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CN104950578B - Colored photosensitive resin composition and color filter produced therefrom - Google Patents

Colored photosensitive resin composition and color filter produced therefrom Download PDF

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Publication number
CN104950578B
CN104950578B CN201510148676.XA CN201510148676A CN104950578B CN 104950578 B CN104950578 B CN 104950578B CN 201510148676 A CN201510148676 A CN 201510148676A CN 104950578 B CN104950578 B CN 104950578B
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group
acid
compound
resin
pigment
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CN104950578A (en
Inventor
申奎澈
康德基
崔和燮
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G03F7/0295—Photolytic halogen compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a colored photosensitive resin composition and a color filter manufactured by the same, and more particularly, to a colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and to a colored photosensitive resin composition which has a wide color reproduction range, high contrast and brightness, and excellent coloring power, pattern formability, developability, sensitivity and adhesion, by allowing the colorant to contain a green pigment of pigment green 7, allowing the alkali-soluble resin to contain a1 st resin having an epoxy group, and a2 nd resin having an acid group (acid group) capable of reacting with the epoxy group and having an acid value of 170 to 300 mgKOH/g.

Description

Colored photosensitive resin composition and color filter produced therefrom
Technical Field
The present invention relates to a colored photosensitive resin composition and a color filter produced therefrom, and more particularly, to a colored photosensitive resin composition exhibiting high contrast and brightness and excellent in tinting strength, pattern formability, developability, sensitivity and adhesion, and a color filter produced therefrom.
Background
recently, liquid crystal display devices are technologically intensive products with low power consumption and good portability, and have attracted attention as next-generation display (display) elements with high added value.
Among such liquid crystal display devices, active matrix liquid crystal display devices including thin film transistors as switching elements capable of adjusting the on/off of the voltage for each pixel (pixel) are attracting attention because they are excellent in resolution and video display capability.
In general, a liquid crystal display device is completed through a liquid crystal cell process in which an array substrate manufacturing process for forming a thin film transistor and a pixel electrode and a color filter substrate manufacturing process for forming a color filter and a common electrode are separately formed, and liquid crystal is present between these 2 substrates.
The color filter includes pixels of red (R), green (G), and blue (B) colors, and light transmitted through the liquid crystal cell is transmitted through the color filter and exhibits a desired hue.
However, recently, with the spread of liquid crystal display devices, their applications are expanding to various monitors and televisions, and further improvement in color reproducibility is demanded. In order to cope with this demand, it is required to provide a color filter having a wide color reproduction region. In particular, in television applications, it is required to further expand the color reproduction region than in the past.
In addition to the expansion of the color reproduction range, there is a demand for improvement in display quality by increasing the luminance and contrast. However, there is a trade-off relationship between the color reproduction range and the transmittance, and between the color reproduction range and the contrast ratio, and if the color reproduction range is to be expanded, there is a problem that the transmittance and the contrast ratio are reduced.
In this regard, korean patent laid-open publication No. 2005-0014725 proposes a mixed pigment of c.i. pigment green 7 alone or c.i. pigment green 7 and c.i. pigment yellow 150 as a pigment for a green color filter.
however, c.i. pigment green 7 alone cannot sufficiently satisfy the required characteristics, and c.i. pigment yellow 150 is an environmental control substance and has limitations in use.
Documents of the prior art
Patent document
Patent document 1: korean patent laid-open No. 2005-0014725
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a colored photosensitive resin composition which not only has a wide color reproduction range and exhibits high contrast and brightness, but also has excellent coloring power, pattern formability, developability, sensitivity and adhesiveness.
Another object of the present invention is to provide a color filter produced from the colored photosensitive resin composition and an image display device including the color filter.
Means for solving the problems
1. A colored photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent,
The colorant (A) is a green pigment containing pigment green 7,
the alkali-soluble resin (B) contains a1 st resin having an epoxy group and a2 nd resin having an acid group (acid group) capable of reacting with the epoxy group and having an acid value of 170 to 300 mgKOH/g.
2. The colored photosensitive resin composition according to the above 1, wherein the colorant further contains at least 1 yellow pigment selected from the group consisting of pigment yellow 129 and pigment yellow 139.
3. The colored photosensitive resin composition according to the above 2, wherein the mass ratio of the green pigment to the yellow pigment in the colorant is 100:0 to 80: 20.
4. The colored photosensitive resin composition according to 1, wherein the 1 st resin is a resin obtained by copolymerization of a compound having an unsaturated bond and a carboxyl group and at least 1 compound of the following chemical formula 1 to chemical formula 2:
[ chemical formula 1]
(wherein R1 represents hydrogen, an optionally heteroatom-containing alkyl group or cycloalkyl group having 1 to 20 carbon atoms, R2 represents a single bond, or an optionally heteroatom-containing alkylene group or cycloalkylene group having 1 to 20 carbon atoms, and R1 and R2 which is the alkylene group or cycloalkylene group are independently optionally further substituted with a hydroxyl group.)
[ chemical formula 2]
(wherein R1 represents hydrogen, or an alkyl or cycloalkyl group having 1 to 20 carbon atoms and optionally containing a hetero atom, R2 represents a single bond, or an alkylene or cycloalkylene group having 1 to 20 carbon atoms and optionally containing a hetero atom, and R1 and R2 which are the alkylene or cycloalkylene groups are independently further substituted with a hydroxyl group).
5. The colored photosensitive resin composition according to claim 1, wherein the 2 nd resin is a resin obtained by copolymerizing a compound having 1 or more kinds of skeletons selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in a molecule and having an unsaturated bond, a compound having an aromatic vinyl group, and a compound having an acid-acting group capable of ring-opening an epoxy group of the 1 st resin.
6. The colored photosensitive resin composition according to the above 5, wherein the compound having an acid-acting group is at least 1 compound selected from the group consisting of an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid.
7. The colored photosensitive resin composition according to claim 1, wherein the 2 nd resin is a resin obtained by copolymerization of a compound having an unsaturated bond and an epoxy group or a compound having an unsaturated bond and a hydroxyl group in 1 molecule.
8. a color filter produced from the colored photosensitive resin composition described in any one of the above 1 to 7.
9. An image display device comprising the color filter of 8.
ADVANTAGEOUS EFFECTS OF INVENTION
the colored photosensitive resin composition of the present invention is excellent in developability, sensitivity and adhesion by allowing an alkali-soluble resin to contain a1 st resin having an epoxy group and a2 nd resin in which an acid-acting group for opening the epoxy group is present at a high acid value.
The colored photosensitive resin composition of the present invention contains pigment green 7 as a colorant, is excellent in coloring power and pattern formability, and can reproduce a green color that has not been exhibited so far when used in the case where at least 1 yellow pigment selected from the group consisting of pigment yellow 129 and pigment yellow 139 is further contained as required, and can maintain excellent brightness and contrast.
Detailed Description
The present invention relates to a colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and relates to a colored photosensitive resin composition which has a wide color reproduction range, high contrast and brightness, and excellent coloring power, pattern formability, developability, sensitivity and adhesiveness, by the (A) colorant containing a green pigment of pigment green 7, and the (B) alkali-soluble resin containing a1 st resin having an epoxy group and a2 nd resin having an acid group (acid group) capable of reacting with the epoxy group and an acid value of 170 to 300 mgKOH/g.
The present invention will be described in detail below.
Colored photosensitive resin composition
The colored photosensitive resin composition of the present invention may contain (a) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. Of course, additional components, such as additives, which are generally used in this field are not limited to the additive components.
(A) colorant
Colorant (A)
The colorant of the present invention contains a green pigment of pigment green 7 as an essential component.
the pigment green 7 plays a main function of making the coloring composition exhibit green color, and when used together with the alkali-soluble resin of the present invention described later, can exhibit high brightness and contrast as well as excellent coloring power and pattern formability.
As a preferable specific example of the present invention, the colorant of the present invention may further contain at least 1 yellow pigment selected from the group consisting of pigment yellow 129 and pigment yellow 139, as required. The pigment yellow 129 and the pigment yellow 139 function as a color tone adjustment function.
The composition of the present invention can exhibit a wide color reproduction range of green and can exhibit more excellent brightness, contrast, coloring power and pattern formability by additionally using the specific yellow pigment as a colorant without using pigment yellow 150, which is an environmental regulation substance.
In the present invention, when the yellow pigment is further contained, the mass ratio of the green pigment to the yellow pigment is preferably 100:0 to 80: 20. Wide color reproduction range, high brightness and contrast, excellent coloring power, and the like can be most remarkably expressed within the foregoing range.
The colorant of the present invention may further contain, in addition to the aforementioned pigments, pigments and dyes used in this field within a range not departing from the object of the present invention.
(a1) Pigment (I)
The pigment (a1) that can be additionally used in the present invention includes organic pigments and inorganic pigments.
As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used, and specific examples thereof include: phthalocyanine (water-soluble azo pigment, insoluble azo pigment), phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, perylene pigment, perinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, anthraxanthone (anthrone) pigment, indanthrone (indanthrone) pigment, Plavanthrone pigment, pyranthrone (pyranthrone) pigment, diketopyrrolopyrrole pigment, or the like.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specific examples thereof include: oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony.
In particular, specific examples of The organic pigment and The inorganic pigment include compounds classified as pigments in The color index (published by The Society of Dyers and Colourists), more specifically, pigments numbered in The color index (c.i.) below, but The organic pigment and The inorganic pigment are not necessarily limited thereto.
As the pigment used in the pigment-dispersion composition of the present invention, organic pigments or inorganic pigments conventionally used in this field can be used, and these may be used alone or in combination of 2 or more.
The pigment may be subjected to a resin treatment, a surface treatment with a pigment derivative having an acid group or a basic group introduced thereto, a grafting treatment with a polymer compound or the like, a microparticulation treatment with a sulfuric acid microparticulation method or the like, a washing treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method or the like, as necessary.
Specific examples of the pigment include:
C.i. pigment yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, 173, 180 and 185;
C.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;
C.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;
C.i. pigment violet 14, 19, 23, 32, 33, 36 and 38;
C.i. pigment blue 15(15:3, 15:4, 15:6, etc.), 21, 28, 64 and 76;
C.i. pigment green 10, 15, 25, 36, 47 and 58;
C.i. pigment brown 28, etc.
The pigment is preferably a pigment dispersion liquid in which the particle diameter is uniformly dispersed. Examples of a method for uniformly dispersing the particle size of the pigment include a method of performing a dispersion treatment while containing a pigment dispersant, and according to this method, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.
In the colored photosensitive resin composition of the present invention, the pigment (a1) may be contained in the form of a pigment dispersion composition.
The pigment dispersion composition contains (a1) a pigment, (a2) a dispersant, (a3) a dispersing aid and (a4) a dispersing solvent, and (a5) a dispersing resin may be added for storage stability and ease of dispersion.
The pigment (a1) may be contained in an amount of 20 to 90% by mass, preferably 30 to 70% by mass, based on the total mass of the solid components in the pigment-dispersion composition. When the content of the pigment is out of the above range, the viscosity is high, the storage stability is poor, the dispersion efficiency is low, and the contrast ratio is adversely affected.
(a2) Dispersing agent
The dispersant is added for pigment deagglomeration and stability maintenance, and a dispersant conventionally used in this field may be used without limitation. The foregoing dispersant preferably includes an acrylate dispersant containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) (hereinafter referred to as an acrylate dispersant). Examples of commercially available products of the acrylic dispersant include: DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER BYK-2150, etc., and the above-mentioned acrylate dispersants may be used singly or in combination of 2 or more.
The dispersant of the present invention may be other resin type pigment dispersants in addition to the above-mentioned acrylate type dispersant. As the other resin type pigment dispersants, there are known resin type pigment dispersants, and particularly, there are water-soluble resins or water-soluble polymer compounds represented by polyurethanes, polyacrylates, polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of polycarboxylic acids substituted with hydroxyl group and modified products thereof, amides or salts thereof formed by reaction of polyesters having free (free) carboxyl group with poly (lower alkylene imine), (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, and the like; a polyester; a modified polyacrylate; ethylene oxide/propylene oxide addition products and phosphate esters, and the like.
As a commercial product of the resin type pigment dispersant, there is, for example, a product name of BYK chemical: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade name of BASF corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; trade name of Lubirzol corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Kawaken Fine Chemicals co., ltd.: HINACT T-6000, HINACT T-7000, HINACT T-8000; trade name of Aomoto Co., Ltd: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha chemical Co., Ltd: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc.
The dispersant is contained in an amount of 5 to 60 parts by mass, preferably 15 to 50 parts by mass, based on 100 parts by mass of the pigment in the colorant. When the amount of the dispersant is more than 60 parts by mass, the viscosity may be increased, and when the amount is less than 5 parts by mass, the pigment may be hardly pulverized or gelation may occur after dispersion.
In addition to the above-mentioned dispersants, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine and the like can be used as the dispersants, and they may be used singly or in combination of 2 or more.
Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines, and in addition, the following may be mentioned as trade names: KP (manufactured by shin-Etsu chemical industries Co., Ltd.), POLYFLOW (manufactured by Kyoho chemical Co., Ltd.), EFTOP (manufactured by Tohkem products Corporation), MEGAFAC (manufactured by DIC Corporation), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon (manufactured by Asahi Niger Co., Ltd.), SOLSPERSE (manufactured by Zeneca Limited), EFKA (manufactured by EFKA Chemicals B.V.), PB821 (manufactured by K.K.), and the like.
(a3) dispersing aid
The dispersing aid is a preparation that functions to disperse the pigment into fine particles and prevent reagglomeration. The dispersion aid is effective for forming a colored layer having a high contrast ratio and excellent transmittance.
Dispersing aids which can be used in the present invention are { [2- (diethylamino) ethyl ] amino } anthracene-9, 10-quinone, 1, 8-bis (benzamide) anthraquinone, 1, 4-bis { [2- (4-hydroxyphenyl) ethyl ] amino } anthracene-9, 10-quinone, 1, 4-bis { [2- (dimethylamino) ethyl ] amino } -5, 8-dihydroxyanthracene-9, 10-quinone, 1, 8-dihydroxy-4- [4- (2-hydroxyethyl) anilino ] -5-nitroanthracene-9, 10-quinone, 1, 4-dihydroxyanthraquinone, 1, 4-bis (4-butylanilino) -5, 8-dihydroxyanthraquinone, 4' - (4-hydroxy-1-anthraquinonylamino) -acetoacetanilide, 1, 4-bis [ (2, 6-diethyl-4-methylphenyl) amino ] anthraquinone, 1, 4-bis (butylamino) -9, 10-anthracenedione, 1, 4-bis (4-butylanilino) -5, 8-dihydroxyanthraquinone, 1, 5-bis [ (3-methylphenyl) amino ] -9, 10-anthracenedione, 1, 5-dicyclohexylaminoanthraquinone, 1, 4-bis (isopropylamino) anthraquinone, 1, 4-bis (methylamino) anthraquinone, 1, 4-bis (2, 6-diethyl-4-methylanilino) anthraquinone, 2' - (9, 10-dioxoanthracene-1, 4-diyldiimino) bis (5-methylsulfonate), 1-anilino-4-hydroxyanthraquinone, 1-hydroxy-4- [ (4-methylphenyl) amino ] -9, 10-anthracenedione, 1, 4-bis (p-tolylamino) anthraquinone, 1-amino-4-pentylaminoanthraquinone, N- [4- [ (4-hydroxy-anthraquinone-1-yl) amino ] phenyl ] acetamide, 1- (methylamino) -4- (4-methylanilino) anthracene-9, 10-dione, 1,4,5, 8-tetrahydroxyanthraquinone, and the like.
if necessary, a commercially available dispersion aid may be further contained in addition to the dispersion aid. Specific examples thereof include: SOLSPERSE-5000, SOLSPERSE-12000, SOLSPERSE-22000, BYK-SYNERGIST2100, BYK-SINERGIST2105, and EFKA-6745 or EFKA-6750 from BASF corporation, all of which are available from Lubrizol corporation.
The dispersion aid is contained in an amount of 1 to 30 parts by mass per 100 parts by mass of the pigment in the colorant. When the amount of the dispersion aid exceeds 30 parts by mass, the color inherent in the colorant (a) may be deteriorated, and the color of the colored layer may be discolored by hard baking in the production process of the colored layer.
(a4) dispersing solvent
The dispersion solvent is not particularly limited, and various organic solvents used in this field can be used.
Specifically, examples thereof 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, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerol, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, esters such as ethyl acetate and methyl ethyl cello, Cyclic esters such as γ -butyrolactone. Esters such as alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate can be preferably used, and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate can be more preferably used.
The dispersion solvents can be used alone or in combination of 2 or more.
The dispersion solvent is contained in an amount of 60 to 90% by mass, preferably 70 to 85% by mass, based on the total mass of the pigment dispersion composition. When the amount is outside the above range, the storage stability of the pigment dispersion composition may be poor.
(a5) dispersing resins
The dispersion resin (a) functions as a dispersion medium for the colorant (a), and can be optionally added, and when the dispersion resin (a5) is used in combination, a more excellent pigment dispersion composition can be produced than when the dispersant (a2) is used alone. The dispersion resin may be used without limitation as long as it functions as a dispersion medium, and preferably has an acid value because of its solubility in an alkaline developer in view of the developability of a colored photosensitive resin composition produced from the pigment dispersion composition.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1g of the acrylic polymer, and can be usually determined by titration with an aqueous potassium hydroxide solution.
The dispersion resin having an acid value can be produced by copolymerizing a compound (b1) having a carboxyl group and an unsaturated bond and a compound (b2) having an unsaturated bond copolymerizable with the compound (b 1).
Specific examples of the compound (b1) having a carboxyl group and an unsaturated bond include: monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of the foregoing dicarboxylic acids; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferred. In the present invention, (meth) acrylate means acrylate, methacrylate or both of them.
The compounds exemplified as the compound (b1) may be used singly or in combination of 2 or more. Examples of the compound (b2) having an unsaturated bond copolymerizable with the compound (b1) include: aromatic vinyl compounds such as styrene, vinyltoluene, α -methylstyrene, 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, or p-vinylbenzyl glycidyl ether; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate; alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; n-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide and N-p-methoxyphenylmaleimide; unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; unsaturated oxetane compounds such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like, but are not limited thereto.
The compounds exemplified as the compound (b2) may be used singly or in combination of 2 or more.
the dispersion resin is contained in an amount of 5 to 60 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass of the pigment solid content in the colorant. When the amount of the dispersion resin is more than 60 parts by mass, the viscosity may be increased depending on the dispersion resin, and when the amount is less than 5 parts by mass, the amount of the dispersion resin is insufficient, and thus a micronized pigment dispersion composition cannot be obtained.
(a6) Dye material
The dye may be used without limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and capable of ensuring reliability such as solubility in an alkaline developer, heat resistance, and solvent resistance is preferably used.
As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye with a nitrogen-containing compound, a sulfonamide of an acid dye, or the like, and a substance selected from derivatives thereof may be used, and in addition, an azo-based, xanthene-based, phthalocyanine-based acid dye, and a derivative thereof may be selected.
Preferably, The dye includes a compound classified as a dye in The color index (published by The Society of Dyers and Colourists), and a known dye described in dyeing notes (color dyeing Co., Ltd.).
as specific examples of the foregoing dyes, as c.i. solvent dyes, there can be mentioned:
C.i. solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162;
C.i. solvent red 8, 45, 49, 122, 125 and 130;
C.i. solvent orange 2, 7, 11, 15, 26 and 56;
C.i. solvent blues 35, 37, 59, and 67;
C.i. solvent green 1,3, 4,5, 7, 28, 29, 32, 33, 34, 35 and the like.
Further, as the c.i. acid dye, there may be mentioned:
C.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, and 251;
C.i. acid reds 1,4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, and 426;
c.i. acid oranges 6, 7, 8,10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, and 173;
C.i. acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, and 340;
C.i. acid violet 6B, 7, 9, 17 and 19;
C.i. acid green 1,3,5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109, and the like.
Further, as the c.i. direct dye, there can be mentioned:
C.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138 and 141;
C.i. direct reds 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, and 250;
C.i. direct oranges 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;
C.i. direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, and 293;
c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;
C.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82, etc.
Further, as c.i. mordant dyes, there can be mentioned:
C.i. mordant yellows 5,8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65; c.i. mordant reds 1, 2,3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;
C.i. mordant oranges 3,4, 5,8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;
c.i. mordant blues 1, 2,3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84;
c.i. mordant violet 1, 2,4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;
C.i. mordant green 1,3, 4,5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53, and the like.
The colorant (a) is contained in an amount of 20 to 80 wt%, preferably 35 to 70 wt%, based on the total weight of the solid components in the colored photosensitive resin composition of the present invention.
Alkali soluble resin (B)
the alkali-soluble resin has reactivity to light, heat, and alkali solubility, and functions as a dispersion medium for each component in the composition of the present invention.
The alkali-soluble resin of the present invention comprises (B-1) a1 st resin having an epoxy group and (B-2) a2 nd resin having an acid group (acid group) capable of reacting with the epoxy group and having an acid value of 170 to 300 mgKOH/g.
(B-1) the 1 st resin
the 1 st resin is a resin having an epoxy group and is a resin having an alkali solubility. As such a resin, any resin known in the art may be used without particular limitation. For example, the resin may be a resin obtained by copolymerization of (B-1-1) a compound having an unsaturated bond and a carboxyl group and (B-1-2) at least 1 compound belonging to the following chemical formula 1 to chemical formula 2.
[ chemical formula 1]
(wherein R1 represents hydrogen, an optionally heteroatom-containing alkyl group or cycloalkyl group having 1 to 20 carbon atoms, R2 represents a single bond, or an optionally heteroatom-containing alkylene group or cycloalkylene group having 1 to 20 carbon atoms, and R1 and R2 which is the alkylene group or cycloalkylene group are independently optionally further substituted with a hydroxyl group.)
[ chemical formula 2]
(wherein R1 is hydrogen, or an alkyl or cycloalkyl group having 1 to 20 carbon atoms and optionally containing a hetero atom; R2 is a single bond, or an alkylene or cycloalkylene group having 1 to 20 carbon atoms and optionally containing a hetero atom; and R1 and R2 which are the alkylene or cycloalkylene groups are independently further substituted with a hydroxyl group).
(B-1-1) Compound having an unsaturated bond and a carboxyl group
The compound having an unsaturated bond and a carboxyl group is not limited if it is a carboxylic acid compound having a polymerizable unsaturated double bond, and specific examples thereof include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and a polycarboxylic acid having 2 or more carboxyl groups in the molecule, such as an unsaturated tricarboxylic acid.
Examples of the unsaturated monocarboxylic acid include: acrylic acid, methacrylic acid, crotonic acid, and the like.
Examples of the unsaturated polycarboxylic acid include: maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like.
The polycarboxylic acid may be an acid anhydride, and examples of the unsaturated polycarboxylic acid anhydride 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: succinic acid mono (2-acryloyloxyethyl ester), succinic acid mono (2-methacryloyloxyethyl ester), phthalic acid mono (2-acryloyloxyethyl ester), phthalic acid mono (2-methacryloyloxyethyl ester), and the like.
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 polycarboxylic acid may be an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, and examples thereof include α - (hydroxymethyl) acrylic acid.
among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of high copolymerization reactivity.
The compounds having an unsaturated bond and a carboxyl group of the present invention may be used singly or in combination of 2 or more.
(B-1-2) at least 1 compound belonging to chemical formula 1 to chemical formula 2
at least 1 compound of chemical formula 1 to chemical formula 2 of the present invention is a compound having a polymerizable unsaturated bond and an epoxy group that increases the crosslinking density.
In the foregoing chemical formula 1 and chemical formula 2, as a more specific example of R1, may be, independently of each other: hydrogen; alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl; a hydroxyalkyl group such as a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxy-n-propyl group, a 2-hydroxy-n-propyl group, a 3-hydroxy-n-propyl group, a 1-hydroxyisopropyl group, a 2-hydroxyisopropyl group, a 1-hydroxy-n-butyl group, a 2-hydroxy-n-butyl group, a 3-hydroxy-n-butyl group, or a 4-hydroxy-n-butyl group. Of these, R1 independently of one another is preferably hydrogen, methyl, hydroxymethyl, 1-hydroxyethyl or 2-hydroxyethyl, particularly preferably hydrogen or methyl.
In the foregoing chemical formula 1 and chemical formula 2, as a more specific example of R2, may be, independently of each other: a single bond; alkylene groups such as methylene, ethylene, and propylene; a hydroxyalkylene group such as a hydroxymethylene group, a 1-hydroxyethylene group, a 2-hydroxyethylene group, a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, or a 3-hydroxy-n-propylene group; heteroatom-containing alkylene groups such as oxymethylene, oxyethylene, oxypropylene, thiomethylene, thioethylene, thiopropylene, aminomethylene, aminoethylene and aminopropylene. Among these, R2 is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, and particularly preferably a single bond or an oxyethylene group. In the present invention, the case where R2 is a single bond means a case where the carbon at the 8-or 9-position of the tricyclodecanyl group is directly linked to the oxygen of the acrylate group.
More specific examples of the compound represented by chemical formula 1 include the following chemical formulae 1-1 to 1-15.
More specific examples of the compound represented by the above chemical formula 2 include the following chemical formulas 2-1 to 2-15.
The compounds exemplified by the compounds represented by the above chemical formulas 1 and 2 may be used alone or in combination of 2 or more.
Further, the copolymer of the aforementioned (B-1-1) and (B-1-2) in the 1 st resin (A) may be copolymerized together with a compound having an unsaturated bond capable of polymerizing with the aforementioned (B-1-1) and (B-1-2) in addition to the aforementioned (B-1-1) and (B-1-2).
As the compound having an unsaturated bond polymerizable with the above-mentioned (B-1-1) and (B-1-2), specific examples thereof include: 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; 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; acrylonitrile compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic co-used dienes such as 1, 3-butadiene, isoprene and chloroprene; and polystyrene, polymethacrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polysiloxane.
when the 1 st resin (A) in the alkali-soluble resin of the present invention is a copolymer obtained by copolymerizing the above-mentioned (B-1-1) and (B-1-2) (the case where the copolymer further contains monomers other than B-1-1 and B-1-2 is also included in the present invention), the ratio of the structural units derived from each of (B-1-1) and (B-1-2) in the above-mentioned copolymer is preferably in the following range in terms of mole fraction relative to the total number of moles of the structural units constituting the above-mentioned copolymer.
A structural unit derived from (B-1-1): 5 to 75 mol%,
a structural unit derived from (B-1-2): 25 to 95 mol%.
In particular, the ratio of the structural units is more preferably in the following range.
a structural unit derived from (B-1-1): 10 to 70 mol%
A structural unit derived from (B-1-2): 30 to 90 mol%
When the ratio of the structural units is within the above range, a photosensitive resin composition having excellent developability, solvent resistance, heat resistance and mechanical strength can be produced.
The 1 st resin (A) can be produced, for example, by referring to the method described in the document "Experimental method for Polymer Synthesis" (published by Otsuka corporation, chemical Co., Ltd., 1 st edition, 1 st printing, 3/1/1972).
Specifically, a predetermined amount of the units (B-1-1) and (B-1-2) constituting the copolymer, a polymerization initiator and a solvent are charged into a reaction vessel, and the mixture is stirred, heated and kept warm in the absence of oxygen by replacing oxygen with nitrogen, thereby obtaining a polymer. The obtained copolymer may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
The acid value of the resin 1 is preferably in the range of 20 to 200 (KOHmg/g). When the acid value is within the above range, a green coating film having excellent developability with a developer, excellent sensitivity and adhesion, and no pattern peeling can be produced.
The polystyrene-equivalent weight average molecular weight of the 1 st resin may be 3,000 to 100,000, and may preferably be 5,000 to 50,000. When the weight average molecular weight of the 1 st resin is in the above range, the film reduction at the time of development can be prevented and the pattern portion peeling property is good, so that it is preferable.
The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the 1 st resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] falls within the above range, the developability is excellent, and therefore, it is preferable.
(B-2) No. 2 resin
The 2 nd resin is a resin obtained by polymerizing a compound having an acid group (acid group) capable of opening the ring of the epoxy group of the 1 st resin, and has a high acid value of 170 to 300 mgKOH/g. The compound has an acid functional group to open the epoxy group of the 1 st resin to increase the crosslinking density, thereby providing excellent adhesion, and when the acid value is in the above range, a pattern having excellent developability can be formed in a developer, and a green coating film having excellent sensitivity and no pattern peeling can be formed.
As the more specific 2 nd resin, there may be mentioned a resin obtained by polymerizing the following compounds (B-2-1), (B-2-2) and (B-2-3):
(B-2-1): 1 molecule has more than 1 kind of skeletons selected from the group consisting of tricyclodecane skeleton and dicyclopentadiene skeleton and has unsaturated bond;
(B-2-2): a compound having an aromatic vinyl group;
(B-2-3): a compound having an acid-acting group capable of opening the epoxy group of the 1 st resin.
As the compound (B-2-1) having 1 or more kinds of skeletons selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in 1 molecule and having an unsaturated bond, for example, as the compound having an unsaturated bond in 1 molecule and a tricyclodecane skeleton and (or) a dicyclopentadiene skeleton, specific examples include: dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecane mono (meth) acrylate, and the like. Herein, (meth) acrylate refers to acrylate and (or) methacrylate.
Examples of the compound having an aromatic vinyl group (B-2-2) include aromatic vinyl compounds such as styrene, α -methylstyrene and vinyltoluene.
The compound (B-2-3) having an acid-acting group capable of opening the epoxy group of the 1 st resin is not limited as long as it is a carboxylic acid compound having an unsaturated double bond capable of polymerizing, and specific examples thereof include polycarboxylic acids having 2 or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids.
Examples of the unsaturated monocarboxylic acid include: acrylic acid, methacrylic acid, crotonic acid, and the like.
Examples of the unsaturated polycarboxylic acid include: maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like.
The polycarboxylic acid may be an acid anhydride, and examples of the unsaturated polycarboxylic acid anhydride 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: succinic acid mono (2-acryloyloxyethyl ester), succinic acid mono (2-methacryloyloxyethyl ester), phthalic acid mono (2-acryloyloxyethyl ester), phthalic acid mono (2-methacryloyloxyethyl ester), and the like.
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 polycarboxylic acid may be an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, and examples thereof include α - (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of high copolymerization reactivity.
The compounds having an unsaturated bond and a carboxyl group of the present invention may be used singly or in combination of 2 or more.
the resin 2 of the present invention may be a resin obtained by copolymerization of a monomer other than the above-mentioned monomers (B-2-1) to (B-2-3). Specific examples of the compound having an unsaturated bond copolymerizable with (B-2-1) to (B-2-3) include: unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and aminoethyl (meth) acrylate;
Unsaturated carboxylic ester compounds having an alicyclic substituent such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, pentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pinene (meth) acrylate;
Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;
Unsaturated carboxylic acid ester compounds having aromatic ring-containing substituents such as benzyl (meth) acrylate and phenoxyl (meth) acrylate;
Vinyl carboxylates such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α -chloroacrylonitrile; and maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide. These may be used alone or in combination of 2 or more.
The ratio of the constituent components derived from each of (B-2-1) to (B-2-3) used in the present invention is preferably in the following range in terms of a mole fraction relative to the total number of moles of the constituent components constituting the copolymer.
10 to 80 mol% of a structural unit derived from (B-2-1),
10 to 80 mol% of a structural unit derived from (B-2-2),
10 to 80 mol% of a structural unit derived from (B-2-3).
In particular, the ratio of the structural units is more preferably in the following range.
20 to 40 mol% of a structural unit derived from (B-2-1),
20 to 50 mol% of a structural unit derived from (B-2-2),
10 to 60 mol% of a structural unit derived from (B-2-3).
When the ratio of the structural units is within the above range, a favorable balance among developability, solubility, and heat resistance is obtained, and therefore a preferable copolymer can be obtained.
In one embodiment of the present invention, the copolymer can be produced by the following method.
a solvent is collectively introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet in an amount of 0.5 to 20 times by mass based on the total amount of (B-2-1) to (B-2-3), and the atmosphere in the flask is replaced with nitrogen gas from air. Then, the solvent is heated to 40 to 140 ℃, and then 0 to 20 times the amount of the solvent based on the total amount of (B-2-2) and (B-2-3) and a solution prepared by adding a polymerization initiator such as azobisisobutyronitrile or 2-ethylhexyl tert-butylperoxycarbonate in an amount of 0.1 to 10 mol% based on the total number of moles of (B-2-1), (B-2-2) and (B-2-3) (dissolved by stirring at room temperature or under heating) are added dropwise to the flask from a dropping funnel over 0.1 to 8 hours, and the mixture is further stirred at 40 to 140 ℃ for 1 to 10 hours, whereby a copolymer can be obtained.
In the above step, part or all of the polymerization initiator may be charged into the flask, or part or all of (B-2-1), (B-2-2) and (B-2-3) may be charged into the flask. Further, α -methylstyrene dimer or mercapto compound can be used as a chain transfer agent for controlling the molecular weight and the molecular weight distribution. The amount of the alpha-methylstyrene dimer and the mercapto compound is 0.005 to 5% by mass based on the total amount of (B-2-1), (B-2-2) and (B-2-3). The polymerization conditions may be adjusted as appropriate in consideration of the production equipment, the amount of heat generated by polymerization, and the like.
the resin (B-2) of the invention of the 2 nd aspect is not particularly limited, and is more preferably an unsaturated group-containing resin obtained by further reacting a copolymer obtained by copolymerizing (B-2-1), (B-2-2) and (B-2-3) with a compound (B-2-4a) having an unsaturated bond and an epoxy group or a compound (B-2-4B) having an unsaturated bond and a hydroxyl group in 1 molecule. By adding the above (B-2-4) to the above copolymer, the 2 nd resin can be provided with a photo/thermosetting property.
Specific examples of the compound (B-2-4a) having an unsaturated bond and an epoxy group in the molecule of 1 in the present invention include: glycidyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is preferably used. These may be used alone or in combination of 2 or more.
Specific examples of the compound (B-2-4B) having an unsaturated bond and a hydroxyl group in the molecule of 1 include: 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate, glycerol (meth) acrylate and the like are usable compounds, that is, are not limited, and are included in the present invention.
The ratio of the structural unit derived from (B-2-4) in the 2 nd resin (B-2) is preferably 5 to 80 mol%, and more preferably 10 to 70 mol%, based on the number of moles of the constituent component derived from (B-2-3) in the 2 nd resin (B-2).
When the composition ratio of (B-2-4) is within the above range, a green photosensitive resin composition having sufficient developability, excellent adhesion and exposure sensitivity, and no pattern peeling can be produced.
In the embodiment of the present invention, the 2 nd resin (B-2) can be produced by reacting the aforementioned copolymer with (B-2-4) in such a manner as described below, for example.
replacing the atmosphere in the flask with nitrogen gas, charging 5 to 80 mol% of (B-2-4) as a reaction catalyst for a carboxyl group and an epoxy group, based on the molar fraction, based on the structural unit derived from (B-2-3) in the copolymer, 0.01 to 5% of tris (dimethylamino) methylphenol as a reaction catalyst for a carboxyl group and an epoxy group, based on the total amount of (B-2-1), (B-2-2) and (B-2-3), and 0.001 to 5% of hydroquinone as a polymerization inhibitor, based on the total amount of (B-2-1), (B-2-2) and (B-2-3), into the flask, the copolymer and (B-2-4) can be reacted with each other by reacting at 60 to 130 ℃ for 1 to 10 hours. In addition, as in the case of the polymerization conditions, the addition method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like.
The polystyrene-equivalent weight average molecular weight of the 2 nd resin may be 3,000 to 100,000, and may preferably be 5,000 to 50,000. When the weight average molecular weight of the 2 nd resin (B-2) is in the range of 3,000 to 100,000, the film reduction during development is less likely to occur, and the non-pixel portion tends to have good releasability during development, which is preferable.
The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the 2 nd resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. A molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of 1.5 to 6.0 is preferred because it is excellent in developability.
In the present invention, the alkali-soluble resin may be used by mixing the 1 st resin and the 2 nd resin as appropriate, and as a specific example, the alkali-soluble resin may be used by mixing the 1 st resin and the 2 nd resin in a mixing weight ratio of 1:0.5 to 1: 2.
The content of the alkali-soluble resin is 5 to 90 wt%, preferably 10 to 70 wt%, based on the total solid content of the colored photosensitive resin composition. When the content of the alkali-soluble resin is 5 to 90% by weight based on the above, the solubility in a developer is sufficient, the developability is excellent, the stability of a coating film is improved, and accordingly, the pattern is not peeled off.
Photopolymerizable compound (C)
The photopolymerizable compound contained in the colored photosensitive resin composition of the invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, difunctional monomers, and other polyfunctional monomers.
The photopolymerizable compound used in the present invention may be mixed with 2 or more photopolymerizable compounds having different structures of functional groups or different numbers of functional groups in order to improve developability, sensitivity, adhesion, surface problems, and the like of the colored photosensitive resin composition, and the range is not limited. Specific examples of the monofunctional monomer include: nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. Specific examples of the bifunctional monomer include: 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of the other polyfunctional monomers include: trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like. Among these, a polyfunctional monomer having two or more functions is preferably used.
The photopolymerizable compound is used in an amount of 1 to 90 parts by weight, preferably 10 to 80 parts by weight, based on the solid content of the colored photosensitive composition, relative to 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound.
(D) photopolymerization initiator
The photopolymerization initiator may be applied to those conventionally used in this field without limitation.
For example, 1 or more compounds selected from the group consisting of triazine compounds, acetophenone compounds, bisimidazole compounds, and oxime compounds can be used. The photosensitive resin composition containing the photopolymerization initiator has high sensitivity.
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-piperonyl-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) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.
Examples of the acetophenone compounds include: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, oligomers of 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and the like.
examples of the acetophenone compounds include compounds represented by the following chemical formula 4.
[ chemical formula 4]
In chemical formula 4, R1-R4 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group optionally substituted with an alkyl group having 1-12 carbon atoms, a benzyl group optionally substituted with an alkyl group having 1-12 carbon atoms, or a naphthyl group optionally substituted with an alkyl group having 1-12 carbon atoms.
Specific examples of the compound represented by the above chemical formula 4 include: 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2-amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, and mixtures thereof, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, and the like.
Examples of the bisimidazole compound include: 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4 ', 5, 5' -tetraphenylbiimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (alkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole, imidazole compounds in which the phenyl group at the 4,4 ', 5, 5' position is substituted with a carboalkoxy group, and the like. Of these, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole and 2, 2' -bis (2, 3-dichlorophenyl) -4,4 ', 5, 5' -tetraphenylbiimidazole are preferably used.
Examples of the oxime compound include O-ethoxycarbonyl- α -oxyimino-1-phenylpropan-1-one, and the following chemical formulae 5, 6, and 7.
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
in addition, other photopolymerization initiators and the like generally used in this field may be added and used in combination if the effects of the present invention are not impaired. Examples of the other photopolymerization initiator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and anthracene compounds. These may be used alone or in combination of 2 or more.
Examples of the benzoin compound include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.
Examples of the benzophenone compound include: benzophenone, methyl O-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 thioxanthone compound include: 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Examples of the anthracene compound include: 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, etc.
In addition, other photopolymerization initiators include: 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9, 10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, and the like.
Further, as the photopolymerization initiator, a photopolymerization initiator having a group capable of initiating chain transfer can be used. Examples of such photopolymerization initiators include those described in Japanese patent application laid-open No. 2002-544205.
Examples of the photopolymerization initiator having a group capable of initiating chain transfer include compounds represented by the following chemical formulas 8 to 13.
[ chemical formula 8]
[ chemical formula 9]
[ chemical formula 10]
[ chemical formula 11]
[ chemical formula 12]
[ chemical formula 13]
In the present invention, a photopolymerization initiator may be used in combination with a photopolymerization initiation aid. When the photopolymerization initiator and the photopolymerization initiation assistant are used in combination, the photosensitive resin composition containing them has higher sensitivity, and can form a pattern of a green coating film having excellent sensitivity.
As the photopolymerization initiation aid, an amine compound or a carboxylic acid compound is preferably used.
Specific examples of the amine compound in the photopolymerization initiation aid include: aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, and aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson) and 4, 4' -bis (diethylamino) benzophenone. Among these, as the amine compound, an aromatic amine compound is preferably used.
Specific examples of the carboxylic acid compound in the photopolymerization initiation aid include: aromatic heteroacetates such as 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 and naphthyloxyacetic acid.
The content of the photopolymerization initiator is 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the solid content in the colored photosensitive resin composition, relative to 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound, and the content of the photopolymerization initiation assistant is 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, based on the solid content. When the content of the photopolymerization initiator is within the above range, the photosensitive resin composition has high sensitivity, and a coating film formed using the composition has excellent sensitivity, and no pattern peeling occurs, and therefore, the content is preferable. When the content of the photopolymerization initiation assistant is within the above range, the sensitivity of the photosensitive resin composition is further improved, which is advantageous for the pattern stability of a coating film formed using the composition.
Solvent (E)
As the solvent, any one can be used without limitation if it is a substance generally used in this field.
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 ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether 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; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, and propylene glycol ethyl propyl ether; propylene glycol alkyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; butanediol monoalkyl ethers such as methoxybutanol, ethoxybutanol, propoxybutanol and butoxybutanol; butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate; butanediol monoalkyl ether propionate such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate and the like; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxylacetate, ethyl propoxyethyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-, Propyloxypropyl acetate, propyloxy acetate, butoxymethyl acetate, butoxyethyl acetate, butoxypropyl acetate, butoxybutyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl n-butoxypropionate, n, Esters such as propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and pyran; cyclic esters such as γ -butyrolactone. The solvents exemplified herein may be used alone or in combination of 2 or more.
In consideration of coatability and drying properties, the solvent may preferably be an alkylene glycol alkyl ether acetate, a ketone, a butylene glycol alkyl ether acetate, a butylene glycol monoalkyl ether, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, or other esters, and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, or the like may further preferably be used.
The content of the solvent is 50 to 90 wt%, preferably 60 to 85 wt%, based on the total weight of the photosensitive resin composition containing the solvent. If the solvent content is within the above range, the coating properties are good when the coating is performed by a coating device such as a spin coater, a slit & spin coater, a slit coater (also referred to as a die coater or a curtain coater), or an ink jet, and therefore, the content is preferable.
additive (F)
The photosensitive resin composition of the present invention may further contain additives such as a filler, other polymer compound, a curing agent, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent, and a chain transfer agent, as required.
specific examples of the filler include glass, silica, and alumina.
Specific examples of the other polymer compounds include: curable resins such as epoxy resins and maleimide resins; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
The curing agent is used for improving deep-part curing and mechanical strength, and specific examples thereof include: epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.
Among the curing agents, specific examples of the epoxy compound include: bisphenol a-based epoxy resins, hydrogenated bisphenol a-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolac-type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester-based resins, glycidyl amine-based resins, brominated derivatives of these epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxies, isoprene (co) polymer epoxies, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate, and the like.
Among the curing agents, specific examples of the oxetane compound include: carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, terephthalate dioxetane, cyclohexane dicarboxylic acid dioxetane, and the like.
the curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerizing the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators.
The carboxylic acid anhydrides can be used as commercially available curing agents for epoxy resins. Examples of the epoxy resin curing agent include: trade name (ADEKA HARDENER EH-700) (manufactured by ADEKA CORPORATION), trade name (RIKACID HH) (manufactured by Nippon chemical Co., Ltd.), and trade name (MH-700) (manufactured by Nippon chemical Co., Ltd.), and the like. The curing agents exemplified above may be used singly or in combination of 2 or more.
as the leveling agent, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric and other surfactants, and these surfactants can be used singly or in combination of 2 or more.
Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines, and the surfactants are represented by the following trade names: KP (manufactured by shin-Etsu chemical Co., Ltd.), POLYFLOW (manufactured by Kyoho chemical Co., Ltd.), EFTOP (manufactured by Tohkem products Corporation), Megafac (manufactured by DIC Corporation), Fluorad (manufactured by Sumitomo 3M Limited), Asahi Guard, Surflon (manufactured by Asahi Niger Co., Ltd.), SOLSPERSE (manufactured by Zeneca Limited), EFKA (manufactured by EFKA CHEMICALS B.V.), PB821 (manufactured by K.K.), and the like.
The adhesion promoter is preferably a silane compound, and specific examples thereof include: 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 and the like.
Specific examples of the antioxidant include: 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-di-tert-pentylphenyl) ethyl ] -4, 6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8, 10-tetra-tert-butylbenzene [ d, f ] [1,3,2] dioxaphosphorinane, 3, 9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy } -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2 ' -methylenebis (6-tert-butyl-4-methylphenol), 4 ' -butylidenebis (6-tert-butyl-3-methylphenol), 4 ' -thiobis (2-tert-butyl-5-methylphenol), 2 ' -thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3 ' -thiodipropionate, dimyristyl 3,3 ' -thiodipropionate, distearyl 3,3 ' -thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione, 3 ', 5,5 ' -hexa-tert-butyl-alpha, alpha ' - (mesitylene-2, 4, 6-triyl) tri-p-cresol, pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 6-di-tert-butyl-4-methylphenol, and the like.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the agglomeration inhibitor include sodium polyacrylate and the like.
Specific examples of the chain transfer agent include dodecylmercaptan and 2, 4-diphenyl-4-methyl-1-pentene.
Color filter and image display apparatus
The invention provides a color filter manufactured by the colored photosensitive resin composition and an image display device comprising the color filter.
The image display device that can include such a color filter may be a liquid crystal display device, an OLED, a flexible display, or the like, but is not limited thereto, and any image display device known in the art can be used.
the color filter can be produced by applying the colored photosensitive resin composition of the present invention to a substrate, photocuring and developing the composition, and forming a pattern.
First, a colored photosensitive resin composition is applied to a substrate, and then heated and dried to remove volatile components such as a solvent, thereby obtaining a smooth coating film.
The coating method may be performed by, for example, spin coating, cast coating, roll coating, slit & spin coating, slit coating, or the like. After coating, the coating is dried by heating (prebaking) or after drying under reduced pressure, and then heated to volatilize volatile components such as a solvent. The heating temperature is usually 70 to 200 ℃ and preferably 80 to 130 ℃. The thickness of the coating film after the heating and drying is usually about 1 to 8 μm. The coating film obtained as described above is irradiated with ultraviolet rays through a mask for forming a target pattern. In this case, the entire exposure portion is uniformly irradiated with parallel light, and it is preferable to perform accurate alignment between the mask and the substrate by using a device such as a mask aligner or a stepper. When ultraviolet rays are irradiated, the portion irradiated with the ultraviolet rays is cured.
As the ultraviolet ray, g rays (wavelength: 436nm), h rays, i rays (wavelength: 365nm) and the like can be used. The dose of the ultraviolet ray irradiation may be appropriately selected as needed, but is not limited in the present invention. The cured coating film is brought into contact with a developer to dissolve the unexposed portion and develop the resultant to form a desired pattern shape.
The developing method may be any of a liquid addition method, a dipping method, a spraying method, and the like. In addition, the substrate may be inclined at an arbitrary angle during development. The aforementioned developer is usually an aqueous solution containing an alkali compound and a surfactant. The aforementioned basic compound may be any of inorganic and organic basic compounds. Specific examples of the inorganic basic compound include: sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, diammonium hydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia water and the like. Further, specific examples of the organic basic compound include: tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like.
These inorganic and organic basic compounds may be used singly or in combination of 2 or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.
The surfactant in the alkaline developer may use at least 1 selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.
Specific examples of the nonionic surfactant include: polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene alkylamines, and the like.
Specific examples of the anionic surfactant include: higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylallyl sulfonate salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.
Specific examples of the cationic surfactant include amine salts such as stearyl amine hydrochloride and lauryl trimethyl ammonium chloride, and quaternary ammonium salts. These surfactants may be used alone or in combination of 2 or more.
The concentration of the surfactant in the developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. After the development, the resultant is washed with water, and if necessary, post-baking may be performed at 150 to 230 ℃ for 10 to 60 minutes.
Preferred embodiments are given below to help understanding the present invention, but these embodiments are merely illustrative of the present invention and do not limit the scope of claims, and it is clear to those skilled in the art that various changes and modifications of the embodiments can be made within the scope and technical spirit of the present invention, and such changes and modifications are of course included in the appended claims.
Synthesis example 1: synthesis of resin No. 1 (B-1) in alkali-soluble resin >
On the one hand, a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet was prepared, and on the other hand, 40 parts by weight of a mixture (50:50 molar ratio) of 3, 4-epoxytricyclodecan-8-yl (meth) acrylate (chemical formula 1) and 3, 4-epoxytricyclodecan-9-yl (meth) acrylate (chemical formula 2) and 50 parts by weight of methyl methacrylate were charged as a monomer dropping funnel, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, 4 parts by weight of t-butyl peroxy-2-ethylhexanoate, and 40 parts by weight of Propylene Glycol Monomethyl Ether Acetate (PGMEA) were stirred and mixed for use, and 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added to a dropping tank as a chain transfer agent and stirred and mixed for use. Then, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ℃ with stirring. Subsequently, dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dropping was carried out for 2 hours while maintaining 90 ℃ and after 1 hour, the temperature was raised to 110 ℃ and maintained for 5 hours to obtain a resin (B-1-1) having an acid value of a solid content of 75 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.
Synthesis example 2: synthesis of the 2 nd resin (B-2-a) in the alkali-soluble resin
Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, 182g of propylene glycol monomethyl ether acetate was introduced, the atmosphere in the flask was changed from air to nitrogen gas, the temperature was raised to 100 ℃ and then a solution of 66.0g (0.3 mol) of monomethacrylate containing (B-2-1) tricyclodecane skeleton (FA-513M manufactured by Hitachi chemical Co., Ltd.), 35.0g (0.30 mol) of (B-2-2) α -methylstyrene, 28.8g (0.40 mol) of (B-2-3) acrylic acid and 136g of propylene glycol monomethyl ether acetate, 3.6g of azobisisobutyronitrile was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for 5 hours from 100 ℃. Next, the atmosphere in the flask was changed from nitrogen to air, and 42.0g (0.28 mol) of glycidyl methacrylate (B-2-4), 0.9g of tris (dimethylamino) methylphenol and 0.145g of hydroquinone were charged into the flask, and the reaction was continued at 110 ℃ for 6 hours to obtain a resin (B-2-a) having an acid value of 170.7mgKOH/g as a solid. The weight average molecular weight in terms of polystyrene measured by GPC was 22,180, and the molecular weight distribution (Mw/Mn) was 2.3.
Synthesis examples 3 to 18: synthesis of the 2 nd resin (B-2-B. about. q.) in the alkali-soluble resin
Synthesis example 2 was repeated in the same manner as in Synthesis example 2 except that the respective components and ratios of (B-2-1 to 4) were changed as shown in Table 1.
[ Table 1]
The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resin is performed by GPC under the following conditions.
The device comprises the following steps: HLC-8120GPC (manufactured by Tosoh corporation)
A chromatographic column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 deg.C
Mobile phase solvent: tetrahydrofuran (THF)
Flow rate: 1.0 ml/min
Injection amount: 50 μ l
a detector: RI (Ri)
And (3) measuring the concentration of the sample: 0.6% by mass (solvent ═ tetrahydrofuran)
Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corp.)
The ratio of the weight average molecular weight to the number average molecular weight obtained above was taken as the molecular weight distribution (Mw/Mn).
< example 1: production of colored photosensitive resin composition
The colored photosensitive resin composition (unit is part by weight) was produced according to the components and composition shown in table 2 below.
[ Table 2]
< example 2: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-B.
< example 3: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-c in example 1.
< example 4: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-d in example 1.
< example 5: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-e in example 1.
< example 6: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-f in example 1.
< example 7: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-g in example 1.
< example 8: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-h in example 1.
Example 9: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-i in example 1.
Example 10: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-j in example 1.
Example 11: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-k in example 1.
Example 12: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-l in example 1.
Example 13: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-m in example 1.
Example 14: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-n in example 1.
Comparative example 1: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-o in example 1.
Comparative example 2: production of colored photosensitive resin composition
the production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-p in example 1.
Comparative example 3: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-2-q in example 1.
Comparative example 4: production of colored photosensitive resin composition
The production was carried out in the same manner as in example 1 except that the resin B-2-a was changed to the resin B-1 in example 1.
Experimental example 1
A2-inch square glass substrate (EAGLE 2000; manufactured by Corning Incorporated) was washed with a neutral detergent, water and alcohol in this order and then dried. The photosensitive resin compositions produced in the examples and comparative examples were spin-coated on the glass substrates, and then prebaked at 90 ℃ for 3 minutes in a clean oven. After the substrate after the pre-baking was cooled to room temperature, the distance from the quartz glass photomask was set to 150 μm, and the substrate was irradiated with light at an exposure amount of 60mJ/cm2 (405nm standard) using an exposure apparatus (TME-150 RSK; manufactured by TOPCON CORPORATION). In this case, the polymerizable resin composition was irradiated with light having a wavelength of 400nm or less by passing the light emitted from an ultrahigh-pressure mercury lamp through a filter (LU 0400; manufactured by Nissan spectral Co., Ltd.). In this case, the photomask used was one having the following pattern formed on the same plane.
The coating film was developed by immersing the coating film in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ℃ for 100 seconds after light irradiation, washed with water, and baked in an oven at 220 ℃ for 20 minutes. The resulting film thickness was 3.6. mu.m. The film thickness was measured using a film thickness measuring apparatus (DEKTAK 6M; manufactured by Veeco). The pattern thus obtained was subjected to physical property evaluation as described below, and the results are shown in table 2 below.
1. Evaluation of developability (residue characteristics)
After the development, the presence or absence of residue and residual amount left without being washed off at the desired portion was observed. The evaluation was good when no residue was present, and was poor when residue was present.
2. Evaluation of adhesion
The degree of peeling of the 20 μm pattern was evaluated by an optical microscope, and is shown in table 3 below.
o: no peeling off on the pattern
And (delta): the number of the peeling on the pattern is 1 to 3
x: the number of the peeling on the pattern is more than 4
3. Line width and cross-sectional shape
The line width of the formed pattern was measured by a scanning electron microscope (S-4600; manufactured by Hitachi, Ltd.) using a Mask of 14 μm, and the cross-sectional shape of the cured film was evaluated as follows. The cross-sectional shape is determined to be a forward taper when the pattern angle with respect to the substrate is less than 90 degrees, and to be an inverted taper when the pattern angle is 90 degrees or more.
The forward taper shape is preferable because pattern peeling is less likely to occur when forming a display device.
4. Sensitivity of light
Regarding development adhesion, a Pattern was formed with a film thickness of 3 μm using each photomask having 1000 circular patterns with a diameter (Size) interval of 1 μm and a diameter of 5 μm to 20 μm, and the diameter (Pattern Size) of a Pattern formed with a Mask (Mask) was evaluated by a microscope to be free from defects and 100% remained. The sensitivity is more excellent as the diameter of the mask is smaller.
[ Table 3]
Referring to table 3, it can be confirmed that the example containing the 2 nd resin of the present invention has good adhesion to the substrate and pattern shape and good sensitivity at a low exposure amount as compared with the comparative example not containing the resin.
Examples 15 to 23 and comparative examples 5 to 10
Colored photosensitive resin compositions (unit: mass%) were prepared according to the components and contents shown in tables 4 and 5 below.
[ Table 4]
[ Table 5]
Experimental example 2
Preparation of measurement test piece
Colored layers were produced from the colored photosensitive resin compositions produced in examples 15 to 23 and comparative examples 5 to 10. That is, after coating on a glass substrate by spin coating, the glass substrate was laid on a hot plate and kept at 100 ℃ for 3 minutes to form a thin film. Next, irradiation was performed at an illuminance of 100mJ/cm2 using a 1kw high-pressure mercury lamp including all g, h, and i rays. In this case, no special filter is used. The ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to be developed. The glass substrate covered with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ℃ for 30 minutes. The thickness of the colored layer obtained in this way is 1 to 5 μm, and more preferably about 2 to 4 μm.
1. Measurement of luminance
The OSP-SP2000 was measured using a microspectrometer. The luminance is shown in table 6 below, and the chromaticity coordinates Gx-0.1670 and Gy-0.6610.
The evaluation criteria of the luminance (Y) are as follows.
○：Y≥24、△：20≤Y<24、×：Y<20
2. Contrast determination
The contrast 1/30000 standard of the glass substrate (before the colored layer was formed) was used as a measurement standard, which was measured by using TOPCON CORPORATION CONTRAST-INDICATOR BM-5A. The results are shown in Table 6 below.
The evaluation criteria for Contrast Ratio (CR) are as follows.
◎：CR≥10000、○：7000≤CR<10000、△：5000≤CR<7000、×：CR<5000
3. determination of tinting strength
The ratio of the weight of the pigment in the colored photosensitive resin composition added to produce a target coating film thickness (3.5 to 3.8 μm) was measured.
O: tinting strength <0.35, Δ: 0.35. ltoreq. tinting strength <0.45, ×: tinting strength >0.45
4. Measurement of Pattern formability
the colored photosensitive resin composition thus produced was applied to a glass substrate (#1737, manufactured by Corning Incorporated) by a spin coating method, and then laid flat on a hot plate and held at a temperature of 100 ℃ for 3 minutes to form a thin film. Next, a test photomask having a pattern whose transmittance varied stepwise within a range of 1 to 100% was placed flat on the film, and the test photomask was irradiated with light at an exposure (365nm) of 40mJ/cm2 in an atmospheric atmosphere using an ultra-high pressure mercury lamp (manufactured by USH-250D, USHIO inc.). The ultraviolet-irradiated film was developed with a KOH aqueous solution developing solution having a pH of 12.5 for 80 seconds by a spray developing machine. The glass substrate covered with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ℃ for 20 minutes to produce a color filter. The thickness of the pattern shape (thin film) of the manufactured color filter is 3.5 to 3.8 μm.
The pattern was formed by gradually decreasing the exposure amount with respect to the initial exposure amount irradiated at the time of pattern formation, and the pattern formability was evaluated by the ratio (%) of the exposure amount of the formed pattern with respect to the initial exposure amount.
O: pattern formability <0.2,
And (delta): 0.2 or less than 0.6,
X: pattern formability >0.6
[ Table 6]
brightness of light Contrast ratio Coloring power Pattern formability
Example 15 △ ○ ○ ○
Example 16 ○ ○ ○ ○
Example 17 ○ ○ ○ ○
Example 18 ○ △ ○ △
Example 19 ○ ○ ○ ○
Example 20 ○ △ ○ △
Example 21 ○ ○ ○ ○
Example 22 ○ △ ○ ○
Example 23 ○ △ ○ △
Comparative example 5 △ △ × △
Comparative example 6 ○ △ × △
Comparative example 7 △ △ × △
Comparative example 8 × × × △
Comparative example 9 ○ × △ ×
Comparative example 10 △ △ × ×
As shown in table 6, the examples of the present invention are superior to the comparative examples in all properties such as brightness, contrast, coloring power, and pattern formability.
Among them, in examples 18, 20 and 23 in which the mixing ratio of the green pigment and the yellow pigment was slightly deviated from 100:0 to 80:20, it was found that the contrast and the pattern formability were slightly lowered.
As is clear from table 6, in the comparative examples and comparative examples, the luminance and contrast values of the examples are superior to those of the comparative examples from the viewpoint of the same chromaticity coordinates, the coloring power is also excellent, and the possibility of occurrence of display failure in the liquid crystal display device is low.

Claims (7)

1. A colored photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent,
The colorant (A) contains a green pigment of pigment green 7 and at least 1 yellow pigment of pigment yellow 129 and pigment yellow 139,
The mass ratio of the green pigment to the yellow pigment in the colorant is 100: 0-80: 20 and does not include 100:0,
The alkali-soluble resin (B) contains a1 st resin which has an epoxy group and an acid value of 20-200 mgKOH/g, and a2 nd resin which has an acid group (acid group) capable of reacting with the epoxy group and an acid value of 170-300 mgKOH/g.
2. The colored photosensitive resin composition according to claim 1, wherein the 1 st resin is a resin obtained by copolymerization of a compound having an unsaturated bond and a carboxyl group and at least 1 compound of the following chemical formula 1 to chemical formula 2:
[ chemical formula 1]
Wherein R1 is hydrogen, or C1-20 alkyl or cycloalkyl optionally containing heteroatom, R2 is single bond, or C1-20 alkylene or cycloalkylene optionally containing heteroatom, and R1 and R2 as the alkylene or cycloalkylene are independently further substituted by hydroxyl;
[ chemical formula 2]
wherein R1 is hydrogen, or C1-20 alkyl or cycloalkyl optionally containing heteroatom, R2 is single bond, or C1-20 alkylene or cycloalkylene optionally containing heteroatom, and R1 and R2 as the alkylene or cycloalkylene are independently further substituted by hydroxyl.
3. The colored photosensitive resin composition according to claim 1, wherein the 2 nd resin is a resin obtained by copolymerizing a compound having 1 or more kinds of skeletons selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in 1 molecule and having an unsaturated bond, a compound having an aromatic vinyl group, and a compound having an acid-acting group capable of opening an epoxy group of the 1 st resin.
4. The colored photosensitive resin composition according to claim 3, wherein the compound having an acid-acting group is at least 1 compound selected from the group consisting of an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated tricarboxylic acid.
5. The colored photosensitive resin composition according to claim 1, wherein the 2 nd resin is a resin obtained by copolymerization of a compound having an unsaturated bond and an epoxy group or a compound having an unsaturated bond and a hydroxyl group in 1 molecule.
6. A color filter produced from the colored photosensitive resin composition according to any one of claims 1 to 5.
7. An image display device comprising the color filter according to claim 6.
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