JPWO2005105866A1 - Photocurable composition and antireflection film using the same - Google Patents

Abstract

The photocurable composition has the general formula (1): (wherein R1 to R3 each independently represents a hydrogen atom or a methyl group, and R4 to R6 each independently represents an unsubstituted or substituted straight chain. A chain or branched alkylene group, R7 represents hydrogen or a monovalent organic group, and R8 represents a tetravalent aromatic group, provided that at least one of R7 and R8 includes a biphenyl skeleton. .) And a filler (B) having a refractive index of 1.60 or more. The antireflection film is formed by sequentially laminating a high refractive index hard coat layer formed of the photocurable composition and a low refractive index layer having a refractive index of 1.20 to 1.50 on one surface of a plastic substrate. Has been.

Description

  The present invention relates to a photocurable composition that has both a high refractive index and hard coat properties such as pencil hardness and scratch resistance and is excellent in light resistance.

  The present invention also relates to an antireflection film used for the purpose of protecting the surface of a display device such as a word processor, a computer, a television, such as a plasma display device, a CRT display device, a liquid crystal display device, a projection display device, or an EL display device. About.

  2. Description of the Related Art In recent years, high-refractive-index plastic materials have made significant progress in optical devices, and are actively studied as antireflection films for various display devices.

  In addition to high refractive index, high refractive index materials used for antireflection films need hard coat properties such as pencil hardness and scratch resistance, transparency, low specific gravity, light resistance, etc. Materials are being considered.

  For example, a compound having two (meth) acrylates and a biphenyl skeleton is disclosed as a material exhibiting a high refractive index. This shows a high refractive index derived from the biphenyl skeleton, but since it has only two (meth) acrylates in the molecule, it has a low probability of being incorporated into the polymerization system during light irradiation, resulting in a hard coat such as pencil hardness. In addition, there is a drawback in that the volumetric shrinkage during photocuring is severe and the adhesion to the substrate deteriorates even when efficiently incorporated into the polymerization system during light irradiation. .

In order to remedy such drawbacks, studies have been made to increase the distance between the biphenyl skeleton in the molecule and (meth) acrylate, but the hard coat properties such as pencil hardness are improved, but the biphenyl skeleton in the system is improved. There is a drawback in that the concentration of the toner decreases and a sufficient refractive index cannot be obtained. Further, as another method, when another photopolymerizable material is used in combination, the concentration of the biphenyl skeleton in the system is similarly lowered, and as a result, a sufficient refractive index cannot be obtained. (JP 2003-64025 A, JP 2003-64026 A)
As described above, according to the conventional technique, a photocurable material having a high refractive index, a hard coat property such as high pencil hardness and scratch resistance, and a light resistance has not been obtained.

  An object of this invention is to provide the photocurable composition which has high refractive index, the outstanding hard-coat property, and light resistance.

  Another object of the present invention is to provide an antireflection film having excellent hard coat properties and light resistance and having good optical properties.

  According to the 1st side surface of this invention, the photocurable material containing the photocurable material containing the compound (A) shown by following General formula (1), and the filler (B) whose refractive index is 1.60 or more. A composition is provided.

General formula (1):

(Wherein R ^{1 to} R ³ each independently represents a hydrogen atom or a methyl group, and R ^{4 to} R ⁶ each independently represents an unsubstituted or substituted linear or branched alkylene group. R ⁷ represents hydrogen or a monovalent organic group, and R ⁸ represents a tetravalent aromatic group, provided that at least one of R ⁷ and R ⁸ includes a biphenyl skeleton.)
In the photocurable composition of the present invention, it is preferable that both R ⁷ and R ⁸ in the general formula (1) include a biphenyl skeleton.

  Moreover, in the photocurable composition of the present invention, the filler (B) is preferably a metal oxide.

  According to the second aspect of the present invention, a high refractive index hard coat layer formed from the photocurable composition according to the first aspect of the present invention and a refractive index of 1. An antireflection film in which low refractive index layers of 20 to 1.50 are sequentially laminated is provided.

  In the antireflection film of the present invention, the refractive index of the high refractive index hard coat layer is preferably in the range of 1.60 to 1.75, and the pencil hardness of the high refractive index hard coat layer is 2H or more. preferable.

  First, the photocurable composition of the present invention will be described.

  The photocurable composition of the present invention includes a photocurable material containing the compound (A) represented by the general formula (1) and a filler (B) having a refractive index of 1.60 or more.

  The compound (A) represented by the general formula (1) is a component that imparts a high refractive index and excellent hard coat properties, and when it does not contain a halogen atom, yellowing or the like is extremely low and light resistance is excellent. Is. In particular, among the compounds (A) represented by the general formula (1), those having a number average molecular weight of more than 300 per polymerizable unsaturated double bond group are preferable because excellent hard coat properties can be obtained. .

In General formula (1), R < ¹ > -R < ³ > is a hydrogen atom or a methyl group each independently.

R ^{4 to} R ⁶ each independently represents an unsubstituted or substituted linear or branched alkylene group. The substituent which this alkylene group may optionally have includes an aromatic group (for example, phenoxy group), a halogen atom, and a hydroxyl group. The alkylene group preferably has 1 to 8 carbon atoms. R ⁶ usually has one hydroxyl group as a substituent, and this hydroxyl group is usually bonded to the β-position carbon relative to the —O— group of the acyl group to which R ⁶ is bonded.

R ⁷ represents hydrogen or a monovalent organic group. The latter organic group has the formula:
—R ⁶ —OC (O) —C (R ³ ) ═CH ₂
(Wherein R ⁶ and R ³ are as defined in general formula (1)) or are represented by the formula —CH ₂ —C (OH) CH ₂ —O—R ⁷¹ (where , R ⁷¹ can be a substituted or unsubstituted biphenyl). Examples of the substituent that biphenyl may optionally include include a hydroxyl group, a cyano group, and a vinyl group.

R ⁸ is a tetravalent aromatic group. Examples of the aromatic group include benzene, benzophenone, biphenyl, phenyl ether, diphenyl sulfone, diphenyl sulfide, perylene, and naphthalene.

In the present invention, one of R ⁷ and R ⁸ include a biphenyl group, preferably each of R ⁷ and R ⁸ comprises a biphenyl group.

In order to produce the compound (A) represented by the general formula (1), first, the following formula (A):

(Wherein R ⁸ is as defined in the general formula (1)) an aromatic tetracarboxylic dianhydride represented by the following formula (B):
CH ₂ = C (R ¹ ) COOR ⁴ OH
(Wherein R ¹ and R ⁴ are as defined in the general formula (1)) and a first hydroxyl group-containing (meth) acrylate represented by the following formula (C):
^{_{CH 2 = C (R 2)}} COOR 5 OH
(Wherein R ² and R ⁵ are as defined in the general formula (1)) and are reacted with a second hydroxyl group-containing (meth) acrylate represented by the formula (D):

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁸ are as defined in the general formula (1)) can be obtained.

  Examples of the aromatic tetracarboxylic dianhydride represented by the formula (A) include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl Examples include sulfonetetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, and naphthalenetetracarboxylic dianhydride. Among these aromatic tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton can be efficiently introduced into the molecule of the compound (A). Further, the compound (A) Is particularly preferable because the refractive index is 1.57 or more.

  The first and second hydroxyl group-containing (meth) acrylates may be the same or different. Examples of such hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate. 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-hydroxy-3-phenoxypropyl methacrylate.

  The reaction of the aromatic tetracarboxylic dianhydride with the first and second hydroxyl group-containing (meth) acrylates is carried out by reacting the two carboxylic anhydride groups of the aromatic tetracarboxylic dianhydride with the first and second carboxylic anhydride groups. The reaction with the hydroxyl groups each of the two hydroxyl group-containing (meth) acrylates is known per se. For example, the aromatic tetracarboxylic dianhydride and the first and second hydroxyl group-containing (meth) acrylates are mixed in an organic solvent such as cyclohexanone with 1,8-diazabicyclo [5.4.0] -7-. The reaction can be carried out at a temperature of 50 to 120 ° C. in the presence of a catalyst such as undecene. In this case, a polymerization inhibitor such as methoquinone can be added to the reaction system.

After the reaction, the reaction product containing the compound of the formula (D), which is a reaction product, can be purified without purification, for example, the following formula (E):

(Where R ⁰ is a CH ₂ ═C (R ³ ) —C (O) O— group (where R ³ is as defined above) or an R ⁷¹ —O— group (where R ⁷¹ Can be obtained by adding an epoxy group-containing compound as defined above and reacting to obtain the compound represented by the general formula (1).

  Examples of the compound represented by the formula (E) include glycidyl methacrylate, epoxy group-containing (meth) acrylate such as glycidyl acrylate, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, monostyrenated phenol glycidyl ether, Examples include aromatic glycidyl ether compounds such as 4-cyano-4-hydroxybiphenyl glycidyl ether, 4,4′-biphenol monoglycidyl ether, and 4,4′-biphenol diglycidyl ether.

  The reaction between the compound represented by formula (D) and the compound represented by formula (E) is a reaction between the carboxyl group possessed by the compound represented by formula (D) and the epoxy group possessed by the compound represented by formula (E). As such, it is well known in the art. For example, this reaction can be carried out at a temperature of 50 to 120 ° C. in the presence of an amine catalyst such as dimethylbenzylamine.

  The refractive index and hard coat property of the photocurable composition containing the compound (A) represented by the general formula (1) can be appropriately adjusted by the following method.

<Method for adjusting refractive index and hard coat property (1)>
A plurality of compounds (A) represented by the general formula (1) having different numbers of polymerizable unsaturated double bond groups and biphenyl groups in one molecule are separately prepared as a simple substance, and optionally later The refractive index and the hard coat property can be appropriately adjusted by mixing these simple substances at a ratio of In this case, since the mixing ratio of the simple substance can be easily changed, in the sense that it is easy to consider approaching the target physical properties when the target refractive index and hard coat property values are not grasped in advance. Useful for.

<Method for adjusting refractive index and hard coat property (2)>
When the compound of the formula (E) is reacted with the compound of the formula (D) prepared in advance, a plurality of compounds of the formula (E) (for example, R ⁰ is CH ₂ ═C (R ³ ) —C (O) A compound of the formula (E) that is an O-group and a compound in which R ⁰ is an R ⁷¹ -O- group) are mixed and added to react. At this time, the refractive index and the hard coat property can be appropriately adjusted by changing the mixing ratio of the compound of the formula (E). In this case, a mixture of a plurality of types of compounds (A) is obtained in a single reaction. Therefore, this method is very useful in the sense that the preparation process can be shortened compared to the adjustment method (1) when the target refractive index and hard coat property values can be roughly grasped in advance. It is.

In addition, in the compound (A) represented by the general formula (1), the compound in which R ⁷ is a hydrogen atom is a compound of the formula (E) having a number of moles smaller than the number of moles of the carboxyl group of the compound represented by the formula (D). It can obtain by making this compound react.

In the present invention, the photocurable material, if composed of a mixture of a plurality of types of the compound (A), a compound in which at least one contains a biphenyl skeleton of R ⁷ and R ^8, 95 of the total amount of the mixture It is preferable to occupy at least mol%. Similarly, in the compound (A) represented by the general formula (1), the compound in which R ⁷ is a hydrogen atom preferably occupies 5 mol% or less of the total amount of the mixture.

  Since the compound of the general formula (1) having a carboxyl group has alkali developability, it can be suitably used when a hard coat layer is formed by alkali development of an uncured portion after photocuring. Moreover, it can also be used as an aqueous | water-based photocurable high refractive index hard-coat material by neutralizing this carboxyl group and making it water-based. In addition, the compound having a carboxyl group is mixed with a general thermosetting agent, for example, an epoxy type, an isocyanate type, a vinyl ether type, and the like, and is cured by heat to form a photocurable / thermosetting high refractive index hard coat. It can also be used as a material.

  The filler (B) having a refractive index of 1.60 or more is a component that functions to lower the surface resistance value of the hard coat layer or increase the refractive index. When the refractive index of the filler is lower than 1.60, the refractive index is lower than that of the compound (A) represented by the general formula (1), and the function of increasing the refractive index is lost.

  Examples of the filler (B) include metal oxides, metal fluorides, mixtures thereof, and composite compounds, but metal oxides are preferably used because of excellent chemical stability and high conductivity.

Examples of the metal oxide include TiO ₂ (refractive index: 2.3 to 2.7), Y ₂ O ₃ (refractive index: 1.9), La ₂ O ₃ (refractive index: 2.0), ZrO ₂ ( Refractive index: 2.1), Al ₂ O ₃ (refractive index: 1.6), Nb ₂ O ₃ (refractive index: 1.9 to 2.1), In ₂ O ₃ (refractive index: 1.9 to 2.1), Sn ₂ O ₃ (refractive index: 1.9 to 2.1), In—Sn composite oxide (ITO, refractive index: 1.9 to 2.1), ZnO (refractive index: 2. 0 to 2.1), Sb ₂ O ₅ (refractive index: 1.8 to 2.1), CaO (refractive index: 1.75 to 1.90), BaO (refractive index: 1.80 to 1.21). ), Sb—Sn composite oxide (refractive index: 1.70 to 1.90), Sb—Zn composite oxide (refractive index: 1.70 to 1.90), Zn—Al composite oxide (refractive index: 1.80 to 1.21) P-Sn complex oxide (refractive index: 1.70 to 1.90), and the like. Examples of fillers other than metal oxides include calcium carbonate, magnesium carbonate, and aluminum hydroxide. These fillers are used alone or as a mixture of two or more.

  The compounding amount of the compound (A) in the photocurable composition of the present invention is preferably in the range of 6 to 70% by weight based on the total solid content of the photocurable composition, and is 6 to 49. More preferably, it is in the range of% by weight. When the compounding quantity of a compound (A) is outside the said range, the hard coat property of a photocurable composition will become low.

  Moreover, it is preferable that the compounding quantity of a filler (B) exists in the range of 30-80 weight% on the basis of the total amount of solid content of a photocurable composition, and exists in the range of 50-80 weight%. Is more preferable. When the blending amount of the filler (B) is less than 30% by weight, the refractive index of the high refractive index hard coat layer is low, and when it exceeds 80% by weight, the scratch resistance of the high refractive index hard coat layer is low. Lower.

  When the photocurable composition of the present invention is cured by ultraviolet rays, a photopolymerization initiator is added to the composition. In addition, when making it harden | cure by an electron beam, there may not be an initiator.

  The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl A compound etc. can be used.

  Specific examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl- Enetanone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3 ′, 4,4′- Tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethyl-1-propanamine hydrochloride, 4-benzoyl-N, N-dimethyl-N-2- (1-oxo-2-) Propenyloxyethyl) methammonium succinate, 2- / 4-iso-propylthioxanthone 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H thioxanthone-2-yloxy-N, N , N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline, and the like.

  Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2,1,1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1, diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- -(4-morpholinophenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino-propanonyl)- Examples thereof include 9-butylcarbazole.

  Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide, and the like.

  Examples of aminocarbonyl compounds include methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2 -(Dimethylamino) ethyl benzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,5'-bis (4-diethylaminobenzal) cyclopentanone, etc. Is mentioned.

  The photopolymerization initiator is not limited to the above compound, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization by ultraviolet rays. These can be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the usage-amount of a photoinitiator, It is preferable to use within the range of 1-20 weight part with respect to 100 weight part of dry weight of to-be-cured material.

  Moreover, a well-known organic amine etc. can also be added as a sensitizer.

  Furthermore, an initiator for cationic polymerization can be used in combination with the initiator for radical polymerization.

  In addition to the compound (A) represented by the above general formula (1), other binder resins and photocurable components may be added to the photocurable composition of the present invention.

  Examples of the binder resin include polyurethane resin, polyurea resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, melamine resin, polyamide resin, phenol resin, and vinyl resin. Etc. These resins may be added alone, or two or more kinds of resins may be added. The binder resin is preferably blended within a range of 20% by weight or less based on the total amount of the solid content of the photocurable composition.

  As a photocurable component, for example, a compound having a polymerizable unsaturated double bond group such as a (meth) acrylic compound, a fatty acid vinyl compound, an alkyl vinyl ether compound, an α-olefin compound, a vinyl compound, or an ethynyl compound is used. Can do. These compounds having a polymerizable unsaturated double bond group may further have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, or a silanol group. The photocurable component other than the compound (A) is preferably blended within a range of 49% by weight or less, particularly within a range of 6 to 49% by weight, based on the total amount of the solid content of the photocurable composition.

  Examples of the (meth) acrylic compound include benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, a compound having a carboxyl group and a polymerizable unsaturated double bond group, and a hydroxyl group ( Examples include meth) acrylic compounds and nitrogen-containing (meth) acrylic compounds. Moreover, a monofunctional and polyfunctional compound can be used suitably. From the viewpoint of coating film hardness, polyfunctional ones are preferred.

  Specific examples of monofunctional (meth) acrylic compounds include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (Meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl Meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, alkyl (meth) acrylates having 1 to 22 carbon atoms such as docosyl (meth) acrylate. For the purpose of adjusting the polarity, it is preferable to use an alkyl group-containing acrylate having 2 to 10 carbon atoms, more preferably an alkyl group having 2 to 8 carbon atoms, or a corresponding methacrylate. Moreover, when aiming at adjustment of leveling property etc., it is preferable to use the alkyl (meth) acrylate which has a C6 or more alkyl group.

  Moreover, as alkylene glycol type (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, polyethylene glycol mono ( It has a hydroxyl group at the terminal such as (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, and polyoxy Monoacrylate having an alkylene chain or the corresponding monomethacrylate, methoxyethylene glycol (meth) acrylate, methoxydiethyle Glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meta ) Acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxy Tetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol ( ) Acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, etc., having an alkoxy group at the terminal and having a polyoxyalkylene chain or a corresponding monomethacrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, Phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate Polyoxyalkylene-based acrylates having a phenoxy or aryloxy group at the terminal, such as phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenoxytetrapropylene glycol (meth) acrylate, or corresponding methacrylates Can be mentioned.

  Furthermore, examples of the compound having a carboxyl group and a polymerizable unsaturated double bond group include maleic acid, fumaric acid, itaconic acid, citraconic acid, alkyl or alkenyl monoesters thereof, and phthalic acid β- (meth) acryloxy. Examples include ethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid.

  Examples of hydroxyl group-containing (meth) acrylic compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene. , 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like.

Nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- ( Monoalkylol (meth) acrylamide such as (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N- Methoxymethyl (meth) acrylamide, N, N-di (methylol) acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethyl meta Acrylic net N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide and other acrylamide-based unsaturated compounds such as dialkyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, Unsaturated compounds having a dialkylamino group such as diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene and the like, such as Cl ⁻ , Br ⁻ and I ⁻ And quaternary ammonium salts of dialkylamino group-containing unsaturated compounds having a halogen ion or QSO3- (Q: an alkyl group having 1 to 12 carbon atoms).

  Furthermore, as other unsaturated compounds, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl ( Perfluoro having 1 to 20 carbon atoms such as (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate Perfluoroalkyl (meth) acrylates having an alkyl group can be exemplified.

  In addition, perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and perfluoroalkyl group-containing vinyl monomers such as alkylene, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) Examples thereof include alkoxysilyl group-containing vinyl compounds such as silane, vinyltriethoxysilane, and γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof, and glycidyl group-containing acrylates such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate.

  Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate.

  Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.

  Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.

  Examples of the vinyl compound include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, and the like. It is done.

  Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like.

  These can be used alone or in combination of two or more.

  Further, the photocurable composition of the present invention includes a solvent, a dye, an antioxidant, a polymerization inhibitor, a leveling agent, a moisturizer, a viscosity modifier, an antiseptic, an antibacterial agent, an antiblocking agent, an ultraviolet absorber, an infrared ray. An absorbent or the like may be added.

  When adding a solvent, the curing process may be performed after the solvent is volatilized. As the solvent, various known organic solvents can be used. Examples of the organic solvent include cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methyl propylene glycol acetate, methanol, ethanol, isopropyl alcohol, butanol, tetrahydrofuran, methyl pyrrolidone, and the like.

  Next, the antireflection film of the present invention will be described.

  The antireflection film of the present invention has a high refractive index hard coat layer formed from the photocurable composition of the present invention on one surface of a plastic substrate and a low refractive index of 1.20 to 1.50. The refractive index layer is sequentially laminated, and the high refractive index hard coat layer is coated on the plastic substrate so that the film thickness is 0.1 to 30 μm on the plastic substrate, It can be formed by curing treatment.

  As a coating method, a known method can be used. For example, a method using a rod or a wire bar, or various coating methods such as a micro gravure, a gravure, a die, a curtain, a lip, or a slot can be used.

  Moreover, a hardening process can be performed by irradiating active energy rays, such as an ultraviolet-ray, an electron beam, and visible light with a wavelength of 400-500 nm, using a well-known technique. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet rays and visible light having a wavelength of 400 to 500 nm. As the electron beam source, a thermionic emission gun, an electrolytic emission gun, or the like can be used.

  The active energy dose to be irradiated is preferably in the range of 5 to 2000 mJ, and more preferably in the range of 50 to 1000 mJ from the viewpoint of easy management in the process.

  In addition, these active energy ray irradiations can be used in combination with heat treatment by infrared rays, far infrared rays, hot air, high frequency heating or the like.

  The high refractive index hard coat layer may be formed by applying a photo-curable composition to a plastic substrate and performing natural or forced drying followed by a curing treatment, or after coating and curing treatment. Although natural or forced drying may be performed, it is more preferable to perform the curing treatment after natural or forced drying.

  In particular, when curing with an electron beam, it is more preferable to perform the curing treatment after natural or forced drying in order to prevent the inhibition of curing by water or the decrease in strength of the coating film due to the remaining organic solvent.

  Moreover, the timing of a hardening process may be simultaneous with coating, and may be after coating.

  As the plastic substrate, a polyester-based, acrylic-based, triacetate-based or the like can be used, but it is preferable to use a polyester-based substrate from the viewpoint of strength and refractive index. Examples of the polyester base material include polyethylene terephthalate (PET, refractive index: 1.60 to 1.67), polyethylene naphthalate (PEN, refractive index: 1.68 to 1.72), and the like.

  The plastic substrate may be subjected to pretreatment such as corona treatment or plasma treatment. By performing the pretreatment, the adhesion of the hard coat layer to the plastic substrate is improved.

  The refractive index of the high refractive index hard coat layer is preferably such that the difference in refractive index from the substrate is in the range of less than 0.01, since the occurrence of interference fringes can be suppressed. For example, when a polyester-based substrate is used as the plastic substrate, the occurrence of interference fringes can be suppressed when the refractive index of the high refractive index hard coat layer is in the range of 1.60 to 1.75. preferable.

  The pencil hardness of the high refractive index hard coat layer is preferably 2H or more in order to protect the plastic substrate.

The low refractive index layer laminated on the high refractive index hard coat layer includes a low refractive index MgF ₂ (refractive index: about 1.4), SiO ₂ (refractive index: about 1.2 to 1.5). LiF (refractive index: about 1.4), 3NaF.AlF ₃ (refractive index: about 1.4), Na ₃ AlF ₆ (refractive index: about 1.33), and the like can be used. In addition, although fine particles such as MgF ₂ and SiO ₂ dispersed in ultraviolet and electron beam curable resins or silicon alkoxide matrices can be used, the present invention is not limited to this.

  When the low refractive index layer is formed of the matrix containing the low refractive fine particles, the low refractive index fine particles are coated so that the film thickness is 0.01 to 1 μm, and if necessary, a drying treatment, It can be formed by performing ultraviolet irradiation treatment or electron beam irradiation treatment.

  As a coating method, a known method can be used. For example, a method using a rod or a wire bar, or various coating methods such as a micro gravure, a gravure, a die, a curtain, a lip, or a slot can be used.

  Further, the low refractive index layer may be formed using a vacuum deposition method, a sputtering method, a reactive sputtering method, an ion plating method, an electroplating method, or the like.

  In the antireflection film of the present invention, not only one low refractive index layer but also a plurality of layers having different refractive indexes may be laminated. Examples include, but are not limited to, a structure in which a low refractive index layer, a high refractive index layer having a higher refractive index than the low refractive index layer, and a low refractive index layer are provided on the high refractive index hard coat layer. is not.

  Moreover, you may provide another functional layer in the antireflection film of this invention. Examples of the functional layer include a contamination prevention layer, an antistatic layer, an electromagnetic wave shielding layer, a neon light correction layer, and an infrared cut layer. These functional layers can be formed by a known method using a known material. In addition, the functional layer may have a plurality of functions in one layer.

  When the antireflection film of the present invention is used for display applications, the antifouling layer is preferably provided on the antireflection layer on the surface side.

  In addition, when the antireflection film of the present invention is used for plasma display applications, it is preferable to provide one or all of an electromagnetic wave shielding layer, a neon light correction layer, and an infrared cut layer, and may be provided anywhere. When visibility etc. are considered, it is preferable to provide in the opposite side to the side which provided the antireflection layer of the base material.

  Hereinafter, the present invention will be described in detail with reference to production examples and examples, but the present invention is not limited thereto. In the following production examples and examples, “parts” means “parts by weight” unless otherwise specified.

<Production Example 1: Production of photocurable compound (a)>
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, gas inlet tube, and dropping funnel,
525 parts of biphenyltetracarboxylic dianhydride,
475 parts β-hydroxyethyl acrylate,
1,8-diazabicyclo [5.4.0] -7-undecene 10 parts,
0.25 parts of methoquinone,
111 parts of cyclohexanone was charged, the temperature was gradually raised while stirring, and the reaction was carried out at 90 ° C. in a dry air atmosphere. During the reaction, stirring was continued while a total of 889 parts of cyclohexanone was appropriately diluted according to the viscosity. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 ⁻¹ cm and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 215 mgKOH / g.

Subsequently, in this solution,
164 parts of glycidyl methacrylate,
607 parts of o-phenylphenol glycidyl ether (“OPP-G” manufactured by Sanko Co., Ltd.)
13 parts of dimethylbenzylamine was added, the temperature was gradually raised, and the reaction was carried out at 90 degrees in the presence of dry air. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 10 mgKOH / g or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained photocurable compound (a) is 5 mgKOH / g, the average number of biphenyl skeletons in one molecule is 1.70, and the number per polymerizable unsaturated double bond group. The average molecular weight was 264, and the average number of polymerizable unsaturated double bond groups in one molecule was 3.30. Moreover, the molar ratio of the biphenyl group and the methacryl group in the obtained reaction product was 0.7: 0.3.

<Production Example 2: Production of photocurable compound (b)>
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, gas inlet tube, and dropping funnel,
525 parts of biphenyltetracarboxylic dianhydride,
475 parts β-hydroxyethyl acrylate,
1,8-diazabicyclo [5.4.0] -7-undecene 10 parts,
0.25 parts of methoquinone,
111 parts of cyclohexanone was charged, the temperature was gradually raised while stirring, and the reaction was performed at 90 degrees in a dry air atmosphere. During the reaction, stirring was continued while a total of 889 parts of cyclohexanone was appropriately diluted according to the viscosity. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 215 mgKOH / g.

Subsequently, 382 parts of glycidyl methacrylate in this solution,
260 parts of o-phenylphenol glycidyl ether (“OPP-G” manufactured by Sanko Co., Ltd.)
13 parts of dimethylbenzylamine was added, the temperature was gradually raised, and the reaction was carried out at 90 degrees in the presence of dry air. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 10 mgKOH / g or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained photocurable compound (b) is 6 mgKOH / g, the number of biphenyl skeletons in one molecule is 1.30 on average, and the number per polymerizable unsaturated double bond group The average molecular weight was 226, and the average number of polymerizable unsaturated double bond groups in one molecule was 3.70. Moreover, the molar ratio of the biphenyl group and the methacryl group in the obtained reaction product was 0.3: 0.7.

<Production Example 3: Production of photocurable compound (c)>
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, gas inlet tube, and dropping funnel,
525 parts of biphenyltetracarboxylic dianhydride,
475 parts β-hydroxyethyl acrylate,
1,8-diazabicyclo [5.4.0] -7-undecene 10 parts,
0.25 parts of methoquinone,
111 parts of cyclohexanone was charged, the temperature was gradually raised while stirring, and the reaction was performed at 90 degrees in a dry air atmosphere. During the reaction, stirring was continued while a total of 889 parts of cyclohexanone was appropriately diluted according to the viscosity. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 215 mgKOH / g.

Subsequently, 463 parts of glycidyl methacrylate in this solution,
130 parts of o-phenylphenol glycidyl ether (“OPP-G” manufactured by Sanko Co., Ltd.)
13 parts of dimethylbenzylamine was added, the temperature was gradually raised, and the reaction was carried out at 90 degrees in the presence of dry air. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 10 mgKOH / g or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained photocurable compound (c) is 4 mgKOH / g, the number of biphenyl skeletons in one molecule is 1.15 on average, and the number per polymerizable unsaturated double bond group The average molecular weight was 203, and the average number of polymerizable unsaturated double bond groups in one molecule was 3.85. Moreover, the molar ratio of the biphenyl group and the methacryl group in the obtained reaction product was 0.15: 0.85.

<Production Example 4: Production of photocurable compound (d)>
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, gas inlet tube, and dropping funnel,
525 parts of biphenyltetracarboxylic dianhydride,
475 parts β-hydroxyethyl acrylate,
1,8-diazabicyclo [5.4.0] -7-undecene 10 parts,
Metoquinone (0.25 part) and cyclohexanone (111 parts) were charged, gradually heated while stirring, and reacted at 90 degrees in a dry air atmosphere. During the reaction, stirring was continued while a total of 889 parts of cyclohexanone was appropriately diluted according to the viscosity. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 215 mgKOH / g.

Subsequently, 767 parts of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.) and 14 parts of dimethylbenzylamine are added to this solution, and the temperature is gradually raised, and the reaction is carried out at 90 degrees in the presence of dry air. It was. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 10 mgKOH / g or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained photocurable compound (d) is 5 mgKOH / g, the number of biphenyl skeletons in one molecule is 1.00 on average, and the number per polymerizable unsaturated double bond group The average molecular weight was 246, and the average number of polymerizable unsaturated double bond groups in one molecule was 4.00.

Examples 1-5, Comparative Examples 1-3
Using the photocurable compounds (a) to (d) prepared in Production Examples 1 to 5, a photocurable composition having the composition shown in Table 1 was prepared, and the film thickness of the PET film having a thickness of 50 μm was measured with a bar coder. After coating to 4 μm, 400 mJ ultraviolet rays were irradiated with a metal halide lamp to form a high refractive index hard coat layer. The obtained high refractive index hard coat layer was evaluated for light resistance, refractive index, scratch resistance, pencil hardness and surface resistance by the following methods. The results are shown in Table 1.

In addition, the following low refractive index layer coating solution is applied on the high refractive index hard coat layer using a wire bar so that the cured coating thickness is about 0.1 μm, and then a 400 mJ ultraviolet ray is applied with a metal halide lamp. , And a low refractive index layer was laminated to produce an antireflection film. About the obtained anti-reflective film, the following method evaluated the presence or absence of an interference fringe. The results are shown in Table 1.

In Table 1,
Benzyl methacrylate: “Light Ester BZ” manufactured by Kyoeisha Chemical Co., Ltd.
Phenol EO-modified acrylate: “Aronix M102” manufactured by Toagosei Co., Ltd.
Hydroxyphenoxypropyl acrylate: “Kayarad R128H” manufactured by Nippon Kayaku Co., Ltd.
MIBK: methyl isobutyl ketone antimony pentoxide dispersion: antimony pentoxide MIBK dispersion, solid content 30% by weight
Photopolymerization initiator: “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.
<Coating liquid for low refractive index layer>
10 parts of pentaerythritol tetraacrylate (“PET-30” manufactured by Nippon Kayaku Co., Ltd.) are dissolved in 200 parts of isopropyl alcohol, and 0.8 parts of photopolymerization initiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) And stirred until dissolved. Stir 44 parts of silica sol (refractive index 1.3, ethanol solvent, solid content 15% by weight), add the total amount of the pentaerythritol tetraacrylate solution prepared above, stir until uniform, low refractive index layer A coating solution was obtained.

(1) Light resistance Yellowing over time during continuous light irradiation is very undesirable for application development. Therefore, yellowing during continuous light irradiation was confirmed.

First, the coated material was exposed for 24 hours with a light resistance tester (light source: xenon lamp, illuminance: 100 W / cm ² , black panel temperature: 60 ° C., 60% RH). Thereafter, the coated material was placed on white paper, and coloring was measured using a colorimeter (Minolta CR-300). The colorimetric value was displayed as Lab *, and the standard of yellowing was judged by the b value. The smaller the b value, the smaller the degree of yellowing and the better the light resistance. In consideration of practical required physical properties, those having a b value of less than 3.5
X 3.5 or more
It was determined.

(2) Refractive index The refractive index of the coated material was measured using an Abbe refractometer (Atago Co., Ltd.).

(3) Scratch resistance The coated material was set on a seismic vibration test machine, and steel wool No. Using 0000, it was shaken 10 times with a load of 250 g. About the taken-out coating material, the cracking degree was visually judged in the following five steps. The larger the value, the better the scratch resistance.

5 ... No scratches 4 ... Slightly scratched 3 ... Scratches are attached, but the base material is not visible 2 ... Scratches are present and some of the coated material is peeled off 1 ... Coated (4) Pencil hardness Using a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON), variously changing the hardness of the pencil core, and 5 times at a load of 500 g Tested. The hardness of the core when the scratch was not scratched or scratched only once out of 5 times was defined as the pencil hardness of the coated material. In consideration of practical required physical properties, a pencil with a hardness of 2H or more ○
X lower than 2H
It was determined.

(5) Interference fringes The surface of the antireflection film on which the high refractive index hard coat layer was not formed was roughened with sandpaper, and the back surface was subjected to antireflection treatment. The obtained sample was visually observed from the distance of 20 cm closest to the 20 W fluorescent lamp, and the presence or absence of interference fringes was evaluated.

  As is clear from the evaluation results in Table 1, the high refractive index hard coat layer formed from the photocurable composition of the present invention has a high refractive index of 1.64 or more, pencil hardness, scratch resistance, Excellent light resistance. As a result, the photocurable composition of the present invention has all of high refractive index, hard hardness such as pencil hardness and scratch resistance, and light resistance, which could not be achieved by materials that have been studied conventionally. It is shown that. As can be seen from the results shown in Table 1, the refractive index does not reach the required level unless a filler is added to the photocurable compound. Moreover, in the composition which does not contain a photocurable compound and consists of microparticles | fine-particles and another resin, a coating film becomes brittle and abrasion resistance and pencil hardness do not reach a required level.

  As described above, according to the present invention, a photocurable composition having all of high refractive index, excellent hard coat properties, and light resistance can be provided. Moreover, according to the present invention, an antireflection film having excellent hard coat properties and light resistance and having good optical properties can be provided.

Claims (12)

General formula (1):

(Wherein R ^{1 to} R ³ each independently represents a hydrogen atom or a methyl group, and R ^{4 to} R ⁶ each independently represents an unsubstituted or substituted linear or branched alkylene group. R ⁷ represents hydrogen or a monovalent organic group, R ⁸ represents a tetravalent aromatic group, provided that at least one of R ⁷ and R ⁸ includes a biphenyl skeleton. A photocurable composition comprising a photocurable material containing at least one compound (A) and a filler (B) having a refractive index of 1.60 or more. The composition of claim 1, wherein both R ⁷ and R ⁸ comprise a biphenyl skeleton. The composition according to claim 1, wherein R ^{4 to} R ⁶ are unsubstituted or substituted alkylene groups having an alkylene moiety having 1 to 8 carbon atoms. The composition according to claim 3, wherein R ⁶ is a β-hydroxyalkylene group. R ⁷ has the formula:
—R ⁶ —OC (O) —C (R ³ ) ═CH ₂
(Wherein R ⁶ and R ³ are as defined in general formula (1)) or are represented by the formula —CH ₂ —C (OH) CH ₂ —O—R ⁷¹ (where , R ⁷¹ is a substituted or unsubstituted biphenyl). 6. The group according to claim 5, wherein R ⁷ is a group represented by the formula: —CH ₂ —C (OH) CH ₂ —O—R ^71, wherein R ⁷¹ is substituted or unsubstituted biphenyl. Composition. The composition according to claim 5, wherein R ⁸ is benzene, benzophenone, biphenyl, phenyl ether, diphenyl sulfone, diphenyl sulfide, perylene, or naphthalene. ^8. A composition according to claim 7, wherein R8 is biphenyl. Filler (B) is a metal oxide, The photocurable composition of any one of Claims 1-8. A high refractive index hard coat layer formed from the photocurable composition according to claim 1 and a low refractive index layer having a refractive index of 1.20 to 1.50 are sequentially laminated on one surface of a plastic substrate. Antireflection film. The antireflection film according to claim 10, wherein the refractive index of the high refractive index hard coat layer is in the range of 1.60 to 1.75. The antireflection film according to claim 10, wherein the pencil hardness of the high refractive index hard coat layer is 2H or more.