JP2006235153A - Photosensitive resin composition for forming light shielding layer, and light shielding layer and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for forming a light shielding layer for favorably forming a light shielding layer of a thick film. <P>SOLUTION: The photosensitive resin composition for forming a light shielding layer contains (A) a light shielding dye, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, and used to form a light shielding layer with over 2 μm film thickness, wherein the (A) light shielding dye contains a perylene-based black pigment. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition for forming a light shielding layer, and a light shielding layer and a color filter formed using the same.

For example, in a color filter used in a color display device, pixels of each color of red (R), green (G), and blue (B) are generally surrounded by a grid-like black light shielding layer called a black matrix. It has the composition which is.
As one method for manufacturing such a color filter, a method of forming a colored layer of a color filter by an ink jet method using a black matrix as a partition is proposed (for example, Patent Document 1 below).
In addition to color filters, various display devices may improve image contrast by providing a black matrix on the boundary between pixels.

The black matrix is formed by, for example, a photolithographic method using a photoresist composition containing a black pigment. Carbon black is generally used as the black pigment (for example, Patent Document 1).
As for the perylene dye, Patent Documents 2 and 3 below describe examples of a resist for forming a light shielding layer using a black pigment such as carbon black and a perylene dye in combination.
JP 2004-325736 A Japanese Patent Laid-Open No. 4-190362 JP-A-6-289602

In recent years, higher optical density (hereinafter referred to as OD value) has been required for black matrices. In general, the black matrix is formed with a film thickness of 2 μm or less. However, if the black matrix can be formed thicker than before, a black matrix having a higher OD value can be formed.
However, even if an attempt is made to form a thick black matrix with a photoresist composition containing a general black pigment, transmission of exposure light in the exposure process becomes insufficient, and non-uniform exposure failure tends to occur. In other words, since the sensitivity is low, curing failure occurs, and it is difficult to form a thick black matrix well.

  The present invention has been made in view of the above circumstances, and is formed using a photosensitive resin composition for forming a light-shielding layer that can satisfactorily form a thick light-shielding layer, and the photosensitive resin composition for forming a light-shielding layer. An object is to provide a light shielding layer and a color filter.

  In order to achieve the above object, the light-sensitive layer forming photosensitive resin composition of the present invention comprises (A) a light-shielding dye, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) light. A photosensitive resin composition for forming a light-shielding layer containing a polymerization initiator and having a film thickness of more than 2 μm, wherein the (A) light-shielding dye contains a perylene-based black pigment.

This invention provides the light shielding layer formed using the photosensitive resin composition for light shielding layer formation of this invention.
This invention provides the color filter provided with the black matrix formed using the photosensitive resin composition for light shielding layer formation of this invention.

According to the photosensitive resin composition for forming a light shielding layer of the present invention, a thick light shielding layer can be formed satisfactorily. Thereby, a black matrix having a higher OD value can be formed. Furthermore, even if the red (R), green (G), and blue (B) colored layers are thickened to darken the color, sufficient contrast can be obtained.
Since the color filter provided with the black matrix formed using the photosensitive resin composition for forming a light shielding layer of the present invention can have sufficient contrast as described above, a clearer color display is possible. Become.

<(A) Light-shielding dye>
In the present invention, a perylene black pigment (hereinafter simply referred to as a perylene pigment) is used as the light-shielding dye. Specific examples include perylene pigments represented by the following general formula (I) and perylene pigments represented by the following general formula (II). For commercial products, product names such as K0084, K0086, and BASF can be preferably used.

(In the formula, R ¹ and R ² each independently represent an alkylene group having 1 to 3 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or an acetyl group.)

(In formula, R < ⁵ >, R < ⁶ > represents a C1-C7 alkylene group each independently.)

  The compound represented by the general formula (I) and the compound represented by the general formula (II) are synthesized using, for example, the methods described in JP-A Nos. 62-1753 and 63-26784. be able to. That is, perylene-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and amines are used as raw materials, and a heating reaction is performed in water or an organic solvent. The obtained crude product is reprecipitated in sulfuric acid or recrystallized in water, an organic solvent or a mixed solvent thereof to obtain the target product.

In the present invention, perylene pigments may be used alone or in combination of two or more.
Moreover, in order to make a perylene pigment into a dispersed state in the photosensitive resin composition for light shielding layer formation, it is preferable that the average particle diameter of a perylene pigment is 10-1000 nm.
As for content of the perylene pigment in the photosensitive resin composition for light shielding layer formation of this invention, 5-250 mass parts is preferable with respect to 100 mass parts of (B) alkali-soluble resin. A more preferable range is 10 to 200 parts by mass. When the content of the perylene pigment is not less than the lower limit of the above range, good light shielding properties can be obtained. Moreover, it is preferable when it is below the upper limit of the said range, when exposure failure and hardening failure are prevented.

Moreover, (A) Color tone etc. may be adjusted by using together black, red, blue, green, yellow, and purple pigments other than the light-shielding pigment. As the other dye, known ones can be used as appropriate, and a black pigment such as carbon black is preferable. The amount of the other dye used is preferably set so that the ratio of the whole dye, that is, the perylene pigment to the total of the perylene pigment and the other dye is 85% by mass or more. More preferably, it is 90 mass% or more, and may be 100 mass%.
By setting it to the above lower limit value or more, it is possible to obtain sensitivity when forming a thick film exceeding 2 μm using the photosensitive resin composition for forming a light shielding layer, and achieve a good light shielding rate of the light shielding film. can do.
In particular, when carbon black is used as the other pigment, if the carbon black is less than 15% by mass in the total pigment, the light shielding ratio is reduced without reducing the sensitivity of the photosensitive resin composition for forming the light shielding layer. Can be improved.

<(B) Alkali-soluble resin>
(I) Alkali-soluble resin As the alkali-soluble resin in the present invention, at least one selected from monomers having a carboxy group such as acrylic acid and methacrylic acid, and methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate , 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl 1 selected from acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, acrylamide, acrylonitrile, etc. Copolymer with more than species;
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 following General formula (1) is also applicable as alkali-soluble resin. The compound represented by the general formula (1) itself has photopolymerizability (photocurability). Therefore, in the photosensitive resin for forming a light-shielding film containing the compound, by increasing the transmittance of ultraviolet rays, Sensitivity can be improved.

(Wherein X is a group represented by the following chemical formula (2), Y is a residue obtained by removing a carboxylic acid anhydride group (—CO—O—CO—) from dicarboxylic acid 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. Moreover, only the said alkali-soluble resin (I) may be used, only the alkali-soluble resin (II) which has photocurability may be used, and both may be used together.
The mass average molecular weight (Mw) of the alkali-soluble resin (Mw) in the present invention (polystyrene conversion standard by gel permeation chromatography) is not particularly limited, but is preferably 1000 to 1000000, 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 alkali-soluble polymer is contained in the (B) alkali-soluble resin (II), and the photopolymerizable monomer is contained in the (C) photopolymerizable compound. And

(C) The compounding quantity of a photopolymerizable compound has the range of 5-500 mass parts with respect to 100 mass parts of this resin (I), when using the said alkali-soluble resin (I) as (B) alkali-soluble resin. preferable. 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, it is preferable to make it into the upper limit value or less of the said range, when obtaining favorable film formation ability and preventing the film residue after image development.

<(D) Photopolymerization initiator>
Examples of the (D) photopolymerization initiator in the present invention include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 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-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Butyl aminobenzoate, 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- Chloro Oxanthene, 2,4-diethylthioxanthene, 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 Mer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxyben Phenone, 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-dimethylamino Propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, Nthyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) Propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methyl) Furan-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- (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-trichloro Methyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) ) Styrylphenyl-s-triazine and the like.

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.
Other preferred photopolymerization initiators include compounds represented by the following general formula (III).

(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 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.

In the present invention, a plurality of types may be used in combination as the photopolymerization initiator. In particular, it is preferable to use a compound represented by the general formula (III) in combination with at least one other compound. 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.
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) (especially triazine compound, imidazolyl compound and aminoketone compound) is 10:90 to 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. Further, the sensitivity and development margin of the photosensitive resin composition for forming a light shielding layer can be further improved.

  The blending amount of the (D) photopolymerization initiator in the photosensitive resin composition for forming a light shielding layer 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. .

The photosensitive resin composition for forming a light shielding layer of the present invention may contain (E) an organic solvent 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 for the soluble component in the photosensitive resin composition for forming a light shielding layer, but also improves dispersibility of insoluble components such as pigments. is there.
(E) 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 for forming a light shielding layer in the present invention is 5 to 100 cp, preferably 10 to 50 cp, more preferably 20 to 30 cp. Moreover, solid content concentration is 5-100 mass%, Preferably it is the range of 20-50 mass%.

Moreover, you may add a thermal polymerization inhibitor, an antifoamer, surfactant, etc. to the photosensitive resin composition for light shielding layer formation 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.

<Preparation method of photosensitive resin composition for light shielding layer formation>
The photosensitive resin composition for light shielding layer formation of this invention can be prepared with the following method.
(A) light-shielding dye, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photopolymerization initiator, and a three-roll mill, ball mill, sand mill, etc., if necessary, with organic additives Are mixed (dispersed and kneaded) with, for example, a 5 μm membrane filter to prepare a light-sensitive layer forming photosensitive resin composition.

  The photosensitive resin composition for forming a light shielding layer of the present invention is suitably used for the purpose of forming a light shielding layer having a film thickness of more than 2 μm (thickness greater than 2 μm). The upper limit of the light shielding layer is not particularly limited, and may be formed as thick as possible. A preferable range of the thickness of the light shielding layer is about 3 to 10 μm, a more preferable range is 3 to 8 μm, and a further preferable range is about 4 to 6 μm.

  The light shielding layer in the present invention is, for example, a black matrix provided around each pixel in various display devices or at a boundary portion between the display unit and the non-display unit. Examples of the display device provided with such a black matrix include a liquid crystal display device and a plasma display display device.

<Method for forming light shielding layer>
Hereinafter, an example of a method for forming a black matrix will be described as an embodiment of a method for forming a light shielding layer using the photosensitive resin composition for forming a light shielding layer of the present invention.
First, a photosensitive resin composition for forming a light-shielding layer is formed on a substrate by using a contact transfer type coating device such as a roll coater, reverse coater or bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. Use to apply. 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 for forming a light shielding layer, a silane coupling agent may be applied on the glass substrate in advance. Or you may add a silane coupling agent at the time of preparation of the photosensitive resin composition for light shielding layer formation.
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 one of a method of leaving for several days, and a method of removing the solvent by putting 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 light-sensitive layer forming photosensitive resin composition, but is preferably about 30 to 2000 mJ / cm ² , for example.
The exposed film is developed using a developer to form a black matrix pattern. 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.

According to the photosensitive resin composition for forming a light shielding layer of the present invention, a good pattern can be formed by the photolithography method even if the film thickness is more than 2 μm. Accordingly, a thick light shielding layer such as a thick black matrix can be formed.
This is considered to be realized by using a perylene pigment as a light-shielding dye, whereby the resin composition can transmit exposure light and shield visible light.

<Spacer>
The light-shielding layer having a constant film thickness formed using the photosensitive resin composition for forming a light-shielding layer of the present invention is a liquid crystal display having a configuration in which liquid crystal is accommodated between two substrates. In order to keep the distance between the substrates constant, it can also serve as a spacer provided between the two substrates. The thickness of the light shielding layer having such a spacer function is not particularly limited, but is preferably more than 2 μm.

In a conventional liquid crystal display, a spacer formed of spherical spacer particles or a photosensitive resin composition is disposed between two substrates. When spherical spacer particles are used, the spacer may move in the liquid crystal when vibration or impact is applied, and the alignment film provided on the inner surface of the substrate may be damaged. The problem can be solved. Further, when the spacer formed of the photosensitive resin composition is used as described above, it is necessary to form the black matrix separately, but according to the present invention, it is not necessary to form the black matrix separately. The manufacturing process can be reduced.
Furthermore, since the spacer has a light-shielding property, “white spots” due to the spacer portion being always in a light transmitting state can be prevented.

<Color filter>
According to the present invention, the black matrix can be formed in a thick film. Therefore, the photosensitive resin composition for forming a light shielding layer of the present invention is particularly suitable for forming a black matrix in a method for forming a color filter by forming a colored layer in an opening of a previously formed black matrix by an inkjet method. is there. The black matrix in the method serves as a so-called partition wall (bank).
In the present invention, the film thickness of the black matrix used as the partition (bank) in the ink jet system is not particularly limited, but is preferably more than 2 μm.

A method of forming a black matrix as a partition (bank) using the photosensitive resin composition for forming a light shielding layer of the present invention can be performed in the same manner as the method for forming the light shielding layer.
Then, after forming a black matrix as a partition (bank), a colored layer is formed by repeating a step of applying a colored ink by an inkjet method in an opening of the black matrix and a step of curing the colored ink, Furthermore, a color filter can be manufactured by forming a transparent protective film as needed. A known method can be used as a method of forming a colored layer by an inkjet method.

According to the present invention, since a black matrix used as a partition (bank) in the ink jet system can be formed in a thick film, the color ink applied to the opening of the black matrix exceeds the partition and color mixing occurs between overflowing pixels. It can be prevented from occurring.
Further, compared with a case where the black matrix is thin (the partition walls are low), a colored ink having a low viscosity can be used.
In addition, a color filter can be formed by a photolithography method as usual.

(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. Here, although the solution gradually became transparent and viscous, 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 (3) 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 (1) (wherein X represents the above) It is a divalent residue obtained by removing two hydroxyl groups from the compound represented by the chemical formula (3), and Y is 2 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
Each component was mixed by the following mixing | blending and the photosensitive resin composition for light shielding layer formation was prepared.
(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 dipentaerythritol tetraacrylate was used.
(A) 30 parts by mass of perylene-based black pigment dispersion (CI Pigment Black 31: 15%, dispersant 10%, solvent: PGMEA) was used as a light-shielding dye.
(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 30 parts by mass was used.
(E) As the organic solvent, a mixed solvent having a mass ratio of 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 for forming a light shielding layer prepared above is applied to a glass substrate using a spin coater (1H-360s: manufactured by Mikasa), and dried on a hot plate at 90 ° C. for 2 minutes to form a coating film. Formed.
Subsequently, it exposed with the irradiation energy dose of 20 mJ / cm < ² > with the exposure machine (EXM-1066-E01: product made from Oak Co.). After the exposure, development was performed for 60 seconds by a spray method using a potassium hydroxide 0.04% developer. Further, post baking was performed at 200 ° C. for 30 minutes to form a 20 μm matrix pattern, a dot pattern, and an isolated pattern black matrix having a film thickness of 2.5. The OD value of the formed black matrix was 3.0.
The shape of the obtained black matrix was good.

(Comparative Example 1)
In the formulation of Example 1 above, (A) As a light-shielding dye, a perylene pigment was not used, and instead a carbon black dispersion “CF Black EX-1455” (manufactured by Mikuni Dye Co., Ltd., containing 24% carbon black) was used. A photosensitive resin composition for forming a light shielding layer was prepared in the same manner as in Example 1 except that parts by mass were used.
Using the obtained photosensitive resin composition for forming a light shielding layer, an attempt was made to form a 20 μm matrix pattern, a dot pattern, and an isolated pattern black matrix having a film thickness of 2 μm in the same manner as in Example 1. All were peeled off and could not be formed.

(Example 2)
In the formulation of Example 1, instead of 30 parts by mass of the perylene pigment dispersion, a pigment mixture in which the perylene pigment dispersion and the carbon black dispersion “CF Black EX-1455” were mixed at a ratio of 90:10 A light-sensitive layer forming photosensitive resin composition was prepared using 40 parts by mass of the liquid.
Using the obtained photosensitive resin composition for forming a light shielding layer, a coating film was formed in the same manner as in Example 1, and exposed at 30 mJ / cm ² . After the exposure, development was performed for 60 seconds by a spray method using a potassium hydroxide 0.04% developer. Further, post-baking was performed at 200 ° C. for 30 minutes to form a black matrix of 20 μm matrix pattern, dot pattern, and isolated pattern with a film thickness of 3 μm. The OD value of the formed black matrix was 4.5.
The shape of the obtained black matrix was good.

(Example 3) Spacer In the formulation of Example 1, instead of 30 parts by mass of the perylene pigment dispersion, the perylene pigment dispersion and the red pigment dispersion (CI Pigment Red 177 were contained in 23.4%) ) And a blue pigment dispersion (containing 23.4% including CI Pigment Blue 15: 6) at a ratio of 88: 5: 7 in a ratio of 88: 5: 7, the light-sensitive layer-forming photosensitivity. A resin composition was prepared.
Using the obtained photosensitive resin composition for forming a light shielding layer, a coating film was formed in the same manner as in Example 1 and exposed at 200 mJ / cm ² . After the exposure, the film was developed with a TMAH 0.1% developer by a spray method for 60 seconds. Further, post-baking was performed at 250 ° C. for 30 minutes to form a spacer composed of a 20 μm dot pattern having a thickness of 5 μm. The OD value of the formed spacer was 4.0.
The shape of the obtained spacer was good.

(Comparative Example 2)
In the formulation of Example 3 above, instead of 40 parts by mass of the pigment mixture, 40 parts by mass of carbon black dispersion “CF Black EX-1455” (manufactured by Mikuni Dye Co., Ltd., containing 24% carbon black) was used. Prepared a light-sensitive layer-forming photosensitive resin composition in the same manner as in Example 1.
Using the obtained photosensitive resin composition for forming a light shielding layer, a dot pattern of 20 μm having a thickness of 5 μm was formed in the same manner as in Example 3. The OD value of the formed spacer was 4.0.
The surface of the obtained spacer was wrinkled, and could not be used as a spacer.

Claims (7)

Photosensitive resin for forming a light-shielding layer having a thickness of more than 2 μm, comprising (A) a light-shielding dye, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator. A composition comprising:
(A) The light-shielding pigment | dye contains the perylene-type black pigment in (A) light-shielding pigment | dye, The photosensitive resin composition for light shielding layer formation characterized by the above-mentioned.   The photosensitive resin composition for forming a light shielding layer according to claim 1, wherein the film thickness is 3 to 10 μm.   The photosensitive resin composition for light shielding layer formation of Claim 1 or 2 which contains 5-250 mass parts of said perylene type black pigments with respect to 100 mass parts of said (B) alkali-soluble resin.   The photosensitive resin composition for forming a light shielding layer according to claim 1, wherein the light shielding layer is a light shielding layer having a spacer function.   The light shielding layer formation according to any one of claims 1 to 4, wherein the light shielding layer is a black matrix in a method for producing a color filter by forming a colored layer in an opening of a black matrix formed in advance by an ink jet method. Photosensitive resin composition.   The light shielding layer formed using the photosensitive resin composition for light shielding layer formation as described in any one of Claims 1-5. The color filter provided with the black matrix formed using the photosensitive resin composition for light shielding layer formation as described in any one of Claims 1-5.