Antistatic curable composition, cured product, laminate, polarizer protective film, and polarizer plate

Abstract

To provide a curable composition that can form a high refractive index hard coat layer having excellent antistatic properties and transparency, a polarizer protection film composed of a laminate having a hard coat layer comprising a cured product of the curable composition on a base film surface, and a polarizing plate formed by bonding the polarizer protection film to a polarizer.SOLUTION: A curable composition comprises two or more components (A) illustrated below, and a component (B) illustrated below. The components (A): compounds each comprising at least an aromatic ring structure and a methacryloyl group, and having a refractive index of 1.50-1.70. The component (B): a methacrylic polymer comprising an ionic group in each molecule.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition suitable as a high refractive index hard coat material for an antireflection film.

Background Art

[0002] Generally, a display is used in an environment where external light such as sunlight enters, regardless of whether it is used indoors or outdoors. This incident light such as external light is specularly reflected on the display surface or the like, and the reflected image thereby mixes with the display image, deteriorating the screen display quality. Therefore, it is required to impart an antireflection function to the display surface or the like. In addition, the display surface is required to have antistatic properties in order to prevent contamination due to adhesion of dust or the like and to prevent the influence on the inside of the display due to the electrostatic charge on the display surface.

[0003] Generally, the antireflection function is obtained by forming an antireflection layer having a multilayer structure with an alternating laminated structure of a high refractive index layer and a low refractive index layer using a metal oxide such as ITO, carbon, a thiophene-based conductive polymer, or the like on a transparent substrate. In addition, a material using a metal oxide, carbon, a thiophene-based conductive polymer, or the like can also impart an antistatic function, and a high refractive index layer having antistatic properties can be formed. As an example of such a thing, for example, Patent Document 1 describes using conductive particles in a high refractive index layer. However, this technique has a problem that the transparency is impaired by using conductive particles.

[0004] Regarding the coating material for forming the high refractive index layer, in recent years, inorganic high refractive index coatings such as ITO As an alternative to the acetate material, a high refractive index acrylic compound having an aromatic ring structure is used as the main component. An organic coating material has been proposed. This acrylic coating material has a high refractive index and is transparent. It has excellent properties and, being acrylic-based, also forms a high refractive index hard coat layer with high surface hardness. This can be done, but because acrylic materials have high insulating properties, this acrylic high refractive index The coating layer has the disadvantage of being prone to static electricity.

[0005] On the other hand, Patent Document 2 describes an acrylic material that can impart antistatic properties as quaternary ammonia Acrylic polymers containing a base have been proposed, and if this acrylic polymer is suitable, It has been disclosed that brightness and antistatic properties can be obtained. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2010-217873 [Patent Document 2] Japanese Patent Publication No. 2015-069058 [Patent Document 3] Japanese Patent Publication No. 2016-088943 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, the curable composition described in Patent Document 2 contains a quaternary ammonium compound effective in imparting antistatic properties. It contains acrylic monomers with a mononium base, but the aroma is generally known This technology is intended to be applied to coating materials primarily composed of high-refractive-index acrylic compounds with a ring structure. Therefore, achieving both antistatic properties and a high refractive index is difficult. Furthermore, the acrylic polymer having a quaternary ammonium base described in Patent Document 3 is The Sp value of an acrylic polymer having a quaternary ammonium base is determined by the aromatic ring structure and high fluoropolymer. Unless adjusted each time to match the refractive index of the acrylic compound, it will contain a quaternary ammonium base. Because acrylic polymers and high-refractive-index acrylic compounds having an aromatic ring structure have poor compatibility. This presented a significant problem: a major loss of transparency.

[0008] Therefore, the present invention forms a high refractive index hard coat layer that is excellent in antistatic properties and transparency. A curable composition that can be cured, and a hard coat layer made of the cured product of this curable composition on a substrate. A polarizer protective film having a laminate on the surface of a film, and this polarizer protective film The objective is to provide a polarizing plate formed by bonding a polarizer to a polarizer. [Means for solving the problem]

[0009] The aforementioned problems are solved by the present invention. That is, the gist of the present invention is as follows [1] to

[0013] .

[0010] [1] A curable composition characterized by containing two or more of the following components (A) and component (B). thing. Component (A): Having at least an aromatic ring structure and a (meth)acryloyl group, and having a refractive index Compounds with a ratio of 1.50 to 1.70 Component (B): (meth)acrylic polymer containing ionic groups in its molecule [2] At least one of the components (A) is a diphenylmethane structure, a fluorene structure, or The structure described in [1] is selected from the group consisting of a ruvacole structure and a biphenyl structure. Curable composition. [3] At least one of the components (A) is a bisphenol A diglycidyl ether The curable composition described in [1] or [2] which is a crotonic acid adduct (A1). [4] The curable composition described in [3], wherein the proportion of (A1) is 5 to 55% by weight based on the total mass of all the constituent units constituting component (A). [5] The curable composition according to any one of [1] to [4], wherein component (B) is a (meth)acrylic polymer containing a structural unit derived from a compound represented by the following formula (1) in the molecule . CH2=C(R 1 )-C(O)-Q 1 -(CH2) m -N + R 2 R 3 R 4 ·X - …(1) (In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each independently represent a hydrocarbon group having 1 to 24 carbon atoms, R represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms or -C 4 H2-CH(OH)-CH2-N R + R 5 R 6 R 7 ·Y - represents, and R 5 ~R 7 each independently represent a hydrocarbon group having 1 to 24 carbon atoms. Q 1 is O or NH. X - and Y - each independently represent an anion. m is an integer of 1 to 10.) [6] The curable composition according to any one of [1] to [5 , wherein the mass average molecular weight of component (B) is 1000 or more and 100000 or less. [7] Component (B) contains 10 to 90% by weight of a structural unit derived from a compound represented by formula (1) in the molecule based on the total mass of all the constituent units constituting component (B), and is a (meth)acrylic ​​​ A curable composition according to [5] or [6], comprising a polymer system. [8] The total amount of component (A) and component (B) is 1 to 99% by weight of component (B) [ A curable composition according to any one of items [1] to [7]. [9] Contains component (C) which does not contain an aromatic ring structure and has one or more (meth)acryloyl groups. A curable composition as described in any one of items [1] to [8].

[10] A curable composition according to any one of [1] to [9], containing a polymerization initiator. Hard consisting of a hard product of a curable composition described in any one of items

[11] [1] to

[10] . A laminate in which the coating layer is applied to only one side of the substrate. A polarizer protective film containing the laminate described in

[12]

[11] .

[13]

[12] The side of the polarizer protective film described above that does not have a hard coat layer is a polarizer A polarizing plate made by laminating two materials together. [Effects of the Invention]

[0011] According to the present invention, a high refractive index hard coat layer with excellent antistatic properties and transparency is formed. A curable composition that can produce a hard coat layer made of the cured product of this curable composition, and a substrate fill A polarizer protective film made of a laminate having a surface on the surface of the polarizer, and a polarizer protective film made of a polarizer A polarizing plate can be provided that is bonded to photons. [Modes for carrying out the invention]

[0012] The embodiments of the present invention will be described in detail below, but the following description is based on the embodiments of the present invention. This is just one example, and the present invention is not limited to the following description unless it exceeds the gist of the invention. i. In this specification, when the expression "~" is used, the numbers or physical properties before and after it are used. It shall be used as an expression that includes the following. In this invention, "(meth)acrylic" When using this expression, it means either "acrylic" or "methacrylic" or both. The same meaning applies to "(meth)acryloyl" and "(meth)acrylate". Let's do that.

[0013] [Curable composition] The curable composition of the present invention contains two or more of the following components (A) and component (B). It is characterized by. Component (A): Having at least an aromatic ring structure and a (meth)acryloyl group, and having a refractive index Compounds with a ratio of 1.50 to 1.70 Component (B): Contains 10 to 90 structural units derived from the compound represented by the following formula (1) in the molecule. (meth)acrylic polymer containing weight % CH2=C(R 1 )-C(O)-Q 1 -(CH2) m -N + R 2 R 3 R 4 ·X - …(1) (In formula (1), R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 Each is independently a carbon Represents 1 to 24 hydrocarbon groups, R 4 is a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms, or -C H2-CH(OH)-CH2-N + R 5 R 6 R 7 ·Y - Represents R 5 ~R 7 Each is independent This represents a hydrocarbon group with 1 to 24 carbon atoms. 1 X is either O or NH. - and Y - That Each represents an anion independently. m is an integer between 1 and 10. This curable composition may further contain, if necessary, component (C), a polymerization initiator, and an organic solvent. That's fine. This curable composition may further contain other components not listed above, if necessary.

[0014] In the following, the compound represented by formula (1) will be referred to as "compound (1)," and all other compounds will be referred to as "compound (1)." The compound is sometimes referred to as "compound (2)". Furthermore, the structural unit derived from compound (1) is called "structural unit (1)," and compound (2) The derived structural unit is sometimes referred to as "structural unit (2)".

[0015] [Ingredients (A)] Component (A) of the composition of the present invention comprises at least an aromatic ring structure and (meth)acryloy It is a compound having a 1.50 to 1.70 refractive index.

[0016] If the refractive index of compound (A) is lower than 1.50, the desired high refractive index can be obtained. This is not possible. From the perspective of high refractive index, the refractive index of compound (A) must be 1.51 or higher. The refractive index of the compound of component (A) is preferably 1.52 or higher. From the viewpoint of high refractive index, a higher value is preferable, but the upper limit of the refractive index for organic compounds is usually 1.7. It is approximately 0. Note that the refractive index of component (A) of the present invention is the refractive index of the compound alone in its uncured state. Furthermore, the refractive index of component (A) is as described in the Examples section below.

[0017] Component (A), as described above, has an aromatic ring structure and a (meth)acryloyl group, and is refraction Any compound with a ratio of 1.50 to 1.70 is acceptable, whether it be a monomer or a polymer. It is also acceptable for the compound to have two or more aromatic ring structures, in which case... In this case, the two or more aromatic ring structures may be identical or different. (t) The acryloyl group may have only one, or it may have two or more. That is also acceptable.

[0018] Component (A) has an aromatic ring structure as the structural part responsible for its high refractive index. There are no particular restrictions on the aromatic ring structure, but for example, the following structure can be considered. Regarding those having the aromatic ring structure exemplified below, the type and number of substituted functional groups are particularly important. There are no restrictions. In the following, "Ph" refers to a phenyl group.

[0019] [ka]

[0020] Of these aromatic ring structures, the diphenylmethane structure and the full ring structure are particularly important from the viewpoint of high refractive index. The olene structure and carbazole structure have high electron density and are prone to exhibiting high refractive index. Preferably, the biphenyl structure is also preferable because it has a high electron density and readily exhibits a high refractive index. It is preferable. More preferred aromatic ring structures are the diphenylmethane structure, the fluorene structure, and bif It has a henyl structure.

[0021] <Acrylate adduct of bisphenol A diglycidyl ether (A1)> In particular, bisphenol A diglycidyl ether having a diphenylmethane structure The acrylic acid adduct (A1) has good compatibility with component (B) and contributes to the transparency of the cured layer. Therefore, it is preferable that the curable composition of the present invention contains at least (A1). If all components other than (A1) among component (A) are designated as (A2), then these In the total amount, the proportion of (A1) is preferably 5 to 55% by weight, and more preferably 10 to 50% by weight. A concentration of 20-40% by weight is particularly preferred. The higher this percentage, the better the transparency of the cured layer. Furthermore, the less of it there is, the higher the antistatic properties tend to be.

[0022] [Component (B)] Component (B) of the composition of the present invention contains an ionic group in the molecule (meth)actin It is a lyl polymer and contributes to the antistatic properties of the cured layer.

[0023] Component (B) is expressed by the following formula (1) with respect to the total mass of all constituent units that make up component (B). The molecule contains 10-90% by weight of structural unit (1) derived from the compound (1) ( (T) It is an acrylic polymer. <Compound (1)> Compound (1) is represented by the following formula (1) and is a component that contributes to antistatic properties. CH2=C(R 1 )-C(O)-Q 1 -(CH2) m -N + R 2 R 3 R 4 ·X - …(1) (In formula (1), R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 Each is independently a carbon Represents 1 to 24 hydrocarbon groups, R 4 is a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms, or -C H2-CH(OH)-CH2-N + R 5 R 6 R 7 ·Y - Represents R 5 ~R 7 Each is independent This represents a hydrocarbon group with 1 to 24 carbon atoms. 1 X is either O or NH. - and Y - That Each represents an anion independently. m is an integer between 1 and 10.

[0024] In the above equation (1), R 1 is a hydrogen atom or a methyl group, preferably a methyl group. ru. R 2 and R 3 Each of these is independently a hydrocarbon group having 1 to 24 carbon atoms. Here, hydrocarbon group Examples include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. 4 , R 5 ~R 7 The same applies to the hydrocarbon group. R 2 and R 3 Each of these is independently preferably a methyl group or an ethyl group, with the methyl group being more preferred. It's nice. R 4 The group is preferably a methyl group, an ethyl group, or a butyl group, with a methyl group being more preferred. R 5 ~R 7 Each of these is independently preferably a methyl group or an ethyl group, with the methyl group being more preferred. stomach.

[0025] X - and Y - The anions represented by these are, independently, chloride ions, iodine ions, Halide ions such as bromide ions, hexafluorophosphate ions (PF) 6- ), Tetrafluoroborate ion (BF 4- ) or sulfate ions are preferred, and among these, From the standpoint of good antistatic properties, halide ions, and furthermore, the availability of raw materials and compounding Chloride ions are more preferable because they are relatively easy to form. Q 1 It is preferable that is O (oxygen atom), and m is preferably an integer from 1 to 5, with 3 being more preferable.

[0026] Specifically, compound (1) is N,N-dimethylaminoethyl (meth)acrylate Methyl chloride, N-(meth)acryloyloxyethyl-N,N,N-trimethic acid Ammonium chloride, N-(meth)acryloyloxypropyl-N,N,N- Limethylammonium chloride, N-(meth)acryloyloxyethyl-N-ethyl -N,N-dimethylammonium monoethyl sulfate, N-(meth)atalloyloxy Ethyl-N,N,N-triethylammonium monoethyl sulfate, N-[3-{N,- (meth)acryloyloxyethyl-N',N,-dimethylammonium}-2-hydro [Xypropyl]-N,N,N-trimethylammonium chloride, N-[3-{N'- (meth)acryloyloxyethyl-N',N,-diethylammonium}-2-hydro It has cationic groups such as oxypropyl-N,N,N-triethylammonium chloride. (meth)acrylic esters; N-(meth)acryloylaminopropyl-N,N, N-trimethylammonium chloride, N-(meth)acryloylaminopropyl-N , N-diethyl-N-methylammonium chloride, N-(meth)acryloylamino Propyl-N-ethyl-N,N-dimethylammonium chloride, N-(meth)acrylate Roylaminopropyl-N,N,N-trimethylammonium monosulfate, N-(meth ) Acryloylaminopropyl-N,N-diethyl-N-methylammonium monosulfate Salt, N-(meth)acryloylaminopropyl-N-ethyl-N,N-dimethylammonium Um-monosulfate, N-[3-{N'-(meth)acryloylaminopropyl-N',N '-Diethylammonium}-2-hydroxypropyl]-N,N,N-trimethylammonium Examples include (meth)acrylamides having cationic groups such as mononium chloride. .

[0027] In particular, N-(meth)acryloyloxyethyl-N,N,N-trimethylammonium Umum chloride, N-(meth)acryloyloxypropyl-N,N,N-trimethyl N-(meth)acryloylaminopropyl-N,N,N-trimeth Tylammonium chloride is preferably used, particularly N-(meth)acryloyl oxy Ethyl-N,N,N-trimethylammonium chloride, N-(meth)acryloyl Minopropyl-N,N,N-trimethylammonium chloride is preferred.

[0028] The (meth)acrylic polymer of component (B) contains only one type of structural unit (1) described above. It is acceptable for one type to be present, and it is also acceptable for two or more types to be included.

[0029] <Compound (2)> The (meth)acrylic polymer of component (B) contains structural units derived from compound (1) above. In addition to (1), structural unit (2) derived from compound (2) constitutes all constituent units of component (B). It is present in 10-90% by weight relative to the total mass of the components. Compound (2) consists of component (A) and component ( This component enhances compatibility with B) and contributes to improving the transparency of the cured layer.

[0030] Examples of compound (2) include methyl (meth)acrylate and ethyl (meth)acrylate. Rate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl Sil(meth)acrylate, stearyl(meth)acrylate, lauryl(meth)acrylate Alkyl (meth)acrylates such as tridecyl (meth)acrylate; the above Mino alcohol (meth)acrylic acid ester; 2-hydroxyethyl (meth)acrylic acid 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate Hydroxyalkyl (meth)acrylates such as phosphates; benzyl (meth)acrylate, Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclohexyl Penthenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate Ethoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, b Toxyethyl (meth)acrylate, cyanoethyl (meth)acrylate, glycidyl ( Meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-di Ethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate Various (meth)acrylates such as acrylate and N,N-diethylaminopropyl (meth)acrylate Crilate, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide Rylamide, N,N-dipropyl(meth)acrylamide, N,N-di-n-butyl(meth ) Acrylamide, N,N-diisobutyl(meth)acrylamide, N,N-di-t-butyl N,N-(meth)acrylamide, N,N-dipentyl(meth)acrylamide, N,N-di- Chlohexyl (meth)acrylamide, N,N-di-2-ethylhexyl (meth)acrylamide Luamide, N,N-didodecyl(meth)acrylamide, N,N-ditridecyl(meth) Acrylamide, N,N-dioctadecyl(meth)acrylamide, N-ethyl-N-meth N-methyl-N-propyl(meth)acrylamide, N- n-butyl-N-methyl(meth)acrylamide, N-methyl-N-octyl(meth) Acrylamide, N-dodecyl-N-methyl(meth)acrylamide, N-methyl-N-o kutadecyl(meth)acrylamide, N-ethyl-N-propyl(meth)acrylamide N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N Various (meth)acrylamides such as N-diethylaminopropyl(meth)acrylamide Examples include styrene and methylstyrene. Only one of these may be used, or two may be used. The above can be combined. Among these, the polymerizable monomer having an amino group is component (A). This is preferable because it can improve compatibility with component (B) and enhance the transparency of the cured layer. Examples of polymerizable monomers having such amino groups include N,N-dimethylaminoethyl (methylaminoethyl) Examples include acrylate and N,N-diethylaminoethyl (meth)acrylate. Furthermore, among these, polymerizable monomers having highly hydrophobic long-chain alkyl groups are component (B) This is preferable because it allows the material to segregate at the air interface of the cured layer, thereby improving the antistatic properties of the cured layer. It seems so. Examples of polymerizable monomers having such long-chain alkyl groups include stearyl(meth) Examples include acrylate, lauryl (meth)acrylate, and tridecyl (meth)acrylate. It is possible.

[0031] The ratio of compound (1) in component (B) to the total mass of all constituent units of component (B) The proportion is preferably 10-90% by weight, more preferably 20-80% by weight, and 30-70% by weight. A percentage is preferable. A higher percentage results in better antistatic properties, while a lower percentage results in a lower cured layer. Transparency tends to improve.

[0032] The weight-average molecular weight (Mw) of the (meth)acrylic polymer of component (B) is the amount of bleed in the coating film. From the perspective of suppressing discharge and improving the durability of antistatic properties, the value should be over 1,000. Preferably it is 5,000 or more, and more preferably 10,000 or more. From the viewpoint of compatibility with the components, it is 100,000 or less, more preferably 80,000 or less. Yes, and more preferably 60,000 or less. In this invention, the weight-average molecular weight (Mw) of component (B) is defined as gel permeation. This is a polystyrene-converted value measured by chromatography (GPC), and is specific. This is measured by the method described in the Examples section below.

[0033] Component (B) can be produced by radical polymerization reaction using the above-mentioned raw material monomers. Radical polymerization reactions are preferably carried out in an organic solvent in the presence of a radical polymerization initiator. It seems so.

[0034] 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) Alcohol-based solvents such as isobutanol; ethylene glycol dimethyl ether, p ether solvents such as propyl glycol monomethyl ether; ethyl acetate, propylene glycol Ester compounds such as monomethyl ether acetate and 2-ethoxyethyl acetate Solvents include aromatic hydrocarbon solvents such as toluene. Only one of these organic solvents may be used. You may use one type or a combination of two or more types.

[0035] Examples of radical polymerization initiators used in radical polymerization reactions include benzoyl peroxide. Organic peroxides such as di-t-butyl peroxide; 2,2'-azobisbutyronite Ryl, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( Examples include azo compounds such as 4-methoxy-2,4-dimethylvaleronitrile. The radical polymerization initiator may be used alone or in combination of two or more. The CAL polymerization initiator is added in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the total amount of raw material monomers. It is preferable to use it.

[0036] Furthermore, during radical polymerization reactions, chain reactions are used to control the weight-average molecular weight of component (B). A chain transfer agent can be used. Examples of chain transfer agents include butanethiol and octane. Thiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol All, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, 2 - Octyl mercaptopropionate, 3-Octyl mercaptopropionate, mercapto 2-ethylhexyl propionate, 2-ethylhexyl thioglycolate, buty Lu-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl- 3-Mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanol Nthiol, 4-methylbenzenethiol, 2-mercaptoethyl octanoate, 1,8-Dimercapto-3,6-Dioxaoctane, Decantrichol, Dodecylmel Captan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto 1-Propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycerol Licolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercapto Examples include succinic acid, 2-mercaptoethanesulfonic acid, and other thiol compounds. This can be done by using only one type or by using a combination of two or more types.

[0037] The amount of chain transfer agent used is 0.1 to 25 parts by weight per 100 parts by weight of the total raw material monomers. Preferably, 0.5 to 20 parts by weight, more preferably, and even more preferably 1.0 to 15 parts by weight.

[0038] The reaction time for the radical polymerization reaction is preferably 1 to 20 hours, and more preferably 3 to 12 hours. Furthermore, the reaction temperature is preferably 40 to 120°C, and more preferably 50 to 100°C.

[0039] [Content ratio of ingredient (A) and ingredient (B)] The curable composition of the present invention has component (B) in relation to the total amount of component (A) and component (B). , containing 1-99% by weight. Component (B) functions as an additive for imparting antistatic properties. Therefore, the product contains at least 1% by weight of component (B) relative to the total amount of component (A) and component (B). This allows for good antistatic properties. From the viewpoint of antistatic properties, the present invention The chemical composition contains component (B) in an amount of 2% by weight or more relative to the total amount of component (A) and component (B). It is preferable to include it, more preferably to include 3% by weight or more, and more preferably to include 5% by weight or more. It is preferable. On the other hand, the content of component (B) in the curable composition of the present invention is the sum of component (A) and component (B). The content of component (A), which is a high refractive index compound, is 99% by weight or less relative to the total amount. By ensuring this, a curable composition with a high refractive index can be obtained. From the viewpoint of high refractive index, this invention The curable composition of the present invention contains component (B) at 80 times the total amount of component (A) and component (B). It is preferable to contain less than % by amount, more preferably 60% by weight or less, and 40% by weight or less. It is even preferable to include it.

[0040] [Component (C)] The curable composition of the present invention further comprises the following component (C) in addition to components (A) and (B). , 1 to 99 parts by weight per 100 parts by weight of the total amount of component (A), component (B), and component (C) Including it is preferable in terms of curability, hardness of the cured film, and scratch resistance. Component (C): A compound that does not contain an aromatic ring structure and has one or more (meth)acryloyl groups.

[0041] Component (C) contains one or more (meth)acryloyl groups that do not contain an aromatic ring structure. Any compound will do, and even monofunctional (meth)acrylate compounds can be bifunctional or multifunctional. It may also be a functional (meth)acrylate compound.

[0042] Examples of monofunctional (meth)acrylate compounds include 2-hydroxyethyl(meth)acrylate. ) Acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate Acryloyl t-butyl (meth)acrylate, glycidyl (meth)acrylate, acryloyl Lumorpholin, N-vinylpyrrolidone, tetrahydrofurfuryl(meth)acrylate T, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Isobornyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate )Acrylate, Tridecyl (meth)acrylate, Cetyl (meth)acrylate, Ste Allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxy Butyl (meth)acrylate, ethyl carbitol (meth)acrylate, phosphoric acid (meth ) Acrylate, ethylene oxide-modified phosphate (meth)acrylate, methoxydiethyl Polyethylene glycol (meth)acrylate, Methoxypolyethylene glycol (meth)acrylate Methoxypropylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate Acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoro Propyl (meth)acrylate, octafluoropropyl (meth)acrylate, 2-A Monovalent mono(meth)acrylates derived from damantane and adamantanediol Sharp adamantyl acrylate and other adamantane derivatives mono(meth)acrylate These are some examples.

[0043] Examples of bifunctional (meth)acrylate compounds include ethylene glycol di(meth)acrylate. )Acrylate, diethylene glycol di(meth)acrylate, butanediol di(meth)acrylate (T)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate ) Acrylate, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol Xanediol di(meth)acrylate, diethylene glycol di(meth)acrylate Polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate ) Acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol Collagen di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate , tripropylene glycol di(meth)acrylate, hydroxypivalate neophosphate Examples include di(meth)acrylates such as ethyl glycol di(meth)acrylate. .

[0044] Examples of trifunctional (meth)acrylate compounds include trimethylolpropane. Tri(meth)acrylate, ethoxylated trimethylolpropane, tri(meth)acrylate T, Propoxylated Trimethylolpropane Tri(meth)acrylate, Tris-2-Hydro Xyethyl isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate Tri(meth)acrylate, pentaerythritol tri(meth)acrylate , dipentaerythritol tri(meth)acrylate, succinic acid modified pentaerythritol Tri(meth)acrylate, ditrimethylolpropanetri(meth)acrylate, etc. Trifunctional (meth)acrylate compounds, and pentaerythritol tetra(meth)acrylate Pentaerythritol tetra(meth)acrylate, succinate-modified pentaerythritol, ditrimethylol Lupropanetetra(meth)acrylate, dipentaerythritoltetra(meth)acrylate Rate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane Dipenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Ditrimethylolpropanehexa(meth)acrylate and other polyfunctional (meth) compounds with three or more functions. Acrylate compounds, and some of these (meth)acrylates, are converted into alkyl groups or ε-caprolamine. Polyfunctional (meth)acrylate compounds substituted with kutone; nitrogen sources such as isocyanurate structures. Polyfunctional (meth)acrylates having a heterocyclic structure containing chromosomes; polyfunctional (meth)acrylates having a dendrimer structure. methacrylates, polyfunctional methacrylates with hyperbranched structures, etc. Polyfunctional (meth)acrylates having a highly branched resinous structure; isocyanates and triisosodium Anates, isocyanurates, for example, pentaerythritol tri(meth)acrylate Dipentaerythritol tri(meth)acrylate, dipentaerythritol penta (Meth)acrylates and other hydroxyl group-containing (meth)acrylates are added to urethane (meth)acrylates. Examples include acrylates, etc.

[0045] Among these (meth)acrylate compounds, the balance of the physical properties of the resulting cured product is considered important. Polyfunctional (meth)acrylate compounds are preferred because they can be easily extracted. Pentaerythritol tri(meth)acrylate, pentaerythritol tetra( Meth)acrylate, pentaerythritol penta(meth)acrylate, pentaerythritol Litol hexa(meth)acrylate, dipentaerythritol tri(meth)acrylate Dipentaerythritol tetra(meth)acrylate, dipentaerythritol pen Metaacrylate, dipentaerythritol hexa(meth)acrylate, or These acid-modified products are preferred.

[0046] These components (C) may be used individually or in combination of two or more.

[0047] The curable composition of the present invention is, with respect to the total amount of component (A), component (B), and component (C), The composition contains 1 to 99% by weight of component (C). The content of component (C) in the curable composition of the present invention is such that the content of component (C) (A) At least 1 part by weight per 100 parts by weight of the total of components (B) and (C). As a result, the inclusion of component (C) improves curability, hardness of the cured film, scratch resistance, and other properties. This can be effectively obtained. From these viewpoints, the curable composition of the present invention has component (C) Contains at least 1 part by weight per 100 parts by weight of the total of components (A), (B), and (C). It is preferable that it contains 2 parts by weight or more, and more preferably 2 parts by weight or more. On the other hand, the content of component (C) of the curable composition of the present invention is component (A), component (B), and component (C) is 99 parts by weight or less per 100 parts by weight of total, so that component (A) and High refractive index, antistatic properties, and transparency can be effectively obtained by (B). From this point of view, the curable composition of the present invention comprises component (C) and component (A), component (B), and component (C). Preferably, it contains 85 parts by weight or less per 100 parts by weight of the total amount, and preferably 70 parts by weight or less. That is preferable.

[0048] [Polymerization initiator] The curable composition of the present invention, in order to improve curability by active energy rays, polymerization opening It is preferable that the product contains an initiator.

[0049] As a polymerization initiator, a photopolymerization initiator is preferred, for example, 2-ethylanthraquinone. Benzophenones, consisting of 2,4-diethylthioxanthone, benzophenone, and its derivatives , 1-hydroxy-cyclohexyl-phenyl-ketone [for example, trade name "Omni rad(registered trademark)184", manufactured by IGM, 2-hydroxy-1-{4-[4-(2- Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-prop n-1-on [For example, product name "Omnirad(registered trademark) 127", 2,2-dimethyl Xy-1,2-diphenylethane-1-one [For example, trade name "Omnirad (Registered Trade Name [Standard 651], manufactured by IGM, 2,4,6-trimethylbenzoyl-diphenyl-phosphorus Fin oxide [For example, product name "Omnirad(registered trademark) TPO H", IGM] [Manufactured by the company], bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [For example, product name "Omnirad(registered trademark) 819", manufactured by IGM], 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [for example, Product name "Omnirad(registered trademark) 907", manufactured by IGM, 2-benzyl-2-dimethyl Tylamino-1-(4-morpholinophenyl)-butanone-1 [For example, product name "Om nirad(registered trademark)369", 2-hydroxy-2-methyl-1-phenylpropane -1-On [For example, product name "Omnirad(registered trademark) 1173", manufactured by IGM, etc.] These polymerization initiators can be used individually or in combination of two or more. These are also acceptable. Among these, α-hydroxyketone compounds with excellent reactivity are preferred. Examples of such compounds include 1-hydroxycyclohexylphenyl-keto [For example, the product name "Omnirad(registered trademark) 184," manufactured by IGM] is one example. .

[0050] The content of polymerization initiators is determined from the viewpoint of improving curability, and consists of component (A), component (B), and, if necessary... Preferably, 0.01 parts by weight or more per 100 parts by weight of the total amount of component (C) used accordingly. It is more preferably 0.05 parts by weight or more, and even more preferably 0.1 parts by weight or more. It is. Furthermore, from the viewpoint of the stability of the curable composition, the content of the polymerization initiator is preferably 20. It is less than or equal to parts by weight, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less. That is the case.

[0051] [organic solvent] The curable composition of the present invention typically contains an organic solvent and is adjusted to have a solid content concentration of approximately 5 to 95% by weight. It is manufactured. A solid content concentration of 5% by weight or more is necessary for the curable composition to undergo an unintended curing reaction. It is preferable from the viewpoint of preventing gelation, etc., and from the viewpoint of coating properties, it is preferable that it is 95% by weight or less. Therefore, it is preferable. From these viewpoints, the solid content concentration is more preferably 10% by weight or more. More preferably 20% by weight or more, and more preferably 90% by weight or less, Preferably, it is 85% by weight or less, and particularly preferably 80% by weight or less. In the Ming Dynasty, "solid content" referred to the components excluding the solvent, and not only the solid components. This also includes semi-solid and viscous liquid substances.

[0052] The organic solvent is not particularly limited and may include component (A), component (B), and as needed. Depending on the type of component (C) used and the type of substrate used when forming the hard coat layer, The appropriate choice can be made considering the method of application to the substrate, etc. Specific examples of organic solvents include: For example, n-hexane, n-heptane, n-octane, n-decane, n-dodecane, thic Saturated hydrocarbon solvents such as hydroxyhexane and methylcyclohexane; aromatics such as toluene and xylene. Fragrance-based solvents; methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexano Ketone solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Ether-based solvents such as propylene glycol monomethyl ether, anisole, and phenetol Insulators: Ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate, etc. Ester solvents: dimethylformamide, diethylformamide, N-methylpyrrolidone Amide solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc. Lubricant solvents; methanol, ethanol, propanol, isopropanol, butanol, etc. Examples include alcohol-based solvents; halogen-based solvents such as dichloromethane and chloroform. .

[0053] These solvents may be used individually or in combination of two or more. Among them, ester-based solvents and esters are chosen because they exhibit good compatibility with component (A) and component (B). Alkaline solvents, alcoholic solvents, and ketone solvents are preferred.

[0054] [Other ingredients] The curable composition of the present invention contains components (A) and (B) to the extent that they do not impair the effects of the present invention. It may contain other components besides component (C), polymerization initiators, and organic solvents. The ingredients include UV absorbers, hindered amine light stabilizers, fillers, and silane capping. Grinding agent, reactive diluent, antistatic agent other than component (B), organic pigment, slip agent, dispersant, Xotropic agents (thickeners), antifoaming agents, antioxidants, leveling agents, inorganic particles, organic Examples include particles and photoacid generators.

[0055] [Method for producing a curable composition] The method for producing the curable composition of the present invention is not particularly limited, but for example, components (A) and (B) And, as necessary, mix component (C), polymerization initiator, organic solvent, and other components as appropriate. This can be obtained by the following. When mixing each component, ensure uniformity using a disperser, stirrer, etc. It is preferable to mix them together.

[0056] [Cured product / laminate] By curing the curable composition of the present invention by irradiating it with active energy rays, etc., this A cured product of the invention can be obtained. In particular, by applying the curable composition of the present invention onto a substrate or the like... By curing, a cured layer made of the curable composition of the present invention is formed on a substrate. It can be formed into layers. Furthermore, the curable composition of the present invention can be applied to a substrate or the like in this manner. By hardening it into a film, a hard coat film (high refractive index hard coat layer) is created. This can be obtained. Furthermore, the curable composition of the present invention can be applied to another resin film as a substrate. By applying and curing the film to form a hard coat film, a high refractive index can be achieved on other resin films. A film laminate is obtained by laminating a hard coat film. Therefore, the term "coating" will be used to encompass the concept of what is generally called "coating work."

[0057] The substrates used in the above laminates include organic materials such as plastic substrates; metal substrates, glass Examples of inorganic materials include substrates, but the cured product obtained by curing the curable composition of the present invention is Because it has excellent transparency, it is preferable to apply it to transparent substrates. Plastic substrates Examples include various synthetic resins, for example, acrylonitrile-butadiene-styrene copolymer (A BS resin, polycarbonate (PC) resin, polyethylene terephthalate (PET) resin Fat, polybutylene terephthalate (PBT) resin, polymethyl methacrylate (PMMA) ) made of resin, polystyrene (PS) resin, polyolefin resin, cellulose resin, etc. This is one example. There are no particular limitations on the metal base material, but for example, steel such as hot-rolled sheets and cold-rolled sheets. Sheet metal, hot-dip galvanized steel sheet, electro-galvanized steel sheet, tinplate, tin-free steel, and others. Various types of plated or alloy-plated steel sheets, stainless steel sheets, aluminum sheets, and other metal sheets These can be listed. Furthermore, these can be treated with phosphate treatment, chromate treatment, organic phosphate treatment, organic phosphate treatment, etc. Even if various surface treatments such as romating and heavy metal substitution treatments like nickel have been applied, Good. As a glass substrate, in addition to ordinary glass, various types of chemically treated glass (for example) For example, Corning's Gorilla Glass (registered trademark) and AGC's DragonTrail (registered trademark) ) etc.) or multi-component glass may be used. The curable composition of the present invention is a plastic substrate, It is suitable for glass substrates, and particularly suitable for plastic substrates.

[0058] The hard coat layer (high refractive index layer) formed on the substrate is, for example, the curable compound of the present invention. The material can be formed by coating it onto a substrate and then irradiating it with active energy rays. For example, a method of applying (coating) the curable composition of the present invention onto a substrate is to reverse Coating method, gravure coating method, rod coating method, bar coating method, Meyer bar coating method, Examples include die coating and spray coating methods. Furthermore, the form of the cured product of the present invention is not particularly controlled. Although not limited to these, typically, cured products obtained by curing a substrate by irradiating it with active energy rays are A cured film (hardened coating) can be obtained on at least one side of the substrate.

[0059] The active energy rays that can be used when curing the curable composition of the present invention include violet. This includes external rays, electron beams, X-rays, infrared rays, and visible light. From the viewpoint of curing properties and prevention of resin degradation, ultraviolet light and electron beams are preferred.

[0060] When curing the curable composition of the present invention by ultraviolet irradiation, various ultraviolet irradiation devices are used. It can be used as a light source, and the light sources include xenon lamps, high-pressure mercury lamps, and metal halide lamps. Lamps, LED-UV lamps, excimer lamps, etc. can be used. The amount of ultraviolet irradiation. (Units are mJ / cm) 2 ) is typically 10 to 10,000 mJ / cm². 2 The curability of the present invention From the viewpoint of the curability of the composition and the flexibility of the cured product (cured film), a value of 100 to 5,000 is preferred. mJ / cm 2 And more preferably 200 to 3,000 mJ / cm² 2 That is the case.

[0061] Furthermore, when curing the curable composition of the present invention by electron beam irradiation, various electron beam irradiation devices are used. It can be used. The electron beam irradiation dose (Mrad) is typically 0.5 to 20 Mrad. Therefore, from the viewpoint of curability of the curable composition of the present invention, flexibility of the cured product, and prevention of damage to the substrate, Preferably, it is 1 to 15 Mrad.

[0062] [Application] The cured product obtained from the curable composition of the present invention has a high refractive index, excellent antistatic properties, and good transparency. Therefore, it is useful as a hard coat layer (high refractive index layer) for optical films such as anti-reflective films. Furthermore, in applications as a high refractive index layer, the cured film is made from the curable composition of the present invention. There are no particular restrictions on the film thickness, but it is usually around 1 to 20 μm, preferably 1 to 10 μm. be.

[0063] The thickness of the substrate is arbitrary. If the substrate is in film form, its thickness must be between 5 μm and 3 mm. The lower part is preferable, 10 μm or more and 2 mm or less is more preferable, and 15 μm or more and 1 mm or less is even preferable. Preferably, the particle size is 20 μm or more and particularly preferably 250 μm or less.

[0064] Furthermore, the thickness of the laminate is also arbitrary. In the case of a film-like laminate, each layer fully performs its respective function. Due to the need to fully utilize the material, the thickness of the laminate is preferably 6 μm or more, and 10 μm or more is preferable. Preferably, 15 μm or more is preferred. Also, the laminate can be used to thin the product to which it is applied. From the standpoint of reducing weight, the thickness of the laminate is preferably 3 mm or less, and more preferably 2 mm or less. Furthermore, a thickness of 1 mm or less is more preferable, and a thickness of 300 μm or less is particularly preferable.

[0065] A laminate in which a cured layer of the composition of the present invention is laminated on a substrate as a hard coat layer is formed by the substrate and It exhibits excellent adhesion to the coating layer and surface hardness. For this reason, this laminate is used in liquid crystal televisions. For optical displays such as OLED TVs, e-paper, touch panels, and smartphones. Parts; lamp-related items, window-related items (rear windows, side windows, skylights) Automotive-related parts such as (etc.); housings for various electrical equipment, decorative panels, furniture, and other household goods. It can be suitably used as a surface cover for articles. Among these, it is suitable for optical displays. It is suitable as a product, and is particularly suitable for use when bonded to a polarizer in the manufacture of polarizing plates for displays. It can be suitably used in polarizer protective films and display protective films.

[0066] [Polarizer protective film, polarizing plate] The polarizer protective film of the present invention has a hard coat layer made of a cured product of the composition of the present invention, It consists of a laminate formed by laminating on only one side of a plastic film. Furthermore, the polarizing plate of the present invention The polarizer protective film of the present invention is bonded to the polarizer with the side that does not have a hard coat layer. The polarizer protective film is applied to one or both sides of the polarizer. This can be done. Adhesives or adhesives can be used for bonding.

[0067] Optical films such as anti-reflective films having a high refractive index hard coat layer made from the cured product of the present invention The film is suitable as an optical film to be provided on the surface of a display such as a liquid crystal display. Furthermore, an optical film having a high refractive index hard coat layer made of the cured product of the present invention is used for liquid crystal displays. By applying it to the display surface of games, etc., its excellent transparency, antistatic properties and anti-reflective properties The anti-blight function provides a display surface that is highly visible and resistant to dirt and dust. ru. [Examples]

[0068] The present invention will be described in more detail below with reference to examples, but the present invention will not exceed its gist. The following examples are not the only examples of the various manufacturing processes described below. The values ​​of the items and evaluation results are meant as preferred upper or lower limits in the embodiments of the present invention. The preferred range is the upper or lower limit value mentioned above, and the value or actual value of the example below. The range may also be defined by the combination of values ​​between the examples.

[0069] [Evaluation Method] In the following examples and comparative examples, the cured film was evaluated using the following method.

[0070] <Antistatic properties: Surface resistance value> After the cured film has been kept in a constant temperature room at 23°C and 50% RH for 24 hours, it is then placed in the same constant temperature room. Inside, a high-resistivity resistivity meter (Mitsubishi Chemical Analytec "High Resta-UP MCP-HT4") The surface resistivity was measured after applying a voltage of 500V using a 50" ( ) and the antistatic properties were determined. This was used as an indicator. A smaller surface resistivity indicates better antistatic properties.

[0071] <Transparency: Haze> For the cured film, use a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS K-7136. The haze value was measured using a spectroscopic haze meter (SH7000). The evaluation criteria were as follows, with ◎ to △ representing the acceptable range. ◎: 2.0% or less ○: 2.1~10.0% △: 10.1~20.0% ×: 20.1% or more

[0072] <Hardness: Pencil hardness> For the hardened layer side of the laminate, a JIS-compliant pencil hardness tester was used to determine the hardness of the surface according to JIS K-540. Based on a baseline of 0, the pencil hardness was measured to determine the degree to which a pencil could not be scratched under a load of 500g. Pencil hardness is used in various applications. Considering its use, it is preferable that it be F or higher.

[0073] <Refractive index> The refractive index of component (A) was measured by the following method. Measurements were taken using an ATAGO DR-M2 multi-wavelength Abbe refractometer at a measurement temperature of 25°C. The refractive index is preferably 1.55 or higher, considering its use in various applications.

[0074] [Weight-average molecular weight (Mw) of component (B)] The weight-average molecular weight (Mw) of an acrylic polymer (P) is determined by gel permeation chromatography ( The measurement was performed using GPC) "HLC-8120" (manufactured by Tosoh Corporation). The column used was: TSKgel G5000HXL*GMHXL-L (manufactured by Tosoh Corporation) was used. Standard polystyrene: F288 / F80 / F40 / F10 / F4 / F1 / A500 Calibration curves were created using 0 / A1000 / A500 (manufactured by Tosoh Corporation) and styrene. . The measurement was performed using a solution 10 in which the polymer was dissolved in tetrahydrofuran to a concentration of 0.4%. The procedure was performed using 0 μl at a column oven temperature of 40°C. The weight-average molecular weight (Mw) was measured using standard polypropylene. Calculated using restyrene equivalents.

[0075] [Ingredient (A)] The following commercially available product was used as component (A). The refractive index values ​​were all taken from the manufacturer's catalog. I referred to it. Note that (a-1) corresponds to (A1) above, and (a-2) and (a-3) correspond to (A2). Applicable.

[0076] (a-1) • Miwon Miramer PE210 Bisphenol A epoxy diacrylate Refractive index: 1.558

[0077] (a-2) • Miwon Miramer M240 Ethoxylated bisphenol A diacrylate Refractive index: 1.537

[0078] (a-3) ·Shin Nakamura Chemical Co., Ltd. A-LEN-10T Compounds having a biphenyl structure and an acryloyl group Refractive index: 1.577

[0079] [Component (B)] As component (B), an acrylic polymer was manufactured as follows. Note that the raw materials used were as follows: Its abbreviations are as follows: <Compound (1)> DQ-100: N,N-dimethylaminoethyl methacrylate methyl chloride Quaternary ammonium compounds (Kyoeisha Chemical Co., Ltd. "Light Ester (Registered Trademark) DQ-100") <Compound (2)> DMMA: N,N-dimethylaminoethyl methacrylate (manufactured by Mitsubishi Chemical Corporation) Ester (registered trademark) DM) SLMA: 45:55 (by weight) of lauryl methacrylate and tridecyl methacrylate. ) A mixture of (Mitsubishi Chemical Corporation's "Acryester (registered trademark) SL")

[0080] (b-1) In a reactor equipped with a stirrer, reflux condenser, and thermometer, add DQ100: 18 parts by weight, S LMA: 7.5 parts by weight, DMMA: 4.5 parts by weight, Methyl ethyl ketone (MEK): 20 Add parts by weight and 50 parts by weight of isopropyl alcohol (IPA), and after starting to stir, the system The mixture was purged with nitrogen and heated to 55°C. Then, 2,2'-azobis(2,4-dimethylvalero) was added. Nitrile (Wako Pure Chemical Industries, Ltd. "V-65")): 0.6 parts by weight are added, and the system is heated to 65°C. After raising the temperature and stirring for 3 hours, further heating is performed using 2,2'-azobis(2,4-dimethylvaleronite 0.6 parts by weight of lyl was added and stirred at 65°C for 3 hours. The temperature in the system was raised to 80°C, and 2 After stirring for a certain amount of time, the mixture was cooled to room temperature to obtain a solution of polymer b-1. The composition of the reaction solution was polymer - The ratio of b-1 / MEK / IPA was 30 / 20 / 50 (by weight). The weight-average molecular weight (Mw) of polymer b-1 was 45,200.

[0081] [Component (C)] The following commercially available products were used as component (C).

[0082] (c-1) · Aronix (registered trademark) M-510 manufactured by Toagosei Co., Ltd. Succinic acid-modified product of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate

[0083] (c-2) · Kayarad (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd. Mixture of dipentaerythritol tetraacrylate and dipentaerythritol hexaacrylate

[0084] (c-3) · Mitsui Chemicals, Inc. manufactured紫光(registered trademark) UV7600B Condensate of isophorone diisocyanate and pentaerythritol triacrylate and mixture with pentaerythritol tetraacrylate

[0085] [Example 1] As component (A), 5% by weight of "a-1" and 85% by weight of "a-2", as component (B) , 6.6% by weight of "b-1", as component (C), 3.4% by weight of "c-2" (here, the "[% by weight]" of components (A) to (C) is the weight percentage of the solid content).), and as a polymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone ("Omnirad (registered trademark) 184" manufactured by IGM Co., Ltd. (abbreviated as "Omn184" in the table)) 4 parts by weight (based on 100 parts by weight of the solid content of components (A) to (C)) were mixed, and this was diluted with a 50:50 (weight ratio) mixed solvent of n-butanol and methyl ethyl ketone to a solid content concentration of 30% by weight to obtain a curable composition.

[0086] ​​​​​​​The resulting curable composition is applied to a polyethylene terephthalate (PET) film that serves as the base material. (Toyobo Co., Ltd. Cosmo Shine (registered trademark) A4100, thickness: 188 μm) with barcode Apply using TER #14 so that the coating thickness after drying is 5 μm, and heat at 80°C for 2 minutes. Dry. The coating film of the curable composition was treated with Iwasaki Electric's "US5-X04" using a high-pressure mercury lamp as the light source. Using "01", the cumulative light amount in one pass is 300 mJ / cm2 at a UV irradiance of 120 mW / cm2. A cured film (high refractive index hard coat film) was obtained by irradiating with ultraviolet light in two passes. The transparency, antistatic properties, hardness, and refractive index of the material were evaluated as described above. The results are shown in the table. As shown in 1.

[0087] [Examples 2-6 and Comparative Examples 1-7] The procedure was the same as in Example 1, except that the composition of the curable composition was changed as shown in Tables 1 and 2. Each curable composition was obtained, and then a cured film was obtained. For each cured film, the transparency described above was obtained. The antistatic properties, hardness, and refractive index were evaluated. The results are shown in Tables 1 and 2.

[0088] [Table 1]

[0089] [Table 2]

[0090] [Evaluation Results] As can be seen from Tables 1 and 2, all of Examples 1 to 6 exhibited transparency, antistatic properties, and hardness. The refractive index was good. While all of Examples 1 to 6 had a refractive index of 1.55 or higher, Comparative Example 1, which did not contain component (A), had a lower refractive index. Also, the ratio without component (B) Comparison examples 2-4 were inferior in antistatic properties. Furthermore, the total amount of component (A) was set to 100% by weight. In this case, Comparative Example 5, in which the proportion of (A1) is greater than 55% by weight, has inferior antistatic properties, and (A1) Comparative Examples 6 and 7, which contained less than 5% by weight, exhibited inferior transparency.

Claims

1. It contains two or more of the following ingredients (A) and the following ingredient (B), A curable composition in which at least one of component (A) is an acrylic acid adduct (A1) of bisphenol A diglycidyl ether. Component (A): A compound having at least an aromatic ring structure and a (meth)acryloyl group, and having a refractive index of 1.50 to 1.

70. Component (B): (meth)acrylic polymer containing ionic groups in its molecule

2. The curable composition according to claim 1, wherein at least one of component (A) has a structure selected from the group consisting of a diphenylmethane structure, a fluorene structure, a carbazole structure, and a biphenyl structure.

3. The curable composition according to claim 1 or 2, wherein the proportion of (A1) is 5 to 55% by weight with respect to the total mass of all constituent units that make up component (A).

4. The curable composition according to any one of claims 1 to 3, wherein the mass-average molecular weight of component (B) is 1,000 or more and 100,000 or less.

5. The curable composition according to any one of claims 1 to 4, wherein component (B) is a (meth)acrylic polymer containing a structural unit derived from a compound represented by the following formula (1) in its molecule. CH2=C(R1)-C(O)-Q1-(CH2)m-N+R2R3R4・X-...(1) (In formula (1), R1 represents a hydrogen atom or a methyl group, R2 and R3 each independently represent a hydrocarbon group having 1 to 24 carbon atoms, R4 represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms, or -CH2-CH(OH)-CH2-N+, and R5, R6, R7, and R7 each independently represent a hydrocarbon group having 1 to 24 carbon atoms. Q1 is O or NH. X- and Y- each independently represent an anion. m is an integer from 1 to 10.)

6. The curable composition according to claim 5, wherein component (B) contains a (meth)acrylic polymer that contains 10 to 90% by weight of structural units derived from a compound represented by formula (1) in its molecule, relative to the total mass of all structural units constituting component (B).

7. A curable composition according to any one of claims 1 to 6, wherein component (B) is present in an amount of 1 to 99% by weight relative to the total amount of component (A) and component (B).

8. A curable composition according to any one of claims 1 to 7, further comprising a component (C) that does not contain an aromatic ring structure and has one or more (meth)acryloyl groups.

9. A curable composition according to any one of claims 1 to 8, further comprising a polymerization initiator.

10. A laminate in which a hard coat layer made of a cured product of a curable composition according to any one of claims 1 to 9 is laminated on only one side of a substrate.

11. A polarizer protective film comprising the laminate described in claim 10.

12. A polarizing plate obtained by laminating the side of the polarizer protective film described in claim 11 that does not have a hard coat layer to a polarizer.

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