JP2013101588A - Resin composition, and protective film and touch panel insulating film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a resin composition which is excellent in adhesion with a substrate, an undercoat etc. and has high film hardness and etchant resistance; and a touch panel insulating film using the same.SOLUTION: The resin composition contains a resin (A1) having a hydroxyl group in a side chain thereof, an isocyanate group-containing silane compound (B) represented by the general formula (1), and a solvent (C). The general formula (1) is defined by (OCN-R)-Si-(R), where Rrepresents an alkylene group with the carbon number 1 to 5, Rrepresents an alkoxy group with the carbon number 1 to 5 or a hydroxyl group, and n is an integer from 1 to 3.

Description

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

  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: adhesion to substrates, bases, and other layers (glass, inorganic materials, metal materials, transparent electrodes such as ITO, organic materials, etc.), etching of ITO and molybdenum There are demands for resistance to liquids (etchant resistance), heat resistance to a high-temperature firing process in the touch panel manufacturing process, and transmittance when a laminated substrate is used.

In addition, an insulating film and a protective film used for touch panel applications are required to have high surface hardness, and Patent Document 4 discloses a method of adding inorganic oxide fine particles to a resin component.
Further, Patent Document 5 discloses a method for improving adhesion to a substrate using an isocyanate group-containing silane compound.

However, these methods have problems such as yellowing due to a baking process at a high temperature, low transmittance, and insufficient stability.
That is, the conventional resin composition is excellent in adhesion to the base material, film hardness, and resistance, and cannot satisfy all of the transmittance and stability.

JP 2008-65748 A JP 2009-15490 A JP 2010-44453 A JP 2000-281863 A JP 2011-102385 A

  An object of the present invention is to provide a resin composition capable of forming a coating film having good adhesion to a base material or a base, and having excellent film hardness and etchant resistance, and a protective film or an insulating film for a touch panel using the same. The purpose is to provide.

  As a result of intensive studies on new means that can solve the above problems, the present inventors have made a resin composition containing a resin (A1) having a hydroxyl group in the side chain and an isocyanate group-containing silane compound (B) having a specific structure. Thus, the inventors have found that the above-described problems can be solved, and have reached the present invention.

That is, the present invention includes a resin composition comprising a resin (A1) having a hydroxyl group in a side chain, an isocyanate group-containing silane compound (B) represented by the following general formula (1), and a solvent (C). About.
General formula (1)
_{(OCN-R 1) n -Si-} (R 2) 4-n
[In General Formula (1), R ₁ represents an alkylene group having 1 to 5 carbon atoms, R ₂ represents an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group, and n is an integer of 1 to 3. ]

  The present invention also relates to the resin composition, wherein the molar ratio of the hydroxyl group of the resin (A1) to the isocyanate group of the isocyanate group-containing silane compound (B) is 0.40 to 1.60.

  In the present invention, the resin (A1) is a resin having an ethylenically unsaturated double bond in the side chain, the hydroxyl group equivalent is 300 to 1000 g / mol, and the double bond equivalent is 350 to 1200 g / mol. It is related with the said resin composition characterized by the above-mentioned.

The present invention also relates to the resin composition, wherein the solvent (C) includes an alcohol solvent (C-a1) having a boiling point of less than 130 ° C. at 760 mmHg.
Further, the present invention relates to the resin composition, wherein the content of the alcohol solvent (Ca) is 25 to 300 parts by weight with respect to 100 parts by weight of the solid content of the resin composition.
In addition, the present invention relates to a resin composition in which the solvent (C) further contains an ester solvent having a boiling point of 200 ° C. or higher and lower than 250 ° C. at 760 mmHg.
About.

The present invention further includes inorganic oxide fine particles (D) of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium and zinc. The resin composition according to item.
The present invention also relates to the resin composition, wherein the content of the inorganic oxide fine particles (D) is 5% by weight or more and less than 40% by weight in a total solid content of 100% by weight of the resin composition. .

[一般式（２）において、ｍは０〜４の整数であり、Ｒ₃はエーテル基、アルキレン基、トリレン基、アリーレン基、カルボニル基、スルホニル基、エステル基、および一般式（３）で表される構造を有する２価の基からなる群より選ばれるいずれかであり、Ｒ₄は水素原子またはメチル基であり、Ｒ₅はヒドロキシル基、カルボキシル基、および（メタ）アクリロイル基からなる群より選ばれるいずれかである。]
一般式（３）：

[一般式（３）において、Ｒ₆は脂肪族、脂環式または芳香族の構造を表す。] Further, the present invention further includes a polyfunctional monomer (E) having 7 or more ethylenically unsaturated double bonds represented by the following general formula (2). About.
General formula (2):

[In General Formula (2), m is an integer of 0 to 4, and R ₃ is an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, and a general formula (3). R ₄ is a hydrogen atom or a methyl group, R ₅ is selected from the group consisting of a hydroxyl group, a carboxyl group, and a (meth) acryloyl group. One of the choices. ]
General formula (3):

[In General Formula (3), R ₆ represents an aliphatic, alicyclic or aromatic structure. ]

  The present invention also relates to the resin composition, further comprising an acetophenone photopolymerization initiator or an oxime ester photopolymerization initiator.

The resin composition further comprises at least one antioxidant (F) selected from the group consisting of phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Related to things.
The present invention also relates to the resin composition, wherein the antioxidant (F) is 0.1 wt% or more and less than 4 wt% in a total solid content of 100 wt% of the resin composition.

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

  With the photosensitive resin composition of the present invention, it is possible to form a coating film that has good adhesion to a substrate, a base, and the like, and is excellent in film hardness and etchant resistance, and an excellent protective film or insulating film for touch panel Can be provided.

Hereinafter, the present invention will be described in detail.
In the present application, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, or “(meth) acrylate”, unless otherwise specified, It shall represent "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid" or "acrylate and / or methacrylate".

First, various components of the resin composition of the present invention will be described.
<Resin (A1)>
The resin composition of the present invention includes a resin (A1) having a hydroxyl group in a side chain.
As the resin having a hydroxyl group in the side chain (A1), a resin obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another ethylenically unsaturated monomer copolymerizable with a hydroxyl group Copolymerized with ethylenically unsaturated monomer and other copolymerizable ethylenically unsaturated monomer, and modified side chain carboxyl group with ethylenically unsaturated monomer having epoxy group Resin or an ethylenically unsaturated monomer having an epoxy group and another copolymerizable ethylenically unsaturated monomer are copolymerized, and the side chain epoxy group is converted to an ethylenically unsaturated monomer having a carboxyl group. Examples include resins formed by modification with a monomer.

When the structure of the resin (A1) is classified,
Resin (A1-a); a resin having a hydroxyl group in the side chain and not having an acid group such as a carboxyl group and an ethylenically unsaturated double bond;
Resin (A1-b); a resin having a hydroxyl group in the side chain and an acid group such as a carboxyl group and having no ethylenically unsaturated double bond,
Resin (A1-c); a resin having a hydroxyl group in the side chain and no acid group such as a carboxyl group and having an ethylenically unsaturated double bond;
Resin (A1-d); a resin having a hydroxyl group in the side chain and an acid group such as a carboxyl group and an ethylenically unsaturated double bond;
Is mentioned.
Among these, the resin (A1) is preferably a resin (A1-b) or a resin (A1-d) having an acid group such as a carboxyl group in order to exhibit alkali solubility, and also exhibits increased photosensitivity and pencil hardness. It is preferably a resin (A1-c) or a resin (A1-d) having an ethylenically unsaturated double bond, particularly a resin having both an ethylenically unsaturated double bond and an acid group ( A1-d) is more preferred.

<< Method of introducing hydroxyl group >>
As a method for introducing a hydroxyl group into the resin (A1), a method (I) of copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another ethylenically unsaturated monomer copolymerizable with a hydroxyl group, There is a method (II) of generating.
Examples of the method (II) for generating a hydroxyl group include copolymerization of an ethylenically unsaturated monomer having a carboxyl group with another ethylenically unsaturated monomer that can be copolymerized, and a carboxyl group in a side chain. Is modified with an ethylenically unsaturated monomer having an epoxy group to produce a hydroxyl group (II-1), or another ethylenic copolymerizable with an ethylenically unsaturated monomer having an epoxy group Examples include a method (II-2) in which an unsaturated monomer is copolymerized and a side chain epoxy group is modified with a compound having a carboxyl group to generate a hydroxyl group.

・ Method of introducing hydroxyl group (I)
As a method for introducing a hydroxyl group (I), a resin (A1) can be obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another ethylenically unsaturated monomer copolymerizable. it can.

(Ethylenically unsaturated monomer having a hydroxyl group)
Examples of the ethylenically unsaturated 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.

(Other ethylenically unsaturated monomers that can be copolymerized)
Examples of other copolymerizable ethylenically unsaturated monomers include ethylenically unsaturated monomers (a1) represented by the general formula (4), side chain cyclic ether-containing ethylenically unsaturated monomers (a2). ), An ethylenically unsaturated monomer having an acid group (a3), an ethylenically unsaturated monomer having an epoxy group (a4), and other ethylenically unsaturated monomers (a5). One or more of these ethylenically unsaturated monomers can be used and can be prepared in a form that meets their requirements. In particular, at least the ethylenically unsaturated monomer (a1) represented by the general formula (4) is used. By using a resin obtained by copolymerization of a monomer containing the polymer, a coating film excellent in transmittance (transparency), adhesion and etchant resistance can be obtained, which is particularly preferable.

[一般式（４）において、Ｒ₇およびＲ₈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。] [Ethylenically unsaturated monomer (a1)]
The ethylenically unsaturated monomer (a1) is an ethylenically unsaturated monomer represented by the following general formula (4).
General formula (4):

[In General Formula (4), R ₇ and R ₈ 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 (4), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₇ and R ₈ is not particularly limited, and examples thereof include methyl, ethyl, linear or branched alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butyl An alicyclic group such as cyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; an alkyl group substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a hydrocarbon group which is difficult to be removed by heat are preferable from the viewpoint of heat resistance. R ₇ and R ₈ may be the same type of hydrocarbon group or different hydrocarbon groups.

Specific examples of the ethylenically unsaturated monomer (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-ethoxy) Ethyl) -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-butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate , Di (tricyclodecanyl) -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.
These ethylenically unsaturated monomers (a1) can be used singly or as a mixture of two or more at any ratio as required.

  When the resin (A1) is obtained by copolymerizing the ethylenically unsaturated monomer (a1) with another ethylenically unsaturated monomer copolymerizable, the ethylenically unsaturated monomer ( The cyclization reaction of a1) proceeds to form a tetrahydropyran ring structure.

  Although the ratio of the ethylenically unsaturated monomer (a1) in the ethylenically unsaturated monomer component in obtaining the resin (A1) is not particularly limited, it is 2 to 50 in the total ethylenically unsaturated monomer component. % By weight, preferably 5 to 55% by weight, more preferably 5 to 50% by weight. If the amount of the ethylenically unsaturated monomer (a1) is too large, it may be difficult to obtain a low molecular weight during the copolymerization or may be easily gelled. The film performance such as transparency and heat resistance may be insufficient.

[Ethylenically unsaturated monomer (a2)]
The ethylenically unsaturated monomer (a2) is a side chain cyclic ether-containing ethylenically unsaturated monomer. Examples of the ethylenically unsaturated monomer (a2) include an ethylenically unsaturated monomer containing 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 there.
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 and availability.
These ethylenically unsaturated monomers (a2) can be used singly or in combination of two or more at any ratio as required.

  The ratio of the ethylenically unsaturated monomer (a2) in the ethylenically unsaturated monomer component in obtaining the resin (A1) is not particularly limited, but is 3 to 80 in the total ethylenically unsaturated monomer component. % By weight, preferably 5 to 70% by weight, more preferably 10 to 60% by weight. If the amount of the ethylenically unsaturated monomer (a2) is too large, the hydrophilicity becomes too strong and the surface is whitened during alkali development, the pattern is missing, or the adhesion to the glass tends to be reduced. On the other hand, if the amount is too small, performance such as heat resistance may be insufficient.

[Ethylenically unsaturated monomer (a3)]
The ethylenically unsaturated monomer (a3) is an ethylenically unsaturated monomer having an acid group. By using the ethylenically unsaturated monomer (a3), an acid group can be introduced into the resin (A1). As a result, the curable resin composition obtained is a curable resin composition capable of a crosslinking reaction utilizing the fact that an ester bond is formed by the reaction of an acid group with an epoxy group or a hydroxyl group, or an uncured portion is treated with an alkaline developer. It is preferable to use the ethylenically unsaturated monomer (a3). The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a polybasic acid anhydride group. These acid groups may be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer (a3) having an acid group include (meth) acrylic acid, itaconic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α of (meth) acrylic acid. It has a phenolic hydroxyl group such as an ethylenically unsaturated monomer (unsaturated monobasic acid) having a carboxyl group such as a monocarboxylic acid such as a haloalkyl, alkoxyl, halogen, nitro or cyano substituent, and N-hydroxyphenylmaleimide. Examples include ethylenically unsaturated monomers, tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, polybasic acid anhydrides such as succinic anhydride and maleic anhydride. Among these, (meth) Acrylic acid is preferred.

  When the ethylenically unsaturated monomer (a3) is included, the content ratio is not particularly limited, but is 5 to 70% by weight, preferably 10 to 60%, out of the total 100% by weight of all ethylenically unsaturated monomer components. It should be weight percent.

[Ethylenically unsaturated monomer (a4)]
Examples of the ethylenically unsaturated monomer (a4) include an ethylenically unsaturated monomer having an epoxy group. Examples of the ethylenically unsaturated monomer (a4) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-propylglycidyl (meth) acrylate, β-methylglycidyl-α-ethyl acrylate, 3 -Methyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate, glycidyl vinyl ether, etc. Glycidyl (meth) acrylate is preferred. These may be used alone or in combination of two or more.

  When the ethylenically unsaturated monomer (a3) is included, the content ratio is not particularly limited, but is 5 to 70% by weight, preferably 10 to 60%, out of the total 100% by weight of all ethylenically unsaturated monomer components. It should be weight percent.

[Ethylenically unsaturated monomer (a5)]
Examples of the ethylenically unsaturated monomer (a5) include other ethylenically unsaturated monomers. Examples of the ethylenically unsaturated monomer (a5) include (meth) acrylic acid esters, N-vinylpyrrolidone, styrenes, acrylamides, other vinyl compounds, and macromonomers.

  (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl ( (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) Examples include acrylate, tetrahydrofurfuryl (meth) acrylate, and paracumyl EO-modified (meth) acrylate.

  As styrenes, styrene and its derivatives, methylstyrene and the like can be used.

  Examples of acrylamides include (meth) acrylamide, methylol (meth) acrylamide, alkoxymethylol (meth) acrylamide, diacetone (meth) acrylamide, and the like.

  As other vinyl compounds, (meth) acrylonitrile, ethylene, propylene, butylene, vinyl chloride, vinyl acetate and the like can be applied.

Examples of the macromonomer include macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer.
These ethylenically unsaturated monomers (a5) can be used singly or in combination of two or more at any ratio as required.

<Method of introducing acid group>
The resin (A1) is preferably a resin having an acid group. As a method for introducing the acid group, the above-described method using the ethylenically unsaturated monomer (a3) having an acid group, or an acid after polymerization is used. A method of polymerizing an ethylenically unsaturated monomer capable of imparting a group as an ethylenically unsaturated monomer component may be used. In the case where an acid group is introduced using an ethylenically unsaturated 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 ethylenically unsaturated monomer that can impart an acid group after polymerization include, for example, an ethylenically unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and an epoxy group such as glycidyl (meth) acrylate. An ethylenically unsaturated monomer (a4) having
When using an ethylenically unsaturated monomer having a hydroxyl group, for example, it is obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another copolymerizable ethylenically unsaturated monomer. The hydroxyl group of the obtained copolymer can be reacted with a polybasic acid anhydride to introduce an acid group (carboxyl group).
Or when using the ethylenically unsaturated monomer (a4) which has an epoxy group, for example, the ethylenically unsaturated monomer (a4) which has an epoxy group, and the other ethylenically unsaturated monomer which can be copolymerized An unsaturated monobasic acid having a carboxyl group is added to the side chain epoxy group of the copolymer obtained by copolymerizing with the monomer, and a polybasic acid anhydride is further reacted with the generated hydroxyl group. Acid groups (carboxyl groups) can be introduced. In this method, when a hydroxyl group and a polybasic acid anhydride having an ethylenically unsaturated double bond are reacted without excess or deficiency, the hydroxyl group disappears. On the other hand, a resin (A1-d) having a hydroxyl group in the side chain and an acid group such as a carboxyl group and an ethylenically unsaturated double bond is obtained by reacting a part of the hydroxyl group with a polybasic acid anhydride. can get.

  When an ethylenically unsaturated monomer for imparting an acid group after polymerization is included, the content ratio is not particularly limited, but is 5 to 70% by weight in a total of 100% by weight of all ethylenically unsaturated monomer components. Preferably, it is 10 to 60% by weight.

<Method of introducing ethylenically unsaturated double bond>
As the method for introducing an ethylenically unsaturated double bond, the ethylenically unsaturated monomer (a4) having an epoxy group described above in the method for introducing an acid group and other ethylenically unsaturated monomers capable of copolymerization are used. An unsaturated monobasic acid is added to the side chain epoxy group of the copolymer obtained by copolymerizing with the monomer, and a polybasic acid having a radical polymerizable double bond in the generated hydroxyl group. Examples include a method of reacting an anhydride to introduce an acid group (carboxyl group) and an ethylenically unsaturated double bond.

Also, copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with an ethylenically unsaturated monomer of an unsaturated monobasic acid having another carboxyl group or another ethylenically unsaturated monomer The method of making the isocyanate group of the ethylenically unsaturated monomer which has an isocyanate group react with the side chain hydroxyl group of the copolymer obtained by this is mentioned.
At this time, when an unsaturated monobasic acid monomer is used, a resin having a hydroxyl group in the side chain and having an acid group of a carboxyl group and an ethylenically unsaturated double bond (A1-d) When an unsaturated monobasic acid monomer is not used, the side chain has a hydroxyl group, does not have an acid group such as a carboxyl group, and has an ethylenically unsaturated double bond. Resin (A1-c) is obtained.

  As the ethylenically unsaturated monomer having a hydroxyl group used at this time, in addition to the ethylenically unsaturated monomer having a hydroxyl group described in the introduction method (I) of the hydroxyl group, hydroxyalkyl (meth) acrylate, ethylene oxide, propylene Polyether mono (meth) acrylate obtained by addition polymerization of oxide and / or butylene oxide, (poly) γ-valerolactone, (poly) ε-caprolactone, and / or (poly) 12-hydroxystearic acid Added (poly) ester mono (meth) acrylates 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.

  As the ethylenically unsaturated monomer having an isocyanate group, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, or the like can be used. These ethylenically unsaturated monomers can be used singly or as a mixture of two or more at any ratio as required.

・ Hydroxyl introduction method (II)
Examples of the method (II) for introducing a hydroxyl group include a method for producing a hydroxyl group. As the method (II), for example, an ethylenically unsaturated monomer having a carboxyl group described in the ethylenically unsaturated monomer having an acid group (a3) and other copolymerizable ethylenically unsaturated monomers And a method of producing a hydroxyl group by modifying the side chain carboxyl group with an ethylenically unsaturated monomer (a4) having an epoxy group, or an ethylenically unsaturated group having an epoxy group. The saturated monomer (a4) is copolymerized with another copolymerizable ethylenically unsaturated monomer, and the side chain epoxy group is described as an ethylenically unsaturated monomer having an acid group (a3). The method (II-2) etc. which modify | denaturate with the ethylenically unsaturated monomer which has the carboxyl group produced | generated, and produce | generate a hydroxyl group etc. are mentioned.

  In the method (II) for generating these hydroxyl groups, a double bond can be introduced together with the hydroxyl groups. In the method (II-1), when a part of the side chain carboxyl group is modified with an ethylenically unsaturated monomer having an epoxy group, the side chain has a hydroxyl group and an acid group such as a carboxyl group. And a resin (A1-d) having an ethylenically unsaturated double bond is obtained, and when all of the side chain carboxyl groups are modified with an ethylenically unsaturated monomer having an epoxy group, And an acid group such as a carboxyl group and an ethylenically unsaturated double bond (A1-c). In the method (II-2), a resin (A1-d) having a hydroxyl group in the side chain and an acid group such as a carboxyl group and an ethylenically unsaturated double bond is obtained.

  The resin (A1) preferably has an ethylenically unsaturated double bond. Furthermore, it is preferable that an acid group equivalent is 300-1000 g / mol and a double bond equivalent is 350-1200 g / mol. When the hydroxyl group equivalent is smaller than 300 g / mol, the hydroxyl group becomes excessive, which is not preferable because the affinity with the etching solution is increased and the etchant resistance is deteriorated. When the hydroxyl equivalent exceeds 1000 g / mol, the pencil hardness and the substrate adhesion decrease because the number of reaction points between the resin and the isocyanate group of the silane coupling agent is small. When the double bond equivalent is less than 350 g / mol, the adhesiveness of the substrate may be deteriorated because the curing shrinkage of the resin increases. When the double bond equivalent exceeds 1200 g / mol, sufficient pencil hardness may not be satisfied. When the hydroxyl group equivalent is 300 to 1000 g / mol and the double bond equivalent is 350 to 1200 g / mol, it is possible to draw out excellent pencil hardness and substrate adhesion.

  The theoretical Tg of the resin (A1) can be controlled by the type and blending of the ethylenically unsaturated monomer to be copolymerized, and the weight average molecular weight can be controlled by the polymerization conditions such as the type and amount of the polymerization initiator. Is possible.

  The synthesis of the resin (A1) is generally performed at 50 to 150 ° C. for 2 to 10 hours in the presence of a polymerization initiator and under an inert gas stream. The synthesis of the resin may be performed in the presence of a solvent as necessary.

  As the polymerization initiator used for the synthesis of the resin (A1), an organic peroxide, an azo compound, or the like can be used. Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, t-butyl peroxybenzoate and the like. Examples of the azo compound include azo compounds such as 2,2′-azobisisobutyronitrile. The polymerization initiator is preferably used in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.

  As a solvent used for the synthesis of the resin (A1), water, a water-miscible organic solvent, acetate, ketones, xylene, ethylbenzene, or the like can be used. Examples of the water-miscible organic solvent include alcohol solvents such as ethyl alcohol, isopropyl alcohol, and n-propyl alcohol, and mono- or dialkyl ethers of ethylene glycol or diethylene glycol. Examples of the acetic acid ester include ethyl cellosolve acetate and propylene glycol monomethyl ether acetate. Examples of the ketones include cyclohexanone and methyl isobutyl ketone.

  The method for the polymerization reaction of the ethylenically unsaturated monomer component is not particularly limited, and various conventionally known polymerization methods can be adopted, 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.

  The resin (A1) is preferably used in an amount of 10 to 60% by weight in a total of 100% by weight of the solid content of the resin composition. When the amount of the resin (A1) is less than 10% by weight, sufficient adhesion improvement and high transmittance cannot be obtained. It is difficult to obtain the hardness of the film.

<Other resins (A2)>
The resin composition of the present invention may contain other resin (A2). Examples of the other resin (A2) include a resin having no hydroxyl group or a resin having neither a hydroxyl group nor an ethylenically unsaturated double bond. These resins (A2) may contain the above-mentioned side chain type cyclic ether-containing monomer or a monomer for introducing an acid group as a copolymerization component. Further, it may be a thermosetting resin, and examples thereof include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

<Isocyanate group-containing silane compound (B)>
The resin composition of the present invention contains an isocyanate group-containing silane compound (B) represented by the following general formula (1).
General formula (1)
_{(OCN-R 1) n -Si-} (R 2) 4-n
[Wherein R ₁ represents an alkylene group having 1 to 5 carbon atoms, R ₂ represents an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group, and n represents an integer of 1 to 3. ]

  By including the isocyanate group-containing silane compound (B), adhesion to a member used for a touch panel such as a glass substrate, ITO, or molybdenum is improved.

  Examples of the isocyanate group-containing silane compound include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatepropyltripropoxysilane. The isocyanate group-containing silane compound may be a hydrolysis product thereof.

  The molar ratio of the hydroxyl group of the resin (A1) to the isocyanate group of the isocyanate group-containing silane compound (B) is preferably 0.40 to 1.60. A molar ratio of 0.40 or more is preferable because of excellent adhesion and significantly improved transmittance. The case of 1.60 or less is preferable because the pencil hardness is improved.

  The isocyanate group-containing silane compound (B) is preferably used in an amount of 0.1 to 30% by weight in a total of 100% by weight of the solid content of the resin composition. When the content is 0.1% by weight or more, the adhesion improving effect is excellent. When the content is 30% by weight or less, the resin, polyfunctional monomer, photopolymerization initiator, and the like in the resin composition are relatively suitable. Therefore, characteristics such as substrate adhesion and pencil hardness tend to be improved.

<Solvent (C)>
Examples of the solvent (C) used in the resin composition of the present invention include alcohol solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate Ester solvents such as ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate; ether solvents such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; benzene , Aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone And the like.

Among these solvents, an alcohol solvent is preferably included. In addition to improving the stability of the isocyanate group-containing silane coupling agent (B) by including an alcohol solvent, the hydrolysis reaction rate of the isocyanate group-containing silane coupling agent is appropriately controlled, pencil hardness, A coating film excellent in substrate adhesion and etchant resistance can be obtained.
Furthermore, among alcohol solvents, methanol (bp 65 ° C.), ethanol (bp 78 ° C.), 1-propanol (bp 83 ° C.), 1-butanol (bp 117 ° C.), ethylene glycol monohexyl ether (bp 98 ° C.), etc. at 760 mmHg It is particularly preferable to include an alcohol solvent (C1) having a boiling point of less than 130 ° C.

  The content of the alcohol solvent (C1) is preferably 25 to 300 parts by weight with respect to 100 parts by weight of the solid content of the resin composition. In the case of 25 to 300 parts by weight, the drying time of the alcohol-based solvent is improved in the drying process at the time of film formation, so that the reaction of the isocyanate group-containing silane compound (B) with the substrate proceeds efficiently. Moreover, it is preferable because the self-condensation reaction rate of the isocyanate group-containing silane compound (B) is kept good, the storage stability is improved, and the coating property is also improved.

Furthermore, since the solvent (C) contains an alcohol solvent (C1) having a boiling point of less than 130 ° C. at 760 mmHg and a solvent having a boiling point of 760 mmHg of 130 ° C. or more and less than 250 ° C., the wettability to the base material is improved. preferable. The solvent having a boiling point at 760 mmHg of 130 ° C. or higher and lower than 250 ° C. is preferably an ester solvent, and most preferably an ester solvent at 760 mmHg of 200 ° C. or higher and lower than 250 ° C.
In a solvent having a boiling point of 750 mmHg or higher at 250 ° C., the volatility is too low and the condensation reaction of the isocyanate group-containing silane compound (B) may be hindered to deteriorate the adhesion to the substrate.

  Examples of alcohol solvents having a boiling point at 760 mmHg of 130 ° C. or higher and lower than 250 ° C. include 1,3-butanediol (bp 207.5 ° C.), 1,3-butylene glycol (bp 207.5 ° C.), 2-heptanone (bp 151). .3 ° C.), 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 3-methoxybutanol (bp 161 ° C.), ethylene glycol monotertiary Butyl ether (bp 152.5 ° C.), ethylene glycol monobutyl ether (bp 171 ° C.), ethylene glycol monopropyl ether (bp 150 ° C.), ethylene glycol monomethyl ether (bp 124.1 ° C.), diethylene glycol monobutyl ether (bp 230 ° C.), diethyl Glycol monomethyl ether (bp 194 ° C.), cyclohexanol (bp 161 ° C.), dipropylene glycol monoethyl ether (bp 197.8 ° C.), dipropylene glycol monobutyl ether (bp 230.6 ° C.), dipropylene glycol monopropyl ether (bp 210 ° C.) ), Dipropylene glycol monomethyl ether (bp 190 ° C.), diacetone alcohol (bp 169.2), tripropylene glycol monomethyl ether (bp 243 ° C.), propylene glycol phenyl ether (bp 243 ° C.), propylene glycol monoethyl ether (bp 133 ° C.), Propylene glycol monobutyl ether (bp 170.2 ° C), propylene glycol monopropyl ether (bp 150 ° C), benzyl Lucol (bp 205 ° C.), 1-methylcyclohexanol (bp 168 ° C.), 2-methylcyclohexanol (bp 172 ° C.), 4-methylcyclohexanol (bp 172 ° C.), octanol (bp 195 ° C.), 2-methyl-1,3- Examples include propanediol (bp 123 ° C.), isobutyl alcohol (bp 108 ° C.), ethylene glycol monoisopropyl ether (bp 42 ° C.), propylene glycol monomethyl ether (bp 120 ° C.), and these can be used alone or in combination.

  Among these, diethylene glycol monobutyl ether (bp 230 ° C.), 1,3-butanediol (bp 207.5 ° C.), 3-methyl-1,3-, which are alcohol solvents having a boiling point at 760 mmHg of 200 ° C. or higher and lower than 250 ° C. It is preferable to use butanediol (bp 203 ° C.), dipropylene glycol monobutyl ether (bp 230.6 ° C.), and 1,3-butylene glycol (bp 207.5 ° C.).

Examples of solvents other than alcohols having a boiling point at 760 mmHg of 130 ° C. or higher and lower than 250 ° C. include 1,2,3-trichloropropane (bp 156 ° C.), 1,3-butylene glycol diacetate (bp 232 ° C.), 3, 3 , 5-trimethylcyclohexanone (bp 188 ° C.), ethyl 3-ethoxypropionate (bp 166 ° C.), 1,4-butanediol diacetate (bp 220 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), 3- Methoxybutyl acetate (bp 171 ° C), 4-heptanone (bp 149 ° C), m-diethylbenzene (bp 182 ° C), m-dichlorobenzene (bp 173 ° C), N, N-dimethylacetamide (bp 165 ° C), N, N-dimethylformamide (Bp 153 ° C), n-buty Benzene (bp183.3 ° C), N-methylpyrrolidone (bp202 ° C), o-chlorotoluene (bp158.9 ° C), o-diethylbenzene (bp183 ° C), o-dichlorobenzene (bp180 ° C), p-chlorotoluene ( bp162.4 ° C), p-diethylbenzene (bp184 ° C), sec-butylbenzene (bp173 ° C), tert-butylbenzene (bp169 ° C), γ-butyrolactone (bp204 ° C), isophorone (bp215.2 ° C), ethylene glycol Diethyl ether (bp 121.4 ° C.), ethylene glycol dibutyl ether (bp 202 ° C.), ethylene glycol monoethyl ether (bp 135 ° C.), ethylene glycol monoethyl ether acetate (bp 156.3 ° C.), ethylene glycol monobutyl Chill ether acetate (bp 192 ° C.), ethylene glycol monomethyl ether acetate (bp 145 ° C.), diisobutyl ketone (bp 168 ° C.), diethylene glycol diethyl ether (bp 180 ° C.), diethylene glycol dimethyl ether (bp 162 ° C.), diethylene glycol monoethyl ether acetate (bp 218 ° C.), Diethylene glycol monobutyl ether acetate (bp 246.8 ° C), cyclohexanol acetate (bp 173 ° C), cyclohexanone (bp 155.6 ° C), cyclopentanone (bp 130 ° C), dipropylene glycol dimethyl ether (bp 175 ° C), dipropylene glycol methyl ether acetate (Bp 209 ° C.), propylene glycol diacetate (bp 190 ), Propylene glycol monoethyl ether acetate (bp 158 ° C.), propylene glycol monomethyl ether acetate (bp 146 ° C.), propylene glycol monomethyl ether propionate (bp 160 ° C.), n-amyl acetate (bp 149 ° C.), isoamyl acetate (bp 142 ° C.) And dibasic acid esters.
These solvents can be used singly or in combination of two or more at any ratio as required.

  Among these solvents, ester solvents are preferable, propylene glycol diacetate (bp 190 ° C.) and diethylene glycol monoethyl ether acetate (bp 218 ° C.) are preferable, 1,3-butylene glycol diacetate (bp 232 ° C.), 1,4 -Butanediol diacetate (bp 220 ° C.) is particularly preferred.

  In the resin composition of the present invention, in order to adjust the volatility of the solvent, a solvent other than an alcohol having a boiling point of less than 130 ° C at 760 mmHg or a boiling point of 250 ° C at 760 mmHg is within a range not impairing the effects of the present invention. For example, propyl acetate (bp 96.6 ° C.), n-propyl acetate (bp 102 ° C.), n-butyl acetate (bp 126 ° C.), isobutyl acetate (bp 118 ° C.), 3,5,5- Trimethyl-2-cyclohexen-1-one (bp 289 ° C.), triacetin (bp 258 ° C.), tripropylene glycol monobutyl ether (bp 276 ° C.), 1,6-hexanediol diacetate (bp 260 ° C.) and the like may be contained.

  The content of the solvent (C) can be used in an amount of 25 to 6000 parts by weight with respect to 100 parts by weight of the total solid content in the resin composition.

<Inorganic oxide fine particles (D)>
The resin composition of the present invention preferably contains inorganic oxide fine particles (D). The inorganic oxide fine particles may be surface-treated, and from the viewpoint of colorlessness of the cured film of the resulting curable composition, oxidation of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium and zinc It is preferable that it is a physical particle. Of these, from the viewpoint of transmittance, oxide particles of silicon, zirconium, or aluminum are preferable, and silicon oxide particles are particularly preferable.
By using the inorganic oxide fine particles (D), the pencil hardness can be further increased, and a coating film having high etchant resistance can be obtained.

  Inorganic oxide fine particles are used in physical dispersions such as plasma discharge treatment and corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding to the binder component. Surface treatment, chemical surface treatment with a surfactant, a coupling agent, or the like may be performed.

  The average primary particle diameter of the inorganic oxide particles is preferably 1 nm to 1000 nm, more preferably 3 nm to 100 nm, and particularly preferably 5 nm to 30 nm. When the average primary particle diameter exceeds 1000 nm, the transparency when cured is reduced, or the surface state when coated is liable to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.

  The average primary particle diameter of the inorganic oxide fine particles is measured using, for example, the BET method. Specifically, the specific surface area of the inorganic oxide fine particles obtained by the BET method is obtained, the ratio of volume to surface area is calculated using the specific gravity of the inorganic oxide, and the particles are assumed to be true spheres. There is a method of obtaining the particle diameter from these ratios to obtain the average primary particle diameter.

The inorganic oxide particles are preferably used as an organic solvent dispersion. When used as an organic solvent dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such organic solvents include alcohol solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ -Ester solvents such as butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ether solvents such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; dimethyl Examples include amide solvents such as formamide, dimethylacetamide, and N-methylpyrrolidone.
Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  Commercially available products as silicon oxide fine particle dispersions particularly preferably used in the present invention include MA-ST-MS, IPA-ST, IPA-ST-MS, and IPA-ST- manufactured by Nissan Chemical Industries, Ltd. L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc., hollow silica CS60-IPA manufactured by Catalyst Kasei Kogyo Co., Ltd., etc. Can be mentioned. As powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Examples of products that are commercially available as zirconia oxide fine particle dispersions preferably used in the present invention include ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH manufactured by Nissan Chemical Industries, Ltd., Sumitomo Osaka Cement ( HXU-110JC manufactured by Co., Ltd. can be mentioned.

  Commercially available products as aluminum oxide fine particle dispersions preferably used in the present invention include alumina sol-100, alumina sol-200, alumina sol-520 manufactured by Nissan Chemical Industries, Ltd. and AS- manufactured by Sumitomo Osaka Cement Co., Ltd. 150I, AS-150T.

  In addition, examples of the inorganic oxide fine particle dispersion preferably used in the present invention include oxide fine particle dispersions of titanium, zinc and the like, and examples of commercially available products include Nanotech manufactured by C-Kasei Co., Ltd.

  The addition amount of the inorganic oxide fine particles is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, in the total solid content of 100% by weight in the resin composition. When the addition amount is less than 5% by weight, it is difficult to obtain effects such as improvement in pencil hardness and etchant resistance. On the other hand, when the addition amount exceeds 40% by weight, problems such as deterioration of substrate adhesion may occur. is there.

<Polyfunctional monomer>
The resin composition of the present invention can contain a polyfunctional monomer.
Especially, it is especially preferable that the polyfunctional monomer (E) which has 7 or more ethylenically unsaturated double bonds in 1 molecule is included. By including this, it will be excellent in pencil hardness and etchant tolerance. Moreover, it is preferable that it is a polyfunctional monomer which has 7-16 ethylenically unsaturated double bonds from viewpoints, such as the maintenance of a transmittance | permeability, and pencil hardness and base-material adhesiveness, Furthermore, it is 7-12 pieces. In some cases, it is more preferable because it is excellent in pencil hardness, substrate adhesion, and etchant resistance.

[一般式（２）において、ｍは０〜４の整数であり、Ｒ₃はエーテル基、アルキレン基、トリレン基、アリーレン基、カルボニル基、スルホニル基、エステル基、および一般式（３）で表される構造を有する２価の基からなる群より選ばれるいずれかであり、Ｒ₄は水素原子またはメチル基であり、Ｒ₅はヒドロキシル基、カルボキシル基、および（メタ）アクリロイル基からなる群より選ばれるいずれかである。] << Polyfunctional monomer (E) >>
The polyfunctional monomer (E) having 7 or more ethylenically unsaturated double bonds is preferably, for example, a polyfunctional monomer represented by the following general formula (2).
General formula (2):

[In General Formula (2), m is an integer of 0 to 4, and R ₃ is an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, and a general formula (3). R ₄ is a hydrogen atom or a methyl group, R ₅ is selected from the group consisting of a hydroxyl group, a carboxyl group, and a (meth) acryloyl group. One of the choices. ]

[一般式（３）において、Ｒ₆は脂肪族、脂環式または芳香族の構造を表す。] General formula (3):

[In General Formula (3), R ₆ represents an aliphatic, alicyclic or aromatic structure. ]

Among the compounds represented by the general formula (2), R ₃ is preferably an ether group or a divalent group having a structure represented by the general formula (3) in terms of pencil hardness and substrate adhesion. .

Examples of compounds in which R ₆ is an ether group include a compound obtained by reacting dipentaerythritol penta (meth) acrylate and polyfunctional isocyanate, and reacting dipentaerythritol penta (meth) acrylate and tetrabasic acid dianhydride. And a compound obtained by reacting dipentaerythritol penta (meth) acrylate with a polyfunctional epoxy compound.

Specific examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.
Specific examples of tetrabasic acid dianhydrides include pyromellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride. , Cyclopentanetetracarboxylic dianhydride, oxydiphthalic anhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimellitate monoacetate), benzophenone tetracarboxylic dianhydride, methylcyclohexylene tetracarboxylic acid A dianhydride etc. can be mentioned.
Specific examples of the polyfunctional epoxy compound include tris (glycidylphenyl) methane, triglycidyl isocyanurate, bis (3,4-epoxycyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl). Examples thereof include adipate, methylene bis (3,4-epoxycyclohexane), bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and novolak type epoxy resin.

Among the polyfunctional monomers in which R ₃ is an ether group in the general formula (2), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetra Pentaerythritol deca (meth) acrylate, pentapentaerythritol undeca (meth) acrylate, or pentapentaerythritol dodeca (meth) acrylate is preferred.
Among these, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, or pentapentaerythritol dodeca (meth) acrylate is most preferable. It may be included.

  As such a polyfunctional monomer (E), commercially available products include, for example, biscoat # 802 (mixture of tripentaerythritol octaacrylate, tetrapentaerythritol decaacrylate, and pentapentaerythritol dodecaacrylate, manufactured by Osaka Organic Chemical Industries, Ltd. ).

[一般式（３）において、Ｒ₆は脂肪族、脂環式または芳香族の構造を表す。] When R ₆ is a divalent group having a structure represented by the general formula (3), it is more preferable in terms of pencil hardness if n = 1 and R ₅ is a (meth) acryloyl group.
General formula (3)

[In General Formula (3), R ₆ represents an aliphatic, alicyclic or aromatic structure. ]

  As such a polyfunctional monomer (E), commercially available products include, for example, TO-2323, TO-2324, TO-2325, TO-2326, TO-2327 and TO-2328 (manufactured by Toa Gosei Co., Ltd.). be able to.

  The content of the polyfunctional monomer (E) is preferably used in an amount of 5 to 80% by weight in a total of 100% by weight of the solid content of the resin composition. In this case, if the polyfunctional monomer (C) is less than 5% by weight, the effects of increasing pencil hardness, imparting etchant resistance, and imparting solvent resistance cannot be obtained. Decrease in adhesion is likely to occur. More preferably, it is 10 to 50% by weight.

《Other polyfunctional monomers》
In the present invention, in addition to the above polyfunctional monomer (E), other polyfunctional monomers may be included. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Examples thereof include various acrylic esters and methacrylic esters such as acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and propylene oxide-modified trimethylolpropane tri (meth) acrylate.

  Further, it may contain a polyfunctional monomer having an acid group, for example, an esterified product of a poly (meth) acrylate containing a free hydroxyl group of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; And esterified products with monohydroxyalkyl (meth) acrylates. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.

Moreover, the compound represented by following General formula (5) can also be used preferably.
General formula (5):
_{(H 2 C = C (R} 9) COO) h -X- (OCOCH (R 9) CH 2 S (R 10) COOH) i ··· (5)
[In General Formula (5), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is a hydrocarbon group having 1 to 12 carbon atoms, and X is an (h + i) -valent carbon number 3 to 60 H represents an integer of 2 to 18, and i represents an integer of 1 to 3. ]

Here, the compound represented by the general formula (5) can be easily obtained, for example, by the following method.
(1) A method of adding a mercapto compound to an obtained compound after esterifying the compound giving an organic group represented by X with acrylic acid to acrylate, and (2) a compound giving an organic group represented by X Is modified with a polyisocyanate compound, and then the resulting compound is acrylated with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound. (3) An organic group represented by X is given. A method in which a compound is esterified with acrylic acid to be acrylated, then modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

  Examples of the compound giving an organic group represented by X include pentaerythritol, pentaerythritol modified caprolactone, pentaerythritol modified polyisocyanate, dipentaerythritol, dipentaerythritol caprolactone modified, dipentaerythritol polyisocyanate Denatured products can be mentioned.

  Examples of the mercapto compound include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

<Photopolymerization initiator>
In the resin composition of the present invention, in order to cure the composition by ultraviolet irradiation and form a coating film by a photolithography method, a photopolymerization initiator is added and a solvent development type or alkali development type photosensitive resin composition is added. It can be prepared in the form of a product.

  Examples of the photopolymerization initiator 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- [4- (methylthio) phenyl] -2-morpholinopropane- Acetophenone photopolymerization initiators such as 1-one, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl]-, oxy such as 1- (o-acetyloxime) Ester photopolymerization initiators, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxy Benzophenone photopolymerization initiators such as benzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropyl Thioxanthone photopolymerization initiators such as thioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-tria 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 (trichloro Methyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine photopolymerization initiators such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazoles These are used alone or in combination of two or more.

Among them, acetophenone photopolymerization initiators and oxime ester photopolymerization initiators are preferable because they have high sensitivity and can be added in a small amount, so that the transmittance increases.
Among acetophenone photopolymerization initiators and oxime ester photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1 , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], especially 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)] has a high transmittance as an insulating film because it does not turn yellow during the heating step, and particularly has a transmittance around 400 nm. This is more preferable because it can provide a resin composition having a high value. These may be used alone or in combination.
The photopolymerization initiator is preferably used in an amount of 1 to 30% by weight in a total of 100% by weight of the solid content of the resin composition, and more preferably 1 to 10% by weight from the viewpoint of transmittance. .

The resin composition of the present invention further includes α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4 as a sensitizer. , 4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like can be used in combination.
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>
The resin composition of the present invention can contain an antioxidant. The antioxidant can suppress a decrease in transmittance due to yellowing or the like due to the heating process. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

<< Antioxidant (F) >>
Among these antioxidants, from the viewpoint of compatibility between the transmittance and sensitivity of the coating film, a preferable one is at least selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants. One type of antioxidant (F) is mentioned. Among phenol-based compounds, hindered phenol-based antioxidants having high steric hindrance are particularly preferable.

[Phenolic antioxidant]
For example, 2,6-di-t-butyl-4-ethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 , 5-triazine, 2,2-thio-diethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -Isocyanurate, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methoxyphenol, triethylene glycol- Bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Examples include propionate and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenyl) benzene. .

  Among them, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t- A hindered phenolic antioxidant selected from the group consisting of butyl-4-hydroxybenzylphosphonate-diethyl ester and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate is: It is preferable from the viewpoint of photocurability.

[Phosphorus antioxidant]
Although what is marketed can be used as phosphorus antioxidant, Tris [2,4-di- (tert) -butylphenyl] phosphinetris [2-[[2,4,8,10-tetrakis ( 1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-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, ethylbisphosphite (2,4-ditert-butyl-6-) It is preferable that it is at least one compound selected from the group consisting of these, and these may be used alone or in combination of two or more.

[Sulfur antioxidants]
A sulfur-based antioxidant is an antioxidant containing sulfur in the molecule. As such a sulfur-containing antioxidant, commercially available ones can be used, but dioctadecyl 3,3′-thiodipropanoate, dimyristyl-3,3′-thiodipropionate, dipalmityl-3,3′- Thiodipropionate, distearyl-3,3′-thiodipropionate, 4,4′-thiobis-3-methyl-6-tert-butylphenol, thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], and is preferably at least one compound selected from the group consisting of these, and one or more of these may be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  The content of the antioxidant (F) is preferably 0.1% by weight or more and less than 4% by weight in a total solid content of 100% by weight of the resin composition. When the amount is less than 0.1% by weight, it is difficult to obtain the yellowing prevention effect due to insufficient antioxidant, and when the amount is more than 4% by weight, the radicals generated during UV exposure are captured. May be insufficiently cured.

<Other ingredients>
In the resin composition of the present invention, a monofunctional monomer, a surfactant, a storage stabilizer, a leveling agent, a light stabilizer and the like can be used as necessary.

《Monofunctional monomer》
Examples of the monofunctional monomer include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxypropyl succinic acid. Acid, 2-methacryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, Methoxydipropylene glycol Acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and commercially available products such as 2-acryloyloxyethyl succinic acid (trade name M-5300) Can be mentioned.
These monofunctional monomers can be used singly or as a mixture of two or more at any ratio as required.

<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% by weight in a total of 100% by weight of the resin composition.

《Leveling agent》
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-330 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in a total of 100% by weight of the resin composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Production method of resin composition>
The resin composition of the present invention comprises a resin (A), an isocyanate group-containing silane compound (B), a solvent (C) and, if necessary, inorganic oxide fine particles (D), a polyfunctional monomer (E), photopolymerization. It can be obtained by stirring and mixing the initiator (F), the antioxidant (G) and the like.
The resin composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust and foreign matter.

<Coating film>
The resin composition according to the present invention is applied to a glass substrate, ITO, molybdenum, other metal film, organic film, etc. by spin coating such as spin coating, casting coating such as die coating, coating by roll coating, roll transfer method A coating film is formed by coating with, for example.
In addition, the resin composition of the present invention may be used for any protective film application, flat film application, touch panel insulating film application, and may be patterned by photolithography in each application. However, pattern formation by lithography is particularly preferable.

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, methods for measuring the weight average molecular weight of the resin, the hydroxyl value of the resin, and the double bond equivalent of the resin will be described.

(Weight average molecular weight of resin)
The weight average molecular weight (Mw) of the resin was measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. The molecular weight in terms of polystyrene.

(Hydroxyl value of resin)
The marine base value (JIS hydroxyl value) of the resin can be determined by the following method.
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value of the binder resin is measured according to “JIS K 0070-1992”, and specifically, it is measured according to the following procedure.
Preparation of reagent 25 g of special grade acetic anhydride is put into a 100 mL volumetric flask, pyridine is added to make a total volume of 100 mL, and shaken well to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.
Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95 vol%), add ion exchange water to make 100 mL, and obtain a phenolphthalein solution.
Dissolve 35 g of special grade potassium hydroxide in 20 mL of water and add ethyl alcohol (95 vol%) to make 1 liter (L). In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution is 25 mL of 0.5 mol / L hydrochloric acid in an Erlenmeyer flask, added several drops of the phenolphthalein solution, titrated with the potassium hydroxide solution, and required for neutralization. From the amount of. As the 0.5 mol / L hydrochloric acid, one prepared according to “JIS K 8001-1998” is used.

Operation (A) 1.0 g of the measurement sample pulverized in this test is precisely weighed into a 200 mL round bottom flask, and 5.0 mL of the above acetylating reagent is accurately added thereto using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.
A small funnel is placed on the mouth of the flask, and the bottom of the flask is immersed in a glycerin bath at about 97 ° C. and heated. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.
After 1 hour, remove the flask from the glycerin bath and treat. After standing to cool, 1 mL of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5 mL of ethyl alcohol.
Add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration similar to the above operation (A) main test is performed except that the measurement sample is not used.
Calculation of hydroxyl value The obtained result is substituted into the following formula to calculate the hydroxyl value.
A = [[(B−C) × 28.05 × f] / S] + D
(A: hydroxyl value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution of blank test, C: addition amount (mL) of potassium hydroxide solution of this test, f: potassium hydroxide solution Factor, S: Sample (g), D: Acid value of binder resin (mgKOH / g))

(Double bond equivalent of resin)
Double bond equivalent is a measure of the amount of double bonds contained in a molecule. If the compounds have the same molecular weight, the amount of double bonds introduced increases as the double bond equivalent value decreases. .
The double bond equivalent was calculated by the following formula.
[Double bond equivalent] = [Molecular weight of monomer component having double bond] / [Composition ratio of monomer component having double bond in resin]

Then, the manufacturing method of resin (A1) solution and other resin (A2) solutions is demonstrated.
<Method for Producing Resin (A1) Solution>
(Resin solution (A1-2))
Process 1
PGMEA 100 parts is put into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heated to 80 ° C. while injecting nitrogen gas into the vessel, 25.0 parts of styrene at the same temperature, A mixture of 1.0 part of 2-hydroxyethyl methacrylate, 30.0 parts of cyclohexyl methacrylate, 27.0 parts of methacrylic acid and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 40 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours to obtain a copolymer. It was.
Process 2
Next, dry air was introduced into the reaction vessel, charged with 45.0 parts of glycidyl methacrylate, 37.0 parts of PGMEA, 1.0 part of dimethylbenzylamine, and 0.1 part of methoquinone, and then continued stirring at the same temperature for 10 hours. It was. After cooling to room temperature, a resin solution (A1-2) having a weight average molecular weight, a hydroxyl value, and a double bond equivalent as shown in Table 1 having a solid content of 40% was obtained by diluting with PGMEA.

(Resin solution (A1-3, A1-4, A1-6, A1-7, A1-10))
The weight average molecular weight as shown in Table 1 or Table 2 is adjusted by the same method as the resin solution (A1-2) except that the composition is changed to the composition shown in Table 1 or Table 2 and the blending amount (parts by weight). , A resin solution (A1-3, A1-4, A1-6, A1-7, A1-10) having a hydroxyl value and a double bond equivalent was obtained.

(Resin solution (A1-5))
Process 1
In a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, 100 parts of PGMEA was charged and heated to 80 ° C. while injecting nitrogen gas into the vessel, and 4.0 parts of styrene at the same temperature, A mixture of 4.0 parts of cyclohexyl methacrylate, 46.6 parts of glycidyl methacrylate, 20.0 parts of 2-hydroxyethyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours to obtain a copolymer. It was.
Process 2
Next, dry air was introduced into the reaction vessel, charged with 28.2 parts of methacrylic acid, 100 parts of PGMEA, 1 part of dimethylbenzylamine and 0.1 part of methoquinone, and then continued stirring at the same temperature for 10 hours.
Process 3
Further, 120.0 parts of tetrahydrophthalic anhydride was charged, and stirring was continued at the same temperature for 10 hours. After cooling to room temperature, the resin solution (A1-5) having a weight average molecular weight, a hydroxyl value, and a double bond equivalent as shown in Table 1 having a solid content of 40% was obtained by diluting with PGMEA.

(Resin solution (A1-8, A1-9))
The weight average molecular weight, the hydroxyl value, and the double as shown in Table 2 were adjusted in the same manner as in the resin solution (A1-5) except that the composition and the amount (parts by weight) shown in Table 1 were changed. Resin solutions (A1-8, A1-9) having a binding equivalent weight were obtained.

(Resin solution (A1-11))
Process 1
150 parts of PGMEA is placed in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 20.0 parts of methacrylic acid at the same temperature. , A mixture of 30.0 parts of 2-hydroxyethyl methacrylate, 10.0 parts of styrene, 50.0 parts of cyclohexyl methacrylate, and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. Thereafter, stirring was continued at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, a resin solution (A1-11) having a weight average molecular weight and a hydroxyl value as shown in Table 2 having a solid content of 40% was obtained by diluting with PGMEA.

<Method for producing other resin (A2) solution>
(Resin solution (A2-1))
Process 1
PGMEA 100 parts is put into a reaction vessel equipped with a stirrer, a thermometer, a dripping device, a reflux condenser, and a gas introduction pipe, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 10.0 parts of methacrylic acid at the same temperature. , 22.5 parts of 2-hydroxyethyl methacrylate, 20.0 parts of styrene, 30.0 parts of cyclohexyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile were added dropwise over 1 hour to carry out the polymerization reaction. went. After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 20 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours to obtain a copolymer. It was.
Process 2
Subsequently, the temperature of the reaction vessel was cooled to 70 ° C., and dry air was further introduced into the reaction vessel, and 50.0 parts of 2-methacryloyloxyethyl isocyanate, 37 parts of PGMEA, 0.1 part of dibutyltin dilaurate, 0.1 part of methoquinone 0.1 Then, stirring was continued at the same temperature for 10 hours. After cooling to room temperature, a resin solution (A2-1) having a weight average molecular weight and a double bond equivalent as shown in Table 2 having a solid content of 40% was obtained by diluting with PGMEA.

(Resin solution (A2-2))
Process 1
PGMEA 100 parts is put into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction pipe, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 30.0 parts of methacrylic acid at the same temperature. A mixture of 40.0 parts of styrene, 30.0 parts of cyclohexyl methacrylate, and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 40 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours to obtain a copolymer. It was. After cooling to room temperature, the resin solution (A2-2) having a weight average molecular weight and a double bond equivalent as shown in Table 2 having a solid content of 40% was obtained by diluting with PGMEA.

PGMEA: propylene glycol monomethyl ether acetate St: styrene HEMA: 2-hydroxyethyl methacrylate CHMA: cyclohexyl methacrylate MAA: methacrylic acid MMA: methyl methacrylate GMA: glycidyl methacrylate THPA: tetrahydrophthalic anhydride (4-cyclohexene-1,2-dicarboxylic acid) Anhydride)

[Example 1]
(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 resin composition 1.

Resin solution A1-2 20.86 parts Polyfunctional monomer 4.00 parts (V # 802 “Biscoat # 802” (Osaka Organic Chemical Co., Ltd.))
Isocyanate group-containing silane compound 6.35 parts (3-isocyanatopropyltriethoxysilane)
Photopolymerization initiator 1.30 parts (IRGACURE OX-01 (manufactured by BASF); 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)])
Leveling agent 1.00 parts (BYK-330 2% (by Big Chemie); PGMEA solution of polyether structure-containing dimethylsiloxane (adjusted to 1% solid content)))
Solvent 66.49 parts (propylene glycol monomethyl ether acetate)

[Examples 2-36, Comparative Examples 1-5]
(Resin compositions 2 to 42 (R2 to R42))
After stirring and mixing the mixture shown in Tables 3 to 6 and the blending amount (parts by weight) uniformly, the mixture was filtered through a 1 μm filter, and in the same manner as the resin composition 1, Example 2 37, resin compositions 2-42 (R1-R42) corresponding to Comparative Examples 1-5 were obtained.

<< Inorganic oxide fine particle dispersion (D) >>
ZR-40BL (Nissan Chemical Co., Ltd.); tetramethylammonium hydroxide dispersion of fine zirconia oxide particles (solid content 40%)
PMA-ST (manufactured by Nissan Chemical Co., Ltd.); PGMEA dispersion of silicon oxide fine particles (solid content 30%)
<< Polyfunctional monomer (E) >>
・ V # 802; Biscote # 802 (Osaka Organic Chemical Co., Ltd.)
Mixture of tripentaerythritol octaacrylate and tetrapentaerythritol decaacrylate pentapentaerythritol dodecaacrylate, tripentaerythritol octaacrylate, DPCA30; Kayacure DPCA30 (manufactured by Nippon Kayaku Co., Ltd.)
Caprolactone-modified dipentaerythritol hexaacrylate M-402; Aronix M-402 (manufactured by Toagosei Co., Ltd.); dipentaerythritol hexaacrylate << isocyanate group-containing silane compound (B) >>
・ 3-Isocyanatopropyltriethoxysilane ・ 3-Isocyanatepropyltrimethoxysilane << other organic group-containing silane compounds >>
・ 3-glycidoxypropyltrimethoxysilane ・ 3-acryloxypropyltrimethoxysilane ・ N-phenyl-3-aminopropyltrimethoxysilane

<< Photopolymerization initiator >>
OXE-01; IRGACURE OX-01 (manufactured by BASF); 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]
・ Irg. 907; IRGACURE907 (manufactured by BASF); 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one-Irgacure 819 (manufactured by BASF); bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide

《Leveling agent》
-BYK-330 2% (manufactured by Big Chemie); polyether structure-containing dimethylsiloxane PGMEA solution (adjusted to 1% solids)
<< Solvent (C) >>
・ PGMEA: Propylene glycol monomethyl ether acetate ・ Ethanol (Kishida Chemical Co., Ltd.)
Butanol (made by Kishida Chemical Co., Ltd.); 1-butanol, 1,3-BGDA (made by Daicel Chemical Industries, Ltd.); 1,3-butylene glycol diacetate, 1,6-HDDA (made by Daicel Chemical Industries, Ltd.); 6-Hexanediol diacetate << Antioxidant (G) >>
IRGANOX 1010 (manufactured by BASF); pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
IRGANOX 1035 (manufactured by BASF); thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
TINUVIN123 (manufactured by BASF); decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reactivity of 1,1-dimethylethyl hydroperoxide and octane Creature

<Evaluation of resin composition>
The resin compositions (R1 to R42) were evaluated by the following evaluation methods. The results are shown in Tables 12-16.
(Measurement of transmittance)
The finished film thickness after heating the resin composition (R1 to R42) to a glass substrate (Corning Glass Eagle 2000) of 100 mm × 100 mm and 0.7 mm thickness using a spin coater at 230 ° C. for 20 minutes is 2.0 μm. A substrate coated so as to be obtained was obtained. Next, after holding for 2 minutes on a hot plate heated to 110 ° C., ultraviolet exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . 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.
Transmittance 97% or more: Good level transmittance 95% or more and less than 97%: Practical level transmittance <95%: Unsuitable level for practical use

(Heat resistance; measurement of transmittance after additional baking)
The resin composition coated substrate obtained by the same method as that prepared for transmittance measurement was heated at 300 ° C. for 20 minutes, allowed to cool, and then using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) The transmittance | permeability in wavelength 400nm of the obtained coating film was calculated | required.
Transmittance 97% or more: Good level transmittance 95% or more and less than 97%: Practical level transmittance <95%: Unsuitable level for practical use

(Measurement of pencil hardness)
The pencil hardness of the insulating film was measured by a scratch hardness (pencil method) test according to JIS K5600-5-4 for the resin composition-coated substrate obtained by the same method as that prepared for measuring transmittance. When this value is 5H or higher, the pencil hardness is good. Pencil hardness of 7H is very good, 6H is good, 5H is practically excellent pencil hardness, pencil hardness is 4H, practical minimum pencil hardness, 3H or less, unsuitable for practical use Hardness.

(Measurement of adhesion to glass, ITO and Mo)
The substrate adhesion of the coating film is evaluated by an adhesion (cross-cut method) test according to JIS K5600-5-6 for the resin composition coated substrate obtained by the same method as that prepared for the measurement of transmittance, The number of peels in 25 grids was counted.
As the substrate, Corning Glass Eagle 2000, Geomatek ITO film, and Toho Kaken Mo film were used.
Number of cross-cuts peeled off 0 → Very good level Number of cross-cuts peeled less than 1 (edge peeling; level at which cross-cuts are peeled off) → Practically excellent level Number of cross-cuts peeled 1 to 3 The following → Levels where there is no practical problem More than 3 peeled grids → Levels where there is a practical problem

(ITO etchant resistance)
After coating on the ITO substrate by the same method as that prepared for the measurement of transmittance, it was immersed in ITO etchant; nitric acid / hydrochloric acid / water = 0.1 / 1/1 for 5 minutes at 40 ° C. And washed for 24 hours. The obtained substrate was evaluated for substrate adhesion of the coating film by an adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peels in 25 grids was counted.
Number of cross-cuts peeled off 0 → Very good level Number of cross-cuts peeled less than 1 (edge peeling; level at which cross-cuts are peeled off) → Practically excellent level Number of cross-cuts peeled 1 to 3 The following → Levels where there is no practical problem More than 3 peeled grids → Levels where there is a practical problem

(Mo etchant resistance)
After being coated on the Mo substrate by the same method as that prepared for the measurement of transmittance, it was immersed in Mo etchant; phosphoric acid / acetic acid / nitric acid / water = 80/5/5/10 at 40 ° C. for 5 minutes, After washing with pure water, it was left for 24 hours. The obtained substrate was evaluated for substrate adhesion of the coating film by an adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peels in 25 grids was counted.
Number of cross-cuts peeled off 0 → Very good level Number of cross-cuts peeled less than 1 (edge peeling; level at which cross-cuts are peeled off) → Practically excellent level Number of cross-cuts peeled 1 to 3 The following → Levels where there is no practical problem More than 3 peeled grids → Levels where there is a practical problem

(Stability over time)
Measure the viscosity immediately after adjusting the resin composition and the viscosity of the sample left at 40 ° C. for 7 days,
Thickening rate = [(viscosity after 7 days at 40 ° C.) / (Viscosity immediately after adjustment)] was determined.
○: Thickening rate is within 100% ± 10% ×: Thickening rate is not within 100% ± 10%

(Coating property)
The finished film thickness after heating the resin composition (R1 to R42) to a glass substrate (Corning Glass Eagle 2000) of 100 mm × 100 mm and 0.7 mm thickness using a spin coater at 230 ° C. for 20 minutes is 2.0 μm. A substrate coated so as to be obtained was obtained. Next, after holding for 2 minutes on a hot plate heated to 110 ° C., ultraviolet exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . The coated substrate was heated at 230 ° C. for 20 minutes, allowed to cool, and then visually checked for film thickness unevenness.
○: Unevenness is not observed Δ: Unevenness is observed but there is no problem in practical use ×: Unevenness is observed

  As shown in Table 11, a resin composition containing a resin (A) having a hydroxyl group in a side chain, a isocyanate group-containing silane compound (B), and a solvent (C), which is a feature of the present invention, By using a resin composition in which (A) has a hydroxyl group in the side chain, adhesion to a substrate such as pencil hardness, glass, ITO, Mo, etchant resistance, transmittance, heat resistance, stability over time, coating properties, etc. In both cases, good results were obtained.

  In particular, when a resin resin (A1-d) having a hydroxyl group in the side chain and having an acid group such as a carboxyl group and an ethylenically unsaturated double bond (A1-d) is used, the pencil hardness is high and good results are obtained. It was.

  Examples 1, 2, and 37 and Comparative Examples 1 and 2 were excellent results in pencil hardness, substrate adhesion, and etchant resistance.

  When Examples 1 and 2 were compared with Comparative Examples 3 to 5, Examples 1 and 2 having an isocyanate group-containing silane compound resulted in high pencil hardness, substrate adhesion, and etchant resistance.

  When Examples 1, 2, 3, 4, and 5 are compared, the molar ratio of the hydroxyl group of the resin (A) and the isocyanate group of the isocyanate group-containing silane compound (B) is included in the range of 0.40 to 1.60. In Examples 1, 2, and 4, the pencil hardness was high.

  Moreover, when Example 1 and Examples 6-13 are compared, resin (A1) is resin which has an ethylenically unsaturated double bond in a side chain, and a hydroxyl equivalent is 300-1000 g / mol, a double bond. Examples 1 and 6 to 9 having an equivalent weight of 350 to 1200 g / mol achieved both excellent pencil hardness and substrate adhesion, and were particularly excellent.

  Comparing Example 1 and Examples 14-18, the solvent (C) is an alcohol solvent (C1) having a boiling point of less than 130 ° C. at 760 mmHg, and the content of the alcohol solvent (C1) is a resin composition. When the solid content was 25 to 300 parts by weight with respect to 100 parts by weight, the result was excellent in substrate adhesion, etchant resistance, and stability over time.

  When Example 1 and Example 18 were compared, when the solvent (C) contained ethanol having a lower boiling point among alcoholic solvents having a boiling point of less than 130 ° C. at 760 mmHg, higher pencil hardness was obtained. .

  When Example 18 and Examples 19 and 20 are compared, the solvent (C) contains an alcohol solvent (C1) having a boiling point of less than 130 ° C. at 760 mmHg, and further has an ester solvent having a boiling point of 760 mmHg of 200 ° C. or more and less than 250 ° C. As a result, the wettability to the ITO or molybdenum substrate was improved and the coating property was improved.

  Further, as in Examples 21 and 22, in combination with the inorganic oxide fine particles (D), the pencil hardness was improved, and the normally reduced transmittance was maintained, and the heat resistance was improved. .

  Moreover, when Example 21 and Examples 23-25 are compared, the content of the inorganic oxide fine particles (D) is 5% by weight or more and 40% by weight or less in the total solid content of the resin composition of 100% by weight. 22 and Example 25 were excellent in pencil hardness, heat resistance, and etchant resistance.

  Moreover, when Example 21 and Examples 26-28 are compared, V # 802 in which a polyfunctional monomer (B) has seven or more ethylenically unsaturated bonds represented by following General formula (2) is used. Examples 21 and 26 were the most excellent results in pencil hardness and etchant resistance.

  Further, when Example 26 and Examples 29 and 30 are compared, Example 26 and Example 29 in which the photopolymerization initiator is an acetophenone photopolymerization initiator or an oxime ester photopolymerization initiator have particularly high transmittance. Met.

  Moreover, when Example 26 and Examples 31-34 were compared, it was a result in which the heat resistance of Example 31 and 32 in which antioxidant (F) contains a phenol type compound is especially excellent.

  Further, when Example 31 and Examples 35 and 36 are compared, Examples 31 and 35 containing 0.1 wt% or more and 4 wt% or less of the antioxidant (F) in the total solid content of 100 wt% of the resin composition are as follows: The heat resistance was particularly excellent.

Claims (15)

A resin composition comprising a resin (A1) having a hydroxyl group in a side chain, an isocyanate group-containing silane compound (B) represented by the following general formula (1), and a solvent (C).
General formula (1)
_{(OCN-R 1) n -Si-} (R 2) 4-n
[In General Formula (1), R ₁ represents an alkylene group having 1 to 5 carbon atoms, R ₂ represents an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group, and n is an integer of 1 to 3. ]   The resin composition according to claim 1, wherein the molar ratio of the hydroxyl group of the resin (A1) to the isocyanate group of the isocyanate group-containing silane compound (B) is 0.40 to 1.60.   The resin (A1) is a resin having an ethylenically unsaturated double bond in the side chain, and has a hydroxyl group equivalent of 300 to 1000 g / mol and a double bond equivalent of 350 to 1200 g / mol. The resin composition according to claim 1 or 2.   The resin composition according to any one of claims 1 to 3, wherein the solvent (C) contains an alcohol solvent (C1) having a boiling point of less than 130 ° C at 760 mmHg.   The resin composition according to claim 4, wherein the content of the alcohol solvent (C1) is 25 to 300 parts by weight with respect to 100 parts by weight of the solid content of the resin composition.   5. The resin composition according to claim 4, wherein the solvent (C) further contains a solvent having a boiling point of 130 ° C. or more and less than 250 ° C. at 760 mmHg.   The resin composition according to claim 4, wherein the solvent (C) further contains an ester solvent having a boiling point at 760 mmHg of 200 ° C. or higher and lower than 250 ° C. 6.   The resin composition according to any one of claims 1 to 7, further comprising inorganic oxide fine particles (D) of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium and zinc. object.   The resin composition according to claim 8, wherein the content of the inorganic oxide fine particles (D) is 5% by weight or more and less than 40% by weight in a total solid content of 100% by weight of the resin composition. Furthermore, the polyfunctional monomer (E) which has a 7 or more ethylenically unsaturated double bond represented by following General formula (2) is included, The any one of Claims 1-9 characterized by the above-mentioned. The resin composition as described.
General formula (2):

[In General Formula (2), m is an integer of 0 to 4, and R ₃ is an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, and a general formula (3). R ₄ is a hydrogen atom or a methyl group, R ₅ is selected from the group consisting of a hydroxyl group, a carboxyl group, and a (meth) acryloyl group. One of the choices. ]
General formula (3):

[In General Formula (3), R ₆ represents an aliphatic, alicyclic or aromatic structure. ]   The resin composition according to any one of claims 1 to 10, further comprising an acetophenone photopolymerization initiator or an oxime ester photopolymerization initiator.   Furthermore, at least 1 sort (s) of antioxidant (F) chosen from the group which consists of a phenolic antioxidant, phosphorus antioxidant, and sulfur type antioxidant is included, The any one of Claims 1-11 characterized by the above-mentioned. The resin composition described in 1.   The resin composition according to claim 12, wherein the antioxidant (F) is 0.1 wt% or more and less than 4 wt% in a total solid content of 100 wt% of the resin composition.   The protective film formed using the resin composition of any one of Claims 1-13.   The insulating film for touchscreens formed using the resin composition of any one of Claims 1-13.