JP2004285320A - Curable composition and cure-treated article using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cure-treated article with a cured resin layer of high hardness and small cure shrinkage, especially a cure-treated article which is hard to cause film delamination and cracks and which has sufficient hardness, and to provide a curable composition for use in it. <P>SOLUTION: The cure-treated article with a cured resin layer is obtained by coating a base material with a curable composition comprising at least a monofunctional macromonomer of a weight-average molecular weight of 20,000 or less, wherein at least one end group of the main chain of a polymer with a polyester structure is connected with a polymerizable unsaturated group, and a polymerization initiator and then by curing it. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable composition having high hardness and low curing shrinkage obtained by applying and curing on a substrate, and a cured article having a cured resin layer obtained by curing the curable composition. . More specifically, the present invention relates to a curable composition and a cured article that have less film peeling and cracking and have excellent scratch resistance and surface hardness. The present invention also relates to a curable composition and a cured article having excellent scratch resistance and surface hardness with less occurrence of film peeling and cracking and less curling after curing.

  In recent years, plastic products have been replaced with glass products in terms of workability and weight reduction, but the surface of these plastic products is easily damaged, so a cured resin layer can be directly applied for the purpose of imparting scratch resistance, In many cases, a plastic film with a cured resin layer (also referred to as a cured film) is bonded and used. In addition, with regard to conventional glass products, plastic films are increasingly being bonded to prevent scattering, and it is useful to form a cured resin layer on the surface of these films in order to enhance the hardness. Yes, it is widely done.

  Conventionally, various cured films obtained by applying a thermosetting composition or an active energy ray-curable composition and then curing it have been proposed. In particular, active energy rays (such as ultraviolet rays) curable compositions that can be cured at low temperatures are widely used. Generally, the curable component used in the ultraviolet curable composition is a compound called a polyfunctional acrylate monomer having 2 to 6 acrylate groups in the molecule or polyurethane diacrylate (Patent Document 1, etc.) , Polyester diacrylate (Patent Document 2 etc.), epoxy acrylate (Patent Document 3 etc.), a molecule having several acrylate groups in the molecule and an oligomer having a molecular weight of several hundred to several thousand, and inorganic or organic Fine particles are used in combination (Patent Documents 4 to 5 etc.). Also, a technique using a cationically polymerizable propenyl group-containing polyester compound capable of avoiding the inhibition of oxygen polymerization of radically polymerizable compounds (Patent Document 6), and polyester modification and acrylic monomer copolymerization to improve the abrasion resistance of the film. A technique using polyester (Patent Document 7) is known.

Furthermore, it is known to use a curable composition for a high refractive index layer in a multilayer laminated antireflection film having at least a high refractive index layer and a low refractive index layer on a transparent substrate such as glass or plastic. . Such a multilayer laminated type antireflection film is used in an image display device such as a liquid crystal display device. When an antireflection film is prepared by applying a curable composition, various types of cured films in which ultrafine particles of inorganic fine particles having a refractive index of 1.7 or more are dispersed in a binder are proposed as a coating-type high refractive index layer. Has been. In consideration of the hardness, adhesion, toughness, and dispersibility of high refractive index ultrafine particles, the binder is conventionally known thermoplastic resin, thermosetting resin, ionizing radiation curable resin, or a mixture thereof. Organic binder-based cured films such as Patent Documents 8 and 9 and the like, and cured film systems obtained by polymerizing and curing a polyfunctional compound having a plurality of polymerizable groups and a polymerization initiator (Patent Documents 10, 11 and the like) are disclosed. Has been.
JP 59-151110 A JP 59-151112 A JP-A-105738 JP 2000-912 A JP 2000-112379 A Japanese Patent Laid-Open No. 10-7754 JP-A-8-333467 JP-A-8-110401 [0018] JP-A-8-122504 [0034] JP-A-8-244178 JP 2000-47004 A

Among these methods, active energy ray curable compositions that are easy to process large areas and excellent in productivity are often used. However, in these methods, adhesion between the cured resin layer and the substrate, film folding, etc. The pencil hardness of the cured resin layer is often the limit (2H to 3H level) as long as the cracks and curls of the film are not practically problematic. Even if the hardness is insufficient, if the thickness of the cured resin layer is simply made thicker than the usual 3 to 10 μm, the hardness of the resulting cured film will be improved, but cracking of the cured resin layer tends to occur and at the same time during curing There is a problem that the adhesion to the base material is deteriorated due to the volume shrinkage of the film and peeling occurs, or the curling of the cured film becomes large.
In recent years, there has been an increasing demand for a cured resin layer that is further excellent in appearance, surface hardness, scratch resistance, adhesion, bending workability, and the like.

Further, in the high refractive index layer of the antireflection film, in recent years, the demand for the sharpness of the display image and the durability as a protective film is increasing due to the progress of the enlargement of the image display device or the mobile use.
However, in order to obtain a high refractive index layer as an antireflection film of a multilayer laminated type, it is necessary to increase the use ratio of the inorganic particles such as titanium-based high refractive index fine particles that determine optical characteristics in the layer. In addition, it is difficult to maintain sufficient strength (physical strength such as hardness, scratch resistance, and adhesion) in the antireflection film. Since these optical multilayer films are used as the outermost layer of the article, a protective film having further durability is desired.

Accordingly, an object of the present invention is to provide a curable composition capable of obtaining a cured resin layer (cured film) having high hardness and low curing shrinkage by applying the curable composition onto a substrate and then curing it. Is to provide.
It is a further object of the present invention to provide a cured article that has a sufficient hardness and is unlikely to cause film peeling or cracking. Another object of the present invention is to provide a cured film having a sufficient hardness that hardly causes film peeling and crack curl even when a plastic film substrate is used.
A further object of the present invention is to provide an antireflection film having high antireflection performance, excellent physical strength, low cost and excellent productivity.
A further object of the present invention is to provide a polarizing plate and an image display device that are anti-reflection treated by appropriate means, that are excellent in physical strength, inexpensive and excellent in productivity.

The above problems have been achieved by the following means.
(1) It has a polymerizable group at one end of the polymer main chain and contains a monofunctional polyester macromonomer (M) having a weight average molecular weight of 2 × 10 ⁴ or less and a polymerization initiator (L). A curable composition characterized by the above.

  (2) The curable composition according to the above (1), wherein the macromonomer (M) has a repeating part represented by the following general formula (MI) or general formula (M-II). .

In the formula, T represents a polymerizable group.
B ¹ represents a divalent organic residue that links T and D ^1, and B ² represents a divalent organic residue that links T and D ² .
E ¹ and E ² may be the same as or different from each other, and each is a divalent aliphatic group, a divalent aromatic group [-C (k ² ) ( k ³ ) —, —O—, —S—, —N (k ⁴ ) —, —SO ₂ —, —COO—, —OCO—, —CONHCO—, —NHCOO—, —NHCONH—, —CON (k _{^{4) -, - SO 2 N}} (k 4) - and ^{-Si (k 5) (k 6} ) - (k 2, k 3 and k ⁴ each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms , K ⁵ and k ⁶ each represent a hydrocarbon group having 1 to 12 carbon atoms), or an organic residue composed of a combination of these residues. Represent.
D ¹ represents —CH ₂ — or —CO—, and D ² represents —O— or —NH—.
R ¹ represents —OH, —OR ⁵ or —N (R ⁶ ) (R ⁷ ) (R ⁵ represents a hydrocarbon group having 1 to 12 carbon atoms. R ⁶ and R ⁷ represent a hydrogen atom or 1 carbon atom. Represents ~ 12 hydrocarbon groups).
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, —COR ⁸ or —CONHR ⁹ (R ⁸ and R ⁹ each represent a hydrocarbon group having 1 to 12 carbon atoms).

(3) The curable composition as described in (1) or (2) above, wherein the macromonomer (M) contains at least one alicyclic aliphatic component.
(4) The curable composition according to the above (3), wherein the macromonomer (M) contains at least one polycyclic aliphatic ring component.
(5) The curable composition according to any one of (1) to (4), wherein the polymerizable group of the macromonomer (M) is any one of a radical polymerization reactive group and a cationic polymerization reactive group.

(6) The curable composition as described in any one of (1) to (5) above, which further contains a polymerizable monomer (A).
(7) The curable composition as described in (5) above, wherein the polymerizable monomer (A) is a compound containing two or more polymerizable groups in the same molecule.
(8) The polymerizable monomer (A) contains two or more polymerizable groups in the molecule, and at least one ring-opening polymerizable group and at least one ethylenically unsaturated group as the polymerizable group. The curable composition as described in (7) above, which is a compound containing

  (9) A cured article obtained by applying the curable composition according to any one of (1) to (8) above onto a substrate and curing it.

(10) A multilayer antireflection film in which at least a high refractive index layer and a low refractive index layer are sequentially laminated on a transparent support, wherein the high refractive index layer contains inorganic particles having a refractive index of 1.70 or more. Further, an antireflection film obtained by curing the curable composition according to any one of (1) to (8).
(11) A refractive index layer having at least three layers of a high refractive index layer of two layers having different refractive indexes and a low refractive index layer having a refractive index of less than 1.55 laminated on these layers on a transparent support. And an antireflection film obtained by curing at least one of the two high refractive index layers according to any one of (1) to (8).

(12) The antireflection film as described in (10) or (11) above, wherein a hard coat layer is provided between the transparent support and the high refractive index layer.
(13) A polarizing plate, wherein the antireflection film according to any one of (10) to (12) is used for at least one of a protective film of a polarizing film.

(14) The antireflection film according to any one of (10) to (12) is used for one of the protective films for the polarizing film, and an optical compensation film having optical anisotropy is used for the other protective film for the polarizing film. A polarizing plate characterized by that.
(15) An image display device, wherein the polarizing film according to any one of (10) to (12) or the polarizing plate according to (13) or (14) is disposed on an image display surface. .

The curable composition of the present invention comprises a monofunctional polyester macromonomer (M) having a polymerizable group at one end of the polymer main chain and having a weight average molecular weight of 2 × 10 ⁴ or less and a polymerization initiator. (L) is contained, and it has been found that by having such a configuration, the film strength of the obtained cured resin layer is remarkably improved, and a cured article having high hardness and less curing shrinkage can be obtained. .

  Furthermore, it is preferable to contain the polymerizable monomer (A) copolymerizable with the macromonomer (M) in the curable composition, thereby further improving the film strength. It is considered that a block copolymer having polyester as a graft chain is formed as a matrix binder for the membrane, and a microphase separation structure is formed due to the interaction between the polymer chains. The polymerizable monomer (A) is preferably a polyfunctional monomer having two or more polymerizable groups, which further improves the film strength of the cured film. This is presumed to be due to the polymer phase forming a higher order structure together with the same microphase separation structure as described above. Further, by allowing the radical polymerizable component and the cationic polymerizable component to coexist in the curable composition, the matrix binder (cured film) is cured by coexisting the radical polymerization system and the cationic polymerization system. A network structure is formed, and a further effect of improving the film strength can be obtained. These radical polymerizable components and cationic polymerizable components may be present in the same monomer or different monomers. Moreover, it is preferable that the curable composition of this invention contains inorganic or organic fine particles according to a use.

  The cured article of the present invention has a cured resin layer formed by applying and curing the curable composition of the present invention on a substrate. A base material is not specifically limited, A surface protective film is formed by apply | coating and hardening | curing the curable composition of this invention on this base material, and providing a cured resin layer. The base material is preferably a plastic product, glass, plastic film (sheet), etc., and can be widely used, for example, building materials, automobile surfaces, electrical appliances and the like.

  The cured resin layer may be a single layer or a plurality of layers. In terms of the production process, a simple single layer is preferable. In this case, the single layer means a cured resin layer formed of the same composition, and may be formed by multiple times of application as long as the composition after application and drying is of the same composition. On the other hand, the term “multiple layers” means that the layers are formed of a plurality of compositions having different compositions. In the present invention, at least one layer is a cured resin layer formed by applying and curing the curable composition of the present invention. In particular, the outermost layer is preferably a cured resin layer formed by applying and curing the curable composition of the present invention. In the case of a multi-layer structure, layers having different filling rates of hard inorganic fine particles and soft fine particles can be appropriately laminated in the order of hardness.

  Moreover, on these cured resin layers, a film having functions such as an antireflection layer, an ultraviolet / infrared absorbing layer, a selective wavelength absorbing layer, an electromagnetic wave shielding layer, an antifouling layer, etc. can be provided, It can serve as a functional film.

  Further, the cured article of the present invention may be a multilayer antireflection film in which a high refractive index layer and a low refractive index layer are sequentially laminated on a transparent support, and the high refractive index layer is the present invention. It is preferable that it is a cured resin layer formed by applying and curing the curable composition. The high refractive index layer preferably further contains inorganic particles having a refractive index of 1.70 or more. The cured film thus obtained is excellent in optical transparency and film strength.

Since the curable composition of the present invention has high hardness and little curing shrinkage, film peeling and cracking are unlikely to occur, and a cured product having sufficient hardness can be provided. In addition, when a plastic film substrate is used, a cured film having sufficient hardness that hardly peels off and cracks and curls can be obtained.
The curable composition of the present invention can be used as a cured article, as a hard coat layer of a laminated antireflection film, or as a high refractive index layer. In particular, when used in a high refractive index layer, the antireflection film has excellent optical properties as an antireflection film in terms of haze and reflectance, excellent adhesion, and excellent weather resistance (particularly polarization). Is obtained. Furthermore, an image display device having excellent performance can be obtained.

The present invention is described in further detail below.
First, the monofunctional polyester macromonomer (M) used in the present invention will be described.
The monofunctional polyester macromonomer (M) of the present invention is a compound having a polyester structure and having a weight average molecular weight of 2 × 10 ⁴ or less, wherein a polymerizable group is bonded only to one end of the polymer main chain. It is.

The monofunctional polyester macromonomer (M) is preferably copolymerized with the polymerizable monomer (A) to form a comb-type block copolymer.
The copolymerization reaction of the monofunctional polyester macromonomer (M) and the polymerizable monomer (A) used in the present invention sufficiently proceeds, and is derived from the macromonomer (M) of the formed block polymer. The weight average molecular weight of the monofunctional polyester macromonomer is preferably 3 × 10 ³ to 2 × 10 in order to sufficiently exhibit the entanglement effect between the polymer chains due to the polymer chain length of the comb portion and improve the film strength. ⁴ , more preferably 5 × 10 ^{3 to} 1.5 × 10 ⁴ .

Specifically, the monofunctional polyester macromonomer (M) is preferably a macromonomer represented by the above general formula (MI) or general formula (M-II).
In general formula (M-I) or general formula (M-II), T represents a polymerizable group, and preferably represents a radical polymerizable group or a cationic polymerizable group.
Specifically, when T is a radical polymerizable group, a group represented by the following general formula (Ia) is exemplified.

In general formula (Ia), x ¹ and x ² may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—T ⁰ or a carbon number. -COO-T ⁰ via a hydrocarbon group of 1 to 8 (T ⁰ represents a hydrocarbon group having 1 to 18 carbon atoms). Preferably, each is a hydrogen atom, a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, etc.) ), -COO-T ⁰ or -CH ₂ COOT ⁰ {T ⁰ is an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, etc.), An aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, etc.) or an optionally substituted phenyl group (for example, phenyl group, tolyl group, xylyl group, methoxyphenyl group, etc.)} Represents. More preferably, ^one of x ¹ and x ² represents a hydrogen atom.

In general formula (Ia), A ¹ is a single bond or —COO—, —OCO—, — (CH ₂ ) _a —COO—, —CO—, — (CH ₂ ) _b —OCO— (a, b are Each represents an integer of 1 to 3), —CON (k ¹ ) — [k ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms], —CONHCONH—, —CONHCOO—, —O—, — C ₆ H ₄ — or —SO ₂ — is represented. Preferably, -COO -, - OCO -, - CH 2 COO -, - CH 2 OCO -, - CONH- , or _{-C 6 H 4 -, - CON} (k 1) - represents a. When A ¹ represents —C ₆ H ₄ —, the benzene ring may have a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, etc.), an alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (for example, methoxy group, Ethoxy group, propoxy group, butoxy group, etc.).

  In the general formula (M-I) or general formula (M-II), when T represents a cationic polymerizable group, the cationic polymerizable group was irradiated with active energy rays in the presence of an active energy ray-sensitive cationic polymerization initiator. A functional group containing a polymerizable group that sometimes causes a polymerization reaction and / or a crosslinking reaction may be mentioned. Representative examples include an epoxy group, a cyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester compound, and a vinyloxo group. More specifically, what is illustrated by the cationically polymerizable monomer (A2) mentioned later is mentioned.

In General Formula (M-I) or General Formula (M-II), B ¹ and B ² each represent a single bond or a linking group that connects T and D ¹ , and T and D ² . Specifically as a linking group,

Divalent alicyclic group (the hydrocarbon ring of the alicyclic structure includes, for example, a cycloheptane ring, a cyclohexane ring, a cyclooctane ring, a bicyclopentane ring, a tricyclohexane ring, a bicyclooctane ring, a bicyclononane ring, and a tricyclodecane ring. Etc.) It is comprised by arbitrary combinations of atomic groups, such as a group shown by a bivalent aryl ring group (As an aryl ring, for example, a benzene ring, a naphthalene ring etc.).

In the above, j ¹ and j ² may be the same or different, and may be a hydrogen atom, a halogen atom (fluorine atom, halogen atom, bromine atom, iodine atom) or an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, a pentyl group, a hexyl group, a trifluoromethyl group, a methoxyethyl group, a cyanoethyl group, a chloroethyl group, etc.), j ³ is a hydrogen atom or 1 to 12 carbon atoms An optionally substituted hydrocarbon group (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, benzyl group, phenethyl group, phenyl group, chlorophenyl group, methoxyphenyl group, acetyl group) phenyl group, a trifluorophenyl group or the like), j ^4, j ⁵ may be the same or different, carbon atoms from 1 to 12 It represents an optionally substituted hydrocarbon group (concretely the same meaning as above j ^3).

In general formula (M-I) or general formula (M-II), E ¹ and E ² may be the same or different from each other, and each is a divalent aliphatic group, a divalent aromatic group [each 2 during valence bond of the organic ^{residue, -C (k 2) (k} 3) -, - O -, - S -, - N (k 4) -, - SO 2 -, - COO -, - OCO- , —CONHCl—, —NHCOO—, —NHCONH—, —CON (k ⁴ ) —, —SO ₂ N (k ⁴ ) — and —Si (k ⁵ ) (k ⁶ ) — (k ² , k ³ and k ⁴ represents the same content as k ^1, and k ⁵ and k ⁶ each represent a hydrocarbon group having 1 to 12 carbon atoms) may be interposed] or the remaining It represents an organic residue composed of a combination of groups.
In General Formula (M-I) or General Formula (M-II), D ¹ represents —CH ₂ — or —CO—. D ² represents —O— or —NH—.

Specificity of the linking moiety {-B ¹ -D ^1- } or {-B ² -D ^2- } between the polymerizable group T and the repeating unit [] in the general formula (M-I) or the general formula (M-II) For example, in the case where the polymerizable group T is represented by the general formula (Ia) [CH (x ¹ ) = C (x ² ) -A ^1- ], which is a radical polymerizable group, {T-B ¹ Although shown below in the form of -D ^1- } or {TB ² -D ^2- }, the connecting portion is not limited thereto. Moreover, the part corresponded to the connection part of the following specific example can be used also when the polymeric group T is a cation polymeric group.

In general formula (M-I) or (M-II), R ¹ represents —OH, —OR ⁵ or —N (R ⁶ ) (R ⁷ ) (R ⁵ represents a hydrocarbon group having 1 to 12 carbon atoms. R ⁶ and R ^{7 each} represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms).
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, —COR ⁸ or —CONHR ⁹ (R ⁸ and R ⁹ each represent a hydrocarbon group having 1 to 12 carbon atoms).

In general formula (M-I) or (M-II), E ¹ and E ² may be the same as or different from each other, and each of them contains a divalent aliphatic group or a divalent aromatic group. Represents an organic residue.
Examples of the divalent aliphatic group include an alkylene group having 2 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkane ring group having 3 to 30 carbon atoms, and 6 carbon atoms. The cycloalkene ring group of ˜30 and the divalent aromatic group are 5-membered containing at least one aryl group having 6 to 14 carbon atoms and a hetero atom (as a hetero atom, oxygen atom, sulfur atom, nitrogen atom). Examples thereof include heterocyclic groups having 6-membered ring number or heterocyclic groups that may form a condensed ring structure.
Preferably, at least one of E ¹ and E ² contains a divalent alicyclic aliphatic group having 3 to 30 carbon atoms. More preferably, an alicyclic aliphatic group having a polycyclic or bridged cyclic structure is exemplified. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, pentacyclo structure or the like having 5 or more carbon atoms. In particular, 6 to 25 carbon atoms are preferable.

  The structural example of an alicyclic part is shown below among alicyclic hydrocarbon groups. In addition, in the following structural example, you may contain a double bond in the position which is not conjugated.

  Moreover, these alicyclic hydrocarbon groups may have at least one kind of substituent. As the substituent of the alicyclic hydrocarbon group, an alkyl group, a substituted alkyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, alkoxy group, amide group, acyl group, alkoxycarbonyl group Etc. Specific contents of these substituents include those having the same contents as exemplified by R in the formula (A1-I) described later.

Specific examples of E ¹ and E ² include the following organic residues, but the present invention is not limited thereto.

The macromonomer represented by the general formula (M-I) (hereinafter sometimes referred to as macromonomer (M1)) is exemplified in “Polymer Data Handbook [Basic]” (published in 1986) Baifukan etc. A hydroxyl group at one end of a polyester oligomer having a weight average molecular weight of 2 × 10 ³ to 2 × 10 ⁴ synthesized by a polycondensation reaction between a diol and a dicarboxylic acid, a dicarboxylic acid anhydride or a dicarboxylic acid ester. However, it can be easily produced by a method of introducing a polymerizable group by a polymer reaction.

  Polyester is synthesized by a conventionally known polycondensation reaction. Specifically, Eiichiro Takiyama “Polyester Resin Handbook”, published by Nikkan Kogyo Shimbun (1986), edited by Polymer Society of Japan, “Polycondensation and Polyaddition” It can be synthesized according to the method described in Kyoritsu Shuppan (1980), I. Goodman “Encyclopedia of Polymer Science and Engineering Vol. 12” p1. John Wiley & Sons (1985).

  As a method for introducing a polymerizable group only into one hydroxyl group of a polyester oligomer, when introducing a radical polymerizable group, a reaction of esterifying from an alcohol in a conventionally known low-molecular compound or urethanization from an alcohol It can be synthesized by using a reaction. That is, a method of synthesizing a macromonomer by esterification by reaction with a carboxylic acid, a carboxylic acid ester, a carboxylic acid halide or a carboxylic acid anhydride containing a polymerizable double bond group in the molecule, It can be achieved by a method of urethanization by reaction with monoisocyanates containing a polymerizable double bond group to synthesize macromonomers. Specifically, the Chemical Society of Japan “New Experimental Chemistry Lecture 14, Synthesis and Reaction of Organic Compounds [II]”, Chapter 5, Maruzen Co., Ltd. (published in 1977), “Synthesis and Reaction of Organic Compounds” [III] ”, page 1652, Maruzen Co., Ltd. (published in 1978) and the like.

Further, the macromonomer represented by the general formula (M-II) (hereinafter sometimes referred to as macromonomer (M2)) is a polymerizable group only on the carboxyl group at one end of the polyester oligomer synthesized as described above. It can synthesize | combine by the method of introduce | transducing. As the introduction method, when a radical polymerizable group is introduced, it can be synthesized by using a reaction of esterifying from a carboxylic acid or a reaction of acid amidation from a carboxylic acid in a conventionally known low molecular weight compound. That is, a functional group containing a polymerizable double bond group in the molecule and chemically reacting with a carboxyl group (for example, —OH, halogen compound (chloride, bromide, iodide), —NH ₂ , —COOR ³¹ (R ³¹ is a macromolecule reaction of a compound containing a methyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, etc.), a group represented by the following formula (a)) and a polyester oligomer. Monomers are synthesized.

  In either case of the macromonomer (M1) or the macromonomer (M2), as a method for introducing the cationic polymerizable group only at one end, polymerization is performed in the molecule mentioned in the case of introducing the radical polymerizable group. In the compound containing a polymerizable double bond group, a method of synthesizing using a compound containing a cationic polymerizable group in advance instead of the polymerizable double bond can be mentioned.

Next, the polymerizable monomer (A) preferably used in the curable composition of the present invention will be described in detail.
The polymerizable monomer (A) may be any as long as it is copolymerizable with the macromonomer (M), and examples thereof include a radical polymerizable monomer (A1) and a cationic polymerizable monomer (A2).

  Examples of the radical polymerizable monomer (A1) include a compound containing a polymerizable unsaturated double bond group that initiates a polymerization reaction with a radical species, and may be either a monomer or an oligomer. One type or two or more types may be used. Specific examples of the radical polymerizable monomer (A1) include monomers represented by the following general formula (A1-I).

In general formula (A1-I), V ¹ represents the same content as A ^{1 in} general formula (MI). a ¹ and a ² may be the same or different and each represents the same contents as x ¹ and x ² in the formula (MI).

R represents an aliphatic group, an aryl group, or a heterocyclic group. As the aliphatic group, a linear or branched alkyl group having 1 to 22 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group) Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nanodecyl group, eicosanyl group, heneicosanyl group, docosanyl group, etc.), straight chain having 2 to 22 carbon atoms Or branched alkenyl groups (for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, dococenyl, butadienyl Group, pentadienyl group, hexadi Nyl group, octadienyl group, etc.), C2-C22 linear or branched alkynyl group (eg, ethynyl group, propynyl group, butynyl group, hexynyl group, octanyl group, decanyl group, dodecanyl group, etc.), carbon Aliphatic hydrocarbon groups of 5 to 22 (the alicyclic hydrocarbon group includes monocyclic, polycyclic, and bridged cyclic aliphatic hydrocarbon groups, and specific examples thereof include cyclohexane Pentane, cyclopentene, cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, cycloheptane, cycloheptene, cycloheptadiene, cyclooctane, cyclooctene, cyclooctadiene, cyclooctatriene, cyclosonane, cyclosonene, cyclodecane, cyclodecene, cyclodecandiene, cyclo Decatriene, Cycloundeca , Cyclododecane, bicycloheptane, bicyclohexane, bi- cyclohexene, tri-cyclohexene, norcarane, norpinane, norbornane, norbornene, norbornadiene, tricyclo heptane, tricyclo-heptene, decalin, cyclic structures hydrocarbons such adamantane, etc.).
Among these, linear aliphatic groups having 1 to 18 carbon atoms, branched structures having 3 to 18 carbon atoms, and cyclic aliphatic groups having 5 to 16 carbon atoms are more preferable.

Such an aliphatic group may have a substituent, and as the substituent that can be introduced, a monovalent nonmetallic atomic group excluding hydrogen is used.
Specific examples of the nonmetallic atomic group include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, —OH group, —OR ¹¹ , —SR ¹¹ , —COR ¹¹ , —COOR ¹¹ , —OCOR ¹¹ , —SO ₂ R ¹¹ , —NHCONHR ¹¹ , —N (R ¹² ) COR ¹¹ , —N (R ¹² ) SO ₂ R ¹¹ , —N (R ¹³ ) (R ¹⁴ ), — CO (R ¹³ ) (R ¹⁴ ), —SO ₂ (R ¹³ ) (R ¹⁴ ), —P (═O) (R ¹⁵ ) (R ¹⁶ ), —OP (═O) (R ¹⁵ ) (R ¹⁶ ), -Si (R ¹⁷ ) (R ¹⁸ ) (R ¹⁹ ), an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and an alkyl group having 5 to 10 carbon atoms. An alicyclic hydrocarbon group, an aryl group having 6 to 18 carbon atoms (the aryl ring includes benzene, naphthalene, dihydronaphthalene, indene Heterocyclic groups having a monocyclic or polycyclic ring structure containing at least one of fluorene, acenaphthylene, acenaphthene, biphenylene, etc., oxygen atoms, sulfur atoms, nitrogen atoms, , Furanyl group, tetrahydrofuranyl group, pyranyl group, pyroyl group, chromenyl group, phenoxathiinyl group, indazoyl group, pyrazoyl group, pyridiyl group, pyrazinyl group, pyrimidinyl group, indoyl group, isoindoyl group, quinoniyl group, pyrrolidinyl group, Pyrrolinyl group, imidazolinyl group, pyrazolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, thienyl group, benzothienyl group and the like.

  The alkenyl group, alkynyl group, alicyclic hydrocarbon group, aryl group, and heterocyclic group may further have a substituent, and the substituent may be a group that can be introduced into the aliphatic group. The thing similar to what was illustrated as is mentioned.

R ¹¹ represents an aliphatic group having 1 to 22 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group. The aliphatic group for R ¹¹ has the same meaning as the aliphatic group represented by R. Examples of the aryl group for R ¹¹ include the same aryl groups as those exemplified as the substituent that can be introduced into the aliphatic group represented by R. Such an aryl group may further have a substituent, and examples of the substituent include the same groups as those exemplified as the substituent that can be introduced into the aliphatic group represented by R. R ¹² represents the same as the hydrogen atom or the R ¹¹ group.

R ¹³ and R ¹⁴ each independently represents a hydrogen atom or the same as R _11, and R ¹³ and R ¹⁴ are bonded to each other to form a 5-membered or 6-membered ring containing an N atom. It may be formed.
R ¹⁵ and R ¹⁶ each independently represent —OH, an aliphatic group having 1 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, or —OR ¹¹ . The aliphatic group for R ¹⁵ and R ¹⁶ has the same meaning as the aliphatic group represented by R. Examples of the aryl group in R ¹⁵ and R ¹⁶ include the same aryl groups as those exemplified as the substituent that can be introduced into the aliphatic group represented by R. Such an aryl group may further have a substituent, and examples of the substituent include those exemplified as the substituent that can be introduced into the aliphatic group represented by R. However, in such polar substituents, both R ¹⁵ and R ¹⁶ are not represented by —OH.
R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrocarbon group having 1 to 22 carbon atoms or —OR ^20, and at least one of these substituents represents a hydrocarbon group. The hydrocarbon group represents the same aliphatic group and aryl group represented by R, and —OR ²⁰ represents the same contents as —OR ¹¹ .

  Examples of the aryl group represented by R in the above formula (A1-I) include the same aryl groups as those exemplified as the substituent that can be introduced into the aliphatic group represented by R. The aryl group may further have a substituent, and the substituent that can be introduced is the same as those exemplified as the substituent that can be introduced into the aliphatic group represented by R. Can be mentioned.

  Examples of the heterocyclic group represented by R in the above formula (A1-I) include the same heterocyclic groups as those exemplified as the substituent that can be introduced into the aliphatic group represented by R. The heterocyclic group may further have a substituent, and the substituent that can be introduced is the same as those exemplified as the substituent that can be introduced into the aliphatic group represented by R. Is mentioned.

The radically polymerizable monomer (A1) is more preferably a cyclic fat described as being preferable when at least one of E ¹ and E ² is contained in the general formula (M-I) or (M-II). And monomers containing a group group in the substituent. Especially, the monomer represented with the following general formula (A1-II) is preferable.

In the general formula ^{(A1-II), a 1} , a 2 and V ¹ was the same meaning as a ^1, a ² and V ¹ in the general formula respectively (A1-I).

R ⁰ is a hydrocarbon group constituting a cyclic structure having 5 to 30 carbon atoms, and examples thereof include monocyclic, polycyclic, bridged cyclic, and spirocyclic cyclic structures. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, pentacyclo structure or the like having 5 or more carbon atoms. Preferably C6-C25 is preferable.

Among these alicyclic hydrocarbon groups, as an example of the structure of the alicyclic moiety, it is preferable that at least one of E ¹ and E ^{2 in} the general formula (MI) or (M-II) contains Examples of structural examples (1) to (51) exemplified in the cyclic aliphatic group described.

  Moreover, these alicyclic hydrocarbon groups may have at least one kind of substituent. As the substituent of the alicyclic hydrocarbon group, an alkyl group, a substituted alkyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, hydroxyl group, nitro group, alkoxy group, carboxyl group, amino group Group, amide group, acyl group, alkoxycarbonyl group and the like. Specific contents of these substituents include the same contents as exemplified for R in the formula (A1-I).

L ¹ represents a group for linking -V ¹ -and -R ⁰ in formula (A1-II), and is a direct bond or a linking group having 1 to 22 total atoms (the total number of atoms herein includes: Represents a hydrogen atom bonded to a carbon atom, a nitrogen atom or a silicon atom). Preferably, it represents a direct bond or a linking group having 1 to 12 total atoms. However, when R ⁰ is a monocyclic aliphatic group, L ¹ is preferably not a direct bond but a linking group having 1 to 12 total atoms, and more preferably a linking group having 1 to 8 total atoms. It is preferable that

As the linking group in L ^{1, a} carbon atom-carbon atom bond (single bond or double bond), a carbon atom-heteroatom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom), a complex It is composed of any combination of atomic groups composed of atom-heteroatom bonds and the like. For example, as the atomic group, those similar to B ^{1 in the} general formula (MI) can be mentioned.

  As the cationically polymerizable monomer (A2) used in the present invention, any compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator is used. Typical examples include epoxy compounds, cyclic ether compounds, cyclic acetal compounds, cyclic lactone compounds, cyclic thioether compounds, spiro orthoester compounds, vinyl ether compounds, and the like. In the present invention, one or more of the above cationic polymerizable monomers may be used.

  Specific examples of the cationically polymerizable monomer (A2) include epoxy group-containing compounds (alicyclic epoxy resins, aliphatic epoxy resins, aromatic epoxy resins, etc.), cyclic ethers or cyclic acetal compounds, cyclic lactone compounds, and thiirane compounds. , A thietane compound, a vinyl ether compound containing a vinyloxy group, a spiro orthoester compound obtained by a reaction between an epoxy compound and a lactone, an ethylenically unsaturated hydrocarbon compound (vinyl hydrocarbon compound), and the like.

  Among these, as the cationically polymerizable monomer (A2), an epoxy group-containing compound and a vinyloxy group-containing compound (hereinafter also referred to as “vinyloxy compound”) are preferably used, and a polyepoxy having two or more epoxy groups in one molecule. Compounds, polyvinyloxy compounds having two or more vinyloxy groups in one molecule, and compounds having at least one epoxy group and one vinyloxy group in each molecule are more preferably used. In particular, as a cationically polymerizable monomer, an alicyclic polyepoxy compound having two or more epoxy groups in one molecule is contained, and the content of the alicyclic polyepoxy compound is 30 based on the total mass of the epoxy compound. When a mixture of epoxy compounds that is at least 50% by mass, more preferably at least 50% by mass is used, the cationic polymerization rate, thick film curability, resolution, ultraviolet transparency and the like are further improved, and the viscosity of the resin composition is low. As a result, film formation is performed smoothly.

  As the alicyclic epoxy resin described above as the cationic polymerizable monomer (A2), polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring, or unsaturated alicyclic ring (for example, cyclohexene, cyclopentene, Examples thereof include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidizing a compound containing dicyclooctene, tricyclodecene, etc.) with a suitable oxidizing agent such as hydrogen peroxide or peracid.

In addition, as other types of aliphatic epoxy resins, for example, polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate, etc. Can be mentioned.
In addition to these epoxy compounds, for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene Etc. can also be used. Further, epoxy silicones such as K-62-722 manufactured by Shin-Etsu Silicone and UV9300 manufactured by Toshiba Silicone, and silicones described in Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 28, 497 (1990) Polyfunctional epoxy compounds such as epoxy compounds can also be used.

Examples of the aromatic epoxy resin as the cationic polymerizable monomer (A2) include mono- or polyglycidyl ethers of mono- or polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof. it can. Examples of these epoxide compounds include compounds described in JP-A-11-242101 [0084] to [0086], compounds described in JP-A-8-277320 [0016] to [0029], and JP-A-10-158385. Examples include compounds described in publications [0044] to [0046].
Among these epoxides, in view of fast curability, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable. In the present invention, one of the epoxides may be used alone, or two or more may be used in appropriate combination.

As a compound containing an oxetanyl group which is a cyclic ether compound, the number of oxetanyl groups contained in the molecule is 1 to 10, preferably 1 to 4. These compounds are preferably used in combination with an epoxy group-containing compound.
Specifically, for example, compounds described in JP-A-2000-239309 [0024] to [0025], JVCRIVELLO et al, JMSPUREAPPL.CHEM., A30, p.173 to 187 (1993) Oxetane compounds and the like.

Examples of the spiro orthoester compound include compounds described in JP 2000-506908 A.
Examples of vinyl hydrocarbon compounds include styrene compounds such as styrene, α-methylstyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-vinylbiphenyl, vinylnaphthalene, and vinyl group substitution such as vinylcyclohexane and vinylbicycloheptene. An alicyclic hydrocarbon compound, a compound described in the radical polysynthetic monomer (a compound in which V ¹ corresponds to -O-), an alkenyl vinyl ether compound such as 2-methacryloyloxyethyl vinyl ether, 2-acryloyloxyethyl vinyl ether, N- Cationic polymerizable nitrogen-containing compounds such as vinyl carbazole and N-vinyl pyrrolidone, butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzenedimethanol divinyl Polyfunctional vinyl compounds such as ether, hydroquinone divinyl ether and sasolcinol divinyl ether, propenyl compounds described in Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 32, 2895 (1994), Journal of Polymer Science: Part A : Alkoxy allene compounds described in Polymer Chemistry, Vol. 33, 2493 (1995), Journal of Polymer Science: Part A: vinyl compounds described in Polymer Chemistry, Vol. 34, 1015 (1996), Journal of Examples thereof include isopropenyl compounds described in Polymer Science: Part A: Polymer Chemistry, Vol. 34, 2051 (1996).

  Of these vinyl ether compounds, di- or trivinyl ether compounds are preferred in view of curability, adhesion, and surface hardness. In the present invention, one of the above vinyl ether compounds may be used alone, or two or more thereof may be used in appropriate combination.

In the present invention, one or more of the above-mentioned cationic polymerizable monomers (A2) can be used, and in particular, those having an oxirane structure in vinyl ethers, epoxy compounds and oxetane compounds as described above are photopolymerization reactions. Is preferable from the viewpoint of improving the properties and film properties of the polymer.
A cationically polymerizable monomer containing a polyfunctional compound having two or more cationically polymerizable groups in one molecule at a ratio of 30% by mass or more is preferably used.

  In the curable composition of this invention, it is preferable to use together said radically polymerizable monomer (A1) and cationically polymerizable monomer (A2). Thereby, since the radical polymerization system and the cationic polymerization system coexist and cure, a higher-order network structure is formed, and the film strength is improved.

Furthermore, the polymerizable compound (A) of the present invention is preferably a polyfunctional monomer containing two or more polymerizable groups in the molecule.
When the polymerizable compound (A) is a radical polymerizable compound, the polyfunctional monomer is preferably selected from compounds having at least two unsaturated bonds. Preferably, it is a compound having 2 to 10 terminal ethylenically unsaturated bonds in the molecule, and more preferably 2 to 6. Such a compound group is widely known in the polymer material field, and these can be used without particular limitation in the present invention. These can have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.

Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, unsaturated carboxylic acid esters having nucleophilic substituents such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional isocyanates with amides, addition reaction products with epoxies, polyfunctional carboxylic acids A dehydration-condensation reaction product and the like is also preferably used. Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols. . As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene or the like instead of the unsaturated carboxylic acid.
Ethylene glycol, propylene glycol, butanediol, neopentyl glycol, trimethylolpropane, hexanediol, cyclohexanediol, cyclohexanedimethanol, pentaerythritol, sorbitol, dipentaerythritol, etc. as unsaturated polyhydric alcohol compounds and unsaturated carboxylic acids Mono- or poly-substituted polymerizable monomers with (crotonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc.) can be used.

  Examples of other esters include, for example, vinyl methacrylate, allyl methacrylate, allyl acrylate, aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, Those having an aromatic skeleton described in JP-A-59-5240, JP-A-59-5241, JP-A-2-226149, and those having an amino group described in JP-A-1-165613 are preferably used. It is done.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis- (meth) acrylamide, 1,6-hexamethylene bis- (meth) acrylamide, diethylenetriamine trisacrylamide, xylylene bis ( Meta) acrylamide.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  Also, vinyl urethane compounds containing 2 or more polymerizable vinyl groups in one molecule (Japanese Patent Publication No. 48-41708, etc.), urethane acrylates (Japanese Patent Publication No. 2-16765, etc.), urethane having an ethylene oxide skeleton Compounds (Japanese Examined Patent Publication No. 62-39418, etc.), polyester acrylates (Japanese Examined Patent Publication No. 52-30490, etc.), and the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 (1984), those introduced as photocurable monomers and oligomers can also be used.

  When the polymerizable compound (A) is a cationic polymerizable compound, the number of cationic polymerizable groups in one molecule in the polyfunctional cationic polymerizable group-containing compound is preferably 2 to 10, particularly preferably 3 to 5. It is. The molecular weight of the curing agent is 3000 or less, preferably in the range of 200 to 2000, particularly preferably in the range of 400 to 1500. If the molecular weight is too small, volatilization in the film formation process becomes a problem.

Examples of the polyfunctional compound having a cationic polymerizable group include those having the same content as the cationic polymerizable monomer, an epoxy compound described in JP-A-8-277320, a vinyloxy group-containing compound described in JP-A-2002-29162, and the like. .
In addition, as the polyfunctional monomer of the present invention, it is preferable to use a compound containing at least one selected from the above radical polymerizable group and cationic polymerizable group in the molecule. Thereby, since the radical polymerization system and the cationic polymerization system coexist and cure, a higher-order network structure is formed, and the film strength is improved. Examples of the compound containing a radical polymerizable group and a cationic polymerizable group include, for example, compounds described in paragraphs [0031] to [0052] of JP-A-8-277320, and JP-A 2000-191737. And the compounds described in paragraph [0015]. The compounds used in the present invention are not limited to these.

It is preferable that the usage-amount of all the polymerizable group containing compounds in this invention is the range of 5 mass%-95 mass% with respect to the total amount of a curable composition. More preferably, it is 10 mass%-80 mass.
Moreover, the usage ratio of each polymerizable group-containing compound of the present invention is preferably as follows.
The total amount of the macromonomer (M) is preferably 5% by mass to 80% by mass with respect to the total amount of the polymerizable compounds (macromonomer (M), compound (A) and other polymerizable compounds) in the present invention, more preferably. Is 10% by mass to 60% by mass.
The total amount of the polymerizable monomer (A) is preferably 20% by mass to 95% by mass, and more preferably 40% by mass to 90% by mass with respect to the total amount of the polymerizable compound in the present invention.

Although the use ratio in the case of using together a radically polymerizable compound and a cationically polymerizable compound is arbitrary, (5/95)-(95/5) mass ratio is preferable. More preferred is (10/90) to (90/10) mass ratio, and still more preferred is (20/80) to (80/20) mass ratio. Within this range, the viscosity and reaction rate of the curable composition are in a preferable range, the resulting cured resin layer is excellent in mechanical properties, and a very uniform planar cured film free from point defects can be obtained. Furthermore, even a thin film of 80 μm or less is preferable because a film having good film strength can be obtained.
When using a polyfunctional monomer, 1 mass%-50 mass% are preferable with respect to the whole quantity of all the polymeric compounds (macromonomer (M), a compound (A), and another polymeric compound), More preferably, 3 masses % To 30% by mass.

Next, the polymerization initiator (L) used in the present invention will be described in detail.
The polymerization initiator (L) of the present invention is a compound that generates radicals or acids by light and / or heat irradiation. The photopolymerization initiator (L) used in the present invention preferably has a maximum absorption wavelength of 400 nm or less. By setting the absorption wavelength in the ultraviolet region in this way, handling can be performed under white light. A compound having a maximum absorption wavelength in the near infrared region can also be used.

First, the compound (L1) that generates radicals will be described in detail.
The compound (L1) that generates radicals preferably used in the present invention refers to a compound that initiates and accelerates polymerization of a compound having a polymerizable unsaturated group by generating radicals by irradiation with light and / or heat.
A known polymerization initiator or a compound having a bond with a small bond dissociation energy can be appropriately selected and used. Moreover, the compound which generate | occur | produces a radical can be used individually or in combination of 2 or more types.

  Examples of the radical generating compound include conventionally known organic peroxide compounds, thermal radical polymerization initiators such as azo polymerization initiators, amine compounds (described in Japanese Patent Publication No. 44-20189), organic halogen compounds, and carbonyl compounds. And photoradical polymerization initiators such as metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, and disulfone compounds.

Specific examples of the organic halogen compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A 63-298339, M . P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds.
More preferred are s-triazine derivatives in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring.

  Examples of other organic halogen compounds include ketones, sulfides, sulfones, and nitrogen atom-containing heterocycles described in JP-A-5-27830, [0039] to [0048].

  Examples of the carbonyl compound include “Latest UV Curing Technology”, pages 60 to 62 (published by Technical Information Association, 1991), JP-A-8-134404 [0015] to [0016], and 11-217518. Benzoin compounds such as acetophenone, hydroxyacetophenone, benzophenone, thioxan, benzoin ethyl ether, benzoin isobutyl ether, ethyl p-dimethylaminobenzoate, and the like. Benzoic acid ester derivatives such as ethyl p-diethylaminobenzoate, benzyl dimethyl ketal, acylphosphine oxide and the like.

Examples of the organic peroxide compound include compounds described in JP-A No. 2001-139663 [0019].
Examples of the metallocene compound include various titanocene compounds described in JP-A-2-4705 and JP-A-5-83588, iron-arene complexes described in JP-A-1-304453, JP-A-1-152109, and the like. Is mentioned.
Examples of the hexaarylbiimidazole compound include various ones described in JP-B-6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. And the like.

Examples of the organic borate compounds include, for example, Japanese Patent Nos. 2766769 and 2002-116539, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. Listed are the described organic borates. For example, the compounds described in JP-A-2002-116539, [0022] to [0027] can be mentioned.
As other organic boron compounds, organic boron such as JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, etc. Specific examples include transition metal coordination complexes and the like.
Examples of the sulfone compound include compounds described in JP-A-5-239015, and examples of the disulfone compound include general formulas (II) and (III) described in JP-A 61-166544. Compounds and the like.

  These radical generating compounds may be used alone or in combination of two or more. As addition amount, it is 0.1-30 mass% with respect to the whole quantity of a radically polymerizable monomer, Preferably it is 0.5-25 mass%, Most preferably, it can add at 1-20 mass%. Within this range, high polymerizability can be obtained without any problem with respect to the temporal stability of the curable composition.

The acid generator (L2) that can be used as the polymerization initiator (L) will be described in detail.
Examples of the acid generator (L2) include a known compound such as a photo-initiator for photocationic polymerization, a photo-decoloring agent for dyes, a photo-discoloring agent, or a known acid generator used in a micro-resist. A mixture thereof may be used.
Examples of the acid generator (L2) include organic halogenated compounds and disulfone compounds. Specific examples of these organic halogen compounds and disulfone compounds are the same as those described for the compound generating a radical.

Examples of the onium compounds include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like, for example, described in JP-A-2002-29162 [0058] to [0059]. And the like.
In the present invention, the acid generator (L2) that is particularly preferably used includes onium salts. Among them, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are used for photosensitivity at the start of photopolymerization, stability of compound materials It is preferable in terms of properties.

  Specific examples of onium salts that can be suitably used in the present invention include, for example, an amylated sulfonium salt described in JP-A-9-268205 [0035], and JP-A 2000-71366 [0010]. To [0011] diaryl iodonium salt or triarylsulfonium salt, thiobenzoic acid S-phenyl ester sulfonium salt described in JP-A-2001-288205 [0017], JP-A-2001-133696 [0030] To the onium salt described in [0033].

  Other examples of the acid generator include organic metal / organic halides described in JP-A-2002-29162, [0059] to [0062], a photoacid generator having an o-nitrobenzyl type protecting group, photolysis And compounds that generate sulfonic acid (iminosulfonate, etc.).

  These acid generators may be used alone or in combination of two or more. These acid generators are preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1 to 10% by mass with respect to 100% by mass of the total mass of the total cationic polymerizable monomer. It can be added in proportions. It is preferable from the stability of the curable composition, polymerization reactivity, etc. that the addition amount is in the above range.

  Moreover, the curable composition of this invention is 0.5-10 mass% of radical polymerization initiators, and 1-10 mass% of cationic polymerization initiators with respect to the total mass of a radically polymerizable compound and a cationically polymerizable compound. It is preferable to contain in the ratio. More preferably, it contains 1 to 5% by mass of a radical polymerization initiator and 2 to 6% by mass of a cationic polymerization initiator. In this range, a higher-order network structure is formed, and the film strength can be further improved.

  The curable composition of the present invention may be used in combination with a conventionally known ultraviolet spectral sensitizer or chemical sensitizer when the polymerization reaction is carried out by ultraviolet irradiation. Examples include Michler's ketone, amino acids (such as glycine), and organic amines (such as butylamine and dibutylamine).

Moreover, when performing a polymerization reaction by near infrared irradiation, it is preferable to use a near infrared spectral sensitizer together.
The near-infrared spectral sensitizer used in combination may be a light-absorbing substance having an absorption band in at least a part of the wavelength range of 700 nm or more, and a compound having a molecular extinction coefficient of 10,000 or more is preferable. Furthermore, the absorption is preferably in the range of 750 to 1400 nm and the molecular extinction coefficient is preferably 20000 or more. Moreover, it is more preferable that there is a trough of absorption in the visible light wavelength region of 420 nm to 700 nm, and it is optically transparent. As the near-infrared spectral sensitizer, various pigments and dyes known as near-infrared absorbing pigments and near-infrared absorbing dyes can be used. Among these, it is preferable to use a conventionally known near-infrared absorber.
Commercially available dyes and literature (for example, “Chemical Industry”, May 1986, p. 45-51, “Near Infrared Absorbing Dye”, “Development and Market Trends of Functional Dyes in the 90s”, Chapter 2.3. (1990) CMC), “special function pigments” (edited by Ikemori and Piladani, 1986, issued by CMC Corporation), J. Am. FABIAN, Chem. Rev., 92, pp. 1197 to 1226 (1992), a catalog published in 1995 by Nippon Sensitive Dye Research Institute, Exciton Inc. Known dyes described in the laser dye catalog or patent issued in 1989.

The curable composition of the present invention preferably uses fine particles in combination. By containing these fine particles, the universal hardness of the film can be adjusted and the crosslinking shrinkage rate can be reduced, thereby reducing the curl of the film. As the fine particles, any of inorganic particles, polymer resin particles, and inorganic-organic composite particles can be used without any particular limitation.
The fine particles can be used alone or in combination of two or more. In addition, the fine particles may have a spherical shape, a needle shape, a plate shape, or an indefinite shape as a single particle shape. The average particle size of these fine particles is preferably 1 nm to 400 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. If it is 1 nm or less, it is difficult to disperse and aggregated particles are formed, and if it is 400 nm or more, haze increases.
The addition amount of these fine particles is preferably 1 to 90% by mass of the total solid content of the curable composition, more preferably 5 to 80% by mass, and still more preferably 10 to 50% by mass. .

As inorganic particles, metal particles (iron, copper, nickel, stainless steel, silicon, etc.), metal nitrides (silicon nitride, boron nitride, titanium nitride, etc.), metal oxides (Mg, Ca, Si, Al, Ti, Zr) , V, Nb, La, In, Ce, La, Ta, Y, Zn, Sb, B, Sn, Fe, W, Ir, Cr, Mo, Sr, Pt, etc.), mixed metal oxides ( Composite oxides such as the aforementioned metals), metal carbonates (carbonates such as Ca, Ba, Mg), metal sulfates (sulfates such as Ba, Ca, Sr), metal halides (magnesium fluoride, fluoride) Calcium, etc.), metal carbides (such as tungsten carbide, molybdenum carbide, silicon carbide), carbon allotropes (graphite, diamond, etc.), and the like.
Among these fine particles, preferred are metal nitrides, metal oxides, and more preferred are metal oxides. Among them, preferred are silicon oxide, titanium oxide, and aluminum oxide.

  In general, since inorganic fine particles have poor affinity with the binder polymer, the interface is easily broken by simply mixing the two, and the film is easily broken and it is difficult to improve the scratch resistance. In order to improve the affinity between the inorganic fine particles and the polymer binder, the surface of the inorganic fine particles can be treated with a surface modifier containing an organic segment. The surface modifier preferably forms a bond with the inorganic fine particles on the one hand and has a high affinity with the binder polymer on the other hand. As the functional group capable of forming a bond with the surface of the inorganic fine particles, a metal alkoxide compound such as silane, aluminum, titanium, and zirconium, and a compound having an anionic group such as phosphoric acid, sulfonic acid, and carboxylic acid group are preferable. The binder polymer is preferably chemically bonded, and a polymer having a vinyl polymer group or the like introduced at the terminal is suitable. For example, when a binder polymer is synthesized from a monomer having an ethylenically unsaturated group as a polymerizable group and a crosslinkable group, the ethylenically unsaturated group is terminated at the end of the metal alkoxide compound or anionic compound described in JP-A-2000-9908. Compounds having a group are preferred. Moreover, it is also preferable to surface-treat with the anionic group containing compound (phosphoric acid, a sulfonic acid, carboxylic acid etc.) as described in Unexamined-Japanese-Patent No. 2001-310423.

  Examples of the organic fine particles include (meth) acrylate resin, (meth) acrylamide resin, polystyrene resin, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene and other fluorine resins, vinylidene fluoride resin, epoxy resin, phenol There are resin particles such as resin, polyurethane resin, cellulose acetate, polycarbonate, nylon resin, and crosslinked rubber fine particles such as SBR and NBR, and particles made of these composites are preferable. Internally crosslinked polymer resin fine particles obtained by copolymerization with a monomer having a bifunctional or higher functional group are preferred.

The organic crosslinked fine particles can be arbitrarily selected from soft rubber particles to hard particles. For example, the above-described inorganic crosslinked fine particles having high hardness may be fragile and easily broken, although the amount of cure shrinkage and the hardness are improved as the amount added to the cured resin layer is increased. In such a case, it is preferable that the organic crosslinked fine particles whose hardness is arbitrarily adjusted can be added at the same time to make it difficult to break. Alternatively, a core-shell particle such as a hard core and a low hardness shell or a low hardness core and a high hardness shell can be used. It is also preferable to use core-shell particles with different hydrophilicity / hydrophobicity for the purpose of ensuring dispersion stability in the cured resin layer or in the coating solvent. Moreover, it can also be set as the organic-inorganic composite fine particle which used the inorganic bridge | crosslinking fine particle for the core. When these crosslinked fine particles are used as core-shell particles, both the core part and the shell part may be crosslinked, or one of them may be crosslinked.
The fine particles are preferably contained in an amount of 1% by mass to 90% by mass in the total amount of the cured article. More preferably, it is 3-60 mass%. Within this range, the strength, hardness, and surface flatness of the film can be maintained.

  The curable composition of the present invention further comprises a monofunctional ethylenically unsaturated group-containing compound (for example, acrylates, methacrylates, vinyl carboxylates, acrylamides, rattans, or conventionally known resins (for example, polyether polyether). Acrylate, polyurethane polyacrylate, polyester polyacrylate, epoxy resin, melamine resin, etc.) In addition, conventionally known additives such as UV absorbers, surfactants for improving coating properties, antistatic agents, etc. An agent may be added.

  In the cured article of the present invention, each composition as described above may be used together with a dispersion medium. The solvent is appropriately selected from water and organic solvents. As the organic solvent, it is preferable to use a liquid having a boiling point of 50 ° C. or higher. Furthermore, an organic solvent having a boiling point in the range of 60 ° C to 180 ° C is more preferable. Examples of dispersion media include alcohols (eg, methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monoacetate, etc.), ketones (eg, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl Cyclohexanone, etc.), esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, etc.), aliphatic hydrocarbons (eg, hexane, cyclohexane, etc.), halogen Hydrocarbons (eg, methyl chloroform, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.), ethers (eg, Dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), ether alcohols (e.g., 1-methoxy-2-propanol, ethyl cellosolve, methyl carbinol and the like). These may be used alone or in combination of two or more.

  In the present invention, the cured film which is one embodiment of the cured article is a dip coating method, an air knife method, a curtain coating method, a roller coating method, a wire bar coating, and the curable composition of the present invention on a transparent substrate film. It can be produced by applying a known thin film forming method such as a coating method, a gravure coating method, a micro gravure coating method or an extrusion coating method, followed by drying, light and / or heat irradiation. Preferably, curing by light irradiation is advantageous from the viewpoint of rapid curing. Furthermore, it is also preferable to perform heat treatment in the latter half of the photocuring treatment.

  The light source for light irradiation may be any one in the ultraviolet light region or near infrared light region, and as an ultraviolet light source, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, metal halides. Lamp, xenon lamp, sunlight, and the like. Various available laser light sources having a wavelength of 350 to 420 nm may be irradiated as a multi-beam. Further, examples of the near infrared light source include a halogen lamp, a xenon lamp, a high pressure sodium lamp, and the like. Various available laser light sources having a wavelength of 750 to 1400 nm may be irradiated in a multi-beam form.

In the case of radical photopolymerization by light irradiation, it can be carried out in air or in an inert gas, but in order to shorten the polymerization induction period of the radically polymerizable monomer or sufficiently increase the polymerization rate, etc. It is preferable that the atmosphere has a reduced oxygen concentration. The irradiation intensity of the ultraviolet rays to be irradiated is preferably about 0.1 to 100 mW / cm ² , and the light irradiation amount on the coating film surface is preferably 100 to 1000 mJ / cm ² . Further, the temperature distribution of the coating film in the light irradiation step is preferably as uniform as possible, preferably within ± 3 ° C., and more preferably controlled within ± 1.5 ° C. In this range, the polymerization reaction in the in-plane and in-layer depth directions of the coating film proceeds uniformly, which is preferable.

  Furthermore, for the purpose of improving the adhesion between the transparent substrate and the cured resin layer, a surface treatment can be performed on one side or both sides as desired. For example, corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like can be mentioned. Furthermore, one or more undercoat layers can be provided. Examples of the material for the undercoat layer include copolymers such as vinyl chloride, vinylidene chloride, butadiene, (meth) acrylic acid ester, vinyl ester, latex, and low molecular weight polyester.

  The cured resin layer may have a multi-layer structure, and may be prepared by appropriately laminating layers having different filling rates of hard inorganic fine particles and soft fine particles in the order of hardness.

  On these prepared cured resin layers, a film having functions such as an antireflection layer, an ultraviolet / infrared absorbing layer, a selective wavelength absorbing layer, an electromagnetic wave shielding layer, an antifouling layer and the like can be provided. It can serve as a functional film. These functional films can be produced by applying a solution of a known material or by vacuum film formation such as sputtering or vapor deposition. Examples of the transparent conductive layer, the antireflection layer, and the antifouling layer used in the cured film of the present invention include, for example, JP-A-1-164991, JP-A-4-338901, JP-A-3-90345, and the like. The preferred ones such as surface resistivity, average reflectance, and antifouling property are the same as those described in the publication.

  The cured film of the present invention is a display such as a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display panel (PDP), a field emission display (FED), a touch panel for home appliances, a protection for glass, etc. Suitable for film.

  Furthermore, the case where the curable composition of the present invention is used as a high refractive index layer in a laminated antireflection film which is an embodiment of a cured article will be described in detail below.

[High refractive index particles]
The high refractive index inorganic fine particles have a refractive index of 1.70 to 2.80 and an average primary particle size of 1 to 150 nm. Particles having a refractive index of less than 1.80 are not preferred because the effect of increasing the refractive index of the film is small, and particles having a refractive index of more than 2.80 are colored. In addition, particles having an average primary particle size exceeding 150 nm are not preferable because the haze value when a film is formed is high, and the transparency of the film is impaired, and the refractive index is less than 1 nm and the refractive index is 1.80 to 2.80. There are no inorganic fine particles. In the present invention, more preferred inorganic fine particles are those having a refractive index of 1.90 to 2.80 and an average primary particle size of 3 to 100 nm, and more preferably a refractive index of 1.90 to 2.80. And the average particle diameter of a primary particle is a particle | grain of 5-80 nm.

  Specific examples of preferable high refractive index inorganic fine particles include Ti, Zr, Ta, In, Sn, Sb, Zn, La, W, Ce, Nb, V, Sm, Y and other oxides or composite oxides, zinc sulfide. The particle | grains which have a main component are mentioned. Here, the main component refers to a component having the largest content (mass%) among the components constituting the particles. In the present invention, particles mainly composed of an oxide or composite oxide containing at least one metal element selected from Ti, Zr, Ta, In, and Sn are preferred. The inorganic fine particles used in the present invention may contain various elements in the particles. Examples thereof include Li, Si, Al, B, Ba, Co, Fe, Hg, Ag, Pt, Au, Cr, P, and S. In tin oxide and indium oxide, it is preferable to contain elements such as Sb, Nb, P, B, In, V, and halogen in order to increase the conductivity of the particles, and in particular, about 5 to 20 mass of antimony oxide. % Is most preferable. These inorganic particles may have any of a crystal structure such as rutile, a mixed crystal of rutile / anatase, an anatase, an amorphous structure, or an amorphous structure, and those containing a crystal structure having a high refractive index are preferable.

The inorganic fine particles of the present invention may be surface treated. In the surface treatment, the surface of the particles is modified using an inorganic compound and / or an organic compound, the wettability of the surface of the inorganic particles is adjusted, and the particles are finely divided in an organic solvent. Improve dispersibility and dispersion stability. Examples of inorganic compounds to be physicochemically adsorbed on the particle surface include inorganic compounds containing silicon (such as SiO ₂ ), inorganic compounds containing aluminum (such as Al ₂ O ₃ and Al (OH) ₃ ), and cobalt. Inorganic compounds containing (CoO ₂ , Co ₂ O ₃ , Co ₃ O ₄ etc.), inorganic compounds containing zirconium (eg ZrO ₂ , Zr (OH) ₄ etc.), inorganic compounds containing iron (Fe ₂ O ₃ etc.) ).

As examples of organic compounds used for the surface treatment, conventionally known surface modifiers of inorganic fillers such as metal oxides and inorganic pigments can be used. For example, it is described in “Pigment Dispersion Stabilization and Surface Treatment Technology / Evaluation”, Chapter 1 (Technical Information Association, 2001).
Specifically, an organic compound having a polar group having an affinity for the surface of the inorganic particles and a coupling compound are exemplified. Examples of the polar group having affinity with the inorganic particle surface include a carboxy group, a phosphono group, a hydroxy group, a mercapto group, a cyclic acid anhydride group, an amino group, and the like, and a compound containing at least one kind in the molecule is preferable. . For example, long chain aliphatic carboxylic acids (eg stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid etc.), polyol compounds (eg pentaerythritol triacrylate, dipentaerythritol pentaacrylate, ECH modified glycerol triacrylate etc.), Examples include phosphono group-containing compounds (for example, EO (ethylene oxide) -modified phosphoric triacrylate) and alkanolamines (ethylenediamine EO adduct (5 mol), etc.).
As a coupling compound, a conventionally well-known organometallic compound is mentioned, A silane coupling agent, a titanate coupling agent, an aluminate coupling agent etc. are contained. Silane coupling agents are most preferred. Specific examples include the compounds described in JP-A-2002-9908 and 2001-310423 [0011] to [0015]. Two or more kinds of these surface treatments can be used in combination.

  The oxide fine particles used in the high refractive index layer of the present invention are also preferably fine particles having a core / shell structure that forms a shell made of an inorganic compound with the oxide fine particles as a core. As the shell, an oxide composed of at least one element selected from Al, Si and Zr is preferable. Specifically, for example, the contents described in JP-A-2001-166104 can be mentioned.

  The shape of the inorganic fine particles used in the high refractive index layer of the present invention is not particularly limited, but a rice grain shape, a spherical shape, a cubic shape, a spindle shape, and an indefinite shape are preferable. The inorganic fine particles of the present invention may be used alone or in combination of two or more. These inorganic particles are dispersed and used by a known method. As the dispersant, any of anionic, cationic, amphoteric, and nonionic surfactants can be preferably used, and anionic surfactants are particularly preferable. Furthermore, polymer dispersing agents such as block copolymers, coupling agents such as silane coupling agents, titanate coupling agents, aluminum coupling agents, and zircoaluminate coupling agents can also be preferably used. Moreover, what is called a polymeric dispersing agent in which these dispersing agents have a functional group copolymerizable with a binder in the same molecule can also be used preferably. Specific examples include compounds described in JP-A-11-153703.

  The content of the inorganic fine particles in the cured film with a high refractive index is preferably 30 to 75% by mass, more preferably 44 to 65% by mass, based on the total mass of the cured film. Two or more inorganic fine particles may be used in combination in the high refractive index layer. In this range, the film strength and high refractive index can be satisfied.

In the high refractive index layer of the present invention, other compounds can be appropriately added depending on applications and purposes. For example, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support, and the high refractive index layer includes an aromatic ring, a halogenated element other than fluorine (for example, Br, I, Cl, etc.), S, Binders obtained by crosslinking or polymerization reaction of curable compounds containing atoms such as N and P can also be preferably used.
In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.65 to 2.50, more preferably 1.70 to 2.40, particularly preferably 1.80 to 2.20.

  In addition to the above-mentioned components (inorganic fine particles, polymerization initiators, sensitizers, etc.), the high refractive index layer includes resins, surfactants, antistatic agents, coupling agents, thickeners, anti-coloring agents, and coloring agents. (Pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, conductive metal fine particles, etc. are added. You can also

  Examples of the coating solvent for the high refractive index layer include those similar to the dispersion medium for the cured article of the present invention. Preferably, a coating solvent system mainly containing a ketone solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) is preferable, and the content of the ketone solvent is preferably 10% by mass or more of the total solvent. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

  The high refractive index layer is preferably constructed directly on the transparent support or via another layer. Examples of the coating method and the curing method include the same methods as the coating method and the curing method described for the curable composition in the previous cured product.

  The strength of the high refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better. The haze of the high refractive index layer is preferably as low as possible. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

[Low refractive index layer]
The antireflection film of the present invention is formed by sequentially laminating a low refractive index layer on a high refractive index layer provided on a transparent support. The refractive index of the low refractive index layer is preferably 1.20 to 1.55, more preferably 1.30 to 1.50, and particularly preferably 1.35 to 1.48.
The low refractive index layer is preferably constructed as an outermost layer having scratch resistance and antifouling properties. As means for greatly improving the scratch resistance, it is effective to impart slipperiness to the surface, and conventionally known thin film layer means such as introduction of silicone or introduction of fluorine can be applied.

In the present invention, “mainly containing a fluorine-containing compound” means that the fluorine-containing compound contained in the outermost layer is 50% by mass or more with respect to the total mass of the outermost layer, and is contained by 60% by mass or more. It is more preferable.
The refractive index of the fluorine-containing compound is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47. Moreover, it is preferable that a fluorine-containing compound contains a fluorine atom in 35-80 mass%.
Examples of the fluorine-containing compound include a fluorine-containing polymer, a fluorine-containing surfactant, a fluorine-containing ether, and a fluorine-containing silane compound. Specifically, for example, Japanese Patent Application Laid-Open No. 9-222503 [0018] to [0026], Japanese Patent Application Laid-Open No. 11-38202 [0019] to [0030], Japanese Patent Application Laid-Open No. 2001-40284 [0027] to [0028], etc. And the like.

As the fluorine-containing polymer, a copolymer comprising a repeating structural unit containing a fluorine atom, a repeating structural unit containing a crosslinkable or polymerizable functional group, and a repeating structural unit composed of other substituents is preferable. Examples of the crosslinkable or polymerizable functional group are the same as those of the material for a high refractive index layer.
As the other repeating structural unit, a hydrocarbon copolymer component is preferable for solubilization of the coating solvent, and a fluorine polymer introduced by about 50% is preferable. In this case, it is preferable to combine with a silicone compound.

The silicone compound is a compound having a polysiloxane structure, preferably containing a curable functional group or a polymerizable functional group in the polymer chain and having a crosslinked structure in the film. Examples thereof include reactive silicones such as commercially available Silaplane (manufactured by Chisso Corporation), and compounds containing silanol groups at both ends of the polysiloxane structure described in JP-A-11-258403.
The crosslinking or polymerization reaction of the fluorine-containing polymer having a crosslinking or polymerizable group is preferably carried out by irradiating or heating the coating composition for forming the outermost layer simultaneously with or after coating. Examples of the polymerization initiator and the sensitizer include those similar to those used in the high refractive index layer.

  Also preferred is a sol-gel cured film in which a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent are cured by a condensation reaction in the presence of a catalyst. For example, polyfluoroalkyl group-containing silane compounds or partially hydrolyzed condensates thereof (compounds described in JP-A-58-142958, JP-A-58-147483, JP-A-58-147484, etc.), JP-A-9-157582 Perfluoroalkyl group-containing silane coupling agents described in Japanese Patent Publication No. JP-A-2000-117902, JP-A-2000-117902, JP-A-2001-48590, And the like described in JP-A-2002-53804).

The low refractive index layer contains a filler (for example, inorganic fine particles, organic fine particles, etc.), a silane coupling agent, a slip agent (silicon compound such as dimethyl silicon), a surfactant, etc. as additives other than the above. Can do. In particular, it is preferable to contain inorganic fine particles, a silane coupling agent, and a slip agent.
As the inorganic fine particles, low refractive index compounds such as silicon dioxide (silica) and fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride, etc.) are preferable. Particularly preferred is silicon dioxide (silica). The weight average diameter of the primary particles of the inorganic fine particles is preferably 3 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 80 nm. The inorganic fine particles are preferably more finely dispersed. The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a short fiber shape, a ring shape, or an indefinite shape.

The low refractive index layer preferably has a surface dynamic friction coefficient of 0.25 or less. The dynamic friction coefficient described here refers to a dynamic friction coefficient between a surface and a stainless steel hard sphere having a diameter of 5 mm when a load of 0.98 N is applied to a stainless steel hard sphere having a diameter of 5 mm and the surface is moved at a speed of 60 cm / min. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.
Further, the contact angle with water on the outermost surface is preferably 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.

When the low refractive index layer is located below the outermost layer, the low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.). The coating method is preferable because it can be manufactured at a low cost.
The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.
The haze of the low refractive index layer is preferably as low as possible. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
The strength of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400. Further, the same performance as that of the uppermost layer is preferable for the wear amount, the surface dynamic friction coefficient, and the contact angle with water in the Taber test according to JIS K5400.

[Medium refractive index layer]
The antireflection film of the present invention preferably has a two-layer structure in which the high refractive index layer is composed of different refractive indexes. That is, the low refractive index layer formed by applying the composition by the above method is formed on the high refractive index layer having a higher refractive index, adjacent to the high refractive index layer, and low refractive index. A three-layer structure in which an intermediate refractive index layer having a refractive index intermediate between the refractive index of the support and the refractive index of the high refractive index layer is formed on the opposite side of the refractive index layer is preferable. As described above, the refractive index of each refractive index layer is relative.
The material constituting the middle refractive index layer of the present invention may be any conventionally known material, but the same material as the high refractive index layer is preferable. The refractive index is easily adjusted by the type and amount of inorganic fine particles, and a thin layer having a thickness of 30 to 500 nm is formed in the same manner as described in the refractive index layer. More preferably, the film thickness is 50 to 300 nm.

[Hard coat layer]
The hard coat layer is provided on the surface of a transparent support (which may have an undercoat layer) in order to impart physical strength to the antireflection film. In particular, it is preferably provided between the transparent support and the high refractive index layer, or between the transparent support and the medium refractive index layer.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a light and / or heat curable compound. For example, a coating composition containing a polyester (meth) acrylate, polyurethane (meth) acrylate, a polyfunctional monomer, a polyfunctional oligomer, or a hydrolyzable functional group-containing organometallic compound is coated on a transparent support, and a curable compound is applied. It can be formed by a crosslinking reaction or a polymerization reaction.
The curable functional group is preferably a photopolymerizable functional group, and the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound.
The hard coat layer preferably contains inorganic fine particles having an average primary particle size of 300 nm or less. More preferably, it is 10-150 nm, More preferably, it is 20-100 nm. The average particle diameter here is a weight average diameter. By setting the average particle size of the primary particles to 200 nm or less, a hard coat layer that does not impair the transparency can be formed.

The inorganic fine particles have functions of increasing the hardness of the hard coat layer and suppressing curing shrinkage of the coating layer. It is also added for the purpose of controlling the refractive index of the hard coat layer.
Specific examples of the composition of the hard coat layer include those described in JP-A Nos. 2002-144913, 2000-9908, and WO00 / 46617.
The content of the inorganic fine particles in the hard coat layer is preferably 10 to 90% by mass and more preferably 15 to 80% by mass with respect to the total mass of the hard coat layer.

Since the high refractive index layer obtained using the curable composition of the present invention has a hard coat property, it can also serve as the hard coat layer. When the high refractive index layer also serves as the hard coat layer, it is preferably formed by finely dispersing inorganic fine particles and using the technique described in the high refractive index layer to be contained in the hard coat layer.
The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 0.2 to 10 μm, more preferably 0.5 to 7 μm, and particularly preferably 0.7 to 5 μm.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

[Other layers]
The laminated antireflection film may further be provided with a moisture proof layer, an antistatic layer, a primer layer, an undercoat layer, a protective layer, a shield layer, a sliding layer, and the like. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Transparent support]
Except when the curable composition of the present invention is directly provided on a substrate such as a CRT image display surface or lens surface as an antireflection film, the antireflection film preferably has a transparent support (transparent substrate). As the transparent support, a plastic film is preferable to a glass plate. Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose, etc.), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). Phthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate, etc.), polystyrene (for example, syndiotactic polystyrene), polyolefin (Eg, polypropylene, polyethylene, polymethylpentene, etc.), polysulfone, polyethersulfone, polyarylate, polyether Examples include terimide, polymethyl methacrylate, and polyether ketone. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred.

The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7. An infrared absorber or an ultraviolet absorber may be added to the transparent support. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass. As a slip agent, particles of an inert inorganic compound may be added to the transparent support. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin.

  A surface treatment may be performed on the transparent support. Examples of surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, acid treatment, alkali treatment (including alkali saponification treatment). ) And ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, flame treatment and alkali treatment are preferred, and glow discharge treatment, ultraviolet treatment and alkali saponification treatment are particularly preferred.

[Formation of antireflection film]
Each layer of the antireflection film having a multilayer structure is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (described in US Pat. No. 2,681,294). , Can be formed by coating. Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,789, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

  The lower the reflectance of the antireflection film, the better. Specifically, the average reflectance in the wavelength region of 450 to 650 nm is preferably 2% or less, more preferably 1% or less, and most preferably 0.7% or less. The haze of the antireflection film (when the antiglare function described below is absent) is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The strength of the antireflection film is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400.

[Surface unevenness of antireflection film]
The antireflection film used in the present invention can impart antiglare properties by forming irregularities on the surface having the high refractive index layer.
The antiglare property correlates with the average surface roughness (Ra) of the surface. It is preferable that the surface roughness is 1 mm ² randomly extracted from an area of 100 cm ² , and the average surface roughness (Ra) is 0.01 to 0.4 μm per 1 mm ² area of the extracted surface. More preferably, it is 0.03-0.3 micrometer, More preferably, it is 0.05-0.25 micrometer, Most preferably, it is 0.07-0.2 micrometer.
The average surface roughness (Ra) is described in the techno compact series (6) (surface roughness measurement / evaluation method, author: Jiro Nara, publisher: General Technology Center, Inc.).

The concave and convex shapes on the surface of the antireflection film used in the present invention can be evaluated by an atomic force microscope (AFM).
A well-known method is used as a method of forming surface irregularities. For example, fine particles are used in the low refractive index layer, thereby forming irregularities on the film surface (for example, JP-A-2000-271878), and the irregular shape is physically transferred to the low refractive index layer surface (embossing). And the like) (for example, JP-A 63-278839, JP-A 11-183710, 11-268800, JP-A 2000-275401, etc.).
Moreover, the laminated body which provided the hard-coat layer which contained the mat | matte particle between the transparent support body and the low-refractive-index layer as an anti-glare antireflection film is mentioned. That is, an antiglare hard coat layer obtained by adding light scattering particles having a particle size of 0.2 to 10 μm together with the curable composition of the present invention to impart an antiglare function (antiglare function) is preferable. Examples of the mat particles include materials described in JP-A Nos. 2000-258606 and 2002-40204.

[Protective film for polarizing plate]
When the antireflection film of the present invention is used as a protective film for a polarizing film (protective film for polarizing plate), the surface of the transparent support opposite to the side having the high refractive index layer, that is, the surface to be bonded to the polarizing film It is preferable that the contact angle with respect to water be 40 ° or less to ensure sufficient adhesion to the polarizing film.
As the transparent support, it is particularly preferable to use a triacetyl cellulose film.

The following two methods are mentioned as a method of producing the protective film for polarizing plates in this invention.
(1) A method of coating each of the above-described layers (eg, hard coat layer, high refractive index layer, low refractive index layer) on one surface of the saponified transparent support.
(2) A method in which the above layers (eg, hard coat layer, high refractive index layer, low refractive index layer, etc.) are coated on one surface of the transparent support, and then the side to be bonded to the polarizing film is saponified.

  Furthermore, a saponification treatment solution can be applied to the surface of the transparent support on the side to be bonded to the polarizing film of the antireflection film, and the side to be bonded to the polarizing film can be saponified.

  Protective films for polarizing plates have optical performance (antireflection performance, antiglare performance, etc.), physical performance (such as scratch resistance), chemical resistance, antifouling performance (contamination resistance, etc.), and weather resistance (moisture and heat resistance, light resistance). In terms of properties, it is preferable to satisfy the performance described in the antireflection film of the present invention.

[surface treatment]
The hydrophilic treatment of the surface of the transparent support can be performed by a known method. For example, it is preferable to saponify the transparent support or the antireflection film in an alkali solution by immersing it for an appropriate time or applying an alkali solution.
Examples of the alkaline solution and treatment include the contents described in JP-A No. 2002-82226 and WO 02/46809. The saponification treatment is preferably carried out so that the contact angle with water on the film surface is 45 ° or less.
The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.

[Polarizer]
The preferable polarizing plate of this invention has the antireflection film of this invention in at least one of the protective film (protective film for polarizing plates) of a polarizing film. As described above, the polarizing plate protective film has a water contact angle of 40 ° or less on the surface of the transparent support opposite to the side having the high refractive index layer, that is, the surface to be bonded to the polarizing film. It is preferable.
By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having an antireflection function can be produced, and the cost can be greatly reduced and the display device can be thinned.
Further, by preparing a polarizing plate using the antireflection film of the present invention as one of the protective films for polarizing plates and an optical compensation film having optical anisotropy described later as the other protective film of the polarizing film, Thus, a polarizing plate capable of improving the contrast in the bright room of the liquid crystal display device and greatly widening the vertical and horizontal viewing angles can be produced.

[Optical compensation film]
The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
As the optical compensation film, a known film can be used, but in terms of widening the viewing angle, it has a layer made of a compound having a discotic structural unit described in JP-A-2001-100042, An optical compensation film characterized in that the angle formed by the discotic compound and the support varies in the depth direction of the layer.
The angle preferably increases as the distance from the support surface side of the optically anisotropic layer increases.
When the optical compensation film is used as a protective film for the polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.
Moreover, the aspect in which the optically anisotropic layer further contains a cellulose ester is also preferable.

[Image display device]
The antireflection film can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). The antireflection film adheres the transparent support side of the antireflection film to the image display surface of the image display device.

The antireflection film and polarizing plate used in the present invention are twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB). It can be preferably used for a transmissive, reflective or transflective liquid crystal display device of the mode.
When used in a transmissive or transflective liquid crystal display device, it is used in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). Thus, a display device with higher visibility can be obtained.
Further, when combined with a λ / 4 plate, it can be used to reduce reflected light from the surface and inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display.

  Specific examples of the curable composition of the present invention, and the cured article and antireflection film using the curable composition will be described below, but the present invention is not limited thereto.

<Synthesis Example of Macromonomer (M1)>
Synthesis Example 1 of Macromonomer (M1) 1: Macromonomer (M1-1)
A mixture of 26.4 g of 1,6-hexanediol, 38 g of tricyclo [5.2.1.0 ^2,6 ] decane-8,9-dicarboxylic acid, 0.01 g of dibutyltin oxide and 150 g of mesitylene was added to a Dean-Star reflux apparatus. The mixture was heated under reflux in the attached flask for 4 hours. The amount of water distilled off azeotropically with the toluene solvent was about 3.5 g. After cooling to room temperature, it was reprecipitated in 800 ml of methanol, and the liquid was collected after decanting and dried under reduced pressure.
The above reaction product was dissolved in dimethylformamide, and the hydroxyl group and carboxyl group were measured by potentiometric titration with a 0.1N sodium methylate methanol solution.

A mixture of 50 g of the above solid substance, 4.3 g of methacrylic acid, 1.0 g of t-butylhydroquinone and 200 g of methylene chloride was dissolved at room temperature with stirring. A mixed solution of 10.2 g of dicyclohexylcarbodiimide (DCC), 0.2 g of 4- (N, N-dimethyl) aminopyridine and 50 g of methylene chloride was titrated to the above mixture with stirring for 1 hour. The mixture was further stirred for 4 hours.
D. C. As the solution C was dropped, insoluble crystals were deposited. 3 g of 3% aqueous formic acid solution was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered by suction filtration using celite, the filtrate was reprecipitated in 500 ml of methanol, and the solid matter was collected by filtration. This was dissolved in 100 ml of tetrahydrofuran and then reprecipitated again in 500 liters of methanol. After collecting the solid matter, it was dried under reduced pressure. The yield of the obtained product was 42 g, and Mw was 5 × 10 ³ . When the amount of hydroxyl group of the obtained macromonomer was measured by the same potentiometric titration method as described above, it was 5 μmol / gr and the reaction rate was 99%.

Synthesis Example 2 of Macromonomer (M1): Macromonomer (M1-2)
A mixture of 72.1 g of 1,4-cyclohexanemethanediol, 50 g of succinic anhydride, 0.7 g of p-toluenesulfonic acid monohydrate and 200 g of xylene was reacted in the same manner as in Macromonomer (M1) Synthesis Example 1. .
Next, a mixed solution of 8.6 g of acrylic acid and 75 g of toluene and 0.5 g of t-butylhydroquinone were added to the reaction product, and then reacted for 4 hours under reflux with further stirring. After cooling to room temperature, it was reprecipitated in 1 liter of methanol, and the precipitated solid was collected by filtration and dried under reduced pressure. The yield was 67 g, and the weight average molecular weight of the obtained macromonomer (M1-2) was 8 × 10 ³ .

Synthesis Example 3 of Macromonomer (M1): Macromonomer (M1-3)
A mixture of 64.5 g of a diol compound having the following structure, 28.6 g of glutaric anhydride, 0.4 g of p-toluenesulfonic acid and 220 g of mesitylene was reacted in the same manner as in Synthesis Example 1 for the macromonomer (M1).
After cooling to room temperature, it was reprecipitated in 1 liter of methanol, and the precipitate was collected by filtration and dried under reduced pressure. Using 50 g of the solid, the D.C. described in Synthesis Example 2 of the macromonomer (M1). C. By the method using C, reaction was performed using a polymerizable group-containing carboxylic acid having the following structure to obtain 40 g of a macromonomer (M1-3). Mw was 7 × 10 ³ .

Synthesis Example 4 of Macromonomer (M1): Macromonomer (M1-4)
A mixture of 77.1 g of 5-norbornene-2,3-dimethanol, 54.2 g of glutaric anhydride, 6.7 g of dodecenyl succinic anhydride and 0.01 g of dizutyl tin oxide was heated to a temperature of 120 ° C. The mixture was stirred under a nitrogen stream at a reduced pressure of about 30 mmHg for 2 hours, further heated to 150 ° C. and stirred at a reduced pressure of about 5 mmHg for 2 hours. After allowing to cool, 300 g of tetrahydrofuran was added and dissolved, and then reprecipitated in 1 liter of methanol. The precipitate was collected by filtration and dried under reduced pressure.
A mixture of 50 g of the above solid substance, 6.2 g of 2-methacryloyloxyethyl isocyanate, 0.01 g of t-butylhydroquinone, 0.01 g of tetrabutoxytitanate and 120 g of tetrahydrofuran was stirred at a temperature of 60 ° C. for 6 hours.
After allowing to cool, it was reprecipitated in 600 ml of methanol, and the precipitate was collected and dried under reduced pressure to obtain a macromonomer (M1-4) having an Mw of 8 × 10 ^{3 in} a yield of 41 g.

Synthesis Example 5 of Macromonomer (M1): Macromonomer (M1-5)
To a mixed solution of 50 g of macromonomer (M1-1), 3 g of methanol, 0.5 g of t-butylhydroquinone and 150 g of methylene chloride, C. C. A mixed solution of 6 g, 0.1 g of 4-N, N-dimethylaminopyridine and 10 g of methylene chloride was added dropwise with stirring at a temperature of 20 to 25 ° C. over 30 minutes, and the mixture was further stirred for 4 hours. After adding 5 g of formic acid to this reaction mixture and stirring for 1 hour, the precipitated insoluble matter was filtered off. The filtrate was reprecipitated in 1 liter of methanol, the solvent was removed by decantation, and the precipitate was collected and dried under reduced pressure. The resulting viscous product had a yield of 28 g and Mw of 6.8 × 10 ³ .

Synthesis Examples 6 to 11 of Macromonomer (M1): Macromonomer (M1-6) to (M1-11)
Each macromonomer shown in Table 1 below was synthesized in the same manner as in Synthesis Example 1 of Macromonomer (M1). Mw of each macromonomer (M1-6) to (M1-11) was in the range of 6 × 10 ₃ to 8 × 10 ³ .

Synthesis Example 12 of Macromonomer (M1): Macromonomer (M1-12)
A mixture of 26.4 g of 1,6-hexanediol, 38 g of tricyclo [5.2.1.0 ^2,6 ] decane-8,9-dicarboxylic acid, 0.01 g of dibutyltin oxide and 150 g of mesitylene was added to a Dean-Star reflux apparatus. The mixture was heated under reflux in the attached flask for 4 hours. The amount of water distilled off azeotropically with the toluene solvent was about 3.5 g. After cooling to room temperature, it was reprecipitated in 800 ml of methanol, and the liquid was collected after decanting and dried under reduced pressure.
The above reaction product was dissolved in dimethylformamide, and the hydroxyl group and carboxyl group were measured by potentiometric titration with a 0.1N sodium methylate methanol solution.

A mixture of 50 g of the above solid, 10.6 g of 2- [2-carboxyethylcarbonyloxy] ethyl methacrylate, 1.0 g of t-butylhydroquinone and 200 g of methylene chloride was dissolved at room temperature with stirring. A mixed solution of 10.2 g of dicyclohexylcarbodiimide (DCC), 0.2 g of 4- (N, N-dimethyl) aminopyridine and 50 g of methylene chloride was titrated to the above mixture with stirring for 1 hour. The mixture was further stirred for 4 hours.
D. C. As the solution C was dropped, insoluble crystals were deposited. 3 g of 3% aqueous formic acid solution was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered by suction filtration using celite, the filtrate was reprecipitated in 500 ml of methanol, and the solid matter was collected by filtration. This was dissolved in 100 ml of tetrahydrofuran and then reprecipitated again in 500 liters of methanol. After collecting the solid matter, it was dried under reduced pressure. The yield of the obtained product was 42 g, and Mw was 5 × 10 ³ . When the amount of hydroxyl group of the obtained macromonomer was measured by the same potentiometric titration method as described above, it was 5 μmol / gr and the reaction rate was 99%.

Synthesis Example 13 of Macromonomer (M1): Macromonomer (M1-13)
A mixture of 77.1 g of 5-norbornene-2,3-dimethanol, 54.2 g of glutaric anhydride, 6.7 g of dodecenyl succinic anhydride and 0.01 g of dizutyl tin oxide was heated to a temperature of 120 ° C. The mixture was stirred under a nitrogen stream at a reduced pressure of about 30 mmHg for 2 hours, further heated to 150 ° C. and stirred at a reduced pressure of about 5 mmHg for 2 hours. After allowing to cool, 300 g of tetrahydrofuran was added and dissolved, and then reprecipitated in 1 liter of methanol. The precipitate was collected by filtration and dried under reduced pressure.
A mixture of 50 g of the above solid substance, 6.2 g of 2-methacryloyloxyethyl isocyanate, 0.01 g of t-butylhydroquinone, 0.01 g of tetrabutoxytitanate and 120 g of tetrahydrofuran was stirred at a temperature of 60 ° C. for 6 hours.
After allowing to cool, it was reprecipitated in 600 ml of methanol, and the precipitate was collected and dried under reduced pressure to obtain a macromonomer (M1-13) having an Mw of 8 × 10 ^{3 in} a yield of 41 g.

Synthesis Example 14 of Macromonomer (M1): Macromonomer (M1-14)
A mixture of 64.5 g of a diol compound having the following structure, 28.6 g of glutaric anhydride, 0.4 g of p-toluenesulfonic acid and 220 g of mesitylene was reacted in the same manner as in Synthesis Example 11 for the macromonomer (M1).
After cooling to room temperature, it was reprecipitated in 1 liter of methanol, and the precipitate was collected by filtration and dried under reduced pressure. Using 50 g of the solid, the D.C. described in Synthesis Example 2 of the macromonomer (M1). C. In the method using C, reaction was performed using an epoxy group-containing carboxylic acid having the following structure to obtain 40 g of macromonomer (M1-14). Mw was 7 × 10 ³ .

Synthesis Examples 15 and 16 of Macromonomer (M1): Macromonomer (M1-15) and (M1-16)
To a mixed solution of 50 g of macromonomer (M1-16) having the following structure synthesized in the same manner as in Synthesis Example 11 of macromonomer (M1), 3 g of methanol, 0.5 g of t-butylhydroquinone and 150 g of methylene chloride, C. C. A mixed solution of 6 g, 0.1 g of 4-N, N-dimethylaminopyridine and 10 g of methylene chloride was added dropwise with stirring at a temperature of 20 to 25 ° C. over 30 minutes, and the mixture was further stirred for 4 hours. After adding 5 g of formic acid to this reaction mixture and stirring for 1 hour, the precipitated insoluble matter was filtered off. The filtrate was reprecipitated in 1 liter of methanol, the solvent was removed by decantation, and the precipitate was collected and dried under reduced pressure. The obtained viscous product (macromonomer (M1-15)) had a yield of 28 g and Mw of 8.0 × 10 ³ .

Synthesis Examples 17 to 21 of Macromonomer (M1): Macromonomer (M1-17) to (M1-21)
Each macromonomer of the following Table-2 was synthesize | combined like the said synthesis example. Mw of each macromonomer (M1-17) to (M1-21) was in the range of 6 × 10 ³ to 8 × 10 ³ .

<Synthesis Example of Macromonomer (M2)>
Synthesis Example 1 of Macromonomer (M2) 1: Macromonomer (M2-1)
B: sphenol A ethoxylate (manufactured by Aldvich) 80.8 g, succinic anhydride 1.0 g, p-toluenesulfonic acid monohydrate 1.6 g and toluene 200 g in a flask equipped with a Dean-Star reflux apparatus The mixture was heated at reflux for 4 hours with stirring. The amount of water distilled off azeotropically with the xylene solvent was about 3.4 g.
After cooling, it was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried under reduced pressure to obtain a product with a yield of 88 g. The reaction product was dissolved in toluene, and the carboxyl group content was measured by neutralization titration with 0.1N potassium hydroxide and methanol solution to give 500 μmol / gr.

Next, after adding 50 g of the reaction product, 6.5 g of 2-hydroxyethyl methacrylate and 150 g of toluene and 0.3 g of t-butylhydroquinone to the reaction product, C. C. A mixed solution of 10.3 g, 4- (N, N-dimethylamino) pyridine (0.1 g) and methylene chloride (30 g) was added dropwise to the above mixture over 1 hour with stirring. Further, the mixture was stirred as it was for 4 hours.
The reaction mixture was passed through a 200-mesh nylon cloth, and the insoluble material was filtered off. The filtrate was reprecipitated in 800 ml of methanol and the powder was collected by filtration. This was dissolved in 100 g of methylene chloride and reprecipitated again in 500 ml of methanol. The powder was collected by filtration and dried under reduced pressure to obtain 35 g of a macromonomer having a weight average molecular weight (hereinafter referred to as Mw) of 6.3 × 10 ³ . The macromonomer was titrated by the neutralization titration method and the residual carboxyl group content was measured. As a result, it was 8 μmol / gr, and the reaction rate was 99.8%.

Synthesis Example 2 of Macromonomer (M2): Macromonomer (M2-2)
Tricyclo [5.2.1.0. ^2,6 ] A mixture of 67.2 g of decane-3,4-diol, 40.1 g of pimelic acid, 0.7 g of para-toluenesulfonic acid and 250 g of mesitylene was reacted in the same manner as in Synthesis Example 1 of the macromonomer (M2). I let you. After cooling to room temperature, it was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried under reduced pressure to obtain a product with a yield of 91 g.
A mixture of 50 g of the above solid, 5.4 g of glycidyl methacrylate, 1.0 g of t-butylhydroquinone, 1.0 g of N, N′-dimethyldodecylamine and 200 g of xylene was stirred at a temperature of 140 ° C. for 5 hours.
After cooling, the reaction solution was reprecipitated in 800 ml of methanol, and the liquid was decanted and collected, and dried under reduced pressure to obtain a product of Mw 5 × 10 ³ in a yield of 42 g.

Synthesis Example 3 of Macromonomer (M2): Macromonomer (M2-3)
A mixture of 43.0 g of 1,3-cyclohexanedicarboxylic acid, 36.1 g of 1,4-cyclohexanemethanediol and 0.005 g of dibutyltin oxide was heated to a temperature of 140 ° C. in a nitrogen atmosphere. After stirring at a reduced pressure of 20 mmHg for 1 hour, the mixture was stirred at a temperature of 160 ° C. at a reduced pressure of 5 mmHg for 2 hours.
After allowing to cool, 180 g of toluene was added and dissolved, and then re-precipitated in 1 liter of methanol, and the precipitate was collected and dried under reduced pressure to obtain a yield of 68 g.
Using the above reaction product (50 g) and the following compound (a) (4.5 g), the same D.S. C. A macromonomer was synthesized by a method using C. The yield was 43 g and the Mw was 8 × 10 ³ .

Synthesis Example 4 of Macromonomer (M2): Macromonomer (M2-4)
A mixture of 120 g of 1,6-hexanediol, 114.1 g of glutaric anhydride, 3.0 g of p-toluenesulfonic acid monohydrate and 250 g of toluene was reacted under the same conditions as in Synthesis Example 1 for the macromonomer (M2). did. After cooling to room temperature, it was reprecipitated in 2 liters of n-hexane and collected after decanting and drying under reduced pressure.
To a mixture of 100 g of a polyester oligomer, 200 g of methylene chloride and 1 cc of dimethylformamide, 15 g of thionyl chloride was added dropwise with stirring at a temperature of 25 to 30 ° C. It stirred for 2 hours as it was after completion | finish of dripping. Next, after distilling off methylene chloride and excess thionyl chloride under reduced pressure of an aspirator, 200 g of tetrahydrofuran and 11.9 g of pyridine were added to the residue and dissolved, and 8.7 g of allyl alcohol was stirred at a temperature of 25 to 30 ° C. It was dripped in. After dropping, the mixture was further stirred for 3 hours, and then the reaction mixture was put into 1 liter of water and stirred for 1 hour. After standing, the precipitated liquid was separated by decantation. 1 liter of water was added to this liquid material, stirred again for 30 minutes, allowed to stand still, and the liquid material that settled was collected by decantation. This operation was repeated until the supernatant solution became neutral. Next, 500 ml of diethyl ether was added to this liquid and stirred to form a solid.
The solid was collected by filtration and dried under reduced pressure to obtain 59 g of a macromonomer (M2-4) having a weight average molecular weight of 1.2 × 10 ⁴ .

Synthesis Example 5 of Macromonomer (M2): Macromonomer (M2-5)
50 g of the macromonomer (M2-3) and 5 g of triethylamine were dissolved in 100 g of tetrahydrofuran and cooled to a temperature of 5 degrees or less. To this, 4.0 g of acetyl chloride was added dropwise so that the temperature did not exceed 5 ° C., and the mixture was stirred as it was for 4 hours. The reaction mixture was then reprecipitated in 800 ml of methanol, the precipitate collected, dissolved in 80 ml of tetrahydrofuran and reprecipitated again in 500 ml of methanol. The precipitate was collected and dried under reduced pressure to obtain a product of Mw 8 × 10 ^{3 in} a yield of 33 g.

Synthesis Examples 6 to 11 of Macromonomer (M2): Macromonomer (M2-6) to (M2-11)
The macromonomers (M2-6) to (M2-11) shown in Table 3 below were synthesized in the same manner as in Synthesis Example 1 of the macromonomer (M2). The Mw of each macromonomer was in the range of 6 × 10 ³ to 1 × 10 ⁴ .

Synthesis Example 12 of Macromonomer (M2): Macromonomer (M2-12)
A mixture of 120 g of 1,6-hexanediol, 114.1 g of glutaric anhydride, 3.0 g of p-toluenesulfonic acid monohydrate and 250 g of toluene was reacted under the same conditions as in Synthesis Example 1 for the macromonomer (M2). did. After cooling to room temperature, it was reprecipitated in 2 liters of n-hexane and collected after decanting and drying under reduced pressure.
A mixture of 50 g of the above polyester oligomer, 7.0 g of epibromohydrin, 0.1 g of potassium iodide and 105 g of methyl ethyl ketone was stirred at a temperature of 80 ° C. for 8 hours, and then 30 g of methyl ethyl ketone was driven out and left overnight at room temperature. The filtrate obtained by filtering off the insoluble material by suction filtration using Celite was reprecipitated in 400 ml of n-hexane. The liquid that settled down and settled was collected by decantation, dissolved in 80 g of tetrahydrofuran, and reprecipitated in 400 ml of diethyl ether.
The solid was collected by filtration and dried under reduced pressure to obtain 59 g of a macromonomer (M2-4) having a weight average molecular weight of 1.2 × 10 ⁴ .

Synthesis Examples 13-15 of Macromonomer (M2): Macromonomer (M2-13)-(M2-15)
In the same manner as in Synthesis Example 1 for Macromonomer (M2), Macromonomers (M2-13) to (M2-15) shown in Table 4 below were synthesized. The Mw of each macromonomer was in the range of 6 × 10 ³ to 1 × 10 ⁴ .

Example 1 and Comparative Example 1
<Preparation of inorganic fine particle dispersion (R-1)>
The following amounts of each reagent were weighed in a ceramic coated vessel.

234 g of methyl isobutyl ketone
Anionic functional group-containing surface treatment agent:
H ₂ C═C (H) COO (C ₅ H ₁₀ COO) ₂ H 36 g
180 g of alumina fine particles (average particle size: 15 nm)

  The above mixture was finely dispersed in a sand mill (1/4 G sand mill) at 1600 rpm for 10 hours. The media used was 1400 g of 1 mmφ zirconia beads. After dispersion, the beads were separated to obtain a surface-modified inorganic crosslinked fine particle dispersion.

<Preparation of inorganic fine particle dispersion (R-2)>
While stirring 20.0 g of ultrafine silica (“Aerosil 200” (average particle diameter of primary particles: 12 nm): Nippon Aerosil Co., Ltd.) as inorganic fine particles, 3% by mass of γ-methacryloxypropyltrimethoxysilane 10 ml of a tetrahydrofuran solution was added dropwise over about 2 minutes using a glass Pasteur pipette. Thereafter, this solution was heated and stirred for 1 hour under a nitrogen stream to introduce a methacryloyl group on the surface. After completion of the reaction, after washing several times by the centrifugal sedimentation method, the ultrafine silica was taken out, and after removing the solvent by a vacuum drying method, it was ground in an agate mortar to obtain ultrafine silica having a methacryloyl group introduced.

<Preparation of curable composition>
-Macromonomer (M1-1) of the present invention 50 g
・ Cyclohexyl acrylate 25g
・ Methyl methacrylate 25g
・ 40 g of the fine particle dispersion (R-1) (as solid content)
・ Methyl isobutyl ketone 300g
・ Irgacure 184 (trade name, manufactured by Ciba Geigy) 8.5g

  The mixture was stirred for 30 minutes and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for an active energy ray cured layer.

<Production of Cured Film Sample (F-1)> (Example 1)
After glow discharge treatment on a 188 μm polyethylene terephthalate film as a transparent substrate, the curable composition prepared above was applied with a slot coater to a film thickness of 20 μm, dried at 120 ° C. for 2 minutes, and 750 mj / cm ² . After ultraviolet irradiation, a cured film (F-1) was produced by heating at 120 ° C. for 10 minutes.

<Preparation of Comparative Cured Film Sample (FR-1)> (Comparative Example 1)
In the curable composition of Example 1, except for 50 g of the macromonomer (M1-1), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name DPHA, manufactured by Nippon Kayaku Co., Ltd.) was used instead. A cured film (FR-1) was produced in the same manner as in Example 1 except that the above macromonomer (M1-1) was used.

  The performance results of each sample obtained are shown in Table-5.

The sample was evaluated by the following method.
(Evaluation method for pencil hardness)
The prepared cured film and cured glass sample were allowed to stand for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%, and then, using a test pencil specified by JIS S6006, in accordance with the pencil hardness evaluation method specified by JIS K5400. , The hardness value of a pencil with no scratches observed at a load of 9.8 N. The scratches defined in JIS K5400 are (1) paint film tears, (2) paint film scratches, and (3) paint film dents are not covered. (3) It was judged as a scratch including the dent of the coating film.

(Scratch resistance evaluation method)
Using # 0000 steel wool, the surface of the cured resin film was applied with a load of 1.96 N / cm ² under the same environment as described above, and rubbed 50 times (reciprocating) to visually observe the occurrence of scratches. The case where no scratch was observed was marked with ◯, the occurrence of slight scratches was marked with Δ, and the occurrence of many scratches was marked with ×.

(Evaluation method for film peeling)
100 pieces of 1 mm × 1 mm cross hatches are placed on the surface of the cured resin layer of the cured film and the cured glass sample with a cutter and left for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%. Cellotape (registered trademark; manufactured by Nichiban Co., Ltd.) was applied, and the value was measured by measuring the number of squares from which the cured film was peeled off from the film substrate when the cellotape was peeled off. The case where 100 squares remained was indicated as ◯, the case where some of the squares were missing was indicated as Δ, and the case where a plurality of squares were peeled off was indicated as ×.

(Curl evaluation method)
A cured film sample was cut into 35 mm × 140 mm, left on a horizontal surface with the cured resin layer side up for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%, Evaluation was made by measuring the average value. A sample having a distance from the flat plate of less than 5 mm was evaluated as ◯, a sample having a distance of less than 10 mm was evaluated as Δ, and a sample having a distance of 10 mm or more was evaluated as ×.

(Evaluation method for cracks)
The cured film sample was cut into 35 mm x 140 mm, left at a temperature of 25 ° C and a relative humidity of 60% for 2 hours, and then measured for the diameter of curvature at which cracking began to occur when rolled into a cylindrical shape. Evaluated. Moreover, the crack of the edge part was evaluated visually. A sample having no cracks was marked with ◯, and a sample with slight cracks was marked with ×.

  As shown in Table-5, Example 1 showed good performance in terms of pencil hardness, scratch resistance, film peeling, curl and cracking. In Comparative Example 1, the pencil hardness and scratch resistance were poor, the film was peeled off, and the curl was low. As described above, the cured film of the present invention has excellent film hardness and brittleness resistance and excellent film adhesion. This is presumably because the cured film of the present invention forms a microphase-separated structure by the interaction between the polymer molecules in which the polyester polymer portion and the vinyl monomer polymer portion are copolymerized.

Examples 2-7
In the curable composition of Example 1, instead of the macromonomer (M1-1), curing was performed in the same manner as in Example 1 except that the same amount of each macromonomer (M) described in Table-6 below was used. Processed films (F-2) to (F-7) were prepared.

  When the obtained films were evaluated for the same performance as in Example 1, each film showed good results equivalent to or better than Example 1.

Examples 8-12
In the curable composition of Example 1, in place of the macromonomer (M1-1), DPHA (polymerizable monomer), fine particle dispersion, and Irgacure 184 (initiator), the respective compositions shown in Table 7 below were the same. Cured films (F-8) to (F-12) were prepared in the same manner as in Example 1 except that the amount was used.

  When the obtained films were evaluated for the same performance as in Example 1, each film showed good results equivalent to or better than Example 1. The cured film (F-12) of Example 12 was even better in terms of curling and cracking.

Examples 13-17
In Example 12, each cured film was treated in the same manner as in Example 12 except that each compound described in Table 8 below was used in place of the macromonomer (M2-1), DT-401, and DAICAT12 (initiator). (F-13) to (F-17) were prepared.
When the obtained films were evaluated for the same performance as in Example 1, each film showed good results equivalent to or better than Example 1.

Example 18
<Preparation of coating solution for high refractive index layer>
Titanium dioxide fine particles (TTO-55B, manufactured by Ishihara Sangyo Co., Ltd.) 30.0 parts by mass, carboxylic acid group-containing monomer (Aronix M-5300 manufactured by Toagosei Co., Ltd.) 4.5 parts by mass and cyclohexanone 65.5 parts by mass Was dispersed by a sand grinder mill to prepare a titanium dioxide dispersion having a mass average diameter of 55 nm. Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), photo radical polymerization initiator: Irgacure 184, total amount of monomers (dipentaerythritol hexaacrylate, anionic monomer and cationic) to the titanium dioxide dispersion 5% with respect to the total amount of monomers) and the refractive index of the high refractive index layer was adjusted to 1.85.

<Preparation of coating solution for low refractive index layer>
30.0 parts by mass of silicon dioxide fine particles (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.), 4.5 parts by mass of a carboxylic acid group-containing monomer (Aronix M-5300 manufactured by Toagosei Co., Ltd.) and 65.5 parts by mass of cyclohexanone Then, a silicon dioxide fine particle dispersion liquid having a mass average diameter of 12 nm prepared by dispersion using a sand grinder mill was prepared. To the silicon dioxide dispersion, 60 parts by mass of pentaerythritol tetraacrylate (PETA, Nippon Kayaku Co., Ltd.), radical photopolymerization initiator: Irgacure 184, 2 parts by mass, Megafuck 531A (C ₈ F ₇ SO ₂ N ( _{C 3 H 7) CH 2 CH} 2 OCOCH = CH 2, manufactured by Dainippon Ink and Chemicals, Inc.) 9 parts by weight, and mixed methyl ethyl ketone, and stirred to prepare a coating solution having a low refractive index layer. The addition amount of the silicon dioxide fine particle dispersion was adjusted so that the refractive index of the low refractive index layer was 1.50.

<Preparation of cured film with antireflection layer and cured glass sample>
On the cured films (F-1) to (F-17) prepared above, the high refractive index layer coating solution prepared above was applied using a bar coater (spray coating for glass samples), and at 120 ° C. After drying for 1 minute, the coating layer was cured by irradiating with 350 mj / cm ² of ultraviolet rays to form a high refractive index layer having a thickness of 75 nm. The low refractive index layer coating solution prepared above is coated on each high refractive index layer using a bar coater, dried at 120 ° C. for 1 minute, and then irradiated with 350 mj / cm ² of ultraviolet rays to cure the coated layer. Thus, a low refractive index layer having a thickness of 90 nm was formed. In addition, when the average reflectance of regular reflection in incident light 5 ° in a wavelength region of 450 to 650 nm was measured using a spectrophotometer (manufactured by JASCO Corporation), 1.0 to 1.0 for all samples with an antireflection layer. It was 1.2% and showed good antireflection performance.

<Image display device with a film provided with an antireflection cured resin layer>
An acrylic pressure-sensitive adhesive is applied to the surface of each of the cured film samples with antireflection layers prepared above, which is not provided with a cured resin layer. PDP: Hitachi 42-type plasma display (CMP4121HDJ), CRT: 28 manufactured by Matsushita Corporation Type flat TV (TH-28FP20), LCD: 15 type TFT liquid crystal monitor (RDT151A) manufactured by Mitsubishi, and touch panel: Zaurus (MI-L1) manufactured by Sharp Co., respectively. As a result of visual evaluation of the reflection, it was difficult to see the reflection in the image display device to which all the cured films with an antireflection layer were attached, and had good image visibility (however, curing with an antireflection layer). The treated film sample (FR-1) has a large curl and could not be attached to any image display device. Evaluation of the elevation was not carried out).

Examples 19-20 and Comparative Examples 2-3
<Preparation of coating solution for hard coat layer>
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) (315.0 g), silica fine particle methyl ethyl ketone dispersion (MEK-ST, solid content concentration 30 mass%, Nissan Chemical ( 450.0 g, 15.0 g of methyl ethyl ketone, 220.0 g of cyclohexanone, and 16.0 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Japan, Inc.) were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a hard coat layer.

<Preparation of oxide fine particle dispersion (PL-1)>
Dispersant (D-1) having the structure shown below in 218 g of titanium dioxide fine particles surface-treated with aluminum oxide and stearic acid (TTO-51 (C): titanium oxide content 79 to 85%: manufactured by Ishihara Sangyo Co., Ltd.) 38. 6 g, 0.5 g of polymerization inhibitor t-butylhydroquinone and 702 g of methyl isobutyl ketone were added and dispersed by dynomill to prepare an oxide fine particle dispersion (PL-1) having a weight average diameter of 60 nm.

<Preparation of Medium Refractive Index Layer Coating Solution (ML-1)>
88.9 g of the above composite oxide fine particle dispersion (PL-1), 23.4 g of macromonomer (M1-2), 29.2 g of methyl acrylate (MMA), 5.8 g of trimethylolpropane triacrylate (TMPTA), Irgacure 907, 3.1 g, 1.1 g photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.), 482.4 g methyl ethyl ketone, and 1869.8 g cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a medium refractive index layer.

<Preparation of coating liquid for high refractive index layer (HL-1)>
In 586.8 g of the above oxide fine particle dispersion (PL-1), 19.2 g of macromonomer (M1-2), 23.9 g of methyl acrylate (MMA), 4.8 g of trimethylolpropane triacrylate (TMPTA), Irgacure 907, 4.0 g, Kayacure DETX 1.3 g, methyl ethyl ketone 455.8 g, and cyclohexanone 1427.8 g were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.

<Preparation of coating solution for low refractive index layer>
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (OPSTAR JN7228, solid content concentration of 6% by mass, manufactured by JSR Corp.) is solvent-substituted, and the thermal crosslinkable fluoropolymer has a solid content concentration of 10% by mass of methyl isobutyl. A ketone solution was obtained. In the above heat-crosslinkable fluoropolymer solution 56.0 g, methyl ethyl ketone dispersion (MEK-ST, solid content concentration 30% by mass, manufactured by Nissan Chemical Co., Ltd.) 8.0 g, 1.75 g of the following silane compound, 73.0 g of methyl isobutyl ketone and 33.0 g of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a low refractive index layer.

<Preparation of silane compound>
A reactor equipped with a stirrer and a reflux condenser, 161 g of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 123 g of oxalic acid, and 415 g of ethanol were added and mixed. After making it react for 4 hours, it cooled to room temperature and obtained the transparent silane compound as a curable composition.

<Preparation of antireflection film> (Example 19)
The hard coat layer coating solution was applied on a triacetyl cellulose film (TD-80UF, manufactured by Fuji Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ^{2. The} coating layer was cured by irradiating ultraviolet rays with an irradiation amount of 300 mJ / cm ² to form a hard coat layer with a thickness of 3.5 μm.
On the hard coat layer, a medium refractive index layer coating solution was applied using a gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with 240 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 volume% or less. ^2. Irradiation with an irradiation amount of 600 mJ / cm ² was applied to cure the coating layer to form a medium refractive index layer (refractive index 1.65, film thickness 70 nm).

A coating solution for a high refractive index layer was applied on the middle refractive index layer using a gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with 240 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 volume% or less. ^{2. The} coating layer was cured by irradiating with an irradiation amount of 600 mJ / cm ² to form a high refractive index layer (refractive index 1.96, film thickness 100 nm).

On the high refractive index layer, the low refractive index layer coating solution was applied using a gravure coater. After drying at 80 ° C., an irradiance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ^2. Irradiation with an irradiation amount of 600 mJ / cm ² and irradiation for 10 minutes at 120 ° C. formed a low refractive index layer (refractive index 1.43, film thickness 86 nm). In this way, an antireflection film was produced.

<Preparation of antireflection film> (Example 20)
In place of the macromonomer (M1-2) and methyl methacrylate (monomer (A-1)) in the coating liquid for the middle refractive index layer (ML-1) and the coating liquid for the high refractive index layer (HL-1) in Example 19 An antireflection film was produced in the same manner as in Example 19 except that the same amount of the macromonomer (M1-12) and the monomer (A-2) having the following structure were used.

<Creation of antireflection film> (Comparative Example 2)
In the composition of Example 19 for preparing the medium refractive index layer coating solution (ML-1) and the high refractive index layer coating solution (HL-1), instead of the macromonomer (M1-2), An antireflection film was produced in the same manner as in Example 19 except that the polyester compound was used.

<Creation of antireflection film> (Comparative Example 3)
Polymerization of each liquid except for the macromonomer (M1-2) in the composition in the preparation of the coating liquid for the middle refractive index layer (ML-1) and the coating liquid for the high refractive index layer (HL-1) in Example 19. An antireflection film was produced in the same manner as in Example 19 except that the amount of the active compound was changed to the following amount.

Medium refractive index layer coating solution: (MMA) 52.6 g, (TMPTA) 5.8 g
Coating solution for high refractive index layer: (MMA) 43.1 g, (TMPTA) 4.8 g

<Evaluation of high refractive index layer film>
Using the film provided up to the high refractive index layer, the following items were evaluated. The results are shown in Table-9.

(1) Evaluation of adhesion Each film was exposed to the conditions of a sunshine carbon arc lamp, a relative humidity of 60%, and 100 hours using a sunshine weather meter (S-80, manufactured by Suga Test Instruments Co., Ltd.).
Each film before and after the weathering test was conditioned for 2 hours under conditions of a temperature of 25 ° C. and a relative humidity of 60%.
On the surface of each film having the high refractive index layer, 11 vertical and 11 horizontal cuts were made with a cutter knife in the shape of a base, and a total of 100 square squares were engraved, made by Nitto Denko Corporation. The adhesion test on the polyester adhesive tape (No. 31B) was repeated three times at the same place. The presence or absence of peeling was visually observed, and the following four-stage evaluation was performed.

A: No peeling at 100 mm was observed. ○: No peeling was observed at 100 mm within 2 mm. Δ: 10-100 mm was observed at 100 mm. Thing that has been peeled off at 100 mm exceeds 10 mm

(2) Evaluation of pencil hardness The film before and after exposure is conditioned at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, and then a pencil specified in JIS K5400 using a test pencil specified in JIS S6006. According to the hardness evaluation method, the pencil hardness at 1 kg load was evaluated.

(3) Evaluation of still-wool rubbing resistance In the film before and after the exposure, a load of 300 g / cm ² was applied to # 0000 still wool, and the state of scratches when observed 5 times was observed, and evaluated in the following three stages. did.
A: No scratch at all, B: Slightly scratched but difficult to see, C: Scratched

(4) Evaluation of cracks A film sample was cut into 35 mm x 140 mm, left to stand for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, and then measured for the diameter of curvature at which cracking began to occur when rolled into a cylinder. The surface cracks were evaluated. Moreover, the crack of the edge part was evaluated visually.
A sample having no cracks was marked with ◯, and a sample with slight cracks was marked with ×.

<Evaluation of antireflection film>
About each produced antireflection film, the following items were evaluated. The results are shown in Table-9.

(5) Evaluation of haze The haze of the antireflection film was evaluated using a haze meter (NHD-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.).

(6) Evaluation of reflectivity Using a spectrophotometer (V-550, ARV-474, manufactured by JASCO Corporation), the spectral reflectivity at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. The average reflectance in the wavelength range of 450 to 650 nm was determined.

(7) Evaluation of adhesiveness It measured and evaluated on the same conditions as said (1).

The film properties (adhesiveness, pencil hardness, abrasion resistance, cracking) of the film that becomes the surface of the high refractive index layer obtained in Example 19 of the present invention were all good and practical. Furthermore, Example 20 gave better results for any of the properties. Moreover, the performance of the optical characteristics as an antireflection film is good in both Example 19 and Example 20, and Example 20 has further improved adhesion.
On the other hand, the samples of Comparative Example 2 and Comparative Example 3 both had poor film characteristics and were not practically usable.
From the above, only those of the present invention exhibited good characteristics as an antireflection film.

Examples 21-25
In Example 19, the medium refractive index layer coating solution (ML-1) and the high refractive index layer coating solution (HL-1), the macromonomer (M1-2), the monomer (A-1), and a photopolymerization initiator. Each antireflection film was produced in the same manner as in Example 19 except that the same amount of each compound shown in Table 10 below was used instead of (L-1).

  The antireflection films of Examples 21 to 25 thus obtained were evaluated and evaluated in the same manner as in Example 19. The performance of each example was as good as or better than that of Example 19.

Example 26
<Formation of hard coat layer>
125 g of polyfunctional acrylate monomer DPHA and 125 g of urethane acrylate oligomer UV-6300B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were dissolved in 439 g of industrial modified ethanol. A solution prepared by dissolving Irgacure 907, 7.5 g and Kayacure DETX, 5.0 g in 49 g of methyl ethyl ketone was added to the resulting solution. After the mixture was stirred, it was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a hard coat layer coating solution.
The hard coat layer coating solution was applied to the triacetyl cellulose film (TAC-TD80U) using a bar coater and dried at 120 ° C. Next, the coating layer was cured by irradiating ultraviolet rays to form a hard coat layer having a thickness of 7.5 μm.

<Preparation of oxide fine particle dispersion (PL-2)>
Compound oxide consisting of titanium, zirconium and aluminum [Ti / Ti + Zr + Al = 0.80 molar ratio, Zr / Ti + Zr + Al = 0.15 molar ratio] (P-2) 257.1 g, 38.6 g of the following dispersant, and cyclohexanone 704.3 g was added and dispersed by dynomill. The average diameter of the dispersed particles of the obtained dispersion was 70 nm.

<Preparation of Medium Refractive Index Layer Coating Solution (ML-8)>
88.9 g of the above oxide fine particle dispersion (PL-2), 29.2 g of macromonomer (M1-20), 29.2 g of diacrylate having the following structure, Irgacure 907, 3.1 g, Kayacure DETX, 1.1 g , 482.4 g of methyl ethyl ketone, and 1869.8 g of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a medium refractive index layer.

<Preparation of coating liquid for high refractive index layer (ML-8)>
To 586.8 g of the above oxide fine particle dispersion (PL-2), 24.0 g of macromonomer (M1-20), 24.0 g of diacrylate having the following structure, Irgacure 907, 2.4 g, Kayacure DETX, 0.8 g , 455.8 g of methyl ethyl ketone, and 1427.8 g of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.

<Preparation of antireflection film>
On the hard coat layer, a medium refractive index layer coating solution (ML-8) was applied using a gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with 240 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 volume% or less. ^2. An ultraviolet ray with an irradiation amount of 600 mJ / cm ² was irradiated to cure the coating layer to form a medium refractive index layer (refractive index 1.65, film thickness 67 nm).

On the middle refractive index layer, a coating solution for high refractive index layer (HL-8) was applied using a gravure coater. After drying at 100 ° C., the coating layer was cured by heating at 120 ° C. for 2 hours to form a high refractive index layer (refractive index 1.95, film thickness 107 nm).
On the high refractive index layer, the low refractive index layer (refractive index 1.44, film thickness 82 nm) was formed according to the composition for low refractive index layer described in Example 1 of JP-A-2000-241603 and the formation method. ) Was formed. In this way, an antireflection film was produced.

  As a result of evaluating the performance and evaluation of the obtained antireflection film in the same manner as in Example 19, the performance was equivalent to or better than that of Example 19, and it was good.

Examples 27-30
In the composition in the preparation of the coating solution for high refractive index layer (HL-8) of Example 26, each of the components described in Table 11 below instead of the macromonomer (M1-20), the polymerizable monomer and the polymerization initiator. An antireflection film was produced in the same manner as in Example 26 except that the compound was used.

  As a result of evaluating the performance of the obtained antireflection film in the same manner as in Example 19, it was as good as or better than that of Example 19.

Example 31
<Preparation of protective film for polarizing plate>
In the antireflection films produced in Examples 19 to 30, the surface of the transparent support opposite to the side having the high refractive index layer of the present invention was saponified by keeping a 1.5N sodium hydroxide aqueous solution at 50 ° C. The solution was saponified.
The aqueous sodium hydroxide solution on the surface of the saponified transparent support was thoroughly washed with water and then sufficiently dried at 100 ° C. Thus, the protective film for polarizing plates was produced.

<Preparation of polarizing plate>
A polyvinyl alcohol film having a thickness of 75 μm (manufactured by Kuraray Co., Ltd.) was immersed in an aqueous solution consisting of 1000 g of water, 7 g of iodine and 105 g of potassium iodide to adsorb iodine. Subsequently, this film was uniaxially stretched 4.4 times in the longitudinal direction in a 4% by mass boric acid aqueous solution, and then dried in a tension state to produce a polarizing film.
Using a polyvinyl alcohol-based adhesive as an adhesive, a saponified triacetyl cellulose surface of the antireflection film of the present invention (a polarizing plate protective film) was bonded to one surface of the polarizing film. Furthermore, a cellulose acylate film TD-80UF saponified in the same manner as above was bonded to the other surface of the polarizing film using the same polyvinyl alcohol-based adhesive.

<Evaluation of image display device>
The TN, STN, IPS, VA, OCB mode transmission type, reflection type, or semi-transmission type liquid crystal display device equipped with the polarizing plate of the present invention produced in this way has excellent antireflection performance, and is extremely Visibility was excellent.

Example 32
<Preparation of polarizing plate>
The disc surface of the discotic structural unit is inclined with respect to the transparent support surface, and the angle formed by the disc surface of the discotic structural unit and the transparent support surface changes in the depth direction of the optical anisotropic layer. In the optical compensation film (wide view film SA-12B, manufactured by Fuji Photo Film Co., Ltd.) having the optical compensation layer, the surface opposite to the side having the optical compensation layer was saponified under the same conditions as in Example 31. .
The polarizing film produced in Example 31 was saponified with the antireflection film (protective film for polarizing plate) produced in Example 20 on one surface of the polarizing film using a polyvinyl alcohol adhesive as an adhesive. The triacetyl cellulose surface was bonded. Further, the triacetyl cellulose surface of the saponified optical compensation film was bonded to the other surface of the polarizing film using the same polyvinyl alcohol adhesive.

<Evaluation of image display device>
The TN, STN, IPS, VA, OCB mode transmissive, reflective, or transflective liquid crystal display device equipped with the polarizing plate of the present invention thus manufactured does not use an optical compensation film. Compared with a liquid crystal display device equipped with a polarizing plate, the contrast in a bright room was excellent, the viewing angles of the top, bottom, left and right were very wide, and the antireflection performance was excellent, and the visibility and display quality were extremely excellent.
By producing a high refractive index layer according to the present invention, an antireflection film excellent in weather resistance (particularly polarization) can be provided in a large amount at a low cost.
Furthermore, the polarizing plate and image display apparatus which hold | maintained the said characteristic by these can be provided.

Claims (15)

It has a polymerizable group at one end of the polymer main chain, and contains a monofunctional polyester macromonomer (M) having a weight average molecular weight of 2 × 10 ⁴ or less, and a polymerization initiator (L). A curable composition. The curable composition according to claim 1, wherein the macromonomer (M) has a repeating part represented by the following general formula (MI) or general formula (M-II).

In the formula, T represents a polymerizable group.
B ¹ represents a divalent organic residue that links T and D ^1, and B ² represents a divalent organic residue that links T and D ² .
E ¹ and E ² may be the same as or different from each other, and each is a divalent aliphatic group, a divalent aromatic group [-C (k ² ) ( k ³ ) —, —O—, —S—, —N (k ⁴ ) —, —SO ₂ —, —COO—, —OCO—, —CONHCO—, —NHCOO—, —NHCONH—, —CON (k _{^{4) -, - SO 2 N}} (k 4) - and ^{-Si (k 5) (k 6} ) - (k 2, k 3 and k ⁴ each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms , K ⁵ and k ⁶ each represent a hydrocarbon group having 1 to 12 carbon atoms), or an organic residue composed of a combination of these residues. Represent.
D ¹ represents —CH ₂ — or —CO—, and D ² represents —O— or —NH—.
R ¹ represents —OH, —OR ⁵ or —N (R ⁶ ) (R ⁷ ) (R ⁵ represents a hydrocarbon group having 1 to 12 carbon atoms. R ⁶ and R ⁷ represent a hydrogen atom or 1 carbon atom. Represents ~ 12 hydrocarbon groups).
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, —COR ⁸ or —CONHR ⁹ (R ⁸ and R ⁹ each represent a hydrocarbon group having 1 to 12 carbon atoms).   The curable composition according to claim 1 or 2, wherein the macromonomer (M) contains at least one alicyclic aliphatic component.   The curable composition according to claim 3, wherein the macromonomer (M) contains at least one polycyclic aliphatic ring component.   The curable composition according to any one of claims 1 to 4, wherein the polymerizable group of the macromonomer (M) is either a radical polymerization reactive group or a cationic polymerization reactive group.   The curable composition according to claim 1, further comprising a polymerizable monomer (A).   The curable composition according to claim 5, wherein the polymerizable monomer (A) is a compound containing two or more polymerizable groups in the same molecule.   The polymerizable monomer (A) contains two or more polymerizable groups in the molecule, and contains at least one ring-opening polymerizable group and at least one ethylenically unsaturated group as the polymerizable group. The curable composition according to claim 7, wherein the curable composition is a compound.   A cured article obtained by applying the curable composition according to claim 1 on a substrate and curing the composition.   A multilayer antireflection film in which at least a high refractive index layer and a low refractive index layer are sequentially laminated on a transparent support, the high refractive index layer further comprising inorganic particles having a refractive index of 1.70 or more. An antireflection film obtained by curing the curable composition according to claim 1.   On the transparent support, it has a refractive index layer of at least three layers of two high refractive index layers having different refractive indexes and a low refractive index layer having a refractive index of less than 1.55 laminated on these layers, An antireflection film obtained by curing at least one of the two high refractive index layers by curing the curable composition according to any one of claims 1 to 8.   The antireflection film according to claim 10 or 11, further comprising a hard coat layer between the transparent support and the high refractive index layer.   A polarizing plate comprising the antireflection film according to claim 10 as at least one of a protective film for a polarizing film.   Polarized light characterized in that the antireflection film according to any one of claims 10 to 12 is used for one of the protective films of the polarizing film, and an optical compensation film having optical anisotropy is used for the other of the protective films of the polarizing film. Board.   An image display device, wherein the polarizing film according to claim 10 or the polarizing plate according to claim 13 or 14 is disposed on an image display surface.