JP2014024919A - Energy ray-curable resin composition, protective film using the composition, touch panel component and touch panel component manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an energy ray-curable resin composition which exhibits preferable adhesion to a transparent resin film or an undercoat layer and electrodes even if heat treatment temperature is low.SOLUTION: A composition comprises: an alicyclic hydrocarbon group-containing (meth)acrylic copolymer of an acid value of 30 mg KOH/g or more; a (meth)acryloyl group-containing phosphoric acid ester compound (preferably of the specified general formula (I) or (II)); and one or more silane coupling agents selected from those based on epoxy, isocyanate, acid anhydride, or epoxy oligomer.

Description

  The present invention relates to an energy ray curable resin composition, a protective film using the composition, a touch panel member, and a method for producing the touch panel member.

  An image display device such as a smartphone, a personal computer, or a game machine with a built-in touch panel can be operated by an operator touching the screen with a hand, a pen, or the like. Since these devices can be operated by a method that is easy to understand intuitively, such as an operator pressing and sliding a portion displayed on the screen, the device is very easy to handle, and the market is rapidly expanding.

  As an example shown in FIG. 1, the sensor part of this touch panel is usually laminated on the transparent substrate 1 by patterning the first electrode 2, the insulating layer 3, the second electrode 4, and the protective layer 5 into a desired shape. In addition, an extraction electrode 6 and the like are formed. Here, the insulating layer 3 or the protective layer 5 is formed by coating the patterned electrode with an energy ray-curable resin composition, and then irradiating and heating energy rays such as ultraviolet exposure. It is done.

  The insulating layer and the protective layer are required to have various performance requirements. For example, in addition to the electrical insulation and transparency of the insulating layer 3 and the protective layer 5 and the adhesion to the transparent substrate 1 and the electrodes 2 and 4, alkali developability at the time of patterning is required. Regarding the improvement of adhesion to the transparent substrate 1 and the electrodes 2 and 4, Patent Document 1 discloses a polymer containing an aromatic ring-containing vinyl monomer as an essential constituent unit and a polyfunctional containing no carboxyl group in the molecule. A photosensitive resin composition containing a (meth) acrylate monomer and a radical photopolymerization initiator is disclosed. In the invention described in Patent Document 1, an energy ray curable resin composition is applied on a transparent glass plate, and the composition is preheated (prebaked) at 80 ° C. for 3 minutes to activate the composition. After irradiating energy rays and developing with an alkaline aqueous solution, the composition is post-heated (post-baked) at 230 ° C. for 30 minutes. Pre-baking here refers to a heating step immediately after application and before irradiation with active energy rays. Post bake is a heating step performed after development processing. In the case where development processing is not performed, the additional heat treatment after pre-baking is referred to as post-baking.

JP 2012-48185 A

  By the way, in patent document 1, although the inflexible glass plate is used as a transparent substrate, in order to respond to the request | requirement of the weight reduction of a touch panel, and flexibility, a transparent resin film is used as a transparent substrate instead of a glass plate. Is required. However, since the transparent resin film is inferior in heat resistance to the glass plate, it may not be able to withstand post-baking at a high temperature of 200 ° C. or higher after alkali development.

  In order to prevent the deterioration of the transparent resin film, it is conceivable to lower the heat treatment temperature, but the heat treatment does not react only with ultraviolet irradiation, the polymerizable resin component reacts to increase the degree of polymerization, or the stress is relaxed by heating. This is effective in reducing the strain and increasing the adhesion, but if the temperature is 150 ° C. or less, these effects are small and the adhesion tends to be inferior. The heat treatment here indicates a pre-bake step and a post-bake step, and the heat treatment temperature indicates a temperature applied to the pre-bake step and the post-bake step. In the above-mentioned Patent Document 1, it is disclosed that the post-baking temperature may be set to 50 ° C. to 280 ° C. and the post-baking time may be set to 5 minutes to 2 hours (paragraph 0111). There is no disclosure or suggestion about making a transparent substrate, and as described in a later comparative example, the composition described in Patent Document 1 actually has poor adhesion when heated at a low temperature. Therefore, there is a need for an energy ray curable resin composition that can have sufficient adhesion to the transparent resin film or undercoat layer and the electrode even when the post-baking temperature is low.

  The present invention has been made in view of the above circumstances, and the purpose thereof is, for example, when a protective film having a transparent resin film as a substrate is manufactured, even when the heat treatment temperature is lowered, the transparent film is transparent. It is to provide an energy ray curable resin composition having sufficient adhesion to a resin film or undercoat layer and an electrode.

  The present inventor has made extensive studies to solve the above-mentioned problems, and as a result, a (meth) acryloyl ester containing an alicyclic hydrocarbon group-containing (meth) acrylic copolymer having an acid value of 30 mgKOH / g or more as a resin component is used. By using a group-containing phosphate ester compound and one or more silane coupling agents selected from epoxy, isocyanate, acid anhydride or epoxy oligomers as adhesion aids, a transparent resin film or under It has been found that sufficient adhesion to the coat layer and the electrode can be obtained, thereby meeting the demand for weight reduction and flexibility of the touch panel, and the present invention has been completed. Specifically, the present invention provides the following.

  (1) The present invention relates to an alicyclic hydrocarbon group-containing (meth) acrylic copolymer having an acid value of 30 mgKOH / g or more, a polyfunctional (meth) acrylate monomer, a (meth) acryloyl group-containing phosphate ester compound, An energy ray-curable resin composition containing a silane coupling agent, an energy ray polymerization initiator, and a solvent selected from the group consisting of epoxy, isocyanate, acid anhydride, and epoxy oligomers It is.

（式（Ｉ）中、ｎは１以上１０以下の整数を示し、ａ＋ｂ＝３であり、ａは１〜２であり、ｂは１〜２である。Ｒ_１及びＲ_２は水素又はメチル基であることを示す。） (2) Moreover, this invention is an energy-beam curable resin composition as described in (1) whose said (meth) acryloyl group containing phosphate ester compound is a compound represented by the following general formula (I). .

(In the formula (I), n represents an integer of 1 to 10, a + b = 3, a is 1 to 2, and b is 1 to 2. R ₁ and R ₂ are hydrogen or a methyl group. (Indicates that

（式（ＩＩ）中、ｎは１以上１０以下の整数を示し、ａ＋ｂ＝３であり、ａは１〜２であり、ｂは１〜２である。Ｒ_３は水素又はメチル基であることを示す。） (3) Moreover, this invention is an energy-beam curable resin composition as described in (1) whose said (meth) acryloyl group containing phosphate ester compound is a compound represented by the following general formula (II). .

(In formula (II), n represents an integer of 1 to 10, a + b = 3, a is 1 to 2, and b is 1 to 2. R ₃ is hydrogen or a methyl group. Is shown.)

  (4) Moreover, this invention is energy ray hardening in any one of (1) to (3) currently formed on the transparent conductive film patterned on the single layer or multilayer transparent base material It is the protective film formed by hardening | curing an adhesive composition.

  (5) Further, in the present invention, a transparent conductive film is patterned as a transparent electrode on a single-layer or multilayer transparent substrate, and the insulating film comprising the protective film according to (4) is formed on the transparent conductive film. The touch panel member is formed with a layer and / or a protective layer, and at least one layer of the transparent substrate is a transparent resin film. In addition, this invention is not restricted to the aspect in which a transparent electrode is directly formed on a transparent base material, The aspect in which an undercoat layer is formed on a transparent base material, and a transparent electrode is formed on this undercoat layer Are also included in the technical scope. Examples of the undercoat layer include a layer formed by printing or vapor deposition on a transparent substrate, specifically, an inorganic layer such as an organic layer, a metal oxide layer, or a glass layer. It is provided for the purpose of improvement in heat resistance, improvement in heat resistance, improvement in chemical resistance, and invisibility (for example, a layer having a high refractive index of about 1.65 to 1.75 is provided to make transparent electrodes such as ITO difficult to see). . The undercoat layer may cover the entire surface of the transparent substrate or may cover a part thereof.

  (6) Further, in the present invention, the transparent substrate is a polyethylene film, a polyester film, a (meth) acrylic film, a polyamide film, a polyacetal film, a polybutylene terephthalate film, a polyethylene naphthalate film, or a triacetyl cellulose film. , Syndiotactic polystyrene film, polyphenylene sulfide film, polyether ketone film, polyether ether ketone film, fluororesin film, polyether nitrile film, polycarbonate film, modified polyphenylene ether film, polycyclohexene film, polynorbornene resin film, Polysulfone film, polyarylate film, polyamideimide film, polyetherimide Irumu, thermoplastic polyimide film, comprising at least one layer of film selected from the triacetyl cellulose film or a cycloolefin polymer film, a touch panel member according to (5).

  (7) Moreover, this invention is a manufacturing method of the touch-panel member as described in (5) or (6), Comprising: It heat-processes the energy-beam curable resin composition in any one of (1) to (3). It is a manufacturing method of the touch panel member whose temperature at the time of carrying out is 50 to 150 degreeC.

  According to the present invention, when a protective film having a transparent resin film as a substrate is produced, sufficient adhesion to the transparent resin film or the undercoat layer and the electrode can be obtained even when the heat treatment temperature is 50 to 150 ° C. The energy beam curable composition of the present invention is particularly suitable as a material for an insulating layer and / or a protective layer of a touch panel having a transparent resin film as a substrate.

It is (a) top view and (b) AA sectional drawing which show an example of a touch panel. It is sectional drawing which shows the other example of a touchscreen. It is sectional drawing which shows the other example of a touchscreen.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Energy ray curable composition>
The energy beam curable composition of the present invention (hereinafter also simply referred to as a composition) contains at least the following a) to f). Moreover, you may contain g). This will be described in order below.
a) An alicyclic hydrocarbon group-containing (meth) acrylic copolymer having an acid value of 30 mgKOH / g or more b) a polyfunctional (meth) acrylate monomer c) a (meth) acryloyl group-containing phosphate ester compound d) epoxy-based, isocyanate A silane coupling agent that is one or more selected from a system, an acid anhydride system or an epoxy oligomer system e) an energy ray polymerization initiator f) a solvent g) other

[A) (Meth) acrylic copolymer containing an alicyclic hydrocarbon group having an acid value of 30 mgKOH / g or more]
The (meth) acrylic copolymer used in the present invention has an acid value of 30 mgKOH / g or more and contains an alicyclic hydrocarbon group. When the acid value is less than 30 mgKOH / g, it is not preferable from the viewpoint of alkali development and adhesiveness when producing a protective film having a transparent resin film as a base material. When the alicyclic hydrocarbon group is not included, sufficient adhesion between the transparent resin film or the undercoat layer and the electrode may not be obtained if the heat treatment temperature is set to 50 ° C. to 150 ° C. to prevent the deterioration of the transparent resin film. It is not preferable in terms of the nature.

  In order to make an acid value 30 mgKOH / g or more, the acidic functional group illustrated by the carboxyl group etc. is included. In the present embodiment, the acid value is measured according to JIS-K0070, preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, and further preferably 50 mgKOH / g or more. On the other hand, the upper limit is not particularly limited, but is usually preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less. The acid value is a value obtained by titration with a potassium hydroxide ethanol solution using phenolphthalein as an indicator. If the acid value is within the above range, it is easy to control the pattern shape at the time of pattern exposure, the problem of film thickness reduction during development (film reduction) is suppressed, and the viscosity when resisted is difficult to become too high, preferable. In addition, if the acid value is within the above range, acid-base interaction works on the metal oxide interface such as glass or ITO that exhibits basicity, and further, it has affinity with the phosphoric acid-based material that is an adhesion aid. Since it is good, there exists an effect which adhesiveness improves.

  The (meth) acrylic copolymer used in the present invention is a copolymer polymerized from a monomer having an acidic functional group, an alicyclic hydrocarbon group-containing monomer, and the like. Examples thereof include compounds having at least one acidic functional group and one ethylenically unsaturated double bond, and a preferred example of the acidic functional group is a carboxyl group. For example, (meth) acrylic acid, dimer of acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2 -(Meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, and one or more selected from these acid anhydrides. Among them, (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- ( (Meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate and the like are preferable, and (meth) acrylic acid is particularly preferable. In addition, the monomer which has an acidic functional group may be used individually by 1 type, and may use 2 or more types together.

  Examples of the alicyclic hydrocarbon group-containing monomer include compounds having at least one alicyclic hydrocarbon group in one molecule and one ethylenically unsaturated double bond, and having an alicyclic hydrocarbon group. (Meth) acrylic monomers are preferably used. For example, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol monoacrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecane (Meth) acrylates, adamantane (meth) acrylates, isobornyl (meth) acrylates, 2-methyl-3,4-epoxy-cyclohexyl (meth) acrylates, and their macromonomers; N-substituted maleimides such as N-cyclohexylmaleimide And (4-hydroxymethylcyclohexyl) methyl methacrylate and the like. Preferably, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and adamantane (meth) acrylate are used. By using the alicyclic hydrocarbon group-containing (meth) acrylic monomer, sufficient adhesion to the transparent resin film or the undercoat layer and the electrode can be obtained even when the heat treatment temperature is 50 ° C to 150 ° C. There is an effect.

  The (meth) acrylic copolymer used in the present invention can be copolymerized with an acid functional group-containing monomer and an alicyclic hydrocarbon group-containing monomer as long as the object of the present invention can be achieved. Compounds (hereinafter sometimes referred to as “other copolymerizable compounds”), such as a hydroxyl group-containing (meth) acrylate monomer or an aliphatic (meth) acrylate monomer. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxybutyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, dimethylacrylamide, dimethylamino ester (Meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, etc. These (meth) acrylate monomers are used singly or in combination of two or more. be able to.

  Further, when a compound having both an epoxy group and an ethylenically unsaturated group in the molecule, such as glycidyl (meth) acrylate, is added and an ethylenically unsaturated group is introduced into the side chain, b) Polymerization with a polyfunctional (meth) acrylate monomer as a component is possible, and the cured film layer constituting the insulating layer or protective layer is preferable in that it is more stable.

  The mass average molecular weight (hereinafter referred to as “Mw”) of the (meth) acrylic copolymer is not particularly limited, but from the viewpoint of appropriately exhibiting heat resistance and alkali developability, 40 to 40. 5,000 or less, more preferably 6,000 or more and 15,000 or less. In addition, the mass mean molecular weight in this invention is a mass mean molecular weight of polystyrene conversion at the time of measuring by gel permeation chromatography (GPC).

  Content of a (meth) acryl copolymer is the ratio in the total solid of a resin composition, and is 5-40 mass% normally, Preferably it is 10-30 mass%. If the copolymer content is too small, sufficient photocurability may not be obtained, or adhesion may be reduced due to generation of residues or curing shrinkage during development. If the content is too large, development failure or curing failure may occur. This is not preferable because the film strength may decrease and durability may decrease.

  In addition, among the alicyclic hydrocarbon group-containing (meth) acrylic copolymer, the content of the alicyclic hydrocarbon-containing (meth) acrylic monomer is the same as that of the alicyclic hydrocarbon group-containing (meth) acrylic copolymer. The proportion in the solid content is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, more preferably 80% by mass or less, and 65% by mass or less. Further preferred. When the amount is 5% by mass or less, adhesion failure may occur. When the amount exceeds 80% by mass, a sufficient acid value for development may not be obtained, which is not preferable.

  Moreover, it is preferable that the content rate of the monomer which has an aromatic ring is 5 mass% or less among the monomers which comprise an alicyclic hydrocarbon group containing (meth) acrylic copolymer, and it is further more preferable that it does not contain. If it exceeds 5 mass%, yellowing or poor adhesion may occur, which is not preferable.

[B) Multifunctional (meth) acrylate monomer]
The polyfunctional (meth) acrylate monomer used in the present invention is not particularly limited as long as it can be polymerized by the energy ray polymerization initiator as the component e). For example, a compound having two or more ethylenically unsaturated double bonds is used. Among these, bifunctional (meta) having two or more (meth) acryloyl groups from the viewpoint that, by sufficiently proceeding photocuring, elution of the exposed portion can be suppressed and development of the unexposed portion can be more reliably performed. ) Acrylate and trifunctional or higher functional (meth) acrylates are preferable, and trifunctional or higher functional (meth) acrylates are more preferable. A compound having two or more ethylenically unsaturated double bonds may be used alone or in combination of two or more.

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol (meth) acrylate, long chain aliphatic di (meth) acrylate, and neopentyl glycol di (meth). Acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, propylene di (meth) acrylate, glycerol (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate Polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylated cyclohexyl di ( (Meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) ) Acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, zinc di (meth) acrylate, and the like.

  Examples of trifunctional or higher functional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and alkyl-modified pentaerythritol. Tri (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, tri (meth) acrylate phosphate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate Dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) ) Acrylate, carboxylic acid-modified dipentaerystol penta (meth) acrylates, urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate and more (Meth) acrylate is mentioned. Preferably, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, carboxylic acid modified dipentaerythritol penta (meth) acrylate, succinic acid modified dipentaerythritol penta (meth) acrylate, tris (acrylic) Roxyethyl) isocyanurate. By using dipentaerythritol hexa (meth) acrylate, carboxylic acid-modified dipentaerystole penta (meth) acrylate, and tris (acryloxyethyl) isocyanurate, the photocuring proceeds sufficiently to prevent elution of exposed areas. And development of unexposed portions can be performed more reliably.

  Commercially available products of the above polyfunctional (meth) acrylate monomers can be used, and specific examples include Aronix M-403, Aronix M-315, Aronix M520 (all manufactured by Toagosei Co., Ltd.) and the like.

  Content of the said polyfunctional (meth) acrylate monomer is the ratio in the total solid of a resin composition, and is 10-70 mass% normally, Preferably it is 20-60 mass%, More preferably, it is 30-55. % By mass. If the content of the polyfunctional (meth) acrylate monomer is too small, sufficient photocurability may not be obtained. If the content is too large, adhesion failure due to curing shrinkage and development suitability may be reduced. Therefore, it is not preferable.

（式（Ｉ）中、ｎは１以上１０以下の整数を示し、ａ＋ｂ＝３であり、ａは１〜２であり、ｂは１〜２であり、Ｒ_１及びＲ_２は水素又はメチル基であることを示す。） [C) (Meth) acryloyl group-containing phosphate ester compound]
The phosphate ester compound used in the present invention contains a (meth) acryloyl group. The (meth) acryloyl group-containing phosphate ester compound is used to increase the adhesion between the transparent resin film or the undercoat layer and the electrode. The phosphoric acid ester compound is not particularly limited, and has high adhesion to the transparent resin film or undercoat layer and the electrode, and includes an alicyclic hydrocarbon group-containing (meth) acrylic copolymer and a polyfunctional (meth) acrylate monomer. It is preferable to use a compound represented by the following general formula (I) or (II) from the viewpoint that the compatibility with the resin is good and the transparency of the cured film can be ensured.

(In the formula (I), n represents an integer of 1 to 10, a + b = 3, a is 1 to 2, b is 1 to 2, and R ₁ and R ₂ are hydrogen or a methyl group. (Indicates that

（式（ＩＩ）中、ｎは１以上１０以下の整数を示し、ａ＋ｂ＝３であり、ａは１〜２であり、ｂは１〜２である。Ｒ_３は水素又はメチル基であることを示す。）

(In formula (II), n represents an integer of 1 to 10, a + b = 3, a is 1 to 2, and b is 1 to 2. R ₃ is hydrogen or a methyl group. Is shown.)

  Specific examples of the compound represented by the general formula (I) include mono [poly (ethylene oxide) methacrylate] phosphate ester (trade name: PAM-100, manufactured by Rhodia Nikka Co., Ltd.), mono [poly (propylene oxide) methacrylate]. Phosphate ester (trade name: PAM-200, manufactured by Rhodia Nikka Co., Ltd.), mono [poly (propylene oxide) acrylate] phosphate ester (trade name: PAM-300, manufactured by Rhodia Nikka Co., Ltd.) .

  Specific examples of the compound represented by the general formula (II) include 2- (meth) acryloyloxyethyl caproate acid phosphate (trade name: PM-21, manufactured by Nippon Kayaku Co., Ltd.).

  As described above, by including a long chain between the (meth) acryloyl group and the phosphoric acid group, such as ethylene oxide-modified-phosphoric dimethacrylate, an alicyclic hydrocarbon group-containing (meth) acrylic copolymer or Insulating film and / or protection with improved compatibility with polyfunctional (meth) acrylate monomer, improved transparency of resin composition in liquid state and coating state, low haze value, and excellent optical properties A membrane can be obtained.

  The content of the phosphoric acid ester compound is not particularly limited as long as it can have a desired adhesion to the transparent resin film or the undercoat layer and the electrode, but the entire resin composition The ratio in the solid content is usually 2 to 10% by mass, preferably 3 to 8% by mass, and more preferably 4 to 6% by mass. If the content of the phosphate ester compound is less than 2% by mass, the desired adhesion to the transparent resin film or undercoat layer and the electrode may not be obtained, and if it exceeds 10% by mass, poor adhesion may occur. This is not preferable. Further, when the phosphate ester compound is used in combination with a silane coupling agent, the alkoxy group of the silane coupling agent is silanolized, and the reaction with a metal oxide such as a transparent electrode is activated. As a result, adhesion with metal oxides such as transparent electrodes increases.

[D) One or more silane coupling agents selected from epoxy, isocyanate, acid anhydride, and epoxy oligomers]
A silane coupling agent is used in order to improve the adhesiveness with respect to a transparent resin film or an undercoat layer, and an electrode. The silane coupling agent of this invention is 1 or more types selected from an epoxy type, an isocyanate type, an acid anhydride type, or an epoxy oligomer type. (Meth) acryloyl-based or mercapto-based, when manufacturing a conductive laminate using a transparent resin film as a substrate, sufficient adhesion to the transparent resin film or undercoat layer and the electrode when the heat treatment temperature is lowered Is not preferable in that it may not be obtained.

  Examples of the epoxy silane coupling agent include alkoxysilanes having at least one epoxy group, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 3-glycidoxypropylethyldiethoxysilane, 3- (NN-glycidyl) aminopropyltri And methoxysilane.

  Examples of the isocyanate-based silane coupling agent include alkoxysilanes having at least one isocyanate group, such as 2-isocyanatepropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropyl. Examples include methyldimethoxylane, γ-isocyanatopropyldimethylmethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropyldimethylethoxysilane.

  The acid anhydride-based silane coupling agent is an alkoxysilane compound having at least one acid anhydride ring in the molecule, the acid anhydride ring is an organic carboxylic acid anhydride, and the organic carboxylic acid anhydride ring is Examples of these include a succinic anhydride ring, a glutaric anhydride ring, and an adipic anhydride ring. Among them, a succinic anhydride ring is preferable. Specific examples of such silane compounds include trimethoxysilylpropyl succinic anhydride, methyldimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride, trimethoxysilylmethyl succinic anhydride, And methoxysilylhexyl succinic anhydride.

  Examples of the epoxy oligomer-based silane coupling agent include alkoxysilanes having both at least one epoxy group and at least one alkoxy group, specifically, X-41-1053, X-41-1059A, X-12. -1056, X-12-981, X-12-984 (all manufactured by Shin-Etsu Silicone) and the like.

  Commercially available products can be used as the silane coupling agent, and preferred examples include KBM-403 as an epoxy specific example, KBM9007 as an isocyanate specific example, and X-12 as an acid anhydride specific example. Specific examples of -967C and epoxy oligomers include the above X-41-1053 (all manufactured by Shin-Etsu Silicone).

  The content of the silane coupling agent is not particularly limited as long as adhesion to the transparent resin film or the undercoat layer and the electrode can be increased, but is usually a ratio in the total solid content of the resin composition. It is 0.1-25 mass%, More preferably, it is 1-15 mass%, More preferably, it is 3-10 mass%. When the content of the silane coupling agent is too small, when manufacturing a protective film using a transparent resin film as a substrate, when the heat treatment temperature is lowered, sufficient adhesion to the transparent resin film or the undercoat layer and the electrode is obtained. There is a possibility that it may not be obtained, and if there is too much content, there is a risk of causing poor curing or development failure, and when further layers are formed on the formed resin composition layer, repelling occurs at the time of application, or the composition above This is not preferable because it may reduce the adhesion of objects.

[E) Energy beam polymerization initiator]
An energy beam polymerization initiator is further blended in the energy beam curable resin composition of the present invention. Examples of such energy beam polymerization initiators include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,4) 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) ], Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime), and the like. Further, from the viewpoint of sensitivity, transparency, and plate-making suitability, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] is preferred.

  The blending ratio of the energy ray polymerization initiator is preferably 1 to 10% by mass, more preferably 4 to 9% by mass, based on the total solid content of the resin composition.

[F) Solvent]
The energy ray-curable resin composition of the present invention can be adjusted for solid content by appropriately adding a solvent. The solvent is not particularly limited as long as it is an organic solvent that does not react with each component of the energy ray curable resin composition and can dissolve or disperse them. Specifically, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycols such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME) Ethers; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether Glycols; 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; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy Ketones such as -4-methyl-2-pentanone; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl propionic acid, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, 3-methoxybutyl acetate, esters such as 3-methyl-3-methoxybutyl acetate; and the like. These solvents may be used alone or in combination of two or more. Among these, PGMEA, PGME, or a mixed solvent of both is preferable from the viewpoint of coating suitability and solubility.

  The amount of the solvent can be appropriately selected according to the intended coating property and dispersion solubility, but preferably the solid content in the energy ray curable resin composition may be adjusted to 10 to 40% by mass. .

[G) Others
The energy ray curable resin composition of the present invention appropriately contains a surfactant, a polymerization inhibitor, an antioxidant, a light stabilizer, a dispersant, a leveling agent, and inorganic fine particles (such as colloidal silica) for improving hardness. May be used. For example, as a surfactant, DIC's “MegaFac” F-477, F-555, F-552, etc., which are fluorine-based, silicone-based BYK-333, BYK-301, etc. 0.1-5 mass% can be mix | blended in the ratio in the total solid of a resin composition.

<Transparent laminated member 10 / Touch panel>
The energy beam curable composition of the present invention is applied onto a substrate having the patterned thin film electrode, and is photocured by ultraviolet rays or the like to form a cured product, thereby forming an insulating layer and / or a protective layer. This constitutes the transparent laminated member of the present invention, and the transparent laminated member constitutes a part of the touch panel.

  Referring to FIG. 1 again, the present invention will be described. The sensor portion of the transparent laminated member 10 is generally formed of a first electrode 2, an insulating layer 3, a second electrode 4, and a protective layer 5 on a transparent substrate 1 in a desired shape. It is manufactured by patterning and laminating. The insulating layer and / or protective layer in the present invention can be applied to either or both of the insulating layer 3 and the protective layer 5.

[Transparent substrate 1]
In the present invention, the transparent substrate 1 is a resin member having a resin Tg of 80 ° C. or higher, preferably 100 ° C. or higher, and is a flexible member such as a light-transmitting sheet, film, or film, and a touch panel member As long as it can be a base material, it may be appropriately selected and used. For example, as an example of a film formed of a light-transmitting resin, any insulating film that can transmit light can be appropriately selected without particular limitation. Examples of the film include, for example, polyethylene terephthalate film (PET film) or polyether sulfone film (PES film), acrylic such as polymethyl methacrylate, polyamide, polyacetal, polybutylene terephthalate, polyethylene naphthalate, Or syndiotactic polystyrene, polyphenylene sulfide, polyether ketone, polyether ether ketone, fluororesin, or polyether nitrile, polycarbonate, modified polyphenylene ether, polycyclohexene, polynorbornene resin, or polysulfone, poly Examples include films made of arylate, polyamideimide, polyetherimide, or thermoplastic polyimide. It can be, but is not limited to this. Moreover, there are a triacetyl cellulose film (TAC film) and a cycloolefin polymer film (COP film), and a polyethylene terephthalate film and a cycloolefin polymer film are preferable from the viewpoint of transparency and heat resistance.

  When the transparent substrate 1 has a multilayer structure, it is necessary to match the highest heat treatment temperature with the layer having the lowest heat resistance. For example, even when the base material is glass, the heat treatment temperature needs to be set to a low temperature when there is a layer having low heat resistance as another layer. In view of this, it is sufficient that the film has one or more layers in the single-layer or multilayer transparent substrate 1, and if so, the other layer has a layer different from the film, for example, a glass layer. Is also included in the technical scope of the present invention.

  The thickness of the substrate 1 is not particularly limited, but is generally about 10 μm to 300 μm from the viewpoint of flexibility.

[Electrodes 2, 4]
The arrangement of the first electrode 2 and the second electrode 4 is not particularly limited as long as a touch operation can be detected. As shown in FIG. 1B, the first electrode 2 and the second electrode 4 are arranged. In addition to the mode in which the insulating layer 3 is formed between the electrodes 4, the mode in which the first electrode 2 is formed on one surface of the transparent substrate and the second electrode 4 is formed on the other surface (FIG. 2), transparent An embodiment (FIG. 3) in which both the first electrode and the second electrode are directly formed on the substrate can be mentioned. Of these, the embodiment shown in FIG. Even if the electrode on the insulating layer 3 is a transparent electrode and a heat treatment is performed at a high temperature when the transparent electrode is formed, the insulating layer 3 is insulated by using the cured film of the energy ray curable composition of the present invention. This is because deterioration of the layer 3 can be suppressed. Therefore, the effect of the present invention can be exhibited more effectively.

  The 1st electrode 2 and the 2nd electrode 4 should just have desired electroconductivity, The transparent electrode formed using the transparent electrode material which has transparency may be sufficient, and the light shielding which has light-shielding property It may be a light-shielding electrode formed using a conductive electrode material.

  When the electrodes 2 and 4 are transparent electrodes, specific examples include indium tin oxide (ITO), zinc oxide, indium oxide, antimony-added tin oxide, fluorine-added tin oxide, aluminum-added zinc oxide, potassium-added zinc oxide, silicon Examples include additive zinc oxide, metal oxides such as zinc oxide-tin oxide, indium oxide-tin oxide, zinc oxide-indium oxide-magnesium oxide, and materials in which two or more of these metal oxides are combined. It is done. Moreover, organic type transparent electrodes, such as a graphene transparent electrode, are also mentioned.

  When the electrodes 2 and 4 are light shielding electrodes, for example, those described in JP 2010-238052 A can be used. Specifically, metals such as aluminum, molybdenum, silver, and chromium and alloys thereof can be used.

  About the pattern and thickness in planar view of the 1st electrode 2 and the 2nd electrode 4, it can be the same as that of a general touch panel. Specifically, the patterns described in JP2011-210176A and 2010-238052A can be used.

  The present invention is not limited to an embodiment in which the first electrode 2 and / or the second electrode 4 are directly formed on the transparent substrate 1, and an undercoat layer is formed on the transparent substrate 1, and this undercoat layer A mode in which the first electrode 2 and / or the second electrode 4 are formed on the upper side is also included in the technical scope. Examples of the undercoat layer include a layer formed by printing or vapor deposition on the transparent substrate 1, and specifically include inorganic layers such as an organic layer, a metal oxide layer, and a glass layer. It is provided for the purpose of improvement in heat resistance, improvement in heat resistance, improvement in chemical resistance, and invisibility (for example, a layer having a high refractive index of about 1.65 to 1.75 is provided to make transparent electrodes such as ITO difficult to see). . The undercoat layer may cover the entire surface of the transparent substrate or may cover a part thereof.

<The manufacturing method of the transparent laminated member 10>
Here, the manufacturing method of the transparent laminated member 10 illustrated by FIG. 1 is demonstrated. As described above, the first electrode 2 is formed on one surface of the transparent substrate and the other surface is not limited to the aspect in which the insulating layer 3 is formed between the first electrode 2 and the second electrode 4. 1 is a conductive laminate different from the embodiment illustrated in FIG. 1, such as an embodiment in which the second electrode 4 is formed on the transparent substrate, an embodiment in which both the first electrode and the second electrode are directly formed on the transparent substrate. Is also included in the technical scope of the present invention.

  First, the first electrode 2 patterned into a desired shape is formed on the transparent substrate 1 by a known method. Thereafter, the energy ray-curable resin composition of the present invention is applied on the substrate having the first 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.

  Next, the applied insulating layer 3 is dried by applying heat as necessary (pre-baking). The drying conditions can be appropriately set in the same range as usual, for example, in the range of 50 to 150 ° C. and 0.5 to 10 minutes. At this time, a vacuum drying process may be performed to about 0.2 Torr (27 Pa) with a vacuum dryer.

Next, a mask having an opening pattern of a predetermined shape is placed on the energy ray curable resin composition, and active energy rays are irradiated. Examples of the active energy ray include ultraviolet rays and electron beams. The irradiation amount can be appropriately set within the range used for normal patterning, and can be set within the range of, for example, 30 to 300 mJ / cm ² , preferably 50 to 150 mJ / cm ² .

  After irradiation with active energy rays, the coating film is alkali-developed by a usual method. Examples of the developer include aqueous solutions of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; aqueous solutions of carbonates such as sodium carbonate, potassium carbonate and sodium hydrogencarbonate; hydroxytetramethylammonium and hydroxytetraethylammonium An aqueous solution of an organic alkali can be mentioned. These can be used alone or in combination of two or more kinds, and a surfactant such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be added and used. Examples of the alkali development method include a dipping method and a shower method, and the shower method is preferable. The temperature of the developer is preferably 25 to 40 ° C. The development time is appropriately determined according to the film thickness and the solubility of the energy beam curable resin composition.

  Next, the energy beam curable resin composition after the alkali development treatment is heated (post-baked). In the present invention, since the transparent substrate 1 is a transparent resin film, when heated under the same conditions (200 to 300 ° C.) as those for forming a normal insulating layer and / or protective layer, the heating temperature is too high and the transparent substrate 1 is deteriorated. Or a change such as curling or distortion may occur. In order to prevent the deterioration and the like of the transparent substrate 1, it is preferable to heat at a low temperature in the present invention. The heating temperature is more preferably 50 ° C to 150 ° C, and further preferably 50 ° C to 100 ° C. The heating time is preferably 10 minutes to 90 minutes, and more preferably 30 minutes to 60 minutes. This is because changes such as curling and distortion can be reduced.

  By passing through said process, the insulating layer 3 which consists of hardened | cured material of the energy-beam curable resin composition of this invention is pattern-formed. Although it does not specifically limit as a film thickness (at the time of drying) of an insulating layer, Usually, 0.5-5 micrometers, Preferably it can set suitably in the range of 0.75-3 micrometers.

  Thereafter, in the same manner as described above, the second electrode 4 and the protective layer 5 are sequentially formed, and the transparent laminated member 10 illustrated in FIG. 1 is manufactured. Here, the protective layer 5 may be formed of the same composition as the insulating layer 3 by the same method as described above.

  In the present invention, an alicyclic hydrocarbon group-containing (meth) acrylic copolymer having an acid value of 30 mgKOH / g or more, and a (meth) acryloyl group-containing phosphate ester compound, an epoxy-based, an isocyanate-based, an acid anhydride One or more silane coupling agents selected from physical or epoxy oligomers were used as adhesion assistants. Thereby, when manufacturing the transparent laminated member 10 which uses a transparent resin film as the transparent substrate 1, even if it is a case where heat processing temperature is as low as 50 to 150 degreeC, the high adhesion with respect to a transparent resin film or an undercoat layer and an electrode Have sex. Therefore, the energy beam curable composition of the present invention is particularly suitable as a material for the insulating layer 3 and / or the protective layer 5 of the touch panel using the transparent resin film as the transparent substrate 1.

<Image display device>
The present invention also provides an image display device including the touch panel. Examples of such an image display device include a cathode ray tube (CRT), a plasma display panel (PDP), a liquid crystal display device, and the like. In addition, the image display device of the present invention includes a smartphone, a personal computer, a game machine, and the like provided with the liquid crystal display device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. In addition, unless there is particular notice, a mixing | blending is a mass part of solid content.

酸価の単位はｍｇＫＯＨ／ｇである。
<A) Synthesis of alicyclic hydrocarbon group-containing (meth) acrylic copolymer having an acid value of 30 mgKOH / g or more>

The unit of the acid value is mgKOH / g.

[Synthesis Example A]
A polymerization tank was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 300 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), heated to 100 ° C. in a nitrogen atmosphere, and then cyclohexyl. A mixture for main chain formation containing 34.3 parts by weight of methacrylate (CHMA), 21.4 parts by weight of methyl methacrylate (MMA) and 21.9 parts by weight of methacrylic acid (MAA) is continuously added dropwise over 1.5 hours. did. Thereafter, the reaction was continued while maintaining 100 ° C., and after 2 hours from the completion of dropping of the main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization. Next, while blowing air, 22.4 parts by mass of glycidyl methacrylate (GMA) was added as a compound having both an epoxy group and an ethylenically unsaturated group in the molecule, and the temperature was raised to 110 ° C. 8 parts by mass was added and subjected to addition reaction at 110 ° C. for 15 hours to obtain a (meth) acrylic copolymer (acid value: 64 mg KOH / g, mass average molecular weight (Mw): 8,700) according to Synthesis Example A. . The acid value was measured based on JIS K 0070, and the mass average molecular weight was measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

[Synthesis Example B]
Example 1 except that 1-adamantyl methacrylate (ADAMA) and CHMA were used as the alicyclic (meth) acrylate of the main chain forming mixture, and the formulation was as shown in Table 1 (mass part of solid content). In the same manner, a (meth) acrylic copolymer (acid value: 73 mgKOH / g, mass average molecular weight (Mw): 11,900) according to Synthesis Example B was obtained.

[Synthesis Example C]
ADAMA is used as the alicyclic (meth) acrylate of the main chain forming mixture, and 2-hydroxyethyl methacrylate (2-HEMA) is used as the other main chain forming mixture. (Meth) acrylic copolymer (acid value: 67 mgKOH / g, mass average molecular weight (Mw): 11,200) according to Synthesis Example C was obtained in the same manner as in Synthesis Example A, except that .

[Synthesis Example D]
Synthesis Example A, except that CHMA and dicyclopentanyl methacrylate (DCPMA) were used as the alicyclic (meth) acrylate of the main chain forming mixture, and the blending was set to the blending shown in Table 1 (part by mass). The (meth) acrylic copolymer (acid value: 70 mgKOH / g, mass average molecular weight (Mw): 11,000) according to Synthesis Example D was obtained by the same method.

[Synthesis Example E]
Except that DCPMA was used as the alicyclic (meth) acrylate of the main chain forming mixture, 2-HEMA was used as the other main chain forming mixture, and the formulation was as shown in Table 1 (mass part of solid content). The (meth) acrylic copolymer (acid value: 72 mgKOH / g, mass average molecular weight (Mw): 9,800) according to Synthesis Example E was obtained in the same manner as in Synthesis Example A.

[Synthesis Example F]
In the same manner as in Synthesis Example A, except that isobonyl methacrylate (IBX) was used as the alicyclic (meth) acrylate of the main chain forming mixture and the blending was changed to the blending of Table 1 (part by mass). A (meth) acrylic copolymer (acid value: 68 mgKOH / g, mass average molecular weight (Mw): 8,300) according to Synthesis Example F was obtained.

[Synthesis Example G]
Synthesis example, except that 1,4-cyclohexanedimethanol monoacrylate (CHDMMA) was used as the alicyclic (meth) acrylate of the main chain forming mixture, and the blending was changed to the blending of Table 1 (parts by mass of solid content). A (meth) acrylic copolymer (acid value: 79 mgKOH / g, mass average molecular weight (Mw): 12,000) according to Synthesis Example G was obtained in the same manner as A.

表１、表２とも、酸価の単位はｍｇＫＯＨ／ｇである。 <A ′) Synthesis of (meth) acrylic copolymer containing no alicyclic hydrocarbon group>

In both Table 1 and Table 2, the unit of the acid value is mgKOH / g.

[Synthesis Example H]
According to Synthesis Example H in the same manner as Synthesis Example A, except that benzyl methacrylate (BzMA) is used instead of CHMA as the main chain forming mixture, and the formulation is the formulation shown in Table 2 (part by mass of solid content). A (meth) acrylic copolymer (acid value: 74.5 mg KOH / g, mass average molecular weight (Mw): 9,200) was obtained.

[Synthesis Example I]
According to Synthesis Example I in the same manner as Synthesis Example A, except that styrene (St) is used instead of CHMA as the main chain forming mixture and the formulation is the formulation shown in Table 2 (parts by mass of solid content) ( A (meth) acrylic copolymer (acid value: 74 mgKOH / g, mass average molecular weight (Mw): 13,100) was obtained.

<Comparison of (meth) acrylic copolymer>
The composition in an Example and a comparative example was obtained for the following a) to g1) as the composition of Table 3 (mass part of solid content).
a) An alicyclic hydrocarbon group-containing (meth) acrylic copolymer having an acid value of 30 mgKOH / g or more: any one of Synthesis Examples A to G above a ′) (meth) acrylic copolymer not containing an alicyclic hydrocarbon group Polymer: Synthesis example H or I above
b) Multifunctional (meth) acrylate monomer (trade name: Aronix M-403, DPHA polyfunctional acrylate, manufactured by Toagosei Co., Ltd.)
c) (Meth) acryloyl group-containing phosphate ester compound (trade name: PAM-200, mono [poly (propylene oxide) methacrylate] phosphate ester, manufactured by Rhodia Nikka)
d) One or more silane coupling agents selected from epoxy, isocyanate, acid anhydride or epoxy oligomer (trade name: KBM403, epoxy silane coupling agent, manufactured by Shin-Etsu Silicone)
e) Energy beam polymerization initiator (trade name: Irgacure 907, radical photopolymerization initiator, manufactured by BASF)
f) Solvent (Propylene glycol-1-monomethyl ether acetate (PGMEA), adjusted so that the solid content is 25%)
g1) Leveling agent (Brand name: MegaFuck F-555, manufactured by DIC Corporation)

本実施例において、「特定のシランカップリング剤」とは、エポキシ系、イソシアネート系、酸無水物系又はエポキシオリゴマー系から選択される１種以上であるシランカップリング剤をいう。実施例１〜７及び比較例１、２では、一例としてエポキシ系のシランカップリング剤を用いている。

In this example, the “specific silane coupling agent” refers to one or more silane coupling agents selected from an epoxy system, an isocyanate system, an acid anhydride system, or an epoxy oligomer system. In Examples 1 to 7 and Comparative Examples 1 and 2, an epoxy silane coupling agent is used as an example.

[Evaluation items and methods]
Table 4 summarizes the results of the following evaluations.
(1) Resolution / development residue PET film ITO film is formed on the deposition of SiO ₂ on the surface (trade name: Lumirror U46, manufactured by Toray Industries, Inc.) on the compositions obtained in Examples and Comparative Examples It spin-coated so that the thickness after drying might be set to 1.5 micrometers, and left still (prebaked) for 2 minutes on a 100 degreeC hotplate, and mask exposure was performed. Subsequently, development was performed for 60 seconds using a 0.05% aqueous potassium hydroxide solution as an alkaline developer, and the developability of the unexposed area was evaluated. The exposure conditions were as follows. For evaluation of developability, a mask having a line-and-space type pattern having a line width of 10 to 100 μm was placed, and development processing was performed after irradiation with ultraviolet rays under the above conditions. The obtained substrate was observed with an optical microscope, and the line width of the smallest pattern that remained on the substrate and was resolved was defined as the resolution. When a pattern of 100 μm could not be developed, or when a film flowed during development, it was evaluated as “−”. Further, for the presence or absence of development residue, the unexposed portion was visually observed, ○: no residue visually, Δ: no residue visually, pattern edge disturbance, ×: residue visually evaluated. Those in which a 100 μm pattern could not be developed in the resolution evaluation were evaluated as “−” without evaluation of the residue. ○ and Δ are practical ranges.

(Exposure conditions)
Exposure machine: Proxy exposure machine Mask: Chrome mask Exposure gap: 150 μm
Light source: Ultra high pressure mercury lamp Exposure amount: 100 mJ / cm ²

(2) Adhesiveness The coating film formed on the PET film under the same conditions as the above “(1) Resolution / Developability” was subjected to a post-baking treatment at 100 ° C. for 30 minutes, and then using a cellophane adhesive tape. A cross-cut peel test was performed. Here, the cross-cut peel test produced 100 squares of 1 mm × 1 mm by drawing parallel straight lines of 11 vertical and horizontal lines at 1 mm intervals so as to reach the base of the ITO film with a cutter knife, Cellophane adhesive tape (trade name: Cellotape (registered trademark), product number: CT405AP-24, manufactured by Nichiban Co., Ltd.) is attached with an eraser, peeled off at right angles, and the number of cells remaining is evaluated visually. did. In addition, the peeling area of the grid was determined according to the following criteria. Evaluation 4-5 is a practical range, and 5 is preferable.
5: peeling area is 0%
4: Peeling area is more than 0% to 25% 3: Peeling area is more than 25% to 50% 2: Peeling area is more than 50% to 75% 1: Peeling area is more than 75% to 100%

(3) Transparency The coating film formed on the PET film under the same conditions as in (1) above was subjected to post-baking treatment at 100 ° C. for 30 minutes, and then visually evaluated for transparency. , Δ: Slightly opaque, x: Whitening. ○ is the practical range.

(4) Refractive index First, the post-baking process was performed for 30 minutes at 100 degreeC about the coating film formed into a film on the said PET film on the conditions similar to said (1).
Then, in order to prevent back surface reflection, a black tape was applied to the PET base material side, and from the cured film surface, a reflectance in a wavelength range of 380 to 780 nm was measured using a spectrophotometer UV-3150 manufactured by Shimadzu Corporation. The average reflectance R which is an average was calculated.
Thereafter, the refractive index n1 of the present invention was calculated from the following formula using the average reflectance R. However, n0 is the refractive index of air and calculated as 1.000.
R = (n0−n1) ² / (n0 + n1) ²

  As is apparent from Table 4, the composition of the present invention comprises a (meth) acryloyl group-containing phosphate ester containing a (meth) acrylic copolymer containing an alicyclic hydrocarbon group having an acid value of 30 mgKOH / g or more as a resin component. When an insulating layer and / or protective layer is formed because the compound and one or more silane coupling agents selected from epoxy, isocyanate, acid anhydride or epoxy oligomer are used as adhesion aids Even though the heat treatment temperature is low, the adhesion between the transparent resin film or undercoat layer and the ITO electrode is excellent. Also preferred are resolution / development residue, transparency and refractive index.

  On the other hand, since the composition of the comparative example does not contain an alicyclic hydrocarbon group, if the heat treatment temperature is low, the adhesion between the transparent resin film or the undercoat layer and the ITO electrode is poor with an evaluation of 3, which is preferable. Absent.

<Comparison of phosphate ester compounds>
The composition in an Example and a comparative example was obtained by setting the following a) to g1) as a combination of Table 5 (mass part of solid content).
a) Aliphatic hydrocarbon group-containing (meth) acrylic copolymer having an acid value of 30 mgKOH / g or more: Synthesis example A above
b) Multifunctional (meth) acrylate monomer: M-403 above
c) (Meth) acryloyl group-containing phosphate ester compound c1) Product name: PM-21,2- (meth) acryloyloxyethyl caproate acid phosphate, manufactured by Nippon Kayaku Co., Ltd. c2) Product name: PM-2, Ethyl (meth) acrylate acid phosphate, manufactured by Nippon Kayaku Co., Ltd. c3) Product name: PAM-100, mono [poly (ethylene oxide) methacrylate] phosphate ester, Rhodia Nikka Co., Ltd. c4) Product name: PAM-200, mono [ Poly (propylene oxide) methacrylate] phosphate ester, Rhodia Nikka Co., Ltd. c5) Trade name: PAM-300, mono [poly (propylene oxide) acrylate] phosphate ester, Rhodia Nikka Corporation d) Epoxy system, isocyanate system One or more selected from acid anhydrides or epoxy oligomers A silane coupling agent: The above KBM403
e) Energy beam polymerization initiator: Irgacure 907
f) Solvent: PGMEA, adjusted so that the solid content is 25% g1) Leveling agent: MegaFak F-555 above

本実施例において、「特定のシランカップリング剤」とは、エポキシ系、イソシアネート系、酸無水物系又はエポキシオリゴマー系から選択される１種以上であるシランカップリング剤をいう。実施例１、１１〜１６及び比較例１１では、一例としてエポキシ系のシランカップリング剤を用いている。

In this example, the “specific silane coupling agent” refers to one or more silane coupling agents selected from an epoxy system, an isocyanate system, an acid anhydride system, or an epoxy oligomer system. In Examples 1, 11 to 16, and Comparative Example 11, an epoxy silane coupling agent is used as an example.

  Examples and Comparative Examples (1) Resolution / development residue and (2) Adhesiveness, (5) Haze (Hz), (6) Transmittance (Tt), (7) Ink transparency, and (8) Ink stability was evaluated. (1) Resolution / development residue and (2) adhesion were evaluated by the same method as described above. (5) Haze, (6) Ink transparency, and (7) Ink stability were evaluated as follows. The results are summarized in Table 6.

(5) Haze Measurement of haze is based on JIS K7361-1 (plastics-test method for total light transmittance of transparent material), haze value is based on JIS K7105, haze meter HM-150 (Murakami Color Technology Research). It is a value measured using The haze is preferably 1.5 or less when a PET film is used as the substrate.

(6) Ink transparency The above composition was visually observed to evaluate the presence or absence of cloudiness. ○: Transparent (no cloudiness), Δ: slightly opaque, ×: cloudiness was evaluated.

(7) Ink Stability Ink stability was evaluated by visually observing ink prepared by storing the produced ink in a 40 ° C. oven for one month and by the presence or absence of precipitates. ○: Evaluation was made on the basis of no precipitate, Δ: slightly opaque, x: precipitate was present (precipitate was also generated).

  As is apparent from Table 6, the composition of the present invention comprises a (meth) acryloyl group-containing phosphate ester comprising a (meth) acrylic copolymer containing an alicyclic hydrocarbon group having an acid value of 30 mgKOH / g or more as a resin component. Since the compound and the epoxy silane coupling agent are used as adhesion aids, when forming the insulating layer and / or protective layer, the transparent resin film or undercoat layer and ITO are formed even though the heat treatment temperature is low. Excellent adhesion to electrodes. Also preferred are resolution / development residue, transparency and refractive index. In particular, the phosphate ester compound is preferably a compound represented by the above general formulas (I) and (II) (Examples 1, 11 to 16), and the content of the phosphate ester compound is that of the resin composition. It is suitable that it is 0.1-10 mass% in the ratio in a total solid.

  On the other hand, since the composition of the comparative example does not contain a phosphate ester compound, if the heat treatment temperature is low, sufficient adhesion to the transparent resin film or the undercoat layer and the ITO electrode cannot be obtained, and the film does not develop during development. Since it may flow, it is not preferred (Comparative Example 11).

<Comparison of silane coupling agents>
The composition in an Example and a comparative example was obtained by making the following a) to g1) into the mixing | blending of Table 7 (mass part of solid content).
a) Aliphatic hydrocarbon group-containing (meth) acrylic copolymer having an acid value of 30 mgKOH / g or more: Synthesis example A above
b) Multifunctional (meth) acrylate monomer: M-403 above
c) (Meth) acryloyl group-containing phosphate compound: PAM-200
d) One or more silane coupling agents selected from epoxy, isocyanate, acid anhydride or epoxy oligomer d1) Epoxy: KBM403
d2) Isocyanate-based (trade name: KBM9007, isocyanate-based silane coupling agent, manufactured by Shin-Etsu Silicone)
d3) Acid anhydride type (trade name: X-12-967C, succinic anhydride type silane coupling agent, manufactured by Shin-Etsu Silicone)
d4) Epoxy oligomer type (trade name: X-41-1053, epoxy oligomer type silane coupling agent, manufactured by Shin-Etsu Silicone)
d ′) Silane coupling agent different from the above d) d′ 1) Methacryloyl-based (trade name: KBM503, methacryloyl-based silane coupling agent, manufactured by Shin-Etsu Silicone)
d'2) Mercapto type (trade name: KBM803, mercapto type silane coupling agent, manufactured by Shin-Etsu Silicone)
e) Energy beam polymerization initiator: Irgacure 907
f) Solvent: PGMEA, adjusted so that the solid content is 25% g1) Leveling agent: Megafac F-555 above

  Table 8 summarizes the results of evaluation of the above (1) resolution / development residue, (2) adhesion, (3) transparency, and (4) refractive index for Examples and Comparative Examples.

  As is apparent from Table 8, the composition of the present invention comprises a (meth) acryloyl group-containing phosphate ester containing a (meth) acrylic copolymer containing an alicyclic hydrocarbon group having an acid value of 30 mgKOH / g or more as a resin component. When an insulating layer and / or protective layer is formed because the compound and one or more silane coupling agents selected from epoxy, isocyanate, acid anhydride or epoxy oligomer are used as adhesion aids Even though the heat treatment temperature is low, the adhesion between the transparent resin film or undercoat layer and the ITO electrode is excellent. Also preferred are resolution / development residue, transparency and refractive index.

  On the other hand, among the compositions of comparative examples, a composition containing no silane coupling agent (Comparative Example 21), a composition having a (meth) acryloyl silane coupling agent (Comparative Example 22) or a silane coupling agent The composition (Comparative Example 23) that is a mercapto-based composition may not have sufficient adhesion to the transparent resin film or the undercoat layer and the ITO electrode when the heat treatment temperature is low, and the developability may also deteriorate. It is not preferable.

※表９において、ＰＥＴは、表面にＳｉＯ_２を蒸着した上にＩＴＯ膜が形成されたＰＥＴフィルム（商品名：ルミラーＵ４６、東レ社製）を示す。
ＣＯＰは、表面にＳｉＯ_２を蒸着した上にＩＴＯ膜が形成されたシクロオレフィンポリマーフィルム（商品名：ＺｅｏｎｏｒＦｉｌｍ ＺＦ１４、日本ゼオン社製）を示す。
ＴＡＣは、表面にＳｉＯ_２を蒸着した上にＩＴＯ膜が形成されたトリアセチルセルロースフィルム（商品名：フジタック、富士フィルム社製）を示す。
ガラスは表面にＩＴＯ膜が形成された厚さ０．７ｍｍのガラス基材（コーニング社製、１７３７）を示す。
※表９において、「実１」、「比１」及び「比２」はそれぞれ実施例１、比較例１、比較例２を示す。 <E) Comparison of post bake temperature>
On the substrate shown in Table 9, the composition shown in Table 9 was spin-coated so that the thickness after drying was 1.5 μm, and left on a 100 ° C. hot plate for 2 minutes (prebaked) to perform mask exposure. went. Next, development was performed for 60 seconds using a 0.05% aqueous potassium hydroxide solution as an alkaline developer. And it heat-processed for 30 minutes at the post-baking temperature shown in Table 9, and measured the change rate of the dimension of the base material before and behind post-baking. About this change rate, it evaluated on the basis of (circle): within 3%, x: 3% or more. The results are shown in Table 10. Further, (1) resolution / development residue, (2) adhesion and (3) transparency were evaluated by the same method as described above. The results are shown in Table 10.

* In Table 9, PET indicates a PET film (trade name: Lumirror U46, manufactured by Toray Industries, Inc.) in which an ITO film is formed on a surface by depositing SiO ₂ .
COP indicates a cycloolefin polymer film (trade name: ZeonorFilm ZF14, manufactured by Nippon Zeon Co., Ltd.) in which an ITO film is formed after vapor-depositing SiO ₂ on the surface.
TAC indicates a triacetyl cellulose film (trade name: Fujitac, manufactured by Fuji Film Co., Ltd.) in which SiO ₂ is deposited on the surface and an ITO film is formed.
Glass indicates a 0.7 mm thick glass substrate (Corning Corp., 1737) with an ITO film formed on the surface.
* In Table 9, “Actual 1”, “Ratio 1” and “Ratio 2” indicate Example 1, Comparative Example 1, and Comparative Example 2, respectively.

  As is apparent from Table 10, the composition of the present invention comprises a (meth) acryloyl group-containing phosphate ester containing a (meth) acrylic copolymer containing an alicyclic hydrocarbon group having an acid value of 30 mgKOH / g or more as a resin component. When an insulating layer and / or protective layer is formed because the compound and one or more silane coupling agents selected from epoxy, isocyanate, acid anhydride or epoxy oligomer are used as adhesion aids Although the heat treatment temperature is as low as 100 ° C., the adhesion between the substrate or the undercoat layer and the ITO electrode is excellent as in the case where the substrate is glass and the heat treatment temperature is 230 ° C. (Example 31) ~ 33). Also, resolution / development residue and transparency are suitable (Examples 31 to 33).

  On the other hand, in the composition of the comparative example, when the base material is glass and the heat treatment temperature is 230 ° C., the base material is a transparent resin film and the heat treatment temperature is 100 ° C., even though it showed suitable adhesion. And sufficient adhesion could not be obtained (Comparative Examples 31, 32). Moreover, when the base material is a transparent resin film and the heat treatment temperature is 230 ° C., the size of the base material changes before and after post-baking, which is not preferable (Comparative Example 33).

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 1st electrode 3 Insulating layer 4 2nd electrode 5 Protective layer 6 Extraction electrode 10 Transparent laminated member

Claims (7)

An alicyclic hydrocarbon group-containing (meth) acrylic copolymer having an acid value of 30 mgKOH / g or more;
A polyfunctional (meth) acrylate monomer;
A (meth) acryloyl group-containing phosphate compound,
A silane coupling agent that is at least one selected from an epoxy system, an isocyanate system, an acid anhydride system, or an epoxy oligomer system;
An energy ray polymerization initiator;
Solvent,
An energy ray-curable resin composition containing The energy ray-curable resin composition according to claim 1, wherein the (meth) acryloyl group-containing phosphate compound is a compound represented by the following general formula (I).

(In the formula (I), n represents an integer of 1 to 10, a + b = 3, a is 1 to 2, and b is 1 to 2. R ₁ and R ₂ are hydrogen or a methyl group. (Indicates that The energy ray-curable resin composition according to claim 1, wherein the (meth) acryloyl group-containing phosphate ester compound is a compound represented by the following general formula (II).

(In formula (II), n represents an integer of 1 to 10, a + b = 3, a is 1 to 2, and b is 1 to 2. R ₃ is hydrogen or a methyl group. Is shown.)   The protective film formed by hardening | curing the energy-beam curable composition in any one of Claim 1 to 3 currently formed on the transparent conductive film patterned on the single layer or the multilayer transparent base material.   A transparent conductive film is patterned on a single-layer or multilayer transparent substrate, and an insulating layer and / or a protective layer made of the protective film according to claim 4 is formed on the transparent conductive film, The touch panel member whose at least 1 layer of the said transparent base material is a transparent resin film.   The transparent substrate includes polyethylene film, polyester film, (meth) acrylic film, polyamide film, polyacetal film, polybutylene terephthalate film, polyethylene naphthalate film, triacetyl cellulose film, syndiotactic polystyrene film, polyphenylene Sulfide film, polyether ketone film, polyether ether ketone film, fluororesin film, polyether nitrile film, polycarbonate film, modified polyphenylene ether film, polycyclohexene film, polynorbornene resin film, polysulfone film, polyarylate film, polyamideimide Film, polyetherimide film, thermoplastic poly Bromide films, including films selected from triacetylcellulose film or a cycloolefin polymer film at least one layer, the touch panel member according to claim 5.   It is a manufacturing method of the touch panel member of Claim 5 or 6, Comprising: The temperature at the time of heat-processing the energy-beam curable resin composition in any one of Claim 1 to 3 is 50 to 150 degreeC. Manufacturing method of member.

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