JP2015137357A - Method of preparing photosensitive resin composition, photosensitive resin composition, touch panel material, touch panel protection film, touch panel insulating film, and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of preparing a photosensitive resin composition which makes it possible to obtain a cured film having excellent transparency, and also having excellent adhesion to an inorganic material surface even after chemical treatment.SOLUTION: A method of preparing a photosensitive resin composition is selected, the photosensitive resin composition comprising (A) a photopolymerizable monomer, (B) a transparent resin, (C) a photopolymerization initiator, (D) a solvent and (E) a silane coupling agent, where with respect to the total mass of the (E) silane coupling agent, moisture of 5.0-18.0 mass% is added.

Description

  The present invention relates to a method for preparing a photosensitive resin composition, a photosensitive resin composition and a material for a touch panel including the photosensitive resin composition, a touch panel protective film and a touch panel insulating film obtained by curing the photosensitive resin composition, and the touch panel protective film. Alternatively, the present invention relates to a touch panel manufactured using at least one of touch panel insulating films.

  The touch panel is a component of an input device that allows the operator to touch a transparent surface on the display screen with a finger or a pen to detect a touched position and input data. In recent years, it has become widely used because it enables intuitive input.

  The touch panel detection method includes a resistance film type, a capacitance type, an ultrasonic type, and an optical type, and until now, the resistance film type, which was relatively excellent in terms of manufacturing cost, has been the mainstream. However, a resistance film type touch panel having a structure in which an air layer is provided between two transparent conductive films has low optical characteristics (transmittance) and is not sufficient in durability and operating temperature characteristics.

  On the other hand, a capacitive touch panel having no movable part has high optical characteristics (transmittance) and is superior to the resistive film type in durability and operating temperature characteristics.

  However, in a capacitive touch panel, since a conductive film, for example, an ITO (Indium Tin Oxide) film or the like is formed on a substrate, it is necessary to form a surface protective film to protect the conductive film. And in the capacitive touch panel, since it is necessary to perform pattern processing for circuit connection with respect to the conductive film after providing the surface protective layer on the upper layer, in addition to the photosensitivity, Higher adhesion in heat treatment and chemical treatment is required.

On the other hand, as a capacitive touch panel, for example, one having a protective film formed of high-hardness inorganic SiO ₂ , SiNx, transparent resin or the like using glass with ITO film as a substrate is disclosed. (For example, refer to Patent Document 1). However, since the inorganic protective film is formed of SiO ₂ or SiNx by a CVD method or a sputtering method, energy consumption increases. Further, when the glass substrate is enlarged, a long time is required for film formation, and the production efficiency is lowered. Further, since the inorganic protective film does not have photosensitivity, it is necessary to separately perform a protective film processing for circuit connection, which increases the number of processes, resulting in an increase in manufacturing cost.

  On the other hand, as an organic protective film material, a UV curable coating composition containing a polymerizable group-containing oligomer, monomer, photopolymerization initiator and other additives is known. (For example, refer patent document 2) The film which consists of these compositions has pattern workability, and when these compositions are used, the cured film which has high hardness and transparency can be obtained. However, since the composition as described in Patent Document 2 contains a large amount of organic components, the surface of an inorganic material layer such as a glass substrate surface or a conductive film after chemical treatment, particularly after acid treatment, compared to an inorganic protective film. And there was a problem that sufficient adhesiveness could not be obtained.

  From the above situation, touch panel protective film and touch panel insulating film have pattern processability by photolithography method, excellent transparency, and adhesion to inorganic material surface even under high temperature and high humidity conditions after heat treatment or chemical treatment Development of an excellent photosensitive resin composition having high hardness has been desired.

  In addition, the touch panel has a configuration that requires an insulating film on and between the electrodes made of a conductive film on a glass substrate or a film substrate, and similarly provides sufficient adhesion to the surface of the inorganic material forming the conductive film. A photosensitive resin composition that can be obtained has been desired. In addition, as a configuration that requires an insulating film between the electrodes, for example, there is a projection type of a capacitive touch panel, and in the projection type, the sensor unit is provided between two transparent electrodes in the X-axis direction and the Y-axis direction. In addition, an insulating film is required.

JP 2007-279819 A JP 2010-027033 A

  The subject of this invention is providing the adjustment method of the photosensitive resin composition which can obtain the cured film which was excellent in transparency and was excellent in the adhesiveness with the surface of an inorganic material after chemical processing.

  Furthermore, the present invention provides a photosensitive resin composition obtained by the method for preparing the photosensitive resin composition, a touch panel material containing the photosensitive resin composition, and a touch panel protective film formed by curing the photosensitive resin composition. It is an object of the present invention to provide a touch panel insulating film obtained by curing the photosensitive resin composition, and a touch panel manufactured using at least one of the touch panel protective film and the touch panel insulating film.

  In order to solve the above-described problems, the method for preparing the photosensitive resin composition according to claim 1 includes (A) a photopolymerizable monomer, (B) a transparent resin, (C) a photopolymerization initiator, (D). A method for preparing a photosensitive resin composition containing a solvent and (E) a silane coupling agent, wherein 5.0 to 18.0% by mass of water is added to the total amount of the (E) silane coupling agent. It is characterized by doing.

  It is preferable that the content rate of the said (E) silane coupling agent is 1.0-5.0 mass% with respect to the total amount of all the solid content.

  Furthermore, the (E) silane coupling agent is preferably a methacryloxy-based or acryloxy-based silane coupling agent.

  Further, the (B) transparent resin is preferably a copolymer.

  Moreover, the photosensitive resin composition of Claim 5 was obtained by the adjustment method of the photosensitive resin composition as described in any one of Claims 1 thru | or 4.

  In addition, the photosensitive resin composition according to claim 6 includes (A) a photopolymerizable monomer, (B) a transparent resin, (C) a photopolymerization initiator, (D) a solvent, (E) a silane coupling agent, and (F) A photosensitive resin composition containing moisture, wherein (E) the moisture is contained in an amount of 5.0 to 18.0% by mass with respect to the total amount of the silane coupling agent. .

A touch panel material according to a seventh aspect includes the photosensitive resin composition according to the fifth or sixth aspect.
Moreover, the touchscreen protective film of Claim 8 hardens the photosensitive resin composition of Claim 5 or 6, It is characterized by the above-mentioned.
Furthermore, the touch panel insulating film of Claim 9 hardens the photosensitive resin composition of Claim 5 or 6, It is characterized by the above-mentioned.
Furthermore, the touch panel according to claim 10 is manufactured by using at least one of the touch panel protective film according to claim 8 or the touch panel insulating film according to claim 9.

  According to the method for preparing a photosensitive resin composition of the present invention, it is possible to provide a cured film having excellent transparency and excellent adhesion to the surface of an inorganic material even after chemical treatment.

It is sectional drawing which shows the principal part of an example touch panel which concerns on this invention. It is a top view which shows the principal part of the touch panel of an example which concerns on this invention seeing through a protective film.

  The method for preparing the photosensitive resin composition of the present invention comprises (A) a photopolymerizable monomer, (B) a transparent resin, (C) a photopolymerization initiator, (D) a solvent, and (E) a silane coupling agent. A method for preparing a photosensitive resin composition, characterized in that 5.0 to 18.0% by mass of (F) moisture is added to the total amount of the (E) silane coupling agent. Thereby, when the photosensitive resin composition is cured to form a protective film or an insulating film, it is possible to improve adhesion to the transparent substrate or film provided in these lower layers.

  The photosensitive resin composition of the present invention comprises (A) a photopolymerizable monomer, (B) a transparent resin, (C) a photopolymerization initiator, (D) a solvent, (E) a silane coupling agent, and (F). It is a photosensitive resin composition containing water, wherein the (F) water is contained in an amount of 5.0 to 18.0% by mass with respect to the total amount of the (E) silane coupling agent.

"(A) Photopolymerizable monomer"
(A) The photopolymerizable monomer is not particularly limited as long as it can be crosslinked by light, and a photopolymerizable monomer used in a general photosensitive resin composition may be used. it can. The photosensitive resin composition of the present invention contains (A) a photopolymerizable monomer and (C) a photopolymerization initiator, which will be described later. Alternatively, (A) a photopolymerizable monomer and a transparent resin (B) described later are polymerized, whereby a film made of the composition can be cured well. Also, by irradiating with light through a mask, the physical properties and solubility in the developer differ between the portion irradiated with light (exposed portion) and the portion not irradiated with light (unexposed portion). Thus, a pattern can be obtained satisfactorily.

  In the present invention, “light” is a concept including not only visible light but also infrared rays, ultraviolet rays, and various types of radiation (X-rays, γ-rays, electron beams, etc.). The monomer is preferably one that is favorably polymerized by various light rays described below.

  (A) Specifically, as a photopolymerizable monomer, 1,9-nonanediol diacrylate, EO (ethylene oxide) modified bisphenol A diacrylate, PO (propylene oxide) modified bisphenol A diacrylate, EO modified bisphenol F diacrylate , ECH (epichlorohydrin) modified phthalic diacrylate, PO modified glycerol triacrylate, EO modified trimethylolpropane triacrylate, PO modified trimethylolpropane triacrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide adduct of trimethylolpropane Tri (meth) acrylate, trimethylolpropane propylene oxide adduct tri (meth) acrylate, trimethylolethanetri (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetra (meth) acrylate of pentaerythritol ethylene oxide adduct, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Penta (meth) acrylate of ethylene oxide adduct of dipentaerythritol, penta (meth) acrylate of caprolactone adduct of dipentaerythritol, tripentaerythritol poly (meth) acrylate, glycerol tri (meth) acrylate, ethylene oxide addition of glycerol And tri (meth) acrylate of the product, dipentaerythritol hexa (meth) acrylate, and the like.

  (A) Only 1 type may be used for a photopolymerizable monomer and it may use 2 or more types together. Although the content rate of (A) photopolymerizable monomer in the photosensitive resin composition of this invention is not specifically limited, (A) photopolymerizable monomer is 30 with respect to 100 mass parts of (B) transparent resin. It is preferable that it is -150 mass parts, It is more preferable that it is 30-100 mass parts, It is further more preferable that it is 40-80 mass parts. By setting it as 30 mass parts or more, the developability and sensitivity at the time of pattern processing can be improved especially, and by setting it as 150 mass parts or less, adhesiveness with the inorganic material surface can be made especially favorable.

"(B) Transparent resin"
(B) As monomers applicable to the transparent resin, o-, m-, p-vinylbenzoic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, mesaconic acid, itaconic acid, crotonic acid , (Meth) acryloyloxyethyl monosuccinate, (meth) acryloyloxyethyl monotetrahydrophthalate, (meth) acrylic acid, (meth) acryloyloxyethyl monophthalate, (meth) acryloyloxyethyl monohexahydrophthalate, (meth) Carboxyl group-containing monomers such as caprolactone adducts of acrylic acid; hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; (meth) acrylamide, Amide group-containing monomers such as toximethylol (meth) acrylamide; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth And alkyl acrylates such as acrylate and t-butyl (meth) acrylate. In the present invention, “(meth) acrylic acid” and “(meth) acrylate” collectively refer to both acrylic acid and methacrylic acid.
Among these, carboxyl groups such as (meth) acrylic acid, (meth) acryloylethyl monophthalate, (meth) acryloylethyl monohexahydrophthalate, (meth) acryloylethyl monotetrahydrophthalate, caprolactone adducts of (meth) acrylic acid, etc. It is preferable to use a carboxyl group-containing monomer such as a monomer.
Furthermore, a copolymer using two or more of the above-described monomers may be used as a transparent resin.

"(C) Photopolymerization initiator"
(C) Examples of the photopolymerization initiator include acetophenone, 2,2′-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone and the like. Acetophenones; benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone, 2-chloro Sulfur compounds such as thioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; benzyldimethyl ketal 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2 -Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) Alkylphenones such as -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 1,2-octanedi ON, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, Oxime esters such as 1- (0-acetyloxime); anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; 2,4-trichloromethyl- (4 '-Methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxynaphthyl) -6-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl And triazines such as-(4'-methoxystyryl) -6-triazine.

  (C) A photoinitiator may use only 1 type and may use 2 or more types together. Although the content rate of (C) photoinitiator in the photosensitive resin composition of this invention is not specifically limited, (C) Photoinitiator is 5 with respect to 100 mass parts of (B) transparent resin. It is preferably ˜20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 5 to 10 parts by mass. By setting it as 5 mass parts or more, the sensitivity at the time of pattern processing can be improved especially, and transparency can be made especially favorable by setting it as 20 mass parts or less.

"(D) Solvent"
(D) As a solvent, methanol, ethanol, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve, methyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n-amyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, ethylene glycol Butyl ether acetate, triethylene glycol, triethylin glycol monomethyl ether, triethylin glycol monomethyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether Examples include acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether acetate, lactic acid ester, methyl methoxypropionate, and ethyl ethoxypropionate.

(D) Only 1 type may be used for a solvent and it may use 2 or more types together.
Moreover, although the content rate of the (D) solvent in the photosensitive resin composition of this invention is not specifically limited, It uses so that the solid content rate in all the photosensitive resin compositions may be 20-30 mass%. Is preferred. By setting the solid content ratio within the above range, the viscosity of the photosensitive resin composition can be made moderate, and the coating property when forming a film by coating on an inorganic material (substrate) is particularly high. improves.

"(E) Silane coupling agent"
(E) The silane coupling agent is not particularly limited, and a silane coupling agent used for improving adhesion with an inorganic base material or an organic material as a base can be used.
(E) Specific examples of the silane coupling agent include vinylmethoxysilane, vinylethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxy. Silane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Acryloxypropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like.
Among these, the (E) silane coupling agent in the present invention includes methacryloxy-based or acryloxy-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacrylic. Roxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane are more preferable.

(E) Although the content rate of a silane coupling agent is not specifically limited, It is preferable that it is 1.0-5.0 mass% in the total amount of all the solid content. When the content ratio of the silane coupling agent is less than 1.0% by mass, sufficient adhesion cannot be obtained because the bond between the organic substance in the composition and the inorganic substrate such as hydrogen bond or chemical bond is weak.
Moreover, only 1 type may be used for a silane coupling agent and it may use 2 or more types together.

“(F) Moisture”
In the photosensitive resin composition of the present invention, it is preferable to add moisture so that (E) moisture is contained in an amount of 5.0 to 18.0 mass% with respect to the total amount of (E) the silane coupling agent. Here, when the moisture content is less than 5.0% by mass with respect to the total amount of the silane coupling agent, the adhesion of the photosensitive resin composition to the substrate is not preferable. On the other hand, when the water content exceeds 18.0% by mass with respect to the total amount of the silane coupling agent, it is not preferable because white turbidity occurs in the photosensitive resin composition and the transparency is impaired. On the other hand, if the water content is within the above range, the photosensitive resin composition is excellent in transparency and can provide a cured film excellent in adhesion to the surface of the inorganic material even after chemical treatment. It becomes.

By the way, in the cured film obtained by hardening the conventional photosensitive resin composition, there existed a subject that sufficient adhesive force was not acquired between the inorganic material surfaces under acidic conditions.
On the other hand, according to the photosensitive resin composition of the present invention, 5.0 to 18.0 mass relative to the total amount of (E) silane coupling agent and the silane coupling agent in the photosensitive resin composition. % (F) moisture. As a result, the silane coupling agent is hydrolyzed to produce silanol, and the bonding strength with the substrate is increased, so that a cured film having excellent adhesion to the surface of the inorganic material can be obtained even under acidic conditions.

  The photosensitive resin composition of the present invention described above can be used as a touch panel material. Specifically, a film containing the photosensitive resin composition of the present invention is formed by applying a material for a touch panel containing the photosensitive resin composition of the present invention on a substrate and irradiating and curing the light. be able to. Moreover, it is also possible to pattern-process the film | membrane containing the photosensitive resin composition of this invention by irradiating light through a mask, developing, and heat-processing as needed.

  Since the film | membrane formed by hardening the photosensitive resin composition of this invention is excellent in transparency, it can be used suitably as a film | membrane for touchscreens. Although the use in a touch panel is not specifically limited, It is preferable to use as a protective film or insulating film for touch panels especially, and it is especially preferable to be used as a touch panel protective film. Since the film | membrane formed by hardening the photosensitive resin composition of this invention is excellent in transparency, it can be used suitably for a touchscreen use.

  Since the touch panel protective film and the touch panel insulating film obtained by curing the photosensitive resin composition of the present invention adhere well to the surface of the inorganic material layer, the touch panel protective film and the touch panel insulating film are formed on the surface of the underlying inorganic material layer. In this case, the mechanical strength can be increased. In addition, since the touch panel protective film and the touch panel insulating film of the present invention have chemical resistance, they can function well even when these films are exposed to chemicals in the touch panel manufacturing process.

  The type of touch panel using the photosensitive resin composition of the present invention is not particularly limited, but is preferably a capacitive touch panel, and particularly preferably a capacitive and projection touch panel. .

  One configuration of a capacitive (projection type) touch panel using the photosensitive resin composition of the present invention will be described in detail below. In addition, the touch panel of this invention is not limited to the following structures, unless the summary is exceeded.

FIG. 1 is a cross-sectional view showing a main part of a touch panel according to an example of the present invention, and FIG. 2 is a plan view showing the main part of the touch panel of the present invention through a protective film.
The touch panel of the present invention has a transparent electrode or a metal electrode 5 on the substrate 1 for connecting a transparent electrode 2, a metal wiring 3, an insulating film 4, and an array perpendicular to the pattern conducting with the transparent electrode 2. The insulating film 4 is disposed in order to prevent conduction between both patterns when connecting a pattern in an array orthogonal to the conduction pattern formed by the transparent electrode 2. The touch panel of the present invention can further have a protective film 6.

  Although it does not specifically limit as the board | substrate 1, For example, glass plates, such as a soda lime glass, a low alkali borosilicate glass, an alkali free alumino borosilicate glass, or a polyethylene terephthalate (PET), a triacetyl cellulose (TAC) Plastic plates and plastic films made of polymethyl methacrylate (PMMA), polycarbonate (PC), or the like are used.

  The transparent electrode 2 is not particularly limited as long as it can be disposed on the surface of the substrate 1. However, an inorganic conductive material such as ITO (indium tin oxide) or ZnO (zinc oxide), PEDOT / PSS Organic conductive materials such as (polyethylenedioxythiophene / polystyrene sulfonic acid), polyaniline, and polypyrrole can be used. These materials may be used alone or in combination of two or more. Among these, it is preferable to use ITO as the transparent electrode 2.

  As the metal wiring 3, a metal material such as Mo (molybdenum), Al (aluminum), Ag (silver), or Pd (palladium) can be used, and it is preferable to use one or more of Mo and Al. As the electrode (transparent electrode or metal electrode) 5, the same material as the material of the transparent electrode 2 or the metal wiring 3 can be used.

  In the touch panel of the present invention, at least one of the insulating film 4 and the protective film 6 is formed by curing a touch panel material containing the photosensitive resin composition of the present invention. Either one may be formed using a known material conventionally used for an insulating film or a protective film, but both the insulating film 4 and the protective film 6 are obtained by curing the touch panel material of the present invention. It is preferable. By using the touch panel material of the present invention for a capacitive and projection touch panel, a touch panel having the above-described effects can be obtained.

In the capacitive and projection touch panel, the method of forming a film made of the touch panel material of the present invention is not particularly limited. For example, the lower layer (for example, the insulating film 4 is the base material 1). In the case of the transparent electrode 2 and the protective film 6, the protective film is applied on the transparent electrode 2, the metal wiring 3 and the metal electrode 5) by a coating method such as spray coating, spin coating, slit die coating, roll coating or bar coating. If it is an insulating film, the dry film thickness is 0.2 to 10 μm, more preferably 0.5 to 5 μm so that the dry film thickness is 0.5 to 20 μm, more preferably 1.0 to 10 μm. The said photosensitive resin composition is apply | coated so that it may become. If necessary, the dried film is exposed through a mask having a predetermined pattern provided in contact with or not in contact with the film. The kind of the light beam at the time of exposure is not particularly limited, and examples thereof include visible light, ultraviolet rays, far infrared rays, electron beams, X-rays, etc. Among them, ultraviolet rays are preferable. Is not particularly limited illuminance of the light beam is preferably 5~150mW / cm ² at 365 nm, and particularly preferably 15~35mW / cm ^2.

  Then, if necessary, it is immersed in an aqueous alkaline developer such as sodium carbonate or sodium hydroxide, or the developer is sprayed by spraying or the like to remove uncured portions and form a desired pattern. Furthermore, in order to accelerate | stimulate superposition | polymerization of the photosensitive composition and to harden | cure, it heats (post-bake) as needed, respectively.

  Examples according to the present invention are shown below. In addition, this invention is not limited to a following example, unless the summary is exceeded.

<Synthesis example>
<Synthesis of copolymer>
A flask equipped with a stirrer was charged with 4 parts by mass of 2,2-azobisisobutyronitrile (AIBN) and 200 parts by mass of cyclohexanone, followed by 25 parts by mass of methacrylic acid, 25 parts by mass of glycidyl (meth) acrylate, and cyclohexylmaleimide 50. After charging a part by mass and substituting with nitrogen, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 8 hours for reaction.
Subsequently, the temperature of the reaction solution was lowered to room temperature to obtain a polymer solution containing the copolymer (solid content concentration = 30.0 mass%). According to gel permeation chromatography, the copolymer had a molecular weight of 5,000. This copolymer is referred to as “(B) transparent resin”.

<Comparative Example 1>
<Preparation of photosensitive resin composition>
(A) 50 parts by mass of tricyclodecane dimethanol dimethacrylate as a photopolymerizable monomer, (B) 100 parts by mass of a copolymer as a transparent resin, (C) 2-methyl-1-as a photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 10 parts by mass, (D) 450 parts by mass of cyclohexanone as a solvent, 150 parts by mass of propylene glycol monomethyl ether acetate, (E) 3 as a silane coupling agent -A photosensitive resin composition was prepared by mixing 5 parts by mass of isocyanatepropyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.).

<Test Example 1>
<Preparation of photosensitive resin composition>
(A) 50 parts by mass of tricyclodecane dimethanol dimethacrylate as a photopolymerizable monomer, (B) 100 parts by mass of a copolymer as a transparent resin, (C) 2-methyl-1-as a photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 10 parts by mass, (D) 450 parts by mass of cyclohexanone as a solvent, 150 parts by mass of propylene glycol monomethyl ether acetate, (E) 3 as a silane coupling agent -Mixing 5 parts by mass of isocyanatepropyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.1 part by mass of water (2.0 parts by mass with respect to the total amount of silane coupling agent) The resin composition was prepared.

<Test Example 2>
<Preparation of photosensitive resin composition>
(A) 50 parts by mass of tricyclodecane dimethanol dimethacrylate as a photopolymerizable monomer, (B) 100 parts by mass of a copolymer as a transparent resin, (C) 2-methyl-1-as a photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 10 parts by mass, (D) 450 parts by mass of cyclohexanone as a solvent, 150 parts by mass of propylene glycol monomethyl ether acetate, (E) 3 as a silane coupling agent -5 parts by mass of isocyanate propyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and (F) 0.15 parts by mass of water (3.0 parts by mass with respect to the total amount of silane coupling agent) The resin composition was prepared.

<Test Example 3>
<Preparation of photosensitive resin composition>
(A) 50 parts by mass of tricyclodecane dimethanol dimethacrylate as a photopolymerizable monomer, (B) 100 parts by mass of a copolymer as a transparent resin, (C) 2-methyl-1-as a photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 10 parts by mass, (D) 450 parts by mass of cyclohexanone as a solvent, 150 parts by mass of propylene glycol monomethyl ether acetate, (E) 3 as a silane coupling agent -5 parts by mass of isocyanate propyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.), (F) 0.25 parts by mass of water (5.0 parts by mass with respect to the total amount of silane coupling agent) The resin composition was prepared.

<Test Example 4>
<Preparation of photosensitive resin composition>
(A) 50 parts by mass of tricyclodecane dimethanol dimethacrylate as a photopolymerizable monomer, (B) 100 parts by mass of a copolymer as a transparent resin, (C) 2-methyl-1-as a photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 10 parts by mass, (D) 450 parts by mass of cyclohexanone as a solvent, 150 parts by mass of propylene glycol monomethyl ether acetate, (E) 3 as a silane coupling agent -5 parts by mass of isocyanatepropyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.), (F) 0.35 parts by mass of moisture (7.0 parts by mass with respect to the total amount of silane coupling agent) The resin composition was prepared.

<Test Example 5>
<Preparation of photosensitive resin composition>
(A) 50 parts by mass of tricyclodecane dimethanol dimethacrylate as a photopolymerizable monomer, (B) 100 parts by mass of a copolymer as a transparent resin, (C) 2-methyl-1-as a photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 10 parts by mass, (D) 450 parts by mass of cyclohexanone as a solvent, 150 parts by mass of propylene glycol monomethyl ether acetate, (E) 3 as a silane coupling agent -5 parts by mass of isocyanate propyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.), (F) 0.5 parts by mass of water (10.0 parts by mass with respect to the total amount of silane coupling agent) are mixed, and photosensitive The resin composition was prepared.

<Test Example 6>
<Preparation of photosensitive resin composition>
(A) 50 parts by mass of tricyclodecane dimethanol dimethacrylate as a photopolymerizable monomer, (B) 100 parts by mass of a copolymer as a transparent resin, (C) 2-methyl-1-as a photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 10 parts by mass, (D) 450 parts by mass of cyclohexanone as a solvent, 150 parts by mass of propylene glycol monomethyl ether acetate, (E) 3 as a silane coupling agent -5 parts by mass of isocyanate propyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.7 parts by mass of water (14.0 parts by mass with respect to the total amount of silane coupling agent) The resin composition was prepared.

<Test Example 7>
<Preparation of photosensitive resin composition>
(A) 50 parts by mass of tricyclodecane dimethanol dimethacrylate as a photopolymerizable monomer, (B) 100 parts by mass of a copolymer as a transparent resin, (C) 2-methyl-1-as a photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 10 parts by mass, (D) 450 parts by mass of cyclohexanone as a solvent, 150 parts by mass of propylene glycol monomethyl ether acetate, (E) 3 as a silane coupling agent -5 parts by mass of isocyanate propyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.9 part by mass of (F) moisture (18.0 parts by mass with respect to the total amount of silane coupling agent), The resin composition was prepared.

<Test Example 8>
<Preparation of photosensitive resin composition>
(A) 50 parts by mass of tricyclodecane dimethanol dimethacrylate as a photopolymerizable monomer, (B) 100 parts by mass of a copolymer as a transparent resin, (C) 2-methyl-1-as a photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 10 parts by mass, (D) 450 parts by mass of cyclohexanone as a solvent, 150 parts by mass of propylene glycol monomethyl ether acetate, (E) 3 as a silane coupling agent -5 parts by mass of isocyanate propyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and (F) 1.0 part by mass of water (20.0 parts by mass with respect to the total amount of silane coupling agent) The resin composition was prepared.

(1) Acid resistance adhesion evaluation The photosensitive resin composition was applied onto three types of substrates, a soda-lime glass substrate, a substrate having an ITO film, and a substrate having a molybdenum film, by a spin coating method. A coating film was formed by pre-baking on a hot plate for 1 minute and irradiated with 150 mJ / cm ² of light from an ultrahigh pressure mercury lamp (illuminance at 365 nm: 30 mW / cm ² ). Thereafter, development was performed with an alkali developer for 60 seconds, and heating was performed at 235 ° C. for 20 minutes to prepare a coated substrate having a thickness of 2.0 μm.
The substrate having the coating film thus prepared was immersed in a mixed aqueous solution of phosphoric acid and nitric acid at 43 ° C. for 5 minutes. The substrate after immersion was washed with water and dried, and then the adhesion of the coating film was evaluated by the cross-cut method of JIS K5600-5-6. The ratio of the area of the remaining coating film in 100 grids was shown.
The evaluation criteria were “基準” when there was no film peeling, “◯” when almost no peeling was seen, and “Δ” when some peeling was seen. The results are shown in Table 1.

(2) Evaluation of white turbidity of photosensitive resin composition When water is added to a silane coupling agent or a photosensitive resin composition containing the silane coupling agent, a phenomenon of white turbidity occurs and it cannot be used as a composition material. Therefore, the evaluation criteria was “Yes” when white turbidity occurred, and “No” when no turbidity occurred. The results are shown in Table 1.

<Evaluation results>
As shown in Table 1, from the results of Test Examples 3 to 7, the water content is 5 to 18% based on the total amount of the silane coupling agent (0.25 to 0.9% based on the total amount of the photosensitive resin composition). It was found that the acid resistance adhesion was improved. However, if the moisture content is less than this range, the adhesiveness deteriorates (Test Examples 1 and 2), and if it is too much, the photosensitive resin composition becomes cloudy (Test Example 8). confirmed.

  It should be noted that the acid resistance adhesion is improved by incorporating moisture in the photosensitive resin composition containing the silane coupling agent because the silane coupling agent is hydrolyzed to produce silanol, It is assumed that this is due to an increase in binding force.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Transparent electrode 3 ... Metal electrode 4 ... Insulating film 5 ... Electrode 6 ... Protective film

Claims (10)

(A) A photopolymerizable monomer, (B) a transparent resin, (C) a photopolymerization initiator, (D) a solvent, and (E) a photosensitive resin composition containing a silane coupling agent,
(E) The adjustment method of the photosensitive resin composition characterized by adding 5.0 to 18.0 mass% of water | moisture content with respect to the total amount of a silane coupling agent.   The content ratio of said (E) silane coupling agent is 1.0-5.0 mass% with respect to the total amount of all the solid content, Adjustment of the photosensitive resin composition of Claim 1 characterized by the above-mentioned. Method.   The method for adjusting a photosensitive resin composition according to claim 1 or 2, wherein the (E) silane coupling agent is a methacryloxy-based or acryloxy-based silane coupling agent.   The method for adjusting a photosensitive resin composition according to any one of claims 1 to 3, wherein the transparent resin (B) is a copolymer.   A photosensitive resin composition obtained by the method for preparing a photosensitive resin composition according to any one of claims 1 to 4. A photosensitive resin composition comprising (A) a photopolymerizable monomer, (B) a transparent resin, (C) a photopolymerization initiator, (D) a solvent, (E) a silane coupling agent, and (F) moisture. ,
(E) The photosensitive resin composition characterized by including the said (F) moisture 5.0-18.0 mass% with respect to the total amount of the said silane coupling agent.   The material for touchscreens containing the photosensitive resin composition of Claim 5 or 6.   A touch panel protective film obtained by curing the photosensitive resin composition according to claim 5.   A touch panel insulating film obtained by curing the photosensitive resin composition according to claim 5.   A touch panel produced using at least one of the touch panel protective film according to claim 8 or the touch panel insulating film according to claim 9.

Images