JP2011232584A - Photosensitive resin composition and insulating film for touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which shows high hardness, excellent adhesion to base material or backing, good electric characteristics including low permittivity and low dielectric tangent, a high permeability, and particularly a high permeability in the vicinity of a wavelength of 400 nm.SOLUTION: The above-described problem is solved by a photosensitive resin composition which contains a resin (A), a photopolymerization initiator (B), and an antioxidant (C), with the resin (A) containing a resin (A1) prepared by copolymerizing a compound (a1) expressed by formula (1) and another compound (a2) copolymerizable with the compound (a1).

Description

  The present invention relates to a photosensitive resin composition and an insulating film for a touch panel using the same.

  In recent years, as electronic devices have become more sophisticated, diversified, and smaller and lighter, a transparent touch panel is mounted on the front surface of a display element such as a liquid crystal, and characters, symbols, patterns, etc. displayed on the display element through this transparent touch panel There are an increasing number of devices that perform visual recognition and selection, and switch each function of the device by operating a transparent touch panel.

  The touch panel is, for example, a bank ATM, a vending machine, a personal digital assistant (PDA, UMPC), a copier, a facsimile, a portable game machine, a guide board, a car navigation, a multimedia station (a multifunction terminal installed in a convenience store) ), And rapidly becoming widespread as input devices such as mobile phones, railway vehicle monitoring devices, and answering devices such as quiz programs.

Existing touch panel systems can be classified into a resistive film system, an optical system, an electrostatic capacity system, an ultrasonic system, a pressure system, an electromagnetic wave induction system, an image recognition system, a vibration detection system, and the like.
Specific examples of a touch panel arranged on a display device such as a liquid crystal include a resistance film method and a capacitance method. The resistance film method is a method of detecting a pressed position by voltage, and a capacitance method. Detects the position by capturing the change in capacitance caused by pressing.
As for the electrostatic capacity method, Patent Documents 1 to 3 and the like are disclosed, and an insulating film and a protective film are provided in the laminated structure in order to prevent erroneous recognition of a contact position.

  The performance required for this insulating film and protective film is as follows: Adhesion with substrates, bases, and other layers (glass, inorganic materials, metal materials, transparent electrodes such as ITO, organic materials, etc.) In addition, low dielectric constant and dielectric loss tangent are required in order to obtain the transmittance of the liquid crystal display, and further, drive stability and high-speed response as a touch panel.

JP 2008-65748 A JP 2009-15490 A JP 2010-44453 A

  An object of the present invention is to have high hardness, good adhesion to a base material, an underlayer, etc., low dielectric constant and dielectric loss tangent, good electrical characteristics, high transmittance, especially transmittance around 400 nm wavelength. It aims at providing the photosensitive resin composition with high.

[一般式（１）中、Ｒ¹およびＲ²は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。] As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventor has found that a photosensitive resin composition containing the materials described below can solve the above-mentioned problems, leading to the present invention.
That is, the present invention is a photosensitive resin composition containing a resin (A), a photopolymerization initiator (B), and an antioxidant (C), wherein the resin (A) is represented by the following general formula (1). And a resin (A1) obtained by copolymerizing the compound (a1) represented by (2) and another compound (a2) copolymerizable with the compound (a1). .
General formula (1):

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. ]

  Further, the present invention is characterized in that the antioxidant (C) is any compound selected from the group consisting of a hindered phenol-based antioxidant, a hindered amine-based antioxidant, and a phosphorus-based antioxidant. The present invention relates to the photosensitive resin composition.

  The present invention also relates to the photosensitive resin composition, wherein the resin (A) further contains a thermosetting resin (A2).

[一般式（２）中、Ｒ^３〜Ｒ^８は、独立して水素原子、または−ＣＨ₂ＯＨ、−ＣＨ₂ＯＣＨ₃、および−ＣＨ₂ＯＣ₄Ｈ₉からなる群より選ばれるいずれかの置換基を表す。] In the present invention, the photosensitive resin is characterized in that the thermosetting resin (A2) is a mixture of a thermosetting melamine compound represented by the following general formula (2) and / or a partial condensate thereof. Relates to the composition.
General formula (2):

[In General Formula (2), R ^{3 to} R ⁸ are each independently a hydrogen atom, or any one selected from the group consisting of —CH ₂ OH, —CH ₂ OCH ₃ , and —CH ₂ OC ₄ H ₉ . Represents a substituent. ]

  In the present invention, the ratio ([C] / [A2]) of the weight [C] of the antioxidant (C) to the weight [A2] of the thermosetting resin (A2) is 0.005 to 0.00. It is related with the said photosensitive resin composition characterized by being 1.

  In the present invention, the photopolymerization initiator (B) is at least one compound selected from the group consisting of an acetophenone photopolymerization initiator and an oxime ester photopolymerization initiator. The present invention relates to a resin composition.

  The present invention also provides that the photopolymerization initiator (B) is 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and / or 1,2-octadion-1- [4- ( Phenylthio)-, 2- (o-benzoyloxime)]. The present invention relates to the photosensitive resin composition.

  Moreover, this invention relates to the said photosensitive resin composition characterized by including an adhesion promotion additive (E) further.

  Moreover, this invention relates to the insulating film for touchscreens formed using the said photosensitive resin composition.

  The photosensitive resin composition of the present invention has high hardness and good adhesion to a substrate and a base, and has high transmittance, particularly high transmittance around a wavelength of 400 nm, and further has a dielectric constant and a dielectric loss tangent. It is suitable for use as an insulating film for a touch panel because of its low and good electrical characteristics.

First, the photosensitive resin composition of the present invention will be described.
The photosensitive resin composition of the present invention is a photosensitive resin composition containing a resin (A), a photopolymerization initiator (B), and an antioxidant (C), and the resin (A) is: It includes a resin (A1) obtained by copolymerizing the compound (a1) represented by the general formula (1) and another compound (a2) copolymerizable with the compound (a1).

<Resin (A)>
In the photosensitive resin composition of the present invention, the resin (A) is obtained by copolymerizing a compound (a1) represented by the following general formula (1) and another compound (a2) copolymerizable with the compound (a1). It is characterized by including resin (A1) formed.

[一般式（１）中、Ｒ¹およびＲ²は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。] (Resin (A1) obtained by copolymerizing compound (a1) represented by general formula (1) and other compound (a2) polymerizable with compound (a1)
The resin (A1) is a resin obtained by copolymerizing a compound (a1) represented by the following general formula (1) and another compound (a2) polymerizable with the compound (a1).
General formula (1):

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. ]

In the general formula (1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited. For example, methyl, ethyl, n Linear or branched alkyl groups such as -propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl , Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as; Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ¹ and R ² may be the same type of substituent or different substituents.

[Compound (a1)]
Specific examples of the compound (a1) include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, Di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n- Butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2 , 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoate Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis (methylene)] Bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t-butyl Chlohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ' -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred, and may be one kind or two or more kinds. Good.

  The ratio of the compound (a1) in the monomer component in obtaining the resin (A1) is not particularly limited, but is 2 to 60% by weight, preferably 5 to 55% by weight, more preferably all monomer components. It should be 5 to 50% by weight. If the amount of the compound (a1) is too large, it may be difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, the transparency and heat resistance may be increased. There is a possibility that the performance of the coating film becomes insufficient.

[Compound (a2)]
The other compound (a2) is not particularly limited as long as it can be polymerized with the compound (a1). Among them, a monomer for introducing an acid group and a radical polymerizable double bond are introduced. Monomers and side chain cyclic ether-containing monomers are preferred.

-Monomer for introducing an acid group The resin (A1) is preferably a polymer having an acid group. Thus, the resulting curable resin composition is a curable resin composition capable of a crosslinking reaction (hereinafter abbreviated as acid-epoxy curing) utilizing the fact that an ester bond is generated by the reaction of an acid group and an epoxy group. Alternatively, the uncured portion can be made a composition that can be developed with an alkali developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.

  In order to introduce an acid group into the resin (A1), for example, a monomer having an acid group and / or a monomer capable of giving an acid group after polymerization (hereinafter also referred to as “monomer for introducing an acid group”). May be polymerized as a monomer component. In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  Examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these. Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types.

When the monomer component for obtaining the resin (A1) also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but is 5 to 70% by weight in the total monomer components. Preferably, it is 10 to 60% by weight.
The resin (A1) may be a polymer having a radical polymerizable double bond.

-Monomer for introducing radical polymerizable double bond In order to introduce a radical polymerizable double bond into the resin (A1), for example, a treatment such as method (i) or method (ii) described later is performed. Just do it.
<< Method (i) >>
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having a radical polymerizable double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to form a radical polymerizable double bond and an acid group (carboxyl group). ).

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when etrahydrophthalic anhydride or maleic anhydride having a radical polymerizable double bond is used as the polybasic acid anhydride, the radical polymerizable double bond can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce a radical polymerizable double bond and an acid group (carboxyl group).

<< Method (ii) >>
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

-Side-chain cyclic ether-containing monomer The side-chain cyclic ether-containing monomer contains, for example, at least one skeleton selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton. Is an unsaturated compound.
Examples of the tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth) acrylic acid tetrahydrofuran-3-yl ester, and the like;
Examples of the furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, and 1-furan. 2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furyl) -6-methyl-1-hepten-3-one, and the like;
Examples of the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. 2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like;
Examples of the pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone and 4- (1,5-dioxa-6-oxo-7-octenyl) -6. -Methyl-2-pyrone and the like;
Examples of the lactone skeleton include 2-propenoic acid 2-methyl-tetrahydro-2-oxo-3-furanyl ester, 2-propenoic acid 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2- Yl ester, 2-propenoic acid 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-yl ester, 2-propenoic acid 2-methyl-tetrahydro-2-oxo- 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro [3,2-b]- 6-yl ester, 2-propenoic acid 2-methyl-2- (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-propenoic acid 2-methyl ester Ru-decahydro-8-oxo-5,9-methano-2H-furo [3,4-g] -1-benzopyran-2-yl ester, 2-propenoic acid 2-methyl-2-[(hexahydro-2- Oxo-3,5-methano-2H-cyclopenta [b] furan-6-yl) oxy] ethyl ester, 2-propenoic acid 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl And 2-propenoic acid 2-methyl-2-oxy-1-oxaspiro [4.5] dec-8-yl ester.
Among these, tetrahydrofurfuryl (meth) acrylate is preferable from the viewpoint of coloring, pigment dispersibility, and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.

  The ratio of the side-chain cyclic ether-containing monomer in the monomer component when obtaining the resin (A1) is not particularly limited, but is 10 to 80% by weight, preferably 20 to 20% in all monomer components. 70% by weight, more preferably 30 to 60% by weight. If the amount of the side chain type cyclic ether-containing monomer is too large, the hydrophilicity becomes too strong and the surface may be whitened during alkali development, the pattern may be lost, or the adhesion to the glass may be reduced. On the other hand, if the amount is too small, performance such as dispersibility of the pigment may be insufficient.

Other copolymerizable monomers Examples of the other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth ) Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as benzyl acrylate and 2-hydroxyethyl (meth) acrylate; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-phenylmaleimide, N-cyclohexylmaleimide and the like N-substituted maleimides; butadiene or substituted butadiene compounds such as butadiene and isoprene; Emissions, propylene, vinyl chloride, ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. In particular, when used as a dispersant, these other copolymerizable monomers may be used alone or in combination of two or more.

  The resin (A1) can be easily obtained by polymerizing the monomer component essentially comprising at least the compound (a1). At this time, the cyclization reaction of the compound (a1) proceeds simultaneously with polymerization to form a tetrahydrofuran ring structure.

  The method for the polymerization reaction of the monomer component is not particularly limited, and various conventionally known polymerization methods can be employed, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. Depending on the molecular weight of the target polymer, the polymerization temperature is preferably 40 to 150 ° C. and the polymerization concentration is 5 to 50%, and more preferably, the polymerization temperature is 60 to 130 ° C. and the polymerization concentration is 10 to 40%. It is good to do.

By adding the resin (A1), it is possible to obtain a coating film that has good adhesion to a substrate, a base, and the like, has low dielectric constant and dielectric loss tangent, and good electrical characteristics.
The resin (A1) is preferably used in an amount of 20 to 50 parts by weight in a total of 100 parts by weight of the solid content of the photosensitive resin composition. When the amount of the resin (A1) is less than 20 parts by weight, a sufficient adhesion improving effect cannot be obtained. When the amount of the resin (A1) is more than 50 parts by weight, the content of the photocuring component is decreased, and the coating film has a sufficient hardness. It is difficult to get.

(Thermosetting resin (A2))
In the present invention, the resin (A) preferably further contains a thermosetting resin (A2).
As a thermosetting resin (A2), an epoxy compound and a melamine compound are mentioned, for example.

  The epoxy compound may be a low molecular compound or a high molecular compound, and representative examples include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac epoxy. Resins, cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxy resins such as epoxidized oil; brominated derivatives of the above epoxy resins, tris (glycidylphenyl) methane, Triglycidyl isocyanurate etc. are mentioned. Among them, bisphenyl A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, cycloaliphatic type epoxy resin, glycidyl ester type resin, glycidylamine type resin, tris (glycidylphenyl) methane This is preferable in that the cured density is high and the adverse effect on the developability of the colored composition is small.

Examples of the melamine compound include melamine in which 1 to 6 hydrogens of amino group (—NH ₂ ) are methylolated, and a water-soluble melamine resin consisting of a quantifier thereof, such as Sumitomo Chemical Co., Ltd. “Smitex Resin” or methylol. Melamine whose group is esterified with C1-4 aliphatic alcohol, and oil-soluble melamine resin consisting of its quantity, such as Dainippon Ink & Chemicals Co., Ltd. "Super Becamine", or polyester resin and acrylic resin as melamine resin Cross-linked with

[一般式（２）中、Ｒ^３〜Ｒ^８は、独立して水素原子、または−ＣＨ₂ＯＨ、−ＣＨ₂ＯＣＨ₃、および−ＣＨ₂ＯＣ₄Ｈ₉からなる群より選ばれるいずれかの置換基を表す。] Among them, a thermosetting melamine compound represented by the following general formula (2) and / or a mixture of partial condensates thereof (thermosetting melamine compound, a mixture of partial condensates thereof, or a thermosetting melamine compound and partial condensation thereof) It is preferable that the hardness of the coating film can be increased.
General formula (2):

[In General Formula (2), R ^{3 to} R ⁸ are each independently a hydrogen atom, or any one selected from the group consisting of —CH ₂ OH, —CH ₂ OCH ₃ , and —CH ₂ OC ₄ H ₉ . Represents a substituent. ]

Examples of the mixture of the thermosetting melamine compound represented by the general formula (2) and / or a partial condensate thereof include the following commercially available products.
Products in which R ^{3 to} R ⁸ are CH ₂ OCH ₃ include Nicarak MW-30M, Nicarak MW-30, Nicarac MW-22, Nicarac MW-21 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 300 , Cymel 301, Cymel 303, and Cymel 350 (manufactured by Nihon Cytec Industries, Inc.) such as R ^{3 to} R ⁸ are CH ₂ OH, Nicalac MS-11, R ^{3 to} R ⁸ are CH ₂ OCH ₃ and CH ₂ OC ₄ H ₉ products include Nikarak MX-45, Nikarak MX-500, Nikarak MX-520, Nikarak MX-43 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 232, Cymel 235, Cymel 236 , And Cymel 238 (manufactured by Nippon Cytec Industries, Inc.), etc., R ^{3 to} R ⁸ are products of CH ₂ OC ₄ H ₉ , Cymel 506 (manufactured by Nippon Cytec Industries, Inc.) And a mixture of hexamethylol melamine full alkyl ether compounds and / or partial condensates thereof (average polymerization degree is 1 to 2).

By adding the thermosetting resin (A2), a coating film having a high hardness can be obtained by reacting during the heating step and forming a network-like coating film structure.
The thermosetting resin (A2) is preferably used in an amount of 3 to 30 parts by weight in a total of 100 parts by weight of the solid content of the photosensitive resin composition. When the thermosetting resin (A2) is less than 3 parts by weight, a sufficient effect of improving the hardness cannot be obtained, and when it is more than 30 parts by weight, the transmittance is significantly lowered due to yellowing of the resin.

(Other resins (A3))
The photosensitive resin composition of the present invention comprises a resin (A1) obtained by copolymerizing the compound (a1) represented by the general formula (1) and another compound (a2) that can be polymerized with the compound (a1), and heat. In addition to the curable resin (A2), other resins (A3) may be included.
The other resin is preferably a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm. Other resins include thermoplastic resins and active energy ray curable resins, and these can be used alone or in admixture of two or more.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  Active energy ray-curable resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. Or a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced by reacting with or cinnamic acid is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

<Photoinitiator (B)>
Examples of the photopolymerization initiator (B) contained in the photosensitive resin composition of the present invention include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2. -Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [ Acetophenone photopolymerization initiators such as 4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime) ], Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyl) Oxime ester photopolymerization initiators such as oxime), benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 -Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichlorome ) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s- Triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) Triazine photopolymerization initiators such as -6-triazine and 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization Initiator, imidazole-based photopolymerization initiator, or the like are used.

Of these, acetophenone-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferable because of high sensitivity, a small amount of addition, and high transmittance.
Among acetophenone photopolymerization initiators and oxime ester photopolymerization initiators, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 1,2-octadion-1- [4- (Phenylthio)-, 2- (o-benzoyloxime)] is a photosensitive resin composition having a high transmittance as a protective film, particularly having a high transmittance in the vicinity of a wavelength of 400 nm, because it does not turn yellow during the heating step. Is more preferable.
The photopolymerization initiator is preferably used in an amount of 1 to 30 parts by weight in a total of 100 parts by weight of the solid content of the photosensitive resin composition.

The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.
The sensitizer can be used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

<Antioxidant (C)>
The photosensitive resin composition of the present invention contains an antioxidant (C) in order to increase the transmittance of the coating film.
Antioxidant (C) is that the photopolymerization initiator (B) and thermosetting resin (A2) contained in the photosensitive resin composition are oxidized and yellowed by a thermal process during thermal curing and ITO annealing. In order to prevent this, the transmittance of the coating film can be increased.
Preferable examples of the antioxidant (C) include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfide-based antioxidants. More preferred are hindered phenol antioxidants, hindered amine antioxidants, and phosphorus antioxidants.
One type or two or more types can be used in combination.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- And di-t-butylanilino) -1,3,5-triazine.

  In the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4- Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4 -Butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) Mino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2 , 6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4 Polycondensates with -hydroxy-2,2,6,6-tetramethylpiperidine and N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine.

  Phosphorus antioxidants include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2- Yl) oxy] ethyl] amine, and ethylbisbis (2,4-ditert-butyl-6-methylphenyl) phosphite.

  As sulfide-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, and the like can be given.

By adding the antioxidant (C), yellowing due to oxidation during the heating step can be prevented, and high coating film transmittance can be obtained.
The antioxidant (C) is preferably used in an amount of 0.1 to 5 parts by weight in a total of 100 parts by weight of the solid content of the photosensitive resin composition. When the amount of the antioxidant (C) is less than 0.1 weight, the effect of increasing the transmittance is small, and when it is more than 5 parts by weight, the hardness is greatly lowered and the sensitivity of the photosensitive resin composition is greatly decreased.

In order to achieve both the hardness of the coating film and the transmittance of the coating film, the ratio of the weight [C] of the antioxidant (C) to the weight [A2] of the thermosetting resin (A2) ([C] / [A2]) is preferably 0.005 to 0.1.
If it is less than 0.005, the effect of increasing the transmittance by the antioxidant (C) is small, and if it exceeds 0.1, the hardness is greatly reduced, and the sensitivity of the photosensitive resin composition is greatly reduced. In the range of 0.005 to 0.1, a synergistic effect of the photocurability improvement effect by reducing the photopolymerization inhibition by the antioxidant and the hardness improvement effect by the thermosetting resin can be expected, which is preferable.

<Photopolymerizable monomer (D)>
The photosensitive resin composition of the present invention may contain a photopolymerizable monomer (D). As the photopolymerizable monomer, a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers can be used.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, N-vinyl pyrrolidone, and the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 3- And methylpentanediol di (meth) acrylate.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa (meth) acrylate. And caprolactone-modified dipentaerythritol hexaacrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, and the like.
The content of the photopolymerizable monomer (D) is preferably used in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of the solid content of the photosensitive resin composition.

<Adhesion promoting additive (E)>
The photosensitive resin composition of this invention is preferable in order that adhesiveness with a glass base material, ITO, etc. may improve by containing an adhesion promotion additive (E) further.
As adhesion promoting additive (E), vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3 Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxy Examples include silane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane. .
Among these, inclusion of a silane-based additive is preferable because adhesion to a glass substrate or ITO is improved, and 3-glycidoxypropyltrimethoxysilane is particularly preferable.
The adhesion promoting additive is preferably used in an amount of 0.1 to 5 parts by weight in a total of 100 parts by weight of the solid content of the photosensitive resin composition.

<Other ingredients>
In the photosensitive resin composition of the present invention, a solvent, a surfactant, a storage stabilizer and the like can be used as necessary.

<Solvent>
Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o- Xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene Glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monomethyl ether Ter, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone , Cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopro Ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene Glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate Isoamyl acetate, isobutyl acetate, propyl acetate, include dibasic acid esters such as, used alone or in combination.

In consideration of the drying property of the solvent, it is preferable to include a high boiling point solvent of 160 ° C. or higher in die coating or printing methods. For example, 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 1, 3 -Butanediol (bp 203 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 2-methyl-1,3-propanediol (bp 213 ° C.), diisobutyl ketone (bp 168.1 ° C.), ethylene glycol mono Butyl ether (bp 171.2 ° C.), ethylene glycol monohexyl ether (bp 208.1 ° C.), ethylene glycol monobutyl ether acetate (bp 191.5 ° C.), ethylene glycol dibutyl ether (bp 203.3 ° C.), diethylene glycol monomethyl ether (bp 194.0) ℃), Diechi Glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol diethyl ether (bp 188.4 ° C.), diethylene glycol monoisopropyl ether (bp 207.3 ° C.), propylene glycol monobutyl ether (bp 170.2 ° C.), propylene glycol diacetate (bp 190 0.0 ° C.), dipropylene glycol monomethyl ether (bp 187.2 ° C.), dipropylene glycol monoethyl ether (bp 197.8 ° C.), dipropylene glycol monopropyl ether (bp 212.0 ° C.), dipropylene glycol dimethyl ether (bp 175 ° C.) ), Tripropylene glycol monomethyl ether (bp 206.3 ° C.), ethyl 3-ethoxypropionate (bp 169.7 ° C.), 3-methoxybutene Ruacetate (bp 172.5 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), γ-butyrolactone (bp 204 ° C.), N, N-dimethylacetamide (bp 166.1 ° C.), N-methylpyrrolidone (bp 202 ° C), p-chlorotoluene (bp162.0 ° C), o-diethylbenzene (bp183.4 ° C), m-diethylbenzene (bp181.1 ° C), p-diethylbenzene (bp183.8 ° C), o-dichlorobenzene (bp180) 0.5 ° C), m-dichlorobenzene (bp 173.0 ° C), n-butylbenzene (bp183.3 ° C), sec-butylbenzene (bp178.3 ° C), tert-butylbenzene (bp169.1 ° C), cyclo Hexanol (bp 161.1 ° C), cyclohexyl acetate (bp 73 ° C.), include such methylcyclohexanol (bp174 ℃), preferably high-boiling solvent or 160 ° C. 5 to 50 wt% based on the total amount of solvent.
The solvent can be used in an amount of 200 to 4000 parts by weight with respect to 100 parts by weight of the total solid content.

<Surfactant>
Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monododecyl sulfate. Anionic properties such as ethanolamine, triethanolamine dodecyl sulfate, ammonium dodecyl sulfate, monoethanolamine stearate, sodium stearate, sodium dodecyl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Surfactant: Polyoxyethylene oleyl ether, polyoxyethylene dodecyl ether, polyoxyethylene nonylphenyl ether Nonionic surfactants such as tellurium, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts Agent: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, which can be used alone or in admixture of two or more.

<Storage stabilizer>
Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 5 parts by weight in a total of 100 parts by weight of the photosensitive resin composition.

<Production method of photosensitive resin composition>
The photosensitive resin composition of the present invention comprises a resin (A1), a photopolymerization initiator (B), an antioxidant (C), a thermosetting resin (A2) as necessary, and a photopolymerizable monomer. (D) can be obtained by stirring and mixing the adhesion promoting additive (E) and the solvent.
The photosensitive resin composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more, by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove the mixed dust and foreign matter.

<Insulating film for touch panel>
The photosensitive resin composition according to the present invention can be applied to a glass substrate, ITO, metal film, organic film, etc. by spin coating such as spin coating, casting coating such as die coating, coating by roll coating, coating by roll transfer method, etc. To form a coating film.
Moreover, the photosensitive resin composition of this invention may be used for any of an insulating film use, a protective film use, and a flat film use, and also in each use, it may be patterned by photolithography.

  Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

Prior to the examples, the weight average molecular weight of the resin, the polymer concentration in the polymer solution, and the method for measuring the acid value will be described.
(Weight average molecular weight)
It measured by polystyrene conversion using the gel permeation chromatograph measuring apparatus ("Shodex GPC System-21H" Showa Denko make).

(Polymer concentration in polymer solution)
A solution obtained by adding 4 g of acetone to 1 g of the polymer solution was naturally dried at room temperature, further dried under reduced pressure (160 ° C./5 mmHg) for 5 hours, and then allowed to cool in a desiccator, and the weight was measured. Then, the nonvolatile content of the polymer solution was calculated from the weight loss, and this was used as the polymer concentration.

(Acid value)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the polymer solution and stirred to dissolve uniformly. An automatic titrator ("COM-555" Hiranuma Sangyo Co., Ltd.) is used with a 0.1 mol / L KOH aqueous solution as a titrant. And the acid value of the solution was measured. Then, the acid value of the polymer was calculated from the acid value of the solution and the polymer concentration.

Then, the manufacturing method of resin (A1) and other resin (A3) is demonstrated.
<Method for Producing Resin (A1) Copolymerized with Compound (a1) Represented by General Formula (1) and Other Compound (a2) Copolymerizable with Compound (a1)>
(Preparation of resin solution (A1-1))
A separable flask with a cooling tube was prepared as a reaction tank, and 40 parts of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, 12.0 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation), propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as “PGMEA”) 40 A part of which part was well stirred and mixed was prepared, and as a chain transfer agent dropping tank, 8 parts of n-dodecanethiol and 2 parts of PGMEA 3 were thoroughly stirred and mixed.
The reaction vessel was charged with 9 5 parts of PGMEA 3 and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed over 1 35 minutes while maintaining the temperature at 90 ° C. After 60 minutes from the end of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (volume ratio) mixed gas was started. Then, 70 parts of glycidyl methacrylate, 2,2′-methylenebis (4-methyl-6-t-butylphenol) 0. 4 parts, triethylamine 0. 8 parts were charged and allowed to react at 1 10 ° C. for 12 hours. Then, 50 parts of PGMEA1 was added and cooled to room temperature. About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The previously synthesized resin solution had a nonvolatile content of 20% by weight. PGMEA was added to obtain a resin solution (A1-1). The weight average molecular weight of the resin was 18000, and the acid value per solid content was 2 mgKOH / g.

(Preparation of resin solution (A1-2))
In a separable flask with a cooling tube, 100 parts by weight of PGMEA was charged and purged with nitrogen, and then heated to 90 ° C. On the other hand, dimethyl-2,2 ′-[oxybis (methylenebis)]-2-propionate 10.0 parts, cyclohexyl acrylate 40.1 parts, methyl acrylate 28.2 parts, acrylic acid 20.7 parts, 2.0 parts of t-butylperoxy-2-ethylhexanoate and 80 parts of PGMEA were mixed. In addition, 3.1 parts of β-mercaptopropionic acid and 6 parts of PGMEA were mixed in the dropping tank 2. While maintaining the reaction temperature at 90 ° C., dropwise addition was performed from the dropping tanks 1 and 2 to the reaction tank at a constant rate over 2.5 hours. After maintaining the temperature at 90 ° C. for 30 minutes, 0.5 part of t-butylperoxy-2-ethylhexanoate was added, and the reaction was further continued at 90 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours. Once cooled to room temperature, 24.7 parts of glycidyl methacrylate, 0.038 part of 6-t-butyl-2,4-xylenol and 0.38 part of dimethylbenzylamine were added to adjust the oxygen concentration to 7%. -The temperature was raised to 110 ° C while bubbling an air mixed gas, and the reaction was performed for 6 hours. Thereafter, the temperature was raised to 115 ° C. and reacted for 2 hours to complete the reaction, cooled to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, the nonvolatile content was measured, and synthesized first. PGMEA was added to the resin solution so that the nonvolatile content was 20% by weight to obtain a resin solution (A1-2). The weight average molecular weight of the resin was 10,000, and the acid value per solid content was 71 mgKOH / g.

(Preparation of resin solution (A1-3))
In a separable flask with a cooling tube, 100 parts by weight of PGMEA was charged and purged with nitrogen, and then heated to 90 ° C. On the other hand, in the dropping tank 1, 10.0 parts of dimethyl-2,2 ′-[oxybis (methylenebis)]-2-propionate, 40.1 parts of cyclohexyl methacrylate, 28.2 parts of methyl methacrylate, 20.7 parts of acrylic acid, 2.0 parts of t-butylperoxy-2-ethylhexanoate and 80 parts of PGMEA were mixed. In addition, 3.1 parts of β-mercaptopropionic acid and 6 parts of PGMEA were mixed in the dropping tank 2. While maintaining the reaction temperature at 90 ° C., dropwise addition was performed from the dropping tanks 1 and 2 to the reaction tank at a constant rate over 2.5 hours. After maintaining the temperature at 90 ° C. for 30 minutes, 0.5 part of t-butylperoxy-2-ethylhexanoate was added, and the reaction was further continued at 90 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours. Once cooled to room temperature, 24.7 parts of glycidyl methacrylate, 0.038 part of 6-t-butyl-2,4-xylenol and 0.38 part of dimethylbenzylamine were added to adjust the oxygen concentration to 7%. -The temperature was raised to 110 ° C while bubbling air mixed gas, and the reaction was performed for 6 hours. Thereafter, the temperature was raised to 115 ° C. and reacted for 2 hours to complete the reaction, cooled to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, the nonvolatile content was measured, and synthesized first. PGMEA was added to the resin solution so that the nonvolatile content was 20% by weight to obtain a resin solution (A1-3). The weight average molecular weight of the resin was 9000, and the acid value per solid content was 70 mgKOH / g.

(Preparation of resin solution (A1-4))
In a separable flask with a cooling tube, 100 parts by weight of PGMEA was charged and purged with nitrogen, and then heated to 90 ° C. On the other hand, in dropping tank 1, 10.0 parts of dimethyl-2,2 ′-[oxybis (methylenebis)]-2-propionate, 40.1 parts of cyclohexyl methacrylate, 24.2 parts of tetrahydrofurfuryl methacrylate, 24.7 parts of methacrylic acid , 2.0 parts of t-butylperoxy-2-ethylhexanoate and 80 parts of PGMEA were mixed. In addition, 3.1 parts of β-mercaptopropionic acid and 6 parts of PGMEA were mixed in the dropping tank 2. While maintaining the reaction temperature at 90 ° C., dropwise addition was performed from the dropping tanks 1 and 2 to the reaction tank at a constant rate over 2.5 hours. After maintaining the temperature at 90 ° C. for 30 minutes, 0.5 part of t-butylperoxy-2-ethylhexanoate was added, and the reaction was further continued at 90 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours. Once cooled to room temperature, 24.7 parts of glycidyl methacrylate, 0.038 part of 6-t-butyl-2,4-xylenol and 0.38 part of dimethylbenzylamine were added to adjust the oxygen concentration to 7%. -The temperature was raised to 110 ° C while bubbling an air mixed gas, and the reaction was performed for 6 hours. Then, the temperature was raised to 115 ° C. and reacted for 2 hours to complete the reaction, cooled to room temperature, sampled about 2 g of the resin solution, dried by heating at 180 ° C. for 20 minutes, and the non-volatile content was measured. PGMEA was added to the solution so that the nonvolatile content was 20% by weight to obtain a resin solution (A1-4). The weight average molecular weight of the resin was 9000, and the acid value per solid content was 70 mgKOH / g.

<Manufacturing method of other resin (A3)>
(Preparation of resin solution (A3-1))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMEA was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. Acrylic resin solution (A3-1) was prepared. The weight average molecular weight (Mw) was 19000.

（但し、ｍ＝１、a＝３、ｂ＝３である）
酸化防止剤； ０．２部
１，３，５−トリス（４−ｔ−ブチル−３−ヒドロキシ−２，６−ジメチルベンジル）
熱硬化性樹脂； ３．０部
「ＭＷ−３０」株式会社三和ケミカル社製
密着促進添加剤； ０．６部
３−グリシドキシプロピルトリメトキシシラン
プロピレングリコールモノメチルエーテルアセテート(PGMEA) ６０．８部 [Example 1]
(Photosensitive resin composition 1)
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive resin composition 1.
Resin solution (A1-1) 28.8 parts Photopolymerization initiator; 0.6 parts “Irgacure 907” (manufactured by Ciba Japan)
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one photopolymerizable monomer; 6.0 parts “KAYARAD DPCA-30” (manufactured by Nippon Kayaku Co., Ltd.)

(However, m = 1, a = 3, b = 3)
Antioxidant; 0.2 parts 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)
Thermosetting resin: 3.0 parts “MW-30” manufactured by Sanwa Chemical Co., Ltd.
Adhesion promoting additive; 0.6 parts 3-glycidoxypropyltrimethoxysilane
Propylene glycol monomethyl ether acetate (PGMEA) 60.8 parts

[Examples 2-14, Comparative Examples 1-4]
Except having changed into the composition shown to Table 1 and Table 2, and the compounding quantity, it carried out similarly to the manufacturing method of Example 1 (photosensitive resin composition 1), and obtained the photosensitive resin compositions 2-18. .

《光重合開始剤（Ｂ）》
・イルガキュア９０７；「イルガキュア９０７」（チバ・ジャパン社製）
２−メチル−１−（４−メチルチオフェニル）−２−モルホリノプロパン−１−オン
・イルガキュア３６９；「イルガキュア３６９」（チバ・ジャパン社製）
２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタン−１−オン
・イルガキュアＯＸＥ−０１；「イルガキュアＯＸＥ−０１」（チバ・ジャパン社製）
１，２−オクタジオン−１−[４−(フェニルチオ)−,２−(ｏ−ベンゾイルオキシム)]
・イルガキュアＯＸＥ−０２；「イルガキュアＯＸＥ−０２」（チバ・ジャパン社製）
エタノン,１−[９−エチル−６−(２−メチルベンゾイル)−９Ｈ−カルバゾール−３−イル]−,１−(ｏ−アセチルオキシム)
《光重合性モノマー（Ｄ）》
・Ｍ−４０２；「アロニックス Ｍ−４０２」（東亜合成社製）
《酸化防止剤（Ｃ）》
・酸化防止剤（Ｃ−１）；
１，３，５−トリス（４−ｔ−ブチル−３−ヒドロキシ−２，６−ジメチルベンジル）
・酸化防止剤（Ｃ−２）；
Ｎ，Ｎ′−ビス（２，２，６，６−テトラメチル−４−ピペリジル）−１，６−ヘキサメチレンジアミン
・酸化防止剤（Ｃ−３）；
亜りん酸エチルビス(２，４−ジｔｅｒｔ−ブチル−６−メチルフェニル)
・酸化防止剤（Ｃ−４）；
２，４−ビス〔（オクチルチオ）メチル〕−ｏ−クレゾール Abbreviations in Table 1 and Table 2 are shown below.
<< Resin (A2) >>
-Resin (A2-1); Nicarak MW-30 (manufactured by Sanwa Chemical Co., Ltd.)
A mixture / resin (A2-2) containing a compound in which R ^{3 to} R ^{8 in} the general formula (2) are CH ₂ OCH ₃ ; epoxy resin EX4931 (epoxy resin represented by the following formula) (manufactured by Nagase Chemtech)

<< Photopolymerization initiator (B) >>
・ Irgacure 907; “Irgacure 907” (manufactured by Ciba Japan)
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one Irgacure 369; “Irgacure 369” (manufactured by Ciba Japan)
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Irgacure OXE-01; “Irgacure OXE-01” (manufactured by Ciba Japan)
1,2-octadione-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]
・ Irgacure OXE-02; “Irgacure OXE-02” (manufactured by Ciba Japan)
Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime)
<< Photopolymerizable monomer (D) >>
M-402; “Aronix M-402” (manufactured by Toa Gosei Co., Ltd.)
<< Antioxidant (C) >>
-Antioxidant (C-1);
1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)
-Antioxidant (C-2);
N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine-antioxidant (C-3);
Ethyl bisphosphite (2,4-ditert-butyl-6-methylphenyl)
-Antioxidant (C-4);
2,4-Bis [(octylthio) methyl] -o-cresol

<Evaluation of photosensitive resin composition>
(Measurement of transmittance)
The photosensitive coloring composition 1-18 obtained by the Example and the comparative example was heated at 230 degreeC for 20 minutes using a spin coater to a 100 mm x 100 mm and 1.1 mm-thick glass substrate (Corning glass Eagle 2000). A substrate coated so that the final finished film thickness was 2.0 μm was obtained. Next, after drying under reduced pressure, ultraviolet exposure was performed with an integrated light quantity of 100 mJ using an ultrahigh pressure mercury lamp. The coated substrate was heated at 230 ° C. for 20 minutes and allowed to cool, and then the transmittance at a wavelength of 400 nm of the obtained coating film was determined using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The film thickness was measured with a stylus type film thickness meter DECTAC-3 manufactured by ULVAC. The results are shown in Table 3.
○: Transmittance 95.0% or more / good level △; Transmittance 90.0% or more and less than 95.0% / Inferior to ○, but practical level ×; Transmittance less than 90.0% / Unsuitable for practical use

(Measurement of glass adhesion and adhesion to ITO)
The adhesiveness of the coating film was evaluated by a cross-cut adhesion test method according to JIS K5400 on a photosensitive resin composition-coated substrate obtained by the same method as that prepared for the measurement of transmittance. The number of peels was counted.
As the substrate, Corning Glass Eagle 2000 and Santo Vacuum Industry ITO film were used. The results are shown in Table 3.

○: Number of cross-cuts <3 △; 3 ≦ Number of cross-cuts ≦ 10 ×; Number of cross-cuts> 10

(Measurement of pencil hardness)
About the photosensitive resin composition application | coating board | substrate obtained by the same method as what was produced for the measurement of the transmittance | permeability, the surface hardness of the protective film was measured by the 8.4.1 pencil scratch test of JISK-5400-1990. This value is shown in Table 3. When this value is 6H or higher, the surface hardness is good.

○: 6H or more △; 5H
×: 4H or less

(Evaluation of change in dielectric constant of coating film)
The photosensitive resin compositions 1 to 18 obtained in the examples and comparative examples are deposited on aluminum for electrodes by 100 mm × 100 mm and 0.7 mm thick glass substrate to a thickness of 2.0 μm using a spin coater. The coated substrate was obtained by coating at a rotational speed. Next, after drying under reduced pressure, ultraviolet exposure was performed using an ultra-high pressure mercury lamp with an integrated light amount of 300 mJ and an illuminance of 30 mW. After the alkali development, the coated substrate was heated at 230 ° C. for 1 hour and allowed to cool. Then, aluminum for an electrode having an area of 3.464 × 10 ⁻⁴ m ² was vapor-deposited on the obtained cured coating film. A sample sandwiched between aluminum electrodes was prepared. The dielectric loss tangent of 10 Hz to 1 MHz of the obtained sample was obtained using an impedance analyzer (“1260 type” manufactured by Solartron) at a printing voltage of 100 mV and a dielectric constant. This value is shown in Table 3.

[Relative permittivity (@ 1kHz)]
○: 3.6 or less ×; exceeding 3.6

[Dielectric loss tangent (@ 1kHz)]
○: 0.012 or less ×;

  As shown in Table 3, a resin obtained by copolymerizing the compound (a1) represented by the general formula (1) and another compound (a2) copolymerizable with the compound (a1), which is a feature of the present invention In photosensitive resin composition 1-16 of Examples 1-16 containing resin (A) containing (A1), a photoinitiator (B), and antioxidant (C), the transmission in wavelength 400nm The result was excellent in rate, hardness, adhesion to glass substrate and ITO layer.

  In particular, when Examples 1 and 8 to 10, which differ only in the type of the antioxidant (C), are compared, the antioxidant (C) is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based oxidation. Examples 1, 8, and 9, which are inhibitors, were particularly excellent in transmittance.

  Further, the resin (A) further contains a thermosetting resin (A2), and the thermosetting resin (A2) is a mixture of a thermosetting melamine compound represented by the general formula (2) and / or a partial condensate thereof. The photosensitive resin composition 1 of a certain example 1 was particularly excellent in coating film hardness.

  Further, when Examples 1, 15 and 16 that differ only in the ratio of the weight of the antioxidant (C) and the weight of the thermosetting resin (A2) are compared, [(C) / (A2)] has a specific range. The photosensitive resin composition 1 of Example 1 which had it was excellent in both the transmittance | permeability and hardness.

  Further, when Examples 1 and 5 to 7 differing only in the type of the photopolymerization initiator (B) were compared, the photopolymerization initiator (B) was 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- Examples 1 and 6 which are 1-one or 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)] were particularly excellent in transmittance.

  Further, when Examples 1, 12 and 13 in which the photosensitive resin composition contains the adhesion promoting additive (D) are compared, Examples 1 and 12 containing the adhesion promoting additive (D) have a good glass substrate, Furthermore, Example 1 in which the adhesion promoting additive (D) is 3-glycidoxypropyltrimethoxysilane was excellent for both the glass substrate and the ITO layer.

  On the other hand, in Comparative Examples 1 to 4 in which any of the resin (A1), the photopolymerization initiator (B), and the antioxidant (C) is not included, the transmittance, hardness, glass substrate, and ITO layer at a wavelength of 400 nm Any of the adhesiveness to was significantly inferior to the examples.

Claims (9)

A photosensitive resin composition containing a resin (A), a photopolymerization initiator (B), and an antioxidant (C), wherein the resin (A) is represented by the following general formula (1) A photosensitive resin composition comprising a resin (A1) obtained by copolymerizing (a1) and another compound (a2) copolymerizable with the compound (a1).
General formula (1):

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. ]   The antioxidant (C) is any compound selected from the group consisting of a hindered phenol-based antioxidant, a hindered amine-based antioxidant, and a phosphorus-based antioxidant. Photosensitive resin composition.   Resin (A) contains thermosetting resin (A2) further, The photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned. The thermosetting resin (A2) contains a compound having a structure represented by the following general formula (2), and has a weight average polymerization degree of 1.0 to 5.0. Photosensitive resin composition.
General formula (2):

[In General Formula (2), R ^{3 to} R ⁸ are each independently a hydrogen atom, or any one selected from the group consisting of —CH ₂ OH, —CH ₂ OCH ₃ , and —CH ₂ OC ₄ H ₉ . Represents a substituent. ]   The ratio ([C] / [A2]) of the weight [C] of the antioxidant (C) and the weight [A2] of the thermosetting resin (A2) is 0.005 to 0.1. The photosensitive resin composition according to claim 3 or 4.   6. The photopolymerization initiator (B) is at least one compound selected from the group consisting of an acetophenone photopolymerization initiator and an oxime ester photopolymerization initiator. The photosensitive resin composition as described in 2.   The photopolymerization initiator (B) is 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and / or 1,2-octadion-1- [4- (phenylthio)-, 2- The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is (o-benzoyloxime)].   The photosensitive resin composition according to any one of claims 1 to 7, further comprising an adhesion promoting additive (E).   The insulating film for touchscreens formed using the photosensitive resin composition of any one of Claims 1-8.