JP4510672B2 - Photosensitive resin composition and color filter - Google Patents

Description

  The present invention relates to a photosensitive resin composition and a color filter having a pattern formed using the same.

For example, in a color filter used in a color display device, pixels (colored layers) each having a color of red (R), green (G), and blue (B) are generally formed in a lattice-shaped light shielding layer called a black matrix. It has the structure enclosed by.
There is known a method for forming a colored layer and a black matrix of such a color filter by a photolithography method using a photoresist composition containing a colorant.

For example, in Patent Document 1 below, a photocurable composition containing an alkali-soluble resin, a photopolymerizable monomer, a specific photo / thermal polymerization initiator having both a benzophenone skeleton and a peroxide skeleton, an oxetane compound, and a solvent, A method is described in which a color filter is produced by coating on a substrate to form a coating film, photocuring into a pattern, alkali developing, and thermosetting under specific conditions.
In Patent Document 2 below, a coating film is formed by applying a radiation-sensitive composition containing a colorant, an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, and an oxetane compound on a substrate. A method is described in which a color filter is produced by forming, partially exposing through a mask, alkali developing to dissolve and remove unexposed portions, and then post-baking.
JP 2003-255531 A Japanese Patent Laid-Open No. 2000-214592

In the photosensitive resin composition used when forming a color filter by the photolithographic method, it is required that a fine pattern such as a black matrix or a colored layer (pixel) can be formed with a good profile shape.
For that purpose, even if it contains a coloring agent, it is necessary to have good sensitivity to exposure light, and it is also important that the heat resistance in the pattern after development is good.

  The present invention has been made in view of the above circumstances. A photosensitive resin composition capable of obtaining good sensitivity even when a colorant is contained and improving heat resistance in a pattern after development, and the photosensitive resin composition. An object of the present invention is to provide a color filter having a pattern formed using a conductive resin composition.

In order to achieve the above object, the photosensitive resin composition of the present invention contains (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator. A photosensitive resin composition comprising (E) an oxetane compound and (F) an epoxy compound.
Moreover, this invention provides the color filter which has a pattern formed using the photosensitive resin composition of this invention.

According to the present invention, in a method of forming a pattern using a difference in solubility caused by exposure, good sensitivity can be obtained even when a colorant is contained, and heat resistance in a pattern after development is improved. The photosensitive resin composition which can be obtained is obtained. Therefore, a pattern having a good profile shape can be formed.
The black matrix or colored layer formed using the photosensitive resin composition of the present invention has a good profile shape.
The color filter of the present invention has a good profile shape of the black matrix and / or the colored layer.

<(A) Colorant>
The colorant in the present invention may be an organic colorant or an inorganic colorant. The color tone of the colorant is not particularly limited, and can be appropriately selected according to the color tone of the colored layer of the color filter to be obtained or the color tone of the black matrix.
Specifically, the organic colorant is preferably a dye, an organic pigment, a natural colorant, and the like, and the inorganic colorant is specifically an inorganic salt such as barium sulfate called extender in addition to an inorganic pigment.
As a colorant for use in a color filter, a colorant having high color developability and high heat resistance, particularly a colorant having high heat decomposition resistance is preferable, and an organic colorant, particularly preferably an organic pigment is usually used.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C .. I.) Numbers can be mentioned.

  C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

  C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 79, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment Black 1 and Pigment Black 7.
Carbon black is also preferred as the black pigment.

These organic pigments can be used alone or in admixture of two or more. The organic pigment can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.
(A) The addition amount of the colorant is appropriately changed according to the target color tone. In general, in the case of an organic pigment, 5 to 5 parts by mass of (B) alkali-soluble resin. It is preferable to add in the range of 250 parts by mass, and a more preferable range is about 10 to 200 parts by mass.

<(B) Alkali-soluble resin>
(I) Alkali-soluble resin As the alkali-soluble resin in the present invention, one or more selected from monomers having a carboxy group such as acrylic acid and methacrylic acid,
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, A copolymer with at least one selected from benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, acrylamide, acrylonitrile, and the like;
Resins such as phenol novolac type epoxy acrylate polymer, phenol novolac type epoxy methacrylate polymer, cresol novolac type epoxy acrylate polymer, cresol novolac type epoxy methacrylate polymer, bisphenol A type epoxy acrylate polymer, bisphenol S type epoxy acrylate polymer Is mentioned.
Since these resins have an acryloyl group or a methacryloyl group introduced, the crosslinking efficiency is improved and the light resistance and chemical resistance of the coating film are excellent.
Of the monomer components constituting the alkali-soluble resin, the content of monomer components having a carboxy group such as acrylic acid and methacrylic acid is preferably in the range of 5 to 40% by mass.

(II) Alkali-soluble resin which has photocurability Moreover, the polymer shown by the following general formula (I) is also applicable as alkali-soluble resin. Since the compound represented by the general formula (I) itself has photopolymerizability (photocurability), the photosensitive resin for forming a light-shielding film containing the compound further increases the transmittance of ultraviolet rays. Sensitivity can be improved.

(Wherein X is a group represented by the following chemical formula (II), Y is a residue obtained by removing a carboxylic anhydride group (—CO—O—CO—) from dicarboxylic anhydride, and Z is a tetra (This is a residue obtained by removing two carboxylic anhydride groups from carboxylic dianhydride.)

Specific examples of the dicarboxylic acid anhydride (the dicarboxylic acid anhydride before removing the carboxylic acid anhydride group) for deriving Y include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Examples thereof include acid, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, and glutaric anhydride.
Specific examples of the tetracarboxylic dianhydride for deriving Z (tetracarboxylic dianhydride before removing two carboxylic anhydride groups) include, for example, pyromellitic anhydride, benzophenone tetracarboxylic acid bis Examples thereof include tetracarboxylic dianhydrides such as anhydrides, biphenyl tetracarboxylic dianhydrides, and biphenyl ether tetracarboxylic dianhydrides.

(B) The alkali-soluble resin may be used alone or in combination of two or more. Further, only the alkali-soluble resin (I) may be used, or only the alkali-soluble resin (II) having photocurability may be used, or both may be used in combination.
The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of (B) alkali-soluble resin in the present invention is not particularly limited, but is preferably 1000 to 100,000, more preferably 3000 to 50000, Most preferred is 5000-15000. If it is smaller than the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist. If it is larger than the lower limit of this range, the resist pattern cross-sectional shape is good.

<(C) Photopolymerizable compound>
Examples of the photopolymerizable compound in the present invention include methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, Triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetra Methacrylate, pe Taerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol Examples include, but are not limited to, diacrylate, benzyl acrylate, benzyl methacrylate, cardo epoxy diacrylate, acrylic acid, methacrylic acid, and the like.
A photopolymerizable compound may be used individually by 1 type, and may use 2 or more types together.
In the present invention, the photopolymerizable polymer is included in the (B) alkaline resin (II), and the photopolymerizable monomer is included in the (C) photopolymerizable compound.

The blending amount of the (C) photopolymerizable compound is preferably in the range of 5 to 500 parts by mass with respect to 100 parts by mass of the resin (I) when the alkaline resin (I) is used as the (B) alkali-soluble resin. A more preferable range is 20 to 300 parts by mass.
(C) By making the compounding quantity of a photopolymerizable compound more than the lower limit of the said range, it is hard to produce the hardening defect at the time of exposure, and sufficient heat resistance and chemical-resistance can be obtained. Moreover, when obtaining favorable film formation ability, it is preferable to set it as the upper limit or less of the said range.

<(D) Photopolymerization initiator>
As the photopolymerization initiator (D) in the present invention, a compound represented by the following general formula (III) is preferable.

(In the formula, X ′ is a group represented by the general formula (IV) or the general formula (V), and R ¹¹ is a phenyl group, an alkyl group having 1 to 20 carbon atoms, CN, NO _2, or 1 carbon atom. -4 halogenated alkyl group, and R ¹² is an acyl group having 2 to 12 carbon atoms or an alkenoyl group having 4 to 6 carbon atoms.)

^(Wherein the R 13 ^{to R 17} each independently represent a hydrogen atom, a halogen atom, an alkyl group, phenyl group having 1 to 12 carbon atoms is a phenylsulfanyl group _{(C 6 H 5 S-).} )

(In the formula, R ^{18 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group.)

  The compound represented by the above general formula (III) is a compound obtained by the method described in JP-A No. 2000-80068. The compound is extremely sensitive to light compared to other known photopolymerization initiators, and can be efficiently activated by a small amount of light to cure the photopolymerizable compound.

  Moreover, photoinitiators other than the compound shown by the said general formula (III) can also be used. Specific examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl. -1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1 -One, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,4,6-trimethyl Nzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4- Dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) ) Oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4 - Tylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene Peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2 -Chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, Dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2- Methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethyl Minobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxy Triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (4-Diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Tenenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- ( 3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6 -(3-Bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s -A triazine etc. can be mentioned.

  Among these, triazines such as p-methoxytriazine; 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis ( Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4- Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 Halomethyl groups such as (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Triazine compounds such as: Triazine compounds such as 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer; Imidazolyl compounds such as 2-benzyl-2-dimethylamino-1 An amino ketone compound such as-(4-morpholinophenyl) -butan-1-one; is preferably used.

In the present invention, it is preferable to use a compound represented by the general formula (III) in combination with at least one other compound as a photopolymerization initiator. Use of at least two kinds of compounds (photopolymerization initiators) in this way is preferable in that they can be efficiently activated by a small amount of light to further increase sensitivity and development margin. This is because a compound having a different electronic band spectrum (photopolymerization initiator) coexists in the photosensitive resin composition, so that the entire photopolymerization initiator broadens the net wavelength range of light having high sensitivity, or at least two. This is thought to be due to the interaction of certain compounds.
Preferred examples (1) to (3) of the combination of the compound represented by the general formula (III) and at least one other compound are shown below.

(1) At least one photopolymerization initiator of the O-acyloxime compound represented by the general formula (III) and a compound other than the O-acyloxime compound (light other than the compound represented by the general formula (III) A combination with a polymerization initiator) is preferred.
Among the above O- acyl oxime compound, in the general formula ^{(III), R 11} is n- hexyl _{(C 6 H 13} ^-), in ^{R 12} is a benzoyl group, X 'is represented by the general formula (IV) And R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ are hydrogen atoms and R ¹⁵ is a phenylsulfanyl group (C ₆ H ₅ S—), that is, 1,2-octanedione represented by the following formula (VI) -1- [4- (Phenylthio) phenyl] -2- (O-benzoyloxime) is preferable in terms of sensitivity to light and availability.

Further, among the O-acyloxime compounds, in general formula (III), R ¹¹ is methyl, R ¹² is an acetyl group, X ′ is represented by general formula (V), and R ¹⁸ is ethyl. R ¹⁹ is a methyl group, that is, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- represented by the following formula (VII) (O-acetyloxime) is more preferable because it has higher sensitivity to light.

(2) A combination of a photopolymerization initiator represented by the above general formula (III) and X ′ represented by the general formula (IV) and a triazine compound is also preferable.
In particular, as the triazine compound, a triazine compound represented by the following formula (VIII), the following formula (IX), or the following formula (X) (wherein R ²¹ and R ²² represent an alkyl group having 1 to 3 carbon atoms). Is particularly preferred. 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one can also be used in the same manner as the triazine compound.

(3) a photopolymerization initiator represented by the above general formula (III) and X ′ represented by the general formula (V), and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane A combination with -1-one is also preferred. Moreover, the above-mentioned triazine compound can be similarly combined instead of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

  The compounding ratio of the compound represented by the general formula (III) and other compounds other than the compound represented by the general formula (III) (particularly triazine compound, imidazolyl compound and aminoketone compound) is 10:90 to 10 by mass ratio. 90:10 is preferable, and 20:80 to 80:20 is particularly preferable. Since the compounding ratio of the compound represented by the general formula (III) and the other compound other than the compound represented by the general formula (III) is within the above-mentioned range, both compounds effectively interact with each other. The sensitivity and development margin of the photosensitive resin composition can be further improved.

  The blending amount of the (D) photopolymerization initiator in the photosensitive resin composition of the present invention is preferably in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the (B) alkali-soluble resin.

<(E) Oxetane compound>
The oxetane-based compound in the present invention is a compound having one or more oxetane rings, preferably 1 to 3, more preferably 1 to 2. Examples of such oxetane compounds include compounds represented by the following general formula (E1), general formula (E2), or general formula (E3).

（式中、Ｒ^３1 およびＲ^３2 はそれぞれ独立に、水素原子、炭素数１〜５のアルキル基、炭素数２〜４のアルケニル基、または炭素数７〜１２のアラルキル基を示す。）

(Wherein R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.)

[Wherein, R ³³ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a carbon number 2-6 monoalkylaminocarbonyl group, dialkylaminocarbonyl group (however, each alkyl group has 1 to 3 carbon atoms), cycloalkyl group with 4 to 12 carbon atoms, aryl group with 6 to 15 carbon atoms Represents an aralkyl group having 7 to 12 carbon atoms or an aralkyloxyalkyl group having 8 to 12 carbon atoms, and R ³⁴ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a carbon number 7 to 12 aralkyl groups are shown. ]

〔式中、Ｒ^３５およびＲ^３６はそれぞれ独立に、水素原子、炭素数１〜５のアルキル基、炭素数２〜４のアルケニル基、または炭素数７〜１２のアラルキル基を示し、Ｘ”はカルボニル基、炭素数１〜３のアルキレン基、炭素数６〜１０のアリーレン基、炭素数８〜１２のアラルキレン基または−ＣＯ−Ｙ”−ＣＯ−基（但し、Ｙ”は炭素数１〜３のアルキレン基、炭素数６〜１０のアリーレン基または炭素数８〜１２のアラルキレン基を示す。）を示す。〕

[Wherein, R ³⁵ and R ³⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and X ″ represents A carbonyl group, an alkylene group having 1 to 3 carbon atoms, an arylene group having 6 to 10 carbon atoms, an aralkylene group having 8 to 12 carbon atoms, or a —CO—Y ″ —CO— group (where Y ″ represents 1 to 3 carbon atoms) An alkylene group, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 8 to 12 carbon atoms.

In the formula (E1), formula (E2) and formula (E3), each organic group present in R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ is a halogen atom at an appropriate position. , A hydroxyl group, a carboxy group, a nitrile group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and the like, and R ³¹ , R ³² , R ³³ , R ³⁴ , R Each cycloalkyl group, aryl group, arylene group and aralkylene group present in ³⁵ and R ³⁶ may each be substituted with an alkyl group having 1 to 6 carbon atoms at an appropriate position.

Specific examples of the oxetane compound include oxetane, 3-methyloxetane, 3-ethyloxetane, 3-n-propyloxetane, 3-n-butyloxetane, 3-vinyloxetane, 3-allyloxetane, 3-benzyloxetane, 3,3-dimethyloxetane, 3,3-diethyloxetane, 3-methyl-3-ethyloxetane, 3-methyl-3-n-propyloxetane, 3-methyl-3-n-butyloxetane, and the following chemical formula (E4 ) To (E51).
In the following, each oxetane compound is sometimes expressed as “oxetane compound (E7)” (in the case of the compound of formula (E7)) with the formula number in parentheses.

  These oxetane compounds are disclosed in, for example, Journal of Macromolecular Science PUREAPPL. CHEM. , A30 (2 & 3), p189-206 (1993) or a method analogous thereto.

  An oxetane compound represented by the following general formula (E52) is also preferable. As a specific example, a compound represented by the following chemical formula (E53) is preferable.

In the formula (E52), R ³⁷ and R ³⁸ are each independent and the same as R ³⁵ and R ³⁶ .

Of the oxetane compounds, oxetane compounds (E5), oxetane compounds (E50), oxetane compounds (E53) and the like are particularly preferable. Of these, an oxetane compound (E53) is more preferable.
In the present invention, the oxetane compounds can be used alone or in admixture of two or more.

As for the usage-amount of (E) oxetane type compound in this invention, 0.1-100 mass parts is preferable with respect to 100 mass parts of (B) alkali-soluble resin, More preferably, it is 1-50 mass parts.
(E) By making the usage-amount of an oxetane type compound more than the lower limit of the said range, sufficient addition effect is acquired, and adhesiveness with a board | substrate can be improved by making it the upper limit of the said range or less.

<(F) Epoxy compound>
The epoxy compound in the present invention is not particularly limited. For example, (F1) an epoxy group-containing unsaturated compound, (F2) a compound having two or more 3,4-epoxycyclohexyl groups in the molecule, (F3) A compound having two or more epoxy groups in the molecule is preferably used.

  (F1) The epoxy group-containing unsaturated compound is a compound having an epoxy group and a polymerizable carbon-carbon double bond in one molecule. Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, and α-ethylacrylic acid. Glycidyl, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, Examples include methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

  (F2) Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3 , 4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4) of ethylene glycol -Epoxycyclohexylmethyl) Ether, ethylenebis (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', may be mentioned 4'-epoxycyclohexane carboxylate.

  Examples of the compound having two or more (F3) epoxy groups include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, Diglycidyl ethers of various bisphenol compounds such as hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether; 1,4-butanediol diglycidyl Ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene Polyglycidyl ethers of polyhydric alcohols such as recall diglycidyl ether and polypropylene glycol diglycidyl ether; by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Polyglycidyl ethers of the resulting polyether polyols; phenol novolac type epoxy resins; cresol novolac type epoxy resins; polyphenol type epoxy resins; diglycidyl esters of aliphatic long-chain dibasic acids; glycidyl esters of higher fatty acids; Examples include bean oil and epoxidized linseed oil.

  (F3) As a commercially available compound having two or more epoxy groups, for example, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (bisphenol A type epoxy resin) As described above, Yuka Shell Epoxy Co., Ltd.), etc .; Bisphenol F type epoxy resin, Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.), etc .; Phenol novolac type epoxy resin, Epicoat 152, 154, 157 S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.), etc .; cresol novolac type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku) Yakuhin Co., Ltd.) Coat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), etc .; as polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, manufactured by Japan Epoxy Resin Co., Ltd.), etc .; Cyclic aliphatic epoxy resin, CY-175, 177 179, Araldite CY-182, 192, 184 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), ERL-4234, 4299, 4221, 4206 (above, made by UC Corporation), Show Dyne 509 (manufactured by Showa Denko KK), Epicron 200, 400 (above, Dainippon Ink Co., Ltd.), Epicoat 871, 872 (above, Japan Epoxy Resin Co., Ltd.), ED-5661, 5562 (Celanese Coating Co., Ltd.) etc .; Aliphatic polymer Epolight 100MF as glycidyl ether (manufactured by Kyoeisha Chemical Co.), Epiol TMP (manufactured by NOF Corporation) and the like.

(F) An epoxy compound may be used individually by 1 type, and can also be used in combination of 2 or more type.
0.05-20 mass parts is preferable with respect to 100 mass parts of (B) alkali-soluble resin, and, as for the usage-amount of the (F) epoxy compound in this invention, More preferably, it is 1-15 mass parts.
(F) Sufficient addition effect is acquired by making the usage-amount of an epoxy compound more than the lower limit of the said range, and storage stability can be improved by making it the upper limit of the said range or less.

In the photosensitive resin composition of the present invention, an organic solvent (G) can be blended for improving coating properties and adjusting viscosity.
Organic solvents include benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol mono Chill ether acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, methyl carbonate, ethyl carbonate, propyl carbonate and carbonate butyl. Among them, 3-methoxybutyl acetate is preferable because it not only exhibits excellent solubility with respect to the soluble component in the photosensitive resin composition but also improves the dispersibility of insoluble components such as pigments.
(G) Although the usage-amount of an organic solvent is not specifically limited, It is a density | concentration which can be apply | coated to a board | substrate etc., and is suitably set according to a coating film thickness. The viscosity of the photosensitive resin composition in the present invention is 5 to 100 cp, preferably 10 to 50 cp, more preferably 20 to 30 cp. Moreover, the solid content concentration is 5 to 100% by mass, preferably 20 to 50% by mass.

Moreover, you may add a thermal-polymerization inhibitor, an antifoamer, surfactant, etc. to the photosensitive resin composition of this invention.
The thermal polymerization inhibitor may be a conventionally known one, and examples thereof include hydroquinone and hydroquinone monoethyl ether.
As said antifoamer, a conventionally well-known thing may be used and a silicone type and a fluorine-type compound are mentioned.
The surfactant may be a conventionally known surfactant, and examples thereof include anionic, cationic and nonionic compounds.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition of the present invention can be prepared by the following method.
(A) Colorant, (B) Alkali-soluble resin, (C) Photopolymerizable compound, (D) Photopolymerization initiator, (E) Oxetane compound, (F) Epoxy compound, and organic additives as required And mixing (dispersing / kneading) with a stirrer such as a three-roll mill, ball mill, or sand mill, and filtering through a 5 μm membrane filter to prepare a photosensitive resin composition.

  The photosensitive resin composition of this invention can be used suitably for the use which forms the black matrix and / or colored layer which comprise a color filter.

<Method for forming color filter>
Hereinafter, the example of the method of forming a color filter using the photosensitive resin composition of this invention is demonstrated.
1. Formation of black matrix (black colored layer) First, a photosensitive resin composition (including a black colorant) is applied onto a substrate by a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or spinner (rotary coating device). ), Using a non-contact type coating device such as a curtain flow coater. As the substrate, a light-transmitting substrate is used, for example, a glass substrate having a thickness of 0.5 to 1.1 mm.
In order to improve the adhesion between the glass substrate and the photosensitive resin composition, a silane coupling agent may be applied on the glass substrate in advance. Alternatively, a silane coupling agent may be added during the preparation of the photosensitive resin composition.
After the application, the solvent is removed by drying. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at 80 ° C. to 120 ° C., preferably 90 ° C. to 100 ° C. for 60 seconds to 120 seconds, (2) several hours at room temperature Any method of leaving for several days or (3) removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours may be used.
Next, exposure is performed partially by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, but is preferably about 30 to 2000 mJ / cm ² , for example.
The exposed film is developed with a developer to be patterned into a desired shape. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
After development, post-baking is performed at about 200 ° C. Further, it is preferable to expose the entire surface of the formed pattern.
2. Formation of other colored layers A photosensitive resin composition is applied to the glass substrate on which the black matrix formed above is formed, dried, exposed and developed in the same manner as described above to form a colored layer of a predetermined color. A pattern (such as a stripe or a dot) is formed at a predetermined position (opening). For example, when an RGB color filter is manufactured, the above steps are repeated using photosensitive resin compositions of R, G, and B colors to form three color layers.
As described above, a color filter can be formed.

According to the photosensitive resin composition of the present invention, by using the (E) oxetane compound and the (F) epoxy compound in combination, good sensitivity to exposure light is obtained, and a pattern having a good shape after development is obtained. It is done. Even if post-baking is performed thereafter, a good pattern shape is maintained, and a pattern having an excellent profile shape is finally obtained. Also, the adhesion is excellent.
In particular, for a black matrix, a colored layer of another color is formed after the black matrix is formed. Therefore, since the number of times of exposure to a developing solution or the like increases, adhesion is required. That is, since the photosensitive resin composition of the present application is excellent in adhesion, it can be particularly useful for forming a black matrix.
Therefore, by using the photosensitive resin composition of the present invention, a black matrix or a colored layer having a good profile shape can be formed, and a high-quality color filter having such a black matrix and / or colored layer is obtained. be able to.

(Synthesis example 1 of alkali-soluble resin)
In accordance with JP 2001-354735 A, in a 500 mL four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tertbutyl-4-methylphenol and Acrylic acid 72.0 g was charged and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 mL / min.
Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. The solution gradually became transparent and viscous, but stirring was continued as it was.
During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by following Chemical formula (1) which is a colorless and transparent solid.

Next, after adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate obtained in this way and dissolving, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed. The temperature was gradually raised and the reaction was carried out at 110 to 115 ° C. for 4 hours.
After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain the above chemical formula (I) (wherein X represents the above A divalent residue obtained by removing two hydroxyl groups from the compound represented by the chemical formula (1), and Y is a compound obtained by removing a carboxylic acid anhydride group from 1,2,3,6-tetrahydrophthalic anhydride. Z is a tetravalent residue obtained by removing two carboxylic anhydride groups from biphenyltetracarboxylic dianhydride, wherein the molar ratio of Y / Z in the formula = 50.0 / The compound 1 represented by this was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

Example 1
A photosensitive resin composition was prepared by mixing each component with the following composition.
(B) 100 parts by mass of Compound 1 obtained in Synthesis Example 1 was used as the alkali-soluble resin.
As the component (C), 50 parts by mass of pentaerythritol tetraacrylate was used.
(A) As a colorant, 30 parts by mass of the dispersion “CF Black PC” (manufactured by Mikuni Color Co., Ltd., containing 24% carbon black) was used.
(D) As a photopolymerization initiator, manufactured by Ciba Specialty Chemicals, product name; Irgacure 369, compound name; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one 25 parts by mass was used.
(E) As an oxetane compound, 25 parts by mass of di [1-ethyl (3-oxetanyl)] methyl ether (a compound represented by the above chemical formula (E53)) was used.
(F) As an epoxy compound, Japan Epoxy Resin Co., Ltd. product name; 5 mass parts of Epicoat-1001 was used.
(G) As the organic solvent, a mixed solvent having a mass ratio PGMEA: 3-methoxybutyl acetate of 1: 3 was used. The amount of the organic solvent used was adjusted so that the solid concentration was 30% by mass.

The photosensitive resin composition prepared above was applied to a glass substrate with a film thickness of 1200 nm using a spin coater (1H-360s: manufactured by Mikasa) and dried on a hot plate at 90 ° C. for 2 minutes. Thus, a coating film was formed.
Next, exposure light was exposed at an irradiation energy dose of 20 mJ / cm ^{2 using} an exposure machine (EXM-1066-E01: manufactured by Oak Corporation). After the exposure, the film was developed for 100 seconds by a spray method with a potassium hydroxide 0.04% developer. Further, post baking was performed at 200 ° C. for 30 minutes to form a 15 μm line pattern.

  At this time, the profile was judged by observing the cross section of the pattern formed before and after the post-bake with an electron microscope. In this example, there was almost no change in shape before and after post-baking, which was good.

(Comparative Example 1)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that (E) the epoxy compound was not added in the formulation of Example 1 above.
Using the obtained photosensitive resin composition, an attempt was made to form a pattern in the same manner as in Example 1. However, the sensitivity was poor and a pattern could not be formed.
Therefore, exposure was performed at an irradiation energy dose of 150 mJ / cm ² to form a pattern.
When the evaluation was performed in the same manner as in Example 1, the pattern after post-baking was sagging and had a poor profile.

Claims (6)

A photosensitive resin composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator,
(E) A photosensitive resin composition comprising an oxetane compound and (F) an epoxy compound.   The photosensitive resin composition of Claim 1 which contains 0.1-100 mass parts of said (E) oxetane compounds with respect to 100 mass parts of said (B) alkali-soluble resin.   The photosensitive resin composition of Claim 1 or 2 which contains 0.05-20 mass parts of said (F) epoxy compounds with respect to 100 mass parts of said (B) alkali-soluble resin. The said (E) oxetane compound contains the compound represented by the following general formula, The photosensitive resin composition of any one of Claims 1-3 characterized by the above-mentioned.

[Wherein, R ³⁷ and R ³⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. ]   The photosensitive resin composition according to claim 1, wherein the colorant (A) is a black pigment. It has a pattern formed using the photosensitive resin composition of any one of Claims 1-5, The color filter characterized by the above-mentioned.