CN113467183A - Resin composition for forming insulating film, insulating film manufactured using same, image display device, and method for manufacturing insulating film - Google Patents

Resin composition for forming insulating film, insulating film manufactured using same, image display device, and method for manufacturing insulating film Download PDF

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CN113467183A
CN113467183A CN202110199968.1A CN202110199968A CN113467183A CN 113467183 A CN113467183 A CN 113467183A CN 202110199968 A CN202110199968 A CN 202110199968A CN 113467183 A CN113467183 A CN 113467183A
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insulating film
forming
resin composition
compound
film according
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CN113467183B (en
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李贤普
金秀虎
金正植
曺升铉
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Dongwoo Fine Chem Co Ltd
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    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
    • H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
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  • Polymers & Plastics (AREA)
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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention provides a resin composition for forming an insulating film, an insulating film manufactured by using the same, an image display device and a method for manufacturing the insulating film, wherein the resin composition for forming the insulating film comprises (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light absorber and (E) a solvent, the (B) photopolymerizable compound comprises a fluorene compound, the (D) light absorber comprises an azole compound, so that the heat resistance, the chemical resistance and the permeability can be improved, the corrosion of a lower metal can be prevented, and the fine pattern and the pore characteristics can be improved.

Description

Resin composition for forming insulating film, insulating film manufactured using same, image display device, and method for manufacturing insulating film
Technical Field
The present invention relates to a resin composition for forming an insulating film, an insulating film manufactured using the same, an image display device, and a method for manufacturing an insulating film.
Background
The photosensitive resin is a material necessary for a color filter, a liquid crystal display material, an organic light emitting element, and other displays, and there are various types of photosensitive resin compositions depending on the purpose of use such as a red pixel (R), a green pixel (G), a blue pixel (B), a Black Matrix (BM), and a Columnar Spacer (CS) used for the color filter.
In addition, the photosensitive resin composition can be used as a photosensitive resin composition for forming an insulating film for the purpose of protecting and insulating a plurality of wirings and circuits included in a plurality of semiconductor elements and displays which have been developed in recent years, and particularly, in recent display devices, such a photosensitive resin composition is actively used because there is an increasing demand for improvement in reliability while the size of a pattern is reduced with an increase in resolution, and protection of the display device due to permeation of external oxygen and moisture is also increased.
As a material that can be used for such an insulating film, various materials such as polyethylene, polyvinyl chloride, natural rubber, polyester, epoxy resin, melamine resin, phenol resin, synthetic resin such as polyurethane, and the like can be used.
On the other hand, as the use of photosensitive resin compositions has increased in many respects, in recent years, the inside of a display or the like has been designed not only for the purpose of electrical insulation of wiring but also for the purpose of planarization or for the purpose of affecting the flow of current.
Specifically, development of a photosensitive resin composition having excellent chemical resistance and capable of adjusting the line width and pore size of an insulating film is required, and particularly, an effect of improving metal corrosion in a portion in contact with the insulating film is required.
In particular, when a metal film such as copper is disposed below the insulating film in order to realize energization for driving the device, corrosion of copper is induced by moisture permeation due to the characteristics of the organic film. Therefore, it is required to prevent or improve the characteristics of the metal film such as copper disposed adjacent to the insulating film from corroding.
Registered patent No. 10-0732641 also discloses a resin composition which exhibits excellent light resistance and does not undergo yellowing even after long-term use by being mixed with the resin composition by combining a cyanoacrylate ultraviolet absorber and a benzotriazole ultraviolet absorber. However, the chemical resistance is limited, and the line width and pore size of the formed coating film or pattern are controlled, and the corrosion prevention effect of the adjacent film is limited. Therefore, in recent years, the need for resin compositions having more various uses has been highlighted for display devices due to the miniaturization of patterns and the thinning of displays.
Documents of the prior art
Patent document
Korean registered patent No. 10-0732641
Disclosure of Invention
Problems to be solved
The purpose of the present invention is to provide a resin composition for forming an insulating film, which has improved pattern characteristics, Hole (Hole) characteristics, and bevel (Taper) characteristics.
Another object of the present invention is to provide a resin composition for forming an insulating film, which has improved chemical resistance.
Another object of the present invention is to provide a resin composition for forming an insulating film, which has improved corrosion resistance against lower metals and the like.
Another object of the present invention is to provide a resin composition for forming an insulating film, which has improved processability at low temperature.
Another object of the present invention is to provide an insulating film produced from the resin composition for forming an insulating film, and an image display device including the insulating film.
Another object of the present invention is to provide a method for producing an insulating film using the resin composition for forming an insulating film.
Means for solving the problems
The present invention relates to a resin composition for forming an insulating film, comprising (a) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light absorber, and (E) a solvent, wherein the (B) photopolymerizable compound comprises a Fluorene (fluoroene) compound, and the (D) light absorber comprises an Azole (Azole) compound.
In the first aspect of the present invention, the binder resin (A) may contain a Tetrahydropyran (THP) ring.
In a second aspect of the present invention, the Tetrahydropyran (THP) -based ring may be polymerized by including at least one of an acyclic compound and a cyclic compound capable of forming a Tetrahydropyran (THP) -based ring upon polymerization.
In a third aspect of the present invention, the acyclic compound may include a compound represented by the following chemical formula 1.
[ chemical formula 1]
Figure BDA0002947769350000031
(in the above chemical formula 1, R1、R2Each independently is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may or may not contain a heteroatom. )
In a fourth aspect of the present invention, the cyclic compound may comprise a compound selected from the group consisting of tetrahydropyran-2-yl (meth) acrylate, (tetrahydropyran-2-yl) methyl (meth) acrylate, 2, 6-dimethyl-8- (tetrahydropyran-2-yloxy) -1-octen-3-one, 1- (tetrahydropyran-2-yloxy) -3-buten-2-one, 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.
In a fifth aspect of the present invention, the (a) binder resin may include an epoxy-based binder resin.
In a sixth aspect of the present invention, the epoxy adhesive resin may include a compound represented by the following chemical formula 2.
[ chemical formula 2]
Figure BDA0002947769350000032
(the above chemistry)In the formula 2, R3And R4Each independently is hydrogen or CH3，
a and b are each independently an integer of 3 to 20. )
In a seventh aspect of the present invention, the fluorene-based compound may include a compound represented by the following chemical formula 3.
[ chemical formula 3]
Figure BDA0002947769350000041
(in the above chemical formula 3, X1And X2Each independently represents A hydroxyl group, - (O-A-O)pH group (A represents an alkylene group having 2 to 3 carbon atoms, p represents an integer of 1 to 10), R5～R8Each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, or a halogen atom, m1 and m2 are each independently an integer of 0 to 3, and n1 to n4 are each independently an integer of 0 to 4. Wherein m1+ n1 and m2+ n2 are each independently an integer of 0 to 5. )
In an eighth aspect of the present invention, the content of the fluorene compound may be 3 to 35% by weight based on the total weight of solid components in the resin composition for forming an insulating film.
In a ninth aspect of the present invention, the azole compound may include one or more selected from the group consisting of Benzotriazole (BTA) and Pyrazole (Pyrazole).
In the tenth aspect of the present invention, (a) 10 to 50% by weight of a binder resin, (B) 5 to 70% by weight of a photopolymerizable compound, (C) 3 to 20% by weight of a photopolymerization initiator, and (D) 1 to 10% by weight of a light absorber may be contained based on the total weight of solid components in the resin composition for forming an insulating film, and (E) 60 to 90% by weight of a solvent may be contained based on the total weight of the resin composition for forming an insulating film.
In an eleventh aspect of the present invention, the resin composition for forming an insulating film can prevent copper corrosion.
In a twelfth aspect of the present invention, the baking temperature of the resin composition for forming an insulating film may be 80 to 150 ℃.
In a thirteenth aspect of the present invention, the firing temperature may be a post-firing temperature.
The present invention also relates to an insulating film formed from the resin composition for forming an insulating film.
The present invention also relates to an image display device including the insulating film.
The present invention also relates to a method for producing an insulating film, which comprises the step of forming an insulating film by using the resin composition for forming an insulating film and performing a low-temperature firing process at 80 to 150 ℃.
Effects of the invention
According to the resin composition for forming an insulating film of the present invention, the pattern characteristics, the hole characteristics, and the slope characteristics can be further improved as compared with conventional resin compositions for forming an insulating film.
Further, according to the resin composition for forming an insulating film of the present invention, chemical resistance can be further improved as compared with conventional resin compositions for forming an insulating film.
Further, according to the resin composition for forming an insulating film of the present invention, the corrosion resistance to a lower metal or the like can be further improved as compared with a conventional resin composition for forming an insulating film.
Further, according to the resin composition for forming an insulating film of the present invention, the workability at low temperatures can be further improved as compared with conventional resin compositions for forming an insulating film.
Detailed Description
The invention provides a resin composition for forming an insulating film, an insulating film manufactured by using the same, an image display device and a method for manufacturing the insulating film.
The resin composition for forming an insulating film of the present invention contains a photopolymerizable compound containing a fluorene-based compound, thereby improving heat resistance, chemical resistance, and permeability and preventing corrosion of lower metals (e.g., copper (Cu)). Further, by including the light absorber containing the azole compound, fine pattern and pore characteristics can be improved by realizing adjustment of the degree of photocuring.
More specifically, the present invention provides a resin composition for forming an insulating film, an insulating film produced using the same, an image display device, and a method for producing an insulating film, wherein the resin composition for forming an insulating film comprises (a) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light absorber, and (E) a solvent, the (B) photopolymerizable compound comprises a fluorene compound, and the (D) light absorber comprises an azole compound.
The term "solid component" as used herein means the remaining components excluding the solvent.
< resin composition for Forming insulating film >
The resin composition for forming an insulating film of the present invention is not particularly limited as long as it contains a photopolymerizable compound containing a fluorene-based compound and a light absorber containing an azole-based compound.
The resin composition for forming an insulating film of the present invention preferably does not contain an amine compound and a diamine compound, from the viewpoint of minimizing a reaction with other functional groups and improving storage stability.
The resin composition for forming an insulating film of the present invention has a function of preventing corrosion of a metal adjacent to an insulating film made of the resin composition for forming an insulating film, and is preferably used for preventing corrosion of adjacent copper (Cu).
The firing temperature of the resin composition for forming an insulating film of the present invention may be 80 to 150 ℃, and preferably the post-firing temperature may be 80 to 150 ℃.
(A) Adhesive resin
The binder resin contained in the resin composition for forming an insulating film of the present invention is not particularly limited as long as it can impart alkali solubility to the insulating film formed from the resin composition for forming an insulating film to impart pattern formability.
In one embodiment, the binder resin may include a Tetrahydropyran (THP) ring. In this case, there is an advantage in that the transparency, heat resistance and pattern characteristics of the coating film can be improved.
The Tetrahydropyran (THP) based ring may be polymerized by including at least one or more of an acyclic compound and a cyclic compound capable of forming a Tetrahydropyran (THP) based ring upon polymerization.
The acyclic compound may have an unsaturated bond in the main chain to form a Tetrahydropyran (THP) ring. For example, a compound represented by the following chemical formula 1 may be contained, and in this case, it is preferable in view of maximizing the ring formation efficiency in the copolymer at the time of polymerization, but it is not necessarily limited thereto.
[ chemical formula 1]
Figure BDA0002947769350000061
In the above chemical formula 1, R1、R2Each independently is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may or may not contain a heteroatom.
As the above-mentioned R1And R2Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-pentyl, stearyl, lauryl, cyclohexyl, ethylhexyl, methoxyethyl, ethoxyethyl, and benzyl, and among them, methyl, ethyl, cyclohexyl, and benzyl are preferable.
The heteroatom may be oxygen (O), sulfur (S), nitrogen (N), or the like, but is not necessarily limited thereto.
In the case of performing polymerization by including the compound of chemical formula 1 as a monomer, the following two kinds of Tetrahydropyran (THP) -based ring-forming repeating units may be formed in a polymer, the ratio of each repeating unit is not particularly limited, and one of the two kinds of repeating units may be a main repeating unit in the binder resin.
Figure BDA0002947769350000071
The cyclic compound may contain a Pyran (Pyran) -based ring and/or a Tetrahydropyran (THP) -based ring in one molecule and may have a polymerizable unsaturated bond. For example, the pyran ring-containing compound may be 4- (1, 4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone, 4- (1, 5-dioxa-6-oxo-7-octenyl) -6-methyl-2-pyrone, or the like, the compound containing a Tetrahydropyran (THP) system ring may be tetrahydropyran-2-yl (meth) acrylate, (tetrahydropyran-2-yl) methyl (meth) acrylate, 2, 6-dimethyl-8- (tetrahydropyran-2-yloxy) -1-octen-3-one, 1- (tetrahydropyran-2-yloxy) -3-buten-2-one, and the like.
The binder resin may contain a compound having an unsaturated bond copolymerizable with the acyclic compound and the cyclic compound. The compound having an unsaturated bond copolymerizable with the above-mentioned monomer is not particularly limited, and examples thereof include an unsaturated carboxyl group-containing monomer and other unsaturated monomers.
Examples of the unsaturated carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated polycarboxylic acids, and the like, which have 1 or more carboxyl groups in the molecule.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, and carnosic acid.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester thereof, and examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, and mono (2-methacryloyloxyethyl) phthalate. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxy polycaprolactone monoacrylate, ω -carboxy polycaprolactone monomethacrylate and the like.
The unsaturated carboxyl group-containing monomers may be used alone or in combination of two or more.
Examples of the other unsaturated monomers include aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, n-butyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, 2-butyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, and 2-butyl acrylate, 2-hydroxy-butyl acrylate, 2-hydroxy-butyl acrylate, 2-butyl acrylate, and, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol diacrylate, allyl methacrylate, benzyl acrylate, cyclohexyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene, Unsaturated carboxylic acid esters such as methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and dicyanovinylene; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; and macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, and the like. These monomers may be used each alone or in combination of two or more.
In one embodiment, the adhesive resin may include an epoxy adhesive resin. In this case, by reducing the firing temperature, preferably the post-firing temperature, of the resin composition for forming an insulating film to 80 to 150 ℃, the process can be appropriately performed even for a substrate that cannot be subjected to the process at a high temperature, and the reliability can be improved.
The epoxy-based binder resin may be selected from a wide variety of polymers used in the art to which the present invention pertains, and one or more of them may be used alone or in combination, and the functional groups constituting the binder may be used in combination according to the intended purpose. When two or more kinds are combined, for example, two or more kinds of binder resins composed of different copolymerization components, two or more kinds of binder resins having different weight average molecular weights, and two or more kinds of binder resins having different degrees of dispersion may be mentioned.
In one or more embodiments, the epoxy-based adhesive resin may include one or more selected from the group consisting of a bisphenol-type epoxy resin, a phenol novolac-type epoxy resin, a tert-butyl catechol-type epoxy resin, a naphthalene-type epoxy resin, a glycidyl amine-type epoxy resin, a biphenyl-type epoxy resin, a phenol aralkyl-type epoxy resin, a cresol novolac-type epoxy resin, a linear aliphatic epoxy resin, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane dimethanol-type epoxy resin, and a halogenated epoxy resin.
In one embodiment, the epoxy-based binder resin may include a compound represented by the following chemical formula 2, and in this case, it is preferable from the viewpoint of developability and reliability. The compound represented by the following chemical formula 2 may include a structure to which a known functional group is added.
[ chemical formula 2]
Figure BDA0002947769350000101
In the chemical formula 2 described above, the,
R3and R4Each independently is hydrogen or CH3Preferably, it may be hydrogen.
a and b are each independently an integer of 3 to 20, and preferably may be an integer of 5 to 15.
The epoxy-based adhesive resin may be prepared by including one or more kinds of resins as a resin containing 3, 4-epoxy tricyclo [5.2.1.0 ]2 ,6]A monomer of a decane ring compound and one or more monomers as an unsaturated carboxylic acid or an acid anhydride thereof may be copolymerized, and may further contain a functional group.
The above-mentioned 3, 4-epoxy-containing tricyclo [ 5.2.1.0%2,6]As the decane ring compound, 3, 4-epoxytricyclo [5.2.1.02,6]Decane-9-yl acrylate, 3, 4-epoxytricyclo [5.2.1.02,6]Decane-8-yl acrylate and the like, preferably 3, 4-epoxytricyclo [5.2.1.02,6]Decane-9-yl acrylate with 3, 4-epoxytricyclo [5.2.1.02,6]A mixture of decane-8-yl acrylate, more preferably the above-mentioned 3, 4-epoxytricyclo [5.2.1.02,6]Decane-9-yl acrylate with 3, 4-epoxytricyclo [5.2.1.02,6]A mixture of decane-8-yl acrylate in a volume ratio of 50: 50.
The carboxylic acid or anhydride thereof may be an α, β -unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, or the like, and an anhydride thereof (maleic anhydride, itaconic anhydride, or the like), and methacrylic acid is preferable.
The factors that greatly affect the patterning of the resin composition for forming an insulating film of the present invention include the molecular weight of the binder resin, which affects the viscosity of the composition and the surface of the pattern to be formed, and the acid value, which affects the pattern formation during the process.
The binder resin of the present invention may have a weight average molecular weight (hereinafter referred to as "molecular weight (Mw)") in terms of polystyrene measured by GPC of 5,000 to 30,000, preferably 7,000 to 28,000, and a molecular weight distribution (Mw/Mn) of 2.0 to 3.0, preferably 2.1 to 2.5.
The acid value of the binder resin of the present invention may be 20 to 100mgKOH/g, and preferably 30 to 90 mgKOH/g.
In the case where the molecular weight (Mw) and the acid value of the binder resin satisfy the above ranges, there are advantages in pattern characteristics, pore characteristics, and improvement in developability.
The content of the binder resin may be 10 to 50% by weight, preferably 20 to 45% by weight, based on the total weight of solid components in the resin composition for forming an insulating film. In the case of satisfying the above range, there are advantages in pattern characteristics, pore characteristics and improvement of developability of the composition.
(B) Photopolymerizable compound
The photopolymerizable compound of the invention is not particularly limited as long as it is polymerized and cured by irradiation with light such as ultraviolet light, and preferably contains a fluorene-based compound. In this case, corrosion of lower copper (Cu) can be prevented, heat resistance and chemical resistance are excellent, and transmittance can be improved.
In one embodiment, the fluorene compound may include a compound represented by the following chemical formula 3.
[ chemical formula 3]
Figure BDA0002947769350000111
In the above chemical formula 3, X1And X2Each independently represents A hydroxyl group, - (O-A-O)pH group (A represents an alkylene group having 2 to 3 carbon atoms, p represents an integer of 1 to 10), R5～R8Each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, or a halogen atom, m1 and m2 are each independently an integer of 0 to 3, and n1 to n4 are each independently an integer of 0 to 4. Wherein m1+ n1 and m2+ n2 are integers of 0-5.
X is above1And X2The substitution position of (b) is not particularly limited, and may be Ortho (Ortho), Meta (Meta) or Para (Para), with Meta or Para being preferred, with respect to fluorene.
The hydrocarbon group may be a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cycloalkenyl group having 5 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms, or the like.
The alkoxy group may be a linear or branched alkoxy group having 1 to 6 carbon atoms.
The halogen atom includes fluorine (F), chlorine (Cl), bromine (Br) and iodine (I) atoms.
When the hydrocarbon group and the alkoxy group have a substituent, the substituent may be an alkoxy group such as methoxy group, an aryl group such as phenyl group, benzyl group, tolyl group, an arylene group such as phenylene group, naphthylene group, etc., (meth) acryloyl group, (meth) acryloyloxy group, nitro group, hydroxyl group, phenoxy group, etc., preferably (meth) acryloyl group, (meth) acryloyloxy group, hydroxyl group. Further, the number of the substituents may be plural. Examples of the substituted hydrocarbon group include a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a 2- (meth) acryloyloxyethyl group, a 2- (meth) acryloyloxypropyl group and the like, and a 2- (meth) acryloyloxyethyl group and a 2- (meth) acryloyloxypropyl group are preferable. Examples of the substituted alkoxy group include a 4-methoxyphenyl group, a 2-methoxy-2-nitroethoxy group, a 2- (meth) acryloyloxyethoxy group, a 3- (meth) acryloyloxy-2-hydroxypropoxy group, and the like.
Each of n1 to n4 may be an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.
The n3 and n4 are preferably integers of 0 to 3, more preferably 0 to 2.
Each of m1 and m2 independently may be an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.
The m1+ n1 and m2+ n2 may be each independently an integer of 0 to 5.
Examples of the compound represented by the above chemical formula 3 include 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene, 9-bis [4- (3-acryloyloxy-2-hydroxypropoxy) phenyl ] fluorene, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (3-hydroxy-2-methylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-2, 6-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-di-tert-butylphenyl) fluorene, 9, 9-bis (3, 4-dihydroxyphenyl) fluorene, 9-bis (2, 5-dihydroxyphenyl) fluorene, 9-bis (3, 4-dihydroxy-5-methylphenyl) fluorene, 9-bis (3, 4-dihydroxy-6-methylphenyl) fluorene, 9-bis (2, 4-dihydroxy-3, 6-dimethylphenyl) fluorene, 9-bis (3,4, 5-trihydroxyphenyl) fluorene, 9-bis (2,4, 6-trihydroxyphenyl) fluorene, 9-bis (2,4, 5-trihydroxyphenyl) fluorene, 9-bis (2,3, 4-trihydroxyphenyl) fluorene, 9, 9-bis (2,3, 5-trihydroxyphenyl) fluorene, 9-bis (2,3, 6-trihydroxyphenyl) fluorene, 9-bis (4-hydroxyethoxyphenyl) fluorene, 9-bis (4-hydroxyethoxy-3-methylphenyl) fluorene, 9-bis (4-hydroxyisopropoxy-3-methylphenyl) fluorene, 9-bis (4-hydroxyethoxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxyisopropoxy-2, 6-dimethylphenyl) fluorene, 9-bis (4-hydroxyethoxy-3-cyclohexylphenyl) fluorene, 9-bis (4-hydroxyethoxy-3-phenylphenyl) fluorene, 9, 9-bis [3, 4-bis (2-hydroxyethoxy) phenyl ] fluorene, 9-bis [3,4, 5-tris (2-hydroxyethoxy) phenyl ] fluorene, and the like.
The content of the fluorene compound may be 3 to 35% by weight based on the total weight of solid components in the photosensitive resin composition for forming an insulating film. When the content of the fluorene-based compound is less than 3 wt%, chemical resistance, bevel characteristics, and copper (Cu) etching resistance may be poor, and when the content is more than 35 wt%, pattern characteristics and hole characteristics may be poor.
In one or more embodiments, the photopolymerizable compound may further include a monofunctional monomer, a difunctional monomer, another polyfunctional monomer, and the like in addition to the compound represented by chemical formula 3.
The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.
The type of the bifunctional monomer is not particularly limited, and examples thereof include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate.
The polyfunctional monomer is not particularly limited in kind, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like.
The content of the photopolymerizable compound may be 5 to 70 wt%, preferably 20 to 60 wt%, based on the total weight of the solid components in the photosensitive resin composition. When the above range is satisfied, there is an advantage in terms of the intensity or smoothness of the pixel portion.
(C) Photopolymerization initiator
The photopolymerization initiator is not particularly limited as long as it is a component capable of initiating polymerization of the photopolymerizable compound or the like by irradiation with actinic rays, and conventionally or later developed photopolymerization initiators can be used.
In one or more embodiments, the photopolymerization initiator of the present invention may include one or more compounds selected from the group consisting of acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin, and bisimidazole compounds.
As the acetophenone-based compound, for example, examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and oligomers of 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl ] propan-1-one.
Examples of the benzophenone-based compound include benzophenone, 2' -hydroxy-4, 4' -dimethoxybenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, and the like.
Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethylene ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) ethylene ] -1,3, 5-triazine, and the like.
Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
Examples of the oxime compound include 1- [4- (phenylthio) phenyl ] -heptane-1, 2-dione 2- (O-benzoyl oxime), 1- [4- (phenylthio) phenyl ] -octane-1, 2-dione 2- (O-benzoyl oxime), 1- [4- (benzoyl) phenyl ] -octane-1, 2-dione 2- (O-benzoyl oxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyl oxime), and 1- [ 9-ethyl-6- (3-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyl oxime -acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetyloxime), 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-tetrahydropyranylphenylbenzoyl) -9.H. -carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofurylbenzoyl) -9.H. -carbazol- 3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydropyranyl-benzoyl) -9.h. -carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) benzoyl } -9.h. -carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranyl-methoxybenzoyl) -9.h. -carbazol-3-yl ] -1- (O-ethylglyoxime) Acyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyl methoxybenzoyl) -9.H. -carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofuranyl methoxybenzoyl) -9.H. -carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydropyranyl methoxymethyloxybenzoyl) -9 Benzoyl) -9.h. -carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9.h. -carbazol-3-yl ] -1- (O-acetyloxime), and the like.
Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Examples of the biimidazole-based compound include 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2' -bis (2-bromophenyl) -4,4',5,5' -tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2,4, 6-trichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2-bromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4-dibromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2,4, 6-tribromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, and the like.
The content of the photopolymerization initiator may be 3 to 20% by weight, preferably 5 to 15% by weight, based on the total weight of solid components in the resin composition for forming an insulating film. In the case of satisfying the above range, there is an advantage in adjusting the pattern formation and improving the degree of curing.
In order to improve the sensitivity of the resin composition for forming an insulating film of the present invention, the photopolymerization initiator may further contain a photopolymerization initiator. The resin composition for forming an insulating film of the present invention contains a photopolymerization initiation aid, and thus can further improve sensitivity and productivity.
The photopolymerization initiator may preferably be one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds.
As the amine compound, an aromatic amine compound is preferably used, and specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone (known as Michler's ketone), 4' -bis (diethylamino) benzophenone and the like can be used.
The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.
Examples of the polyfunctional thiol compound include Tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate (Tris- [ (3-merotropinyloxy) -ethyl ] -isocyanurate), Trimethylolpropane Tris-3-mercaptopropionate (trimethyolpropane Tris-3-merotropinate), Pentaerythritol tetrakis-3-mercaptopropionate (pentaerythritoltetrakis-3-merotropinate), Dipentaerythritol hexa-3-mercaptopropionate (dipentaerythritoltexa-3-merotropinate), and the like.
When the photopolymerization initiator is further contained, the content of the photopolymerization initiator may be 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total weight of the solid components of the binder resin and the photopolymerizable compound. When the above range is satisfied, the sensitivity of the colored photosensitive resin composition can be further improved, and the productivity of a color filter formed using the colored photosensitive resin composition can be improved.
(D) Light absorbing agent
The resin composition for forming an insulating film of the present invention may contain a light absorber. The light absorbing agent is not particularly limited as long as it contains a functional group that absorbs light and a substituent attached to the basic structure, and preferably contains an azole compound. In this case, it is preferable in terms of improving the pattern characteristics, the hole characteristics, and the slope characteristics.
In one embodiment, the azole compound may include one or more selected from the group consisting of Benzotriazole (BTA) and pyrazole.
The light absorber including the Benzotriazole (BTA) and/or pyrazole can improve pattern and hole characteristics, reliability, and the like by adjusting the curing degree by the light absorption characteristics in a long wavelength region.
The case where the insulating film forming resin composition contains Benzotriazole (BTA) and pyrazole can be analyzed by a commonly used analysis method. Specifically, the contents of benzotriazole and pyrazole contained in the resin composition for forming an insulating film can be analyzed by nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, mass spectrometry, or the like.
The content of the light absorber may be 1 to 10% by weight, preferably 2 to 6% by weight, based on the total weight of the solid components in the resin composition for forming an insulating film. In the case where the above range is satisfied, there is an advantage in pattern characteristics as well as hole characteristics.
(E) Solvent(s)
The solvent may be any organic solvent known in the art without particular limitation.
Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, ketones such as ethanol, propanol, butanol, hexanol, cyclohexanol, and ethylene glycol dibutyl ether, ketones such as ethanol, butanol, cyclohexanol, and methyl ethyl ketone, Alcohols such as ethylene glycol and glycerol, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ -butyrolactone.
From the viewpoint of coating properties and drying properties, the solvent is preferably an organic solvent having a boiling point of 100 to 200 ℃, more preferably an ester such as alkylene glycol alkyl ether acetate, a ketone, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate, and further preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate.
The solvents mentioned above may be used each alone or in combination of two or more.
The content of the solvent may be 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the resin composition for forming an insulating film. When the above range is satisfied, it is preferable to perform coating using a coating device such as a roll coater, a spin coater, a slit coater (also referred to as a die coater), or an ink jet printer because the coating device provides an effect of improving coating properties.
(F) Additive agent
The photosensitive resin composition of the present invention may further contain an additive as needed, and the kind of the additive may be determined according to the needs of the user, and the present invention is not particularly limited, and examples thereof include fillers, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-gelling agents, dispersants, and ink repellents. The above-exemplified additives may be used singly or in combination of two or more.
As the filler, glass, silica, alumina, and the like can be used, but the filler is not limited thereto.
As the other polymer compound, specifically, a curable resin such as an epoxy resin or a maleimide resin; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane; and the like, but not limited thereto.
The curing agent is used for improving deep-section curing and mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like can be used, but the curing agent is not limited thereto. Specific examples of the epoxy compound include, but are not limited to, bisphenol a epoxy resins, hydrogenated bisphenol a epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, brominated derivatives of these epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene (co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate. Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, but the oxetane compound is not limited thereto.
The curing agent may be used in combination with a co-curing compound capable of ring-opening polymerizing the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Specifically, polycarboxylic acids, polycarboxylic anhydrides, acid generators, and the like can be used as the curing assistant compound. The carboxylic acid anhydride can be used as a commercially available epoxy resin curing agent. Examples of the commercially available epoxy resin curing agent include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA industries, Ltd.), RIKACID HH (trade name, manufactured by Nissian Chemicals Co., Ltd.), MH-700 (trade name, manufactured by Nissian Chemicals Co., Ltd.), and the like.
The curing agents and co-curing compounds exemplified above may be used each alone or in combination of two or more.
As the surfactant, commercially available surfactants can be used, and examples thereof include silicone surfactants, fluorine surfactants, and mixtures thereof. Examples of the silicone surfactant include surfactants having a siloxane bond. Commercially available products include TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE 29SHPA, TORAY SILICONE SH30PA, polyether-modified SILICONE oil SH8400 (manufactured by Tolyo Silicone Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Toshiba Silicone Co., Ltd.), and the like.
The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specifically, the strains include FLUORINERT FC430, FLUORINERT FC431 (manufactured by SUMOF 3M), MEGAFAC F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F251, MEGAFAC F410, MEGAFAC F430, MEGAFAC F444, MEGAFAC F477, MEGAFAC F551, MEGAFAC F553, MEGAFAC F554, MEGAFAC F556, MEGAFAC F557, MEGAFAC F558, MEGAFAC F559, MEGAFAC F562, MEGAFAC F563, MEGAFAC F1100, MEGAFAC F565, MEGAFAC F570, MEGAFAC R30, MEGAFAC R26, MEGAFAC F6754, MEGAFAC F381, MEGAFAC F382, MEGAFAC F80, MEGAFAC F240, MEGAFAC F44, MEGAFAC F240, MEGARFLE F44, MEGARFLE F53, MEGARFLE F351, MEGARFLE F352, MEGARFLE SAGE FAC 3644, SAGE FAR 3623, SAGE FAR, SAGE FAR, SAGE FAR, SAGE FAR, SAGE FAR, SAGE FAR, SAGE FAR, SAGE FAR, SAGE FAR, SADE FAR, SAGE FAR, SAGE FAR, SAGE FAR, SADE FAR.
As the adhesion promoter, a silane compound selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate propyl trimethoxy silane and 3-isocyanate propyl triethoxy silane.
The antioxidant may include one or more selected from the group consisting of a phosphorus antioxidant, a sulfur antioxidant, and a phenol antioxidant, and in this case, it is possible to suppress a color change phenomenon that may occur at high temperature in the process or yellowing that may occur due to a light source after the display is manufactured. The antioxidant may include one or more selected from the group consisting of a phenolic compound, a phosphorus compound, and a sulfur compound, and they may be used in combination with the phenolic-phosphorus compound, the phenolic-sulfur compound, the phosphorus-sulfur compound, or the phenolic-phosphorus-sulfur compound.
Specific examples of the ultraviolet absorber include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the anti-gelling agent include, but are not limited to, sodium polyacrylate and the like.
The dispersant is added to maintain the dispersion stability of the pigment, and any dispersant generally used in the art may be used without limitation.
The ink repellent has a fluorine atom in the molecule. Thus, the ink repellent has a property of migrating to the upper surface (upper surface migration) and an ink repellency in the process of forming a cured film using the photosensitive resin composition containing the same. By using the ink repellent, the upper layer portion including the upper surface of the obtained cured film becomes a layer in which the ink repellent exists densely (hereinafter, also referred to as "ink repellent layer"), and the ink repellency is imparted to the upper surface of the cured film. Further, from the viewpoint of improving the fixing property of the ink repellent in the ink repellent layer, the ink repellent is preferably a compound having an ethylenic double bond. Since the ink repellent has an ethylenic double bond, the radical acts on the ethylenic double bond of the ink repellent which migrates to the upper surface, and the crosslinking can be achieved by (co) polymerization between the ink repellers or between the ink repellent and other components having an ethylenic double bond contained in the partition wall-forming photosensitive resin composition.
The type of the ink repellent is not particularly limited, and examples thereof include a partial hydrolysis condensate of a hydrolyzable silane compound. The hydrolyzable silane compound may be used alone or in combination of two or more. An ink repellent comprising a partially hydrolyzed condensate of a hydrolyzable silane compound and having a fluorine atom may be used, or an ink repellent comprising a compound having a hydrocarbon chain as a main chain and a fluorine atom as a side chain may be used.
The additives can be added to the composition as appropriate by those skilled in the art within a range not impairing the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10 wt%, preferably 0.1 to 10 wt%, more preferably 0.1 to 5 wt% based on the total weight of the photosensitive resin composition, but is not limited thereto.
< insulating film >
The present invention includes an insulating film formed of a resin composition for forming an insulating film on a substrate.
The substrate is not particularly limited as long as it functions as a structural base (base) for providing other elements and the like by including an insulating film formed of the resin composition for forming an insulating film. In one or more embodiments, the substrate may be a polymerizable film of polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like.
In one embodiment, the insulating film may include a predetermined pattern, for example, a pattern formed by coating the resin composition for forming an insulating film on a substrate, and exposing and developing the resin composition in a predetermined pattern.
Specifically, the method can comprise the following steps: a step (S1) for producing a solution in which a resin composition for forming an insulating film is mixed; a step (S2) of applying the solution produced in the step (S1) to a substrate; a step (S3) of heating the solution applied in the step (S2) to remove the solvent; a step (S4) of forming a pattern by exposure and development; and a step (S5) of heating the pattern to increase the degree of curing of the pattern.
In the step of applying the solution onto the substrate (S2), the resin composition for forming an insulating film is applied onto the substrate and then heated and dried, whereby volatile components such as a solvent can be removed to form a smooth coating film.
The coating method may be performed by, for example, spin coating, a flexible coating method, a roll coating method, slit spin coating, slit coating, or the like. After the coating, the coating is dried by heating (prebaking) or drying under reduced pressure, and then volatile components such as a solvent are volatilized by heating.
The heating step (S3) for removing the solvent may be performed at 70 to 150 ℃, preferably 80 to 130 ℃.
In the step of forming a pattern by exposure and development (S4), first, ultraviolet rays are irradiated through a mask for forming a target pattern. In this case, it is preferable to use a mask aligner, a stepper or the like in order to uniformly irradiate the entire exposure portion with parallel light beams and to perform accurate alignment between the mask and the substrate. In this case, the mask pattern may be formed in direct contact with the insulating film or in contact with a film that can transmit active light, and may be formed at a constant distance.
As the light source of the active light, a light source of active light used in the past or in the future when exposure is performed can be used, and a lamp that efficiently emits ultraviolet rays such as a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp, a lamp that efficiently emits visible rays such as a photographic flat lamp, a solar lamp, or the like can be used.
Then, the photo-cured coating film is brought into contact with a developer to dissolve the unexposed portion, whereby an insulating film having a desired pattern can be formed.
The heating step (S5) for increasing the degree of curing of the formed pattern may be performed at 80 to 150 ℃.
The insulating film formed from the resin composition for forming an insulating film of the present invention has an excellent effect of improving reliability and provides an effect of preventing corrosion of the lower copper substrate.
< image display apparatus >
The invention provides a display device including the insulating film.
The Display device of the present invention may include a Display device which is developed in the past or in the future, and in one or more embodiments, the Display device may be a Liquid Crystal Display (LCD), an Electro Luminescence (EL) Display device, a Plasma Display Panel (PDP), a Field Emission Display (FED), an Organic Light Emitting element (OLED) Display device, or the like.
The display device may include a structure generally known in the art, in addition to the insulating film.
The present invention will be described in more detail below with reference to examples, but the embodiments of the present invention disclosed below are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the appended claims, and includes all modifications within the meaning and range equivalent to the description of the claims. In the following examples and comparative examples, "%" and "part(s)" representing the content are based on mass unless otherwise mentioned.
< production example 1: production of Binder resin >
In a four-necked flask equipped with a dropping funnel, a thermometer, a condenser and a stirrer, 23.3g of methyl-2- (bromomethyl) -acrylate (product of Aldrich), 15.8g of triethylamine (product of Aldrich) and 115.0g of propylene glycol methyl ether (product of TCI) were charged, and the interior of the four-necked flask was replaced with nitrogen gas. Subsequently, the flask was heated to 90 ℃ and a mixed solution of 15.1g of methyl-2- (hydroxymethyl) -acrylate (product of Aldrich Co.), 3.2g of 2,2' -azobisisobutyronitrile (product of Wako Co.) and 110.0g of propylene glycol methyl ether (product of TCI Co.) was added dropwise over 1 hour, followed by polymerization for 30 minutes to produce a pyran-containing polymer. Then, a mixed solution of 37.5g of methacrylic acid, 19.0g of methyl methacrylate, 225.0g of propylene glycol methyl ether and 3.2g of 2,2' -azobisisobutyronitrile (Wako. Co., Ltd.) was slowly added dropwise over 1 hour, followed by polymerization over 8 hours, followed by cooling to room temperature. After the inside of the four-necked flask was replaced with nitrogen gas, 61.5g of glycidyl methacrylate (product of Mitsubishi corporation), 3.6g of tetra-n-butylammonium bromide (product of TCI corporation) and 0.15g of 4-methoxyphenol (product of Methoquinone (4-methoxyphenone, pure corporation)) were added to the flask, and reacted at 80 ℃ for 12 hours to obtain a binder resin B1 in which GMA was added to the carboxyl group of the copolymer. The weight average molecular weight (Mw) of the binder resin B1 measured by GPC was 23,000.
< production example 2: production of Binder resin >
A1 liter separation type flask having an internal volume equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet was charged with 277g of methoxybutyl acetate, and after the temperature was raised to 80 ℃, a mixed solution prepared by dissolving 301g of a mixture [50:50 (molar ratio) ] of 3, 4-epoxytricyclo [5.2.1.0,2,6] decan-9-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0,2,6] decan-8-yl acrylate, 49g of methacrylic acid and 23g of azobisdimethylvaleronitrile in 350g of methoxybutyl acetate was added dropwise thereto over 5 hours, and the mixture was aged over 3 hours to obtain adhesive resin B3[ 35.0 wt% of solid content (NV) ]. The acid value (dry value) of the resulting adhesive resin B3 was 69.8mgKOH/g, the weight-average molecular weight (Mw) was 12,300, and the dispersity (Mw/Mn) was 2.1.
< examples and comparative examples >
Referring to tables 1 to 2 below, resin compositions for forming an insulating film of examples and comparative examples were produced, respectively.
[ Table 1]
Figure BDA0002947769350000231
Figure BDA0002947769350000241
[ Table 2]
Figure BDA0002947769350000242
Figure BDA0002947769350000251
< Experimental example >
The resin compositions for forming an insulating film of examples and comparative examples were evaluated for pattern characteristics, hole characteristics, chemical resistance, copper (Cu) corrosion resistance, and bevel characteristics, and the results are shown in tables 3 to 4 below.
(1) Substrate fabrication
5cm x 5cm substrate was washed with neutral detergent and water and dried. The applicable base material may be a glass substrate (corning corporation) or a substrate with a Cu pattern depending on the evaluation method. The resin compositions for forming an insulating film produced in the examples and comparative examples were each spin-coated on a substrate so that the final film thickness became 2.0 μm, and the solvent was removed by pre-baking at 80 to 120 ℃ for 1 to 3 minutes. Then, the exposure amount is 30 to 80mJ/cm2The substrate was exposed to light to form a pattern, and the unexposed portion was removed using an aqueous alkali solution. Then, the substrate is fired at 100 to 180 ℃ for 20 to 60 minutes to produce a substrate.
(2) Pattern and hole characteristics
A substrate with a pattern was produced according to the above production criteria. The size of the pattern and the size of the pores were determined using an SNU (SIS-2000) apparatus. The CD-bias (CD-bias) is calculated by the difference in the size of the pattern of the mask and the size of the actually generated pattern.
CD shift (Mask Size)) - (actual pattern Size)
< evaluation criteria for Pattern characteristics >
O: CD deviation less than or equal to +4 mu m
X: CD bias > +4 μm
< evaluation criteria for pore characteristics >
O: CD bias of-4 to-7 μm
X: CD deviation less than-7 μm or greater than-4 μm
(3) Resistance to chemical agents
The substrate fabricated as described above was immersed in the etching solution and the stripping solution in this order, and then changes in film thickness were observed. The thickness of the film was confirmed by immersing the substrate for 2 minutes while maintaining the etching solution at 45 ℃. Thereafter, the film was immersed in a stripping solution maintained at 60 ℃ for 5 minutes, and the film thickness was confirmed. After all of these processes were performed, the difference between the film thickness before immersion in the etching solution and the film thickness after immersion in the stripping solution was observed.
Delta film thickness-film thickness after immersion in stripping solution-film thickness before evaluation of chemical resistance
< evaluation criteria for chemical resistance >
O: the thickness of the delta film is less than or equal to 0.2 mu m
X: thickness of delta film >0.2 μm
(4) Corrosion of Cu
The substrates fabricated in accordance with the above criteria were subjected to Pressure Cooker Test (PCT) equipment to confirm Cu corrosion. In the experiment, the substrate was maintained in the apparatus at a temperature of 110 ℃ and a humidity of 100% for 72 hours, and then whether or not the substrate was corroded was determined by a microscope. The evaluation used a Cu-patterned substrate, and it was confirmed that several of 10 etching occurred.
< evaluation criteria for copper (Cu) Corrosion >
O: 10 middle 2 internal corrosion
X: 3 or more corrosion
(5) Bevel feature
The slopes of the patterns prepared in accordance with the above standards were measured using an SEM (Hitachi, Inc., S-4300) apparatus.
< evaluation criteria for bevel characteristics >
O: cone angle (Taper angle) of 15-80 °
X: the cone angle is less than 15 degrees or more than 80 degrees
[ Table 3]
Figure BDA0002947769350000271
[ Table 4]
Figure BDA0002947769350000272
Referring to tables 3 to 4, in the case of manufacturing an insulating film using the resin composition for forming an insulating film according to the embodiment of the present invention, since the CD variation (CD variation) of the pattern shows a value of +4 μm or less and the CD variation of the formed hole shows a value of-4 to-7 μm, it is known that the Undercut (Undercut) phenomenon which may occur in wet etching (wet etching) is reduced, providing advantageous effects in forming a fine pattern and a hole.
Further, since the amount of change in film thickness after immersion in the etching solution (Etchant) and the stripping solution (Stripper) in this order was 0.2 μm or less, it was confirmed that the loss of the insulating film which may occur during the stripping (stripping) process could be minimized.
Further, it was confirmed that the copper pattern within 2 out of 10 total copper patterns on the substrate was corroded, thereby exhibiting an excellent effect on corrosion prevention of copper under high-temperature and high-humidity conditions that may occur in devices, particularly display devices.
Further, the measured taper angle of the formed pattern showed 15 ° or more and less than 80 °, and thus it was found that the formed slope characteristics were good.
On the other hand, in the case of producing an insulating film from the resin composition for forming an insulating film of comparative examples 1 to 4 containing no fluorene compound as a photopolymerizable compound, it was confirmed that the difference in film thickness was more than 0.2 μm and the loss of the insulating film excessively occurred during the peeling process, and that the pattern of 3 or more of the total 10 copper patterns was corroded, which showed that it was not suitable for use in image display devices such as devices, particularly displays.
Further, since the taper angle of the formed pattern was less than 15 ° or 80 ° or more, it was confirmed that the slope characteristics were poor.
In addition, in the case of producing an insulating film using the resin compositions for forming an insulating film of comparative examples 5 and 6 which do not contain Benzotriazole (BTA) and pyrazole as a light absorber, it was confirmed that the chemical resistance, the slope characteristics and the copper (Cu) corrosion resistance were poor, the CD variation of the formed pattern was more than 4 μm, and the CD variation of the formed hole was less than-7 μm or more than-4 μm, and the pattern characteristics and the hole characteristics were also poor, as in the case of comparative examples 1 to 4.

Claims (17)

1. A resin composition for forming an insulating film, comprising (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light absorber, and (E) a solvent,
the photopolymerizable compound (B) comprises a fluorene compound,
the (D) light absorber contains an azole compound.
2. The resin composition for forming an insulating film according to claim 1, wherein the (A) binder resin contains a tetrahydropyran THP-based ring.
3. The resin composition for forming an insulating film according to claim 2, wherein the tetrahydropyran THP-based ring is polymerized by including at least one of an acyclic compound and a cyclic compound which form a tetrahydropyran THP-based ring upon polymerization.
4. The resin composition for forming an insulating film according to claim 3, wherein the acyclic compound comprises a compound represented by the following chemical formula 1,
chemical formula 1
Figure FDA0002947769340000011
In the chemical formula 1, R1、R2Each independently being optionally containing a hetero atomAliphatic hydrocarbon groups having 1 to 20 carbon atoms or aromatic hydrocarbon groups having 6 to 18 carbon atoms.
5. The resin composition for forming an insulating film according to claim 3, wherein the cyclic compound contains one or more selected from the group consisting of tetrahydropyran-2-yl (meth) acrylate, (tetrahydropyran-2-yl) methyl (meth) acrylate, 2, 6-dimethyl-8- (tetrahydropyran-2-yloxy) -1-octen-3-one, 1- (tetrahydropyran-2-yloxy) -3-buten-2-one, 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.
6. The resin composition for forming an insulating film according to claim 1, wherein the (A) binder resin comprises an epoxy-based binder resin.
7. The resin composition for forming an insulating film according to claim 6, wherein the epoxy-based binder resin comprises a compound represented by the following chemical formula 2,
chemical formula 2
Figure FDA0002947769340000021
In the chemical formula 2, R3And R4Each independently is hydrogen or CH3，
a and b are each independently an integer of 3 to 20.
8. The resin composition for forming an insulating film according to claim 1, wherein the fluorene-based compound comprises a compound represented by the following chemical formula 3,
chemical formula 3
Figure FDA0002947769340000022
In the chemical formula 3, X1And X2Each independently represents A hydroxyl group, - (O-A-O)pH, wherein A represents an alkylene group having 2 to 3 carbon atoms, p represents an integer of 1 to 10, and R5～R8Each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, or a halogen atom, m1 and m2 are each independently an integer of 0 to 3, n1 to n4 are each independently an integer of 0 to 4, wherein m1+ n1 and m2+ n2 are each independently an integer of 0 to 5.
9. The resin composition for forming an insulating film according to claim 1, wherein the content of the fluorene compound is 3 to 35% by weight based on the total weight of solid components in the resin composition for forming an insulating film.
10. The resin composition for forming an insulating film according to claim 1, wherein the azole compound comprises one or more selected from the group consisting of benzotriazole BTA and pyrazole.
11. The resin composition for forming an insulating film according to claim 1, comprising
(A) 10 to 50 wt% of a binder resin,
(B) 5 to 70 wt% of a photopolymerizable compound,
(C) 3 to 20% by weight of a photopolymerization initiator,
(D) 1 to 10 wt% of a light absorbing agent,
and, relative to the total weight of the resin composition for forming the insulation film, comprises
(E) 60-90 wt% of a solvent.
12. The resin composition for forming an insulating film according to claim 1, wherein copper corrosion is prevented.
13. The resin composition for forming an insulating film according to claim 1, wherein a firing temperature of the resin composition for forming an insulating film is 80 to 150 ℃.
14. The resin composition for forming an insulating film according to claim 13, wherein the firing temperature is a post-firing temperature.
15. An insulating film formed from the resin composition for forming an insulating film according to any one of claims 1 to 14.
16. An image display device comprising the insulating film according to claim 15.
17. A method for producing an insulating film, comprising the step of forming an insulating film by a low-temperature firing process at 80 to 150 ℃ using the resin composition for forming an insulating film according to any one of claims 1 to 14.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120046462A (en) * 2010-11-02 2012-05-10 동우 화인켐 주식회사 A colored photosensitive resin composition, color filter and liquid crystal display device having the same
JP2013238837A (en) * 2011-11-21 2013-11-28 Toyo Ink Sc Holdings Co Ltd Photosensitive dry film, and protective film and touch-panel insulating film using the same
JP2014091790A (en) * 2012-11-05 2014-05-19 Toyo Ink Sc Holdings Co Ltd Resin composition
JP2014157204A (en) * 2013-02-15 2014-08-28 Toray Ind Inc Photosensitive resin composition, photospacer, color filter substrate and liquid crystal display device
WO2014156520A1 (en) * 2013-03-28 2014-10-02 東レ株式会社 Photosensitive resin composition, protection film or insulation film, touch panel and method for manufacturing same
JP2014197171A (en) * 2013-03-05 2014-10-16 東レ株式会社 Photosensitive resin composition, protective film, insulating film, and touch panel and method for producing the same
CN104981737A (en) * 2013-02-12 2015-10-14 东丽株式会社 PHotosensitive Resin Composition, Protective Film Or Insulation Film Obtained By Heat Curing Said Composition, Touch Panel Using Said Film, And Production Method For Said Touch Panel
JP2016178056A (en) * 2015-03-23 2016-10-06 東洋インキＳｃホールディングス株式会社 Organic electroluminescent element, and organic electroluminescent device

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4152732B2 (en) 2001-12-27 2008-09-17 株式会社トクヤマ Resin composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120046462A (en) * 2010-11-02 2012-05-10 동우 화인켐 주식회사 A colored photosensitive resin composition, color filter and liquid crystal display device having the same
JP2013238837A (en) * 2011-11-21 2013-11-28 Toyo Ink Sc Holdings Co Ltd Photosensitive dry film, and protective film and touch-panel insulating film using the same
JP2014091790A (en) * 2012-11-05 2014-05-19 Toyo Ink Sc Holdings Co Ltd Resin composition
CN104981737A (en) * 2013-02-12 2015-10-14 东丽株式会社 PHotosensitive Resin Composition, Protective Film Or Insulation Film Obtained By Heat Curing Said Composition, Touch Panel Using Said Film, And Production Method For Said Touch Panel
JP2014157204A (en) * 2013-02-15 2014-08-28 Toray Ind Inc Photosensitive resin composition, photospacer, color filter substrate and liquid crystal display device
JP2014197171A (en) * 2013-03-05 2014-10-16 東レ株式会社 Photosensitive resin composition, protective film, insulating film, and touch panel and method for producing the same
WO2014156520A1 (en) * 2013-03-28 2014-10-02 東レ株式会社 Photosensitive resin composition, protection film or insulation film, touch panel and method for manufacturing same
JP2016178056A (en) * 2015-03-23 2016-10-06 東洋インキＳｃホールディングス株式会社 Organic electroluminescent element, and organic electroluminescent device

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