JP2004126549A - Coloring photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring photosensitive resin composition, used for the color filter of a liquid crystal display device or a solid-state imaging device, which has excellent coating property even when a liquid-saving coater such as a spinless coater is used. <P>SOLUTION: The coloring photosensitive resin composition comprising (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent and (F) a surfactant is characterized in that the surface tension is 25.5 mN/m to 29.0 mN/m. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a colored photosensitive resin composition.
[0002]
[Prior art]
The colored photosensitive resin composition is a photosensitive resin composition containing a coloring agent, and is useful as a material for forming a colored pattern constituting a color filter. Here, the color filter is an optical element used for colorizing a display image of a liquid crystal display device or for colorizing an image captured by a solid-state imaging device. The coloring pattern is, for example, a color pixel such as red, green, or blue, a black matrix, or the like, and may be linear or mosaic.
[0003]
Conventionally, in order to form a film using a colored photosensitive resin composition on a substrate to be coated such as a wafer, the colored photosensitive resin composition is dropped from a nozzle near a central portion of the substrate to be coated, or a slit-shaped resin is used. After the colored photosensitive resin composition is dropped on the substrate to be coated from the nozzle, the substrate is rotated at a speed of several hundreds to several thousand rpm, and the solvent and the colored photosensitive resin composition excessively dropped on the substrate are rotated. A flat coating film was obtained using a spin coater that repels objects. However, by using a spin coater, the colored photosensitive resin composition dropped on the substrate excessively is repelled and is discarded without forming a colored photosensitive resin layer, thereby preventing it from being wasted, and With a conventional spin coater, it has become difficult to apply the liquid on a substrate such as glass having a large area such as 1 m square, and a liquid-saving coater such as a spinless coater that does not perform spinning has been developed (Patent Document 1).
On the other hand, even when a colored photosensitive resin composition optimized for a conventional spin coater is applied to a spinless coater, which is one type of liquid-saving coater, flatness tends to be hardly obtained. This is because in a spin coater, the flatness in the applied state is not very important, and a certain degree of flatness can be obtained by spinning, and since most of the solvent is removed by spinning, the process of removing the solvent by heating etc. This is because the flatness is not greatly impaired because the amount of solvent removed from the inside of the formed layer is small.
Furthermore, in the spinless coater, since the solvent is not removed by spinning, most of the flatness is determined in the state of application, and the amount of solvent removed by heating or the like is significantly larger than that of the spin coater, so that the spinless coater is formed. The solvent is also removed from inside the layer, and as a result, the flatness tends to deteriorate.
Conventionally, in order to improve the coating properties of the colored photosensitive resin composition, a method using a polymer additive such as a leveling agent has been used. However, when a polymer additive such as a leveling agent is added, the undried coating film coated with the colored photosensitive resin composition has a frame portion formed along the periphery of the substrate immediately after the coating is completed (the undried coating film). The thick film portion) moves to the center of the substrate, thereby deteriorating the in-plane uniformity.
[0004]
[Patent Document 1] JP-A-2001-62370
[Problems to be solved by the invention]
An object of the present invention is to provide a colored photosensitive resin composition having good coatability even when a liquid-saving coater such as a spinless coater is used.
[0005]
[Means for Solving the Problems]
Therefore, the present inventors have been keen to develop a colored photosensitive composition capable of forming a color pixel or a black matrix that can be uniformly applied even when a liquid-saving type resist coating apparatus such as a spinless coater is used. As a result of the study, it was found that the colored photosensitive resin composition having a surface tension in a specific range can be uniformly applied by a conventional spin coater as well as a liquid-saving coater such as a spinless coater. Reached.
That is, the present invention provides a colored photosensitive composition comprising (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent, and (F) a surfactant. A colored photosensitive resin composition having a surface tension of 25.5 mN / m or more and 29.0 mN / m or less, and a colored photosensitive resin composition using the above colored photosensitive resin composition in a spinless coater. Method for forming a layer made of a photosensitive resin composition, applying the above colored photosensitive resin composition on a substrate or a layer made of the solid content of the previously formed colored photosensitive resin composition, and applying the applied coloring Volatile components are removed from the photosensitive resin composition layer, the layer is exposed through a photomask, a method of forming a pattern to be developed, a color filter including the pattern formed by the method, and the color filter. Use To provide a liquid crystal display apparatus.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The colored photosensitive resin composition of the present invention comprises (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent, and (F) a surfactant. And the surface tension is in the range of 25.5 mN / m to 29.0 mN / m, and preferably in the range of 26.0 mN / m to 28.2 mN / m. When the surface tension is in this range, a layer made of the colored photosensitive resin composition having good flatness and no unevenness can be formed, which is preferable. Particularly, it is preferable when used for a spinless coater.
[0007]
The surfactant (F) in the colored photosensitive resin composition of the present invention is at least one selected from the group consisting of a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. Is preferred.
[0008]
The colorant (A) used in the colored photosensitive resin composition of the present invention may be an organic pigment that is an organic substance or an inorganic pigment that is an inorganic substance. Among them, organic pigments are preferably used because of their excellent heat resistance and coloring properties.
[0009]
Specific examples of the organic pigment and the inorganic pigment include compounds classified as Pigment in the Color Index (published by The Society of Dyers and Colorists). Specifically, for example, C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 20, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 31, C.I. I. Pigment yellow 53, C.I. I. Pigment yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 173, C.I. I. Pigment yellow 194, C.I. I. Yellow pigments such as CI Pigment Yellow 214;
C. I. Pigment Orange 13, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 40, C.I. I. Pigment Orange 42, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 65, C.I. I. Pigment Orange 71, C.I. I. Orange pigments such as CI Pigment Orange 73;
C. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I. I. Pigment Red 105, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 209, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 224, C.I. I. Pigment Red 242, C.I. I. Pigment red 254, C.I. I. Pigment Red 264, C.I. I. Red pigments such as CI Pigment Red 265;
C. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Blue pigments such as Pigment Blue 60;
C. I. Pigment Violet 1, C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Violet color pigments such as CI Pigment Violet 38;
C. I. Pigment Green 7, C.I. I. Green pigments such as Pigment Green 36;
C. I. Pigment Brown 23, C.I. I. A brown pigment such as Pigment Brown 25;
C. I. Pigment Black 1, C.I. I. Black pigments such as C.I. Pigment Black 7, and C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Red 177, C.I. I. Pigment Red 209, C.I. I. Pigment red 254, C.I. I. Pigment Red Violet 23, C.I. I. Pigment Blue 15: 6 and C.I. I. Pigment Green 36 preferably contains at least one pigment.
[0010]
These organic pigments and inorganic pigments may be used alone or in combination of two or more. For example, to form a red pixel, C.I. I. Pigment Red 209 and C.I. I. Pigment Yellow 139 to form green pixels. I. Pigment Green 36 and C.I. I. Pigment Yellow 150 and C.I. I. Pigment Yellow 138 contains at least one selected from the group consisting of C.I. I. Pigment Blue 15: 6 is preferred.
[0011]
Among the above-mentioned pigments, organic pigments include, as required, rosin treatment, surface treatment using a pigment derivative having an acidic or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid fine particles, and the like. An atomization treatment by a chemical conversion method, a cleaning treatment with an organic solvent or water for removing impurities, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed.
[0012]
The amount of the pigment used is preferably 25 parts by mass or more and 60 parts by mass or less, more preferably 27 parts by mass or more and 55 parts by mass or less when the solid content in the colored photosensitive resin composition is 100 parts by mass. And more preferably 30 parts by mass or more and 50 parts by mass or less. When the content of the pigment is 25 parts by mass or more and 60 parts by mass or less, the color density when used as a color filter is sufficient, and the binder resin can be contained in a necessary amount in the composition. Is preferable because a sufficient pattern can be formed.
[0013]
In the colored photosensitive resin composition obtained in the present invention, it is preferable that the pigment as the colorant has a uniform particle size. In order to obtain a uniform particle size of the pigment, a pigment dispersant different from the component (F) described below is contained and dispersion treatment is performed to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solution. Can be.
Examples of the pigment dispersant include cationic, anionic, nonionic and amphoteric surfactants, and these are used alone or in combination of two or more.
The amount of the pigment dispersant used is usually 1 part by mass or less, preferably 0.05 part by mass or more and 0.5 part by mass or less per 1 part by mass of the colorant. When the amount of the pigment dispersant is usually 1 part by mass or less per 1 part by mass of the colorant, a pigment having a uniform particle diameter tends to be obtained, which is preferable.
[0014]
As the binder polymer (B) used in the colored photosensitive resin composition of the present invention, an acrylic copolymer can be used. For example, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable therewith can be used. And the like.
[0015]
Examples of the carboxyl group-containing monomer include, for example, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids such as unsaturated tricarboxylic acids. Carboxylic acids. Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. The unsaturated polycarboxylic acid may be an acid anhydride thereof, specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, or the like. The unsaturated polycarboxylic acid may be its mono (2-methacryloyloxyalkyl) ester, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy) succinate. Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both terminals, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, or the like. These carboxyl group-containing monomers can be used alone or in combination of two or more.
[0016]
Other monomers copolymerizable with the carboxyl group-containing monomer include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene , M-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl Aromatic vinyl compounds such as glycidyl ether and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate; -Propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3- Hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, ant Acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol Acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate Rate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, Unsaturated carboxylic esters such as glycerol monomethacrylate;
2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated carboxylic acid aminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
Vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;
Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, macrosiloxanes having a monoacryloyl group or a monomethacryloyl group at a terminal of a polymer molecular chain of polysiloxane, etc. Can be. These monomers can be used alone or in combination of two or more.
[0017]
The content of the carboxyl group-containing monomer unit in the copolymer is usually 10 to 50% by mass, preferably 15 to 40% by mass, and particularly preferably 25 to 40% by mass. When the content of the above-mentioned carboxyl group-containing monomer unit is 10 to 50% by mass, the solubility in a developing solution is good, and a pattern tends to be formed accurately during development, which is preferable.
Examples of the acrylic polymer include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, and (meth) acrylic acid / 2-hydroxy Ethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) Acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (Meth) acrylic acid / 2-hydroxye (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer , (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono (2-acryloyloxyethyl succinate) / styrene / benzyl (meth) acrylate / N -Phenylmaleimide copolymer, (meth) acrylic acid / mono (2-acryloyloxyethyl succinate) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / benzyl (meth) Acrylate / N-phenylmale De / styrene / such as glycerol mono (meth) acrylate copolymer. Note that (meth) acrylate indicates acrylate or methacrylate.
[0018]
Among them, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) ) Acrylic acid / methyl (meth) acrylate / styrene copolymer is preferred.
[0019]
The weight average molecular weight in terms of polystyrene of the binder polymer (B) contained in the colored photosensitive resin composition of the present invention is preferably 5,000 to 50,000, more preferably 8,000 to 40,000, Especially preferably, it is 10,000 to 35,000. When the weight average molecular weight in terms of polystyrene is 5,000 to 50,000, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution tends to be improved. And is preferred.
The acid value of the binder polymer (B) contained in the colored photosensitive resin composition of the present invention is preferably 50 to 150, more preferably 60 to 140, and particularly preferably 80 to 135. When the acid value is from 50 to 150, the solubility in a developing solution is improved, and the unexposed portion is easily dissolved. In addition, the sensitivity is increased, and the pattern of the exposed portion remains during development, and the residual film ratio is improved. This is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be determined by titration using an aqueous potassium hydroxide solution. .
The content of the binder polymer (B) in the colored photosensitive resin composition of the present invention is preferably from 5% by mass to 40% by mass, more preferably from 5% by mass to 40% by mass, based on the solid content of the colored photosensitive resin composition. It is used in the range of 10% by mass to 35% by mass, particularly preferably in the range of 15% by mass to 30% by mass. When the content of the binder polymer (B) is 5% by mass or more and 40% by mass or less, a pattern can be formed, and the resolution and the residual film ratio tend to be improved.
[0020]
The photopolymerizable compound (C) used in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator when irradiated with light. And a compound having a polymerizable carbon-carbon unsaturated bond.
[0021]
The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include, for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Is mentioned.
The above photopolymerizable compounds are used alone or in combination of two or more.
The photopolymerizable compound (C) is used alone or in combination of two or more, and the content thereof is preferably at least 5% by mass based on the solid content of the colored photosensitive resin composition. It is used in an amount of 45% by mass or less, more preferably 10% by mass or more and 35% by mass or less, particularly preferably 19% by mass or more and 30% by mass or less. When the content of the photopolymerizable compound (C) is 10% by mass or more and 40% by mass or less, curing is sufficiently caused and the residual film ratio is improved, which is preferable.
[0022]
The colored photosensitive resin composition of the present invention contains (D) a photopolymerization initiator.
Examples of the photopolymerization initiator (D) include acetophenone-based compounds. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one. Benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- [ Oligomer of 4- (1-methylvinyl) phenyl] propan-1-one and the like are preferable, and 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like are preferable. Further, a plurality of acetophenone-based and other photopolymerization initiators may be used in combination. Examples of the non-acetophenone-based photopolymerization initiator include an active radical generator that generates active radicals upon irradiation with light, and a sensitizer. Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.
[0023]
Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
[0024]
Examples of the benzophenone-based compound include, for example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3 ′, 4,4′-tetra (t-butylperoxy) Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.
[0025]
Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
[0026]
Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -[2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl]- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl)- - such as [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
[0027]
Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can also be used.
[0028]
Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate; Benzoin tosylate and the like can be mentioned.
[0029]
In addition, among the compounds described as the active radical generator, there are compounds that generate an acid simultaneously with an active radical. For example, a triazine-based photopolymerization initiator is also used as an acid generator.
[0030]
The content of the photopolymerization initiator (D) in the colored photosensitive resin composition of the present invention is preferably 0.1 mass per 100 mass parts of the total amount of the binder polymer (B) and the photopolymerizable compound (C). To 20 parts by mass, more preferably 1 to 15 parts by mass. When the content of the photopolymerization initiator is 0.1 parts by mass or more and 20 parts by mass or less on the basis of the above, the sensitivity is increased, the exposure time is shortened, and the productivity is improved. This is preferable since it does not tend to be defective.
[0031]
In the colored photosensitive resin composition of the present invention, (G) a photopolymerization initiation aid may be used. The (G) photopolymerization initiation aid may be used in combination with the (D) photopolymerization initiator, and is a compound used to promote the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. It is. Examples of the photopolymerization initiation aid (G) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4 ' -Bis (ethylmethylamino) benzophenone and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable.
[0032]
Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. .
[0033]
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
[0034]
(G) The photopolymerization initiator may be used alone or in combination of two or more. In addition, a commercially available photopolymerization initiation aid can be used, and examples of the commercially available photopolymerization initiation aid include “EAB-F” (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.). .
[0035]
The combination of (D) a photopolymerization initiator and (G) a photopolymerization initiation aid in the colored photosensitive resin composition of the present invention includes diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl- 2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4 ′ -Bis (diethylamino) benzophenone, benzyldimethylketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4 , 4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenyl ketone / 4 4′-bis (diethylamino) benzophenone, oligomer of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone; and the like, preferably 2-methyl-2-morpholino-1 -(4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone.
[0036]
When these photopolymerization initiators are used, the amount used is usually 10 mol or less, preferably 0.01 mol or more and 5 mol or less per 1 mol of the photopolymerization initiator.
[0037]
The colored photosensitive resin composition of the present invention contains (E) a solvent. Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.
[0038]
As ethers, for example, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, phenetole, and the like methyl anisole.
Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and the like.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and the like.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and ethyl lactate. , Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl cypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples thereof include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.
Examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide, and the like.
Other solvents include, for example, N-methylpyrrolidone, dimethylsulfoxide and the like.
Among the above solvents, ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate are preferably used.
The above-mentioned solvents can be used alone or in combination of two or more, and the content thereof is preferably 70% by mass or more and 95% by mass or less, more preferably 70% by mass or less in the colored photosensitive resin composition. Is from 75% by mass to 90% by mass. (E) When the content of the solvent is 70% by mass or more and 95% by mass or less on the basis of the above, the flatness at the time of coating is good, and the color density at the time of forming a color filter is sufficient and the display characteristics are poor. Good and preferred.
[0039]
The surfactant (F) used in the colored photosensitive resin composition of the present invention is at least one selected from the group consisting of a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. Seeds are used.
Examples of the silicone-based surfactant include a surfactant having a siloxane bond. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether modified silicone oil SH8400 (trade name: manufactured by Toray Silicone Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by GE Toshiba Silicones).
Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specifically, Florinert (trade name) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (trade name) F142D, F171, F172, F173, F177, F183, R30 (Large) Nippon Ink and Chemicals, Inc.), F Top (trade name) EF301, EF303, EF351, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Surflon (trade name) S381, S382, SC101, same SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all are manufactured by BM Chemie), and the like.
Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples include Megafac (trade name) R08, BL20, F475, F477, and F443 (manufactured by Dainippon Ink and Chemicals, Inc.).
These surfactants can be used alone or in combination of two or more.
These surfactants are used in an amount of from 0.0005 to 0.6 parts by mass, preferably from 0.001 to 0 parts by mass, per 100 parts by mass of the colored photosensitive resin composition excluding the surfactant (F). It is used in a range of 0.5 parts by mass. When the content of the surfactant is 0.0005 parts by mass or more and 0.6 parts by mass or less based on the above criteria, the resulting coating film tends to have good flatness, which is preferable.
To prepare the colored photosensitive resin composition of the present invention, after mixing the components except for the surfactant, the surfactant may be added little by little to adjust the surface tension so as to be in the range of the specified value. Alternatively, the relationship between the amount of surfactant added and the surface tension in the colored photosensitive resin composition may be determined in advance, and the components may be mixed together based on the amount of addition.
[0040]
The colored photosensitive resin composition of the present invention includes a filler, a polymer compound other than a binder polymer, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent, an organic acid, an organic amino compound, and a curing agent. An agent may be contained.
[0041]
Examples of the filler include fine particles such as glass and alumina.
[0042]
Examples of the polymer compound other than the binder polymer include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.
[0043]
Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethyl Examples include methoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
[0044]
Examples of the antioxidant include 4,4′-thiobis (6-t-butyl-3-methylphenol), 2,6-di-t-butyl-4-methylphenol and the like.
[0045]
Examples of the ultraviolet absorber include benzotriazoles such as 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chlorobenzotriazole and benzophenones such as 2-hydroxy-4-octyloxybenzophenone. Benzoate such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate; 2- (4,6-diphenyl-1,3,5-triazine-2 -Yl) -5-hexyloxyphenol and the like.
[0046]
Examples of the aggregation preventing agent include sodium polyacrylate and the like.
[0047]
Examples of the organic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid;
Oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, brasilic, methylmalonic, ethylmalonic, dimethylmalonic, methylsuccinic, tetramethylsuccinic Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelitic acid and mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;
Examples include aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melophanic acid, and pyromellitic acid.
[0048]
Examples of the organic amine compound include n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-propylamine. Monoalkylamines such as octylamine, n-nonylamine, n-decylamine, n-undecylamine and n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine and 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, dii-propylamine, di-n-butylamine, dii-butylamine, disec-butylamine, di-t-butylamine, dialkylamines such as n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i-propylamine, tri-n-butylamine, tri-n-butylamine trialkylamines such as i-butylamine, trisec-butylamine, tri-t-butylamine, tri-n-pentylamine and tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol and 6-amino-1-hexanol Kind;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol; diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, dialkanolamines such as n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine and tri-n-hexanolamine; tri (4 Tricycloalkanolamines such as -cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkanediols such as 2,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;
Amino group-containing cycloalkane methanols such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, and 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi-propylaniline, pn-butylaniline, pt-butylaniline, Aromatic amines such as 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol;
Examples thereof include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.
[0049]
As the curing agent, for example, a compound capable of reacting with a carboxyl group in the binder polymer by heating to crosslink the binder polymer can be used. In addition, a compound that can be polymerized by itself to cure a colored pattern is also included. Examples of the compound include an epoxy compound and an oxetane compound.
[0050]
Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, and alicyclic ring. Epoxy resins such as aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, and epoxidized oils; brominated derivatives of these epoxy resins; and aliphatics other than epoxy resins and their brominated derivatives. , Alicyclic or aromatic epoxy compounds, epoxidized (co) polymer of butadiene, epoxidized (co) polymer of isoprene, (co) polymer of glycidyl (meth) acrylate, triglycidyl isocyanurate, etc. Is mentioned.
[0051]
Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.
[0052]
When the colored photosensitive composition of the present invention contains an epoxy compound, an oxetane compound, or the like as a curing agent, it may contain a compound capable of ring-opening polymerizing the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. . Examples of the compound capable of undergoing ring-opening polymerization include polycarboxylic acids, polycarboxylic anhydrides, and acid generators.
[0053]
Examples of polycarboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 Aromatic polycarboxylic acids such as', 4,4'-benzophenonetetracarboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, and itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid And alicyclic polycarboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid.
[0054]
Examples of polycarboxylic anhydrides include aromatic polycarboxylic acids such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. Acid anhydrides;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Kind;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride and nadic anhydride;
Ester group-containing carboxylic anhydrides such as ethylene glycol bistrimellitate acid and glycerin tristrimellitate anhydride.
[0055]
As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents may be used. Examples of the epoxy resin curing agent include “ADEKA HARDNER EH-700” (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), “RICACID HH” (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and “MH- 700 "(Shin Nippon Rika Co., Ltd.).
[0056]
The above-mentioned curing agents can be used alone or in combination of two or more.
[0057]
As a method of forming a pattern using the colored photosensitive resin composition of the present invention, specifically, the colored photosensitive resin composition of the present invention may be a substrate or a solid colored photosensitive resin previously formed on a substrate. A volatile component such as a solvent is removed from the applied colored photosensitive resin composition layer by applying it on a conductive resin composition layer (hereinafter, this may be referred to as a substrate or the like), and the volatile component is applied through a photomask. After exposing the layer from which is removed, development is performed.
[0058]
Examples of the substrate include substrates having a flat surface such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an Al substrate, and a GaAs substrate. These substrates may be subjected to a pretreatment such as a chemical treatment with a chemical such as a silane coupling agent, a plasma treatment, an ion plating treatment, a sputtering treatment, a gas phase reaction treatment, and a vacuum deposition treatment. When a silicon substrate or the like is used as a substrate, a charge-coupled device (CCD), a thin film transistor (TFT), or the like may be formed on a surface of the silicon substrate or the like.
[0059]
In order to apply the colored photosensitive resin composition on the substrate, it can be applied on a substrate or the like using a conventional spin coater or a liquid-saving coater, especially a spinless coater. Among them, the slit coating method is preferable because the substrate need not be rotated due to the enlargement of the substrate and the colored photosensitive resin composition is not wasted by spinning. Next, a volatile component such as a solvent in the colored photosensitive resin composition may be volatilized by heating. In this manner, a layer made of the solid content of the colored photosensitive resin composition is formed on the substrate or the like with good flatness.
[0060]
【Example】
Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the appended claims, and includes all modifications within the scope and meaning equivalent to the claims. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[0061]
The components used in this example are as follows, and may be abbreviated and described below. (A-1) Colorant: C.I. I. Pigment Red 254
(A-2) Colorant: C.I. I. Pigment Yellow 139
(B) Binder resin: a copolymer of methacrylic acid and benzyl methacrylate [the ratio of methacrylic acid units to benzyl methacrylate units is 27:73 in terms of a mass ratio (molar ratio), the acid value is 83, and the weight-average molecular weight in terms of polystyrene. Is 18,000
(C) Photopolymerizable compound: dipentaerythritol hexaacrylate
(D-1) Photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one
(D-2) Photopolymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine
(G-1) Photopolymerization initiation auxiliary agent: 2,4-diethylthioxanthone
(E-1) Solvent: propylene glycol monomethyl ether acetate
(E-2) Solvent: ethyl 3-ethoxypropionate
[0062]
Example 1
[Preparation of colored photosensitive resin composition 1]
(A-1) 4.070 parts by mass
(A-2) 0.955 parts by mass
1.507 parts by mass of dispersant
(B) 3.229 parts by mass
(C) 3.947 parts by mass
(D-1) 0.431 mass parts
(D-2) 0.431 parts by mass
(G-1) 0.431 parts by mass
(E-1) 76.502 parts by mass
(E-2) 8.500 parts by mass
Was mixed to obtain a mixture 1. The mixture 1 was mixed with 0.010 parts by mass of Megafac F475 (manufactured by Dainippon Ink and Chemicals, Inc.) as a surfactant (F) to obtain a colored photosensitive resin composition 1.
[0063]
(Surface tension evaluation)
A 10 mm glass tube tip having a diameter of 1 mm was immersed perpendicular to the colored photosensitive resin composition 1 obtained above, and the surface tension was determined from the rising distance from the immersion part of the colored photosensitive resin composition. , 28.2 mN / m.
(Formation of coating film)
When one drop (10 μL) of the colored photosensitive resin composition 1 obtained above was dropped from a microsyringe on a glass substrate, it spread in a circle having a diameter of 7 mm, no interference fringes were observed, and the flatness was good. Met.
[Evaluation with spinless coater]
When a coating film was formed from the obtained colored photosensitive resin composition 1 using a spinless coater, a coating film having good flatness and no unevenness was obtained.
[0064]
Example 2
A colored photosensitive resin was prepared in the same manner as in Example 1 except that the content of Megafac F475 (manufactured by Dainippon Ink and Chemicals, Inc.) as the component (F) in Example 1 was changed to 0.050 parts by mass. Composition 2 was obtained.
(Surface tension evaluation)
When the surface tension was determined in the same manner as in Example 1, it was 26.5 mN / m. (Formation of coating film)
When one drop (10 μL) of the colored photosensitive resin composition 2 obtained above was dropped on a glass substrate from a microsyringe, it spread in a circle having a diameter of 7 mm, no interference fringes were observed, and the flatness was good. Met.
[Evaluation with spinless coater]
When a coating film was formed on the obtained colored photosensitive resin composition 2 using a spinless coater, a coating film having good flatness and no unevenness was obtained.
[0065]
Example 3
A colored photosensitive resin was prepared in the same manner as in Example 1 except that the content of MegaFac F475 (manufactured by Dainippon Ink and Chemicals, Inc.), which is the component (F) of Example 1, was changed to 0.075 parts by mass. Composition 3 was obtained.
(Surface tension evaluation)
When the surface tension was determined in the same manner as in Example 1, it was 26.0 mN / m. (Formation of coating film)
When one drop (10 μL) of the colored photosensitive resin composition 3 obtained above was dropped on a glass substrate from a microsyringe, it spread in a circle having a diameter of 7 mm, no interference fringes were observed, and the flatness was good. Met.
[Evaluation with spinless coater]
When a coating film was formed from the obtained colored photosensitive resin composition 3 using a spinless coater, a coating film having good flatness and no unevenness was obtained.
[0066]
Example 4
A colored photosensitive resin was prepared in the same manner as in Example 1 except that the content of Megafac F475 (manufactured by Dainippon Ink and Chemicals, Inc.) as the component (F) in Example 1 was changed to 0.100 parts by mass. Composition 4 was obtained.
(Surface tension evaluation)
When the surface tension was determined in the same manner as in Example 1, it was 26.5 mN / m. (Formation of coating film)
When one drop (10 μL) of the colored photosensitive resin composition 4 obtained above was dropped on a glass substrate from a microsyringe, it spread in a circle having a diameter of 7 mm, no interference fringes were observed, and the flatness was good. Met.
[Evaluation with spinless coater]
When a coating film was formed from the obtained colored photosensitive resin composition 4 using a spinless coater, a coating film having good flatness and no unevenness was obtained.
[0067]
Comparative Example 1
A colored photosensitive resin composition 5 was obtained in the same manner as in Example 1 except that Megafac F475 (manufactured by Dainippon Ink and Chemicals, Inc.) as the component (F) in Example 1 was not added.
(Surface tension evaluation)
When the surface tension was determined in the same manner as in Example 1, it was 29.9 mN / m. (Formation of coating film)
When one drop (10 μL) of the colored photosensitive resin composition 5 obtained above was dropped from a microsyringe on a glass substrate, it spread in a circle having a diameter of 8 mm, interference fringes were observed, and the flatness was poor. there were.
[Evaluation with spinless coater]
When a coating film was formed from the obtained colored photosensitive resin composition 5 using a spinless coater, a coating film having poor flatness and unevenness was obtained.
[0068]
Comparative Example 2
A colored photosensitive resin was prepared in the same manner as in Example 1 except that the content of Megafac F475 (manufactured by Dainippon Ink and Chemicals, Inc.) as the component (F) in Example 1 was changed to 0.200 parts by mass. Composition 6 was obtained.
(Surface tension evaluation)
When the surface tension was determined in the same manner as in Example 1, it was 23.8 mN / m. (Formation of coating film)
When one drop (10 μL) of the colored photosensitive resin composition 6 obtained above was dropped on a glass substrate from a microsyringe, it spread in a circle having a diameter of 8 mm, interference fringes were observed, and the flatness was poor. there were.
[Evaluation with spinless coater]
When a coating film was formed from the obtained colored photosensitive resin composition 6 using a spinless coater, a coating film having poor flatness and unevenness was obtained.
[0069]
Example 5
In Example 1, MegaFac F475 (manufactured by Dainippon Ink and Chemicals, Inc.) as the component (F) was changed to 0.010 parts by mass of polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Silicone Co., Ltd.). Except for the above, a colored photosensitive resin composition 7 was obtained in the same manner as in Example 1.
(Surface tension evaluation)
When the surface tension was determined in the same manner as in Example 1, it was 27.4 mN / m. (Formation of coating film)
When one drop (10 μL) of the colored photosensitive resin composition 7 obtained above was dropped from a microsyringe onto a glass substrate, it spread in a circle having a diameter of 7 mm, no interference fringes were observed, and the flatness was good. Met.
[Evaluation with spinless coater]
When a coating film was formed from the obtained colored photosensitive resin composition 7 using a spinless coater, a coating film having good flatness and no unevenness was obtained.
[0070]
Example 6
In Example 1, Megafac F475 (manufactured by Dainippon Ink and Chemicals, Inc.) as the component (F) was changed to 0.050 parts by mass of polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Silicone Co., Ltd.). Except for the above, a colored photosensitive resin composition 8 was obtained in the same manner as in Example 1.
(Surface tension evaluation)
When the surface tension was determined in the same manner as in Example 1, it was 26.5 mN / m. (Formation of coating film)
When one drop (10 μL) of the colored photosensitive resin composition 8 obtained above was dropped on a glass substrate from a microsyringe, it spread in a circle having a diameter of 7 mm, no interference fringes were observed, and the flatness was good. Met.
[Evaluation with spinless coater]
When a coating film was formed from the obtained colored photosensitive resin composition 8 using a spinless coater, a coating film having good flatness and no unevenness was obtained.
[0071]
Comparative Example 3
In Example 1, Megafac F475 (manufactured by Dainippon Ink and Chemicals, Inc.) as the component (F) was changed to 0.200 parts by mass of polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Silicone Co., Ltd.). Except for the above, a colored photosensitive resin composition 10 was obtained in the same manner as in Example 1.
(Surface tension evaluation)
When the surface tension was determined in the same manner as in Example 1, it was 24.5 mN / m. (Formation of coating film)
When one drop (10 μL) of the colored photosensitive resin composition 10 obtained above was dropped from a microsyringe on a glass substrate, it spread in a circular shape having a diameter of 8 mm, interference fringes were observed, and the flatness was poor. there were.
[Evaluation with spinless coater]
When a coating film was formed from the obtained colored photosensitive resin composition 10 using a spinless coater, a coating film having poor flatness and unevenness was obtained.
[0072]
【The invention's effect】
According to the colored photosensitive resin composition of the present invention, even when the colored photosensitive resin composition is dropped on the substrate, interference fringes are not seen, and a coating film having good flatness is obtained, and a spinless coater is used. Even if a coating film is formed on the substrate by the above, a coating film having good flatness can be formed.

Claims (7)

A colored photosensitive resin composition comprising (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent, and (F) a surfactant. And a colored photosensitive resin composition having a surface tension of 25.5 mN / m or more and 29.0 mN / m or less. The colored photosensitive resin composition according to claim 1, wherein the surfactant is at least one selected from the group consisting of a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. The colored photosensitive resin composition according to claim 1 or 2, wherein the surfactant is added in an amount of 0.001 to 0.2% by mass based on the total amount of the colored photosensitive resin composition. A method for forming a layer comprising the colored photosensitive resin composition from the colored photosensitive resin composition according to claim 1 by using a spinless coater. The colored photosensitive resin composition according to any one of claims 1 to 3, which is applied on a substrate or a layer formed of a solid content of the previously formed colored photosensitive resin composition, and the applied colored photosensitive resin. A method for forming a pattern in which a volatile component is removed from a composition layer, the layer is exposed through a photomask, and developed. A color filter including a pattern formed by the method according to claim 5. A liquid crystal display device using the color filter according to claim 6.