JP2005290199A - Photocurable resin composition and polymer thereof - Google Patents

Abstract

（式（１）中、Ｒ¹は、ラジカル重合可能なビニル基を有する置換基を表し、Ｒ^２は炭素数１〜５の飽和炭化水素基を表す。Ｍは、Ｔｉ、Ｓｂ、Ｗ、Ｚｒ、Ｃｅ、Ｓｎ及びＦｅからなる群より選択される少なくとも一種の金属原子を表す。ｍとｎの和は金属Ｍの価数を表す。）；
（Ｂ）下記式（２）で表されるフルオレン誘導体
【化２】

（式（２）中、Ｒ³およびＲ⁴は、それぞれ独立的に、（メタ）アクリロイルオキシ基、（メタ）アクリロイルオキシアルコキシ基、または末端に（メタ）アクリロイルオキシ基が置換したポリアルキレンオキシ基を表す。）
を含有する。
【選択図】 無し

PROBLEM TO BE SOLVED: To provide a curable resin composition capable of providing a visible light transmissive and high hardness high refractive index film.
The photocurable resin composition comprises the following components (A) and (B):
(A) Metal alkoxide represented by the following formula (1) or a hydrolyzed compound thereof

(In formula (1), R ¹ represents a substituent having a vinyl group capable of radical polymerization, and R ² represents a saturated hydrocarbon group having 1 to 5 carbon atoms. M represents Ti, Sb, W, Zr. And represents at least one metal atom selected from the group consisting of Ce, Sn and Fe. The sum of m and n represents the valence of the metal M).
(B) A fluorene derivative represented by the following formula (2)

(In formula (2), R ³ and R ⁴ are each independently a (meth) acryloyloxy group, a (meth) acryloyloxyalkoxy group, or a polyalkyleneoxy group substituted with a (meth) acryloyloxy group at the end. Represents.)
Containing.
[Selection] None

Description

  The present invention relates to a photocurable resin composition capable of providing a high refractive index film having high visible light permeability and high hardness, a laminate using the same, and production thereof.

  Usually, an antireflection film is formed on the surface of a display element of an image display device such as a liquid crystal display device or an organic EL device. The antireflection film generally has a laminate structure in which a low refractive index layer is provided on the surface of a high refractive index layer. In such an antireflection film, of the incident visible light, the reflected light reflected by the high refractive index layer and the reflected light reflected by the low refractive index layer interfere with each other due to their optical path difference, and the whole As a result, the amount of reflected light decreases.

  By the way, as a material suitable for the antireflection film, a photocurable resin composition in which a metal compound alkoxide or a hydrolyzate thereof and a photocurable resin are combined with a titanium compound as a refractive index improver has been proposed. (Patent Document 1, Patent Document 2). However, in the case of such a photocurable resin composition, since the titanium oxide content is as low as 50% by mass or less of the whole, it cannot be said to be a sufficiently high refractive index material.

  In addition, a technique for adding a metal alkoxide at a relatively high concentration to a photopolymerizable organic compound having two or more polymerizable unsaturated bonds in the molecule has been proposed (Patent Document 3). This is a material, and since there is no reactivity between the added metal alkoxide and the photocurable resin, the metal alkoxide bleeds out from the film of the curable resin composition, or the exposed metal alkoxide hydrolyzate is There is a risk of peeling off.

  Moreover, the photocurable resin composition which mix | blended the metal oxide particle which modified the surface with the silane compound which has a (meth) acryloyloxy group etc. in two or more (meth) acryloyloxy group containing compounds is proposed ( Patent Document 4). Although a cured resin film with improved film hardness can be obtained from this composition, it cannot be said that the refractive index of the silane compound is sufficiently high and is not a high refractive index material.

  Moreover, it has been proposed to use a fluorene derivative as an improvement on the monomer side used in the photocurable resin composition (Patent Documents 5 to 8). However, in the case of a photocurable resin composition containing a fluorene derivative, the hardness is higher than that of the photocurable resin composition to which metal oxide particles are added, but the refractive index is low. For this reason, a system in which metal oxide particles are added to a fluorene derivative has been proposed (Patent Document 9), but the affinity between the metal oxide particles and the fluorene derivative is not sufficient, and the metal oxide particles in the cured resin Transparency is lowered due to insufficient dispersibility.

  As described above, a practical curable resin composition capable of providing a high refractive index film having visible light permeability and high hardness has not yet been obtained.

JP 61-130382 A JP 07-292285 A JP-A-10-176118 Japanese Patent Laid-Open No. 11-116845 Japanese Patent Laid-Open No. 3-106918 Japanese Patent Laid-Open No. 06-21936 Japanese Patent Laid-Open No. 06-220131 Japanese Patent Laid-Open No. 06-220148 JP 05-164903 A

  An object of the present invention is to provide a curable resin composition capable of providing a high refractive index film having high visible light permeability and high hardness, a laminate using the same, and a method for producing the same.

  The present inventors have found that the above-mentioned object can be achieved by a curable resin composition in which a specific metal alkoxide or a hydrolyzed compound thereof is mixed with a specific fluorene compound, and the present invention has been completed.

That is, the present invention includes the following components (A) and (B):
(A) Metal alkoxide represented by the following formula (1) or a hydrolyzed compound thereof

(In the formula (1), R ¹ represents a substituent having 2 to 20 carbon atoms having at least one radical polymerizable vinyl group, and when a plurality of R ¹ are present, they are the same or different from each other. R ² represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and when a plurality of R ² are present, they may be the same or different from each other, and M represents Ti, Sb, W, Zr, Ce. Represents at least one metal atom selected from the group consisting of Sn, Fe, and m and n each represents 0 or a natural number, provided that m and n are not 0 at the same time and the sum of m and n is the same as that of the metal M. Represents valence);

(B) A fluorene derivative represented by the following formula (2)

(In formula (2), R ³ and R ⁴ are each independently a (meth) acryloyloxy group, a (meth) acryloyloxyalkoxy group, or a polyalkyleneoxy group substituted with a (meth) acryloyloxy group at the end. Represents.)
The photocurable resin composition characterized by containing this is provided. Here, in this specification, acryloyl or methacryloyl is referred to as (meth) acryloyl, acrylate or methacrylate is referred to as (meth) acrylate, and acrylic acid or methacrylic acid is referred to as (meth) acrylic acid.

Further, the present invention relates to a polymerization unit comprising the following component (A ′) and a polymerization unit comprising the component (B):
(A ′) Metal alkoxide represented by the following formula (1 ′) or a hydrolyzed compound thereof

(In Formula (1 ′), R ¹ represents a substituent having 2 to 20 carbon atoms having at least one radical polymerizable vinyl group, and when a plurality of R ¹ are present, they are the same or different from each other. R ² represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and when a plurality of R ² are present, they may be the same or different from each other, M ′ represents a metal atom, m and n Each represents 0 or a natural number, provided that m and n are not simultaneously 0 and the sum of m and n represents the valence of the metal M ′);
(B) A polymer having a fluorene derivative represented by the formula (2) and having a refractive index of 1.55 or more is provided.

  Further, the present invention is a laminate in which one or more resin layers are laminated on a substrate, and at least one of the resin layers is a layer made of the polymer of the present invention described above. The featured laminate, in particular, as a specific embodiment, 1 or more high refractive index layers made of the polymer of the present invention, and 1 made of a polymer having a refractive index of 0.1 or more lower than the high refractive index layer. Provided are an antireflection film formed by laminating the above low refractive index layer and a display device including the antireflection film.

The present invention is also a method for producing the laminate, which includes the following steps (a) and (b):
(A) forming a film of the aforementioned photocurable resin composition on a substrate;
(B) A production method comprising a step of polymerizing and curing the resulting photocurable resin composition film by irradiating active energy rays to form a polymer layer of the photocurable resin composition I will provide a.

  A polymer obtained by polymerizing and curing the photocurable resin composition of the present invention containing a specific metal alkoxide or a hydrolyzate thereof and a specific fluorene derivative is visible light transmissive and has high hardness and high refraction. Indicates the rate. Therefore, the photocurable resin composition of the present invention can provide a polymer film having high light hardness, high transparency, and high refractive index. Such a polymer film is suitable as an antireflection film, and is useful as an antireflection material for laminate foil, image display screen protection plate, helmet shield and the like.

The photocurable resin composition of the present invention includes the components (A) and (B) described above:
(A) Metal alkoxide represented by the formula (1) or a hydrolyzed compound thereof

(B) A fluorene derivative represented by the formula (2)

を含有することを特徴とする光硬化性樹脂組成物である。

It is a photocurable resin composition characterized by containing.

  The component (A) is a component for imparting a high refractive index and high hardness to the cured product of the photocurable resin composition. In the present invention, the metal alkoxide of the formula (1) or a hydrolyzate thereof may be used alone as the component (A), or the metal alkoxide and the hydrolyzate may be used in combination. Moreover, you may use together multiple types of metal alkoxide of Formula (1), or its hydrolyzate as a component (A).

Here, R ¹ in formula (1) represents a substituent having 2 to 20 carbon atoms having at least one radical polymerizable vinyl group, and when a plurality of R ¹ are present, they are the same or different from each other. May be. R ¹ may contain a metal atom such as Si. Specific examples of R ¹ include a vinyl group, an allyl group, a (meth) acryloyl group, a styryl group, a substituent having a styryl group at the terminal (for example, p-vinylbenzyl group, p-styrylsilyl group, etc.), γ- (Meth) acryloyloxypropylsilyl group and the like can be mentioned. Among these, from the viewpoint of obtaining a high refractive index film, R ¹ is preferably a styryl group and a substituent having a styryl group at the terminal, and among them, a p-styrylsilyl group is preferable. From the viewpoint of enhancing the reactivity of the photo-curable resin composition, as R ¹ p-Suchirirushiriru group and (meth) acrylic group is preferable. In this case, specifically, it is preferable to use a compound of the formula (1) having a p-styrylsilyl group and a compound of the formula (1) having a (meth) acryl group in combination, or in one molecule, p It is preferred to use a compound of formula (1) having a styrylsilyl group and a (meth) acryl group.

R ² in Formula (1) represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and when a plurality of R ² are present, they may be the same as or different from each other. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a pentyl group. Of these, a methyl group is preferred from the viewpoint of high reactivity.

  M in Formula (1) represents at least one metal atom selected from the group consisting of Ti, Sb, W, Zr, Ce, Sn, and Fe. From the viewpoint of obtaining a cured film having a higher refractive index, M is preferably titanium.

  M and n in Formula (1) represent 0 or a natural number, respectively. However, m and n are not simultaneously 0, and the sum of m and n represents the valence of the metal M. In addition, since the hardness of a cured film will fall when m is too large, 1 or 2 is preferable and 1 is more preferable.

  As the metal alkoxide of the formula (1) of the component (A), a compound of the following formula (3) can be preferably exemplified. In particular, it is preferable to use a metal alkoxide of the formula (3) and a metal alkoxide of the following formula (4) at the same time.

In Formula (3), R ¹¹ represents a saturated hydrocarbon group having 1 to 5 carbon atoms or a phenyl group, and when a plurality of R ¹¹ are present, they may be the same as or different from each other. Specific examples of the saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a pentyl group. Among these, from the viewpoint of not reducing the refractive index of the cured film, R ¹¹ is preferably a methyl group. M, R ² , m and n are as described above.

In the formula (4), R ¹² is a hydrogen atom or a methyl group. When a plurality of R ¹² are present, they may be the same as or different from each other. M, R ² , m and n are as described above.

The hydrolyzed compound of the metal alkoxide of the formula (1) of the component (A) is a compound formed by bringing a metal alkoxide and water into contact with each other, and includes m substituents OR ¹ and n substituents OR ² . Among them, at least a part of them is hydrolyzed to become a hydroxyl group, and further includes those in which the hydroxyl groups are dehydrated and condensed.

  In the present invention, the fluorene derivative of the formula (2) of the component (B) is an ethylenically unsaturated compound that can be polymerized by active energy rays, and a component for forming a matrix of a cured film of the photocurable resin composition And the cure shrinkage is small. Therefore, a cured film with less strain can be obtained from the photocurable resin composition.

In formula (2), R ³ and R ⁴ each independently represents a (meth) acryloyloxy group, a (meth) acryloyloxyalkoxy group, or a polyalkyleneoxy group substituted with a (meth) acryloyloxy group at the end. Represent. Here, the (meth) acryloyloxyalkoxy group is preferably an acryloyloxyethoxy group or an acryloyl (2-hydroxy) propoxy group. Examples of the polyalkyleneoxy group having a (meth) acryloyloxy group substituted at the terminal include [—O— (CH ₂ CH (OH) CH ₂ O) _o —CO—CH═CH ₂ ], [—O— ( _{CH 2 CH 2 O) p -CO} -CH = CH 2] may be preferably mentioned. Here, o and p are preferably 2 or 3 because the hardness and transparency of the cured film tend to be reduced while the adhesion of the obtained cured film to the resin substrate is improved if it becomes too large. . Among these, as R ³ and R ⁴ , both acryloyloxyethoxy groups are particularly preferable from the viewpoints of reactivity and obtained film strength.

  If the blending ratio of the component (A) in the solid content of the photocurable resin composition (including the component that becomes solid content after curing) is too small, the refractive index of the cured film of the photocurable resin composition is excessively lowered. If the amount is too large, the cured film tends to be too brittle, so the content is preferably 50 to 89.9% by mass, more preferably 50 to 80% by mass.

  If the blending ratio of the component (B) in the solid content of the photocurable resin composition (including the component that becomes a solid content after curing) is too small, the cured film of the photocurable resin composition tends to be too brittle. If the amount is too large, the refractive index of the cured film tends to decrease too much, so the content is preferably 10 to 50% by mass, more preferably 10 to 30% by mass.

  The photocurable resin composition of the present invention usually contains a photopolymerization initiator as the component (C) in addition to the components (A) and (B). When the blending ratio is too small, the curability of the photocurable resin composition is excessively decreased, and when it is too large, the blending ratio of the component (A) and the component (B) is relatively decreased, and the polymerization cured film is refracted. Since both the rate and the film hardness are lowered, the solid content (including components that become solid content after curing) is preferably 0.1 to 10% by mass.

  As a component (C) photoinitiator, it can select suitably according to the active energy ray (an ultraviolet ray, visible light, an electron beam, etc.) which is a hardening means. In addition to the photopolymerization initiator, one or more known photocatalyst compounds selected from photosensitizers and photopolymerization accelerators can be preferably used in combination. In some cases, a small amount of a thermal polymerization initiator may be used in combination.

  Specific examples of the component (C) photopolymerization initiator include 2,2-dimethoxy-2-phenylacetone, acetophenone, benzophenone, xanthfluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4. -Diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-thioxanthone, camphorquinone, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like. Further, a photopolymerization initiator having at least one (meth) acryloyl group in the molecule such as N-acryloyloxyethylmaleimide can also be used.

  Specific examples of the photosensitizer include 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. Specific examples of the photo accelerator include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like. be able to.

  In order to facilitate the film formation, it is preferable to add a diluent to the photocurable resin composition of the present invention. The compounding quantity of a diluent can be suitably determined according to the film thickness of the target cured film.

  As such a diluent, a diluent used in general resin coatings can be used. Specifically, ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate , Ethyl lactate, methoxyethyl acetate and other ester compounds; diethyl ether, ethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, dioxane and other ether compounds; toluene, xylene and other aromatic compounds; pentane, hexane and other fats Group compounds; halogenated hydrocarbons such as methylene chloride, chlorobenzene and chloroform; alcohol compounds such as methanol, ethanol, normal propanol and isopropanol; and water.

  In addition, the photocurable resin composition of the present invention has at least one ethylenic double bond in the molecule as necessary, and an active energy ray (for example, ultraviolet ray, visible light, electron beam, X-ray). An ethylenically unsaturated compound that can be polymerized can be blended.

  Specific examples of the ethylenically unsaturated compound polymerizable with active energy rays include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopenteno Xylethyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxy Ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxy Ethyl (meth) acrylate, biphenoxyethyl (meth) acrylate, biphenoxyethoxyethyl (meth) acrylate, norbornyl (meth) acrylate, phenylepoxy (meth) acrylate, (meth) acryloylmorpholine, N- [2- (meth) Acryloylethyl] -1,2-cyclohexanedicarboximide, N- [2- (meth) acryloylethyl] -1,2-cyclohexanedicarbomido-1-ene, N- [2- (meth) acrylic Roylethyl] -1,2-cyclohexanedicarbomido-4-ene and other monofunctional (meth) acrylate monomers; N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam, styrene, α-methylstyrene, vinyl Vinyl monomers such as toluene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonane Diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol pivalate ester di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethyleneglycol Rudi (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol-A-diglycidyl ether di (meth) acrylate, 1,4-cyclohexanedimethanol ethylene oxide modified diacrylate, ethylene oxide modified tetrabromobisphenol-A- Bifunctional (meth) acrylates such as di (meth) acrylate and zinc diacrylate; trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) ) Acrylate, pentaerythritol hexa (meth) acrylate, tri (meth) acrylate of ethylene oxide-added trimethylolpropane, Tetra (meth) acrylate of dioxide trimethylolpropane with addition of lenoxide, tri (meth) acrylate of trimethylolpropane with addition of propylene oxide, tri (meth) acrylate of ethylene oxide modified isocyanuric acid, tetra (meth) acrylate of propylene oxide addition ditrimethylolpropane , Tetra (meth) acrylate of ethylene oxide-added pentaerythritol, tetra (meth) acrylate of propylene oxide-added pentaerythritol, penta (meth) acrylate of ethylene oxide-added dipentaerythritol, penta (meth) acrylate of propylene oxide-added dipentaerythritol , Ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene Polyfunctional monomers such as hexa (meth) acrylates of oxide-added dipentaerythritol, triallyl cyanurate, triallyl isocyanurate, triallyl formal, 1,3,5-triacryloylhexahydro-s-hydrazine; urethane acrylate And oligomeric acrylates such as ester acrylates. Of these, polyfunctional monomers having two or more functions are preferably used. These compounds are used alone or in combination of two or more.

  Moreover, you may mix | blend with the photocurable resin composition of this invention the vinyl ether type | system | group which can superpose | polymerize with an active energy ray, an oxetane type compound, etc. as needed. Specific examples of vinyl ether compounds include ethylene oxide modified bisphenol-A-divinyl ether, ethylene oxide modified bisphenol-F-divinyl ether, ethylene oxide modified catechol divinyl ether, ethylene oxide modified resorcinol divinyl ether, ethylene oxide modified hydroquinone divinyl ether, Examples include ethylene oxide-modified 1,3,5, benzenetriol trivinyl ether. Specific examples of the epoxy compound include 1,2-epoxycyclohexane, 1,4-butanediol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylolpropane diglycidyl. Examples include ether, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, phenol novolac glycidyl ether, and bisphenol A diglycidyl ether. Specific examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3. -(2-ethylhexyloxymethyl) oxetane and the like.

  In the photocurable resin composition of the present invention, if necessary, the following formula (5)

(In Formula (5), R ⁵ represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and when a plurality of R ⁵ are present, they may be the same or different. M represents Ti, Sb, W Z represents at least one metal atom selected from the group consisting of Zr, Ce, Sn, and Fe. Q represents the valence of the metal M.)
Or a hydrolyzate thereof can be added. Here, as M, titanium can be preferably used because a cured film having a higher refractive index can be obtained. Specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a pentyl group, and a methyl group having high reactivity can be preferably exemplified.

The hydrolyzed compound of the metal alkoxide of the formula (5) is a compound formed by bringing a metal alkoxide into contact with water, and at least a part of the q substituents OR ⁵ is hydrolyzed to form a hydroxyl group. In addition, those in which the hydroxyl groups are etherified by dehydration condensation are also included.

  In the photocurable resin composition of the present invention, an inorganic filler, a polymerization inhibitor, a color pigment, a dye, an antifoaming agent, a leveling agent, a dispersing agent, a light diffusing agent, a plasticizer, and an antistatic agent are further included as necessary. , Surfactants, non-reactive polymers, and the like can be blended within a range that does not impair the effects of the present invention.

  The photocurable resin composition of the present invention can be produced by uniformly mixing the component (A) and the component (B), and optionally the component (C) and other additives as required. it can. In addition, when storing for a comparatively long period, you may make it mix immediately before use, without mix | blending the photoinitiator of a component (C).

The polymer of the present invention includes a polymer unit comprising the above-described compound of component (A ′) and a polymer unit of the component (B), and exhibits a visible light transmittance, high hardness, and a high refractive index. In particular, the refractive index for sodium D-line is 1.55 or more. Here, M ′ in the above formula (1 ′) is selected from metal atoms such that the refractive index of the polymer is 1.55 or more, and preferred M ′ is the formula (1) of the component (A). It is synonymous with M defined in. R ¹ , R ² , m and n in formula (1 ′) have the same meanings as R ¹ , R ² , m and n defined in formula (1) of component (A).

  As this polymer, a polymer obtained by polymerizing and curing the above-described photocurable resin composition of the present invention is preferably used.

  In addition, as a preferable polymerization unit comprising the compound of component (A ′), the following formula (3 ′)

(In the formula (3 ′), R ¹¹ represents a saturated hydrocarbon group or phenyl group having 1 to 5 carbon atoms, which may be the same or different. R ² , M ′, m and n Is as defined in formula (1 ′).)
The metal alkoxide represented by these, or its hydrolysis compound is mentioned.

  Further, in the polymer of the present invention, in addition to the polymer unit comprising the compound of the formula (3 ′), the following formula (4 ′)

(In the formula (4 ′), R ¹² represents a hydrogen atom or a methyl group. R ² , M ′, m and n are as defined in the formula (3 ′).)
It is more preferable that a polymer alkoxide represented by the formula (I) or a polymerized unit composed of a hydrolyzed compound thereof coexist. Moreover, as described above, the abundance ratio of the polymer unit composed of the component (A ′) and the polymer unit composed of the component (B) in the polymer is preferably (50 to 89.9): (10 to 10 50), more preferably (50-80) :( 10-30).

  The polymer of this invention can be used as a resin layer which comprises a laminated body using the visible light transmittance | permeability, high hardness, and a high refractive index. That is, according to the present invention, it is a laminate formed by laminating one or more resin layers on a substrate, and at least one of the resin layers is a layer made of the polymer of the present invention. A featured laminate is provided.

  The base material constituting the laminate is a plate or film-like metal (iron, aluminum, etc.) base material, a ceramic base material containing glass, a plastic base material such as acrylic resin, polyethylene terephthalate, polycarbonate, thermosetting, etc. A resin base material or the like can be used.

  The resin layer constituting the laminate may be a single layer or a multilayer, and in the case of a single layer, it is a layer itself made of the polymer of the present invention, and in the case of a multilayer, at least one layer is made of the polymer of the present invention. Any layer can be used. The resin layer that can be used in combination with the polymer layer of the present invention can be appropriately determined according to the use of the laminate.

  As described above, the laminate thus obtained can be applied as an antireflection film because it can obtain a film of a high refractive index film that is transparent to visible light and has high hardness. And an image display screen protection plate, a helmet shield, a display element, and the like.

  The structure of the antireflection film is as follows: base material / high refractive index layer / low refractive index layer, base material / hard coat layer / high refractive index layer / low refractive index layer, base material / low refractive index layer / high refractive index layer / Low refractive index layer, base material / hard coat layer / low refractive index layer / high refractive index layer / low refractive index layer, base material / hard coat layer / transparent conductive layer / high refractive index layer / low refractive index layer, etc. The thing of composition is mentioned. At least one of the high refractive index layers is a layer made of the polymer of the present invention. The low refractive index layer is preferably made of a material having a refractive index lower by 0.1 or more than the refractive index of the material constituting the high refractive index layer. For example, a silicone resin or a fluorine resin can be used.

  The display device having the member provided with the antireflection film is not particularly limited, and for example, a display device using the antireflection film for a surface protective plate, a diffusion plate, a polarizing plate, etc., for example, a liquid crystal display device, an organic An EL display device, a plasma display device, and the like can be given. As the basic structure of these display devices, the structure of the display device of the conventional process can be adopted except that the antireflection film of the present invention is used.

  As described above, the photocurable resin composition of the present invention can be preferably used as a raw material for a resin layer when producing a laminate in which one or more resin layers are laminated on a substrate. Such a laminate can be manufactured according to a manufacturing method including the following steps (a) and (b).

Step (a)
First, a film of the photocurable resin composition of the present invention is formed on a substrate. The film is formed by a known film forming method such as an impregnation method, a relief printing method, a flat plate printing method, a coating method using a roll used in intaglio printing, a spray method of spraying on a substrate, a curtain flow coat, or the like. It can be carried out.

  In addition, when the diluent (solvent) is contained in the photocurable resin composition, it is preferable to remove the diluent before carrying out the step (b) described later. In this case, it is usually evaporated by heating. As the method, a heating furnace, a far infrared furnace, a super far infrared furnace, or the like can be used.

Step (b)
The film of the photocurable resin composition obtained in the step (a) is polymerized and cured by irradiating active energy rays to form a layer made of a polymer of the photocurable resin composition. As a result, even when a substrate having poor wettability with respect to the paint is used, a layer made of a uniform and thin polymer (for example, a thickness of 0.01 μm or more and 10 μm or less) is formed on the substrate. A laminated body can be obtained.

  A wide range of active energy rays such as ultraviolet rays, visible rays, lasers, electron beams, and X-rays can be used. Among these, the use of ultraviolet rays is preferable from the practical aspect. Specific examples of the ultraviolet ray generation source include a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, and a metal halide lamp.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to this.

Example 1
2.84 g of tetraisopropoxytitanium is hydrolyzed in 2-propanol (IPA) to which nitric acid is added, and 2.2 g of dimethylstyrylsilyltrimethoxytitanium (KBM-1403, manufactured by Shin-Etsu Silicone) is added at 50 ° C. The reaction was allowed to proceed for 24 hours, and the solvent was evaporated to obtain a styryl group-containing alkoxytitanium hydrolysis condensate. 0.9 g of this hydrolyzed condensate and 0.1 g of fluorene derivative (bisphenoxyethanol fluorene acrylate) were diluted with methyl ethyl ketone (MEK), and 0.05 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) was added. In addition, a photocurable resin composition was obtained.

Example 2
15 g of tetraisopropoxy titanium and 1.5 g of methacrylic acid are stirred in 4 g of ethyl acetate, and (CH ₂ ═C (CH ₃ ) C (═O) O) _m Ti (O-isoPr) _n (where m and n Is a natural number and the sum of m and n is 4.). 0.5 g of this methacryloyl group-containing compound and 0.5 g of a fluorene derivative (bisphenoxyethanol fluorene acrylate) are diluted with ethyl acetate, and 0.05 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) is added. A photocurable resin composition was obtained.

Example 3
2.84 g of tetraisopropoxy titanium was hydrolyzed in IPA to which nitric acid was added and evaporated to obtain an alkoxy titanium hydrolyzate. This was dissolved in 4 g of ethyl acetate, 0.86 g of methacrylic acid was added and stirred, and a methacryloyl group-containing alkoxytitanium hydrolysis condensate was obtained.

  0.7 g of this methacryloyl group-containing compound and 0.3 g of a fluorene derivative (bisphenoxyethanol fluorene acrylate) are diluted with ethyl acetate, and 0.05 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) is added. A photocurable resin composition was obtained.

Example 4
0.5 g of the styryl group-containing alkoxytitanium hydrolyzed condensate prepared in Example 1, 0.2 g of the methacryloyl group-containing alkoxytitanium compound prepared in Example 2, and 0.3 g of a fluorene derivative (bisphenoxyethanol fluorene acrylate) were mixed with ethyl acetate. And 0.05 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to obtain a photocurable resin composition.

Example 5
0.5 g of styryl group-containing alkoxytitanium hydrolyzed condensate prepared in Example 1, 0.3 g of methacryloyl group-containing alkoxytitanium hydrolyzed condensate prepared in Example 3, 0.2 g of fluorene derivative (bisphenoxyethanol full orange acrylate) Was diluted with ethyl acetate, and 0.05 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) was added to obtain a photocurable resin composition.

Comparative Example 1
A MEK dispersion of 1 g of titanium oxide particles (TTO-51, manufactured by Ishihara Sangyo Co., Ltd.) and 1 g of polyurethane acrylate resin (Beam Set 575CB, manufactured by Arakawa Chemical Industries Co., Ltd.) was prepared.

Comparative Example 2
1 g of titanium oxide particles (TTO-51, manufactured by Ishihara Sangyo Co., Ltd.), 1 g of fluorene derivative (bisphenoxyethanol full orange acrylate) and a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) 0.05 g of MEK dispersion Prepared.

Comparative Example 3
2.84 g of tetraisopropoxy titanium was hydrolyzed in IPA to which nitric acid was added, and the solvent was evaporated to obtain an alkoxy titanium hydrolysis condensate. 0.7 g of this hydrolyzed condensate and 0.3 g of polyurethane acrylate resin (Beamset 575CB, manufactured by Arakawa Chemical Industries) were diluted with MEK to obtain a photocurable resin composition.

(Evaluation)
The photocurable resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were bar-coated on a polyethylene terephthalate film so that the solid content film thickness was 5 μm, and dried at 130 ° C. for 30 seconds. A cured resin layer was formed by irradiation with a high-pressure mercury lamp for 1 minute. Evaluation in Examples and Comparative Examples was performed by the following method. The obtained results are shown in Table 1.

Pencil hardness: The cured resin layer formed on the PET film was measured according to the method defined in JIS.
Refractive index: The cured resin layer formed on the PET film was measured with a reflectance measuring device (F20, manufactured by Filmmetrics).
Haze (%): It measured with the haze meter (Nippon Denshoku Industries Co., Ltd. NDH-1001DP) about the cured resin layer formed on PET film.

  As can be seen from the results of Examples 1 to 5 described in Table 1, the photocurable resin composition obtained in the present invention is transparent in the visible light region (having a haze of 0.5 or more) and has high hardness. A high refractive index film (refractive index of 1.60 or more) having (pencil hardness of 2H or more) can be obtained.

Example 6
A thermosetting resin (OPSTAR 7212, JSR) was applied as a low refractive index layer on the laminate obtained in Example 2 so that the solid film thickness was 0.1 μm, and dried at 120 ° C. for 20 minutes. As a result, a PET film with an antireflection function was obtained. The resulting PET film with antireflection function had a minimum reflectance of 0.2% and a pencil hardness of 3H.

Example 7
After the PET film with an antireflection function obtained in Example 6 was pasted on a liquid crystal display, the display screen was visually observed. As a result, in the case of the liquid crystal display to which the PET film with antireflection function was attached, it was possible to observe a high-quality image with less reflection of the surrounding environment as compared with the case of the liquid crystal display to which it was not attached.

Since the photocurable resin composition of the present invention can provide a film having a high refractive index that is transparent to visible light and has a high hardness, it can be applied as an antireflection film, such as a laminate foil or an image display screen protection plate. It can be advantageously used for articles such as helmet shields.

Claims (17)

The following components (A) and (B):
(A) Metal alkoxide represented by the following formula (1) or a hydrolyzed compound thereof

(In the formula (1), R ¹ represents a substituent having 2 to 20 carbon atoms having at least one radical polymerizable vinyl group, and when a plurality of R ¹ are present, they are the same or different from each other. R ² represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and when a plurality of R ² are present, they may be the same or different from each other, and M is Ti, Sb, W, Zr, Ce. Represents at least one metal atom selected from the group consisting of Sn, Fe, and m and n each represents 0 or a natural number, provided that m and n are not simultaneously 0 and the sum of m and n is the metal M Represents the valence of
(B) A fluorene derivative represented by the following formula (2)

(In formula (2), R ³ and R ⁴ are each independently a (meth) acryloyloxy group, a (meth) acryloyloxyalkoxy group, or a polyalkyleneoxy group substituted with a (meth) acryloyloxy group at the end. Represents.)
The photocurable resin composition characterized by containing. The photocurable resin composition according to claim ¹ , wherein R ¹ in the formula (1) is a styryl group or a substituent having a styryl group at the terminal. Component (A) is represented by formula (3)

(In the formula (3), R ¹¹ represents a saturated hydrocarbon group having 1 to 5 carbon atoms or a phenyl group, and these may be the same or different. R ² , M, m and n are the formulas. (As defined in (1).)
The photocurable resin composition according to claim 1, which is a metal alkoxide represented by the formula (1) or a hydrolyzed compound thereof. In addition to the metal alkoxide of the formula (3), the component (A) is further represented by the following formula (4)

(In Formula (4), R ¹² represents a hydrogen atom or a methyl group. R ² , M, m and n are as defined in Formula (1).)
The photocurable resin composition of Claim 3 containing the metal alkoxide shown by these, or its hydrolysis compound.   Any of 1-4 whose compounding ratio of the component (A) in solid content of a photocurable resin composition is 50-89.9 mass%, and the compounding ratio of a component (B) is 10-50 mass%. A photocurable resin composition according to claim 1.   Furthermore, the photocurable resin composition in any one of Claims 1-5 which contains a photoinitiator as a component (C).   The photocurable resin composition according to claim 6, wherein a blending ratio of the component (C) in the solid content of the photocurable resin composition is 0.1 to 10% by mass. Polymerized units consisting of the following component (A ′) and polymerized units consisting of component (B):
(A ′) Metal alkoxide represented by the following formula (1 ′) or a hydrolyzed compound thereof

(In Formula (1 ′), R ¹ represents a substituent having 2 to 20 carbon atoms having at least one radical polymerizable vinyl group, and when a plurality of R ¹ are present, they are the same or different from each other. R ² represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and when a plurality of R ² are present, they may be the same or different from each other, M ′ represents a metal atom, m and n Each represents 0 or a natural number, provided that m and n are not simultaneously 0 and the sum of m and n represents the valence of the metal M ′);
(B) A fluorene derivative represented by the following formula (2)

(In formula (2), R ³ and R ⁴ are each independently a (meth) acryloyloxy group, a (meth) acryloyloxyalkoxy group, or a polyalkyleneoxy group substituted with a (meth) acryloyloxy group at the end. Represents.)
And a refractive index of 1.55 or more.   The polymer according to claim 8, wherein M 'in the formula (1') is at least one metal atom selected from the group consisting of Ti, Sb, W, Zr, Ce, Sn and Fe. The polymer according to claim 8, wherein R ¹ in the formula (1 ') is a styryl group or a substituent having a styryl group at the terminal. The component (A ′) is represented by the formula (3 ′)

(In the formula (3 ′), R ¹¹ represents a saturated hydrocarbon group or phenyl group having 1 to 5 carbon atoms, which may be the same or different. R ² , M ′, m and n Is as defined in formula (1 ′).)
The polymer of Claim 8 which is a metal alkoxide represented by these, or its hydrolysis compound. In addition to the metal alkoxide of the formula (3 ′) or a hydrolyzed compound thereof, the component (A ′) is represented by the following formula (4 ′)

(In Formula (4 ′), R ¹² represents a hydrogen atom or a methyl group. R ² , M ′, m and n are as defined in Formula (3 ′).)
The polymer of Claim 11 containing the metal alkoxide shown by these, or its hydrolysis compound.   The ratio of the polymer unit consisting of the component (A ') and the polymer unit consisting of the component (B) in the polymer in terms of mass is (50 to 89.9): (10 to 50). Polymer.   It is a laminated body formed by laminating one or more resin layers on a substrate, and at least one of the resin layers is made of the polymer according to any one of claims 8 to 13. Laminated body.   14. An antireflection film in which one or more high refractive index layers and one or more low refractive index layers are laminated on a substrate, and the material constituting the high refractive index layer is any one of claims 8 to 13. And the material constituting the low refractive index layer is a polymer having a refractive index lower by 0.1 or more than the refractive index of the material constituting the high refractive index layer. Prevention film.   A display device comprising the antireflection film according to claim 15. It is a manufacturing method of the laminated body of Claim 14, Comprising: The following processes (a) and (b):
(A) The process of forming the film | membrane of the photocurable resin composition in any one of Claims 1-7 on a base material;
(B) Production comprising the step of irradiating an active energy ray on the resulting photocurable resin composition film to polymerize and curing to form a layer made of a polymer of the photocurable resin composition Method.