CN111278912A - Polymer composition, photosensitive resin composition, and color filter - Google Patents

Polymer composition, photosensitive resin composition, and color filter Download PDF

Info

Publication number
CN111278912A
CN111278912A CN201880070031.0A CN201880070031A CN111278912A CN 111278912 A CN111278912 A CN 111278912A CN 201880070031 A CN201880070031 A CN 201880070031A CN 111278912 A CN111278912 A CN 111278912A
Authority
CN
China
Prior art keywords
meth
acrylic polymer
photosensitive resin
polymer
resin composition
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.)
Granted
Application number
CN201880070031.0A
Other languages
Chinese (zh)
Other versions
CN111278912B (en
Inventor
原司
川口恭章
木下健宏
柳正义
仓本拓树
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.)
Lishennoco Co ltd
Resonac Holdings Corp
Original Assignee
Showa Denko KK
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 Showa Denko KK filed Critical Showa Denko KK
Publication of CN111278912A publication Critical patent/CN111278912A/en
Application granted granted Critical
Publication of CN111278912B publication Critical patent/CN111278912B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—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
    • 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
    • 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
    • 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
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

A photosensitive resin composition comprising: two or more (meth) acrylic polymers having a specific structural unit and different in acid value (mgKOH/g), a solvent, a reactive diluent, and a photopolymerization initiator, wherein the photosensitive resin composition comprises: the acrylic polymer (b) having an acid value of 0.01 to 0.50 times, wherein the (meth) acrylic polymer (a) having the largest acid value among the two or more (meth) acrylic polymers has a weight average molecular weight of 1000 to 10000, and the mass ratio [ (a)/(b) ] of the (meth) acrylic polymer (a) to the (meth) acrylic polymer (b) is 0.01 to 0.50, when the acid value of the (meth) acrylic polymer (a) having the largest acid value among the two or more (meth) acrylic polymers is 1.

Description

Polymer composition, photosensitive resin composition, and color filter
Technical Field
The present invention relates to a polymer composition, a photosensitive resin composition containing the polymer composition, and a color filter produced using the photosensitive resin composition.
Background
In recent years, from the viewpoint of resource saving and energy saving, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of various coatings, printing, paints, adhesives, and the like. In the field of electronic materials such as printed wiring boards, photosensitive resin compositions curable by active energy rays are also used for solder resists, color filters, black matrices, black column spacers (column spacers), photo spacers (photospacers), resists for protective films, and the like.
The color filter is generally composed of a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundary of the pixels, and a protective film formed on the pixels and the black matrix. The color filter having such a configuration is generally manufactured by sequentially forming a black matrix, pixels, and a protective film on a transparent substrate. As a method of forming a pixel and a black matrix (hereinafter, the pixel and the black matrix are referred to as a "colored pattern"), various methods are disclosed. Examples of the method for forming a colored pattern include: the pigment/dye dispersion method includes a photolithography process in which a photosensitive resin composition is used as a resist, and coating, exposure, development, and baking of the photosensitive resin composition are repeated. This pigment/dye dispersion method is widely used at present because it can form a colored pattern having excellent durability such as light resistance and heat resistance and having few defects such as pinholes (Pinhole).
However, the pigment/dye dispersion method has the above-described advantages, and on the other hand, the black matrix, R, G, and B pixel patterns are repeatedly formed at high temperatures, and therefore, a photosensitive resin composition used in this method is required to have high resistance to thermal yellowing.
In addition, a liquid crystal display device is generally manufactured by sandwiching a liquid crystal between a separately manufactured color filter substrate and a TFT (Thin-Film-Transistor) substrate and bonding these members. When these members are bonded, an alignment film such as a polyimide film is provided on the color filter substrate to align the liquid crystal. In this case, the color filter layer is exposed to a highly polar solvent such as N-methylpyrrolidone (NMP) contained in the polyimide resin, and therefore, solvent resistance is required for the photosensitive resin composition used for the color filter layer.
For example, patent documents 1 and 2 propose various photosensitive resin compositions for color filters having excellent heat resistance, solvent resistance, and the like. However, the photosensitive resin composition used for the production of a color filter is required to have further improved thermal yellowing resistance, solvent resistance, and alkali developability.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-029151
Patent document 2: japanese patent laid-open publication No. 2015-174930
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above-mentioned problems, and an object thereof is to provide a photosensitive resin composition having excellent thermal yellowing resistance, solvent resistance, and alkali developability. Further, an object of the present invention is to provide a color filter formed from the photosensitive resin composition, which has excellent resistance to thermal yellowing and solvent resistance.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, they have found that the above problems can be solved by a photosensitive resin composition containing a polymer composition containing two or more (meth) acrylic polymers having a specific structural unit and a specific acid value (mgKOH/g) at a specific mass ratio, and have completed the present invention.
That is, the present invention is as shown in the following [1] to [7 ].
[1] A polymer composition, wherein the polymer composition comprises: two or more (meth) acrylic polymers having a structural unit represented by the following formula 1 or formula 2 and different in acid value (mgKOH/g), the polymer composition comprising: the acrylic polymer (b) having an acid value of 0.01 to 0.50 times, wherein the (meth) acrylic polymer (a) having the largest acid value among the two or more (meth) acrylic polymers has a weight average molecular weight of 1000 to 10000, and the mass ratio [ (a)/(b) ] of the (meth) acrylic polymer (a) to the (meth) acrylic polymer (b) is 0.01 to 0.50, when the acid value of the (meth) acrylic polymer (a) having the largest acid value among the two or more (meth) acrylic polymers is 1.
Figure BDA0002468923480000031
(in formula 1, R1Represents a hydrogen atom or a methyl group. In the formula 2, R2Represents a hydrogen atom or a methyl group, R3The carbon number of the group is 2-30 and has an acid group and an ethylenic unsaturated group. )
[2] The polymer composition according to [1], wherein the (meth) acrylic polymer (a) and the (meth) acrylic polymer (b) have at least one identical structural unit represented by the formula 1 or the formula 2.
[3] The polymer composition according to [1] or [2], wherein the (meth) acrylic polymer (b) has a weight average molecular weight of 1000 to 10000.
[4] The polymer composition according to any one of [1] to [3], wherein the acid value of the (meth) acrylic polymer (b) is 0.01 to 0.30 times that of the (meth) acrylic polymer (a).
[5] A photosensitive resin composition comprising the polymer composition (A) according to any one of [1] to [4], a solvent (B), a reactive diluent (C), and a photopolymerization initiator (D).
[6] The photosensitive resin composition according to [5], further comprising a colorant (E).
[7] A color filter characterized by having a colored pattern formed from the photosensitive resin composition according to [6 ].
Effects of the invention
The present invention provides a photosensitive resin composition having excellent thermal yellowing resistance, solvent resistance and alkali developability. In addition, the present invention can provide a color filter having a colored pattern excellent in resistance to thermal yellowing and solvent resistance.
Drawings
Fig. 1 is a schematic cross-sectional view showing a color filter according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail below.
< Polymer composition (A) >
The polymer composition (a) of the present invention is a polymer composition comprising two or more (meth) acrylic polymers having a structural unit represented by formula 1 or formula 2 containing an acid group and different in acid value (mgKOH/g). In the present invention, "(meth) acrylic acid" means at least one selected from methacrylic acid and acrylic acid.
Figure BDA0002468923480000041
(in formula 1, R1Represents a hydrogen atom or a methyl group. In the formula 2, R2Represents a hydrogen atom or a methyl group, R3The carbon number of the group is 2-30 and has an acid group and an ethylenic unsaturated group. )
As R3Examples of the acid group include, in addition to the carboxyl group: and polybasic acid groups such as dibasic acid groups (sulfonic acid groups, etc.) and tribasic acid groups (phosphoric acid groups, etc.), among which carboxyl groups are preferable. R3Preferably a group having 9 to 20 carbon atoms and having a carboxyl group and an ethylenically unsaturated group. As R3Specific examples of the structure containing a carboxyl group include structures represented by the following formulae 3 to 20. Among them, the structures shown by the following formulae 4 and 11 are preferable from the viewpoints of easiness of obtaining raw materials and reactivity in synthesis. The carboxyl group of formula 3 to formula 20 may be substituted with the polybasic acid group.
Further, as R3Specific examples of the structure containing an ethylenically unsaturated group include structures represented by the following formulae 21 and 22.
The structures represented by the following formulae 3 to 20 and the structures represented by the following formulae 21 and 22 may be bonded independently, if R is3Two or more kinds of carbon atoms may be bonded to each other when the number of carbon atoms of (2) is not more than 30.
Figure BDA0002468923480000051
As R3Preferred specific examples of (3) are as follows.
Figure BDA0002468923480000052
In the above structure, R4An alkyl group having 1 to 5 carbon atoms, having the formula 4 or 11 and the formula 21 or 22 as substituents. Wherein, it is characterized inThe alkyl group having 2 to 3 carbon atoms is preferable from the viewpoint of easiness of obtaining the raw material and reactivity in synthesis. The formula 4 or the formula 11 and the formula 21 or 22 may be bonded to the same carbon of the alkyl group, or may be bonded to different carbons.
The polymer composition (a) of the present invention is characterized by comprising a (meth) acrylic polymer (b) having an acid value of 0.01 to 0.50 times, when the acid value of the (meth) acrylic polymer (a) having the largest acid value among two or more (meth) acrylic polymers contained in the polymer composition (a) is 1.
The acid value in the present invention is an acid value of the (meth) acrylic polymer measured in accordance with JIS K69015.3, and indicates the mg number of potassium hydroxide required for neutralizing the acid component contained in 1g of the (meth) acrylic polymer.
Of the two or more (meth) acrylic polymers contained in the polymer composition (A), the (meth) acrylic polymer (a) having the largest acid value preferably has an acid value of 50 to 1000mgKOH/g, more preferably 100 to 600 mgKOH/g. When the acid value of the (meth) acrylic polymer (a) is within the above range, the (meth) acrylic polymer (b) has good compatibility and can be mixed without separation during synthesis or production of the photosensitive resin composition.
The weight average molecular weight (Mw) of the (meth) acrylic polymer (a) having the largest acid value among the two or more (meth) acrylic polymers contained in the polymer composition (A) is 1000 to 10000, preferably 2000 to 10000. When the weight average molecular weight (Mw) of the (meth) acrylic polymer (a) is within the above range, the (meth) acrylic polymer (b) has good compatibility and can be mixed without separation during synthesis or production of the photosensitive resin composition.
Here, the weight average molecular weight (Mw) in the present invention represents a weight average molecular weight in terms of standard polystyrene measured under the following conditions using Gel Permeation Chromatography (GPC).
Column: SHODEX (registered trademark) LF-804 + LF-804 (manufactured by SHOWA ELECTRIC CORPORATION)
Column temperature: 40 deg.C
Sample preparation: 0.2% tetrahydrofuran solution of (meth) acrylic acid-based polymer
Developing solvent: tetrahydrofuran (THF)
A detector: differential refractometer (SHODEX RI-71S) (manufactured by SHOWA DENKO K.K.)
Flow rate: 1mL/min
When the acid value of the (meth) acrylic polymer (a) having the maximum acid value is 1, the (meth) acrylic polymer (b) has an acid value of 0.01 to 0.50 times, preferably 0.01 to 0.30 times. When the (meth) acrylic polymer (b) having an acid value of 0.01 to 0.50 times is not blended in the polymer composition (a), excellent resistance to thermal yellowing, solvent resistance, and alkali developability cannot be achieved. From the viewpoint of alkali developability, the (meth) acrylic polymer (b) is more preferably a mixture of two or more (meth) acrylic polymers having an acid value in the above range.
The weight average molecular weight (Mw) of the (meth) acrylic polymer (b) may be appropriately adjusted, and is preferably 1000 to 10000, more preferably 2000 to 10000, from the viewpoint of compatibility with the (meth) acrylic polymer (a).
From the viewpoint of developability, the (meth) acrylic polymer (a) and the (meth) acrylic polymer (b) preferably have at least one identical structural unit represented by the above formula 1 or formula 2.
In the polymer composition (A), the mass ratio [ (a)/(b) ] of the (meth) acrylic polymer (a) to the (meth) acrylic polymer (b) is 0.01 to 0.50, preferably 0.01 to 0.30. When the mass ratio [ (a)/(b) ] is within the above range, excellent resistance to thermal yellowing, solvent resistance and alkali developability can be achieved.
The acid value of the (Meth) acrylic polymer (a) and the (Meth) acrylic polymer (b) may be appropriately adjusted by changing the amount and type of the radical polymerizable monomer used for producing each polymer, examples of the radical polymerizable monomer that can be used for producing the (Meth) acrylic polymer (a) and the (Meth) acrylic polymer (b) include dienes such as butadiene, methyl (Meth) acrylate, ethyl (Meth) acrylate, N-propyl (Meth) acrylate, isopropyl (Meth) acrylate, N-butyl (Meth) acrylate, sec-butyl (Meth) acrylate, isobutyl (Meth) acrylate, tert-butyl (Meth) acrylate, pentyl (Meth) acrylate, neopentyl (Meth) acrylate, benzyl (Meth) acrylate, isoamyl (Meth) acrylate, hexyl (Meth) acrylate, 2-ethylhexyl (Meth) acrylate, benzyl (Meth) acrylate, lauryl (Meth) acrylate, dodecyl (Meth) acrylate, cyclododecyl (Meth) acrylate, cyclopentyl (Meth) acrylate, cyclohexyl (Meth) acrylate, methylcyclohexyl (Meth) acrylate, ethylcyclohexyl (Meth) acrylate, 1, 4-cyclohexanedimethanol (Meth) acrylate, 4-2-8-glycidyl (Meth) acrylate, 8) acrylate, 4-2-epoxyethyl (Meth) acrylate, 10) acrylate, 4-N-2-epoxyethyl (Meth) acrylate, N-2-N-2-epoxypropyl) acrylate, N-2-N-N-2-glycidyl (Meth) acrylate, N-2-N-2-ethyl (Meth) acrylate, N-N-2-N-butyl) acrylate, N-N-butyl (Meth) acrylate, N-butyl) acrylate, N-N-2-ethyl) acrylate, N-2-N-2-ethyl) acrylate, N-N-butyl (4-N-2-N-butyl) acrylate, N-butyl (ethyl) acrylate, N-butyl) acrylate, N-ethyl) acrylate, N-2-N-2-ethyl) acrylate, N-2-ethyl-2-N-2-N-ethyl-N-butyl) acrylate, N-ethyl-N-2-ethyl-N-2-N-ethyl-2-ethyl-2, N-2-N-2, N-2-N-ethyl-N-2, N-2-N-ethyl-N-2, N-ethyl-N-2, 10, N-2, N-ethyl-2, 10) acrylate, N-2, N-ethyl-2, N-ethyl-N-ethyl-N-2, N-2-ethyl-2, N-2-N-ethyl-N-butyl, N-ethyl-N-ethyl-butyl, 10, N-butyl, 10, N-butyl, N-ethyl-N-butyl, N-ethyl-N-ethyl-butyl, N-butyl, N-ethyl-butyl, N-ethyl-N-butyl, N-butyl, N-ethyl-N-ethyl-N-ethyl-butyl, N-ethyl, N-butyl, N-ethyl, N-ethyl-butyl, N-.
The (meth) acrylic polymer (a) and the (meth) acrylic polymer (b) can be obtained by polymerizing the above-mentioned radical polymerizable monomers using a radical polymerizable monomer capable of introducing the structural unit represented by the above formula 1 or 2. Specifically, the (meth) acrylic polymer having the structural unit represented by formula 1 can be obtained by dissolving (meth) acrylic acid and, if necessary, other radical polymerizable monomers in a solvent, adding a radical polymerization initiator to the solution, and performing a polymerization reaction at 50 to 120 ℃ for 1 to 20 hours as appropriate. The (meth) acrylic polymer having the structural unit represented by formula 2 can be obtained by dissolving a radical polymerizable monomer having a group reactive with a carboxyl group such as an epoxy group or an oxetane group and, if necessary, another radical polymerizable monomer in a solvent, adding a radical polymerization initiator to the solution, performing polymerization reaction at 50 to 120 ℃ for 1 to 20 hours, adding a radical polymerizable monomer having a carboxyl group to a part of the obtained polymer, and adding a polybasic acid anhydride to a part of hydroxyl groups formed by ring opening. The obtained (meth) acrylic polymer is purified as necessary, the polymer component is separated, the acid value is measured, and two or more (meth) acrylic polymers having different acid values are blended so as to have a predetermined acid value ratio and mass ratio to prepare a polymer composition (a).
The polymer composition (a) of the present invention may contain a (meth) acrylic polymer other than the above-described range of acid value (for example, a (meth) acrylic polymer having an acid value of less than 0.01 times or a (meth) acrylic polymer having an acid value of more than 0.50 times to less than 1 time when the acid value of the (meth) acrylic polymer (a) having the largest acid value is 1) or a polymer other than the (meth) acrylic polymer to such an extent that the effects produced by the present invention are not impaired. From the viewpoint of developability, the average acid value of the polymer contained in the polymer composition (a) is preferably in the range of 50mgKOH/g to 150mgKOH/g, and more preferably in the range of 80mgKOH/g to 120 mgKOH/g. The average acid value of the polymer contained in the polymer composition (a) is calculated based on the following equation.
Average acid value ═ average (acid value of polymer 1 × content of polymer 1 + acid value of polymer 2 × content of polymer 2 + acid value of polymer 3 × content of polymer 3 + … …)/total mass of polymers contained in polymer composition (a)
As the radical polymerization initiator, a thermal radical polymerization initiator which generates thermal radicals by heat is generally used, and any of an organic peroxide-based radical polymerization initiator and an azo-based radical polymerization initiator may be used. The organic peroxide-based radical polymerization initiator is preferably, for example, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxycarbonate, peroxydicarbonate, etc., and particularly preferably, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxyester (for example, t-butylperoxy-2-ethylhexanoate). As the azo-based radical polymerization initiator, for example, 2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), dimethyl-2, 2 ' -azobis (2-methyl propionate), and the like are preferable. These radical polymerization initiators may be used alone, or two or more kinds thereof may be used.
The 10-hour half-life temperature of the radical polymerization initiator used in the present invention is preferably 50 to 120 ℃, more preferably 50 to 90 ℃. By using a radical polymerization initiator having a 10-hour half-life temperature of 50 to 120 ℃, the radical polymerization reaction proceeds sufficiently, the thermal yellowing resistance of the resulting (meth) acrylic polymer is improved, and a (meth) acrylic polymer of stable quality is obtained.
The amount of the radical polymerization initiator used is not particularly limited, but is preferably 0.5 to 100 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of the radical polymerizable monomer. By setting the amount to 0.5 to 100 parts by mass, deterioration of the (meth) acrylic polymer due to decomposition of the radical polymerization initiator during storage can be suppressed.
In addition of the radical polymerizable monomer and addition of the polybasic acid anhydride, an addition reaction catalyst may be used as necessary. Examples of the addition reaction catalyst include: tertiary amines such as triethylamine, benzyldimethylamine, and triethylenediamine; quaternary ammonium salts such as triethylbenzylammonium chloride; phosphorus compounds such as triphenylphosphine, tri-p-tolylphosphine, tris (2, 6-dimethoxyphenyl) phosphine; chelate compounds of chromium and the like. These addition reaction catalysts may be used alone, or two or more kinds thereof may be used. The amount of the addition reaction catalyst used is not particularly limited, but is preferably 0.1 to 1.0 part by mass, and more preferably 0.2 to 0.6 part by mass, per 100 parts by mass of the radical polymerizable monomer. When the amount is 0.1 part by mass or more, a sufficient reaction rate can be obtained, and therefore, it is preferable. When the amount is 1.0 part by mass or less, the influence of coloration due to the catalyst can be suppressed, and therefore, it is preferable.
In addition of the radical polymerizable monomer and addition of the polybasic acid anhydride, a polymerization inhibitor may be used for preventing gelation. Examples of the polymerization inhibitor include: hydroquinone, methoquinone, methyl hydroquinone, hydroquinone monomethyl ether, butyl hydroxy toluene, and the like. These polymerization inhibitors may be used alone, or two or more thereof may be used. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.1 to 1.0 part by mass, and more preferably 0.2 to 0.6 part by mass, per 100 parts by mass of the radical polymerizable monomer. The amount of the polymerization inhibitor to be used is preferably 0.1 part by mass or more because gelation can be suppressed. When the amount is 1.0 part by mass or less, curing is not inhibited even when the composition is used for a photosensitive resin composition, and therefore, it is preferable.
The solvent used for the polymerization is not particularly limited, and a glycol ether solvent is preferred from the viewpoint of solubility of the obtained (meth) acrylic polymer. Specifically, there may be mentioned: ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, and the like. These solvents may be used alone, or two or more thereof may be used. Among them, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable from the viewpoint of availability and reactivity.
The amount of the solvent used is not particularly limited, and is preferably 30 to 1000 parts by mass, and more preferably 50 to 800 parts by mass, based on 100 parts by mass of the radical polymerizable monomer. In particular, by setting the amount of the solvent to 1000 parts by mass or less, the viscosity of the (meth) acrylic polymer can be controlled within an appropriate range while suppressing a decrease in the molecular weight of the (meth) acrylic polymer due to chain transfer. Further, by setting the amount of the solvent to 30 parts by mass or more, abnormal polymerization reaction can be prevented, polymerization reaction can be stably performed, and coloring and gelation of the (meth) acrylic polymer can also be prevented.
When the radical polymerizable monomer is dissolved in the solvent in advance and added, the solvent is mixed and added to the reaction vessel preferably in an amount of 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, based on 100 parts by mass of the radical polymerizable monomer. When the radical polymerization initiator is dissolved in advance in the solvent and added, the solvent is mixed and added to the reaction vessel preferably in an amount of 100 to 10000 parts by mass, more preferably in an amount of 150 to 5000 parts by mass, based on 100 parts by mass of the radical polymerization initiator. When the radical polymerizable monomer and the radical polymerization initiator are mixed and added to the reaction vessel, the solvent is mixed preferably at 1 to 500 parts by mass, more preferably at 10 to 300 parts by mass, based on 100 parts by mass of the mixture, and added to the reaction vessel.
The method of adding the radical polymerizable monomer and the radical polymerization initiator to the reaction vessel is not particularly limited. From the viewpoint of easy control of the amount to be added, the rate of addition, the time of addition, and the like, it is preferable to add the radically polymerizable monomer and the radical polymerization initiator dropwise to the reaction vessel. The radical polymerizable monomer and the radical polymerization initiator may be added as a mixture or may be added separately.
The reaction vessel used in the present invention is not particularly limited as long as it is a reaction vessel industrially used for polymerizing a radical polymerizable monomer. For example, a reaction vessel having a mixing function and a temperature adjusting function and having a supply port and a take-out port through which a raw material can be supplied and a reaction liquid can be taken out can be mentioned.
The dropping time of the radical polymerizable monomer is not particularly limited, and the radical polymerizable monomer is preferably added for 30 minutes to 300 minutes, more preferably for 60 minutes to 250 minutes. The dropping time of the radical polymerization initiator is also not particularly limited, and it is preferably from 30 minutes to 300 minutes, more preferably from 60 minutes to 250 minutes. In view of work efficiency, it is preferable to adjust the dropping time of the radical polymerizable monomer and the radical polymerization initiator to be the same.
In addition, when the mixture of the radical polymerizable monomer and the radical polymerization initiator is added dropwise to the reaction vessel, the addition time is also not particularly limited, and it is preferably 30 minutes to 300 minutes, more preferably 60 minutes to 250 minutes.
In the case where the radical polymerizable monomer is dissolved in the solvent and added to the reaction vessel by dropping, the dropping speed is not particularly limited, and when the total amount of the radical polymerizable monomer and the solvent is set to 100ml, it is preferably 0.1 ml/min to 5 ml/min, and more preferably 0.2 ml/min to 4 ml/min. Further, in the case where the radical polymerization initiator is dissolved in the solvent and added to the reaction vessel by dropping, the dropping rate is preferably 0.1 ml/min to 5 ml/min, more preferably 0.2 ml/min to 4 ml/min, assuming that the total amount of the radical polymerization initiator and the solvent is 100 ml. The dropping rate at the time of dissolving the radical polymerizable monomer and the radical polymerization initiator in the solvent as a mixture and adding the mixture to the reaction vessel is usually 0.1 ml/min to 5 ml/min, preferably 0.2 ml/min to 4 ml/min, assuming that the total amount of the radical polymerizable monomer, the radical polymerization initiator and the solvent is 100 ml.
< photosensitive resin composition >
In the present invention, the polymer composition (a), the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D) may be mixed to prepare a photosensitive resin composition.
The content of the polymer composition (a) in the photosensitive resin composition is preferably 5 to 85 parts by mass, more preferably 9 to 74 parts by mass, and still more preferably 14 to 64 parts by mass, when the total of the components excluding the solvent in the photosensitive resin composition is 100 parts by mass.
The solvent (B) is not particularly limited as long as it is an inert solvent (B) that does not react with the (meth) acrylic polymer.
As the solvent (B), the same solvent as that used in the production of the above-mentioned (meth) acrylic polymer may be used, or a solvent contained after the production of the (meth) acrylic polymer may be used as it is, or may be further added. When other components are added, a solvent may be present in the mixture. Specifically, examples of the solvent (B) include: propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, and the like. These solvents (B) may be used alone, or two or more thereof may be used. Among these solvents, a glycol ether solvent such as propylene glycol monomethyl ether acetate used in the production of a (meth) acrylic polymer is preferable.
The content of the solvent (B) in the photosensitive resin composition is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, and more preferably 100 to 700 parts by mass, when the total of the components other than the solvent (B) in the photosensitive resin composition is 100 parts by mass. When the content is within this range, the photosensitive resin composition has an appropriate viscosity.
The reactive diluent (C) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule. When such a reactive diluent (C) is used in combination with the polymer composition (a), the viscosity can be adjusted, and the strength of the cured product and the adhesion to the substrate can be improved.
The reactive diluent (C) is not particularly limited, and examples thereof include aromatic vinyl monomers such as styrene, α -methylstyrene, α -chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate and diallyl phenylphosphonate, polycarboxylic acid monomers such as vinyl acetate and vinyl adipate, (meth) acrylic acid monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β -hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and tri (meth) acrylate of tris (hydroxyethyl) isocyanurate, and triallyl cyanurate.
The content of the reactive diluent (C) in the photosensitive resin composition is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and still more preferably 25 to 70 parts by mass, when the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. When the content is within this range, the photosensitive resin composition has an appropriate viscosity, and the photosensitive resin composition has an appropriate photocurability.
The photopolymerization initiator (D) is not particularly limited, and examples thereof include: benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and alkyl ethers thereof; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 1-dichloroacetophenone and 4- (1-tert-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4- (1-tert-butyldioxy-1-methylethyl) benzophenone, and 3, 3', 4, 4' -tetrakis (tert-butyldioxycarbonyl) benzophenone; 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinyl-propan-1-one; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; acylphosphine oxides; and xanthones, and the like. These photopolymerization initiators (D) may be used alone or two or more thereof may be used.
The content of the photopolymerization initiator (D) in the photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 1 to 15 parts by mass, when the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. When the content of the photopolymerization initiator (D) is within the above range, the photocurability of the photosensitive resin composition becomes more appropriate.
The photosensitive resin composition of the present invention can be further blended with a colorant (E) to prepare a photosensitive resin composition for a color filter. The colorant (E) is not particularly limited as long as it is a colorant dissolved or dispersed in a solvent, and examples thereof include dyes and pigments.
In particular, in the conventional photosensitive resin composition, when a dye is used, a highly accurate colored pattern can be obtained, but there is a problem that the thermal yellowing resistance of the colored pattern is lowered as compared with the case of using a pigment. In contrast, in the photosensitive resin composition of the present invention, a colored pattern having excellent thermal yellowing resistance can be obtained even when a dye is used.
As the dye, an acid dye having an acid group such as a carboxylic acid, a salt of an acid dye and a nitrogen compound, a sulfonamide of an acid dye, or the like is preferably used from the viewpoints of solubility in a solvent or an alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, and the like. Examples of such dyes include: alizarin violet (acidity alizarin violet) N; acid black (acid black)1, 2, 24, 48; acid blue (acid blue)1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue (solvent blue)38, 44; acid chrome violet (acid chrome violet) K; acid Fuchsin (acid Fuchsin); acid green (acid green)1, 3, 5, 25, 27, 50; acid orange (acid orange)6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red (acid red)1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet (acid violet)6B, 7, 9, 17, 19; acid yellow (acid yellow)1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; edible yellow (food yellow) 3; solvent yellow 82 and their derivatives, and the like. Among them, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These dyes may be used alone or two or more thereof may be used depending on the color of the target pixel.
Examples of pigments include: c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and the like; orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, etc. blue pigments; c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment; green pigments such as c.i. pigment green 7, 36, 58; c.i. brown pigments such as pigment brown 23, 25, etc.; c.i. pigment black 1, 7, carbon black, titanium black, iron oxide, and other black pigments. These pigments may be used alone or two or more thereof may be used depending on the color of the target pixel.
The above-described dye and pigment may be used in combination depending on the color of the target pixel.
The content of the colorant (E) in the photosensitive resin composition is preferably 5 to 80 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 10 to 60 parts by mass, when the total of the components excluding the solvent in the photosensitive resin composition is 100 parts by mass.
When a pigment is used as the colorant (E), a known dispersant may be blended into the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, a polymer dispersant having excellent dispersion stability with time is preferably used. Examples of the polymeric dispersant include: urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. As such a polymer dispersant, commercially available products such as EFKA (EFKA chemical b.v. (EFKA)), Disperbyk (BYK Chemie), Disparlon (macyoto corporation), SOLSPERSE (Zaneca corporation) and the like can be used. The content of the dispersant in the photosensitive resin composition may be appropriately set according to the kind of pigment or the like used.
In addition to the above components, known additives such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor may be added to the photosensitive resin composition in order to impart predetermined characteristics. The amount of these additives to be added is not particularly limited as long as the effect of the present invention is not impaired.
The photosensitive resin composition can be produced by mixing the above components using a known mixing device. The composition may be prepared in advance as desired, and the reactive diluent (C), the photopolymerization initiator (D), and the colorant (E) may be mixed to prepare the composition containing the polymer composition (a) and the solvent (B).
Next, a color filter produced using the photosensitive resin composition of the present invention will be described.
The color filter of the invention has a colored pattern formed by the photosensitive resin composition.
Hereinafter, the color filter of the present invention will be described with reference to the drawings.
Fig. 1 is a schematic cross-sectional view showing a color filter according to an embodiment of the present invention.
As shown in fig. 1, the color filter of the present invention includes: the liquid crystal display device includes a substrate 1, RGB pixels 2 formed on one surface of the substrate 1, a black matrix 3 formed at a boundary between the pixels 2, and a protective film 4 formed on the pixels 2 and the black matrix 3.
The color filter of the present invention may have a known configuration, except that one or more kinds of coloring patterns selected from R, G and B constituting the pixel 2 and the black matrix 3 (coloring pattern) are formed by using the photosensitive resin composition.
The color filter shown in fig. 1 is an example, and the color filter of the present invention is not limited to this configuration.
Next, a method for manufacturing a color filter of the present invention will be described.
First, a colored pattern is formed on one surface of the substrate 1. Specifically, the black matrix 3 and the pixels 2 are formed in this order on one surface of the substrate 1.
The substrate 1 is not particularly limited, and may be: a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, and the like.
The colored pattern may be formed by photolithography. Specifically, after the photosensitive resin composition is applied to one surface of the substrate 1 to form a coating film, the coating film is exposed through a photomask having a predetermined pattern, and the exposed portion is photocured. Then, the unexposed portion is developed with an aqueous alkali solution and then baked, whereby a predetermined colored pattern can be formed.
The method for applying the photosensitive resin composition is not particularly limited, and the following may be used: screen printing, roll coating, Curtain coating (coating method), spray coating, spin coating, and the like.
After the application of the photosensitive resin composition, the solvent (B) may be volatilized by heating using a heating means such as a circulation type oven, an infrared heater, or a hot plate, if necessary. The heating conditions are not particularly limited, and may be appropriately set according to the type of photosensitive resin composition used. Usually, the heating is carried out at a temperature of 50 to 120 ℃ for 30 seconds to 30 minutes.
The light source used for exposure of the coating film formed from the photosensitive resin composition is not particularly limited, and for example, the following can be used: low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like. The amount of exposure is not particularly limited, and may be appropriately adjusted depending on the type of the photosensitive resin composition used.
Specific examples of the aqueous alkaline solution include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc., aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine, etc., aqueous solutions of p-phenylenediamine compounds such as 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- β -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- β -methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N- β -methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonate, etc. among these, aqueous solutions of p-phenylenediamine compounds are preferably used.
The baking conditions are not particularly limited, and the heat treatment may be performed depending on the type of the photosensitive resin composition used. Usually, the heating is carried out at a temperature of 130 to 250 ℃ for 10 to 60 minutes.
By using the photosensitive resin composition, the above-described coating, exposure, development, and baking are sequentially repeated using the photosensitive resin composition for the black matrix 3 and the photosensitive resin composition for the pixel 2, whereby a desired colored pattern can be formed.
In the above description, the method of forming a colored pattern by photocuring was described, but if a photosensitive resin composition containing a curing accelerator and a known epoxy resin in place of the photopolymerization initiator (E) is used, a desired colored pattern can be formed by applying the composition by an ink jet method and then heating the composition.
Next, a protective film 4 is formed on the colored pattern (the pixels 2 and the black matrix 3). The protective film 4 is not particularly limited, and is formed using a known material and a known forming method.
The color filter thus manufactured is manufactured using a photosensitive resin composition that provides a colored pattern that is excellent in alkali developability and is also excellent in thermal yellowing resistance and solvent resistance, and thus has a colored pattern (pixel 2 and black matrix 3) that is excellent in thermal yellowing resistance and solvent resistance. Therefore, the photosensitive resin composition of the present embodiment is suitable for use as various resists, and particularly suitable for use as a resist for producing a color filter incorporated in an organic EL display, a liquid crystal display device, or a solid-state imaging device.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The compounds used in the examples are as follows.
GMA: glycidyl methacrylate (manufactured by Nichisu oil Co., Ltd.)
And (3) OXMA: (3-Ethyloxetan-3-yl) methyl methacrylate (product of Udo Kyoho Co., Ltd.)
MAA: methacrylic acid (manufactured by Cololi corporation)
AA: acrylic acid (manufactured by Toya Synthesis Co., Ltd.)
DCPMA: dicyclopentyl methacrylate (Hitachi chemical industry Co., Ltd.)
SM: styrene (made by the Dai Xing Shu)
THPA: tetrahydrophthalic anhydride (New Ri chemical Co., Ltd.)
V-601: dimethyl-2, 2' -azobis (methyl 2-propionate) (manufactured by Wako Co., Ltd., 10-hour half-life temperature: 66 ℃ C.)
Perbutyl O: t-butyl peroxy-2-ethylhexanoate (manufactured by Nichiku Co., Ltd., 10-hour half-life temperature: 72 ℃ C.)
Propylene glycol monomethyl ether (manufactured by Cololi corporation)
Diethylene glycol methyl ethyl ether (manufactured by Coloray Co., Ltd.)
Propylene glycol monomethyl ether acetate (manufactured by Coloray Co., Ltd.)
DPHA: dipentaerythritol hexaacrylate (New Zhongcun industries Co., Ltd.)
Irgacure 907: 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholin-propan-1-one (BASF Japan Co., Ltd.)
VALIFAST BLUE 2620 (solvent BLUE 44): blue dye (ORIENT chemical industry Co., Ltd.)
(meth) acrylic polymers having different acid values shown in the following synthetic examples 1 to 15 were synthesized. The acid value and the weight average molecular weight of the (meth) acrylic polymer were measured by the above-described measurement methods.
[ Synthesis example 1]
In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 303.7g of propylene glycol monomethyl ether was charged, and the mixture was stirred while being purged with nitrogen, and the temperature was raised to 88 ℃.
Subsequently, a solution prepared by mixing 23.3g of dimethyl-2, 2' -azobis (methyl 2-propionate) and 30.9g of diethylene glycol methyl ether in a monomer solution comprising 116.7g (1.0 mol) of methacrylic acid was added dropwise from a dropping funnel over 2 hours. The temperature was raised to 120 ℃ and the mixture was stirred for 30 minutes to effect polymerization reaction, thereby producing a methacrylic polymer. This was designated as sample 1. The weight average molecular weight (Mw) of the resulting methacrylic polymer was 3900, and the acid value was 543.6.
[ Synthesis examples 2 to 11]
Polymerization was carried out in the same manner as in example 1 except that the raw materials shown in tables 1 and 2 were used, thereby obtaining methacrylic polymers samples 2 to 11. However, when the raw materials shown in Table 2 were used, the polymerization reaction was carried out by stirring at 88 ℃ for 5 hours after the dropwise addition. The weight average molecular weight (Mw) and acid value of the obtained methacrylic polymer are shown in tables 1 and 2.
[ Synthesis example 12]
58.6g of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and stirred while being replaced with nitrogen, and the temperature was raised to 118 ℃.
Subsequently, a solution obtained by mixing 9.2g (PERBUTYL O, manufactured by NIGHT OIL SAGE, 0.068 mol) of t-butylperoxy-2-ethylhexanoate and 25.4g of propylene glycol monomethyl ether acetate with a monomer solution composed of 81.8g (1.0 mol) of glycidyl methacrylate was dropped from a dropping funnel over 2 hours into the flask. After the completion of the dropwise addition, the temperature was raised to 120 ℃ and the mixture was stirred for 30 minutes to effect polymerization reaction, thereby producing a polymer. Thereafter, the flask was charged with air, 41.5g (1.0 mol) of acrylic acid, 0.4g (addition reaction catalyst) of triphenylphosphine and 0.2g (polymerization inhibitor) of methylhydroquinone were added to the polymer solution, and the reaction was continued at 110 ℃ for 10 hours, whereby the epoxy group derived from glycidyl methacrylate was cleaved by the reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid, and an ethylenically unsaturated bond was introduced into the side chain of the polymer. Then, 87.6g (1.0 mol) of tetrahydrophthalic anhydride was charged into the flask, and the reaction was continued at 110 ℃ for 3 hours, whereby a hydroxyl group generated by cleavage of an epoxy group of glycidyl methacrylate was reacted with an acid anhydride group of tetrahydrophthalic anhydride to introduce a carboxyl group into a side chain, thereby producing an acrylic polymer. Subsequently, 145.2g of propylene glycol monomethyl ether acetate was added to the reaction solution to prepare sample 12. The weight average molecular weight (Mw) of the resulting acrylic polymer was 9600, and the acid value was 146.9.
[ Synthesis examples 13 to 15]
Acrylic polymer samples 13 to 15 were obtained by performing the polymerization reaction in the same manner as in Synthesis example 12, except that the raw materials shown in Table 3 were used. Dicyclopentyl methacrylate and styrene were mixed with glycidyl methacrylate to be used as a monomer mixture. The weight average molecular weight (Mw) and acid value of the obtained acrylic polymer are shown in table 3.
[ Table 1]
Figure BDA0002468923480000211
[ Table 2]
Figure BDA0002468923480000212
[ Table 3]
Figure BDA0002468923480000221
Examples 1 to 21 and comparative examples 1 to 18
< preparation of photosensitive resin composition >
Photosensitive resin compositions for color filters of examples 1 to 21 and comparative examples 1 to 18 were prepared by using (meth) acrylic polymer samples 1 to 15 synthesized in synthetic examples 1 to 15, and blending components and blending amounts shown in table 4. The compositions of the polymer compositions (A) used for preparing the photosensitive resin compositions for color filters of examples 1 to 21 and comparative examples 1 to 18 are shown in tables 5 to 11.
In the blending amount of the polymer composition (a) in table 4, a solvent used in the synthesis of the (meth) acrylic polymer is not included. That is, the amount of the solvent (B) added is the sum of propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether used in the synthesis of the methacrylic polymer in synthesis examples 1 to 11, and the sum of propylene glycol monomethyl ether acetate used in the synthesis of the acrylic polymer and propylene glycol monomethyl ether acetate additionally added in synthesis examples 12 to 15.
[ Table 4]
Figure BDA0002468923480000222
[ Table 5]
Figure BDA0002468923480000231
[ Table 6]
Figure BDA0002468923480000232
[ Table 7]
Figure BDA0002468923480000241
[ Table 8]
Figure BDA0002468923480000242
[ Table 9]
Figure BDA0002468923480000243
[ Table 10]
Figure BDA0002468923480000251
[ Table 11]
Figure BDA0002468923480000252
< evaluation of photosensitive resin composition >
(1) Resistance to thermal yellowing
The prepared photosensitive resin composition was spin-coated onto a 5 cm-square glass substrate (alkali-free glass substrate) so that the thickness after exposure became 2.5 μm, and then heated at 90 ℃ for 3 minutes to volatilize the solvent, thereby forming a coating film on the glass substrate.
Subsequently, the obtained coating film was exposed to light having a wavelength of 365nm to cure the exposed portion, and then baked at 230 ℃ for 30 minutes to prepare a cured coating film.
The color change of the coating film before and after baking was measured by a spectrophotometer UV-1650 PC (manufactured by Shimadzu corporation). Evaluation of thermal yellowing resistance was carried out by examining the change in transmittance (Δ Eab) before and after the 30-minute baking operation at 230 ℃. The criteria for this evaluation are as follows. The results are shown in tables 12 and 13.
◎ delta Eab is less than 5
○ delta Eab is greater than 5 and less than 10
△ delta Eab is more than 10 and less than 15
X: Δ Eab greater than 15
(2) Solvent resistance
The prepared photosensitive resin composition was spin-coated onto a 5 cm-square glass substrate (alkali-free glass substrate) so that the thickness after exposure became 2.5 μm, and then heated at 90 ℃ for 3 minutes to volatilize the solvent, thereby forming a coating film on the glass substrate.
Subsequently, the obtained coating film was exposed to light having a wavelength of 365nm to cure the exposed portion, and then baked at 230 ℃ for 30 minutes to prepare a cured coating film.
The glass substrate with the cured coating film was immersed in n-methyl-2-pyrrolidone at 23 ℃ for 1 hour. The change in transmittance (Δ Eab) before and after immersion in n-methyl-2-pyrrolidone was measured by a spectrophotometer UV-1650 PC (product of shimadzu corporation), and the solvent resistance was evaluated based on the results. The criteria for this evaluation are as follows. The results are shown in tables 12 and 13.
◎ delta Eab is less than 1
○ delta Eab is greater than 1 and less than 3
△ delta Eab is greater than 3 and less than 5
X: delta Eab is greater than 5
(3) Alkali developability
The prepared photosensitive resin composition was spin-coated onto a 5 cm-square glass substrate (alkali-free glass substrate) so that the thickness after exposure became 2.5 μm, and then heated at 90 ℃ for 3 minutes to volatilize the solvent, thereby forming a coating film on the glass substrate.
Then, a photomask having a predetermined pattern was placed at a distance of 100 μm from the coating film, and light having a wavelength of 365nm was exposed through the photomask to cure the exposed portion.
Next, an aqueous solution containing 0.1 part by mass of sodium carbonate was sprayed (spray) at a temperature of 23 ℃ and a pressure of 0.3MPa for 90 seconds to dissolve and develop the unexposed portion, and then baked at 230 ℃ for 30 minutes to form a predetermined pattern.
The residue after the alkali development was confirmed by observing the pattern after the alkali development with an electron microscope S-3400 manufactured by Hitachi High Technologies, Ltd. The criteria for this evaluation are as follows. The results are shown in tables 12 and 13.
◎ no residue
○ little residue
△ slight residue
X: with residue and no residual pattern
[ Table 12]
Resistance to thermal yellowing Solvent resistance Alkali developability
Example 1 ◎(3.0) ◎(0.7) △
Example 2 ◎(3.4) ◎(0.8) ○
Example 3 ◎(3.4) ◎(0.7) ○
Example 4 ◎(4.5) ◎(1.0) △
Example 5 ◎(4.7) ◎(0.9) ○
Example 6 ◎(4.8) ◎(0.9) ◎
Example 7 ○(8.6) ○(1.9) △
Example 8 ○(8.7) ○(2.4) ◎
Example 9 ○(8.4) ○(2.5) ◎
Example 10 ◎(4.2) ◎(0.6) △
Example 11 ◎(4.5) ◎(0.6) ○
Example 12 ◎(4.1) ◎(0.8) ○
Example 13 ◎(4.8) ◎(0.8) △
Example 14 ◎(5.0) ◎(0.8) ○
Example 15 ◎(4.9) ◎(0.7) ◎
Example 16 ○(8.5) ○(2.2) △
Example 17 ○(8.5) ○(2.0) ◎
Example 18 ○(8.4) ○(2.5) ◎
Example 19 ○(8.8) ○(3.0) △
Example 20 ○(8.5) ○(2.5) ○
Example 21 ○(7.4) ○(2.3) ○
[ Table 13]
Figure BDA0002468923480000281
From the results shown in tables 12 and 13, it was confirmed that: the photosensitive resin compositions of examples 1 to 21 were superior in thermal yellowing resistance, solvent resistance and alkali developability to the photosensitive resin compositions of comparative examples 1 to 18. In particular, it was confirmed that: the more the kind of the (meth) acrylic polymer (b) having a low acid value is, the more excellent alkali developability is exhibited. In examples 3, 6, 9, 12, 15, 18 and 21, four (meth) acrylic polymers having different acid values were used, but it is considered that the same results were obtained even when five or more (meth) acrylic polymers having different acid values were used.
On the other hand, the photosensitive resin compositions shown in comparative examples 1 to 8 and 15 to 18, which contain only one kind of (meth) acrylic polymer, the photosensitive resin compositions shown in comparative example 12, which contain the (meth) acrylic polymer (a) in a mass ratio to the (meth) acrylic polymer (b) exceeding 0.50, and the photosensitive resin compositions shown in comparative examples 13 and 14, which contain the (meth) acrylic polymer (b) in an acid value exceeding 0.50 times the acid value of the (meth) acrylic polymer (a), are insufficient in at least one of thermal yellowing resistance, solvent resistance and alkali developability. Further, it was confirmed that: as shown in comparative examples 9 to 11, even when two or more (meth) acrylic polymers having different acid values are blended, when the weight average molecular weight of the (meth) acrylic polymer (a) is too large, separation occurs at the time of blending.
Industrial applicability
The cured coating film using the photosensitive resin composition obtained by the present invention has excellent thermal yellowing resistance, solvent resistance and alkali developability, and therefore has extremely high utility value in various resist fields, and is preferably used as a color filter to be incorporated into an organic EL display device, a liquid crystal display device or a solid-state imaging device.
Description of the reference numerals
1: substrate, 2: pixel, 3: black matrix, 4: and (5) protecting the film.

Claims (7)

1. A polymer composition, wherein the polymer composition comprises: two or more (meth) acrylic polymers having a structural unit represented by the following formula 1 or 2 and different in acid value, wherein the unit of acid value is mgKOH/g,
the polymer composition comprises: a (meth) acrylic polymer (b) having an acid value of 0.01 to 0.50 times, when the acid value of the (meth) acrylic polymer (a) having the largest acid value among the two or more (meth) acrylic polymers is 1,
the weight average molecular weight of the (meth) acrylic polymer (a) is 1000 to 10000, and
the mass ratio of the (meth) acrylic polymer (a) to the (meth) acrylic polymer (b), i.e., (a)/(b), is 0.01 to 0.50,
Figure FDA0002468923470000011
in the formula 1, R1Represents a hydrogen atom or a methyl group, in the formula 2, R2Represents a hydrogen atom or a methyl group, R3The carbon number of the group is 2-30 and has an acid group and an ethylenic unsaturated group.
2. The polymer composition according to claim 1,
the (meth) acrylic polymer (a) and the (meth) acrylic polymer (b) have at least one identical structural unit represented by the formula 1 or the formula 2.
3. Polymer composition according to claim 1 or 2,
the weight average molecular weight of the (meth) acrylic polymer (b) is 1000 to 10000.
4. The polymer composition according to any one of claims 1 to 3,
the acid value of the (meth) acrylic polymer (b) is 0.01 to 0.30 times the acid value of the (meth) acrylic polymer (a).
5. A photosensitive resin composition characterized by containing, as a main component,
comprising the polymer composition (A) according to any one of claims 1 to 4, a solvent (B), a reactive diluent (C) and a photopolymerization initiator (D).
6. The photosensitive resin composition according to claim 5,
further comprising a colorant (E).
7. A color filter is characterized in that,
has a colored pattern formed from the photosensitive resin composition according to claim 6.
CN201880070031.0A 2017-12-22 2018-09-28 Polymer composition, photosensitive resin composition, and color filter Active CN111278912B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017-245996 2017-12-22
JP2017245996 2017-12-22
PCT/JP2018/036330 WO2019123761A1 (en) 2017-12-22 2018-09-28 Polymer composition, photosensitive resin composition, and color filter

Publications (2)

Publication Number Publication Date
CN111278912A true CN111278912A (en) 2020-06-12
CN111278912B CN111278912B (en) 2022-03-04

Family

ID=66994581

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880070031.0A Active CN111278912B (en) 2017-12-22 2018-09-28 Polymer composition, photosensitive resin composition, and color filter

Country Status (5)

Country Link
JP (1) JP7246606B2 (en)
KR (1) KR102307921B1 (en)
CN (1) CN111278912B (en)
TW (1) TWI770294B (en)
WO (1) WO2019123761A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021182021A1 (en) * 2020-03-10 2021-09-16 三菱ケミカル株式会社 Active energy ray curable resin composition and cured product thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09278843A (en) * 1996-04-17 1997-10-28 Daicel Chem Ind Ltd Curable resin composition
CN103959167A (en) * 2011-10-02 2014-07-30 可隆工业株式会社 Photosensitive resin composition
CN104109218A (en) * 2013-04-22 2014-10-22 昭和电工株式会社 (meth)acrylate-based polymer, composition comprising same and use thereof
JP2017137483A (en) * 2016-01-28 2017-08-10 三菱ケミカル株式会社 Coloring resin composition, color filter and image display device

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3829480B2 (en) * 1998-07-03 2006-10-04 三菱化学株式会社 Photopolymerizable composition for color filter
JP5523655B2 (en) * 2007-02-23 2014-06-18 富士フイルム株式会社 Pigment dispersion composition, curable composition, color filter and method for producing the same
JP5073556B2 (en) * 2008-03-31 2012-11-14 富士フイルム株式会社 Photosensitive resin composition, light-shielding color filter, method for producing the same, and solid-state imaging device
JP2010145858A (en) * 2008-12-19 2010-07-01 Mitsubishi Chemicals Corp Colored resin composition for color filter, color filter, liquid crystal display, and organic el display
JP6408230B2 (en) 2014-03-17 2018-10-17 株式会社日本触媒 Curable resin composition and color filter
JP6495769B2 (en) 2014-07-18 2019-04-03 株式会社日本触媒 Curable resin composition and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09278843A (en) * 1996-04-17 1997-10-28 Daicel Chem Ind Ltd Curable resin composition
CN103959167A (en) * 2011-10-02 2014-07-30 可隆工业株式会社 Photosensitive resin composition
CN104109218A (en) * 2013-04-22 2014-10-22 昭和电工株式会社 (meth)acrylate-based polymer, composition comprising same and use thereof
JP2017137483A (en) * 2016-01-28 2017-08-10 三菱ケミカル株式会社 Coloring resin composition, color filter and image display device

Also Published As

Publication number Publication date
JPWO2019123761A1 (en) 2021-01-07
WO2019123761A1 (en) 2019-06-27
JP7246606B2 (en) 2023-03-28
TWI770294B (en) 2022-07-11
CN111278912B (en) 2022-03-04
KR20200047747A (en) 2020-05-07
TW201930442A (en) 2019-08-01
KR102307921B1 (en) 2021-10-01

Similar Documents

Publication Publication Date Title
JP6886827B2 (en) Alkali-soluble resin, photosensitive resin composition and its uses
KR20120125511A (en) Addition copolymer, photosensitive resin composition, and color filter
CN110998443A (en) Photosensitive resin composition and method for producing same
KR101758690B1 (en) Thermosetting resin composition, color filter, image display element and production method of color filter
WO2017145771A1 (en) Random copolymer, resist composition, color filter, and method for producing random copolymer
WO2008056750A1 (en) Photosensitive resin composition
KR101756507B1 (en) Method for producing photosensitive resin, and color filter
KR101928251B1 (en) Resin composition, photosensitive resin composition, resin cured film, and image display element
JP2020122052A (en) Alkali-soluble resin, curable resin composition, and use therefor
CN111278912B (en) Polymer composition, photosensitive resin composition, and color filter
KR102094372B1 (en) Alkali soluble resin, photosensitive resin composition and color filter comprising the same
TWI600970B (en) Resin composition, color filter, production method of color filter, and image display element
CN111615650B (en) Photosensitive resin composition for color filter, image display element, and method for producing color filter
JP2005202134A (en) Photosensitive resin composition for color filter and color filter
JP2008248142A (en) Curable resin composition
CN115677939A (en) Photosensitive graft polymer and photosensitive resin composition containing same
JP6408230B2 (en) Curable resin composition and color filter
KR20170139642A (en) COLOR COMPOSITION FOR COLOR FILTER, COLOR FILTER AND IMAGE DISPLAY DEVICE
WO2016075987A1 (en) Resin composition, method for producing same, color filter, and image display element
CN111542554B (en) Polymer, curable resin composition, and use thereof
WO2017022299A1 (en) Curable (meth)acrylate polymer, curable composition, color filter, and image display device
JP2017210568A (en) Method for producing resin and method for producing resin composition for color filter
CN113966489A (en) Photosensitive resin composition, cured resin film and image display element
KR101710409B1 (en) Photosensitive phosphorus-containing unsaturated acrylic compositions and the method of manufacturing the same
JP6545499B2 (en) Method for producing alkali-soluble resin, and photosensitive resin composition containing alkali-soluble resin produced by the method

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
GR01 Patent grant
GR01 Patent grant
CP03 Change of name, title or address

Address after: Tokyo port area, Japan

Patentee after: Lishennoco Co.,Ltd.

Address before: Tokyo

Patentee before: Showa electrical materials Co.,Ltd.

CP03 Change of name, title or address
TR01 Transfer of patent right

Effective date of registration: 20230529

Address after: Tokyo

Patentee after: Showa electrical materials Co.,Ltd.

Address before: Tokyo

Patentee before: SHOWA DENKO Kabushiki Kaisha

TR01 Transfer of patent right