WO2005105866A1

WO2005105866A1 - Photocurable composition and antireflective film using same

Info

Publication number: WO2005105866A1
Application number: PCT/JP2005/008181
Authority: WO
Inventors: Shoichi Mochizuki; Hiroshi Tominaga; Kazunori Shigemori; Nozomu Hatano; Hideki Ochiai; Yukio Amano
Original assignee: Toyo Ink Mfg. Co., Ltd.; Toppan Printing Co., Ltd.
Priority date: 2004-04-28
Filing date: 2005-04-28
Publication date: 2005-11-10
Also published as: TW200540446A; CN100455607C; JPWO2005105866A1; CN1938344A; KR20070001184A

Abstract

Disclosed is a photocurable composition containing a photocurable material including at least one compound (A) represented by the general formula (1) below and a filler (B) having a refractive index of not less than 1.60. (1) (In the formula, R1-R3 independently represent a hydrogen atom or a methyl group; R4-R6 independently represent an unsubstituted or substituted, straight or branched chain alkylene group; R7 represents hydrogen or a monovalent organic group; and R8 represents a tetravalent aromatic group. In this connection, at least one of R7 and R8 contains a biphenyl skeleton.) Also disclosed is an antireflective film wherein a high-refractive-index hard coat layer composed of such a photocurable composition and a low-refractive-index layer having a refractive index of 1.20-1.50 are sequentially arranged on one side of a plastic base.

Description

Specification

Photocurable composition and antireflection film using the same

Technical field

The present invention relates to a photocurable composition having both a high refractive index, hard coat properties such as pencil hardness and scratch resistance, and also having excellent light resistance.

[0002] The present invention also aims at protecting the surfaces of display devices such as word processors, computers, and televisions, for example, plasma display devices, CRT display devices, liquid crystal display devices, projection display devices, and EL display devices. It relates to the antireflection film used.

Background art

[0003] In recent years, the advancement of high refractive index plastic materials into optical devices has been actively studied as antireflection films for various display devices.

[0004] In addition to a high refractive index, a high refractive index material used for an antireflection film needs to have hard coat properties such as pencil hardness and scratch resistance, transparency, low specific gravity, light resistance, and the like. Various materials are being considered.

[0005] For example, as a material having a high refractive index, a compound having two (meth) acrylates and a biphenyl skeleton has been disclosed. This is because the biphenyl skeleton-derived force has a high refractive index. Since two (meth) acrylates are not present in the molecule, the probability of incorporation into the polymerization system during light irradiation is low. Has the disadvantage that the hard coat property tends to decrease, and even when efficiently incorporated into the polymerization system at the time of light irradiation, the adhesiveness to the substrate, which undergoes severe volume shrinkage during photocuring, deteriorates. There were drawbacks.

[0006] In order to improve such disadvantages, studies have been made to increase the distance between the biphenyl skeleton and the (meth) acrylate in the molecule. However, although the hard coat property such as pencil hardness is improved, the system However, the concentration of the biphenyl skeleton in the inside was reduced, and a sufficient refractive index could not be obtained! Further, as another method, when another photopolymerizable material is used in combination, similarly, the concentration of the biphenyl skeleton in the system decreases, and as a result, a sufficient refractive index cannot be obtained. Atsushi. (Column 2003-64025, Column 2003-64026) As described above, with the conventional technology, a photocurable material having both high refractive index, high pencil hardness, hard coat properties such as scratch resistance, and light resistance was not obtained!

Disclosure of the invention

[0007] An object of the present invention is to provide a photocurable composition having high refractive index, excellent hard coat properties, and light resistance.

[0008] Another object of the present invention is to provide an antireflection film having both excellent hard coat properties and light resistance, and having good optical characteristics.

[0009] According to a first aspect of the present invention, a photocurable material containing a compound (A) represented by the following general formula (1) and a filler (B) having a refractive index of 1.60 or more are included. A photocurable composition is provided.

[0010] General formula (1):

[Chemical 1]

(Wherein, R ¹ to! T each independently represent a hydrogen atom or a methyl group, and R ^{4 to} R ⁶ each independently represent an unsubstituted or substituted, linear or branched chain; 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 has a biphenyl skeleton including.)

In the photocurable composition of the present invention, both R ⁷ and R ⁸ in the general formula (1) -It is preferable to include a skeleton.

[0012] 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 on one surface of a plastic substrate by the photocurable composition according to the first aspect of the present invention, and a refractive index 1.20 to: Provided is an antireflection film in which low refractive index layers having L50 are sequentially laminated.

In the antireflection film of the present invention, the high refractive index hard coat layer has a refractive index of 1.60 to

The pencil hardness of the high refractive index hard coat layer, which is preferably within the range of 1.75, is preferably 2H or more.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] First, the photocurable composition of the present invention will be described.

[0016] 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. I do.

[0017] The compound (A) represented by the general formula (1) is a component that imparts a high refractive index and excellent hard coat properties. When no halogen atom is contained, the yellowing and the like are extremely low. It has excellent light fastness. In particular, among the compounds (A) represented by the above general formula (1), those having a number average molecular weight of more than 300 per polymerizable unsaturated double bond group have excellent node coatability. Therefore, it is preferable.

In the general formula (1), R ¹ ! ^ Are each independently a hydrogen atom or a methyl group

R ^{4 to} R ⁶ each independently represent an unsubstituted or substituted, linear or branched alkylene group. The substituents that the alkylene group may optionally have include an aromatic-containing group (eg, a phenoxy group), a halogen atom, and a hydroxyl group. Preferably, the alkylene group has 1 to 8 carbon atoms. R ⁶ typically have one hydroxyl group as a substituent, the hydroxyl groups are usually of Ashiru groups R ⁶ are attached - are attached to j8-position carbon relative O group.

[0020] R ⁷ represents hydrogen or a monovalent organic group. The latter organic group has the formula:

R ⁶ — OC (O) — C (R ³ ) = CH (Where R ⁶ and R ³ are groups defined by the general formula (1)) or the formula —CH—C (OH) CH—O—R ⁷¹ (where , ^R71 is a substituted or unsubstituted biphenyl

-Is a group represented by the formula: Examples of the substituents that the biphenyl may optionally have include a hydroxyl group, a cyano group and a bur group.

R ⁸ is a tetravalent aromatic group. Examples of aromatic groups include benzene, benzophenone, biphenylene, phenyl ether, diphenylsulfone, diphenylsulfide, perylene, and naphthalene.

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

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

[Formula 2]

(Where R ⁸ is as defined in the general formula (1)) with an aromatic tetracarboxylic dianhydride represented by the following formula (B):

CH = C (R ¹ ) COOR ⁴ OH

2

(Where R ¹ and R ⁴ are as defined in the general formula (1)) and a first hydroxyl group-containing (meth) acrylate which has the following formula (C):

CH = C (R ² ) COOR ⁵ OH

2

(Where R ² and R ⁵ are as defined in general formula (1)) and reacted with a second hydroxyl-containing (meth) atalylate of formula (D):

[Formula 3]

[0025] (where,

R ⁵ and R ⁸ are as defined in general formula (1)).

Examples of the aromatic tetracarboxylic dianhydride represented by the formula (A) include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, oxydiphthalic acid Acid dianhydride, diphenylsulfonetetracarboxylic dianhydride, diphenylsulfidetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride. Of these aromatic tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydride has a biphenyl skeleton, and can efficiently introduce a biphenyl skeleton into the molecule of compound (A). It is particularly preferable to make the refractive index of the compound (A) 1.57 or more.

[0027] The first and second hydroxyl group-containing (meth) atalylates may be the same or different. Examples of such hydroxyl-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-phenoxy Contains cypropyl methacrylate.

[0028] The reaction between the aromatic tetracarboxylic dianhydride and the first and second hydroxyl group-containing (meth) acrylates is performed by reacting the two carboxylic anhydride groups of the aromatic tetracarboxylic dianhydride with The reaction with the hydroxyl groups of the first and second hydroxyl-containing (meth) acrylates, respectively, which is well known in the art. For example , An aromatic tetracarboxylic dianhydride and first and second hydroxyl group-containing (meth) acrylates in an organic solvent such as cyclohexanone in 1,8 diazabicyclo [5.4.0]-7 The reaction can be performed at a temperature of 50 to 120 ° C. in the presence of a catalyst such as dendecene. In this case, a polymerization inhibitor such as methoquinone can be added to the reaction system.

[0029] After the above reaction, the reaction mixture containing the compound of the formula (D), which is a reaction product, is purified without purifying it. For example, the following formula (E):

[Formula 4]

R ° — CH ₂ — CH-CH ₂

\ / ²

0

(Where R. is a CHCC (R ³ ) —C (0) 0—group (where R ³ is as defined above) or

2

R ⁷¹ - 0- group (wherein, R ⁷¹ is defined above the street) can be obtained an epoxy group-containing I匕合product is then added Caro, a compound represented by reacting the general formula (1) .

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

[0032] The reaction between the compound represented by the formula (D) and the compound represented by the formula (E) is based on the carboxyl group possessed by the compound represented by the formula (D) and the epoxy group possessed by the compound represented by the formula (E) And is itself well known in the art. For example, this reaction can be performed at a temperature of 50 to 120 ° C. in the presence of an amine catalyst such as dimethylbenzylamine.

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

<Method of Adjusting Refractive Index and Hard Coatability (1)> In advance, 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 single substance. By mixing these simple substances at an arbitrary ratio, the refractive index and the node coat property can be appropriately adjusted. In this case, since the mixing ratio of the simple substance can be easily changed, if the value of the target refractive index and the value of the node coat property cannot be grasped in advance, a study for approaching the target physical properties is performed. Very useful in a sense.

When reacting the compound of the formula (E) with the compound of the formula (D) prepared in advance, a plurality of compounds of the formula (E) (for example, R is CH = C (R ³ ) —C (0) 0— A compound of formula (E)

2

Is a R ⁷¹ —O— group), 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-step reaction. Therefore, this method is very useful in the sense that the production process can be shortened compared to the above-mentioned adjustment method (1) when the target refractive index and the value of the coating property can be roughly grasped in advance. It is.

Further, in the compound (A) represented by the general formula (1), the compound in which R ⁷ is a hydrogen atom has a smaller! /, Less than the number of moles of the carboxyl group of the compound represented by the formula (D) The reaction can be performed by reacting a number of formulas (E).

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

[0038] The compound of the general formula (1) having a carboxyl group has alkali developability, and thus can be suitably used when an uncured portion is alkali-developed after photocuring to form a hard coat layer. Further, by neutralizing this carboxyl group and making it aqueous-based, it can be used as an aqueous photocurable high refractive index hard coat material. The compound having a carboxyl group may be a general thermosetting agent, for example, an epoxy or isocyanate. By mixing and heat-curing with a terpolymer, vinyl ether or the like, it can also be used as a photo-curable and thermo-curable high refractive index node coat material.

[0039] The filler (B) having a refractive index of 1.60 or more is a component that functions to lower the surface resistance of the hard coat layer and 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 effect of increasing the refractive index is lost.

[0040] Examples of the filler (B) include metal oxides, metal fluorides, mixtures thereof, and composite compounds. Metal oxides are preferably used because of their excellent chemical stability and high conductivity. Used.

As metal oxides, TiO (refractive index: 2.3 to 2.7), Y O (refractive index: 1.9), La O (

2 2 3 2 3 Refractive index: 2.0), ZrO (refractive index: 2.1), A10 (refractive index: 1.6), NbO (refractive index: 1.9)

2 2 3 2 3

~ 2.1), Ιη Ο (refractive index: 1.9 to 2.1), SnO (refractive index: 1.9 to 2.1), 111 311 composite

2 3 2 3

Oxide (ITO, refractive index: 1.9 to 2.1), {η} (refractive index: 2.0 to 2.1), SbO (refractive index:

twenty five

1.8 to 2.1), CaO (refractive index: 1.75 to: L90), BaO (refractive index: 1.80 to: L21), Sb—Sn composite oxide (refractive index: 1.70 ~: L90), Sb-Zn composite oxide (refractive index: 1.70 ~: L90), Zn-A1 composite oxide (refractive index: 1.80 ~: L.21), P-Sn composite oxide (Refractive index: 1.70 to: L 90). In addition, examples of the filter other than the metal oxide film include calcium carbonate, magnesium carbonate, aluminum hydroxide and the like. These fillers are used alone or as a mixture of two or more.

[0042] 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. More preferably, it is in the range of 6 to 49% by weight. When the compounding amount of the compound (A) is out of the above range, the hard coat property of the photocurable composition becomes low.

The amount of the filler (B) is preferably in the range of 30 to 80% by weight, and more preferably in the range of 50 to 80% by weight, based on the total solid content of the photocurable composition. More preferably, it is within. When the amount of the filler (B) is less than 30% by weight, the refractive index of the high-refractive-index hard coat layer is low. When the amount exceeds 80% by weight, the scratch resistance of the high-refractive-index hard coat layer is reduced. Becomes lower. [0044] When the photocurable composition of the present invention is cured by ultraviolet rays, a photopolymerization initiator is added to the composition. When curing with an electron beam, an initiator may not be necessary.

The photopolymerization initiator is not particularly limited as long as it has a function of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine Oxide compounds, aminocarboniyl conjugates and the like can be used.

[0046] Specifically, examples of the monocarbol compound include benzophenone, 4-methyl-benzophenone, 2,4,6 trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, and 4- (4- Methylphenylthio) fu-luenetanone, 3,3'-dimethyl-1-methoxybenzophenone, 4- (1,3-atalyloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3 , 3 ', 4, 4'-tetra (t-butylperoxycarbol) benzophenone, 4-benzoyl N, N, N trimethyl 1-propanamine hydrochloride, 4-benzoyl N, N dimethyl N-2- (1-oxo 2 —Pro-Loxoshetyl) meta-ammonium oxalate, 2— Z4 isopropylthioxanthone, 2,4 getyl thioxanthone, 2,4 dichloromouth thioxanthone, 1 chloro-4b mouth Thioxanthone, 2-hydroxy-3- (3,4 dimethyl-9-oxo 9Hthioxanthone-2-yloxy-N, N, N trimethyl-1-propanamine hydrochloride, benzoylmethylene 3-methylnaphtho (1,2-d) thiazoline and the like Can be

[0047] Examples of the dicarbon compounds include 1,7,7 trimethyl-1-bicyclo [2,1,1] heptane-1,2,3-dione, benzyl, 2-ethylanthraquinone, 9,10 phenanthrenequinone, methyl ( X-oxobenzene acetate, 4-phenylbenzoyl and the like.

[0048] Examples of the acetophenone compound include 2-hydroxy-1-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) 2-hydroxy-12-methyl-1-phenyl-1-on , 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxy-1-cyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-styrylpropane Product, ethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane 1one, 2,2 diethoxy-1,2 diphenylethane 1one, 2-methyl-1 [4- (methyl Chichio)) Fuhue-Lulu]] —— 22——Momorlhoholinolinopropropanapan——11 Onon, 22—Bevendidylyl—22—Didimeticityl Aluminimi Non—11—— ((44 Momorulhoholinolinofue-elu)) Butatan 11-11—Onon, 11—22,11,22 Propolopanpandione——22—— ((oo ethoxyethoxy) 33, 66 Bibiss ((22-Memethytyl--22 momollufoholino-no-propropapano-no-rulu)) 99 Bubutyril luka-karlubazozzolulu and the like. I'm terrified. .

[0049] As the compound of bevenzozoinine eateller, bebenzozoinine, bevenzozoinmemethyirurate ether, bevenzozoinein Tetyl-leuate ether, bebenzozoininisosopprolopipirulateatel, bebenzozoininisosobbutytylate

[0050] Examples of the acylphosphinoxide compound include 2,4,6 trimethylbenzoyldiphenylphosphinoxide, 4-n-propylphenyl-l- (2,6 dichlorobenzoyl) phosphinoxide and the like. .

[0051] Examples of the aminocarbon compounds include methyl-4 (dimethylamino) benzoate, ethyl-4 (dimethylamino) benzoate 2-n-butoxyshethyl-4 (dimethylamino) benzoate, isoamyl-4 (dimethylamino) benzoate, and 2- (dimethylamino) ethyl. Lebenzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-ethylethylaminobenzophenone, 2,5'-bis (4 ethylaminobenzal) cyclopentanone, etc. .

[0052] The photopolymerization initiator is not limited to the above compounds, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization by ultraviolet light. These can be used alone or in combination of two or more.

[0053] The amount of the photopolymerization initiator used is not particularly limited, but is preferably in the range of 1 to 20 parts by weight based on 100 parts by weight of the dry weight of the object to be cured.

[0054] In addition, a known organic amine or the like can be added as a sensitizer.

[0055] In addition to the radical polymerization initiator, an initiator for cationic polymerization may be used in combination.

The photocurable composition of the present invention may contain other binder resin and photocurable component in addition to the compound (A) represented by the general formula (1).

[0057] Examples of the noinder resin include polyurethane resin, polyurethane resin, polyurethane rare resin, polyester resin, polyether resin, polycarbonate resin, and epoxy resin. Fat, amino resin, styrene resin, acrylic resin, melamine resin, polyamide resin, phenol resin, bur resin, and the like. These resins may be added alone or a plurality of two or more kinds of resins may be added. The noinder resin is preferably blended in a range of 20% by weight or less based on the total amount of the solid content of the photocurable composition.

As the photocurable component, for example, a polymerizable unsaturated double bond group such as a (meth) acrylic compound, a fatty acid vinyl compound, an alkyl vinyl ether compound, an a-olefin compound, a vinyl compound, and an ethynyl compound is used. Can be used. 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 and a silanol group. The photocurable component other than the compound (A) is preferably blended in an amount of 49% by weight or less, particularly 6 to 49% by weight, based on the total solid content of the photocurable composition.

[0059] The (meth) acrylic compound includes benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, a carboxyl group and a polymerizable unsaturated double bond group. Compounds, hydroxyl-containing (meth) acrylic compounds, and nitrogen-containing (meth) acrylic compounds. In addition, monofunctional or polyfunctional compounds can be appropriately used. From the viewpoint of coating film hardness, polyfunctional ones are preferred.

[0060] Specific examples of monofunctional (meth) acrylic compounds include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , Butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meta) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, Knol (meth) acrylate, decyl (meth) acrylate, pentadecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate Rate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meta) Tarireto, nonadecyl (meth) Atari rate, Ikoshiru (meth) Atari rate, Henikoshiru (meth) Atari rate, alkyl (meth) Atari rate 1 to 22 carbon atoms such as docosyl (meth) § click Relate. When the purpose is to control the polarity, it is preferable to use an alkyl group-containing acrylate having a C 2 to C 10, more preferably C 2 to C 8 alkyl group, or a corresponding methacrylate. Yes. For the purpose of controlling the leveling property, it is preferable to use an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms.

Examples of the alkylene glycol-based (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and hexaethylene glycol mono (meth) acrylate. Rate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) Monoatarylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain, such as acrylate, or the corresponding monomethacrylate, methoxyethylene glycol (meth) acrylate, or methoxydiethylene. Glycol (meth) atalylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n— Butoxytetraethylene glycol (meta) acrylate, n-pentaxytetraethylene glycol (meta) acrylate, tripropylene glycol (meta) acrylate, tetrapropylene glycol (meth) acrylate, methoxy propylene glycol (meta) Atharylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) Atari rate, _n - butoxy tetrapropylene glycol (meth) Atarire over preparative, n- penta alkoxy tetrapropylene glycol (meth) Atari rate, polytetramethylene grayed recall (meth) Atari rate, methoxy polytetramethylene glycol (meth) Atari Rate , Methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, etc. having a terminal alkoxy group and a monooxylate having a polyoxyalkylene chain or the corresponding monomethacrylate, phenoxydiethylene glycol ( (Meta) acrylate, phenoxyethylene glycol (meth) atalylate, phenoxytriethylene glycol (meth) atalylate, phenoxytetraethylene glycol (meth) atalylate, Polyoxyalkylene-based acrylates having a phenoxy or aryloxy group at a terminal such as enoxyhexaethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxytetrapropylene glycol (meth) acrylate Or pair Corresponding meta-atalylates are mentioned.

[0062] Further, as the compound having a carboxyl group and a polymerizable unsaturated double bond group, maleic acid, fumaric acid, itaconic acid, citraconic acid, or an alkyl or alkyl monoester thereof, phthalic acid j8 -(Meth) ataliloxityl monoester, isophthalic acid j8— (meth) atariloxityl monoester, succinic acid j8-(meth) atariloxityl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamon Acids and the like.

[0063] Examples of the hydroxyl group-containing (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) ) Acrylate, 4-hydroxybutylbenzene, 2-hydroxy-13-phenoxypropyl (meth) acrylate.

[0064] Nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, -Propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, etc., monoalkylol (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 Methacrylamide, N, N-di ( (Roxymethyl) acrylamide, N-butoxymethyl-N— (propoxymethyl) methacrylamide, N, N—di (butoxymethyl) acrylamide, N—butoxymethyl—N— (methoxymethyl) methacrylamide, N, N— Acrylamide unsaturated compounds such as dialkylol (meth) acrylamide such as di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, dimethylaminoethyl (meth) acrylate, and methylamino ethyl (meth) Atari rates, methyl E chill aminoethyl (meth) Atari rate, dimethyl chill aminostyrene, Cl ^_ unsaturated compound and counterions having a dialkylamino group such as GETS chill aminostyrene, Br @ -, the厂等Halogen ion or QS03— (Q: carbon number 1-1 Dialkylamino group-containing unsaturated compound having 2 alkyl groups)

There is a quaternary ammonium salt of the product. [0065] Further, other unsaturated compounds include perfluoromethylmethyl (meth) atalylate, perfluoroethylmethyl (meth) atalylate, and 2-perfluorobutylethyl (meth) atalyte. Rate, 2-perfluoro mouth hexylethyl (meta) acrylate, 2-perfluorooctylethyl (meta) acrylate, 2-perfluoroisono-letyl (meta) acrylate, 2-perfluorono-letyl (meta) acrylate , 2—Perfluorodecyl ethyl (meth) acrylate, perfluoropropyl propyl (meth) acrylate, perfluorooctyl propyl (meth) acrylate, perfluoro octyl propyl (meth) acrylate, Perfluoroalkyls with 1 to 20 carbon atoms, such as perfluorooctyldecyl (meta) acrylate Par Full O b alkyl (meth) Atari rate class with Le group leaves with Ageruko transgression.

Further, perfluoroalkylethylene such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene, and perfluoroalkyl group-containing butyl monomers such as alkylenes; Bull trichlorosilane, bi

-Butyl conjugates containing alkoxysilyl groups such as tris (j8-methoxyethoxy) silane, burtriethoxysilane, y- (meth) atalioxypropyl propyltrimethoxysilane and derivatives thereof, glycidino oleatalylate, 4 Glycidyl group-containing atalylates such as epoxycyclohexynoleate tallate.

Examples of the fatty acid bur compound include vinyl acetate, vinyl butyrate, butyl propionate, hexyl acrylate, butyl purylate, butyl laurate, butyl palmitate, and vinyl stearate.

[0068] Examples of the alkyl butyl ether compound include butyl vinyl ether, ethyl butyl ether and the like.

[0069] Examples of the a-olefin compound include 1-hexene, 1-otaten, 1-decene, 1-dodecene, 1-tetradecene, and 11-hexadecene.

[0070] Examples of the bullet compound include aryl compounds such as aryl acetate, aryl alcohol, arylbenzene, and aryl cyanide, butyl cyanide, bulcyclohexane, butyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, Chlorostyrene and the like.

[0071] Examples of the ethur compound include acetylene, ethurbenzene, ethurtoluene, 1 Ethynyl-1-cyclohexanol and the like.

[0072] 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 humectant, a viscosity modifier, a preservative, an antibacterial agent, an antiblocking agent, and an ultraviolet ray. You may add an absorber, an infrared absorber, etc.

When a solvent is added, a curing treatment 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, methylpyrrolidone, and the like.

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

[0076] The antireflection film of the present invention has a high refractive index node coat layer formed from the photocurable composition of the present invention on one surface of a plastic substrate, and a refractive index of 1.20 to: L50. The low refractive index layer is sequentially laminated, and the high refractive index hard coat layer is formed such that the photocurable composition of the present invention has a thickness of 0.1 to 30 m on a plastic substrate. It can be formed by performing a curing treatment after coating.

[0077] 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 microgravure, gravure, die, curtain, lip, and slot can be used. it can.

[0078] The curing treatment can be performed by using a known technique, for example, by irradiating an active energy ray such as an ultraviolet ray, an electron beam, or a visible ray having a wavelength of 400 to 500 nm. For example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, etc. should be used as a source of ultraviolet light and visible light having a wavelength of 400 to 500 nm. Can be. As the electron beam source, a thermionic emission gun, an electron gun or the like can be used.

The active energy dose for irradiation is preferably in the range of 5 to 2,000 mi, and more preferably in the range of 50 to: LOOOiuJ from the viewpoint of easy control in the process.

[0080] In addition, infrared rays, far infrared rays, hot air, high frequency heating, etc. Can be used in combination.

[0081] The high refractive index hard coat layer may be formed by applying a photocurable composition to a plastic substrate, and then performing a curing treatment after natural or forced drying. After the hardening process, it may be natural or forced drying !, but it is more preferable to perform the hardening process after the natural or forced drying.

[0082] In particular, in the case of curing with an electron beam, it is more preferable to perform a curing treatment after natural or forced drying in order to prevent curing inhibition by water or a decrease in the strength of the coating film due to the residual organic solvent. ,.

[0083] Further, the timing of the curing treatment may be the same as the coating, or may be after the coating!

[0084] As the plastic substrate, it is preferable to use a polyester-based substrate because of the strength and refractive index at which a polyester-based, acryl-based, triacetate-based substrate, or the like can be used. Examples of the polyester-based substrate include polyethylene terephthalate (PET, refractive index: 1.60 to: L67), polyethylene naphthalate (PEN, refractive index: 1.68 to: L.72), and the like.

[0085] The plastic substrate may be subjected to a pretreatment such as a corona treatment or a plasma treatment. By performing the pretreatment, the adhesion of the hard coat layer to the plastic substrate is improved.

[0086] The refractive index of the high-refractive-index hard coat layer is preferably such that the difference in refractive index from the substrate is less than 0.01, because the occurrence of interference fringes can be suppressed. For example, when a polyester base is used as the plastic base, the refractive index of the high refractive index hard coat layer is 1.60 to

It is preferable that the ratio be within the range of 1.75, since the occurrence of interference fringes can be suppressed.

[0087] The pencil hardness of the high refractive index node coat layer is preferably 2H or more to protect the plastic substrate.

The low-refractive-index layer laminated on the high-refractive-index and low-coat layers includes MgF (

2 Refractive index: about 1.4), SiO (refractive index: about 1.2 to 1.5), LiF (refractive index: about 1.4), 3NaF'Al

2

F (refractive index: about 1.4), Na A1F (refractive index: about 1.33) and the like can be used. Also,

3 3 6

These fine particles such as MgF and SiO are cured by UV and electron beam curable resin / silicon alkoxide.

twenty two

The ability to use those dispersed in the system matrix Absent.

When the low-refractive-index layer is formed of a matrix containing the low-refractive-index fine particles, the low-refractive-index fine-particle-containing matrix is applied so that the film thickness becomes 0.01 to 1 / ζπι. Accordingly, it can be formed by performing a drying treatment, an ultraviolet irradiation treatment, and an 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 microgravure, gravure, die, curtain, lip, and slot can be used. it can.

[0091] The low refractive index layer may be formed by a vacuum evaporation method, a sputtering method, a reactive sputtering method, an ion plating method, an electroplating method, or the like.

[0092] The antireflection film of the present invention may be formed by laminating a plurality of layers having different refractive indices, each having only one low refractive index layer. For example, 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 further provided on the high refractive index hard coat layer. Not a thing.

[0093] Further, the antireflection film of the present invention may further include another functional layer. 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. The functional layer may have a plurality of functions in one layer.

[0094] When the antireflection film of the present invention is used for a display, the antifouling layer is preferably provided on the antireflection layer on the surface side.

When the antireflection film of the present invention is used for a plasma display, any one or all of the electromagnetic wave shielding layer, the neon light correction layer, and the infrared cut layer are preferably provided wherever it is preferable. However, in consideration of visibility and the like, it is preferable to provide the substrate on the side opposite to the side on which the antireflection layer is provided.

[0096] 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,

β-hydroxyethynoleate tallate 475§,

1,8-diazabicyclo [5.4.0] -7-ndecene 10 parts,

0.25 parts of methquinone,

Cyclohexanone 111 ^^

Was gradually heated while stirring, and reacted at 90 ° C. in a dry air atmosphere. During the reaction, stirring was continued while a total of 889 parts of cyclohexanone were appropriately diluted according to the viscosity. Peak of the acid anhydride group in the IR measurement of the reaction product, i.e., after confirming that the peak around 1780 cm ^_1 and 1850C m ^_1 is disappeared, cooled, the reaction was stopped. At this time, the acid value of the reaction product was measured by a conventional method, and it was 215 mgKOHZg.

[0098] Subsequently, in this solution,

Glycidinoremetharylate 164 咅 ^

o-Phenylphenol glycidyl ether (（-GJ manufactured by Sanko Co., Ltd.) 607 parts, dimethinole pendinoleamine 13

, And 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, and when the acid value became less than lOmgKOHZg, the reaction product was cooled to stop the reaction. The final acid value of the obtained photocurable compound (a) is 5 mg KO HZg, the average number of biphenyl skeletons in one molecule is 1.70, and the number of polymerizable unsaturated double bond groups The number average molecular weight was 264, and the number of polymerizable unsaturated double bond groups in one molecule was 3.30 on average. In addition, the mono ktt of the biphenyl group and the metatanol group in the obtained reaction product was 0.7: 0.3.

[0099] <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,

β-hydroxyethynoleate tallate 475§,

1,8-diazabicyclo [5.4.0] -7-ndecene 10 parts,

0.25 parts of methquinone, Cyclohexanone ιιι§

Was gradually heated with stirring, and reacted at 90 ° C. in a dry air atmosphere. During the reaction, stirring was continued while a total of 889 parts of cyclohexanone were appropriately diluted according to the viscosity. Peak of anhydride groups in the IR measurement of the reaction product, i.e., after confirming that the peak of 1780 cm ^_1 and 1850cm around one ¹ is disappeared, cooled, the reaction was stopped. At this time, the acid value of the reaction product was measured by a conventional method and found to be 215 mgKOHZg.

[0100] Then, in this solution

Guzi Shizinoreme Evening whale 382 咅 ^

o-Phenol phenol glycidyl ether (光 -GJ manufactured by Sanko Co., Ltd.) 260 parts, dimethinole pendinoleamine 13

, And 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, and when the acid value became 10 mgKOHZg or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained photocurable compound (b) is 6 mg KO HZg, the average number of biphenyl skeletons in one molecule is 1.30, and the number of polymerizable unsaturated double bond groups The number average molecular weight was 226, and the number of polymerizable unsaturated double bond groups in one molecule was 3.70 on average. Further, the mono ktt of the biphenyl group and the metatanol group in the obtained reaction product was 0.3: 0.7.

β-hydroxyethynoleate tallate 475§,

1,8-diazabicyclo [5.4.0] -7-ndecene 10 parts,

0.25 parts of methquinone,

Cyclohexanone ιιι§

Was gradually heated with stirring, and reacted at 90 ° C. in a dry air atmosphere. During the reaction, stirring was continued while a total of 889 parts of cyclohexanone were appropriately diluted according to the viscosity. Peak of anhydride groups in the IR measurement of the reaction product, i.e., after confirming that the peak of 1780 cm ^_1 and 1850cm around one ¹ is disappeared, cooled, the reaction was stopped. At this time At this point, the acid value of the reaction product was measured by a conventional method to be 215 mgKOHZg.

[0102] Subsequently, in this solution

463 parts of glycidyl methacrylate

o-Phenylphenol glycidyl ether (（-GJ manufactured by Sanko Co., Ltd.) 130 parts

Dimethinole pendinoleamine 13

, And 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, and when the acid value became less than lOmgKOHZg, the reaction product was cooled to stop the reaction. The final acid value of the photocurable compound (c) obtained was 4 mg KO HZg, the number of biphenyl skeletons in one molecule was 1.15 on average, and the number of biphenyl groups per polymerizable unsaturated double bond group was 1. The number average molecular weight was 203, and the number of polymerizable unsaturated double bond groups in one molecule was 3.85 on average. Further, the mono ktt of the biphenyl group and the metatanol group in the obtained reaction product was 0.15: 0.85.

β-hydroxyethynoleate tallate 475§,

1,8 diazabicyclo [5.4.0] —7 ndene, 10 parts,

0.25 parts of methoquinone, and

Cyclohexanone 111 ^^

[0104] Subsequently, in this solution

4 Hydroxybutyl atalylate glycidyl ether

(Nippon Kasei Co., Ltd.) 767 copies, and 14 parts of dimethylbenzylamine

, And the temperature was gradually raised, and the reaction was carried out at 90 degrees in the presence of dry air. While continuing the reaction, periodically measure the acid value of the reaction product, cool when the acid value becomes less than lOmgKOHZg, and allow the reaction to proceed.

Stopped. The final acid value of the obtained photocurable compound (d) is 5 mg KOHZg, the average number of biphenyl skeletons in one molecule is 1.00, and the number of biphenyl groups per polymerizable unsaturated double bond group is one. Has a number average molecular weight of 246, and the number of polymerizable unsaturated double bond groups in one molecule is 4.00 on average.

Examples 1 to 5, Comparative Examples 1 to 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. After coating so as to have a thickness of 4 μm, a metal nitride lamp was irradiated with ultraviolet rays of 400 mi to form a high refractive index hard coat layer. With respect to the obtained high refractive index hard coat layer, light resistance, refractive index, scratch resistance, pencil hardness and surface resistance were evaluated by the following methods. The results are shown in Table 1.

[0106] Further, the following coating liquid for a low-refractive-index layer was coated on the high-refractive-index hard coat layer using a wire bar so that the cured coating film thickness became about 0.1 μm, (4) A low-refractive-index layer was laminated by irradiating ultraviolet rays of 400 mJ with a ride lamp to prepare an antireflection film. The obtained antireflection film was evaluated for the presence of interference fringes by the following method. The results are shown in Table 1.

[table 1]

table 1

Example 1 Example 2 Example 3 Example 4 Example 5 ϋΜΜ2

Photocurable compound (a) 80 parts 50 parts 65 parts 314 parts

Photocurable compound (b) 50 parts

Photocurable compound (c) 65 parts

Photocurable compound (d) 80 parts

Urethane acrylate 35 parts 50 parts 42 parts 42 parts 42 parts 35 parts 35 parts 35 parts Benzyl methacrylate 15 parts 18 parts 15 parts 15 parts 15 parts Phenol EO modified

20 copies 18 copies

Acrylate

Hydroxyphenoxy

18 copies

Propyl acrylate

IBK 10 parts 10 parts 10 parts 10 parts 10 parts 10 parts 556 parts

Antimony pentoxide dispersion 780 parts 780 parts 780 parts 780 parts 780 parts 780 parts 870 parts Photopolymerization opening 6 parts 6 parts 6 parts 6 parts 6 parts 6 parts 6 parts 6 parts m + 926 parts 916 parts 921 parts 896 parts 921 Part 926 part 926 part 926 part Light fastness (b value) 〇 O 〇 O 〇〇〇 X Refractive index 1.66 1.65 1.65 1.65 1.64 1.61 1.56 1.69 5 5 5 5 5 3 4 1

O 〇〇〇 XXX XXX Interference Not at all Not at all Not at all Not at all Slightly noticeable Notably noticeable Notably noticeable

[0107] In Table 1,

Benzyl methacrylate: Kyoeisha Chemical Co., Ltd. “Light Ester BZ”

Phenol EO-modified acrylate: "ARONIX M102" manufactured by Toagosei Co., Ltd. Hydroxyphenoxypropyl atalylate: "CALAD R128HJ" manufactured by Nippon Daniyaku Co., Ltd.

MIBK: Methinoleisobutynoleketone

Antimony pentoxide dispersion: MIBK dispersion of antimony pentoxide, solid content of 30 weight ^_0/0 light polymerization initiator: Ciba Specialty Chemicals Co., Ltd. "Irugakyua 184"

10 parts of pentaerythritol tetraatalylate ("PET-30" manufactured by Nippon Dani Drug Co., Ltd.) is dissolved in 200 parts of isopropyl alcohol, and a photopolymerization initiator ("IRGACURE 184" manufactured by Ciba 'Specialty' Chemicals Co., Ltd.) 0 8 parts were mixed and stirred until dissolved. 44 parts of silica sol (refractive index: 1.3, ethanol solvent, solid content: 15% by weight) was stirred, and the whole amount of the pentaerythritol tetraatalylate solution previously prepared was added thereto, and stirred until uniform. A coating liquid for a low refractive index layer was obtained.

[0108] (1) Light resistance

Yellowing over time during continuous light irradiation is extremely undesirable in terms of application development. Therefore, yellowing during continuous light irradiation was confirmed.

First, the coating was exposed for 24 hours using a light resistance tester (light source: xenon lamp, illuminance: 100 WZcm ² , black panel temperature: 60 ° C., 60% RH). Thereafter, the coating was placed on white paper, and coloring was measured using a colorimeter (Minolta CR-300). The colorimetric values were indicated by 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 fastness. Considering practical required physical properties, b value is

3.5 for less than 5

3. X over 5

It was determined.

[0110] (2) Refractive index

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

[0111] (3) Scratch resistance The coated product was set on a jolt-type friction tester and jolted 10 times with a load of 250 g using steel wool No. 0000. The removed coating was visually evaluated for the degree of scratching in the following five stages. The larger the value, the better the scratch resistance.

[0112] 5… No scratches

4 ··· Slightly scratched

3 ... Wounds are attached, but the base material is visible!

2… Scratched, some coatings peeled off

1 ... The coated material has peeled off and the substrate is exposed

(4) Pencil hardness

Pencil hardness tester (HEIDON Scratching Tester HEIDO

Using N-14), the hardness of the pencil core was changed variously, and the test was performed five times under a load of 500 g. The hardness of the core when no or only one of the five was scratched was determined as the pencil hardness of the coating. Considering practical required physical properties, pencil hardness

2H or more

X lower than 2H

It was determined.

[0113] (5) Interference fringes

The surface of the anti-reflection film where the high refractive index layer and the non-coated layer were not formed was roughened with a sandpaper, and the back surface was subjected to anti-reflection treatment. The obtained sample was visually observed from a distance of 20 cm immediately from a 20 W fluorescent lamp, and the presence or absence of interference fringes was evaluated.

[0114] As is clear from the evaluation results in Table 1, the high refractive index hard coat layer in which the photocurable composition of the present invention is also formed has a high refractive index of! It was excellent in scratch resistance and light resistance. This result indicates that the photocurable composition of the present invention has all of the hard coat properties such as a high refractive index, pencil hardness and scratch resistance and light resistance that cannot be achieved with the materials studied conventionally. It indicates that. Further, 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 conjugate. In the case of a composition containing fine particles and another resin without containing a photocurable compound, the The film becomes brittle, and the scratch resistance and pencil hardness do not reach the required levels.

As described above, according to the present invention, a photocurable composition having all of high refractive index, excellent hard coat property and light resistance can be provided. Further, according to the present invention, it is possible to provide an antireflection film having both excellent hard coat properties and light resistance, and having good optical characteristics.

Claims

The scope of the claims

[1] General formula (1)

[Formula 5]

(In the formula,! ^ ~ Each independently represents a hydrogen atom or a methyl group, and R ^{4 to} R ⁶ each independently represent 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 contains a biphenyl skeleton ), And a photocurable composition comprising a filler (B) having a refractive index of 1.60 or more.

[2] The composition according to claim 1, which comprises a biphenyl skeleton with both R ⁷ and R ⁸ .

[3] The composition according to claim 1, wherein R ^{4 to} R ⁶ are an unsubstituted or substituted alkylene group having an alkylene moiety having 1 to 8 carbon atoms.

[4] The composition according to claim 3, wherein R ⁶ is a β-hydroxyalkylene group.

[5] R ⁷ has the formula:

R ⁶ — OC (O) — C (R ³ ) = CH

2

(Where R ⁶ and R ³ are as defined in general formula (1)) Or formula — CH— C (OH) CH—O—R ⁷¹ (where R ⁷¹ is a substituted or unsubstituted biphene)

twenty two

4. The composition according to claim 3, which is a group represented by the formula:

[6] R ⁷ has the formula: —CH—C (OH) CH—O—R ⁷¹ (where R ⁷¹ is a substituted or unsubstituted

twenty two

6. The composition according to claim 5, which is a group represented by the formula:

[7] The composition according to claim 5, wherein R ⁸ is benzene, benzophenone, biphenyl, phenol ether, diphenyl sulfone, diphenyl sulfide, perylene, or naphthalene.

[8] The composition according to claim 7, wherein R ⁸ is biphenyl.

[9] Filler (B) power The photocurable composition according to any one of claims 1 to 8, which is a metal oxide.

[10] A high refractive index hard coat layer formed from the photocurable composition according to claim 1 on one surface of a plastic substrate, and a low refractive index layer having a refractive index of 1.20 to L50. Are sequentially laminated to form an anti-reflection film.

[11] 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: L75.

[12] The antireflection finolem according to claim 10, wherein the high-refractive-index, coated coat layer has a pencil hardness of 2H or more.