CN113906344A - Curable resin composition, insulating cured film obtained by curing the composition, insulating cured film for touch panel, and touch panel - Google Patents

Curable resin composition, insulating cured film obtained by curing the composition, insulating cured film for touch panel, and touch panel Download PDF

Info

Publication number
CN113906344A
CN113906344A CN202080040696.4A CN202080040696A CN113906344A CN 113906344 A CN113906344 A CN 113906344A CN 202080040696 A CN202080040696 A CN 202080040696A CN 113906344 A CN113906344 A CN 113906344A
Authority
CN
China
Prior art keywords
group
resin composition
curable resin
film
touch panel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202080040696.4A
Other languages
Chinese (zh)
Inventor
大浦裕贵
阿波茂树
矢头庆树
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Organic Chemical Industry Co Ltd
Original Assignee
Osaka Organic Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Osaka Organic Chemical Industry Co Ltd filed Critical Osaka Organic Chemical Industry Co Ltd
Publication of CN113906344A publication Critical patent/CN113906344A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Theoretical Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Human Computer Interaction (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention relates to a curable resin composition comprising: an alkali-soluble resin (A) which is a copolymer ofThe polymer comprises a structural unit (a-1) derived from at least one selected from the group consisting of a compound represented by the formula (a-1 alpha) and an unsaturated carboxylic acid having a cyclic skeleton, a structural unit (a-2) having a glass transition temperature of 70 to 200 ℃ when the polymer is produced into a homopolymer, and a structural unit (a-3) derived from an epoxy group-containing unsaturated compound; a photoreactive monomer (B) of formula (B-1); and a photopolymerization initiator (C). R1‑R3Is hydrogen atom, methyl group, carboxyl group; x1Is a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 9 carbon atoms which may contain an oxygen atom. R13‑R14Is a hydrogen atom, a methyl group; y is1～Y2Is a straight or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms; x2Is an aliphatic hydrocarbon group or an aromatic group having a cyclic skeleton.

Description

Curable resin composition, insulating cured film obtained by curing the composition, insulating cured film for touch panel, and touch panel
Technical Field
The present invention relates to a curable resin composition and an insulating cured film obtained by curing the composition, and for example, relates to a curable resin composition useful for applications of an insulating cured film used for a touch panel or the like (for example, applications of an insulating film, a protective film, a flat film, and the like), an insulating cured film for a touch panel obtained by curing the composition, and a touch panel provided with the cured film.
Background
In recent years, with the progress of high functionality, diversification, and reduction in size and weight of electronic devices, there have been increasing devices in which a transparent touch panel is attached to the front surface of a display element such as a liquid crystal, characters, symbols, and patterns displayed on the display element are visually recognized and selected by the transparent touch panel, and each function of the device is switched by the operation of the transparent touch panel.
Detection methods for touch panels include a resistive film method, a capacitive method, an ultrasonic method, an optical method, and the like, and in recent years, the resistive film method and the capacitive method have been widely used. For example, the resistive film system is a system in which an upper electrode film and a lower electrode glass are formed on both sides, and a switch is pressed and reacted by applying pressure from above the upper electrode film with a pen tip or the like. The capacitance system is the following: the touch panel is formed of a cover glass and a sensor glass on the surface, and a finger touches the glass on the surface to cause electrostatic coupling, thereby generating a difference in electrostatic capacitance with the glass inside, and the touched portion is defined by the difference.
A capacitive touch panel uses, for example, glass with an ITO film as a substrate, and an insulating film and a protective film are provided in a laminated structure in order to prevent erroneous recognition of a touched position. As such a protective film, inorganic SiO having high hardness is used2A protective film made of SiNx, a transparent resin, or the like, or an organic protective film. As an organic protective film material, for example, a UV-curable coating composition containing an oligomer containing a polymerizable group, a monomer, a photopolymerization initiator, and other additives is known (for example, see patent document 1).
In addition, when the touch panel is combined with the liquid crystal display device, the touch panel can be classified into an Out-cell (Out-cell) structure, an On-cell (On-cell) structure, and an In-cell (In-cell) structure according to a set position. In recent years, an external embedded structure and an internal embedded structure having excellent visibility have become mainstream. In these external-embedded and internal-embedded structures, the touch panel is assembled in the liquid crystal panel. As the structure of the touch panel, a double-sided structure in which an X electrode is disposed on one surface of an insulating film and a Y electrode is disposed on the other surface, and a single-sided structure in which an X electrode and a Y electrode are formed on the same plane are known. In the single-sided touch panel structure, electrodes are separated in an insulating film, and the separated electrodes are electrically connected to each other by, for example, a member called a bridge portion (for example, see patent documents 2 and 3). As such a bridge portion, for example, a bridge portion having an ITO film is known.
In addition, an insulating film is also used in a liquid crystal display device or the like, and as a material usable for the insulating film, for example, a photosensitive resin material for an insulating film containing an alkali-soluble resin, a photocurable monomer, and a photopolymerization initiator is known in many cases (for example, see patent documents 4 and 5).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2010-027033
Patent document 2: japanese patent laid-open publication No. 2017-41204
Patent document 3: japanese laid-open patent publication No. 2012-88836
Patent document 4: japanese patent laid-open publication No. 2017-173525
Patent document 5: japanese patent laid-open publication No. 2017-173526
Disclosure of Invention
Problems to be solved by the invention
As described above, a curable resin composition is often used to form an insulating film used in a touch panel, a liquid crystal display device, or the like. Such an insulating film is required to have adhesion to an ITO film (electrode). As the adhesion to the ITO film, for example, it is required that the adhesion between the insulating film and the ITO film is not easily decreased by chemicals used in the production process ("excellent chemical resistance").
In the case of manufacturing a touch panel using a curable resin composition, for example, the curable resin composition is applied to a substrate by photolithography and the like, and exposed and developed to form an insulating film or the like. In this case, a coating film of the curable resin composition may be formed on a substrate such as a glass substrate at one time, and thereafter, the coating film corresponding to the non-pattern portion may be removed by a developer. When a metal thin film containing Al and Mo and an ITO film are formed by PVD or the like after exposure and development of the curable resin composition, the metal thin film and the ITO film are directly deposited on the substrate from which the coating film of the curable resin composition is removed. However, in such a case, the adhesion force between the glass substrate and the ITO film or the metal thin film may be reduced. Therefore, when an insulating film or the like is formed using a curable resin composition, it is also required that the adhesion force between the glass substrate from which the insulating cured film has been removed after patterning (development) and a metal thin film such as an ITO film or Al or Mo film is excellent ("excellent developability").
In addition, in an insulating film formed using a curable resin composition, when an ITO film is formed on the insulating film and then heat treatment or the like is performed, fine wrinkles may be generated on a contact surface between the ITO film and the insulating film. It is known that fine wrinkles formed in an insulating film affect various physical properties such as transparency of the insulating film. Therefore, development of a curable resin composition is desired: the above-mentioned chemical resistance and developability are excellent, and wrinkles (which are considered to be mainly caused by the film formation of the ITO film and the subsequent heat treatment or the like) generated on the contact surface with the ITO film when the insulating film is formed are few ("excellent wrinkle resistance").
In order to solve the above problems, an object of the present invention is to provide a curable resin composition capable of forming a cured film excellent in chemical resistance, developability, and wrinkle resistance, an insulating cured film obtained by curing the composition, an insulating cured film for a touch panel, and a touch panel provided with the cured film.
Means for solving the problems
The inventors of the present application have conducted intensive studies to solve the above problems. As a result, they have found that the above-mentioned object can be achieved by using a composition containing a copolymer having a specific structure and a monomer having a specific structure, and have completed the present invention.
< 1 > a curable resin composition comprising: an alkali-soluble resin (A) which is a copolymer comprising a structural unit (a-1) derived from at least one member selected from the group consisting of compounds represented by the following formula (a-1 alpha) and unsaturated carboxylic acids having a cyclic skeleton, a structural unit (a-2) having a glass transition temperature of 70 to 200 ℃ when a homopolymer is produced, and a structural unit (a-3) derived from an epoxy group-containing unsaturated compound; a photoreactive monomer (B) represented by the following formula (B-1); and a photopolymerization initiator (C).
[ chemical formula 1]
Figure BDA0003386277660000041
(in the formula, R1～R3Each independently represents a hydrogen atom, a methyl group, or a carboxyl group; x1Represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom. )
[ chemical formula 2]
Figure BDA0003386277660000042
(in the formula (b-1), R13～R14Each independently represents a hydrogen atom or a methyl group; y is1～Y2Each independently represents a single bond, or a straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms; x2Represents an aliphatic hydrocarbon group or an aromatic group having a cyclic skeleton. )
< 2 > the curable resin composition of < 1 >, wherein the structural unit (a-2) is derived from at least one selected from the group consisting of a compound represented by the following formula (a-2 α) and a compound represented by the following formula (a-2 β).
[ chemical formula 3]
Figure BDA0003386277660000043
(in the formula (a-2. alpha.), R4～R6Each independently represents a hydrogen atom or a methyl group; r7Represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic group having 6 to 20 carbon atoms. In the formula (a-2. beta.), R8～R12Each independently represents a hydrogen atom, a methyl group, an acetyl group, a benzoyl group, an isopropyl group, a tert-butyl group or a sec-butyl group. )
< 3 > the curable resin composition according to < 1 > or < 2 >, wherein the content of the photoreactive monomer (B) is 75% by mass or more based on the total amount of the photoreactive monomers in the curable resin composition.
< 4 > the curable resin composition according to any one of the above < 1 > -3 >, wherein the alkali-soluble resin (A) has a weight-average molecular weight of 5000 to 20000.
< 5 > the curable resin composition according to any one of the above < 1 > -4 >, wherein the alkali-soluble resin (A) has a content (mol%) of the structural unit (a-1), the structural unit (a-2) and the structural unit (a-3) of (a-1)/(a-2)/(a-3) of 15-25/40-60/25-35.
< 6 > the curable resin composition according to any one of the above < 1 > -5 >, wherein the alkali-soluble resin (A) comprises a structural unit (a-2) having a glass transition temperature of 100 to 180 ℃ when formed into a homopolymer.
< 7 > the curable resin composition according to any one of the above < 1 > -6 >, wherein Y in the formula (b-1)1And Y2Each independently a single bond or a methylene group.
< 8 > the curable resin composition according to any one of the above < 1 > -7 > for use in forming an insulating film.
< 9 > an insulating cured film obtained by curing the curable resin composition described in any one of the above < 1 > to < 8 >.
< 10 > an insulating cured film for a touch panel, which is obtained by curing the curable resin composition described in any one of the above < 1 > to < 8 >.
< 11 > a touch panel comprising the insulating cured film for a touch panel described in < 10 >.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention aims to provide a curable resin composition capable of forming a cured film excellent in chemical resistance, developability, and wrinkle resistance, an insulating cured film obtained by curing the composition, an insulating cured film for a touch panel, and a touch panel provided with the cured film.
Drawings
Fig. 1 is a plan view showing a configuration of one embodiment of a touch panel of the present embodiment.
FIG. 2 is a cross-sectional view of AA in FIG. 1.
FIG. 3 is an enlarged photograph showing an example of wrinkle evaluation in the example.
Detailed Description
Hereinafter, a specific embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the scope of the invention.
Curable resin composition
The curable resin composition of the present embodiment includes an alkali-soluble resin (a), a photoreactive monomer (B) represented by formula (B-1) described later, and a photopolymerization initiator (C). The alkali-soluble resin (a) in the present embodiment is a copolymer containing: a structural unit (a-1) derived from at least one member selected from the group consisting of a compound represented by the formula (a-1 α) described later and an unsaturated carboxylic acid having a cyclic skeleton; a structural unit (a-2) having a glass transition temperature of 70 to 200 ℃ when a homopolymer is produced; and a structural unit (a-3) derived from an epoxy group-containing unsaturated compound. The curable resin composition of the present embodiment can form a cured film that is less wrinkled (i.e., "excellent wrinkle resistance") when the cured film is formed by curing the composition to form a cured film and then performing heat treatment or the like, and can form a cured film that is excellent in the chemical resistance and the developability described above.
< alkali soluble resin (A) >)
In the present embodiment, the alkali-soluble resin (A) is a copolymer comprising the structural units (a-1), (a-2) and (a-3) described later. The alkali-soluble resin (A) may contain 1 kind of each of the structural units (a-1), (a-2) and (a-3), or may contain 2 or more kinds of the same structural units (for example, 2 kinds of the structural units (a-2)).
(structural Unit (a-1))
The structural unit (a-1) is derived from at least one structural unit selected from the group consisting of a compound represented by the following formula (a-1 α) and an unsaturated carboxylic acid having a cyclic skeleton. Hereinafter, the compound represented by the formula (a-1 α) may be referred to as "unsaturated carboxylic acid (a-1 α)". Similarly, an unsaturated carboxylic acid having a cyclic skeleton may be referred to as "cyclic unsaturated carboxylic acid (a-1 β)". The glass transition temperature (Tg) of the structural unit (a-1) in the case of forming a homopolymer is preferably 80 to 300 ℃ and more preferably 100 to 250 ℃ from the viewpoint of wrinkle resistance and developability. The glass transition temperature can be measured by a Differential Scanning Calorimeter (DSC). The weight average molecular weight of the homopolymer measured by DSC is not particularly limited, and may be set to about 4,000 to 20,000, for example.
Unsaturated carboxylic acid (a-1. alpha.) -
The unsaturated carboxylic acid (a-1 α) is a compound represented by the following formula (a-1 α), and is an unsaturated compound having a carboxyl group.
[ chemical formula 4]
Figure BDA0003386277660000071
(in the formula, R1～R3Each independently represents a hydrogen atom, a methyl group, or a carboxyl group; x1Represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom. )
R1～R3Each independently represents a hydrogen atom, a methyl group, or a carboxyl group.
X1Represents a single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms (divalent linking group) which may contain an oxygen atom. The aliphatic hydrocarbon group preferably has 1 to 7 carbon atoms from the viewpoint of wrinkle resistance. These aliphatic hydrocarbon groups may have an-O-structure (structure containing an oxygen atom: for example, an ester group (-O-), an acid anhydride group (-CO-O-CO-) in the structure. Examples of the linear aliphatic hydrocarbon group include an alkylene group having 1 to 15 carbon atoms, an aliphatic hydrocarbon group having 3 to 15 carbon atoms which may contain a plurality of ester groups or an acid anhydride group (-CO-O-CO-). Examples of the cyclic aliphatic hydrocarbon group include a cycloalkylene group having 3 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms and containing a plurality of ester groups and an acid anhydride group. In addition, X1Or can also be usedSo as to be an aliphatic hydrocarbon group containing both a straight chain portion and a cyclic portion. X having a plurality of ester groups or acid anhydride groups1Examples of (2) include-CO-O-CO-CH2-CH2-、-CO-O-CH2-CH2-O-CO-CH2-CH2-and the like.
Examples of the unsaturated carboxylic acid (a-1 α) include methacrylic acid (hereinafter, sometimes referred to as "MAA"), acrylic acid, crotonic acid (trans), maleic acid (cis), fumaric acid (trans), citraconic acid (cis), mesaconic acid (trans), itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, hexahydro-2-methacryloyloxyethyl phthalate, and the like, and methacrylic acid, crotonic acid (trans), citraconic acid (cis), mesaconic acid (trans), itaconic acid, and itaconic anhydride are preferable, and methacrylic acid is more preferable, from the viewpoints of easiness of polymerization with each structural unit (including the structural unit a-1) (hereinafter, referred to as polymerizability) and wrinkle resistance.
Cyclic unsaturated carboxylic acid (a-1. beta.) -
The cyclic unsaturated carboxylic acid (a-1 β) is an unsaturated compound having an ethylenically unsaturated bond in a cyclic structure and a carboxyl group, and examples thereof include an acid anhydride monomer. The acid anhydride monomer has a carboxyl group directly bonded to the main chain, such as maleic anhydride, and has a structure similar to methacrylic acid after polymerization.
As the cyclic unsaturated carboxylic acid (a-1 β), an acid anhydride monomer which generates 2 carboxyl groups by ring opening after polymerization is preferable. Examples of the cyclic unsaturated carboxylic acid (a-1 β) include a compound having a double bond in a cyclic skeleton, a compound having an α, β unsaturated carbonyl structure in a cyclic skeleton, and a compound having a bicyclic skeleton formed by ring shrinkage.
Examples of the compound having a double bond in the cyclic skeleton include maleic anhydride, citraconic anhydride, and 2, 3-dimethylmaleic anhydride.
Examples of the compound having an α, β unsaturated carbonyl structure in the cyclic skeleton include itaconic anhydride, 2-isopropylidene succinic anhydride, (Z) -benzylidene succinic anhydride, (E) -benzylidene succinic anhydride, (1-phenylethylidene) succinic anhydride, 2- (1-naphthylmethylene) succinic anhydride, diphenylmethylene (benzhydrylene) succinic anhydride, and 2-methyl-3-methylenesuccinic anhydride.
Examples of the compound having a bicyclic skeleton formed by ring condensation include 1,2,3, 6-tetrahydrophthalic anhydride, 5-norbornene-2, 3-dicarboxylic anhydride, and 2,3,4, 5-tetrahydrophthalic anhydride.
Among the above, the cyclic unsaturated carboxylic acid (a-1 β) is preferably 1,2,3, 6-tetrahydrophthalic anhydride from the viewpoint of wrinkle resistance.
(structural Unit (a-2))
The structural unit (a-2) has a glass transition temperature (Tg) (hereinafter, may be referred to simply as "the glass transition temperature of the structural unit (a-2)") of 70 to 200 ℃ when a homopolymer is produced, and has a structure different from that of the structural units (a-1) and (a-3). When the glass transition temperature of the structural unit (a-2) is 70 ℃ or higher, wrinkles are less likely to occur, and when it is 200 ℃ or lower, the developability is excellent. The alkali-soluble resin (A) preferably contains a structural unit (a-2) having a glass transition temperature of 80 to 200 ℃ when made into a homopolymer. The glass transition temperature of the structural unit (a-2) is more preferably 80 to 180 ℃ and most preferably 100 to 180 ℃. The glass transition temperature can be measured by a Differential Scanning Calorimeter (DSC) in the same manner as in the above-mentioned structural unit (a-1).
The structural unit (a-2) is not particularly limited as long as it satisfies the above condition, but is preferably a structural unit derived from at least one selected from the group consisting of a compound represented by the following formula (a-2 α) and a compound represented by the following formula (a-2 β), for example, from the viewpoint of wrinkle resistance.
[ chemical formula 5]
Figure BDA0003386277660000091
(in the formula (a-2. alpha.), R4～R6Each independently represents a hydrogen atom or a methyl group; r7Represents a linear, branched or cyclic carbon number of1 to 12 aliphatic hydrocarbon groups or aromatic groups having 6 to 20 carbon atoms. In the formula (a-2. beta.), R8～R12Each independently represents a hydrogen atom, a methyl group, an acetyl group, a benzoyl group, an isopropyl group, a tert-butyl group or a sec-butyl group. )
In the formula (a-2 alpha), R4～R6Each independently represents a hydrogen atom or a methyl group, and R is preferably R from the viewpoint of wrinkle resistance and polymerizability4And R5Is a hydrogen atom, R6Is methyl.
In the formula (a-2 alpha), R7Represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic group having 6 to 20 carbon atoms. When the number of carbon atoms is 12 or less, the developability is excellent. The aliphatic hydrocarbon preferably has 1 to 12 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of the linear or branched aliphatic hydrocarbon group include an alkyl group having 1 to 12 carbon atoms, a methyl group, a 1-methylethyl group, a 1, 1-dimethylethyl group and the like. Examples of the cyclic aliphatic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms, an isobornyl group, a dicyclopentyl group, an adamantyl group, and a3, 5-dimethyladamantyl group. The number of carbon atoms of the aromatic group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 12. Examples of the aromatic group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and the like. In addition, R7The aliphatic hydrocarbon group may contain a straight chain portion, a branched chain portion, and a cyclic portion.
The compound represented by the formula (a-2. alpha.) includes the following compounds. The temperature in parentheses attached after the compound indicates the glass transition temperature of the compound. However, this value is a literature value and varies depending on the actual molecular weight and the measurement method.
Examples of the compound represented by the formula (a-2. alpha.) include 4-biphenyl acrylate (100. degreeC.), 3, 5-dimethyladamantyl acrylate (106. degreeC.), 2-naphthyl acrylate (85. degreeC.), 3, 5-dimethyladamantyl crotonate (159. degreeC.), methyl methacrylate (hereinafter, sometimes referred to as "MMA") (105. degreeC.), 1-dimethylethyl methacrylate (118. degreeC.), 1-methylethyl methacrylate (81. degreeC.), isobornyl methacrylate (110. degreeC.), phenyl methacrylate (110. degreeC.), adamantyl methacrylate (141. degreeC.), 4- (1, 1-dimethylethyl) cyclohexyl methacrylate (83. degreeC.), 4- (1, 1-dimethylethyl) phenyl ester (98 ℃ C.), 3-dimethyl-1-butyl methacrylate (108 ℃ C.), 3, 5-trimethylhexyl methacrylate (125 ℃ C.), 2, 3-dimethylphenyl methacrylate (125 ℃ C.), dicyclopentyl methacrylate (alias: dicyclopentyl methacrylate) (175 ℃ C.), 3, 5-dimethyladamantyl methacrylate (196 ℃ C.), preferably 4-biphenyl acrylate, 3, 5-dimethyladamantyl crotonate, methyl methacrylate, 1-dimethylethyl methacrylate, isobornyl methacrylate, phenyl methacrylate, adamantyl methacrylate, 3-dimethyl-1-butyl methacrylate, 3, 5-trimethylhexyl methacrylate, 2, 3-dimethylphenyl methacrylate, dicyclopentyl methacrylate, 3-methacrylic acid, 5-dimethyladamantyl ester, methyl methacrylate and dicyclopentyl methacrylate are more preferable.
In the formula (a-2. beta.), R8～R12Each independently represents a hydrogen atom, a methyl group, an acetyl group, a benzoyl group, an isopropyl group, a tert-butyl group or a sec-butyl group, and preferably has an acetyl group or a tert-butyl group from the viewpoint of wrinkle resistance. In addition, R is8～R12May be further substituted with a substituent such as an alkyl group.
Examples of the compound represented by the formula (a-2. beta.) include, for example, 4-acetylstyrene (116 ℃ C.), 4-benzoylstyrene (98 ℃ C.), 5- (1, 1-dimethylethyl) -2-methylstyrene (87 ℃ C.), 4- (1-methylpropyl) styrene (86 ℃ C.), 4- (1, 1-dimethylethyl) styrene (126 ℃ C.), 2, 5-diisopropylstyrene (168 ℃ C.), 2, 4-dimethylstyrene (112 ℃ C.), 2, 5-dimethylstyrene (143 ℃ C.), and preferably 4-acetylstyrene, 4- (1, 1-dimethylethyl) styrene, 2, 5-diisopropylstyrene, 2, 4-dimethylstyrene (143 ℃ C.), from the viewpoint of wrinkle resistance, 2, 5-dimethylstyrene, more preferably 4- (1, 1-dimethylethyl) styrene. In the same manner as above, the temperature in parentheses after the compound indicates the glass transition temperature of the compound, but this value is a literature value and varies depending on the actual molecular weight and the measurement method.
(structural Unit (a-3))
The structural unit (a-3) is a structural unit derived from an epoxy group-containing unsaturated compound. The structural unit derived from an epoxy group-containing unsaturated compound can be appropriately selected from epoxy group-containing unsaturated compounds (or structural units derived therefrom) conventionally used in various photosensitive resin compositions.
The glass transition temperature of the structural unit (a-3) when it is a homopolymer is preferably 20 to 100 ℃, more preferably 30 to 90 ℃, and particularly preferably 30 to 80 ℃ from the viewpoint of improving wrinkle resistance and reactivity with other structural units. The glass transition temperature can be measured by a Differential Scanning Calorimeter (DSC).
From the viewpoint of reactivity with other structural units, the molecular weight of the unsaturated compound containing an epoxy group is preferably 100 to 1000, more preferably 100 to 500, and particularly preferably 100 to 300.
Examples of the epoxy group-containing unsaturated compound include an unsaturated compound having an epoxy structure in a cyclic structure, such as an alicyclic epoxy group, and an unsaturated compound having no alicyclic epoxy group, and preferably an unsaturated compound having an epoxy structure in a cyclic structure, such as an alicyclic epoxy group.
As the unsaturated compound having an alicyclic epoxy group, the alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups.
Examples of the unsaturated compound having an epoxy group include unsaturated compounds having an epoxy group described in, for example, JP-A-2013-228662-0015-0024, and specifically glycidyl methacrylate, 2-methylglycidyl methacrylate, 3, 4-epoxybutyl methacrylate, 6, 7-epoxyheptyl methacrylate, and 3, 4-epoxycyclohexylmethyl methacrylate (3, 4-epoxycyclohexylmethyl methacrylate) are preferable, and 3, 4-epoxycyclohexylmethyl methacrylate is more preferable from the viewpoint of chemical resistance.
(constitution ratio)
From the viewpoint of achieving both chemical resistance and wrinkle resistance, the content (mol%) of the structural unit (a-1), the structural unit (a-2), and the structural unit (a-3) in the alkali-soluble resin (a) is preferably (a-1)/(a-2)/(a-3) in the range of 15 to 25/40 to 60/25 to 35, more preferably 15 to 23/45 to 60/25, and particularly preferably 15 to 21/50 to 60/25 to 29.
(other structural units)
The alkali-soluble resin (A) may contain other structural units not belonging to any of the structural units (a-1) to (a-3). Examples of the other structural units include benzyl methacrylate, 1,3-bis (methacryloyloxy) -2-propanol (1,3-bis (methacryloyloxy) -2-propanol), 2-methacryloyloxyethyl isocyanate, and 2-hydroxyethyl methacrylate.
The content (mol%) of the other structural units in the alkali-soluble resin (a) is preferably 0 to 20 mol%, and more preferably 0 to 10 mol%, from the viewpoint of achieving both chemical resistance and wrinkle resistance.
(molecular weight)
The weight average molecular weight of the alkali-soluble resin (A) is preferably 5000 to 20000, more preferably 6000 to 17000, and particularly preferably 6500 to 14000. The molecular weight of the alkali-soluble resin (A) can be measured by gel permeation chromatography (2-mer: HLC-8120, column: G-5000HXL and G-3000 HXL; detector: RI, mobile phase: tetrahydrofuran, manufactured by TOSOH Co., Ltd.).
(glass transition temperature)
From the viewpoint of wrinkle resistance, the glass transition temperature of the alkali-soluble resin (A) is preferably 50 to 200 ℃, more preferably 70 to 170 ℃, and particularly preferably 80 to 140 ℃. The glass transition temperature can be measured by a Differential Scanning Calorimeter (DSC).
(specific examples)
Specific examples of the alkali-soluble resin (a) include the following polymers. In the following table, a3 contains benzyl methacrylate as another structural unit.
[ Table 1]
Figure BDA0003386277660000131
(content)
The content of the alkali-soluble resin (a) in the curable resin composition of the present embodiment is not particularly limited, and is, for example, preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and particularly preferably 50 to 60% by mass, based on the total solid content in the composition, from the viewpoint of chemical resistance. Throughout the present specification, the term "all solid components" refers to all components in the resin composition except the solvent.
< other Polymer >
The curable resin composition of the present embodiment may contain other polymers than the alkali-soluble resin (a). The other polymer is not particularly limited, and examples thereof include polymers containing any 2 kinds of the above-mentioned structural units (a-1) to (a-3). Examples of the other polymer include the following polymers.
[ Table 2]
Figure BDA0003386277660000141
The content of the other polymer in the curable resin composition of the present embodiment is not particularly limited, and is preferably 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass, based on 100 parts by mass of the alkali-soluble resin (a), from the viewpoint of obtaining an effect by including the other polymer, such as not greatly suppressing chemical resistance of the cured film.
< photoreactive monomer (B) >)
The photoreactive monomer (B) is a compound represented by the following formula (B-1) and has 2 ethylenically unsaturated groups in the molecule.
[ chemical formula 6]
Figure BDA0003386277660000142
(in the formula (b-1), R13～R14Each independently represents a hydrogen atom or a methyl group; y is1～Y2Each independently represents a single bond, or a straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms; x2Represents an aliphatic hydrocarbon group or an aromatic group having a cyclic skeleton. )
In the formula (b-1), R13～R14Each independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of photoreactivity.
Y1～Y2Each independently represents a single bond or a straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms (divalent linking group). The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 3 from the viewpoint of chemical resistance. Examples of the linear or branched aliphatic hydrocarbon group include an alkylene group having 1 to 6 carbon atoms, a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a 1, 1-dimethylethyl group. As Y1And Y2Preferably a single bond or a methylene group.
X2Represents an aliphatic hydrocarbon group or an aromatic group (divalent linking group) having a cyclic skeleton. From the viewpoint of chemical resistance, X is2The number of carbon atoms of (A) is preferably 5 to 20, more preferably 6 to 12. Examples of the aliphatic hydrocarbon having a cyclic skeleton include a cyclohexane ring, a cyclodecane ring, a tricyclodecane ring, an adamantane ring, a norbornane ring and a decamethylene ringThe 2-valent linking group formed by hydrogenating a naphthalene ring includes the 2-valent linking group formed by a benzene ring and a naphthalene ring as the aromatic group having a cyclic skeleton. As X2From the viewpoint of chemical resistance, a 2-valent linking group formed of a cyclohexane ring, a benzene ring, a cyclodecane ring, a tricyclodecane ring, an adamantane ring or a norbornane ring is preferable, and a 2-valent linking group formed of a benzene ring, an adamantane ring or a tricyclodecane ring is more preferable.
Examples of the photoreactive monomer (B) include A-DCP (tricyclodecane dimethanol diacrylate), 1, 4-benzenediol diacrylate and 1, 3-adamantanediol diacrylate, and tricyclodecane dimethanol diacrylate is preferable from the viewpoint of chemical resistance.
The content of the photoreactive monomer in the curable resin composition of the present embodiment is not particularly limited, and is, for example, preferably 30 to 80 parts by mass, more preferably 40 to 70 parts by mass, and particularly preferably 50 to 60 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (a) from the viewpoint of chemical resistance.
In addition, the curable resin composition of the present embodiment may contain a photoreactive monomer other than the photoreactive monomer (B). The other photoreactive monomer is not particularly limited, and examples thereof include compounds having 3 or more ethylenically unsaturated groups in the molecule. Examples of such a compound include trimethylolpropane triacrylate and pentaerythritol triacrylate.
When the curable resin composition of the present embodiment contains the photoreactive monomer (B) and another photoreactive monomer, the content of the photoreactive monomer (B) with respect to the total amount of photoreactive monomers in the curable resin composition is preferably 75% by mass or more, and more preferably 80% by mass or more, from the viewpoint of chemical resistance.
(photopolymerization initiator (C))
The curable resin composition of the present embodiment contains a photopolymerization initiator (C). The photopolymerization initiator (C) is not particularly limited, and for example, a photopolymerization initiator which generates a radical for polymerizing an ethylenically unsaturated group by ultraviolet rays to visible rays can be preferably used.
The photopolymerization initiator is not particularly limited, and examples thereof include acetophenone type photopolymerization initiators such as acetophenone, 2' -diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butyl acetophenone, α -aminoketone type photopolymerization initiators such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like, 1, 2-octanedione-1- [4- (phenylsulfanyl) -2- (O-benzoyl oxime) ], ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyl oxime), 1- [ 9-ethyl-6-benzoyl-9. H ] -carbazol-3-yl ] -octane-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9.H ] -carbazol-3-yl ] -ethane-1-one oxime-O-benzoate, and pharmaceutically acceptable salts thereof, 1- [ 9-n-butyl-6- (2-ethylbenzoyl) -9.h. -carbazol-3-yl ] -ethane-1-ketoxime-O-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofurylbenzoyl) -9.h. -carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9.h. -carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofurylbenzoyl) -9.h. -, ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofurylbenzoyl) Oxime ester photopolymerization initiators such as yl) -9, h. -carbazol-3-yl ] -1- (O-acetyl oxime) and ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9, h. -carbazol-3-yl ] -1- (O-acetyl oxime), benzophenones such as benzophenone, 2-chlorobenzophenone and p, p' -bisdimethylaminobenzophenone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; sulfur compounds such as benzildimethylketal, thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, and anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone and 2, 3-diphenylanthraquinone; triazines such as 2, 4-trichloromethyl- (4 ' -methoxyphenyl) -6-triazine, 2, 4-trichloromethyl- (4 ' -methoxynaphthyl) -6-triazine, 2, 4-trichloromethyl- (piperonyl) -6-triazine and 2, 4-trichloromethyl- (4 ' -methoxystyryl) -6-triazine; and organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide, and thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole. These photopolymerization initiators may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the photopolymerization initiator (C) in the curable resin composition of the present embodiment is not particularly limited, and is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 15 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (a), for example, from the viewpoints of photoreactivity and storage stability.
< method for producing curable resin composition >
The curable resin composition of the present embodiment includes the alkali-soluble resin (a), the photoreactive monomer (B), and the photopolymerization initiator (C), and may be prepared by stirring and mixing the alkali-soluble resin (a), the photoreactive monomer (B), and the photopolymerization initiator (C) with a solvent or the like.
(solvent)
In the present embodiment, the solvent may be appropriately selected from known solvents and used according to the intended purpose.
Examples of the solvent include cyclopentanone, diethylene glycol ethyl methyl ether, acetylacetone, methanol, ethanol, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n-amyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, methanol, ethanol, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, methyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol ether acetate, propylene glycol ether, propylene glycol monomethyl ether acetate, propylene glycol ether, and the like, Dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, lactate, methyl methoxypropionate, ethyl ethoxypropionate, and the like.
The solvent may be used alone in 1 kind, or 2 or more kinds may be used in combination.
The content of the solvent in the curable resin composition of the present embodiment is not particularly limited, and the solvent is preferably used so that the concentration of all solid components (the total mass of components excluding the solvent in the composition) is preferably 1 to 40 mass%, more preferably 5 to 40 mass%, and particularly preferably 10 to 30 mass%, from the viewpoint of, for example, storage stability and coatability. When the solid content ratio is within the above range, the viscosity of the curable resin composition can be adjusted to an appropriate level, and the coating property when the curable resin composition is applied to a substrate or the like to form a film can be particularly improved.
In addition, various additives such as inorganic fine particles, adhesion promoting additives, surfactants, storage stabilizers, leveling agents, light stabilizers, and antioxidants may be used as necessary in the curable resin composition of the present embodiment. Examples of such additives include those described in Japanese patent laid-open publication No. 2012-215833. In addition, a silane coupling agent or the like may be used in order to improve the adhesion between the substrate and the coating film.
Insulating cured film
The curable resin composition of the present embodiment is not particularly limited in its application, and can be used, for example, as an insulating cured film for a touch panel. The insulating cured film for a touch panel can be formed by: a coating film is formed on a substrate such as a glass substrate, ITO, a metal film, or an organic film using a curable resin composition by various application methods such as spin coating, cast coating such as die coating, coating by roll coating, or coating by roll transfer, and the coating film is cured.
Specifically, the curable resin composition may be applied to a substrate such as a glass substrate and cured by irradiation with light to form a cured film of the present embodiment. The cured film of the present embodiment may be subjected to patterning by irradiating light through a mask, developing the light, and then, if necessary, heating the developed light.
The insulating cured film can be used for any application such as an insulating film application, a protective film application, and a planarization film application. The insulating cured film using the curable resin composition of the present embodiment can be preferably used as a protective film for a touch panel and an insulating film for a touch panel, in particular.
The insulating cured film of the present embodiment can be used not only as a so-called permanent film to be maintained in a device such as a touch panel, but also as a resist film to be used when an ITO film is patterned on a glass substrate.
Touch Panel
As described above, the curable resin composition of the present embodiment and the insulating cured film using the same can be preferably used as an insulating film for a touch panel. Hereinafter, the insulating cured film and the insulating film for a touch panel of the present embodiment may be collectively referred to simply as "cured film of the present embodiment". In the case where the cured film of the present embodiment is used for an insulating film, for example, an ITO film may be formed on the cured film, and then heat treatment or the like may be performed thereafter. Even after such treatment, the cured film of the present embodiment has less wrinkles on the contact surface with the ITO film, and transparency is not easily impaired. The cured film of the present embodiment is excellent in developability (adhesion force between the glass substrate and the ITO film after removal of the insulating cured film) and chemical resistance (effect of suppressing decrease in adhesion force between the insulating film and the ITO film when exposed to a chemical used in the production process), and therefore, the cured film of the present embodiment is excellent in productivity of the touch panel including the cured film.
The touch panel of the present embodiment may be any of a resistive type, a capacitive type, an ultrasonic type, and an optical type, but is preferably a capacitive type touch panel.
In the capacitive touch panel, for example, glass with an ITO film is used as a substrate, and an insulating film and a protective film are provided in a laminated structure (for example, between electrodes) in order to prevent erroneous recognition of a touched position. In the case where the touch panel of the present embodiment is an electrostatic capacitance type touch panel, the cured film of the present embodiment may be used, for example, as an insulating film, a protective film, or both in a laminated structure in the touch panel of the present embodiment.
The touch panel may be classified into a double-sided structure in which X electrodes are disposed on one surface of an insulating film and Y electrodes are disposed on the other surface, and a single-sided structure in which X electrodes and Y electrodes are formed on the same plane. The touch panel of the present embodiment may have any of a double-sided structure and a single-sided structure, but a touch panel having a single-sided structure is particularly preferable.
In the single-sided type touch panel structure, the X electrode is electrically separated from the Y electrode. In this case, the pattern of the electrodes can be classified into an island pattern, a via pattern, and the like. For example, in the case of an island pattern, in addition, in a single-sided touch panel structure, the separated electrodes are electrically connected to each other by a member called a bridge portion, for example. In addition, a transparent electrode such as an ITO film is used in the electrode bridge portion, and for example, when the separated Y electrodes are connected to each other in the bridge portion, an insulating layer is provided below the bridge portion in order to ensure insulation from the X electrodes. In addition, an insulating film (protective film) is generally formed on each electrode arranged in a single-sided manner in the same manner.
Therefore, in the case where the touch panel of the present embodiment has a single-sided touch panel structure, the cured film of the present embodiment may be used for, for example, an insulating film formed on an electrode, an insulating layer formed under a bridge portion, or both of them in the touch panel of the present embodiment.
When the touch panel is mounted on the liquid crystal display device, the touch panel can be classified into an external-mount structure, and an internal-mount structure according to the installation location. In the external-embedded structure and the internal-embedded structure, the touch panel is mounted inside the liquid crystal panel, and in the external-hung structure, the touch panel is mounted outside the liquid crystal panel. In the external-embedded structure, a touch panel is provided between a polarizing plate on the observation direction side and a liquid crystal laminate (a laminate composed of a pair of base glasses and a liquid crystal layer interposed therebetween). In the in-cell structure, the liquid crystal layer of the liquid crystal laminate has a touch panel function. The touch panel of the present embodiment can be applied to any structure, and is preferably used in an external structure, for example.
Hereinafter, an embodiment of the touch panel of the present embodiment will be described with reference to the drawings. Fig. 1 is a plan view showing a configuration of one embodiment of a touch panel of the present embodiment. As shown in fig. 1, when the touch panel of the present embodiment is a single-sided touch panel, ITO (indium tin oxide) electrodes (X1 to X4, Y1 to Y3) are formed on a glass substrate 10.
The material of the glass substrate 10 is not particularly limited, and for example, a glass plate such as soda lime glass, low alkali borosilicate glass, or alkali-free aluminoborosilicate glass can be used. Instead of the glass substrate, a plastic plate or a plastic film made of polyethylene terephthalate (PET), triacetyl cellulose (TAC), polymethyl methacrylate (PMMA), Polycarbonate (PC), or the like may be used.
The ITO electrodes (X1 to X4, Y1 to Y3) are transparent electrodes. In the present embodiment, ITO is used as a material of the transparent electrode, but the material is not particularly limited as long as it can be arranged on the surface of the substrate, and in addition to ITO, for example, an inorganic conductive material such as ZnO (zinc oxide), an organic conductive material such as PEDOT/PSS (polyethylene dioxythiophene/polystyrene sulfonic acid), polyaniline, polypyrrole, or the like can be used. These materials may be used alone in 1 kind, or 2 or more kinds may be used in combination.
Although not shown in fig. 1 and 2, a metal thin film having a function as a metal wiring may be used as the lower layer of each electrode and the bridge portion 12 or in place of the transparent electrode. As the metal thin film, a metal material such as Mo (molybdenum), Al (aluminum), Ag (silver), Pd (palladium) or the like can be used, and preferably, one or more of Mo and Al is used.
As shown in fig. 1, ITO electrodes X1 to X4 are electrodes arranged in the direction of arrow X in fig. 1. The ITO electrodes X1 to X4 are continuously connected to the electrodes adjacent in the X direction via a connection portion formed by an ITO film, and are electrically connected in the X direction. In general, the ITO electrodes X1 to X4 and the respective connecting portions are continuously formed as one body at the time of electrode molding.
The ITO electrodes Y1 to Y3 are electrodes arranged in the direction of arrow Y in fig. 1, and the ITO electrodes Y1 to Y3 are separated from adjacent electrodes, but are electrically connected to the electrodes adjacent in the Y direction via the bridge 12. The bridge portion 12 may be formed of the same material as the transparent electrode, such as ITO. Further, an insulating film 14 is interposed between the lower portion of the bridging portion 12 in the thickness direction and the connection portion with the ITO electrode X.
Hereinafter, the electrode group electrically connected in the X direction is referred to as an "X electrode", and the electrode group electrically connected in the Y direction is referred to as a "Y electrode". As shown in fig. 1, in the one-sided touch panel, X electrodes are arranged in the Y direction, and Y electrodes are arranged in the X direction.
Next, a cross-sectional structure of the touch panel in the present embodiment will be described with reference to fig. 2. Fig. 2 is a cross-sectional view AA of fig. 1. As shown in fig. 2, a connection portion X34 between the insulating film 14 and the ITO electrodes X3 and X4 is interposed between the ITO electrodes Y1 and Y2. The ITO electrodes Y1 and Y2 are electrically connected by the bridge 12 as described above. In addition, in the lower portion in the thickness direction of bridge portion 12, a part of insulating film 14 extends between it and connection portion X34, ensuring insulation between bridge portion 12 and connection portion X34. Further, an insulating protective layer 16 is provided on the ITO electrodes Y1 and Y2 and on the upper side in the thickness direction of the bridge portion 12.
As described above, the insulating cured film using the curable resin composition of the present embodiment is excellent in chemical resistance. Therefore, for example, when the cured film of the present embodiment is used as the insulating film 14, the adhesion force at the interface between the insulating film 14 and the ITO film (ITO film/insulating film interfaces K1 and K5 in fig. 2) is excellent due to chemicals used in the manufacturing process (for example, etching of the ITO film). Similarly, when the cured film of the present embodiment is used as the insulating protective layer 16, the adhesion force at the interface between the insulating protective layer 16 and the ITO film (ITO film/protective film interface K2 in fig. 2) is excellent.
In addition, when the cured film of the present embodiment is used as the insulating film 14, the amount of wrinkles generated in the heat treatment step when forming the bridge portion 12 on the insulating film 14 can be reduced. From such a viewpoint, when the cured film of the present embodiment is used as the insulating film 14, the touch panel can be manufactured with good productivity by minimizing the influence on the transparency of the insulating film 14 and the transparency of the touch panel.
In the present embodiment, the cured film of the present embodiment is used for at least one of the insulating film 14 and the insulating protective layer 16. However, although any other one of the insulating film and the protective film may be formed using a known material conventionally used for insulating films and protective films, it is preferable that both the insulating film 14 and the insulating protective layer 16 be the cured film of the present embodiment.
In the touch panel described above, the method of forming the cured film of the present embodiment is not particularly limited, and a coating film may be formed on a lower layer (for example, the glass substrate 10 and the ITO electrode with respect to the insulating film 14, or the ITO electrode with respect to the insulating protective layer 16) by a coating method such as spray coating, spin coating, slot die coating, roll coating, or bar coating. In this case, the dry film thickness of the coating film is not particularly limited, but is preferably 0.5 to 20 μm, and more preferably 1.0 to 10 μm, in the case of the insulating protective layer 16. Similarly, in the case of the insulating film 14, the dry film thickness is preferably 0.2 to 10 μm, and more preferably 0.5 to 5 μm. If necessary, the coating film may be exposed through a mask having a predetermined pattern, which is provided in a state of being in contact with or not in contact with the coating film. The kind of light rays at the time of exposure is not particularly limited, and visible light rays, ultraviolet rays, far infrared rays, electron rays, X-rays and the like can be mentioned, and among them, ultraviolet rays are preferable. The illuminance of light is not particularly limited, but is preferably 5 to 150mW/cm at 365nm2Particularly preferably 15-35 mW/cm2。
Thereafter, if necessary, the substrate is immersed in an aqueous alkaline developer such as sodium carbonate, sodium hydroxide, or potassium hydroxide, or the developer is sprayed with a sprayer or the like to remove uncured portions, thereby forming a desired pattern. In addition, the hard coat is formed to promote polymerization of the photosensitive composition, and heating (post-baking) may be performed as needed.
For example, in the case of forming the bridge portion 12, first, a patterned X electrode is formed on the glass substrate 10, and then, a curable resin composition is applied to the surfaces of the glass substrate 10 and the X electrode, and the curable resin composition is exposed and developed using a mask capable of forming the insulating film 14. Then, a patterned insulating film 14 is formed including a portion extending in a lower portion in the thickness direction of the bridge portion 12, and then ITO or the like is deposited on the substrate by PVD or the like, thereby forming an ITO film on the insulating film 14 and the glass substrate 10 from which the curable resin composition is removed, thereby forming the Y electrode and the bridge portion 12. Therefore, when the curable resin composition of the present embodiment is used for the curable resin composition used for a resist for forming the X electrode and for forming the insulating film 14, the adhesion force at the interface between the glass substrate 10 and each electrode (glass substrate/ITO film interface K4 in fig. 2) is excellent.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited in any way by the following examples.
[ examples and comparative examples ]
The components were mixed in the formulation shown in the following table to prepare a curable resin composition. The mixing was carried out at room temperature, and the ultraviolet rays were blocked so as not to initiate the polymerization reaction.
[ Table 3]
Figure BDA0003386277660000231
In the above tables, the components shown in the following table were used for each component.
[ Table 4]
Figure BDA0003386277660000241
Note that a3 contains benzyl methacrylate as another structural unit.
Evaluation
The curable compositions of examples and comparative examples obtained in the above manner were evaluated. The results are shown in the following table.
(chemical resistance test)
The obtained curable resin composition was applied to a substrate having an ITO film by a spin coating method, and prebaked on a hot plate at 80 ℃ for 100 seconds to form a coating film at a thickness of 50mJ/cm2Light (illuminance at 365 nm: 30 mW/cm) from an ultrahigh-pressure mercury lamp was irradiated2). Thereafter, the substrate was developed for 50 seconds using a 0.3% aqueous solution of sodium carbonate and heated at 150 ℃ for 30 minutes to prepare a substrate having a cured film with a thickness of 2.0. mu.m.
The obtained substrate with the cured film was immersed in a 3.6 mass% oxalic acid aqueous solution at 41 ℃ for about 120 seconds. After the dipping, the substrate was washed with water and further dipped in an amine solution (monoethanolamine/diethylene glycol monobutyl ether: 35/65 (mass%)) at 80 ℃ for about 60 seconds.
After the dipping, the substrate with the cured film was washed with water and dried, and then the surface of the cured film was cross-cut (1mm × 1mm × 100 cells) with a cutter knife.
Thereafter, a scotch tape (cellophane tape) was applied to the cut surface, and then the scotch tape was peeled off. The cured film surface of the substrate was observed with a solid microscope, the number of squares remaining without peeling of the cured film was counted, and the adhesion (chemical resistance) of the cured film after chemical immersion was evaluated against the following criteria.
In examples 1 to 3, the same test was carried out on a substrate using an MAM film instead of the ITO film, and all the results were judged to be "a".
[ Standard ]
A: the number of the remaining squares of the cured film without peeling off is 95 or more
B: the number of the remaining squares of the cured film without peeling is 85 or more and less than 95
C: the number of the squares remaining without peeling the cured film is 65 or more and less than 85
D: the number of the remaining squares of the cured film is 35 or more and less than 65
E: less than 35 squares remaining without peeling of the cured film
(developability test)
The obtained curable resin composition was applied onto a glass substrate by a spin coating method, prebaked on a hot plate at 80 ℃ for 100 seconds to form a coating film, and developed with a 0.3% sodium carbonate aqueous solution for 50 seconds. Thereafter, the substrate was heated at 150 ℃ for 30 minutes to prepare a substrate.
The obtained substrate was subjected to ITO sputtering treatment as follows. Subsequently, the substrate on which the ITO film was formed was subjected to annealing treatment (150 ℃ c, 30 minutes) to obtain a substrate on which the ITO film was formed.
[ Table 5]
Figure BDA0003386277660000251
Subsequently, the surface of the cured film was cross-cut (1mm × 1mm × 100 cells) at a site where the ITO film was directly formed on the glass substrate using a dicing blade.
Thereafter, a transparent adhesive tape was attached to the cut surface, and then the transparent adhesive tape was peeled off. The number of squares remaining without peeling of the cured film was counted by observing the surface of the cured film of the substrate with a solid microscope, and the adhesion (developability) between the glass substrate and the ITO film at the portion from which the curable resin composition was removed was evaluated with reference to the following criteria.
[ Standard ]
A: the number of the remaining squares of the cured film without peeling off is 95 or more
B: the number of the remaining squares of the cured film without peeling is 85 or more and less than 95
C: the number of the squares remaining without peeling the cured film is 65 or more and less than 85
D: the number of the remaining squares of the cured film is 35 or more and less than 65
E: less than 35 squares remaining without peeling of the cured film
(confirmation of wrinkles)
The obtained curable resin composition was applied onto a glass substrate by a spin coating method, prebaked at 80 ℃ for 100 seconds to form a coating film, and the resultant coating film was patterned using a patterned mask at 50mJ/cm2Light (illuminance at 365 nm: 30 mW/cm) from an ultrahigh-pressure mercury lamp was irradiated2). The exposure was performed under the condition that the distance between the mask and the substrate (exposure gap) was 100 μm. The unexposed portions were removed by development with a 0.3% aqueous solution of sodium carbonate for 50 seconds. Thereafter, the substrate was heated at 150 ℃ for 30 minutes to prepare a substrate having a cured film with a thickness of 2 μm and a pattern formed thereon.
The obtained substrate was subjected to ITO sputtering treatment in the same manner as in the developability test described above. Subsequently, the substrate on which the ITO film was formed was subjected to annealing treatment (150 ℃ c, 30 minutes) to obtain a substrate on which the ITO film was formed.
The cured film surface of the obtained substrate on which the ITO film was formed was observed with an ITO film interposed therebetween by a solid microscope (magnification: 40 times), and the occurrence of wrinkles on the cured film surface was evaluated according to the following criteria. Fig. 3 shows a sample image of the following evaluation A, C, E.
[ Standard ]
A: no generation of wrinkles was observed at all.
B: almost no generation of wrinkles was observed.
C: the generation of wrinkles was observed in a part of the range.
D: the generation of wrinkles is observed in many ranges.
E: the generation of wrinkles was observed over the entire surface.
[ Table 6]
Figure BDA0003386277660000271
The entire disclosure of japanese patent application No. 2019-111325 filed on 14/6/2019 is incorporated by reference into the present specification.
All documents, patent applications, and technical standards described in the specification are incorporated by reference in the present specification to the same extent as if each document, patent application, and technical standard was specifically and individually described.
Description of the reference numerals
10: glass substrate, 12: bridge, 14: insulating film, 16: insulating protective layer, X1 to X4, Y1 to Y4: ITO electrode, X34: linker, K1, K5: ITO film/insulating film interface, K2: ITO film/protective film interface, K3, K4: glass substrate/ITO film interface.

Claims (11)

1. A curable resin composition comprising:
an alkali-soluble resin (A) which is a copolymer comprising a structural unit (a-1) derived from at least one member selected from the group consisting of compounds represented by the following formula (a-1 alpha) and unsaturated carboxylic acids having a cyclic skeleton, a structural unit (a-2) having a glass transition temperature of 70 to 200 ℃ when a homopolymer is produced, and a structural unit (a-3) derived from an epoxy group-containing unsaturated compound;
a photoreactive monomer (B) represented by the following formula (B-1); and
a photopolymerization initiator (C),
[ chemical formula 1]
Figure FDA0003386277650000011
In the formula (a-1. alpha.), R1～R3Each independently represents a hydrogen atom, a methyl group, or a carboxyl group; x1A single bond or a linear or cyclic aliphatic hydrocarbon group having 1 to 15 carbon atoms and containing an oxygen atom;
[ chemical formula 2]
Figure FDA0003386277650000012
In the formula (b-1), R13～R14Each independently represents a hydrogen atom or a methyl group; y is1～Y2Each independently represents a single bond, or a straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms; x2Represents an aliphatic hydrocarbon group or an aromatic group having a cyclic skeleton.
2. The curable resin composition according to claim 1, wherein the structural unit (a-2) is derived from at least one selected from the group consisting of a compound represented by the following formula (a-2 α) and a compound represented by the following formula (a-2 β),
[ chemical formula 3]
Figure FDA0003386277650000021
In the formula (a-2 alpha), R4～R6Each independently represents a hydrogen atom or a methyl group; r7Represents a straight-chain, branched or cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic group having 6 to 20 carbon atoms; in the formula (a-2. beta.), R8～R12Each independently represents a hydrogen atom, a methyl group, an acetyl group, a benzoyl group, an isopropyl group, a tert-butyl group or a sec-butyl group.
3. The curable resin composition according to claim 1 or 2, wherein the content of the photoreactive monomer (B) is 75% by mass or more with respect to the total amount of the photoreactive monomers in the curable resin composition.
4. The curable resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin (A) has a weight average molecular weight of 5000 to 20000.
5. The curable resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin (A) has a content ratio (mol%) of the structural unit (a-1), the structural unit (a-2) and the structural unit (a-3) of (a-1)/(a-2)/(a-3) of 15 to 25/40 to 60/25 to 35.
6. The curable resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (A) comprises a structural unit (a-2) having a glass transition temperature of 100 to 180 ℃ when produced as a homopolymer.
7. The curable resin composition according to any one of claims 1 to 6, wherein Y in the formula (b-1)1And Y2Each independently a single bond or a methylene group.
8. The curable resin composition according to any one of claims 1 to 7, which is used for forming an insulating film.
9. An insulating cured film obtained by curing the curable resin composition according to any one of claims 1 to 8.
10. An insulating cured film for a touch panel, which is obtained by curing the curable resin composition according to any one of claims 1 to 8.
11. A touch panel comprising the insulating cured film for a touch panel according to claim 10.
CN202080040696.4A 2019-06-14 2020-06-12 Curable resin composition, insulating cured film obtained by curing the composition, insulating cured film for touch panel, and touch panel Pending CN113906344A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2019-111325 2019-06-14
JP2019111325 2019-06-14
PCT/JP2020/023154 WO2020251004A1 (en) 2019-06-14 2020-06-12 Curable resin composition, insulating cured film provided by curing said composition and insulating cured touch panel film provided by curing said composition, and touch panel

Publications (1)

Publication Number Publication Date
CN113906344A true CN113906344A (en) 2022-01-07

Family

ID=73782024

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080040696.4A Pending CN113906344A (en) 2019-06-14 2020-06-12 Curable resin composition, insulating cured film obtained by curing the composition, insulating cured film for touch panel, and touch panel

Country Status (4)

Country Link
JP (1) JPWO2020251004A1 (en)
CN (1) CN113906344A (en)
TW (1) TW202104280A (en)
WO (1) WO2020251004A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113402697B (en) * 2021-06-25 2023-12-12 厦门赛尔特电子有限公司 Electrical insulation resin and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018004841A (en) * 2016-06-29 2018-01-11 Jsr株式会社 Radiation-sensitive resin composition, pattern, method for forming pattern, and display element
KR20180078828A (en) * 2016-12-30 2018-07-10 코오롱인더스트리 주식회사 Photosensitive resin composition for organic insulator
JP2018165788A (en) * 2017-03-28 2018-10-25 日立化成株式会社 Transfer photosensitive film, curable resin patterning method, and touch panel

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4298391B2 (en) * 2003-06-12 2009-07-15 三菱化学株式会社 Blue-violet light-sensitive composition, and image forming material, image forming material, and image forming method using the same
JP5762834B2 (en) * 2011-06-14 2015-08-12 株式会社ダイセル Alicyclic epoxy group-containing curable resin composition, production method thereof and cured product thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018004841A (en) * 2016-06-29 2018-01-11 Jsr株式会社 Radiation-sensitive resin composition, pattern, method for forming pattern, and display element
KR20180078828A (en) * 2016-12-30 2018-07-10 코오롱인더스트리 주식회사 Photosensitive resin composition for organic insulator
JP2018165788A (en) * 2017-03-28 2018-10-25 日立化成株式会社 Transfer photosensitive film, curable resin patterning method, and touch panel

Also Published As

Publication number Publication date
TW202104280A (en) 2021-02-01
JPWO2020251004A1 (en) 2020-12-17
WO2020251004A1 (en) 2020-12-17

Similar Documents

Publication Publication Date Title
JP5257558B1 (en) Method for forming conductive pattern, conductive pattern substrate, and touch panel sensor
KR102058349B1 (en) Photosensitive resin composition, conductive wire protection film, and touch panel member
JP2013064973A (en) Photosensitive resin composition, material for touch panel, touch panel protective film, touch panel insulating film, and touch panel
JP2016001608A (en) Method of preventing degradation of metal fiber, film, and method of producing film
TW201826101A (en) Transfer film, electrode protective film, laminate, capacitive input device, and method for manufacturing touch panel
WO2016167228A1 (en) Photosensitive conductive film, method for forming conductive pattern, substrate having conductive pattern, and touch panel sensor
JP2012220615A (en) Photocurable resin composition
TW202036602A (en) Conductive transfer material, method for producing substrate with pattern, method for producing circuit board,laminate, and touch panel
TW202041969A (en) Conductive transfer material, method for producing substrate with pattern, laminate, and touch panel
CN113906344A (en) Curable resin composition, insulating cured film obtained by curing the composition, insulating cured film for touch panel, and touch panel
TW201734638A (en) Photosensitive resin composition, cured film, laminate, member for touch panel, and method for manufacturing cured film
JP2014206574A (en) Photosensitive resin composition, material for touch panel, touch panel protective film, touch panel insulating film and touch panel
WO2024005195A1 (en) Curable resin composition, insulating cured film and insulating cured film for touch panel that result from curing said composition, and touch panel
WO2024005189A1 (en) Curable resin composition, insulating cured film and insulating cured film for touch panels each produced by curing said composition, and touch panel
JP6289921B2 (en) Method for adjusting photosensitive resin composition, photosensitive resin composition, touch panel material, touch panel protective film, touch panel insulating film, touch panel
KR102002984B1 (en) Photosensitive Resin Composition for Hard Coating
US10717893B2 (en) Photosensitive film, photosensitive element, cured product and touch panel
JP6740615B2 (en) Resin composition, photosensitive resin composition, method for producing resist pattern, and touch panel member
JP2017198878A (en) Photosensitive conductive film and conductive pattern comprising the same, conductive pattern substrate, and method for producing touch panel sensor
WO2023210746A1 (en) Polymer, curable resin composition, stretchable insulating cured film obtained by curing said composition, insulating cured film for touch panel, touch panel, insulating cured film for flexible printed circuit board, and flexible printed circuit board
JP2016042126A (en) Radiation-sensitive resin composition, interlayer insulation film of display element, method of forming the same, and display element
WO2020137144A1 (en) Photosensitive transfer material, laminate, touch panel, method for producing patterned substrate, method for producing circuit board, and method for producing touch panel
JP2020079408A (en) Resin composition, photosensitive resin composition, method for producing resist pattern, and touch panel member
KR20170033270A (en) Photosensitive resin composition, photosensitive film, pattern substrate, photosensitive conductive film, and conductive pattern substrate
JP2024024776A (en) Photosensitive resin composition for touch panel protective films and method for forming electrode protective film for touch panels

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination