TWI272277B - Photopolymerization initiator for color filter, photosensitive coloring composition and color filter - Google Patents

Abstract

To obtain a photopolymerization initiator for high-sensitivity color filters by incorporating a sensitizer having a specific absorption wavelength region, a specific organic boron complex and a compound having a thiol group. A photopolymerization initiator for producing a color filter including a sensitizer (A) which absorbs light having a wavelength of 300 to 500 nm, an organic boron complex (B), and a thiol-group-containing compound (C); a photosensitive coloring composition including a transparent polymer (D) which is soluble to a solvent or an aqueous alkaline solution, a compound having ethylenic unsaturated bonds (E), a pigment (F), and the photopolymerization initiator; a color filter having a pixel formed by use of the coloring composition on a transparent substrate; and a method for producing the color filter.

Description

1272277 A7 B7 V. Technical Description of the Invention (1) The present invention relates to a photopolymerization initiator for a high-sensitivity color filter which can be imaged in a solvent or an alkaline aqueous solution after exposure to ultraviolet light. A high-quality color filter for a color filter, a solid-state imaging device, a color filter used in a liquid crystal display device, and the like. [Prior Technology] In recent years, liquid crystal display devices have been developed to be thinner and larger, and are required to be thinner and less defective for the color filter to be used, and high in resistance to heat resistance and light resistance. Penetration rate, high contrast. Further, at the same time, the cost of the color filter is strongly demanded, and the productivity in the manufacturing process must be improved and the engineering is shortened. The color filter is formed by a fine band (stnp) in which two or more different hues are arranged in parallel or in a cross section on the surface of a transparent substrate such as glass, or a fine pixel is arranged in a vertical and horizontal sequence. The size of the pixels is 1 〇 to 1 〇 〇 micron fine shapes, and the hues must be arranged neatly in the specified order. Therefore, various methods have been proposed for the method of producing a color filter, and a coloring composition using a disperse pigment in a photosensitive composition called a pigment dispersion method is used in many aspects such as precision and manufacturing cost. The method is widely used as a method of manufacturing a color filter. In the pigment dispersion method, a photosensitive coloring composition containing a resin and a crosslinking agent composed of a pigment and a base material is applied onto a substrate, and an optical lithographic image is used to form a color of each color on a specified pattern shape. Floor. That is, the above-mentioned photosensitive coloring composition of one color filter is applied to a transparent substrate such as glass to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) on the paper scale _ 4 - (Please read the back note first) Fill in this page again)

Γ 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 V. DESCRIPTION OF THE INVENTION (2) Coating, pattern exposure is performed 'The unexposed portion is image-removed by a solvent or an alkaline aqueous solution to form a pattern of the first color. Next, the color filter can be manufactured by repeating the same operation for all the color filters in order.感光 In terms of the physical properties of the color filter and the richness of the material, the photosensitive composition is mainly composed of a negative-type photosensitive composition, and is almost alkaline-free due to environmental problems, and is alkaline. The development of aqueous solutions has become mainstream. Regarding exposure, exposure to ultraviolet light is usually performed. In this production process, only a predetermined position of the photosensitive resin composition is exposed to ultraviolet rays or the like, and a chemical reaction which causes a radical polymerization reaction only by the exposed portion is utilized. Since the negative photosensitive composition mainly utilizes a radical polymerization reaction, even if the reaction is inhibited by oxygen in the air, the sensitivity is lowered. In the case of applying a photosensitive composition, an image of an oxygen barrier film such as polyvinyl alcohol is applied thereto, and then an image is exposed. However, from the viewpoint of shortening engineering as described above, it has recently begun to pursue no need. A photopolymerization initiator for a color filter having a high sensitivity such as an oxygen barrier film is provided. For example, Japanese Laid-Open Patent Publication No. Hei 6-2 1 1 1 1 3 discloses a photopolymerization initiator of a triterpenoid compound or an imidazole compound, which is a single triterpenoid compound or an imidazole compound, and is disclosed in Japanese Patent Publication No. 0 0 - 2 5 3 8 1 In the publication No. 3, a photopolymerization initiator in which a polyfunctional thiol compound is combined with at least one compound selected from the group consisting of a diimidazole compound, a tita η 〇cene compound, a tri-farming compound, and a Df diterpene compound has been described. However, although the photopolymerization initiator is used, the photopolymerizable composition for red, green, and blue has a certain degree of sensitivity, but the photopolymerizable composition for black, particularly a composition containing a high concentration of black pigment. In the exposure, the sensitivity of the black pigment is significantly reduced due to the light-shielding property of the black pigment, and there is exposure (please read the back of the note first and then fill in this page)

-ϋ I an ·1 ϋ ϋ ϋ Jr, · ϋ ·ϋ ϋ ϋ «^1 ^1 ί ιf . , This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -5 - 1272277 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (3) shortcomings of light time, hardening is not enough. [Problem to be Solved by the Invention] An object of the present invention is to provide a photopolymerization initiator for a color filter which is highly sensitive to the above problems, a photosensitive coloring composition containing the initiator, and a color filter excellent in each resistance and Its manufacturing method. [Means for Solving the Problem] The inventors of the present invention have found that the sensitizer (A) having an absorption wavelength region in the range of 300 to 500 nm, and the organoboron complex (B) and having a thiol group The photopolymerization initiator characterized by the compound (C) is suitable for use in a color filter, and the above problems can be solved by using the same, and thus the present invention has been accomplished. That is, the present invention is 1) a photopolymerization initiator for a color filter characterized by containing a sensitizer (A) having an absorption wavelength in the range of 300 to 50,000 nm, and a general formula (1) Organic boron complex (B) and compound having a thiol group (C) General formula (1) R 2 i 3 7 +

R 1 — 巳--R · Z 1 R 4 (wherein R 1 , R 2 , R 3 and R 4 each independently represent an alkyl group, an aryl group, an arylalkyl group, an alkenyl group, a heterocyclic group or an alicyclic group, and Z + is Indicates ammonium cations This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -6- _ III ϋ I ϋ I n ϋ ϋ ϋ ϋ ϋ ϋ _ _ I ϋ ii ϋ ϋ ϋ ϋ I (please Read the back of the note first and then fill out this page) 1272277 A7 B7 V. Description of invention (4), cation cation, oxonium cation, pyridinium cation, phosphonium cation, oxonium cation or iodonium cation.) 2) 1) The photopolymerization initiator described, wherein the compound (C) having a thiol group is at least one selected from the group consisting of 2-hydrothiobenzothiazole, pentaerythritol tetrathiopropionate, 3) as described above 1) or 2) The photopolymerization initiator is described, wherein the sensitizer (A) is a benzophenone-containing and/or bis (2-chloro-pre-reading phenyl) mouth, 4, 4, tetraphenyl- 1 2'Mim 1>1⁄4 page i 4 ) A photosensitive coloring composition for a color filter characterized by being contained in a solvent or an alkaline aqueous solution a medium-soluble transparent polymer (D), a compound (E) having an ethylenically unsaturated bond, a pigment (F), and a photopolymerization initiator as described in the above 1) to 3), 5) The color filter is characterized in that a pixel is formed on the transparent substrate by using the coloring composition described in the above 4). 6) A method for producing a color filter comprising the step of forming a photosensitive coloring composition layer for a color filter described in the above 4) on a transparent substrate, and sensitizing the exposed portion via exposure The coloring composition layer is subjected to photohardening work. [Embodiment of the Invention] The present invention will be described in more detail. In the above general formula, the alkyl group of R3 and R4 may have a substituent, and specifically, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and for example, the paper size is applicable to the Chinese country. Standard (CNS) A4 specification (210 X 297 mm) II Ordered by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, R 1

R 1272277 Α7 Β7 V. Description of the invention (5) Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, N-octyl, decyl, cyanomethyl, 4-chlorobutyl, 2-ethylaminoethyl, 2-methoxyethyl, and the like. The aryl group of R1, R2, R3 and R4 in the general formula (1) may have a substituent, and is specifically a substituted or unsubstituted aryl group, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a fluorenyl group, and the like. 4 monomethoxyphenyl, 2-methoxyphenyl, 4-n-butylphenyl, 4-tributylphenyl, zeoliyl, fluorenyl, phenanthryl, 4-mononitrophenyl, 4-trifluoro Tolyl, 4-fluorophenyl, 4-chlorophenyl, 4-dimethylamine phenyl, and the like. The aralkyl group of R1, R2, R3 and R4 in the general formula (1) may have a substituent, and is specifically a substituted or unsubstituted aralkyl group, and examples thereof include a benzyl group, a phenethyl group, and a 1-naphthyl group. Base, 3-naphthylmethyl, 4-methoxybenzyl, and the like. The alkenyl group of R1, R2, R3 and R4 in the general formula (1) may have a substituent, and is specifically a substituted or unsubstituted alkenyl group, and examples thereof include a vinyl group, a propenyl group, a butenyl group, and an octenyl group. Wait. The heterocyclic group of R1, R2, R3 and R4 in the general formula (1) may have a substituent, and specifically a substituted or unsubstituted heterocyclic group, and examples thereof include a pyridyl group, a 4-methylpyridyl group, and a quinine group. A phenyl group, a fluorenyl group or the like. The alicyclic group of R1, R2, R3 and R4 in the general formula (1) may have a substituent, and is specifically a substituted or unsubstituted alicyclic group, and examples thereof include a cyclohexyl group, a 4-methylcyclohexyl group, and a ring. Butyl, cycloheptyl and the like. Among the Z + in the above general formula (1), the so-called ammonium cation may specifically be, for example, tetramethylammonium cation, tetraethylammonium cation, tetra-n-propylammonium cation paper scale applicable to the Chinese National Standard (CNS) A4 specification. (210 X 297 mm) (Please read the phonetic on the back first----, item on this page) Book! · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1272277 A7 B7 V. Description of Invention (6) Ions, tetra-n-butylammonium cation, n-butyltriphenylammonium cation, tetraphenylammonium cation, benzyltriphenyl Ammonium cations and the like. In the Z + in the general formula (1), specific examples of the phosphonium cation include, for example, a triphenylphosphonium cation, a tris(4-methylphenyl) cation, a 4-dibutylphenyldiphenylphosphonium cation, and the like. In the Z+ in the general formula (1), the oxonium cation is specifically, for example, a triphenyloxonium cation, a tris(4-methylphenyl)oxonium cation, a 4-tert-butylphenyldiphenylphosphonium cation or the like. . In the Z+ in the general formula (1), the oxonium cation is specifically, for example, a triphenyloxonium cation, a tris(4-tolyl)oxy iron cation, a 4-tert-butylphenyldiphenyloxy cation, or the like. . Specifically, the so-called pyridinium cation in the Z + in the general formula (1) may, for example, be an N-methylpyridinium cation, an N-n-butylpyridinium cation or the like. In the Z + in the general formula (1), specific examples of the scale cation include, for example, a tetramethylsulfonium cation, a tetra-n-butyl quaternary cation, a tetra-n-octyl squaride cation, a tetraphenyl cation, and a benzyltriphenylphosphonium. Cation and the like. In the z + of the general formula (1) printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs, the so-called iodine-cation cation may specifically be, for example, a diphenyl iodonium cation, a bis(4-methylphenyl) iodonium cation, or two. (4 - tert-butylphenyl) iodonium cation and the like. Examples of the organoboron compound exemplified in the general formula (1) include, for example, tetramethylammonium n-butyltriphenylborate, tetraethylammonium isobutyltriphenylborate, and tetra-n-butylammonium n-butylate. Base tris(4-tributylphenyl)borate, tetra-n-butylammonium n-butyltrinaphthylborate, tetra-n-butyl mirror methyltris (-9- (please read the back note first) Fill in this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperative Printed 1272277 Α7 Β7 V. Invention Description (7) 4-Methylnaphthyl)borate, three Phenylnonyl n-butyl triphenyl borate, triphenyloxonium n-butyl triphenyl borate, triphenyloxonium n-butyl triphenyl borate, triphenyloxonium n-butyltriphenyl Boronate, N-methyl acridine iron n-butyltriphenylborate, N-methylpyridinium-n-butyltriphenylborate, tetraphenyl-n-butyltriphenylborate, Phenyl iodide n-butyl triphenyl borate or the like. The organoboron compound represented by the general formula (1) generally has almost no absorption of more than 300 nm, so that it is not sensitive to a general ultraviolet light source even when used alone, but can be obtained very high by combining a sensitizer. Sensitivity. In the present invention, the organoboron compound (B) is usually blended in an amount of 1 to 60% by weight, preferably 5 to 30% by weight, based on the compound having an ethylenically unsaturated bond. If the amount of the organic boron complex is too small, the polymerization reaction cannot be sufficiently carried out. If the amount is too large, the stability of the composition is lowered, which is economically disadvantageous, which is not preferable. The sensitizer (A) having an absorption wavelength used in the present invention is used in the present invention, and a light polymerization initiator, a sensitizer, a dye or the like having absorption in the wavelength range can be used. Such compounds can be exemplified by cationic pigments, benzophenones, acetophenones, benzophenones, thioxanthones, imidazoles, biimidazoles, coumarins, ketocoumarins, triphenyls. Compounds such as pyridyl, tri-till, and benzoic acid. Further, a compound such as decylphosphine oxide, methylphenylglyoxylic acid, α-pyridylironate, benzyl, camphorquinone or ethylhydrazine can also be used. These compounds may be used alone or in combination of two or more. (Please read the notes on the back and then on this page)

Order ------; - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -10- 1272277 V. Invention description (8) For example, B asic Y e 11 〇w ] 3 6, Basic Orange 2 1, Λ7 !1, 13, 21, 28, $ 2, etc. cationic pigment, benzophenone 4-methylbenzophenone, 4-dimethylamino benzophenone, 4, 4, one Biphenyl 4 4 , bis(diethylamino ) benzophenone, 2 , 4 - diethyl thioxanthone, 2 - thioxyl ketone, N - methylimidazole, 2, 2, a pair (2 - Chlorophenyl)~4,4,,円,5,tetracycline-1,2,-monomethane (hereinafter referred to as H ab I ), 2, 2, a double (2-chlorophenyl)~4,4 , , 5,5, a tetrakis (ethoxyphenyl)-1,2,-diimidin, 2,2, a pair (2-chlorophenyl)-4,4,5,5,~4 (4-bromophenyl)- 1,2,-diimidazole, 2,2,-bis(2,4-dichlorophenyl)-4'4',5,5',-tetraphenyl-1, 2,-diimidazole, 2,2-bis(2-chlorophenyl)-4,4,3-methoxyphenyl)-1,2'~di propyl)-methylphenyl)-4,4 ' ,5,5 , ,5,5,,- four (2,2 '-double (2 - tetraphenyl-1 ' (please read the back of the note before this page) -------- order_1-- - ί!. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 2'-diimidazole, coumarin, 7-diethylamine coumarin, 4-dimethylaminobenzoic acid ethyl ester, etc. can be used alone or in combination In the present invention, the benzophenone compound, the benzoic acid, and the diimidazole compound are preferred, and the above-mentioned HABI is particularly preferable in view of the stability of the initiator and the composition, the polymerization initiation ability, and the like. The sensitizer (A) having an absorption wavelength at 300 to 500 nm is generally 1 to 60% by weight, preferably 2 to 30% by weight based on the compound having an ethylenically unsaturated bond. If too little, the sensitization effect cannot be obtained. If too much, the light absorption by the sensitizer makes the paper scale applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -11 - Ministry of Economic Affairs Intellectual Property Office staff consumption Cooperatives printed 1272277 Δ7 Α7 Β7 V. Description of invention (9) Light penetration efficiency deteriorates and The compound (c) having a thiol group used in the present invention is a compound having a thiol group in the molecule, and examples thereof include 2-hydrothiobenzothiazole, 2-Hexylthiobenzimidazole, 2-hydrothiobenzobenzoxazole, 5-chloro-2-hydrothiobenzothiazole, 2-hydrothio-5-methoxybenzothiazole, 5-quinone Base-1,3,4-thiadiazole-2-thiol, 5-hydrothiol-l-methyltetrazole, 3-hydrothio-tetramethyl- 4H-1, 2,4-three Oxazole, 2-hydrothiol-1-methylimidazole, 2-hydrothiothiazolidine, octanethiol, hexanedithiol, decanedithiol, 1,4-dimethylthiophenyl , butanediol dithiopropionate, butanediol dithioacetate, ethylene glycol dithioacetate, trimethylolpropane trithioacetate, butanediol dithiopropyl Acid ester, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioacetate, trishydroxyethyl trithiopropionate, etc., and especially α-thiolbenzothiazole, 2-hydrothiobenzoate Imidazole, 2-hydrothiobenzoxazole, Trimethylolpropane thioacetate, pentaerythritol tetrakis thiopropionate a polymerized initiator ability preferred. These compounds having a thiol group may be used alone or in combination of two or more. In the present invention, the compound (C) having a thiol group is usually 1 to 60% by weight, preferably 5 to 30% by weight based on the compound having an ethylenically unsaturated bond. If it is too small, the polymerization initiation cannot be performed efficiently, and even if it is too large, the polymerization initiation function cannot be improved, and the physical properties of the cured product are adversely affected, so that it is not preferable. In the present invention, the absorption of the paper size in the range of 300 to 500 nm is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -12- _ I ϋ ϋ 1 ϋ .^1 ϋ A δ, II n · ϋ ϋ — ϋ · ϋ I (please read the note on the back? Matters again on the ifk page)

Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, Printed 1272277 Δ7 Α7 Β7 V. Description of Invention (10) Long-region sensitizer (A), organic boron complex (B) with general formula (1) and sulfur The combination of the alcohol-based compound (C) improves the polymerization performance. The transparent high molecular polymer (D) which is soluble in a solvent or an alkaline aqueous solution used in the present invention means high transparency, that is, a film thickness of 1 μm in the visible light region of 4 0 0 to 70 nm. A polymer having a preferred transmittance in the wavelength region of 80% or more, more preferably 95% or more, and a soluble solution in a developing solution (solvent or alkaline aqueous solution). Such a polymer is a thermosetting resin, a thermoplastic resin, a photosensitive resin, or the like, and a mixture of two or more kinds thereof may be used singly or in combination. However, in the engineering after the manufacture of the enamel film, it is processed at a high temperature. Since it is treated with various solvents or pharmaceuticals, a compound excellent in heat resistance, solvent resistance, and drug resistance is preferably used as the transparent polymer (D). The compound (E) having an ethylenically unsaturated bond used in the present invention generally employs a compound which can be subjected to a radical polymerization (or crosslinking) reaction, which is called a monomer and an oligomer, and may be exemplified by (methyl). Acrylic acid, methyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Various (meth) acrylate, ethylene glycol di(meth) acrylate, pentaerythritol tri (meth) acrylate, styrene, diethyl benzene, (meth) acrylamide, vinyl acetate, N - Hydroxymethyl (meth) acrylamide, dipentaerythritol hexaacrylate, melamine acrylate, epoxy acrylate prepolymer, and the like. However, a polyfunctional (meth)acrylic monomer is preferably used in terms of exposure sensitivity and effects after the effect. (Please read the precautions on the back page again) -ϋ ϋ ϋ 1 ϋ )fJ· 1 ϋ ϋ ^1 ·ϋ ϋ .^1 I #言. - This paper size applies to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) -13- 1272277 A7 B7 V. INSTRUCTIONS (11) 尙 'The term "(meth)acrylic acid" as used herein means any of "methacrylic acid" and "acrylic acid". The hue of the color filter is mainly the black used in the cyan, magenta, yellow, and black matrix portions of the red, green, blue, and subtractive blending systems of the additive color mixing system. The toner is a dye or a pigment, but a pigment is used in terms of heat resistance, light resistance and the like as described above. Further, in order to obtain an appropriate spectrum, two or more kinds of pigments may be used in combination, for example, blue is a combination of cyan pigment and purple pigment, green is a combination of green pigment and yellow pigment, and red is a combination of red pigment and yellow or orange pigment. Appropriate spectrum. The pigment (F) used in the present invention is exemplified by the following. They are all represented by a Color Index Number. C. I. Pigment

Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 1 6 6 , 1 6 8 , CI Pigment Orange 3 6 . 4 3 . 5 1 , 5 5, 5 9 , 6 1 , C. I· Pigment Red 9, 9 7, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217 , 220, 223, 224, 226, 227, 228, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 1 5 . 15:1, 15:4, 15:6, 2 2, 6 0, 6 4, CI Pigment Green 7 , 3 6. CI Pigment Brown 2 3, 2 5, 26, CI Pigment Black 7, and titanium black. This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back and then this page). Order. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed - 14 - 1272277 A7 B7 (Invention) (12) In the photosensitive coloring composition of the present invention, since it is necessary to sufficiently disperse the pigment, and it is necessary to apply a film thickness of 1 to 3 μm on the transparent substrate, in order to impart suitable coating properties, The viscosity is usually adjusted using a solvent. The solvent may, for example, be methanol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diglyme, ethylene glycol diethyl ether, xylene, ethylbenzene, methyl cellosolve, Ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, isoamyl acetate, ethyl lactate, methyl ethyl ketone, acetone, cyclohexanone, etc., may be used alone or in combination of two or more. The photosensitive coloring composition can be produced by using various dicing means such as three honing, two honing, sanding, ultrafine grinding machines, ball milling, kneaders, and paint shakers. A polymerization inhibitor may be added for the purpose of preventing gelation by polymerization or the like during dispersion, and the monomer and the photoinitiator may be blended after the pigment is dispersed. Further, in order to make the dispersion of the pigment good, an appropriate co-dispersant may be added. Since the dispersant aids in dispersing the pigment and has an effect of preventing aggregation after dispersion, a color filter excellent in transparency can be obtained. The color filter of the present invention is generally obtained by applying the photosensitive coloring composition of the present invention to a transparent substrate such as glass and photocuring by exposure. Generally, it is a first project: a process of forming a photosensitive colored resin layer on a transparent substrate, and a second project: a process of pattern exposure by using a pattern mask having a specified pattern on the photosensitive resin layer, : The photosensitive resin layer is developed after exposure of the above pattern, and according to the specified pattern, the photosensitive national paper scale remaining on the transparent substrate is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). (Please read the phonetic transcription on the back first and then on this page) Order·! : Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing -15- 1272277 A7 ____B7___ V. Inventions (13) Resin layer as a layer of pixels, Four items: a process of baking (post-baking) of a transparent substrate forming a pixel layer, and a process of manufacturing the same, but the method of manufacturing the color filter of the present invention is as long as the photosensitive coloring composition of the present invention is used. The object is not limited to the above method. Hereinafter, a preferred color filter manufacturing process in the present invention will be described in detail. In the first step, the photosensitive coloring composition of the present invention is applied onto a transparent substrate such as glass by a coating method such as spray coating, spin coating, smear coating or screen coating. In order to achieve suitable fluidity in the coating machine, the photosensitive coloring composition of the present invention may contain an extender pigment such as barium sulfate, calcium carbonate or vermiculite, in addition to the above solvent, and A leveling agent or a small amount of a surfactant such as a lanthanide or a fluorine-based surfactant is used as a defoaming agent. The photosensitive coloring composition to be applied is a hot air oven, a hot plate or the like, and the solvent is usually dried (prebaked) under the conditions of 60 to 80 ° C for 10 to 30 minutes. If the temperature at this time is too high and the drying time is too long, partial polymerization or crosslinking occurs, and the solubility of the unexposed portion to the developing liquid is lowered, and the development of so-called sintering is caused, which is not preferable. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. The second project is a photosensitive resin layer obtained from the first project, which is usually exposed to ultraviolet light through a light shield having a color filter pattern. The light source is generally an ultra-high pressure mercury lamp, a metal halide lamp, etc., and the ultraviolet light passing through the light shielding is usually more than 300 nm, so the luminance spectrum of the ultrahigh pressure mercury lamp is called i line (3 6 5 nm), h. Line (4 5 5 nm ), g line (4 3 6 nm ) wavelength light is used for polymerization or this paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau Employee Consumption Cooperative Printed 1272277 A7 B7 V. Invention Description (14) Cross-linking reaction. Therefore, the photosensitive coloring composition for the color filter is important for the sensitivity of the above three kinds of luminance lines. The third project is to remove the unexposed unhardened portion by using a weakly alkaline developing solution for the photosensitive resin layer obtained by the second process, that is, to remove the photosensitive resin layer other than the pixel region. The fourth project is to form a transparent substrate for forming a pixel layer obtained in the third project, and baking at about 160 to 300 ° C for about 20 to 30 minutes to obtain a pixel layer of the first color. For each color repeating the fourth-fourth project, a color filter is obtained. [Examples] Hereinafter, the present invention will be described based on examples. In the examples, the "parts" means that the parts by weight are % by weight. Further, the photosensitive composition of the photosensitive color is simply referred to as a photoresist. In the present embodiment, an alkaline development type black photoresist which is widely used as a pigment dispersion method for producing a color filter for a color liquid crystal display is described. Before the examples, a synthesis example of a resin soluble in an aqueous alkali solution is shown. <Resin Solution Production Example 1 > In a four-liter flask of one liter volume, 350 parts of cyclohexanone, 26 parts of styrene, 23 parts of ethyl hydroxyethyl acrylate, and 35 parts of methacrylic acid were charged. 2 parts of methyl methacrylate, 70 parts of butyl methacrylate, and heated at 90 ° C, and previously dissolved and dissolved cyclohexanone 2000 parts, styrene 26 parts, acrylic acid B - 3 parts of hydroxyethyl ester, 35 parts of methacrylic acid, 21 parts of methyl methacrylate, 70 parts of butyl methacrylate and 1 7.5 parts of azobisisobutyronitrile on 3 paper scales Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -17- (Please read the note on the back page and then on this page) 1·%-.

Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. 1272277 A7 B7 V. Description of the invention (15) Drops in the hour and reacts for another 3 hours at 90 °C. Further, 10 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued for 1 hour to synthesize a resin solution. A part of the resin solution was collected, and dried by heating at 180 ° C for 20 minutes, and the non-volatile component was measured. In the previously synthesized resin solution, cyclohexanone was added to make the non-volatile component 20%, which was prepared into a resin. Solution 1. <Resin Solution Production Example 2 > In a four-liter flask having a volume of one liter, 35 parts of cyclohexanone, 26 parts of styrene, 44 parts of ethyl hydroxyethyl acrylate, 35 parts of acrylic acid, and methyl group were charged. 70 parts of butyl acrylate, heated in 90 t, and previously mixed to dissolve 900 parts of cyclohexanone, 26 parts of styrene, 23 parts of ethyl hydroxyethyl acrylate, 35 parts of acrylic acid, methyl 70 parts of butyl acrylate and 1 · 7 parts of azobisisobutyronitrile were dropped over 3 hours and further reacted at 90 ° C for 3 hours. Further, a solution of 0.15 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was continued for 1 hour to synthesize a resin solution. Next, the internal temperature of the flask was made to 80 ° C, and a solution of 24 parts of cyclohexanone methacrylate dissolved in 4 parts of cyclohexanone and tin octoate 0.1 1 part was dropped over about 10 minutes. And after reacting for 20 minutes after dropping, the resin solution was synthesized. Next, it was treated with the resin solution 1, and cyclohexanone was added to prepare a resin solution 2 having a nonvolatile content of 20%. (Examples 1 to 5) Preparation of black photoresist: Mixed resin solution: 5 5 parts

SpecialBlack (manufactured by Degussa): 5 · 7 copies

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -Ί» - A7 1272277 —__________B7_ V. Description of invention (16) Dispersant: 0.29 parts of cyclohexanone: 7.8 parts It was dispersed by a paint shaker for 24 hours to prepare a black dispersion. Next, the black dispersion: 5 4 ♦ 15 parts of NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.85 parts of sensitizer: 〇·7~1 · 8 parts of organic boron complex: 0 · 9 parts. Compound: 0 · 9 parts of cyclohexanone: 3 9 · 0 parts were thoroughly mixed in a container, and filtered through a filter paper of 1 · 〇 micron to prepare a black resist of about 20% non-volatile content. The composition ratios of the sensitizer, the organoboron compound, the thiol compound, and the sensitizer are shown in Table 1. (Please read the note on the back of the page first) The Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives, Printed on this paper scale, applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -19- 1272277 A7 B7 V. Description of invention (17) Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs [Table 1] 7 to 1.8 parts of the sensitizer) Organic boron complex (0.9 parts) Mercaptan compound (〇.9 m 1 Basic Yellow 21 ( 0.3 parts) ethyl ketone (0.4 parts) HABI (1.0 parts) tetrabutylammonium butyl triphenyl borate 2-hydrothiobenzothiazole 2 Basic Yellow 21 (0.3 parts) ethyl ketone Φ .4 parts) ΗΑΒΙ (1.0 parts) Tetrabutylammonium butyl tris(4-methylnaphthyl)borate 2-Hydroxythiobenzothiazole 3 Basic Yellow 21 (0.3 parts) Ethyl ketone (0.4 parts) HABI (1.0 parts) Tetrabutylammonium methyl tris(4-methylnaphthyl)borate 2-Hydroxythiobenzothiazole 4 Basic Yellow 21 (0.3 parts) Ethyl ketone (0.4 parts) HABI ( 1.0 part) Tetrabutylammonium methyl tris(winter methyl ketone) borate pentaerythritol tetrathiopropionate 5 Basic Yellow 21 Φ.3 parts) HABI (1.0 parts) Tetrabutylammonium methyltris(4-methylnaphthyl)borate 2-Hydroxythiobenzothiazole 6 Basic Yellow 21 (0.3 parts) Ethyl methylene ketone (0.4 parts) Tetrabutylammonium Methyl tris(4-methylnaphthyl)borate 2-Hydroxybenzobenzothiazole 7 Basic Yellow 21 (0.3 parts) Ethyl methylene ketone (0.4 parts) HABI (1.0 parts) Tetrabutylammonium methyl three (4-Methylnaphthyl)borate 2-Hydroxythiothiazoline 8 Basic Yellow 13 (0.3 parts) Ethyl ketone (0.4 parts) HABI (1.0 parts) Tetrabutylammonium methyl three (4-A) Naphthyl) Borate 2-Hydroxythiobenzothiazole 9 Basic Yellow 21 (0.3 parts) Ethyl ketone (0.3 parts) Benzophenone (0.2 parts) HABI (1.0 parts) Tetrabutylammonium methyl three (4-Methylnaphthyl)borate 2-Hydroxythiobenzothiazole 1〇Basic Yellow 21 (0.3 parts) 4-Dimethylaminobenzoate (0.3 parts) HABI (1.0 parts) Tetrabutylammonium Methyl tris(4-methylnaphthyl)borate 2-hydrothiobenzothiazole '^ β (please read the notes on the back and then ►I··!) II ί n II -0, I ϋ III n I · This paper scale applies to China National Standard (CNS) A4 specifications (2 10 X 297 mm) -20- 1272277 A7 B7 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed V. Inventions (18) (Comparative Example) The above black dispersion: 5 41.5 parts NK ester ATMPT (new Nakamura Chemical Co., Ltd.): 4.85 parts 2 - (4 - methoxyphenyl) - 4,6 - bis (trichloromethyl) - 5 - three tillage: 2 parts cyclohexanone: 3 9 · 0 parts in a container The mixture was thoroughly mixed and filtered through a 1.0 μm filter paper to prepare a black photoresist having a non-volatile content of about 20%. In order to determine the spectral sensitivity of the obtained photoresist, on a glass substrate of 100 mm X 1 Ο 0 mm, the photoresist was coated with a spin coater to a dry film thickness of 1.4 μm and at 70 ° C, the hot air oven was dried for 20 minutes, and was exposed to an irradiation spectroscope (J AS C〇CT 215 CP type manufactured by JASCO Corporation). The light source is an ultra high pressure mercury lamp. The exposed substrate was immersed in a 1% aqueous sodium carbonate solution for about 60 seconds to develop a image, and then washed with running water and heated at 2200 ° C for 30 minutes to obtain a spectrophotograph. Table 2 shows the number of segments of the i-line (3 6 5 n m ), the h-line (4 Ο 5 n m ), and the g-line (4 3 6 n m ). The relationship between the number of segments in this experiment and the amount of exposure is as follows. The larger the number of segments, the higher the sensitivity. 0 m. β (Please read the phonetic notes on the back first? 3⁄4•丨丨 on this page) Order ---------

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

2T 1272277 A7 B7 V. INSTRUCTIONS (19) [Table 2] Number of segments (segment) 13 12 11 10 9 Exposure 1.00 1.78 3.16 5.62 10.0 (mj/cm2) Number of segments (segment) 8 7 6 5 4 Exposure 17.8 31.6 56.2 100 177 (mj/cm2) Number of segments (segment) 3 2 1 Exposure (mj/cm2) 316 562 1000 The results are shown in Table 3. (Please read the notes on the back and then the page) 4%., then ^^-4r Order---------· Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printed Paper Scale Applicable to Chinese National Standards (CNS) A4 size (210 X 297 mm) -22-

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, invention description (20) Example i line h line g line - ^ 1 5 3 3 - 7 6 6 -___ 3 9 7 9 __ 4 9 7 9 __ 5 7 6 8 __ 6 7 6 6 __7 8 7 7 — __ 8 8 6 7 9 9 9 10 10 8 7 8 Comparative Example 4 0 0 [Effects of the Invention] As described in the results of Table 3, according to the present invention, high sensitivity sensitivity can be obtained even without forming an oxygen barrier film. By coloring the composition, in the manufacture of the color filter, the engineering can be shortened, and the cost can be reduced by improving the productivity, and at the same time, the color filter excellent in each resistance can be provided. (Please read the notes on the back and then click on this page) ‘% item^^^ too. i7!l[Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative

Zhang scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

1272277 A8 B8 C8 D8 VI. Patent application scope; 94 L 27 Patent application No. 89 1 00023~ Chinese patent application scope revision (please read the back of the cabinet and fill in the page again) January 27, 1994 Correction 1. A photosensitive coloring composition for a color filter, comprising: a sensitizer (A) having an absorption wavelength in the range of 300 to 5 Ο Ο nm, and an organic compound represented by the general formula (1) a photopolymerization initiator of a boron complex (B) and a compound (C) having a thiol group, a transparent polymer (D) which is soluble in a solvent or an alkaline aqueous solution, and a compound having a bivalent unsaturated bond ( E) and a photosensitive composition of the pigment, wherein the sensitizer (a) contains a benzophenone and/or 2,2'-dichlorophenyl)-4,4,5,5'-tetraphenyl —1,2,〜=imidazole, wherein the compound (c) having a thiol group is at least _3^ from 2-hydrothiobenzothiazole, pentaerythritol tetrathiopropionate, general formula (1) R : I R1 — Already - R3 · Z· IR ^ Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative (in the formula, 1^, 1^, 1^ and 1^ independently represents an alkyl group, an aryl group, an arylalkyl group, an alkenyl group, a heterocyclic group or an alicyclic group, and Z+ represents a money cation, a phosphonium cation, an oxonium cation, a pyridine gun cation, a ^^f oxy cation or Iodine cation). 2 - A color filter characterized in that the color filter used in the color filter described in claim 1 of the patent application is used on a transparent base shuttle. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) Small, ----- 8 8 8 8 ABCD 1272277 VI. Patent application scope 匕3 · A method for manufacturing color filters, characterized by The step of forming a photosensitive coloring composition layer for a color filter according to the first aspect of the invention is formed on the transparent substrate, and a step of photohardening the photosensitive coloring composition layer in the exposed portion by exposure. ^—-1 1^—^ 11· ^11^1 m^i imM^§ —>l^i ^11^1 deltf 1 immml —HI— nm·. \ I fm 1_11· I iawmte (Read first Note on the back side of this page.) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)