CN104914666B - Colored photosensitive resin composition for color filter, and liquid crystal display device provided with same - Google Patents

Colored photosensitive resin composition for color filter, and liquid crystal display device provided with same Download PDF

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CN104914666B
CN104914666B CN201510103384.4A CN201510103384A CN104914666B CN 104914666 B CN104914666 B CN 104914666B CN 201510103384 A CN201510103384 A CN 201510103384A CN 104914666 B CN104914666 B CN 104914666B
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photosensitive resin
resin composition
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colored photosensitive
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CN104914666A (en
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申泳璨
安大熙
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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
    • 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
    • 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
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The present invention relates to a colored photosensitive resin composition for a color filter, and a liquid crystal display device provided with the color filter, and more particularly, to a colored photosensitive resin composition for a red color filter used in the production of a red color filter used in a color liquid crystal display device or the like.

Description

Colored photosensitive resin composition for color filter, and liquid crystal display device provided with same
Technical Field
The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a red color filter used in the production of a red color filter used in a color liquid crystal display device or the like.
Background
Color filters are widely used in Plasma Display Panels (PDPs), Liquid Crystal Displays (LCDs), field emission displays (FELs), light emitting diode displays (LEDs), and the like, and their application range is rapidly expanding. In particular, the use in LCDs has recently been further expanded, and therefore, color filters are considered as one of the most important components in reproducing the color tone of LCDs.
Such a color filter is manufactured by a method of forming a desired colored pattern using a colored photosensitive resin composition containing a colorant. Specifically, a color filter is manufactured by repeatedly performing a series of processes of forming a coating layer composed of a colored photosensitive resin composition on a substrate, forming a pattern on the coating layer, performing exposure and development, and heating to thermally cure the coating layer.
Recently, in order to achieve high color purity, the concentration of a colorant of a colored photosensitive resin composition for manufacturing a color filter is continuously increased, and a method of using a pigment and a dye as the colorant at the same time is being studied. On the other hand, in order to improve the productivity and yield in the process, a colored photosensitive resin composition having a high developing speed and excellent sensitivity and reliability even with a low exposure amount is required.
On the other hand, korean laid-open patent No. 2002-0006441 discloses a color filter having excellent pattern precision using a hindered phenol antioxidant, but the above invention has a problem that the pigment is finely pulverized because only the pigment is used as a colorant, and a problem that discoloration occurs after a high temperature process in the case of a red color filter.
Documents of the prior art
Patent document
Patent document 1: korean laid-open patent No. 2008-0103590
Patent document 2: korean laid-open patent No. 2002-0006441
Disclosure of Invention
The invention aims to provide a coloring photosensitive resin composition for a red color filter, which can obtain a color filter with excellent transmittance. In particular, an object of the present invention is to provide a colored photosensitive resin composition for red pixels, which is excellent in transmittance, can minimize the problem of decrease in transmittance occurring in the subsequent process, and is excellent in sensitivity, adhesion and developing speed, so that the pattern is not peeled off in the developing process.
It is another object of the present invention to provide a colored photosensitive resin composition for red pixels, which is less discolored in red and has excellent brightness.
In order to achieve the above object, the present invention provides a colored photosensitive resin composition for a red pixel, comprising a colorant (a), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), an antioxidant (E), and a solvent (F), wherein the colorant (a) comprises one or more pigments and one or more dyes, wherein one or more of the pigments or dyes is a red series, the photopolymerization initiator (D) comprises a dithiophene-containing oxime ester photoinitiator represented by the following chemical formula 1, the antioxidant (E) comprises 1 or more phenolic antioxidants and 1 or more phosphorus antioxidants, and the phenolic antioxidants are not deteriorated at 150 ℃ for 200 hours or more.
[ chemical formula 1]
Figure BDA0000679649750000021
In the above formula, R1 may be the following chemical formula 2, R2 may be C1 to C8 alkyl, phenyl, substituted or unsubstituted benzyl, and R3 may be diphenylthio.
[ chemical formula 2]
-R4-R5
Wherein, R4 can be alkylene of C1-C4, and R5 can be alkyl or cycloalkyl of C3-C8.
According to a preferred embodiment of the present invention, in the above antioxidants, the weight ratio of the phenolic antioxidant to the phosphorus antioxidant may be 1:1 to 5: 1.
In the present invention, the colored photosensitive resin composition may contain 5 to 60% by weight of a colorant (a), 10 to 80% by weight of an alkali-soluble resin (B), and 5 to 45% by weight of a photopolymerizable compound (C) based on the total solid content of the colored photosensitive resin composition; the photopolymerization initiator (D) may be contained in an amount of 0.1 to 40 parts by weight based on the solid content, based on 100 parts by weight of the sum of the alkali-soluble resin (B) and the photopolymerizable compound (C).
The invention provides a color filter made of the colored photosensitive resin composition for red pixels.
The invention provides a liquid crystal display device comprising the color filter.
The color filter manufactured by the colored photosensitive resin composition has excellent adhesiveness, so that the problem of pattern stripping is not generated, and the color filter has the effects of high developing speed, less color difference and excellent transmittance.
Further, the color filter produced from the colored photosensitive resin composition of the present invention is less discolored in red and has excellent brightness.
Detailed Description
The invention provides a colored photosensitive resin composition for red pixels, which is characterized by comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), an antioxidant (E) and a solvent (F), wherein the colorant (A) comprises one or more pigments (a1) and one or more dyes (a2), one or more of the pigments or dyes is red, the photopolymerization initiator (D) comprises an oxime ester photopolymerization initiator containing a diphenylthio group represented by the following chemical formula 1, the antioxidant (E) comprises 1 or more phenolic antioxidants and 1 or more phosphorus antioxidants, and the phenolic antioxidants are not deteriorated for 200 hours or more at 150 ℃,
[ chemical formula 1]
Figure BDA0000679649750000041
In the above formula, R1 may be the following chemical formula 2, R2 may be C1 to C8 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, R3 may be diphenylthio;
[ chemical formula 2]
-R4-R5
In the formula, R4 can be alkylene of C1-C4, and R5 can be alkyl or cycloalkyl of C3-C8.
The colored photosensitive resin composition for red pixels of the present invention comprises a pigment as a colorant and a fuel, and further comprises a phenolic antioxidant and a phosphorus antioxidant which are not deteriorated for 200 hours or more at 150 ℃, and further comprises an oxime ester photopolymerization initiator containing a diphenylthio group, so that a color filter produced from the colored photosensitive resin composition has excellent adhesion, does not cause a problem of pattern peeling, and has the effects of high development speed, less color difference, and excellent transmittance.
Hereinafter, each component constituting the colored photosensitive resin composition for red pixels of the present invention will be described.
Colorant (A)
The colorant (a) contains one or more pigments (a1) and one or more dyes (a2) as essential components.
Pigment (a1)
Organic pigments or inorganic pigments commonly used in the art may be used as the above-mentioned pigments.
The organic pigment can be used in various pigments for printing ink, inkjet ink and the like, and specificallyExamples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, and perylene pigments
Figure BDA0000679649750000043
Oxazine pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, tripheno [ cd, jk ] pigments]Pyrene-5, 10-dione (anthanthrone) pigments, indanthrone (indanthrone) pigments, xanthone pigments, pyranthrone (pyranthrone) pigments, diketopyrrolopyrrole pigments, and the like.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically include metal oxides or complex metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black.
In particular, The organic pigment and The inorganic pigment include, but are not limited to, compounds classified as pigments in color index (published by The society of Dyers and Colourists), and more specifically, pigments numbered by The following color index (c.i.).
Such as c.i. pigment yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 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, 208, 215, 216, 224, 242, 254, 255 and 264.
Among the above exemplified c.i. pigments, pigments selected from c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 185, c.i. pigment orange 38, c.i. pigment red 122, c.i. pigment red 166, c.i. pigment red 177, c.i. pigment red 208, c.i. pigment red 242, c.i. pigment red 254 and c.i. pigment red 255 can be preferably used.
The pigment may use organic pigments or inorganic pigments generally used in the art, and may be used alone or in combination of two or more pigments, respectively.
The pigment is preferably a pigment dispersion liquid in which the pigment is uniformly dispersed in the particle diameter of the pigment. Examples of a method for uniformly dispersing the particle size of the pigment include a method in which a dispersion treatment is performed by including a pigment dispersant (a3), and a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained by this method.
Pigment dispersant (a3)
The pigment dispersant (a3) is for the purpose of anticoagulation of the pigment
Figure BDA0000679649750000051
And a pigment dispersant which is added to maintain stability and is generally used in the art, and examples thereof include surfactants such as cationic, anionic, nonionic, amphoteric, polyester and polyamine surfactants. Preferably, the pigment dispersant includes an acrylate-based dispersant, and the acrylate-based dispersant includes BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). In this case, as disclosed in Korean laid-open patent No. 2004-0014311, it is preferable to produce the acrylate-based dispersant by an activity control method, and examples of commercially available acrylate-based dispersants produced by the activity control method include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like.
The above-exemplified acrylate-based dispersants may be used alone or in combination of two or more.
Other resin type pigment dispersants may be used as the above pigment dispersant (a3) in addition to the above acrylate-based dispersant. Examples of the other resin type pigment dispersants include known resin type pigment dispersants, and particularly include emulsion dispersants such as polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids, modified products thereof, or amines formed by the reaction of polyesters having free (free) carboxyl groups with poly (lower alkylene imines), or salts thereof; water-soluble resins or water-soluble polymers such as (meth) acrylic acid styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, or polyvinyl pyrrolidone; a polyester; a modified polyacrylate; ethylene oxide/propylene oxide addition products, phosphoric esters, and the like.
Examples of commercially available products of the resin type dispersant include trade names 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 chemical company: HINACT T-6000, HINACT T-7000, HINACT T-8000; trade name of Ajinomoto corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha chemical Co: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc.
The resin type pigment dispersants other than the above acrylate type dispersant may be used alone or in combination of two or more, and may be used in combination with the acrylate type dispersant.
The amount of the pigment dispersant (a3) used is 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1) used. If the content of the pigment dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased, and if the content is less than 5 parts by weight, the pigment may be less likely to be finely pulverized, or the pigment may be gelled after dispersion.
Dye (a2)
The use of the above dye (a2) is not limited as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure solubility in an alkali developing solution and reliability such as heat resistance and solvent resistance.
The dye may be selected from acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of the acid dyes with nitrogen-containing compounds, sulfonamide compounds of the acid dyes, and derivatives thereof, and azo-based, xanthene-based, phthalocyanine-based acid dyes, and derivatives thereof. From The viewpoint of color, it is preferable to select dyes of The red, violet, and deep red series, and there are compounds classified as dyes in The color index (published by The Society of Dyers and Colourists) or red dyes, blue dyes, violet dyes among known dyes described in The dye book (dyeing history).
Specific examples of the dye include, first, red dyes such as c.i. solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, and 179 as c.i. solvent dyes, among which c.i. solvent red 8, 49, 89, 111, 122, 132, 146, and 179 which are excellent in solubility in organic solvents in c.i. solvent dyes are preferable, and among them, c.i. solvent red 8, 122, and 132 are more preferable.
Further, as the c.i. acid dye, there are red dyes such as c.i. acid red 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, 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, 426 and the like, and among them, c.i. acid red52, 92 having excellent solubility in an organic solvent is preferable. Further, c.i. acid blue 80, 90 and c.i. acid violet 66 are preferable.
Examples of the c.i. direct dye include red dyes such as c.i. direct red 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.
Further, red dyes such as c.i. media red 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, 95 and the like can be cited.
In the present invention, the above dyes may be used alone or in combination of two or more.
The content of the dye (a2) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, and particularly preferably 1 to 50% by weight, based on the total solid content in the colorant (A). In the above-mentioned manner, when the content of the dye in the colorant (a) is within the above-mentioned range, the problem of lowering the reliability of dye elution due to an organic solvent after patterning can be prevented, and the sensitivity is excellent, which is preferable.
The content of the colorant (a) is 5 to 60% by weight, preferably 10 to 45% by weight, based on the total solid content in the colored photosensitive resin composition of the present invention.
This is because, when the colorant (A) is contained in an amount of 5 to 60% by weight based on the above criteria, the color density of the pixel becomes full even when a thin film is formed, and the omission of the non-pixel portion during development is large
Figure BDA0000679649750000081
It is also preferable because it is not lowered and thus it is difficult to generate residue.
In the present invention, the content of the total solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent in the colored photosensitive resin composition.
Alkali soluble resin (B)
In order to make the alkali developer used in the developing step in forming a pattern soluble, an ethylenically unsaturated monomer (b1) having a carboxyl group is copolymerized as an essential component. The alkali-soluble resin (B) has an acid value of 30 to 150mgKOH/g in order to ensure compatibility with the dye (a2) and storage stability of the colored photosensitive resin composition of the present invention.
If the acid value of the alkali-soluble resin (B) is less than 30mgKOH/g, it is difficult to secure a sufficient development speed in the colored photosensitive resin composition, and if it is more than 150mgKOH/g, a short circuit of a pattern is likely to occur due to a decrease in adhesion to a substrate, and a problem occurs in compatibility with a dye, so that the dye in the colored photosensitive resin composition is precipitated, or the viscosity is likely to increase due to a decrease in storage safety of the colored photosensitive resin composition.
Specific examples of the carboxyl group-containing ethylenically unsaturated monomer (b1) 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 dicarboxylic acids; mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy-polycaprolactone mono (meth) acrylate; among them, acrylic acid and methacrylic acid are preferable.
In order to provide a hydroxyl group to the alkali-soluble resin (B), the resin composition can be produced by copolymerizing an ethylenically unsaturated monomer having a carboxyl group (B1) and an ethylenically unsaturated monomer having a hydroxyl group (B2), and can be produced by reacting an ethylenically unsaturated monomer having a carboxyl group (B1) and a compound having a glycidyl group (B3). The alkali-soluble resin (B) can also be produced by further reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group (B1) and an ethylenically unsaturated monomer having a hydroxyl group (B2) with a compound having a glycidyl group (B3).
Specific examples of the above-mentioned ethylenically unsaturated monomer having a hydroxyl group (b2) include hydroxyethyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and N-hydroxyethyl acrylamide.
Specific examples of the glycidyl group-containing compound (b3) include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-tert-butyl benzoate, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate and the like, and among them, butyl glycidyl ether, aryl glycidyl ether and glycidyl methacrylate are preferable. The glycidyl group-containing compounds (b3) exemplified above may be used alone or in combination of two or more.
In addition, in the production of the alkali-soluble resin (B), the ethylenically unsaturated monomer having a carboxyl group (B1) may be copolymerized with an ethylenically unsaturated monomer having a hydroxyl group (B2) and a compound having a glycidyl group (B3), or may be copolymerized with an unsaturated monomer (B4) capable of copolymerization.
The kind of the above-mentioned copolymerizable unsaturated monomer (b4) is exemplified below, but not limited thereto.
specific examples of the unsaturated monomer (b4) capable of effecting copolymerization 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, p-vinylbenzyl glycidyl ether and the like;
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;
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) acrylic acids such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate, 2-dicyclopentyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;
aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
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.
The monomers exemplified as the above-mentioned copolymerizable unsaturated monomer (b4) may be used alone or in combination of two or more.
The content of the alkali-soluble resin (B) is in the range of 10 to 80 wt%, preferably 10 to 70 wt%, based on the total solid content in the photosensitive resin composition of the present invention. In the above-mentioned manner, when the content of the alkali-soluble resin (B) is 10 to 80% by weight, the alkali-soluble resin (B) is preferably used because it has sufficient solubility in a developer to facilitate patterning, and prevents a decrease in film at a pixel portion of an exposed portion during development and an improvement in omission at a non-pixel portion.
Photopolymerizable compound (C)
The photopolymerizable compound (C) is a compound that can be polymerized by the action of the photopolymerization initiator (D) described below, and a monofunctional monomer (C1), a difunctional monomer (C2), or a polyfunctional monomer (C3) may be used, and preferably, a polyfunctional monomer (C3) having two or more functionalities may be used.
Specific examples of the monofunctional monomer (c1) include, but are not limited to, nonylphenylcarbinol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.
Specific examples of the bifunctional monomer (c2) include, but are not limited to, 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.
Specific examples of the polyfunctional monomer (c3) include, but are not limited to, trimethylolpropane tri (meth) acrylate, ethoxytrimethylolpropane tri (meth) acrylate, propoxytrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxydipentaerythritol hexa (meth) acrylate, propoxydipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
The photopolymerizable compound (C) is contained preferably in an amount of 5 to 45% by weight, more preferably 7 to 45% by weight, based on the total solid content in the colored photosensitive resin composition of the invention. When the photopolymerizable compound (C) is contained in an amount of 5 to 45 wt% based on the above, the strength and smoothness of the pixel portion are preferably improved.
Photopolymerization initiator (D)
The photopolymerization initiator (D) contains a photopolymerization initiator (D1) having a structure of the following chemical formula 1 as a component.
[ chemical formula 1]
Figure BDA0000679649750000111
[ chemical formula 2]
-R4-R5
In chemical formula 1, R1 is represented by chemical formula 2, in chemical formula 2, R4 may be an alkyl group having from C1 to C4, R5 may be an alkyl group having from C3 to C8 or a cycloalkyl group, R2 may be an alkyl group having from C1 to C8, a phenyl group, a substituted or unsubstituted benzyl group, and R3 may be a diphenylthio group.
The photopolymerization initiator (d1) having the structure of chemical formula 1 above can express effective photopolymerization characteristics to a colored photosensitive resin composition containing a dye as a colorant by preventing the decrease in sensitivity and transmittance due to the dye.
Examples of the photopolymerization initiator (d1) of the above chemical formula 1 include TR-PBG-305.
Further, it is also possible to use a photopolymerization initiator (d2) other than the above in combination within a range not impairing the effects of the present invention, and it is typically preferable to use one or more compounds selected from acetophenone compounds, benzophenone compounds, triazine compounds, bisimidazole compounds and thioxanthone compounds.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylmethanone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and mixtures thereof, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
Examples of the benzophenone-based compound include benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone.
Specific 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) ethyl ] triazine Alkenyl ] -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.
Specific examples of the biimidazole compounds 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, 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (trialkoxyphenyl) biimidazole, 2' -bis (2, 6-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, or an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carbonylalkyl group, and the like. Among them, 2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2 '-bis (2, 6-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole are preferably used.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
In order to improve the sensitivity of the colored photosensitive resin composition of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiation aid (D3). The colored photosensitive resin composition of the present invention contains the photopolymerization initiation aid (d3) to improve the sensitivity and improve the productivity.
The photopolymerization initiator (d3) may preferably be at least one compound selected from the group consisting of amine compounds, carboxylic acid compounds and organic sulfur compounds having a thiol group.
As the amine compound, an aromatic amine compound is preferably used, and specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (collectively, mikkonide), 4' -bis (diethylamino) benzophenone and the like can be used.
The carboxylic acid compound is preferably an aromatic heterocyclic acetic acid compound, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.
Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1, 4-bis (3-mercaptobutoxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6, (1H,3H,5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like.
The photopolymerization initiator (D) may be contained in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the solid content, based on 100 parts by weight of the total of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator (D) is in the range of 0.1 to 40 parts by weight, the colored photosensitive resin composition is highly sensitive, and thus the exposure time is shortened, the productivity is improved, and the high resolution can be maintained, which is preferable.
Further, the strength of the pixel portion and the smoothness of the surface of the pixel portion formed by using the composition satisfying the above conditions can be improved. The photopolymerization initiator (D1) having the structure of formula 1 should be contained in an amount of 10 to 100 wt%, preferably 20 to 100 wt%, based on the total amount of the photopolymerization initiator (D).
If the ratio of the photopolymerization initiator (d1) having the structure of chemical formula 1 to the total photopolymerization initiators is less than 10% by weight, the decrease in sensitivity due to the dye cannot be suppressed, and the pattern short-circuit is likely to occur in the developing process
Figure BDA0000679649750000141
When the photopolymerization initiation aid (d3) is used, the photopolymerization initiation aid (d3) may be contained in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the solid content, based on 100 parts by weight of the sum of the alkali-soluble resin (B) and the photopolymerizable compound (C).
When the amount of the photopolymerization initiator aid (d3) is in the range of 0.1 to 40 parts by weight, the sensitivity of the colored photosensitive resin composition can be further improved, and the effect of improving the productivity of a color filter formed by using the composition can be provided.
Antioxidant (E)
The antioxidant (E) contains one or more phenolic antioxidants and one or more phosphorus antioxidants as essential components, and the phenolic antioxidants should not be deteriorated in an oven at 150 ℃ for 200 hours or more.
Most of the problem of the decrease in transmittance is caused by yellowing occurring when hard baking is performed, like the red colored photosensitive resin composition, which can suppress the decrease in transmittance by using the above antioxidant (E), and particularly, since hard baking is mostly performed at 220 degrees or more, the antioxidant should not be deteriorated at the corresponding temperature when hard baking is performed in order to maximize the effect of the antioxidant.
However, if an antioxidant having low heat resistance is used, it is necessary to use an amount of 2 to 3 times that of an antioxidant having high heat resistance in order to obtain an effect of suppressing yellowing, and thus, if an excessive amount of the antioxidant is used, the antioxidant is yellowed, and thus transmittance is decreased, and the effect of suppressing the transmittance decrease is difficult to be expected.
On the other hand, if the phenolic antioxidant satisfying the above-described condition that it is not deteriorated for 200 hours or more in an oven at 150 ℃ is used, it continues to function in the subsequent step, and the problem of the decrease in transmittance occurring when the subsequent step is performed can be minimized.
Therefore, in the present invention, a phenol-based antioxidant which is not deteriorated for 200 hours or more in an oven at 150 ℃ is used, a hindered phenol-based antioxidant is preferably used, and specific examples are as follows.
Octadecyl3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (octadecenyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (264 hours), 1,3,5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (3, 5-di-tert-butyl-b-butyl-4-hydroxybenzyl) bezene) (240 hours), pentaerythrityl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)) (960 hours), the time in parentheses indicates the time during which the phenolic antioxidant is not deteriorated in the oven at 150 ℃.
Specific examples of the above-mentioned phosphorus-based antioxidant are as follows.
Triphenyl phosphate (triphenylphosphate), isodecyldiphenyl phosphate (isodecyldiphenyl phosphate), Tris (2, 4-di-tert-butylphenyl) phosphate (Tris (2, 4-di-tert-butylphenyl) phosphate), 3,9-Bis (octadecyloxy) -2,4,8,10-tetraoxa-3, 9-diphosphospiro [5.5] undecane (3,9-Bis (octadecyloxy) -2,4,8,10-tetraoxa-3, 9-diphosphaspiro [5.5] undecan), 2'-methylenebis (4, 6-di-tert-butylphenyl) -2-ethylhexyl phosphate (2,2' -methylinebis (4, 6-di-tert-butylphenyl) -2-ethylhexyl phosphate).
According to a preferred embodiment of the present invention, the weight ratio of the phenolic antioxidant to the phosphorus antioxidant in the antioxidants may be 1:1 to 5:1, and more preferably 1.5:1 to 3: 1. When the weight ratio is within the above range, yellowing and reduction in transmittance can be prevented. In the composition of the present invention, it is preferable that the amount of the phenolic antioxidant is larger than that of the phosphorus antioxidant because the trapping of the free radicals which function as the phenolic antioxidant exerts a greater influence. However, when the amount of the phenolic antioxidant is too large, a problem of partial transmittance reduction occurs, and therefore, it is preferably used as appropriate.
The antioxidant (E) may be contained in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the photopolymerization initiator (D) as a solid component. When the content of the antioxidant (E) is in the range of 1 to 100 parts by weight, the transmittance of the colored photosensitive resin composition can be expected to be improved without decreasing the sensitivity, and therefore, the content is preferable. If the content of the antioxidant (E) is less than 1 part by weight, it is difficult to expect improvement of transmittance, and if the content of the antioxidant (E) is more than 100 parts by weight, it is difficult to suppress a decrease in sensitivity due to a dye, so that it is difficult to achieve high sensitivity, and a pattern short is easily generated in a developing process.
Solvent (F)
The solvent (F) is not particularly limited as long as it can effectively dissolve other components contained in the colored photosensitive resin composition, and is a solvent (F) generally used for colored photosensitive resin compositions, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, or the like are preferable.
Specific examples of the solvent (F) 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 ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether glycol, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl pentanone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; and esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ -butyrolactone.
The solvent (F) is preferably an organic solvent having a boiling point of 100 to 200 ℃ from the viewpoint of coating properties and drying properties, and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like are more preferably used.
The above-exemplified solvents (F) may be used alone or in combination of two or more, and the solvent (F) may be contained in an amount of 60 to 90 wt%, preferably 70 to 85 wt%, based on the total weight of the colored photosensitive resin composition of the present invention.
When the content of the solvent (F) is in the range of 60 to 90% by weight, an effect of improving the coating property can be provided when the coating is performed by using a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an ink jet.
Additive (G)
In addition to the above components, the colored photosensitive resin composition of the present invention may further contain additives (G) such as a filler (G1), another polymer compound (G2), a curing agent (G3), an adhesion promoter (G4), an ultraviolet absorber (G5) and an anti-agglomeration agent (G6) as required by the skilled person, within a range not to impair the object of the present invention.
Specific examples of the filler (g1) include glass, silica, and alumina, but are not limited thereto.
As the other polymer compound (g2), specifically, a curable resin such as an epoxy resin or a maleimide resin; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane, but the invention is not limited thereto.
The curing agent (g3) is used for achieving deep curing and improving mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound and the like can be used, but is not limited thereto. Specific examples of the epoxy compound include, but are not limited to, bisphenol a epoxy resins, hydrogenated bisphenol a epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, brominated derivatives of these epoxy resins, aliphatic and alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, epoxides of butadiene (co) polymers, epoxides of isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate. Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, but the compound is not limited thereto.
The curing agent may be used together with a curing agent as a curing auxiliary compound capable of ring-opening polymerizing the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. As the curing auxiliary compound, specifically, polycarboxylic acids, polycarboxylic anhydrides, acid generators and the like can be used. The carboxylic acid anhydrides can be used as commercially available epoxy resin curing agents. Examples of the commercially available epoxy resin curing agent include ADEKA HARDENER EH-700 (trade name) (manufactured by Adek industries, Ltd.), RIKACID HH (trade name) (manufactured by Nissian chemical and physical Co., Ltd.), MH-700 (trade name) (manufactured by Nissian chemical and physical Co., Ltd.), and the like.
The curing agents and curing auxiliary compounds exemplified above may be used alone or in combination of two or more.
Specifically, the adhesion promoter (g4) may be selected from 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-epoxycyclohexane) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, thiopropyltrimethoxysilane, and the like, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, or mixtures thereof.
The adhesion promoter may be contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total solid content of the colored photosensitive resin composition of the present invention.
Specifically, the ultraviolet absorber (g5) may be 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, or the like, but is not limited thereto.
Specifically, sodium polyacrylate or the like can be used as the anti-agglomeration agent (g6), but the agent is not limited thereto.
The method for producing the colored photosensitive resin composition of the present invention can be exemplified as follows.
First, the pigment (a1) in the colorant (A) and the solvent (F) are mixed and dispersed by a bead mill or the like until the average particle diameter of the pigment becomes 0.2 μm or less. In this case, the pigment dispersant (a3), a part or the whole of the alkali-soluble resin (B), or the dye (a2) may be mixed with the solvent (F) as needed to dissolve or disperse the pigment dispersant (a3), the alkali-soluble resin, or the dye.
The colored photosensitive resin composition of the present invention can be produced by adding the dye (a2), the remaining alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and the antioxidant (E) to the mixed dispersion, and if necessary, adding the additive (G) and the solvent (F) to a predetermined concentration.
Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are merely illustrative, and the scope of the present invention is not limited to these embodiments. The claims of the present invention show the scope of the present invention, and include all modifications that have the same meaning as described in the claims of the present invention and are within the scope equivalent to the description of the claims of the present invention. In the following examples and comparative examples, unless otherwise specified, "%" and "part(s)" representing the content are based on weight.
Examples of the experiments
Production of pigment Dispersion composition
< pigment Dispersion composition M1>
10.85 parts by weight of C.I. pigment Red 254, 3.80 parts by weight of AJISPUR PB821 (manufactured by Ajinomoto FineTechno Co., Ltd.) as a dispersant, 76.90 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 8.45 parts by weight of cyclohexanone were mixed and dispersed for 12 hours by means of a bead mill, thereby producing a pigment dispersion M1.
Synthesis of alkali soluble resins
< Synthesis example 1>
Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube were charged 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of Azobisisobutyronitrile (AIBN), 13.0 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57.0 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate and 3 parts by weight of n-dodecylmercaptan, and nitrogen substitution was performed. Then, the reaction mixture was stirred, and the temperature of the reaction mixture was raised to 110 ℃ to carry out the reaction for 6 hours. The solid content of the alkali-soluble resin thus synthesized had an acid value of 100.2mgKOH/g and a weight average molecular weight Mw measured by Gel Permeation Chromatography (GPC) was about 15110.
Production of colored photosensitive resin composition
< example 1>
36.50 parts by weight of the above-mentioned < pigment dispersion composition M1>, 0.54 part by weight of Acid Red (Acid Red52, TCI America), 10.11 parts by weight of the resin of < Synthesis example 1>, 3.86 parts by weight of KAYARAD DPHA (manufactured by Nippon Chemicals Co., Ltd.), 1.00 part by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), 0.23 part by weight of 1,3,5-Trimethyl-2,4,6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene (1,3, 5-trimethy-2, 4,6-tris (3, 5-di-t-butyl-4-hydroybenzyl) pentanone) (240 hours, Aldrich Co., 0.15 part by weight of Triphenyl phosphate (triphenyphosphate) (Oxyphenyl) as a phosphorus antioxidant, 12.75 parts by weight of 2-hydroxy methyl-4-benzyl) benzene (3, 5-Trimethyl-2,4,6-tris (3, 5-di-t-tert-butyl-4-hydroxybenzyl) pentanone) (240 hours, Aldrich Co., 4-methyl-4-, 34.85 parts by weight of propylene glycol monomethyl ether acetate to produce a colored photosensitive resin composition.
< example 2>
36.50 parts by weight of the above-mentioned < pigment dispersion composition M1>, 0.54 part by weight of Acid Red (Acid Red52, TCI America), 10.11 parts by weight of the resin of < Synthesis example 1>, 3.86 parts by weight of KAYARAD DPHA (manufactured by Nippon Kagaku Co., Ltd.), 1.00 part by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), a colored photosensitive resin composition was prepared from 0.23 parts by weight of Octadecyl3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (octadecenyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) as a phenolic antioxidant (264 hours, aldrich), 0.15 parts by weight of Triphenyl phosphate (aldrich) as a phosphorus antioxidant, 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone, and 34.85 parts by weight of propylene glycol monomethyl ether acetate.
< example 3>
36.50 parts by weight of the above-mentioned < pigment dispersion composition M1>, 0.54 part by weight of Acid Red (Acid Red52, TCI America), 10.11 parts by weight of the resin of < Synthesis example 1>, 3.86 parts by weight of KAYARAD DPHA (manufactured by Nippon Kagaku Co., Ltd.), 1.00 part by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), 0.23 parts by weight of pentaerythrityl tetrakis (3, 5-di-t-butyl-4-hydroxyhydrocinnamate) (pentaerythrityl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)) as a phenolic antioxidant (960 hours, aldrich), 0.15 parts by weight of Triphenyl phosphate (Triphenyl phosphate) as a phosphorus antioxidant (aldrich), 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone, and 34.85 parts by weight of propylene glycol monomethyl ether acetate were used to prepare a colored photosensitive resin composition.
< comparative example 1>
36.50 parts by weight of the above pigment dispersion composition M1, 0.54 part by weight of Acid Red (Acid Red52, TCI America), 10.56 parts by weight of the resin of Synthesis example 1, 4.03 parts by weight of KAYARAD DPHA (manufactured by Nippon chemical Co., Ltd.), 1.05 parts by weight of TR-PBG-305 (manufactured by TRONLY), 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone, and 34.85 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.
< comparative example 2>
36.50 parts by weight of the above-mentioned < pigment dispersion composition M1>, 0.54 parts by weight of Acid Red (Acid Red52, TCI America), 10.28 parts by weight of the resin of < Synthesis example 1>, 3.93 parts by weight of KAYARAD DPHA (manufactured by Nippon chemical Co., Ltd.), 1.02 parts by weight of TR-PBG-305 (manufactured by TRONLY), 0.24 parts by weight of tetrakis (3, 5-di-t-butyl-4-hydroxyhydrocinnamic Acid) Pentaerythritol ester (Pentaerythritol tetrakis (3, 5-di-t-butyl-4-hydroxyhydrocinnamate)) as a phenolic antioxidant (960 hours, Aldrich), 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone, 34.74 parts by weight of propylene glycol monomethyl ether monoacetate were mixed to produce a colored photosensitive resin composition.
< comparative example 3>
36.50 parts by weight of the above pigment dispersion composition M1, 0.54 part by weight of Acid Red (Acid Red52, TCI America), 10.37 parts by weight of the resin of Synthesis example 1, 3.96 parts by weight of KAYARAD DPHA (manufactured by Nippon Chemicals), 1.03 parts by weight of TR-PBG-305 (manufactured by TRONLY), 0.16 part by weight of Triphenyl phosphate (Triphenyl phosphate) as a phosphorus antioxidant (Aldrich), 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone, and 34.69 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.
< comparative example 4>
36.50 parts by weight of the above-mentioned < pigment dispersion composition M1>, 0.54 part by weight of Acid Red (Acid Red52, TCI America), 10.11 parts by weight of the resin of < Synthesis example 1>, 3.86 parts by weight of KAYARAD DPHA (manufactured by Nippon Kagaku Co., Ltd.), 1.00 part by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), the colored photosensitive resin composition was prepared from 0.23 parts by weight of 2,6-Di-tert-butyl-4-methylphenol (2,6-Di-tert-butyl-4-methylphenol) as a phenolic antioxidant (48 hours, aldrich), 0.15 parts by weight of Triphenyl phosphate (aldrich) as a phosphorus antioxidant, 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone, and 34.85 parts by weight of propylene glycol monomethyl ether acetate.
< comparative example 5>
36.50 parts by weight of the above-mentioned < pigment dispersion composition M1>, 0.54 part by weight of Acid Red (Acid Red52, TCI America), 10.11 parts by weight of the resin of < Synthesis example 1>, 3.86 parts by weight of KAYARAD DPHA (manufactured by Nippon Kagaku Co., Ltd.), 1.00 part by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), the colored photosensitive resin composition was prepared from 0.23 parts by weight of 4,4'-Butylidenebis (6-tert-butyl-m-cresol) (4,4' -Butylidenebis (6-tert-butyl-m-cresol)) as a phenolic antioxidant (48 hours, aldrich), 0.15 parts by weight of Triphenyl phosphate (aldrich) as a phosphorus antioxidant, 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone, and 34.85 parts by weight of propylene glycol monomethyl ether acetate.
< comparative example 6>
36.50 parts by weight of the above-mentioned < pigment dispersion composition M1>, 0.54 parts by weight of Acid Red (Acid Red52, TCI America), 10.11 parts by weight of the resin of < Synthesis example 1>, 3.86 parts by weight of KAYARAD DPHA (manufactured by Nippon Chemicals Co., Ltd.), 1.00 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), 0.23 parts by weight of 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane (1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane (120 hours, Aldrich) as a phenolic antioxidant, 0.15 parts by weight of Triphenyl phosphate (Aldrich) as a phosphorus antioxidant, 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone (Aldrich) were mixed together, 34.85 parts by weight of propylene glycol monomethyl ether acetate to produce a colored photosensitive resin composition.
< Experimental example 1> measurement of adhesion, color difference and transmittance
Color filters were produced using the colored photosensitive resin compositions produced in examples 1 to 3 and comparative examples 1 to 6 described above.
Specifically, each of the colored photosensitive resin compositions was applied on a 2-inch square glass substrate ("EAGLE XG" manufactured by corning corporation) by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes, thereby forming a thin film. Next, a test photomask having a pattern in which the transmittance is changed stepwise in the range of 1% to 100% and a line/space pattern of 1 μm to 100 μm was placed on the above filmUltraviolet rays were irradiated so as to form a space of 300 μm from the test photomask. In this case, a 1KW high-pressure mercury lamp containing g, h and i lines was used as the ultraviolet light source at a rate of 100mJ/cm2Is irradiated, and no special optical filter is used. The film irradiated with ultraviolet rays was immersed in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes to perform development. After the film-coated glass plate was washed with distilled water, it was dried by blowing nitrogen gas and heated in a heating oven at 230 ℃ for 25 minutes, thereby manufacturing a color filter.
The film thickness of the color filter produced in the above was 2.0 μm.
< adhesion >
When the generated pattern was evaluated by an optical microscope, peeling on the pattern was evaluated as follows
Figure BDA0000679649750000221
Degree of phenomenon, and is shown below<TABLE 1>。
No peeling on the pattern.
△ peeling 1-3 patterns.
X: more than 4 strips are peeled off from the pattern.
< measurement of color Difference and transmittance >
The transmittance of the substrate manufactured in < experimental example 1> was measured for a 100 μm pattern using a colorimeter (OSP-200, manufactured by olympus corporation), and then hard baking was additionally performed at 230 degrees for 25 minutes for 6 times, and then the transmittance was measured again, and the average transmittance change rate was shown in table 1.
The results of the above experimental example 1 are shown in table 1.
< developing speed >
The time required for the non-exposed portion to be completely dissolved in the developing solution during development was measured and shown in table 1 below.
TABLE 1
Adhesion Property Development speed (seconds) color difference (△ y) Transmittance of light Average rate of change of transmission
Example 1 ○ 14 0.0025 17.56 97.6％
Example 2 ○ 14 0.0021 17.57 97.9％
Example 3 ○ 14 0.0017 17.66 98.5％
Comparative example 1 △ 18 0.0033 17.35 96.8％
Comparative example 2 △ 18 0.0029 17.38 97.2％
Comparative example 3 ○ 14 0.0031 17.37 97.0％
Comparative example 4 ○ 15 0.0025 17.48 97.2％
Comparative example 5 ○ 14 0.0020 17.46 97.1％
Comparative example 6 ○ 14 0.0020 17.50 97.4％
Referring to table 1 above, it was confirmed that the color filters produced from the colored photosensitive resin compositions of examples 1,2 and 3 did not cause pattern peeling due to excellent adhesion, and were high in development speed, less in color difference and excellent in transmittance.

Claims (6)

1. A colored photosensitive resin composition for red pixels, which comprises a colorant A, an alkali-soluble resin B, a photopolymerizable compound C, a photopolymerization initiator D, an antioxidant E and a solvent F, wherein the colorant A comprises one or more pigments a1 and one or more dyes a2, one or more of the pigments a1 and the dyes a2 is a red color system, the photopolymerization initiator D comprises a dithiophene-containing oxime ester photoinitiator represented by the following chemical formula 1, the antioxidant E comprises 1 or more phenolic antioxidants and 1 or more phosphorus antioxidants, and the phenolic antioxidants are not deteriorated at 150 ℃ for 200 hours or longer,
chemical formula 1:
Figure FDA0002436937140000011
in the above-mentioned formula, the compound of formula,
r1 is represented by the following chemical formula 2,
r2 is C1-C8 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl,
r3 is diphenylthio;
chemical formula 2:
-R4-R5
wherein R4 is an alkylene group having from C1 to C4,
r5 is C3-C8 alkyl or cycloalkyl,
wherein the pigment is selected from the group consisting of c.i. pigment yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 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; at least one of c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264,
wherein the phenolic antioxidant comprises at least one selected from octadecyl3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
the phosphorus antioxidant comprises at least one selected from triphenyl phosphate, isodecyldiphenyl phosphate, tris (2, 4-di-tert-butylphenyl) phosphate, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, and 2,2' -methylenebis (4, 6-di-tert-butylphenyl) -2-ethylhexyl phosphate,
in the antioxidant, the weight ratio of the phenolic antioxidant to the phosphorus antioxidant is 1:1 to 5: 1.
2. The colored photosensitive resin composition for red pixels according to claim 1, wherein the antioxidant E is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the photopolymerization initiator D based on solid content.
3. The colored photosensitive resin composition for red pixels according to claim 1, comprising 5 to 60% by weight of a colorant A, 10 to 80% by weight of an alkali-soluble resin B and 5 to 45% by weight of a photopolymerizable compound C, based on the total solid content in the colored photosensitive resin composition; the photopolymerization initiator D is contained in an amount of 0.1 to 40 parts by weight based on the solid content per 100 parts by weight of the sum of the alkali-soluble resin B and the photopolymerizable compound C.
4. The colored photosensitive resin composition for red pixels according to claim 1, wherein the dye a2 is contained in an amount of 0.5 to 80% by weight based on the total solid content in the colorant A.
5. A color filter comprising the colored photosensitive resin composition for red pixels according to claim 1.
6. A liquid crystal display device comprising the color filter according to claim 5.
CN201510103384.4A 2014-03-10 2015-03-10 Colored photosensitive resin composition for color filter, and liquid crystal display device provided with same Active CN104914666B (en)

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