TWI598393B - Energy ray-curable resin composition - Google Patents

Description

Energy ray curable resin composition

The present invention relates to an energy ray curable resin composition, a transparent laminate member using the cured material of the energy ray curable resin composition as an insulating layer or a protective layer, and a touch panel including the transparent laminate member, and the like An image display device for a touch panel.

An image display device such as a smart phone, a personal computer, or a game machine having a touch panel built therein can be operated by an operator using a hand, a stylus, or the like to touch a screen. These devices can be operated by using an operator's intuitively easy-to-understand method of displaying the portion of the screen with respect to the display, and thus the handling is very easy, and the market demand is rapidly expanding.

As an example shown in FIG. 1 , the sensor portion of the touch panel is generally on the transparent substrate 1 , patterned into a desired shape, and laminated with the first ITO electrode 2 , the insulating layer 3 , the second ITO electrode 4 , and the protective layer 5 . Others form the extraction electrode 6 and the like. Here, the film formation of the insulating layer 3 or the protective layer 5 is performed by applying an energy ray-curable resin composition to a laminate such as a patterned ITO electrode, and then irradiating and heating energy rays such as ultraviolet light exposure. Implementation.

The insulating layer and the protective layer require various required properties. In any of the layers, the adhesion to ITO (tin-doped indium oxide) and the heat resistance at the time of ITO film formation are required, and the hardness and the like which are damaged during the operation in the manufacturing step are also required. Further, since it is necessary to expose a part of the insulating layer and the protective layer to the ITO electrode, developability capable of pattern formation is also required. In the photoelectric conversion element disclosed in Patent Document 1, a cured film containing a photosensitive resin composition containing a metal oxide is provided in the light-receiving element. An inorganic particle having a refractive index of at least 2.0 at a wavelength of 589 nm, a polymerizable compound having a plurality of (meth)acryl fluorenyl groups in the molecule, and an alkali-soluble polymer having at least one of a hydroxyl group and a carboxyl group in the molecule, And a photoradical polymerization initiator having an oxime ester structure. According to the photoelectric conversion element described in Patent Document 1, it is easy to form and has a high refractive index and chemical stability after curing.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-151164

However, the photoelectric conversion element described in Patent Document 1 has poor adhesion to ITO. Therefore, it is desired to provide an energy ray-curable resin composition which is excellent in adhesion to both ITO and developability, and which is capable of obtaining a high refractive index close to an intermediate value between ITO and glass.

The present invention has been made in view of the above circumstances, and an object thereof is to provide an excellent adhesion and developability to ITO, and an intermediate value of high refractive index close to ITO and glass can be obtained. Energy ray curable resin composition.

The present inventors have made intensive studies to solve the above problems, and as a result, it has been found that a combination of a high refractive index and developable cardo resin and an energy ray polymerizable polyfunctional compound further includes a predetermined P/V ratio. When titanium oxide fine particles and/or zirconia fine particles are added, excellent adhesion to ITO and developability, high transparency, and high refractive index close to ITO can be obtained, and the present invention has been completed. Specifically, the present invention provides the following.

(1) The energy ray-curable resin composition of the present invention contains a cardo resin having a refractive index of 1.58 or more and having a carboxyl group, an energy ray-polymerizable polyfunctional compound, and titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less. And/or zirconia fine particles having an average particle diameter of 5 nm or more and 100 nm or less, an energy ray polymerization initiator, and a solvent; wherein the P/V ratio of the total solid content of the total fine particle component to the total solid content other than the fine particle component is 0.3 or more And below 4.0.

(2) The energy ray curable resin composition according to the above aspect, wherein the titanium oxide fine particles are rutile type.

(3) The energy ray-curable resin composition according to (1) or (2), wherein the mass ratio of the cardo resin to the energy ray polymerizable polyfunctional compound depends on the solid content. The conversion system is 20:80~80:20.

(4) The present invention is the energy ray hardening tree according to any one of (1) to (3) In the fat composition, the titanium oxide fine particle content is 30% by mass or less in the total solid content.

(5) The energy ray-curable resin composition according to any one of the above aspects, wherein the P/V ratio is 1.5 or more and 3.5 or less.

(6) The energy ray curable resin composition according to any one of (1) to (5) wherein the refractive index after energy ray hardening is 1.65 or more.

(7) The energy ray-curable resin composition according to any one of (1) to (5), wherein the refractive index after energy ray hardening is 1.8 or more.

(8) The transparent layered member of the present invention is formed by curing the energy ray curable resin composition according to any one of (1) to (7) on the patterned ITO film. The insulating layer and/or the protective layer or the ITO film is formed on the insulating layer and/or the protective layer.

(9) Further, the touch panel of the present invention includes the transparent laminate member described in (8).

(10) Further, the video display device of the present invention includes the touch panel described in (9).

According to the present invention, it is possible to provide an energy ray-curable resin composition which is excellent in adhesion to both ITO and developability, and which is capable of obtaining a high refractive index close to an intermediate value between ITO and glass.

1‧‧‧Transparent substrate

2‧‧‧1st ITO electrode

3‧‧‧Insulation

4‧‧‧2nd ITO electrode

5‧‧‧Protective layer

6‧‧‧Removing the electrode

10‧‧‧Touch panel

1 is an example of a touch panel, in which (a) a plan view and (b) an A-A cross-sectional view.

The specific embodiments of the present invention are described in detail below, but the present invention is not limited by the following embodiments, and may be appropriately modified and implemented within the scope of the present invention.

<Energy ray curable resin composition>

The energy ray curable resin composition (hereinafter also referred to as "resin composition") of the present invention contains at least the following a) to e). The following is explained in order.

a) Cardo resin having a refractive index of 1.58 or more and having a carboxyl group

b) energy ray polymerizable polyfunctional compound

c) titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less and/or zirconia fine particles having an average particle diameter of 5 nm or more and 100 nm or less

d) energy ray polymerization initiator

e) solvent

f) other

[a] Cardo resin having a refractive index of 1.58 or more and having a carboxyl group]

The cardo resin used in the present invention refers to a resin obtained by reacting an epoxy (meth) acrylate having an anthracene skeleton with a polyvalent carboxylic acid or an anhydride thereof. The mass average molecular weight (Mw) is preferably 1,500 to 18,000, and more preferably 1500 to 10,000 from the viewpoint of compatibility and developability. In addition, the "mass average molecular weight" in the present invention means a weight average molecular weight in terms of polystyrene when measured by a gel permeation chromatography (GPC).

The above epoxy (meth) acrylate having an anthracene skeleton is preferably an epoxy (meth) acrylate represented by the general formula (A):

In the general formula (A), the Z system represents a ring structure such as a benzene ring or a condensed polycyclic aromatic hydrocarbon ring; and R ₁ represents a halogen atom, a hydrocarbon group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, or an aryloxy group. , aralkoxy, alkylthio, cycloalkylthio, arylthio, aralkylthio, fluorenyl, carboxy, alkoxycarbonyl, nitro, cyano or substituted amine; R ₂ represents alkyl R ₃ represents a hydrogen atom or a methyl group; k is an integer of 0 or 1 or more; m is an integer of 0 or 1 or more.

Z preferably has a benzene ring which is a naphthalene ring, more preferably a benzene ring. R _{1 is} preferably a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, a decyl group, a nitro group, a cyano group or a substituted amine group, more preferably a halogen atom or an alkyl group ( An alkyl group having 1 to 6 carbon atoms, an alkoxy group (alkoxy group having 1 to 4 carbon atoms, etc.).

The number m of substitutions of R ₁ varies depending on the type of Z, for example, 0 to 8, preferably 0 to 6, more preferably 0 to 4, and particularly excellent 0 to 2. The substitution position of R ₁ is not particularly limited. The alkylene group represented by R _{2 is} preferably an alkyl group having 2 to 4 carbon atoms such as an ethyl group and a propyl group, and is preferably a branched alkyl group having a carbon number of 3 to 4 from the viewpoint of improving the viscosity lowering effect. . Further, k is preferably 0 to 2. Further, when k is 2 or more, the type of R ₂ may be different, but it is usually the same.

The polycarboxylic acid used in the present cardopolycarbonate is a carboxylic acid having a plurality of carboxyl groups such as a dicarboxylic acid or a tetracarboxylic acid, and the polyvalent carboxylic acid or an anhydride thereof may, for example, be the following compounds: maleic acid, succinic acid, Itaconic acid, citric acid, tetrahydrofurfuric acid, hexahydrofuric acid, methyl hexahydrofuric acid, methyl endois tetrahydrofurfuric acid, hexachloro-methylalkenyl-tetrahydrophthalic acid (chlorendic acid) ), a dicarboxylic acid such as methyltetrahydrofurfuric acid or glutaric acid; and the anhydride; trimellitic acid or its anhydride, pyromellitic acid, diphenyl ketone tetracarboxylic acid, 4-(1,2- Tetracarboxylic acid such as dicarboxyethyl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, and the like and many more. Among them, from the viewpoint of improvement in developability, tetracarboxylic acid or an anhydride thereof is preferred, and from the viewpoint of an increase in refractive index, it is preferred to have an aromatic group such as pyromellitic acid or biphenyltetracarboxylic acid.

Preferably, the cardo resin used in the present invention is obtained by reacting an epoxy (meth) acrylate having an anthracene skeleton with a tetracarboxylic acid or an anhydride thereof, and further blocking a terminal hydroxyl group with a dicarboxylic acid or an anhydride thereof. . Thereby, the reaction between the carboxylic acid and the hydroxyl group of the epoxy (meth) acrylate can be suppressed, and the ink stability can be improved.

A preferred example of obtaining a resin by reacting an epoxy (meth) acrylate having an anthracene skeleton with a polyvalent carboxylic acid or an anhydride thereof as the cardo resin of the present invention is as shown in the following formula (B). :[化2]

In the formula, X is a residue obtained by removing an acid anhydride group of a tetracarboxylic acid or a dianhydride thereof; and Y is a residue obtained by removing an acid anhydride group of a dicarboxylic acid or an anhydride thereof. X and Y are preferably aromatic in view of the refractive index.

The Z system represents a ring structure such as a benzene ring or a condensed polycyclic aromatic hydrocarbon ring; and R ₁ represents a halogen atom, a hydrocarbon group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, or an alkane group. a thio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, a decyl group, a carboxyl group, an alkoxycarbonyl group, a nitro group, a cyano group or a substituted amine group; R ₂ represents an alkylene group; and R ₃ represents a hydrogen atom. Or a methyl group; k is an integer of 0 or 1 or more; m is an integer of 0 or 1 or more; n is an integer of 1 or more.

Z preferably has a benzene ring which is a naphthalene ring, more preferably a benzene ring. R _{1 is} preferably a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, a decyl group, a nitro group, a cyano group or a substituted amine group, more preferably a halogen atom or an alkyl group ( An alkyl group having 1 to 6 carbon atoms, an alkoxy group (alkoxy group having 1 to 4 carbon atoms, etc.).

The number of substitutions m of R ₁ varies depending on the type of Z, and is, for example, 0 to 8, preferably 0 to 6, more preferably 0 to 4, and particularly preferably 0 to 2. The substitution position of R ₁ is not particularly limited.

The alkylene group represented by R _{2 is} preferably an alkyl group having 2 to 4 carbon atoms such as an ethyl group and a propyl group, and is preferably a branched alkyl group having a carbon number of 3 to 4 from the viewpoint of improving the viscosity lowering effect. . Further, k is preferably 0 to 2. Further, when k is 2 or more, the types of R ₂ may be different, but they are usually the same. n is preferably 1 to 40, more preferably 5 to 30.

In the case of such a cardo resin having a ruthenium structure, it has a high refractive index of 1.58 or more. Further, since the main skeleton has a ruthenium structure, it is excellent in chemical resistance, water resistance, and electrical properties. Moreover, when the ITO film is formed by sputtering or the like, the heat resistance is also excellent.

The refractive index of the cardo resin is 1.58 or more, preferably 1.60 or more, and the upper limit is 1.68. When the refractive index is less than 1.58, the refractive index of the cured insulating layer and/or the protective layer cannot be sufficiently increased even if fine particles are added, for example. If it exceeds 1.68, manufacturing is difficult. Further, the refractive index of the cardo resin is obtained at a stage after curing, and the value calculated by the reflectance measured by a spectrophotometer by the method described in the examples can be obtained by the method according to JIS K-7142A. The value is the same value.

Further, the cardo resin used in the present invention has a carboxyl group. Therefore, it has developability such as alkali development. More specifically, the acid value obtained according to JIS-K0070 is 30 mgKOH/g or more, preferably 40 mgKOH/g or more. The reason is that if the acid value is within the above range, sufficient alkali solubility can be exhibited. On the other hand, the upper limit is not particularly limited, but is usually 150 mgKOH/g or less. Further, the acid value is a value obtained by using phenolphthalein as an indicator and titrating with a potassium hydroxide ethanol solution.

Specific examples of the cardo resin used in the present invention include, for example, the compounds represented by the following chemical formulas (i) to (ix) (in the above chemical formula, n is an integer of 1 or more). However, the cardo resin of the present invention is not limited to these specific examples.

[Chemical 3]

[Chemistry 7]

[11]

A commercially available product can be used as the cardo resin having a refractive index of 1.58 or more and a carboxyl group. For example, INR-16M (trade name, manufactured by Nagase ChemteX Co., Ltd.), CR-1030 (trade name, manufactured by Osaka Gas Chemicals Co., Ltd.) can be suitably used. ).

The content of the above cardo resin is usually from 3 to 30% by mass, preferably from 4 to 20% by mass, based on the total solid content. If the content of the resin is too small, there is a possibility that sufficient adhesion may not be obtained, and there may be a residue or a pattern shape defect. If the content is too large, residue may occur and the sensitivity may be lowered. It is not preferable because the possibility of surface roughness (insufficiency of hardening) occurs.

[b) Energy ray polymerizable polyfunctional compound]

The energy ray-polymerizable polyfunctional compound used in the present invention is an energy ray-polymerizable polyfunctional compound other than the cardo resin having a refractive index of 1.58 or more and having a carboxyl group, and is added before the polyfunctional group. No special restrictions. In the present specification, the term "energy ray polymerizable polyfunctional compound" means a polymerizable compound having two or more radical polymerizable functional groups in a molecule. When it is a polyfunctional group, the molecular weight between the crosslinking points of the cured product of the obtained resin composition becomes small, and it is easy to obtain the high modulus of elasticity and hardness of the hardened material.

The energy ray-polymerizable polyfunctional compound is removed before the polymerization can be carried out by the energy ray polymerization initiator described later, and the rest thereof is not particularly limited, and a compound having two or more ethylenically unsaturated double bonds is usually used. A polyfunctional (meth) acrylate having two or more acryl fluorenyl groups or methacryl fluorenyl groups is preferred.

Such a polyfunctional (meth) acrylate may be, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, Propylene glycol di(meth)acrylate, glycerol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butanediol di(methyl) Acrylate, butanediol di(meth)acrylate, dicyclopentyl di(meth)acrylate, triglycerol di(meth)acrylate, neopentyl glycol modified methylolpropane di(methyl) Acrylate, allylic cyclohexyl (meth) acrylate, methoxylated cyclohexyl (meth) acrylate, acrylated isocyanurate, bis(propylene oxime neopentyl glycol) Adipate, bisphenol A di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate, bisphenol S di(meth)acrylate, butanediol di(meth)acrylic acid Ester, di(meth) acrylate, di(meth) acrylate, zinc di(meth) acrylate, bisphenol A (meth) acrylate, bisphenol E (meth) acrylate Bisphenol F (meth) acrylate A difunctional (meth) acrylate such as a cresol novolac (meth) acrylate or a novolac type (meth) acrylate.

Further, the trifunctional or higher polyfunctional (meth) acrylate may be, for example, hydroxymethylpropane tri(meth)acrylate, hydroxymethylethane tri(meth)acrylate, or glycerol ( Methyl) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, alkyl modified dipentaerythritol tri(meth) acrylate, succinic anhydride modified pentaerythritol tetra (meth) acrylate , tris(meth)acrylate, iso-cyanuric acid tris(propylene oxyethyl ester), Tris(methacrylic acid), dipentaerythritol tetra(meth)acrylate, dimethylolpropane tetraacrylate, alkyl modified dipentaerythritol tetra(meth)acrylate, two Pentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, succinic anhydride modified dipentaerythritol penta (meth) acrylate, amine formate B Ester tri(meth)acrylate, ester tri(meth)acrylate, urethane hexa(meth)acrylate, ester hexa(meth)acrylate, and the like.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. In addition, when the energy ray-curable resin composition of the present invention is required to have excellent energy ray curability (high sensitivity), the energy ray-polymerizable polyfunctional compound preferably has three (trifunctional) or more double bonds. Preferably, it is a poly(meth) acrylate of a trihydric or higher polyhydric alcohol, or a dicarboxylic acid modified product, and particularly preferably isocyanuric acid tris(propylene oxy oxyethyl ester) or iso-tris Tris(methacrylic acid), hydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate succinic acid modification, pentaerythritol Tetrakis (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate succinic acid modification, dipentaerythritol hexa (methyl) Acrylate and the like.

These energy ray-polymerizable polyfunctional compounds may be used alone or in combination of two or more. From the viewpoint of improvement in sensitivity, it is preferred that the radical polymerizable functional group in the molecule has three or more (meth) acrylate groups. Here, "(meth) acrylate" means methacrylate or acrylate.

The commercially available product of the energy ray-polymerizable polyfunctional compound described above can be, for example,: Aronix M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-400 manufactured by Toagos Corporation , M-402, M-403, M-404, M-405, M-406, M-408, M-450, M-452, M-303, M-305, M-306, M-309, M -310, M-313, M-315, M-321, M-350, M-360, M-510, M-520, M-7100, M-7300K, M-8030, M-8060, M-8100 , M-8530, M-8560, M-9050; Light Acrylate PE-3A, PE-4A, DPE-6A, DTMP-4A, urethane acrylate UA-306H, UA -306T, UA-306I, UA-510H, epoxy acrylate epoxy ester 80MFA, epoxy ester 3002M (N), epoxy ester 3002A (N), epoxy ester 3000MK, epoxy ester 3000A; Nippon Chemical Co., Ltd. KAYARAD D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA; Sartomer SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR- 9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003; Biscoat #802 manufactured by Osaka Organic Chemical Industry Co., Ltd.; tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate; a mixture of TEA-100 manufactured by KSM Co., Ltd., and the like.

The mass average molecular weight (Mw) of the energy ray-polymerizable polyfunctional compound used in the present invention is preferably from 100 to 10,000, more preferably from the viewpoint of compatibility and developability. 200~3000. In addition, the "mass average molecular weight" in the present invention means a weight average molecular weight in terms of polystyrene when measured by a gel permeation chromatography (GPC).

The content of the energy ray polymerizable polyfunctional compound is usually from 3 to 50% by mass, preferably from 5 to 40% by mass, more preferably from 6 to 30% by mass, based on the total solid content. When the content of the energy ray-polymerizable polyfunctional compound is too small, sufficient energy ray hardenability may not be obtained. If the content is too large, there is a possibility of poor adhesion due to hardening shrinkage and deterioration in developability. It is not preferred.

The mass ratio of the cardo resin to the energy ray polymerizable polyfunctional compound is preferably 20:80 to 80:20 in terms of solid content. By being within this range, it is possible to provide a resin composition which is excellent in adhesion to both ITO and developability, and which can obtain a high refractive index close to the middle of ITO and glass. If the proportion of the resin is too small, there is a possibility that the adhesion is poor due to the hardening shrinkage and the developing suitability is lowered, which is not preferable. On the other hand, if the ratio of the energy ray polymerizable polyfunctional compound is too small, sufficient energy ray hardenability may not be obtained, which is not preferable. Further, in particular, when the P/V is high, the mass ratio of the cardo resin to the energy ray-polymerizable polyfunctional compound is preferably 30:70 to 60:40 in terms of solid content.

[c] Titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less and/or zirconia fine particles having an average particle diameter of 5 nm or more and 100 nm or less]

The energy ray curable resin composition of the present invention contains titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less and/or zirconia fine particles having an average particle diameter of 5 nm or more and 100 nm or less.

[c1] Titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less]

In the energy ray curable resin composition of the present invention, the refractive index of the energy ray curable resin composition can be improved by using the above titanium oxide fine particles.

The crystal structure of the titanium oxide fine particles is not particularly limited, and is preferably a rutile type. By belonging to the rutile type, deterioration of the coating film over time due to photocatalytic activity can be suppressed.

The titanium oxide fine particles used in the present invention have an average particle diameter of 5 nm or more and 100 nm or less, and preferably have an average particle diameter of 10 nm or more and 50 nm or less, more preferably 10 nm or more and 30 nm or less. In the present specification, the "average particle diameter" means an average primary particle diameter, and the average primary particle diameter is, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM), by directly observing the microparticles themselves. Determination. When the average primary particle diameter is less than 5 nm, since the cohesive force between the fine particles is extremely large, it is very difficult to disperse the primary particles exhibiting high transparency. On the other hand, when the average primary particle diameter exceeds 100 nm, it is easy to disperse depending on the primary particles. However, since the particle diameter is large, light such as visible light is easily scattered, and the transparency of the cured film is deteriorated. The problem occurred.

A commercially available product of titanium oxide fine particles is a commercially available dispersion containing titanium oxide fine particles, and the like, for example, cerium oxide-coated, tin oxide-containing rutile-type titanium oxide-methanol dispersion (manufactured by TAYCA, TS series), rutile A titanium oxide dispersion (manufactured by TAYCA Co., Ltd., ND139, ND291), a rutile-type titanium oxide dispersion (manufactured by Seiko Chemical Co., Ltd., STR-60C-LP, STR-100C-LP, STR-100A-LP).

[c2] zirconia fine particles having an average particle diameter of 5 nm or more and 100 nm or less]

When the energy ray-curable resin composition of the present invention is used, the zirconia fine particles can be used to improve the haze of the insulating layer and/or the protective layer which are cured without curing the energy ray-curable resin composition. Refractive index.

The zirconia fine particles used in the present invention have an average particle diameter of 5 nm or more and 100 nm or less, and preferably have an average particle diameter of 10 nm or more and 50 nm or less. When the average primary particle diameter is less than 5 nm, since the cohesive force between the microparticles is very large, it is very difficult to disperse the primary particles exhibiting high transparency. On the other hand, when the average primary particle diameter exceeds 100 nm, it is easy to disperse depending on the primary particles. However, since the particle diameter is large, light such as visible light is easily scattered, and the transparency of the cured film is deteriorated. The problem occurred.

The commercially available product of the zirconia fine particles is a commercially available dispersion containing zirconia fine particles, and the like, for example, a zirconia-methyl ethyl ketone dispersion (manufactured by Sumitomo Osaka Cement Co., Ltd., HXU-120JC), a zirconia-methyl ethyl ketone dispersion (Nissan Chemical Co., Ltd.) Company, NANOUSE series), zirconia-methyl ethyl ketone dispersion (manufactured by Suga Chemical Co., Ltd., SZR-K).

However, it is preferable that the titanium oxide fine particles and the zirconia fine particles of the present invention are covered with an oxide such as aluminum, lanthanum or zirconia. Thereby, the dispersibility and weather resistance can be improved.

The titanium oxide fine particles and the zirconia fine particles of the present invention may also be subjected to surface treatment using an organic compound. Examples of the organic compound used for the surface treatment include a polyhydric alcohol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent. Among them, a decane coupling agent is preferred. The surface treatment can be carried out by using one type of surface treatment agent alone or in combination of two or more types. The surface treatment agent is implemented.

Further, in order to enhance the dispersibility of the titanium oxide fine particles and the zirconia fine particles, a dispersing agent may be used. The dispersant is preferably an acrylic resin from the viewpoint of compatibility with the binder resin, and particularly preferably a polymerizable unsaturated group. By having a polymerizable unsaturated group, it is possible to suppress a decrease in sensitivity due to ultraviolet absorption specific to titanium.

The surface treatment and the use of the dispersant may be carried out either singly or in combination.

In the present invention, the titanium oxide fine particles and the zirconia fine particles may be used singly or in combination. In the case of mixing, the titanium oxide fine particles preferably account for 30% by mass or less of the total solid content including the resin. In this range, it is possible to suppress the deterioration of the sensitivity due to the ultraviolet ray absorption characteristic of titanium and the deterioration of the coating film due to the photocatalytic activity, thereby obtaining excellent adhesion to the ITO and developability, and having high transparency and energy. A resin composition close to the high refractive index of ITO was obtained. When the amount of the titanium oxide fine particles is too large, the refractive index is increased, but there is a possibility that the transparency of the coating film is lowered due to the photocatalytic activity, which is not preferable. Further, the lower limit of the content of the titanium oxide fine particles is preferably 15% by mass or more. Further, the zirconia fine particles preferably account for 20% by mass or more and 50% by mass or less of the total solid content including the resin. If the zirconia fine particles are too large, the transparency is good, but the refractive index may not be sufficiently increased.

The mass ratio of the titanium oxide fine particles and the zirconia fine particles is preferably 10:90 to 80:20, more preferably 20:80 to 50:50, in terms of solid content. By being in this range, it is possible to obtain a resin which is excellent in adhesion and developability to ITO and which can obtain a high refractive index close to ITO. Composition.

Further, the present invention is characterized in that the total fine particle component P (the above c) component and the other fine particle component) and the mass ratio P/V ratio of the component V excluding P from the total solid component are 0.3 or more and 4.0 or less. The "total solid content" means a component other than the solvent contained in the energy ray curable resin composition. The P/V ratio is preferably 1.5 or more and 3.5 or less. When the P/V ratio is within this range, the transparency is maintained, and the refractive index of the insulating layer and/or the protective layer is made higher than that of the matrix resin, and the refractive index of the ITO film can be approximated. In addition, the combination can also improve the developability.

If the P/V ratio is less than 0.3, the refractive index of the cured insulating layer and/or the protective layer cannot be sufficiently increased. On the other hand, when it exceeds 3.5, since the organic component is too small, adhesiveness and developability will fall.

[d) Energy ray polymerization initiator]

The energy ray curable resin composition of the present invention is further blended with an energy ray polymerization initiator. The energy ray polymerization initiator is, for example, an azo-based, an alkylphenone-based, a fluorenylphosphine oxide-based, a titanium-based, an oxime-based or a cationic system. Among them, an alkylphenone-based group or a fluorenyl group is preferred. A phosphine oxide-based or oxime ester-based initiator, for example, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propyl) Mercapto)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,2-dimethylamino-2-(4-methyl-benzyl)-1-(4- Physo-4-yl-phenyl)-butan-1-one, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzene Mercaptodiphenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-,2-(o-benzamide), ethyl ketone, 1-[9-ethyl -6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(o-acetamidine), 1-(6-O-methyl-benzhydryl- 9-ethyloxazol-3-yl)-3-cyclohexylacetone-1-indole acetate, 1-(6-O-methyl-benzhydryl-9-ethylcarbazol-3-yl) -3-cyclopentylacetone-1-indole acetate, ethyl ketone, 1-[6-[4-[(2,2-dimethyl-1,3-dioxolancyclo-4-yl)) Methoxy]-2-methylbenzhydryl]-9-ethyl-9H-indazol-3-yl]-, 1-(O-acetamidine), 1,2-propanedione, 3 -cyclopentyl-1-[4-(phenylthio)phenyl]-, 2-(O-benzamide) and the like. Further, from the viewpoints of sensitivity, transparency, and plate-adaptability, 2-methyl-1-[4-(methylthio)phenyl]-2- is preferred. Lolinylpropan-1-one, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 1 ,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzamide), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzamide Mercapto)-9H-carbazol-3-yl]-,1-(O-acetamidine), 1-(6-O-methyl-benzhydryl-9-ethylcarbazol-3-yl )-3-cyclopentylacetone-1-indole acetate, ethyl ketone, 1-[6-[4-[(2,2-dimethyl-1,3-dioxolancyclo-4-yl) Methoxy]-2-methylbenzimidyl]-9-ethyl-9H-indazol-3-yl]-, 1-(O-acetamidine), 1,2-propanedione, 3-Cyclopentyl-1-[4-(phenylthio)phenyl]-, 2-(O-benzamide).

In addition, the energy ray polymerization initiator may be, for example, IRGACURE OXE01 (manufactured by BASF Japan), IRGACURE OXE02 (manufactured by BASF Japan), N-1919 (manufactured by Adeka Co., Ltd.), IRGACURE 819 (manufactured by BASF Japan Co., Ltd.), Commercial products such as LUCIRIN TPO (manufactured by BASF Japan Co., Ltd.) and IRGACURE 907 (manufactured by BASF Japan Co., Ltd.).

The blending ratio of the energy ray polymerization initiator is a ratio of the total solid content, preferably 1 to 15% by mass, more preferably 2 to 10% by mass.

[e) Solvent]

The energy ray curable resin composition of the present invention can be solidified by adding a suitable solvent. Shape adjustment. The solvent does not react with each component of the energy ray curable resin composition, and the organic solvent which is dissolved or dispersed can be removed before, and the rest is not particularly limited. Specifically, for example, alcohols such as methanol, ethanol, 3-methoxy-1-propanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ether, Glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; ethylene glycol alkyl ether acetates such as methyl cyproterone acetate and ethyl cyproterone; diethylene glycol monomethyl ether; Diethylene glycol such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol alkyl ether acetate such as propylene glycol monoethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentyl Ketones such as ketones; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, and ethyl hydroxyacetate Ester, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxyl Ethyl propionate, ethyl acetate, butyl acetate, methyl lactate, milk Ethyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butyl esters and the like. These solvents may be used singly or in combination of two or more. Among these, a solvent is preferred from the viewpoints of coating suitability and solubility, for example, 3-methoxy-1-propanol, diethylene glycol ethyl methyl ether, PGMEA, and acetic acid-3- Methoxybutyl ester, acetic acid-3-methoxy-3-methyl-1-butyl ester. These solvents may be used singly or in combination of two or more.

The amount of the solvent can be appropriately selected in accordance with the target coating property and the dispersion solubility, and it is preferably adjusted to 5 to 40% by mass based on the solid content of the resin composition.

[f)Other]

The energy ray curable resin composition of the present invention may also suitably use an adhesion aid or a boundary Surfactant, sensitizer, polymerization terminator, antioxidant, dispersant, energy ray stabilizer (light stabilizer), leveling agent, hardening aid, fine particles of metal oxides such as hardness increase (colloidal dioxide)矽, etc.).

The adhesion aid which can be used in the present invention is not particularly limited, and has the effect of interposing an organic material and an inorganic material, improving the adhesion to the substrate, and improving the compatibility between the organic material and the inorganic material. Preferably, a decane coupling agent is used. Further, the decane coupling agent may be, for example, an ethylene-based, methacrylic-based, acrylic-based, epoxy-based, amine-based, styrene-based, urea-based, thiol-based, isocyanic acid depending on the functional group of the organic component. In the viewpoint of improving adhesion and compatibility, it is more preferably an ethylene-based, methacrylic-based, acrylic-based, epoxy-based, thiol-based or isocyanic acid-based system. For example, KBM-403, KBM-502, KBM-503, KBM-803, KBM-5103, KBM-9007, etc., which are commercially available, can be blended in a ratio of 0.1 to 10% by mass based on the total solid content. Hehe.

The surfactant which can be used in the present invention is, for example, "MEGAFAC®" R08MH, RS-72-K, RS-75, F-477, F-559, etc., or BYK, which is made of a fluorine-based DIC company. -Chemie. BYK-333, BYK-301, etc., manufactured by Japan Corporation, are blended in a ratio of 0.1 to 5% by mass based on the total solid content.

In order to improve the adhesion of ITO, a phosphoric acid compound having a double bond may be further added to the molecule. The phosphoric acid compound used in the present invention is preferably a phosphoric acid compound having an ethylenically unsaturated double bond in the molecule. For example: 2-methacryloxyethyl phosphate phosphate (trade name: LIGHT ESTER® P-1M, LIGHT ESTER® P-2M, Co., Ltd. Chemical (share) system, ethylene oxide modified phosphoric acid dimethacrylate (trade name: PM-21, manufactured by Nippon Chemical Co., Ltd.), epoxy methacrylate containing phosphoric acid (trade name: NEW A phosphoric acid-based compound such as phosphoric acid (meth) acrylate or vinylphosphonic acid (trade name: VPA-90, VPA-100, manufactured by BASF Corporation) such as FRONTIER S-23A or the first industrial pharmaceutical company.

Further, the energy ray curable resin composition of the present invention may further contain a polyfunctional thiol compound of a hardening aid. The "polyfunctional thiol compound" means a compound having two or more sulfonyl groups (-SH) in the molecule. In particular, when a compound having two or more sulfonium groups bonded to a carbon atom derived from an aliphatic hydrocarbon group is used, the sensitivity of the energy ray-curable resin composition of the present invention tends to be increased. Further, if a structure having a secondary thiol structure is used, the preservation stability is improved, which is preferable.

Specifically, the polyfunctional thiol compound may be, for example, hexanedithiol, decanedithiol, 1,4-bis(methylsulfonyl)benzene, butanediol bis(3-sulfonylpropionate). , butanediol bis(3-sulfonyl acetate), ethylene glycol bis(3-sulfonyl acetate), methylolpropane tris(3-sulfonyl acetate), butanediol double (3) -sulfonylpropionate), hydroxymethylpropane tris(3-sulfonylpropionate), hydroxymethylpropane tris(3-sulfonylacetate), pentaerythritol tetrakis(3-sulfonylpropionic acid) Ester), pentaerythritol tetrakis(3-sulfonylacetate), trishydroxyethyltris(3-sulfonylpropionate), pentaerythritol tetrakis(3-sulfonylbutyrate), 1,4-double ( 3-sulfonylbutoxy)butane, pentaerythritol tetrakis(3-thiol butyrate), methylolpropane tris(3-thiol butyrate), hydroxymethylethane tris(3- Thiol butyl butyrate) and the like.

The content of the polyfunctional thiol compound in the total solid content is preferably from 0.1 to 3% by mass. If the content of the polyfunctional thiol compound is within the above range, oxygen suppression can be alleviated The effect can promote hardening, and the sensitivity of the energy ray hardening resin composition can be improved. Further, it is preferable to have a good surface state after development after pattern formation.

Further, the fine particles of the metal oxide may contain other components in addition to the above component c). The other component preferably contains at least one element selected from the group consisting of zinc, bismuth, indium, tin, antimony, bismuth, antimony, bismuth, tungsten, bismuth and aluminum. Specifically, for example, antimony pentoxide, zinc oxide, antimony oxide, zinc antimonate, antimony doped tin oxide (ATO), tin doped indium oxide (ITO), fluorine doped tin oxide (FTO), phosphorus doped oxidation Tin (PTO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), tin oxide, ATO-coated titanium oxide, gallium-doped zinc oxide, alumina, and the like. These systems are readily available from well-known commercial products.

<Transparent laminated member/touch panel>

The energy ray curable resin composition of the present invention is applied, for example, to the patterned ITO electrode, and is cured by energy ray curing by ultraviolet rays or the like to form an insulating layer and/or a protective layer. The transparent laminate member of the present invention, and the transparent laminate member constitutes a part of the touch panel.

Referring to FIG. 1 again, the sensor portion of the touch panel 10 is usually formed on the transparent substrate 1 and the first ITO electrode 2, the insulating layer 3, and the second ITO are laminated by patterning into a desired shape. The electrode 4 and the protective layer 5 can be obtained. Either or both of the insulating layer 3 and the protective layer 5 may be used for the insulating layer and/or the protective layer of the present invention.

The transparent substrate 1 is not particularly limited as long as it is a substrate transparent to visible light energy rays. Specifically, for example, quartz glass, alkali-free glass, tempered glass, and A transparent transparent material such as a quartz plate or the like which has no flexible transparent material, or a transparent resin film (PET or the like) or an optical resin plate.

First, the first ITO electrode 2 patterned into a desired shape is formed on the transparent substrate 1 by a known method. Then, the energy ray-curable resin composition of the present invention is applied onto the first ITO electrode 2 to form the insulating layer 3. The coating method is not particularly limited, and examples thereof include a spray coating method, a dip coating method, a bar coating method, a roll coating method, and a spin coating method. The pre-drying after coating is performed by using a hot plate, an oven, etc., at 50 to 150 ° C for 10 to 600 seconds.

Next, a photomask having a predetermined shape opening pattern is placed on the energy ray curable resin composition, and irradiation with an active energy ray is performed. The active energy ray system may be, for example, an ultraviolet ray, an electron beam or the like. The irradiation amount can be appropriately set within the range used for the usual patterning, and can be set, for example, in the range of 30 to 300 mJ/cm ² , preferably 50 to 200 mJ/cm ² . The coating film after the irradiation with the active energy ray is developed by an ordinary method. The energy ray curable resin composition after the development treatment is subjected to heating (post-baking). The heating conditions can be set in the same range as when the usual insulating layer and/or the protective layer are formed, and for example, it can be heated at 100 to 300 ° C for 15 to 40 minutes. As a result, in this embodiment, the insulating layer 3 composed of the cured product of the energy ray curable resin composition of the present invention is formed in a pattern. The film thickness (during drying) of the insulating layer is not particularly limited, and can be appropriately set in the range of 0.1 to 5 μm, preferably 0.5 to 3 μm.

Then, the second ITO electrode 4 and the protective layer 5 are sequentially formed as described above to obtain the transparent laminate member of the present invention. Here, the protective layer 5 may be formed in the same manner as described above by using the same resin composition as the insulating layer 3.

The touch panel of the present invention having the transparent laminate member is not particularly limited, and may be arranged in the order of glass, the ITO film, the insulating layer, and/or the protective layer from the touch surface side, or may be in accordance with glass, The insulating layer and/or the protective layer and the ITO film are arranged in this order. Conventionally, when the glass is viewed from the side of the touch surface, it is conventional to see the pattern of the ITO electrode. However, in the present invention, the insulating layer and/or the protective layer are made to have a high refractive index, and the refractive index is preferably set to 1.65 or more, more preferably 1.80 or more. Thereby, since the intermediate value of the refractive index of the glass (1.45 to 1.55) and the refractive index of the ITO (1.8 to 2.2) is approached, it is possible to effectively prevent the pattern of the ITO electrode from being seen through. In addition, the upper limit of the refractive index is preferably 2.0, and if it exceeds the above, there is a possibility that the composition of the present invention (developability, adhesion, etc.) can be synthesized. Accordingly, in the present invention, since the insulating layer and/or the protective layer itself are provided with high refractive index, it is not necessary to use another high refractive index film or the like in combination, and the structure is simple and excellent in terms of cost. Further, the "refractive index of the insulating layer and/or the protective layer" as used in the present invention means a value measured in accordance with the method of the following examples.

<Image display device>

The present invention also provides an image display device including the above touch panel. The image display device may be, for example, a brown tube (CRT), a plasma display panel (PDP), an organic EL display, a liquid crystal display device, or the like. Further, the video display device of the present invention also includes a smart phone, a personal computer, a game machine, a car audio system, a car navigation system, a mobile terminal, and the like including the liquid crystal display device.

[Examples]

The invention will be more specifically illustrated by the following examples, but the invention is not limited to the following examples.

The following components a) to f2) were obtained according to the formulations of Tables 1 to 3 (parts by mass of the solid portion), and the resin compositions of the examples and the comparative examples were obtained.

a) Cardo resin having a refractive index of 1.58 or more and having a carboxyl group (trade name: INR-16M, manufactured by Nagase ChemteX Co., Ltd., refractive index: 1.61, solid content: 55 mass%)

a') acrylic resin

21 parts by mass of methacrylic acid and 70 parts by mass of benzyl methacrylate were copolymerized, and further, 9 parts by mass of glycidyl methacrylate was added in the presence of a triethanolamine catalyst (polyphenylene determined by GPC) The above-mentioned a') acrylic resin was obtained by weight-average molecular weight of ethylene: 12,000 and acid value: 80 mgKOH.

b) energy ray polymerizable polyfunctional compound

B1) Energy ray polymerizable polyfunctional compound 1 (trade name: Aronix M-403, dipentaerythritol hexaacrylate (DPHA), manufactured by Toagosei Co., Ltd., 100% by mass of solid content)

B2) Energy ray polymerizable polyfunctional compound 2 (trade name: Aronix M-315, octadecyl EO modified di- and triacrylate, manufactured by Toagosei Co., Ltd., 100% by mass of solid content)

c) titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less and/or zirconia fine particles having an average particle diameter of 5 nm or more and 100 nm or less

C1-1) Titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less (trade name: ND139, rutile-type titanium oxide fine particles, manufactured by TAYCA Co., Ltd., average particle diameter: 10 nm, and solid form in propylene glycol monomethyl ether (PGME) 32.3% by mass dispersion, solid content of titanium oxide: 26.4% by mass)

C1-2) Titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less (trade name: Nanotek, anatase type titanium oxide fine particles, manufactured by C.I. Chemical Co., Ltd., average particle diameter: 32 nm)

Further, in Example 18, 15.0 parts by mass of the above-mentioned Nanotek, 6.56 parts by mass of a dispersing agent (trade name: DISPERBYK-111, manufactured by BYK-Chemie Co., Ltd.), and 78.44 parts by mass of a solvent (PGEMEA) were used, and the solvent was used for 1 hour. After pre-mixing, a 0.1 mm zirconia ball was used, and a dispersion was carried out for 3 hours using a paint stirrer (manufactured by Asada Iron Works Co., Ltd.).

C2) zirconia fine particles having an average particle diameter of 5 nm or more and 100 nm or less (zirconia having an average particle diameter of 15 nm, dispersed in propylene glycol monomethyl ether (PGME) according to a solid content of 22.5 mass%, and solid content of zirconia: 20.1% by mass)

c') titanium oxide fine particles having an average particle diameter of more than 100 nm and/or zirconia fine particles having an average particle diameter of more than 100 nm

C1') Titanium oxide fine particles having an average particle diameter of more than 100 nm (trade name: CR-58, rutile-type titanium oxide fine particles, manufactured by Ishihara Sangyo Co., Ltd., average particle diameter: 250 nm)

Further, in Comparative Example 4, CR-58: 15.00 parts by mass, 6.56 parts by mass of a dispersing agent (trade name: DISPERBYK-111, BYK-Chemie Co., Ltd.), and 78.44 parts by mass of a solvent (PGEMEA) were used in a dissolver. After pre-mixing for 1 hour, 0.1 mm zirconia beads were used, and a dispersion was carried out for 3 hours using a paint stirrer (manufactured by Asada Iron Works Co., Ltd.).

d) energy ray polymerization initiator

D1) Energy ray polymerization initiator 1 (trade name: IRGACURE 907, manufactured by BASF Corporation)

D2) Energy ray polymerization initiator 2 (trade name: IRGACURE 819, manufactured by BASF Corporation)

D3) Energy ray polymerization initiator 3 (trade name: Lucirin TPO, manufactured by BASF Corporation)

D4) Energy ray polymerization initiator 4 (trade name: N-1919, manufactured by ADEKA)

e) Solvent (propylene glycol monomethyl ether acetate (PGMEA), adjusted to 20% by mass of solid content)

f) other ingredients

F1) Surfactant (trade name: MEGAFAC® F477, DIC)

F2) adhesion aid (decane coupling agent, trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Evaluation items and evaluation methods>

The results of the following evaluations were carried out as shown in Tables 4 and 5.

(1) Refractive index

First, on the glass substrate, the resin composition obtained in the examples and the comparative examples was spin-coated so as to have a thickness of 1.5 μm after drying, and then allowed to stand on a hot plate at 90 ° C for 180 seconds (pre-drying). When exposed to 200 mJ/cm ² , a coating film was obtained. The coating film was subjected to a post-baking treatment at 230 ° C for 20 minutes.

Then, in order to prevent back reflection, a black tape was adhered to the glass surface side, and a spectrophotometer UV-3150 manufactured by Shimadzu Corporation was used from the surface of the cured film, and the reflectance in the wavelength range of 380 to 780 nm was measured, and the average reflectance R of the average value was calculated.

Then, using the average reflectance R, the refractive index n _{1 of the} present invention is calculated by the following formula. Where n ₀ is the refractive index of air and is calculated as 1.000. When the glass substrate is a substrate to be used, the refractive index is preferably 1.65 or more, and more preferably 1.8 or more.

R=(n ₀ -n ₁ ) ² /(n ₀ +n ₁ ) ²

In addition, in another test, the substrate of the present invention was subjected to inspection under the same conditions as the "(1) refractive index", and it was confirmed that the refractive index was 1.65 or less. No effect of pattern invisibility was observed, and the effect appeared at 1.65 to 1.8. If it is 1.8 or more and 1.9 or less, it is almost invisible.

(2) Haze (2-1) Haze 1

The haze of the visible light was measured for the coating film formed by the film under the same conditions as the "(1) refractive index". The haze measurement is based on JIS K7361-1 (Test method for total light transmittance of plastic-transparent materials), and the haze value is a value measured by a HM-150 (manufactured by Murakami Color Research Laboratory Co., Ltd.) according to JIS K7105. . Haze is preferably 1.5 when the glass substrate is used as a substrate. the following. More preferably, the system is 1.0 or less.

(2-2) Haze 2

In addition, in the accelerated test, the heated coating film was obtained under the same conditions as the haze 1, and further, the haze of visible light was measured under the conditions of 120 ° C, 100% RH, and 2 atmospheres for 3 hours. The measurement of the haze was carried out in the same manner as in the above item "(2-1) Haze 1".

(3) Total light transmittance

The total light transmittance was measured for a coating film formed by the same conditions as the "(1) refractive index". The total light transmittance is measured in accordance with JIS K7361-1 (Test method for total light transmittance of plastic-transparent materials), and the total light transmittance value is a value measured by using the above-described test meter HM-150 according to JIS K7105. . The total light transmittance is preferably 85% or more when the glass substrate is used as a substrate.

(4) developability (surface state, development residue)

The reticle exposure was carried out in accordance with the following conditions for the coating film which was subjected to spin coating and pre-drying under the same conditions as the "(1) refractive index". Subsequently, development was carried out for 60 seconds at 23 ° C using a 0.045% potassium hydroxide aqueous solution of an alkali developer, and the developability was evaluated from the exposed portion and the unexposed portion.

(exposure conditions)

Exposure machine: proximity exposure machine

Photomask: chrome mask

Exposure gap: 150μm

Light source: ultra high pressure mercury lamp

Exposure: 200mJ/cm ²

The developability evaluation was carried out as follows. A mask having a line having a resolution of 10 to 100 μm and a pattern such as a spacer type is placed, and after the ultraviolet rays are irradiated under the above conditions, development processing is performed. The developed exposed portion was visually observed with a microscope, and judged based on the following criteria.

"○" and "△" are practical ranges.

○: Microscopically, no roughness was found.

△: The microscope was slightly rough.

×: Microscopically visible roughness

Further, the presence or absence of the development residue was visually observed for the unexposed portion after development, and the judgment was made in accordance with the following criteria. "○" is a practical range.

○: No residue found by visual inspection

×: Visually found residue

(5) Adhesion to glass (5-1) Adhesion 1

A checkerboard peeling test was performed on the glass substrate by using a cellophane adhesive tape in accordance with the coating film formed under the same conditions as the above "(1) refractive index". Here, in the checkerboard peeling test, a parallel straight line of 11 straight and vertical lines is drawn at intervals of 1 mm by means of a utility knife in a manner of reaching the base of the glass substrate, and 100 square meters of 1 mm × 1 mm are produced, and wiped with an eraser. Paste the celluloid adhesive tape (trade name: celluloid tape (registered trademark), model: CT405AP-24, manufactured by NICHIBAN Co., Ltd.), and then peel off at a right angle, and visually evaluate the remaining number of squares. In addition, the peeling area of the square is judged according to the following criteria. set. "5" or "4" is a practical range.

5: peeling area 0%

4: peeling area 0% exceeds ~25%

3: 25% of the peeling area is less than ~50%

3: 50% of the peeling area is over ~75%

1: peeling area 75% over ~100%

(5-2) Adhesion 2

Further, the accelerated test was carried out in the same manner as in the case of the adhesion 1 to obtain a heated coating film, and further carried out for 3 hours under the conditions of 120 ° C, 100% RH, and 2 atmospheres, and then carried out by using a celluloid adhesive tape. Checkerboard peel test. The checkerboard peeling test was carried out and evaluated in accordance with the same conditions as above.

(6) Adhesion to ITO substrate

The adhesion to the ITO substrate was evaluated in the same manner as in the above-mentioned "adhesiveness to glass" except for the glass substrate (ITO substrate) on which the glass substrate was bonded with an ITO film.

It is confirmed that a cardo resin having a refractive index of 1.58 or more and having a carboxyl group, an energy ray polymerizable polyfunctional compound, and titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less and/or an average particle diameter of 5 nm or more and 100 nm or less are contained. The energy ray-curable resin composition having a P/V ratio of 0.3 or more and 4.0 or less in total mass fraction of the total fine particle component and the total solid content of the fine particle component and the fine particle component, can be zirconia fine particles, an energy ray polymerization initiator, and a solvent. The refractive index of the insulating layer and/or the protective layer can be greatly increased, and the refractive index difference between the ITO and the ITO can be reduced, so that the ITO pattern can be effectively prevented from being seen from the side of the touch surface, and the developability and the ITO and the glass substrate are both Both of them have excellent adhesion (Examples 1 to 20).

In particular, in the case of the comparative examples 1 to 4, it is confirmed that the content of the titanium oxide fine particles in the total solid content is preferably 30% by mass or less (Examples 3 and 4).

Further, in Comparative Examples 5 to 10, it was confirmed that when the P/V ratio is 1.5 or more, the refractive index is improved, and when the P/V ratio is 3.5 or less, the P/V ratio is preferably in the viewpoint of excellent developability. 1.5 or more and 3.5 or less (Examples 6 to 9).

Further, from Examples 11 to 13, it was confirmed that the mass ratio of the cardo resin to the energy ray-polymerizable polyfunctional compound is preferably 20:80 to 80:20 in terms of solid content, and the embodiment 3 and the examples are used. In comparison with the above, it was confirmed that the type of the energy ray polymerizable polyfunctional compound was not particularly limited, and it was confirmed from Examples 17 to 20 that the titanium oxide fine particles and the zirconia fine particles were contained as long as they contained either one. When Examples 17 and 18 were compared, the haze 2 value of Example 18 which belongs to the anatase type was high, and it was confirmed that it was preferably a rutile type.

On the other hand, it has been confirmed that when the cardo resin is changed to an acrylic resin, adhesion to ITO is inferior, which is not preferable (Comparative Example 1). Further, it was confirmed that if the component a) is not contained, there is a residue at the time of development, and adhesion to glass and ITO is inferior, which is not preferable (Comparative Example 2). Further, it has been confirmed that if the polymerizable compound is not contained, the residue at the time of development remains, which is not preferable (Comparative Example 3). In addition, when the particle diameter of the titanium oxide fine particles and/or the zirconia fine particles exceeds 100 nm, the transmittance is lowered, and the haze is improved, which is not (Comparative Example 4). Further, when the P/V ratio is less than 0.3, the difference in refractive index from the ITO is large, and there is a possibility that the ITO pattern is seen from the touch surface side (Comparative Example 5). Further, it was confirmed that when the P/V ratio exceeds 4.0, the adhesion to ITO is inferior, which is not preferable (Comparative Example 6).

1‧‧‧Transparent substrate

2‧‧‧1st ITO electrode

3‧‧‧Insulation

4‧‧‧2nd ITO electrode

5‧‧‧Protective layer

6‧‧‧Removing the electrode

10‧‧‧Touch panel

Claims (8)

An energy ray-curable resin composition comprising a cardo resin having a refractive index of 1.58 or more and having a carboxyl group, an energy ray-polymerizable polyfunctional compound, titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less, and an average particle diameter of 5 nm. The zirconia fine particles of 100 nm or less, the energy ray polymerization initiator, and the solvent, wherein the P/V ratio of the total solid content of the total fine particle component to the total solid content other than the fine particle component is 1.5 or more and 3.5 or less; In the above, the content of the titanium oxide fine particles is 30% by mass or less. The energy ray curable resin composition according to claim 1, wherein the titanium oxide fine particles are rutile type. The energy ray curable resin composition according to claim 1 or 2, wherein the mass ratio of the cardo resin to the energy ray polymerizable polyfunctional compound is 20:80 to 80:20 in terms of solid content. . The energy ray curable resin composition according to claim 1 or 2, wherein the refractive index after the energy ray hardening is 1.65 or more. The energy ray curable resin composition according to claim 1 or 2, wherein the refractive index after curing by energy ray is 1.8 or more. A transparent laminate member formed on an patterned ITO film to form an insulating layer and/or a protective layer obtained by curing the energy ray curable resin composition of claim 1 or 2, or in the above insulating layer The above ITO film is formed on the protective layer and/or the protective layer. A touch panel is provided with a transparent laminated member having the sixth item of the patent application. An image display device is provided with a touch panel having the seventh item of the patent application.