KR20150114485A - Energy-ray-curable resin composition - Google Patents

Abstract

The present invention provides an energy ray curable resin composition which is excellent in both adhesion and developability to ITO and has a high refractive index close to that of ITO. The energy ray-curable resin composition of the present invention comprises a cado resin having a carboxyl group having a refractive index of 1.58 or more, 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 / A P / V ratio of not less than 0.3 and not more than 4.0, which is a mass ratio of all the solid components other than the entire fine particle component and the fine particle component, containing zirconium oxide fine particles of 100 nm or less, an energy ray polymerization initiator and a solvent. Since the insulating layer and / or the protective layer obtained by curing the resin composition on the patterned ITO film has a refractive index close to the intermediate value between ITO and glass, it is possible to make it difficult for the user to visually recognize the ITO pattern on the glass side .

Description

ENERGY-RAY-CURABLE RESIN COMPOSITION [0001]

The present invention relates to an energy ray-curable resin composition, a transparent laminate member using a cured product of the energy ray-curable resin composition as an insulating layer or a protective layer, a touch panel having the transparent laminate member, .

An image display device such as a smart phone, a personal computer, or a game machine having a built-in touch panel can be operated by an operator touching the screen with a hand or a pen. These devices are very easy to handle because they can be operated by an intuitive and easy-to-understand method, such as pressing and slipping the portion displayed on the screen, and the market is rapidly expanding.

1, the sensor portion of the touch panel typically includes a first ITO electrode 2, an insulating layer 3, a second ITO electrode 4, (5) are patterned and laminated in a desired shape, and other extraction electrodes (6) are formed. Here, the formation of the insulating layer 3 or the protective layer 5 is performed by coating an energy ray-curable resin composition on a laminate such as a patterned ITO electrode and then irradiating and heating an energy line such as ultraviolet exposure Loses.

The insulating layer and the protective layer are required to have various required performances. Adhesion to ITO (indium tin oxide indium) and heat resistance at the time of ITO film formation are required in all the layers, and hardness is required to prevent breakage during handling during the manufacturing process. Further, since the insulating layer or a part of the protective layer needs to expose the ITO electrode, the developing property for pattern formation is also required. With regard to the application of the developability, Patent Document 1 discloses a light-emitting device comprising an inorganic particle containing a metal oxide as a main component and having a refractive index of 2.0 or more at a wavelength of 589 nm and a polymerizable (meth) acryloyl group A photoelectric conversion element having a cured film of a photosensitive resin composition comprising a compound, an alkali-soluble polymer having at least one of a hydroxyl group and a carboxyl group in the molecule, and a photo radical polymerization initiator having an oxime ester structure is disclosed. According to the photoelectric conversion element described in Patent Document 1, it is easy to mold and exhibits an effect of providing a high refractive index and chemical stability after curing.

Japanese Patent Application Laid-Open No. 11-151164

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

An object of the present invention is to provide an energy ray curable resin composition which is excellent in both adhesion and developability to ITO and has a high refractive index close to the intermediate value between ITO and glass will be.

As a result of intensive research to solve the above problems, the present inventors have found that a combination of a cardo resin having high refractive index and developability and an energy ray-polymerizable polyfunctional compound, and adding titanium oxide fine particles and / It has been found that by adding zirconium oxide fine particles at a predetermined P / V ratio, the adhesion to the ITO and the developability are both excellent, the transparency is high, and a high refractive index close to that of ITO is obtained. Specifically, the present invention provides the following.

(1) According to the present invention, there is provided a curable resin composition comprising a cado resin having a carboxyl group having a refractive index of 1.58 or more, 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 / Of a zirconium oxide fine particle, an energy ray polymerization initiator, and a solvent, and having a P / V ratio of 0.3 or more and 4.0 or less, which is a mass ratio of all the solid components other than the entire fine particle component and the fine particle component.

(2) The present invention is also the energy ray curable resin composition according to (1), wherein the titanium oxide fine particles are rutile.

(3) The energy ray-curable resin composition according to (1) or (2), wherein the mass ratio of the cado resin and the energy ray-polymerizable polyfunctional compound is 20:80 to 80:20 in terms of solid content. to be.

(4) The present invention is also the energy ray curable resin composition according to any one of (1) to (3), wherein the content of the titanium oxide fine particles in the total solid content is 30 mass% or less.

(5) The present invention is also the energy ray curable resin composition according to any one of (1) to (4), wherein the P / V ratio is 1.5 to 3.5.

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

(7) The present invention is also the energy ray curable resin composition according to any one of (1) to (5), wherein the refractive index after the energy ray curing is not less than 1.8.

(8) Further, the present invention provides a method for manufacturing a semiconductor device, comprising: forming an insulating layer and / or a protective layer formed by curing the energy ray-curable resin composition according to any one of (1) to (7) on a patterned ITO film, And a transparent laminated member in which the ITO film is formed on the insulating layer and / or the protective layer.

(9) Further, the present invention is a touch panel including the transparent laminated member according to (8).

(10) Further, the present invention is an image display apparatus having the touch panel according to (9).

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

1 (a) is a plan view and (b) is a cross-sectional view taken along the line A-A, showing an example of a touch panel.

Hereinafter, a specific embodiment of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all, and can be carried out by appropriately modifying it within the scope of the object of the present invention.

<Energy ray curable resin composition>

The energy ray-curable resin composition of the present invention (hereinafter simply referred to as a resin composition) contains at least the following a) to e). Will be described in the following order.

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

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 zirconium oxide 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) a carded resin having a carboxyl group having a refractive index of 1.58 or more]

The cado resin used in the present invention refers to a resin obtained by the reaction of an epoxy (meth) acrylate having a fluorene skeleton with a polybasic carboxylic acid or an anhydride thereof. The mass average molecular weight (Mw) is preferably from 1500 to 18000, and more preferably from 1500 to 10000 from the viewpoint of compatibility and developability. The mass average molecular weight in the present invention is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The epoxy (meth) acrylate having a fluorene skeleton is preferably an epoxy (meth) acrylate represented by the general formula (A).

In formula (A), Z has a ring structure, for example, a benzene ring or a condensed polycyclic aromatic hydrocarbon ring, R ₁ represents a halogen atom, a hydrocarbon group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, An alkoxy group, a nitro group, a cyano group or a substituted amino group, and R ₂ represents an alkylene group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a carboxyl group, an alkoxycarbonyl group, R ₃ represents a hydrogen atom or a methyl group; k represents 0 or an integer of 1 or more; and m represents 0 or an integer of 1 or more.

Z is preferably a benzene ring or 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, an acyl group, a nitro group, a cyano group or a substituted amino group, An alkyl group of 1 to 4 carbon atoms, etc.), an alkoxy group (an alkoxy group of 1 to 4 carbon atoms, etc.).

The substitution number m of R ₁ varies depending on the kind of Z, and is, for example, 0 to 8, preferably 0 to 6, more preferably 0 to 4, particularly 0 to 2. The substitution position of R ₁ is not particularly limited. The alkylene group represented by R ₂ is preferably an alkylene group having 2 to 4 carbon atoms such as ethylene or propylene group, and a branched alkylene group having 3 to 4 carbon atoms is preferable from the viewpoint of enhancing the viscosity reducing effect. Also, k is preferably 0 to 2. When k is 2 or more, the kind of R ₂ may be different, but is usually the same.

The polybasic carboxylic acid used in the present resin is a carboxylic acid having a plurality of carboxyl groups such as a dicarboxylic acid and a tetracarboxylic acid. Examples of such a polybasic carboxylic acid or anhydride thereof include the following compounds : Dicarboxylic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid and glutaric acid, Their anhydrides; Trimellitic acid or an anhydride thereof, pyromellitic acid, benzophenonetetracarboxylic acid, 4- (1,2-dicarboxyethyl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid , Biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid and the like, and acid dianhydrides thereof. Among them, a tetracarboxylic acid or an anhydride thereof is preferable for improving the developing property, and an aromatic compound such as pyromellitic acid or biphenyltetracarboxylic acid is preferable for improving the refractive index.

As the cado resin used in the present invention, it is preferable to react the epoxy (meth) acrylate having a fluorene skeleton with a tetracarboxylic acid or an anhydride thereof and then block the terminal hydroxyl group with a dicarboxylic acid or an anhydride thereof. By doing so, the reaction between the carboxylic acid and the hydroxyl group of the epoxy (meth) acrylate can be suppressed, and the stability of the ink is improved.

A preferable example of the resin obtained by reacting epoxy (meth) acrylate having a fluorene skeleton with a polybasic carboxylic acid or anhydride thereof, which is used as a cado resin of the present invention, is represented by the following formula (B).

Wherein X is a residue other than an acid anhydride group of a tetracarboxylic acid or dianhydride thereof, and Y is a residue other than an acid anhydride group of a dicarboxylic acid or an anhydride thereof. It is preferable that X and Y have an aromatic group in view of the refractive index.

Z represents a cyclic structure, for example, a benzene ring or a condensed polycyclic aromatic hydrocarbon ring; R ₁ represents a halogen atom, a hydrocarbon group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, , alkylthio, cycloalkyl, alkylthio, arylthio, aralkyl, alkylthio group, an acyl group, a carboxyl group, an alkoxycarbonyl group, represents a nitro group, a cyano group or a substituted amino group, R ₂ represents an alkylene group, R ₃ is hydrogen An atom or a methyl group; k is 0 or an integer of 1 or more; m is 0 or an integer of 1 or more; and n is an integer of 1 or more.

Z is preferably a benzene ring or 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, an acyl group, a nitro group, a cyano group or a substituted amino group, An alkyl group of 1 to 4 carbon atoms, etc.), an alkoxy group (an alkoxy group of 1 to 4 carbon atoms, etc.).

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

The alkylene group represented by R ₂ is preferably an alkylene group having 2 to 4 carbon atoms such as ethylene or propylene group, and a branched alkylene group having 3 to 4 carbon atoms is preferable from the viewpoint of enhancing the viscosity reducing effect. Also, k is preferably 0 to 2. When k is 2 or more, the kind of R ₂ may be different, but is usually the same. n is preferably 1 to 40, more preferably 5 to 30.

When such a cadmium resin having a fluorene structure is used, it has a high refractive index of 1.58 or more. Further, since the main skeleton has a fluorene structure, it has good chemical resistance, water resistance and electrical characteristics. Further, the ITO film is excellent in heat resistance when formed by sputtering or the like.

The refractive index of the carded resin is 1.58 or more, preferably 1.60 or more, and the upper limit is 1.68. If the refractive index is less than 1.58, the refractive index of the insulating layer and / or the protective layer after curing can not be sufficiently increased even if fine particles are added. If it exceeds 1.68, it is difficult to manufacture. The refractive index of the cado resin is a value calculated from the reflectance measured by a spectrophotometer by the method described in the embodiment at the stage after curing and a value similar to that measured by the method of JIS K-7142A is obtained .

In addition, the cado resin used in the present invention has a carboxyl group. Therefore, it has developability such as alkali development. More specifically, the acid value according to JIS-K0070 is 30 mgKOH / g or more, and preferably 40 mgKOH / g or more. If the acid value is within the above range, sufficient alkali solubility can be expressed. On the other hand, the upper limit is not particularly limited, but is usually 150 mgKOH / g or less. 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 carboxy resin used in the present invention include compounds represented by the following formulas (i) to (ix) (in the above formulas, n is an integer of 1 or more). However, the cadmium resin of the present invention is not limited to these specific examples.

For example, INR-16M (trade name, manufactured by Nagase ChemteX Corp.) or CR-1030 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.) can be suitably used as the carded resin having a carboxyl group having a refractive index of 1.58 or more .

The content of the cadmium resin is generally 3 to 30 mass%, preferably 4 to 20 mass%, in the proportion of the total solid content. If the content of the cadmium resin is too small, there is a possibility that sufficient adhesion can not be obtained, and there is a possibility that residues are generated and pattern defects are generated. If the content is too large, surface roughness Lack of hardening) may occur.

[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 a carboxy resin having a carboxyl group having a refractive index of 1.58 or more, and is not particularly limited as long as it is polyfunctional. In the present specification, the energy ray-polymerizable polyfunctional compound means a polymerizable compound having two or more radically polymerizable functional groups in the molecule. If it is polyfunctional, the molecular weight between cross-linking points of the cured product of the obtained resin composition becomes small, and the cured product is likely to have a high elastic modulus and hardness.

The energy ray-polymerizable polyfunctional compound is not particularly limited as long as it can be polymerized by an energy ray polymerization initiator described later, and usually a compound having two or more ethylenically unsaturated double bonds is used, and in particular, acryloyl group or methacryloyl group Is preferably a polyfunctional (meth) acrylate having two or more diols.

Examples of such polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, propylene glycol di Acrylates such as glycerol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di Acrylate, trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol modified trimethylol propane di Acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetra Acrylate, di (meth) acrylate, di (meth) acrylate, zinc di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di Such as bisphenol A type (meth) acrylate, bisphenol E type (meth) acrylate, bisphenol F type (meth) acrylate, cresol novolak type (meth) acrylate, phenol novolak type (Meth) acrylate.

Examples of the polyfunctional (meth) acrylate having three or more functional groups include trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, succinic anhydride modified pentaerythritol tetra (Methacryloxyethyl) isocyanurate, dipentaerythritol tetra (meth) acrylate, ditrimethylol propane tetraacrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl (Meth) acrylate, urethane tetra (meth) acrylate, urethane hexa (meth) acrylate, urethane tetra (meth) acrylate, Ester hexa (meth) acrylate, and the like.

These polyfunctional (meth) acrylates may be used singly or in combination of two or more. When the energy ray curable resin composition of the present invention is required to have excellent energy ray curability (high sensitivity), it is preferable that the energy ray-polymerizable polyfunctional compound has three (trifunctional) or more polymerizable double bonds, Poly (meth) acrylates of trihydric or higher polyhydric alcohols or their dicarboxylic acid-modified products are preferable. Specific examples thereof include tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, Succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) Succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) Such as pentaerythritol hexa (meth) acrylate is preferred.

These energy ray-polymerizable polyfunctional compounds may be used singly or in combination of two or more. From the viewpoint of improving the sensitivity, those having three or more (meth) acrylate groups in the molecule as the radical polymerizable functional group are preferable. As used herein, (meth) acrylate means methacrylate or acrylate.

Mention may be made, for example, of Aronix M-208, M-210, M-215, M-220, M-225, M-233 and M M-402, M-245, M-260, M-270, M-400, M-402, M-403, M-404, M-405, M-406, , M-303, M-305, M-306, M-309, M-310, M-313, M-315, M-321, M-350, M-360, M- PE-3A, PE-4A, and PE-4L manufactured by Kyowa Chemical Industry Co., Ltd., Epoxy ester 3002M (N), epoxy ester 3002A (N), epoxy ester &lt; RTI ID = 0.0 &gt; DKA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, and DN-0075 manufactured by Nippon Kayaku Co., 2475, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MAND A-HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, SR-365, SR-365, SR-365, SR-365, SR-395E, SR- -444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-602, SR-610, SR-9003, Osaka Yukikakagakukogyo Co., Ltd., Viscot # 802; Tripentaerythritol hexaacrylate, tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate, and a mixture of TEA-100 manufactured by KSM Corporation.

The weight average molecular weight (Mw) of the energy ray-polymerizable polyfunctional compound used in the present invention is preferably 100 to 10000, more preferably 200 to 3000 from the viewpoint of compatibility and developability. The mass average molecular weight in the present invention is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the energy ray-polymerizable polyfunctional compound is usually 3 to 50% by mass, preferably 5 to 40% by mass, and more preferably 6 to 30% by mass in the total solid content. If the content of the energy ray-polymerizable polyfunctional compound is too small, sufficient energy ray curability may not be obtained. If the content is too large, there is a fear of causing poor adherence due to curing shrinkage or deterioration of developing ability I do not.

It is preferable that the mass ratio of the cado resin and the energy ray-polymerizable polyfunctional compound is 20:80 to 80:20 in terms of solid content. Within this range, it is possible to provide a resin composition which is excellent in adhesion to ITO and developability, and which has a high refractive index close to that of ITO and glass. If the ratio of the cadmium resin is too small, there is a possibility that adhesion failure due to curing shrinkage or deterioration of developing ability may be undesirably caused. On the other hand, if the ratio of the energy ray-polymerizable polyfunctional compound is too small, sufficient energy ray curability may not be obtained, which is not preferable. In particular, when the P / V is high, the mass ratio of the cage resin and the energy ray-polymerizable polyfunctional compound is more 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 zirconium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less]

The energy ray curable resin composition according to 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 zirconium oxide 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]

The energy ray curable resin composition according to the present invention can increase the refractive index of the energy ray curable resin composition by using the titanium oxide fine particles.

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

The titanium oxide fine particles to be used in the present invention have an average particle diameter of 5 nm or more and 100 nm or less, and a preferable average particle diameter is 10 nm or more and 50 nm or less, and 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 can be measured directly by using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM) Can be measured by observation. When the average primary particle diameter is less than 5 nm, it is very difficult to disperse primary particles at a high transparency level because the cohesive force between the fine particles is very large. On the other hand, when the average primary particle diameter exceeds 100 nm, it is easy to disperse the particles at the primary particle level, but scattering is likely to occur with respect to light such as visible light because the particle diameter is large, .

As a commercially available product of titanium oxide fine particles, a dispersion containing titanium oxide fine particles is commercially available, and examples thereof include a silicon oxide-coated tin oxide-containing rutile titanium oxide-methanol dispersion (TS series manufactured by Teika Co., Ltd.), a rutile-type titanium oxide dispersion (STR-60C-LP, STR-100C-LP, STR-100A-LP) manufactured by Takeda Chemical Industries, Ltd., ND139 and ND291) and a rutile titanium oxide dispersion (manufactured by Sakai Kagaku Co., Ltd.).

(C2) Zirconium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less]

The energy ray curable resin composition according to the present invention can increase the refractive index without raising the haze of the insulating layer and / or the protective layer formed by curing the energy ray curable resin composition by using the zirconium oxide fine particles.

The zirconium oxide fine particles to be used in the present invention have an average particle diameter of 5 nm or more and 100 nm or less, and a preferable average particle diameter is 10 nm or more and 50 nm or less. When the average primary particle diameter is less than 5 nm, it is very difficult to disperse primary particles at a high transparency level because the cohesive force between the fine particles is very large. On the other hand, when the average primary particle diameter exceeds 100 nm, it is easy to disperse the particles at the primary particle level, but scattering is likely to occur with respect to light such as visible light because the particle diameter is large, .

As a commercial product of zirconium oxide fine particles, a dispersion containing zirconium oxide fine particles and the like are commercially available, and a dispersion of zirconium oxide-methyl ethyl ketone (HXU-120JC manufactured by Sumitomo Osaka Cement Co., Ltd.), a zirconium oxide- Manufactured by NIPPON KOGYO CO., LTD.), A zirconium oxide-methyl ethyl ketone dispersion (SZR-K, manufactured by Sakai Kagaku Co., Ltd.) and the like.

In the present invention, the titanium oxide fine particles and the zirconium oxide fine particles are preferably covered with an oxide such as aluminum, silicon or zirconia on the surface of the fine particles. As a result, dispersibility and weather resistance are improved.

The titanium oxide fine particles and the zirconium oxide fine particles in the present invention may be surface-treated with an organic compound.

Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. Among them, a silane coupling agent is preferable. The surface treatment may be a single surface treatment agent or a combination of two or more kinds of surface treatment agents.

In order to improve the dispersibility of the titanium oxide fine particles and the zirconium oxide fine particles, a dispersant may also be used. As the dispersing agent, an acrylic resin is preferable from the viewpoint of compatibility with the binder resin, and among them, those having a polymerizable unsaturated group are preferable. By having a polymerizable unsaturated group, deterioration of sensitivity due to ultraviolet absorption peculiar to titanium can be suppressed.

These surface treatments and the use of the dispersant may be carried out alone or in combination.

In the present invention, the titanium oxide fine particles and the zirconium oxide fine particles may be used alone or in combination. In the case of mixing, it is preferable that the titanium oxide fine particles are 30 mass% or less of the total solid content including the resin. Within this range, it is possible to suppress deterioration of coating due to ultraviolet absorption peculiar to titanium and to inhibit coating film deterioration due to photocatalytic activity, to have excellent adhesion to ITO, developability, transparency and high refractive index close to ITO A composition can be obtained. If the amount of the titanium oxide fine particles is too large, the refractive index becomes high, but the transparency of the coating film may be lowered due to the photocatalytic activity, which is not preferable. The lower limit of the content of the titanium oxide fine particles is preferably 15% by mass or more. Further, it is preferable that the zirconium oxide fine particles are contained in an amount of 20 mass% or more and 50 mass% or less in the total solid content including the resin. If the amount of the zirconium oxide fine particles is too large, the transparency is good, but there is a possibility that the refractive index can not be sufficiently increased.

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

Further, the present invention is characterized in that the P / V ratio of the total particulate component P (the component c) and the other particulate component), which is the mass ratio of the total solid component to the component V excluding P, is 0.3 or more and 4.0 or less. The term &quot; total solids &quot; refers to a component other than the solvent contained in the energy ray curable resin composition. The P / V ratio is more preferably 1.5 or more and 3.5 or less. By setting the P / V ratio within this range, the refractive index of the insulating layer and / or the protective layer can be made higher than that of the base resin while maintaining transparency, and the refractive index of the ITO film can be made close to that of the ITO film. In addition, it is possible to improve the developability.

If the P / V ratio is less than 0.3, the refractive index of the insulating layer and / or the protective layer after curing can not be sufficiently increased. On the other hand, if it exceeds 3.5, adhesion and developability are deteriorated because the organic component is small.

[d) Energy ray polymerization initiator]

In the energy ray-curable resin composition of the present invention, an energy ray polymerization initiator is further blended. Examples of such an energy ray polymerization initiator include an azo type, an alkylphenone type, an acylphosphine oxide type, a titanocene type, an oxime ester type, a cation type and the like. Among them, alkylphenone type, acylphosphine oxide type, oxime ester type (2-hydroxy-2-methyl-propionyl) -benzyl] - &lt; / RTI &gt; Phenyl] -2-methyl-propan-1-one, 2-methyl-1- [4- (methylthio) - (4-morpholin-4-yl-phenyl) -butan-1-one (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1- [4- -, 2- (0-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- methylbenzoyl) -9H- , 1- (6-O-methyl-benzoyl-9-ethylcarb 3-yl) -3-cyclohexyl acetone-1-oxime acetic acid ester, 1- (6-O-methyl-benzoyl- Ethyl acetate, ethanone, 1- [6- [4- [(2,2-dimethyl-1,3-dioxolan-4- yl) methoxy] -2- methylbenzoyl] 3-yl] -, 1- (O-acetyloxime), 1,2-propanedione, 3- cyclopentyl-1- [4- (phenylthio) phenyl] And the like. In addition, from the viewpoints of sensitivity, transparency and plate-making suitability, 2-methyl-1- [4- (methylthio) phenyl] 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime), ethane (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- 3-yl) -3-cyclopentyl acetone-1-oxime acetic acid ester, ethanone, 1- [6- [4- [(2,2-dimethyl- Yl) -, 1- (O-acetyloxime), 1,2-propanedione, 3-cyclopentyl-1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime) is preferable.

The energy ray polymerization initiator was IRGACURE OXE01 (manufactured by BASF Japan), IRGACURE OXE02 (manufactured by BASF Japan), N-1919 (manufactured by ADEKA) May be commercially available products such as Gurcure 819 (manufactured by BASF Japan), LUCIRIN TPO (manufactured by BASF Japan), IRGACURE 907 (manufactured by BASF Japan), and the like.

The compounding ratio of the energy ray polymerization initiator is preferably from 1 to 15 mass%, more preferably from 2 to 10 mass%, based on the total solid content.

[e) Solvent]

The energy ray-curable resin composition of the present invention can be suitably subjected to solid content adjustment by adding a solvent. The solvent is not particularly limited as long as it does not react with each component of the energy ray curable resin composition and is an organic solvent capable of dissolving or dispersing the components. Specific examples thereof include alcohols such as methanol, ethanol and 3-methoxy-1-propanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether and propylene glycol monomethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2- Methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, -Methoxy-3-methyl-1-butyl acetate, and the like. These solvents may be used alone or in combination of two or more. Of these, 3-methoxy-1-propanol, diethylene glycol ethyl methyl ether, PGMEA, 3-methoxybutyl acetate and 3-methoxy-3-methyl-1-butyl acetate are dissolved in a preferable solvent . These solvents may be used alone or in combination of two or more.

The amount of the solvent can be appropriately selected depending on the intended coating property and the dispersibility and solubility, but is preferably adjusted to 5 to 40% by mass in terms of solid content in the resin composition.

[f) Other]

The energy ray-curable resin composition of the present invention can be suitably used as an energy ray-curable resin composition for the purpose of improving adhesion, a surfactant, a sensitizer, a polymerization inhibitor, an antioxidant, a dispersant, an energy ray stabilizer (light stabilizer), a leveling agent, Fine particles (colloidal silica or the like) or the like may be suitably used.

The adhesion aid that can be used in the present invention is not particularly limited, but acts as a mediator between an organic material and an inorganic material, and is effective in improving adhesion with a substrate and improving compatibility of an organic material and an inorganic material , And a silane coupling agent are preferably used. Examples of the silane coupling agent include vinyl type, methacrylic type, acrylic type, epoxy type, amino type, styryl type, ureido type, mercapto type, isocyanate type and sulfide type depending on the functional groups of the organic components. Among them, Vinyl, methacrylic, acrylic, epoxy, mercapto and isocyanate are particularly preferred from the viewpoints of adhesion and improvement in compatibility. As commercial products, for example, KBM-403, KBM-502, KBM-503, KBM-803, KBM-5103 and KBM-9007 manufactured by Shinetsuga Kagaku may be blended in an amount of 0.1 to 10 mass% .

Examples of the surfactant that can be used in the present invention include "Megapak" R08MH, RS-72-K, RS-75, F-477 and F- BYK-333, BYK-301 and the like manufactured by Mitsui Chemicals, Inc. can be blended in an amount of 0.1 to 5 mass% in the total solid content.

In order to improve the ITO adhesion, a phosphoric acid compound having a double bond in the molecule may be further added. The phosphoric acid compound used in the present invention is preferably used in a phosphoric acid compound having an ethylenically unsaturated double bond in a molecule. For example, there can be mentioned 2-methacryloyloxyethyl acid phosphate (trade name: Liteester P-1M, Liteester P-2M, Kyoreishakagaku), ethylene oxide modified phosphoric acid dimethacrylate (Meth) acrylates such as: PM-21, Nippon Kayaku Co., Ltd., phosphoric acid-containing epoxy methacrylate (trade name: New Frontier S-23A, manufactured by Daiichi Kyoeil Co., And vinyl phosphates such as phosphonic acid (trade name: VPA-90, VPA-100, BASF).

Further, the energy ray-curable resin composition of the present invention may further contain a polyfunctional thiol compound as a curing aid. The polyfunctional thiol compound means a compound having two or more sulfanyl groups (-SH) in the molecule. In particular, when a compound having two or more sulfanyl groups bonded to carbon atoms derived from an aliphatic hydrocarbon group is used, the sensitivity of the energy ray curable resin composition of the present invention tends to be high. Use of a compound having a secondary thiol structure is preferred because the storage stability is enhanced.

Specific examples of the polyfunctional thiol compound include hexanediol, decanediol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate) , Trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl propionate), ethylene glycol bis Pentaerythritol tetrakis (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris Propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanylbutyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trime Thiol ethane tris (3-mercaptobutyrate), and the like.

The content of the polyfunctional thiol compound is preferably 0.1 to 3% by mass in terms of the total solid content. When the content of the polyfunctional thiol compound is within the above range, the effect of oxygen inhibition can be eased and curing can be promoted, and the sensitivity of the energy ray curable resin composition can be increased. Further, it is preferable since the surface condition after development when the pattern is formed tends to be good.

In addition, as the fine particles of the metal oxide, other components other than the component (c) may be included. The other component preferably contains at least one element selected from the group consisting of zinc, antimony, indium, tin, silicon, hafnium, niobium, tantalum, tungsten, cerium and aluminum. Specific examples thereof include antimony pentoxide, zinc oxide, silicon oxide, zinc antimonate, antimony doped tin oxide (ATO), tin doped indium oxide (ITO), fluorine doped tin oxide (FTO), phosphorus doped tin oxide Doped zinc oxide (AZO), indium-doped zinc oxide (IZO), tin oxide, ATO-coated titanium oxide, gallium-doped zinc oxide, and aluminum oxide (alumina). These can be easily obtained from known commercial products.

<Transparent lamination member / touch panel>

The energy ray-curable resin composition of the present invention is applied to, for example, an ITO electrode of a thin film on which the above-described pattern is formed, and is cured by ultraviolet rays or the like to be cured to form an insulating layer and / The transparent laminated member constitutes the transparent laminated member of the invention, and the transparent laminated member constitutes a part of the touch panel.

1, the sensor portion of the touch panel 10 typically includes a first ITO electrode 2, an insulating layer 3, a second ITO electrode 2, The protective layer 4, and the protective layer 5 in a desired shape. The insulating layer and / or the protective layer in the present invention can be applied to either or both of the insulating layer 3 and the protective layer 5.

The transparent substrate 1 is not particularly limited as long as it is a transparent substrate with respect to a visible energy ray. Specifically, a transparent rigid material having no flexibility such as quartz glass, alkali-free glass, tempered glass or synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film (PET or the like) ).

First, a first ITO electrode 2 patterned in a desired shape is formed on a transparent substrate 1 by a known method. Thereafter, 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. Pre-drying after application is performed at 50 to 150 DEG C for 10 to 600 seconds using a hot plate, an oven or the like.

Then, a mask having an opening pattern of a predetermined shape is placed on the energy ray curable resin composition, and the active energy ray is irradiated. Examples of the active energy ray include ultraviolet rays and electron rays. The irradiation dose can be appropriately set within a range used for normal patterning, but can be set within a range of 30 to 300 mJ / cm 2, preferably 50 to 200 mJ / cm 2. The coating film after irradiation with active energy rays is developed by a conventional method. The energy ray-curable resin composition after the development treatment is heated (post baking). The heating conditions can be set in the same range as the formation of a typical insulating layer and / or the protective layer, but heating can be performed at 100 to 300 占 폚 for 15 to 40 minutes, for example. As a result, in this embodiment, the insulating layer 3 including the cured product of the energy ray-curable resin composition of the present invention is pattern-formed. The thickness of the insulating layer (at the time of drying) is not particularly limited, but may be suitably set in a range of usually 0.1 to 5 占 퐉, preferably 0.5 to 3 占 퐉.

Thereafter, the second ITO electrode 4 and the protective layer 5 are formed in this order in the same manner as above to produce the transparent laminated member of the present invention. Here, the protective layer 5 may be formed with the same resin composition as the insulating layer 3 by the same method as described above.

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, , The insulating layer and / or the protective layer, and the ITO film. In the present invention, in the present invention, the refractive index of the insulating layer and / or the protective layer is made to be high refractive index, preferably 1.65 or more, and more preferably, Was 1.80 or more. As a result, the refractive index (1.45 to 1.55) of the glass is close to the intermediate value of the refractive index (1.8 to 2.2) of ITO, and therefore 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 it may be difficult to synthesize a composition capable of obtaining the effect (developability, adhesion, etc.) of the present invention. As described above, in the present invention, since the insulating layer and / or the protective layer itself is provided with a high refractive index, it is not necessary to use other high refractive index films and the like, so that a simple structure and excellent cost can be obtained. The refractive index of the insulating layer and / or the protective layer in the present invention is a value measured by the method in the following examples.

<Image Display Device>

The present invention also provides an image display apparatus having the touch panel. Examples of such an image display device include a cathode ray tube (CRT), a plasma display panel (PDP), an organic EL display, a liquid crystal display, and the like. The image display apparatus of the present invention also includes a smart phone, a personal computer, a game machine, a car audio system, a car navigation system, and a portable terminal provided with the liquid crystal display device.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

The resin compositions of the examples and comparative examples were obtained by using the following formulations (a) to (f2) shown in Tables 1 to 3 (parts by mass of solids).

a) a carded resin having a carboxyl group with a refractive index of 1.58 or more (trade name: INR-16M, manufactured by Nagase ChemteX, refractive index: 1.61, solid content: 55%

a ') Acrylic resin

21 parts by mass of methacrylic acid and 70 parts by mass of benzyl methacrylate were copolymerized and 9 parts by mass of glycidyl methacrylate was added in the presence of a triethanolamine catalyst (weight average molecular weight in terms of polystyrene measured by GPC: 12,000, Acid value: 80 mgKOH) was used as the above a ') acrylic resin.

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., solids content: 100% by mass)

 b2) Energy ray polymerizable polyfunctional compound 2 (Aronix M-315, isocyanuric acid EO-modified di- and triacrylate, manufactured by Toagosei Co., Ltd., solids content 100% by mass)

c) titanium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less and / or zirconium oxide 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 Teika, average particle diameter: 10 nm, solid content 32.3 mass in propylene glycol monomethyl ether %, Solid content as 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 Shiacase Corporation, average particle diameter: 32 nm)

In Example 18, 15.00 parts by mass of the above-mentioned nanotec, 6.56 parts by mass of a dispersing agent (trade name: DISPERBYK-111, manufactured by BICKEMISA) and 78.44 parts by mass of a solvent (PGEMEA) After mixing, 0.1 mm zirconia beads were dispersed in a paint shaker (manufactured by Asada Tecco) for 3 hours.

(c2) Dispersion of zirconium oxide fine particles having an average particle diameter of 5 nm to 100 nm (zirconium oxide having an average particle diameter of 15 nm and propylene glycol monomethyl ether (PGME) in a solid content of 22.5% by mass, solid content as zirconium oxide: 20.1%

c ') titanium oxide fine particles having an average particle diameter exceeding 100 nm and / or zirconium oxide fine particles having an average particle diameter exceeding 100 nm

c1 ') Titanium oxide fine particles (trade name: CR-58, rutile type titanium oxide fine particles, manufactured by Ishihara Sangyo Co., average particle diameter: 250 nm) having an average particle diameter exceeding 100 nm,

In Comparative Example 4, 15.00 parts by mass of the CR-58, 6.56 parts by mass of a dispersant (trade name: DISPERBYK-111, manufactured by BICKEMISA), and 78.44 parts by mass of a solvent (PGEMEA) Hour preliminary mixing, and then dispersed for 3 hours using a paint shaker (manufactured by Asada Tecco) using 0.1 mm zirconia beads.

d) Energy ray polymerization initiator

 d1) Energy ray polymerization initiator 1 (trade name: Irgacure 907, BASF)

 d2) Energy ray polymerization initiator 2 (trade name: Irgacure 819, BASF)

 d3) Energy ray polymerization initiator 3 (trade name: Lucirin TPO, BASF)

 d4) Energy ray polymerization initiator 4 (trade name: N-1919, manufactured by Adeka)

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

f) Other components

 f1) Surfactant (trade name: Megafac F477, manufactured by DIC)

 f2) Adhesion Adjuster (Silane coupling agent, trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Evaluation Items and Evaluation Methods>

The results of the following evaluation are summarized in Table 4 and Table 5.

(1) Refractive index

First, the resin composition obtained in Examples and Comparative Examples was spin-coated on a glass substrate so as to have a thickness of 1.5 탆 after drying, left standing on a hot plate at 90 캜 for 180 seconds (preliminary drying), exposed at 200 mJ / The coating film was formed. This coating film was post-baked at 230 캜 for 20 minutes.

Thereafter, in order to prevent reflection on the back surface, a black tape was attached to the glass surface side, and the reflectance at a wavelength region of 380 to 780 nm was measured from the cured film surface using a spectrophotometer UV-3150 manufactured by Shimadzu Corporation, The average reflectance R, which is the average, was calculated.

Then, using the average reflectance R, the refractive index n ₁ of the present invention was calculated from the following formula. Where n ₀ is the refractive index of air and is calculated as 1.000. When a glass substrate is used for a substrate, the refractive index is preferably 1.65 or more, more preferably 1.8 or more.

_{R = (n 0 -n 1)} 2 / (n 0 + n 1) 2

In another test, it was confirmed that the composition of the present invention was formed on the substrate on which ITO was patterned under the same condition as the "(1) refractive index." As a result, when the refractive index was 1.65 or less, , The effect was observed at 1.65 to 1.8, and it was confirmed that the state was almost invisible at 1.8 or more and 1.9 or less.

(2) Hayes

(2-1) Hayes 1

The haze of the visible light ray was measured for a coated film formed under the same conditions as in &quot; (1) refractive index &quot;. The haze value was measured in accordance with JIS K7361-1 (test method for total light transmittance of a plastic-transparent material), and the haze value was measured with a haze meter HM-150 (manufactured by Murakami Shikisai Chemical Co., Ltd.) according to JIS K7105 . When a glass substrate is used for a substrate, haze is preferably 1.5 or less. More preferably 1.0 or less.

(2-2) Hayes 2

As a further acceleration test, the coated film obtained under the same conditions as in the case of the haze 1 was further subjected to the conditions of 120 deg. C, 100% RH and 2 atm for 3 hours, and then the haze of the visible ray was measured. The measurement of the haze was performed in the same manner as in the previous item "(2-1) Haze 1".

(3) Total light transmittance

The total light transmittance of the coated film formed under the same conditions as (1) refractive index was measured. The total light transmittance was measured according to JIS K7361-1 (test method for total light transmittance of plastic-transparent material), and the total light transmittance was measured using the haze meter HM-150 according to JIS K7105 Value. When the glass substrate is used for a substrate, the total light transmittance is preferably 85% or more.

(4) Developability (surface state, development residue)

Under the same conditions as in (1) refractive index, the mask coating was subjected to mask exposure under the following conditions. Subsequently, development was carried out for 60 seconds at 23 캜 using 0.045% potassium hydroxide aqueous solution as an alkali developing solution to evaluate developability in the exposed portion and the unexposed portion.

(Exposure conditions)

Exposure Machine: Proxy Exposure Machine

Mask: chrome mask

Exposure gap: 150 탆

Light source: Ultra-high pressure mercury lamp

Exposure dose: 200 mJ / cm 2

Evaluation of developability was carried out as follows. A mask having a line and space type pattern having a line width of 10 to 100 mu m in resolution was irradiated with ultraviolet rays under the above-described conditions, and then developed. The developed portion after exposure was visually observed with a microscope, and it was judged according to the following criteria. ○, and Δ are practical ranges.

○: Microscope No roughness with the naked eye

△: Microscope A little roughness with the naked eye

X: Microscope Harshness with naked eyes

With regard to the presence or absence of a residual developer, the unexposed portion after development was visually observed to determine the following criteria. ○ is the practical range.

○: No residue by the naked eye

X: Residue with naked eyes

(5) Adhesion to glass

(5-1) Adhesion 1

The coating film formed on the glass substrate under the same condition as the above "(1) refractive index" was subjected to a checkerboard peeling test with a cellophane adhesive tape. Here, in the checkerboard peeling test, 100 straight lines of 1 mm x 1 mm were produced by straightly cutting straight straight lines of 11 straight lines vertically and horizontally at intervals of 1 mm so as to reach the base of the glass substrate with a cutter knife , A cellophane adhesive tape (trade name: CELLOTAPE (registered trademark), product number: CT405AP-24, manufactured by Nichiban K.K.) was rubbed with an eraser and peeled at a right angle instantaneously to measure the remaining number of grid patterns visually Respectively. In addition, the peeling area of the lattice pattern was judged by the following criteria. 5 or 4 is the practical range.

5: Peel area is 0%

4: peeling area is more than 0% to less than 25%

3: peeling area is more than 25% to less than 50%

3: Peel area is more than 50% to less than 75%

1: peeled area exceeding 75% to 100%

(5-2) Adhesion 2

As a further acceleration test, the coated film obtained under the same conditions as in the adhesion property 1 was further subjected to a condition of 120 ° C, 100% RH and 2 atm for 3 hours, and then subjected to a checkerboard peeling test with a cellophane adhesive tape . The checkerboard peeling test was conducted and evaluated under the same conditions as described above.

(6) Adhesion to ITO substrate

The adhesion to the ITO substrate was evaluated in the same manner as in the previous item "adhesion to glass" except that the glass substrate was an ITO film-attached glass substrate (ITO substrate).

A carbon-based resin having a refractive index of 1.58 or more, 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 / or zirconium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less, Ray-curable resin composition containing a prepolymerization initiator and a solvent and having a P / V ratio of 0.3 or more and 4.0 or less, which is a mass ratio of the total particulate component to all the solid components other than the particulate component, is 0.3 to 4.0. The refractive index of the insulating layer and / So that the difference in refractive index between ITO and the ITO can be reduced. As a result, it is possible to effectively prevent the ITO pattern from being seen through the touch surface side, and also to improve the adhesion to both the ITO and the glass substrate (Examples 1 to 20).

Particularly, in comparison with Examples 1 to 4, it was confirmed that the content of the titanium oxide fine particles in the total solid content was 30% by mass or less in terms of good transparency (Examples 3 and 4).

In contrast to Examples 5 to 10, it was confirmed that the P / V ratio was 1.5 to 3.5 when the P / V ratio was 1.5 or more and the refractive index was high and the P / V ratio was 3.5 or less (Examples 6 to 9).

From Examples 11 to 13, it is preferable that the mass ratio of the cado resin and the energy ray-polymerizable polyfunctional compound is 20:80 to 80:20 in terms of solid content. From the comparison between Example 3 and Example 16, The kind of the prepolymerizable polyfunctional compound is not particularly limited, and from Examples 17 to 20, it was confirmed that it is sufficient to contain either of the titanium oxide fine particles and the zirconium oxide fine particles. Comparing Examples 17 and 18, it was confirmed that the anatase type 18, which has a high value of haze 2 and the rutile type, is preferable.

On the other hand, when the cado resin is changed to an acrylic resin, adhesion to ITO deteriorates, which is not preferable (Comparative Example 1). In addition, it was confirmed that, when the component (a) is not contained, there is a residue at the time of development, and adhesion to glass and ITO is poor. In addition, it was confirmed that when the polymerizable compound is not contained, the residue is left unfavorably because the residue is left after development (Comparative Example 3). Further, when the particle size of the titanium oxide fine particles and / or the zirconium oxide fine particles exceeds 100 nm, it is confirmed that the transmittance is lowered and the haze is increased (Comparative Example 4). When the P / V ratio was less than 0.3, it was confirmed that the refractive index difference with ITO was large and the ITO pattern could be seen through the touch surface side (Comparative Example 5). Further, it was confirmed that when the P / V ratio exceeds 4.0, the adhesiveness to ITO is lowered, which is not preferable (Comparative Example 6).

1: transparent substrate
2: first ITO electrode
3: Insulating layer
4: second ITO electrode
5: Protective layer
6: extraction electrode
10: Touch panel

Claims (10)

A cardo resin having a carboxyl group having a refractive index of 1.58 or more,
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 / or zirconium oxide fine particles having an average particle diameter of 5 nm or more and 100 nm or less,
An energy ray polymerization initiator,
A solvent,
Wherein the P / V ratio, which is a mass ratio of the total particulate component to all the solid components other than the particulate component, is 0.3 or more and 4.0 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 cado resin and 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 content of the titanium oxide fine particles in the total solid content is 30 mass% or less. The energy ray curable resin composition according to claim 1 or 2, wherein the P / V ratio is not less than 1.5 and not more than 3.5. The energy ray curable resin composition according to claim 1 or 2, wherein the refractive index after the energy ray curing is 1.65 or more. The energy ray curable resin composition according to claim 1 or 2, wherein the refractive index after energy beam curing is 1.8 or more. The insulating layer and / or the protective layer formed by curing the energy ray curable resin composition according to any one of claims 1 or 2 is formed on the patterned ITO film, or the ITO A transparent laminated member having a film formed thereon. A touch panel comprising the transparent laminate member according to claim 8. An image display apparatus comprising the touch panel according to claim 9.

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