.) After performing standard calibration using the substrate, the substrate having the cured film obtained according to the example was measured to determine the coating film. The haze was measured.

[0130] (6) Surface resistance measurement method The cured film for measuring the surface resistance was prepared according to the example. The substrate having the cured film obtained according to the example was conditioned for 30 minutes, and then subjected to a suction test at Mitsubishi Chemical Analytical Co., Ltd. Using a high resistivity meter Hiresta UP MCP-HP450 / URS probe manufactured by CK, The cured film side was measured with an applied voltage of 500 V, and the value 10 seconds after the start of measurement was taken as the surface resistance value. If the surface resistance value shows OVER, it means that the surface resistance value is too high to measure.

[0131] (7) Pencil hardness measurement method The cured film for pencil hardness measurement was prepared according to the example. JIS K5600-5-4:1 999 General Test Methods for Paints - Part 5: Mechanical Properties of Coatings - Section 4: Scratch Hardness (Pencil Method) Therefore, the pencil hardness of the cured film was measured.

[0132] (8) Refractive index measurement method The cured film for refractive index measurement was prepared according to the example. R-M2, wavelength: 589 nm) was used, and 1-bromonaphthalene was used as an intermediate solution on the prism surface. After placing a drop of ethanol on the film, place the cured film side of the film on which the cured film has been formed on the surface and measure at a temperature of 25°C. The measurements were taken at the following points. The refractive index of the liquid before hardening was measured using an Atago multi-wavelength Abbe refractometer (DR-M2, wavelength: 589n The compound before curing was dropped onto the prism surface of m) and the measurement was carried out at 25°C.

[0133] The polyesters used in the production examples were prepared as follows. <Method for producing polyester (A)> Dimethyl terephthalate 100 parts by weight, ethylene glycol 60 parts by weight, ethyl acid Phosphate was generated at 30 ppm for polyester, and magnesium acetate was used as a catalyst. Tetrahydrate is produced. 100 ppm of polyester is added to the ester at 260°C under a nitrogen atmosphere. Subsequently, tetrabutyl titanate was added in an amount of 50% based on the amount of the produced polyester. ppm was added, and the temperature was raised to 280°C over 2 hours and 30 minutes, while the absolute pressure was 0.3 kPa. The pressure was reduced to 1000kJ / min, and melt polycondensation was carried out for a further 80 minutes to obtain polyester (A) with an intrinsic viscosity of 0.63. Got it.

[0134] <Method for producing polyester (B)> Dimethyl terephthalate 100 parts by weight, ethylene glycol 60 parts by weight, acetic acid as a catalyst Magnesium tetrahydrate was added to polyester at 900 ppm under a nitrogen atmosphere for 22 minutes. The esterification reaction was carried out at 5°C. Subsequently, orthophosphoric acid was added to the resulting polyester in an amount of 35 00ppm, germanium dioxide was added to the polyester at 70ppm, and the polyester was left for 2 hours. The temperature was raised to 280°C over 30 minutes, and the absolute pressure was reduced to 0.4 kPa. Melt polycondensation was carried out for 5 minutes to obtain a polyester (B) having an intrinsic viscosity of 0.64.

[0135] <Method for producing polyester (C)> In the process for producing polyester (A), silica particles having an average particle size of 2 μm are added before melt polymerization. The polyester (A) was produced in the same manner as in the production of polyester (A), except that 0.3 parts by weight of polyester (A) was added. Obtained Stell (C).

[0136] Examples of compounds constituting the primer solution used in the production examples are as follows: (Compound example) Isocyanate compounds: (P1) 1,000 parts of hexamethylene diisocyanate was stirred at 60°C, and tetramethyl ... 0.1 parts of ethylammonium caprylate was added. After 4 hours, 0.2 parts of phosphoric acid was added. The reaction was stopped by adding 100 ml of ... 100 parts of cyanurate type polyisocyanate composition, methoxypolyisocyanate having a number average molecular weight of 400 Ethylene glycol 42.3 parts, propylene glycol monomethyl ether acetate 2 parts The reaction mixture was kept at 80°C for 7 hours. Methyl butanoyl acetate 35.8 parts, diethyl malonate 32.2 parts, sodium methoxide 0.88 parts of a 28% methanol solution of n-butanol was added and the mixture was maintained for 4 hours. The reaction mixture was kept at 80°C for 2 hours, and then 2-ethylhexyl acid phosphate was added. Block polyisocyanate with active methylene obtained by adding 0.86 parts of phosphate to.

[0137] Oxazoline compounds: (P2) Acrylic polymer EPOCROS containing oxazoline groups and polyalkylene oxide chains (Amount of oxazoline group = 4.5 mmol / g)

[0138] Polyester resin: (P3) Aqueous dispersion of polyester resin (glass transition temperature: 50°C) consisting of the following composition: Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid Acid / / (Diol component) Ethylene glycol / 1,4-butanediol / Diethylene glycol Recall = 50 / 46 / 4 / / 70 / 20 / 10 (mol%)

[0139] Acrylic resin: (P4) Aqueous dispersion of acrylic resin (glass transition temperature: 40°C) consisting of the following composition: Ethyl acrylate / Methyl methacrylate / N-methylolacrylamide / Acrylate Ruic acid = 48 / 45 / 4 / 3 (wt%)

[0140] Polyester resin: (P5) Aqueous dispersion of polyester resin copolymerized with the following composition Monomer composition: (acid component) 2,6-naphthalenedicarboxylic acid / 5-sodium sulfoiso Phthalic acid / / (diol component) ethylene glycol / diethylene glycol = 92 / 8 / / 80 / 20(mol%)

[0141] Metal oxide particles: (P6) Zirconium oxide particles with an average particle size of 15 nm

[0142] [Manufacturing Example 1] The outermost layer is a mixture of polyester (A) and polyester (B) at a ratio of 95% and 5%, respectively. The raw materials for the surface layer are polyester (A), (B), and (C) at 89%, 5%, and The mixed raw material mixed at a ratio of 6% was used as the raw material for the middle layer and fed to two extruders. After melting at 285℃, two types of three layers (surface layer / intermediate layer / The polyester film is produced by co-extrusion with a layer structure of 1:18:1 (surface layer = 1:18:1 discharge amount) and solidifying it by cooling. I got S1.

[0143] [Manufacturing Example 2] The outermost layer is a mixture of polyester (A) and polyester (B) at a ratio of 95% and 5%, respectively. The raw materials for the surface layer are polyester (A), (B), and (C) at 89%, 5%, and The mixed raw material mixed at a ratio of 6% was used as the raw material for the middle layer and fed to two extruders. After melting at 285℃, two types of three layers (surface layer / intermediate layer / The resulting layer structure (surface layer = 1:18:1 extrusion rate) was co-extruded and cooled to solidify, yielding an unstretched sheet. Next, the film was stretched 3.4 times in the machine direction at a film temperature of 85°C using the difference in roll peripheral speed. A primer solution (composition P1 / P2 / P3 / P4 / P5 / P6) was applied to one side of this longitudinally stretched film. = 10 / 10 / 25 / 10 / 30 / 15 mass% (mass% of non-volatile matter) was applied (pla The film is introduced into a tenter, stretched 4.0 times in the transverse direction at 120°C, and heated at 225°C. After the treatment, the surface was relaxed by 2% in the lateral direction, and a primer layer with a film thickness (after drying) of 0.10 μm was applied. A polyester film S5 having a thickness of 100 μm was obtained.

[0144] [Manufacturing Example 3] Three vertical agitation reactors, one horizontal agitation reactor, and a twin-screw extruder with a vacuum vent are connected in this order. Polycarbonate resin was polymerized using a continuous polymerization facility. PC was melted in a raw material preparation tank, and the molar ratio of ISB / CHDM / DPC was 70 The mixture was continuously fed to the first vertical stirred reactor in a ratio of 0.70 / 0.30 / 1.01. In addition, an aqueous solution of calcium acetate monohydrate was used as a polymerization catalyst. The solution was fed to the first vertical stirred reactor so that the amount of the hydroxybenzoate was 1.5 μmol relative to the amount of the hydroxybenzoate. The temperature, pressure and residence time of each reactor are approximately: First vertical reactor: 190°C, 25kPa , 90 minutes, 2nd vertical type: 195℃, 10kPa, 45 minutes, 3rd vertical type: 210℃, 3kPa, 45 minutes, fourth horizontal: 225°C, 0.5 kPa, 90 minutes. The reduced viscosity of the resulting polycarbonate resin is approximately 0.38 to 0.39 dL / g. The fourth horizontal stirred reactor was operated while adjusting the internal pressure of the reactor so as to keep the temperature constant. The polymerization reaction product was extracted from the fourth horizontal stirred reactor at a flow rate of approximately 60 kg / hour, and then dissolved in water. The mixture was then transferred to a twin-screw extruder equipped with a vacuum vent (TEX30α, L / D=42, manufactured by The Japan Steel Works, Ltd.). Supplied. This extruder is equipped with three decompression vents, and the second vent is used to decompress the molten resin. Water was continuously injected at a rate of approximately 2000 mass ppm to carry out so-called water injection devolatilization. Before the third vent, heat stabilizers such as Irganox1010, AS2112, and E-275 were added. The mixture was continuously fed in ratios of 0.1 part by mass, 0.05 part by mass, and 0.3 part by mass and melt-kneaded. The molten resin that has passed through the discharge machine is filtered out for foreign matter through a candle-type filter with 10 μm openings. The mixture is discharged from the die in the form of strands, solidified by water cooling, and pelletized with a rotary cutter. A copolymer polycarbonate resin having a glass transition temperature of 120°C was obtained. Copolymer polycarbonate resin was fed into the extruder and melted at 240°C. The mixture was cooled and solidified on a cooling roll set at 120°C to form a polycarbonate sheet with a thickness of 50 μm. The resulting film was S4.

[0145] [Synthesis Example 1 Antistatic Agent A1] An antistatic agent (A1), which is a copolymer having an ammonium salt group, was prepared by the following method. A reactor equipped with a stirrer, a reflux condenser, and a thermometer was charged with methacryloyloxyethyl methyl acrylate. Trimethylammonium Chloride 180g, Lauryl Methacrylate and Tridecyl Methacrylate 75 g of a 45:55 (mass %) mixture of N,N-dimethylaminoethyl methacrylate Acrylate 45g, Methyl Ethyl Ketone (MEK) 200g, Isopropyl Alcohol ( 500 g of IPA was charged, and after stirring was started, the system was replaced with nitrogen and the temperature was raised to 55°C. After adding 6 g of 2,2'-azobis(2,4-dimethylvaleronitrile), the system was heated to 6 The temperature was raised to 5°C and stirred for 3 hours, after which 2,2'-azobis(2,4-dimethylvalerate) was added. 6 g of benzotriazole (isothiazolinone) was added and stirred at 65°C for 3 hours. The temperature in the system was raised to 80°C and stirred for 2 hours. After stirring, the mixture was cooled to room temperature to obtain a polymer solution. The weight average molecular weight of the polymer was 45.20 0 and the number average molecular weight was 26,300.

[0146] [Synthesis Example 2 Antistatic Agent A2] After thoroughly replacing the air in the flask equipped with a stirring blade, a dropping funnel, and a gas inlet with dry nitrogen, 32g of n-butyl alcohol and 1g of metallic sodium were charged and stirred to form metallic sodium Next, the flask was immersed in an oil bath at 40°C, and ε-caproate was dissolved in the flask while stirring. 500 g of lactone was added dropwise from the dropping funnel. After 1 hour, stirring was stopped and the contents of the flask were The product was taken out and dissolved in 5 L of chloroform. The resulting solution was poured into 5 L of deionized water. This washing was repeated once more, and the chloroform layer was separated. The solvent was distilled off from the solution under reduced pressure to obtain a colorless, transparent polyester alcohol. The hydroxyl value of the steric alcohol was 56.1 mg-KOH / g.

[0147] Subsequently, the polyester synthesized above was added to a reactor equipped with a stirring blade and a reflux condenser. Alcohol 102.3g, m-isopropenyl-α,α′-dimethylbenzyl isocyanate 20.7 g of dibutyltin dioctoate and 0.05 g of dibutyltin dioctoate were added and heated to 80°C. The reaction was carried out for 6 hours. The infrared spectrum and 1H-NMR measurement results of the product showed that the product was a poly It was confirmed that an ester macromonomer was obtained.

[0148] In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, the above synthesized polyester Thermomacromomer 72.7g, methacryloyloxyethyltrimethylammonium chloride Bromide 121.5g, Cyclohexyl methacrylate 48.8g, Azobisisobutyro 1.2g nitrile, 400g isopropyl alcohol, and 170g methyl ethyl ketone The reaction mixture was then polymerized at 70°C for 8 hours under a nitrogen stream. The resulting product was precipitated and then dried. The number average molecular weight was 28,000 and the yield was 94%.

[0149] <Base material> Substrate (S1): Polyester film obtained in Production Example 1 Refractive index: 1.65 Substrate (S2): Zeon Corporation's "Zeonor Film ZF16" Refractive index: 1.53 Cycloolefin Film Substrate (S3): DingZing polyurethane film, refractive index: 1.50 Substrate (S4): Polycarbonate film obtained in Production Example 3 Refractive index: 1.50 Substrate (S5): Polyester film laminated with the primer layer obtained in Production Example 2 Refractive index :1.65

[0150] <Curable composition> The materials shown below were mixed in the amounts (parts by mass, calculated as non-volatile content) shown in Table 1. Pyrene glycol monomethyl ether (hereinafter referred to as PGM) and methyl isobutyl ketone (hereinafter referred to as A mixed solvent of PGM and MIBK (PGM:MIBK (mass ratio) 5:5) was used to obtain a solids concentration of 50%. % by volume, and the mixture was stirred until uniform. A composition was obtained. Antistatic agent (A1): Antistatic agent A1 prepared in Synthesis Example 1 Antistatic agent (A2): Antistatic agent A2 prepared in Synthesis Example 2 (Meth)acrylate (B1): Bisphenoxyethanol fluorene diacrylate (Refractive index: 1.62) (Meth)acrylate (B2): Ethoxylated o-phenylphenol acrylate ( Refractive index: 1.58) (Meth)acrylate (B3): 2-naphthyl methacrylate (refractive index: 1.60) (Meth)acrylate (B4): 3-phenoxybenzyl acrylate (refractive index: 1. 57) (Meth)acrylate (B5) modified bisphenol fluorene diacrylate (refractive index :1.53) (Meth)acrylate (C1): Pentaerythritol triacrylate (refractive index: 1 .49) (Meth)acrylate (C2): Dipentaerythritol pentaacrylate is the main component Acrylate compound (refractive index: 1.49) (Meth)acrylate (C3): Dipentaerythritol hexaacrylate (refractive index :1.49) (Meth)acrylate (C4): 4,4'-methylenebis(cyclohexylisocyanate) hexafunctional urethane acrylate obtained by reacting acrylate with pentaerythritol triacrylate Route Photopolymerization initiator (D): 1-hydroxycyclohexyl phenyl ketone

[0151] [Example 1] Component (A) was 4 parts by mass of the above-mentioned antistatic agent (A1), and component (B) was the above-mentioned (Meta ) acrylate (B1) 50 parts by mass, and the above-mentioned (meth)acrylate (C 1) 46 parts by mass of the component (D) and 5 parts by mass of the photopolymerization initiator (D) described above were mixed, and then the above The composition was adjusted to a solid content concentration of 50% by mass with a mixed solvent and applied to a polyester film (substrate S1 ) with a bar coater, and then place in a dryer at approximately 80°C for 1 minute. After drying, A high-pressure mercury lamp with a cumulative light output of 300 mJ / cm 2 , peak intensity 120mW / cm 2 The polyester film was cured by irradiating it with ultraviolet light under the conditions of I got the film.

[0152] [Examples 2 to 22] The same procedure as in Example 1 was carried out except that the blending and composition shown in the composition column of Table 1 were used. A radiation-curable resin composition was prepared and evaluated, and the results are shown in Tables 1 and 2.

[0153] [Examples 23 to 28] In Example 1, the resin raw material of the substrate was changed from polyester (substrate S1) to cycloolefin (Base material S2), polyurethane (Base material S3), polycarbonate (Base material S4), primer The fabrication was carried out in the same manner as in Example 1, except that the polyester substrate (substrate S5) was used instead. The results are shown in Table 2.

[0154] [Comparative Example 1] In Example 1, the antistatic agent (A1) was replaced with (meth)acrylate (C1). Other than that, a film was obtained by manufacturing in the same manner as in Example 1. The properties of the obtained film are shown in Table 2. and did not exhibit antistatic properties.

[0155] Comparative Example 2 In Example 1, (meth)acrylate (B1) was replaced with (meth)acrylate (C3). The film was produced in the same manner as in Example 1 except for the above-mentioned substitution. As shown in Fig. 1, the refractive index of the cured film was low and interference unevenness was noticeable.

[0156] [Table 1]

[0157] [Table 2]

[0158] As can be seen from Tables 1 and 2, Examples 1 to 28 use acrylic monomers that exhibit a high refractive index. By using this, the surface resistance is excellent, and the coating has good visibility with no noticeable interference. The film could be obtained. On the other hand, Comparative Example 1, which does not contain an antistatic agent, does not exhibit antistatic properties. In Comparative Example 2, interference unevenness was clearly observed. From the above results, it can be seen that the use of the curable composition of the present invention provides a high refractive index and antistatic properties. It is possible to provide a high refractive index curable resin composition that satisfies the requirements for optical films while achieving both high refractive index and high optical properties. This is what happened.

Claims

1. A coating agent to be laminated on a substrate having a refractive index of 1.45 or more and 1.75 or less, A compound (A) having an ammonium salt group, a (meth)acryloyl group and at least one aromatic A curable composition comprising a compound (B) having a ring structure.

2. a compound (C) having a (meth)acryloyl group, which is different from the compound (B); The curable composition of claim 1.

3. The content of the compound (A) is the ratio of the solid content of the compound (A), the compound (B), and the compound (C). The curable composition according to claim 2, wherein the content of the hydroxybenzoates is 0.5% by mass or more and 20% by mass or less based on the total amount. 。

4. The content of the compound (B) is the ratio of the solid content of the compound (A), the compound (B), and the compound (C) to the solid content of the compound (B). The curable composition according to claim 2 , wherein the content of the curable composition is 10% by mass or more and 80% by mass or less based on the total amount.

5. 3. The compound (C) according to claim 2, wherein the compound (C) has 3 to 10 (meth)acryloyl groups. The curable composition according to claim 1.

6. The compound (C) is selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and a sulfonic acid group. The curable composition according to claim 2, comprising one or more polar groups selected from the group consisting of:

7. The refractive index of a cured film obtained by curing the curable composition is in the range of 1.52 to 1.

80. A cured product obtained by curing the curable composition according to claim 1.

8. The surface resistance of the cured film is 5.0 x 10 １３ The curable composition according to claim 1, wherein the hardness is Ω or less. The hardened product.

9. 2. The method according to claim 1, wherein the refractive index of the liquid of the compound (B) is 1.50 or more and 1.80 or less. A cured product obtained by curing the above curable composition.

10. The curable composition of claim 1 , wherein the substrate is a film.

11. The substrate is any one of polyester, silicon olefin, polyurethane, and polycarbonate. The curable composition of claim 1, which is any one of:

12. A coating composition according to claim 1, comprising a substrate and a cured coating film provided on the surface of the substrate. A laminate comprising a cured product obtained by curing the composition described above.

13. The laminate according to claim 12, wherein a primer is laminated between the substrate and the cured coating film. 。

14. The laminate according to claim 13, wherein the primer contains a polymer.

15. A compound (A) having an ammonium salt group is provided on a substrate having a refractive index of 1.45 or more and 1.75 or less. ), a compound (B) having a (meth)acryloyl group and at least one aromatic ring structure, A laminate having a cured film comprising the above-mentioned compound.

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