TWI506366B - Photosensitive resin composition for black resist and color filter shielding film - Google Patents

Description

Photosensitive resin composition for black resist and color filter film

The present invention relates to an alkaline aqueous solution developing type photosensitive resin composition for forming a fine light-shielding film on a transparent substrate, and a color filter light-blocking film formed using the composition.

In a color filter, a black matrix is formed on the surface of a transparent substrate such as a glass or a plastic sheet, and then three or more different colors such as red, green, and blue are sequentially striped or mosaic. A colored pattern is formed. The black matrix is called a light shielding film by suppressing the color mixture between the colors to enhance the contrast or prevent the TFT from malfunctioning due to the light leakage.

A representative method for producing a color filter is to apply a photopolymerizable composition containing a color material onto a transparent substrate, and repeat exposure of the image, development, and formation of a color filter image in response to hardening required. Dispersion method. This method is widely used because it improves the accuracy of the position and film thickness of the color filter pixels, and is excellent in durability such as light resistance and heat resistance, and has few defects such as pinholes.

In recent years, in order to achieve high-definition colorization and high definition, the resin black matrix which is one of the color filter-related materials is required to have higher light-shielding and thicker film than ever before. Further, recently, since it is not required to be exposed, it is possible to manufacture a color filter by applying only a coloring material to an inkjet method of a required portion. Since the ink jet method uses the black matrix itself as a partition wall, it is required to be thick. In addition, in order to improve panel performance and reduce cost, various types of color filters have been reviewed, and the resin black matrix is required to have a thicker filming opportunity than before.

However, as the film thickness of the resin black matrix increases, the difference in bridging density in the film thickness direction of the exposed portion also increases, and therefore, it is more difficult to obtain a black pattern which achieves high sensitivity and good shape. In addition, in the subsequent thermal firing process, there is a difference in bridging density in the film thickness direction of the exposed portion, so that there is a difference in thermosetting shrinkage between the surface of the coating film and the vicinity of the substrate, and the surface roughness of the coating film is increased. The surface smoothness is also deteriorated, which adversely affects the formation of each of the red, blue, and green pixels. Although the surface roughness can be prevented from being increased by changing the exposure conditions and the thermal firing conditions, it is likely to impair the patterning property and reliability.

Patent Document 1 reports that the addition of an acrylic copolymer as a black resist of an alkali-soluble resin is effective for suppressing wrinkles in a thick film having a thickness of 1 μm or more. However, in the examples, since an acrylic copolymer having no photoreactive group is added as an alkali-soluble resin, when the process conditions such as low exposure amount and excessive development are strict, high sensitivity and image formation are adhered. There is a limit to sex.

Patent Document 2 discloses that, in a polyfunctional acrylate, a small amount of a polyvalent fluorenyl compound is subjected to Michael addition to an ethylene double bond possessed by a polyfunctional acrylate to obtain a dendrimer, and the dendrimer is obtained. The material is of potential value as a UV curable ink material. Here, the dendrimer is also referred to as a dendrimer or a multi-difference polymer.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-286478

[Patent Document 2] International Publication No. 2008/47620

Therefore, an object of the present invention is to provide a photosensitive resin composition for a black resist which solves the above problems, and which is excellent in pattern size stability and image development even if it is a thick film of 1.2 μm or more. Developing margin, pattern edge shape, good sharpness pattern, and in the subsequent thermal firing step, the surface of the coating film is smooth and does not cause surface roughness due to thermal hardening shrinkage. The deterioration of the pattern cross-sectional shape can also maintain the trapezoidal shape after development. Further, another object of the present invention is to provide a light shielding film formed using the photosensitive resin composition for a black resist.

In order to solve the above problems, the results of studies by the present inventors have found that it is only necessary to formulate a reaction between an aromatic epoxy compound derived from bisphenol and a reaction product of (meth)acrylic acid and a polycarboxylic acid or an anhydride thereof. The obtained unsaturated polymer-containing compound and the dendrimer having two or more polymerizable reactive groups at the terminal as a photopolymerizable compound having an ethylenically unsaturated bond can solve the aforementioned problems, and the present invention can be solved. invention.

The photosensitive resin composition for black resists of the present invention is characterized by containing the following components (A) to (D) as essential components:

(A) a dendrimer having two or more ethylenic polymerizable groups at the terminal;

(B) The reaction product obtained by reacting a bisphenol-derived epoxy compound having two glycidyl ether groups and (meth)acrylic acid with a polycarboxylic acid or an anhydride thereof Saturated group of compounds;

(C) a photopolymerization initiator;

(D) One or more kinds of light-shielding components selected from black organic pigments, mixed color organic pigments, and light-shielding materials.

Here, the component (A) is preferably a part of a carbon-carbon double bond in a (meth) acrylate group of the polyfunctional (meth) acrylate compound represented by the following formula (1). A dendrimer obtained by addition to a polyvalent fluorenyl compound represented by the following formula (2).

(wherein R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ² represents that the n hydroxyl groups of the m hydroxyl groups of the polyol R ³ (OH) m are supplied to the ester bond in the formula; Part, m and n represent integers from 2 to 20, respectively, m≧n)

(wherein R ⁴ represents a single bond or a 2 to 6 valent group having a hydrocarbon group having 1 to 6 carbon atoms; when R ⁴ is a single bond, p represents 2, and when R ⁴ is a 2 to 6 valent group, p represents an integer from 2 to 6)

Further, the addition ratio of the fluorenyl group of the polyvalent fluorenyl compound represented by the above formula (2) to the carbon-carbon double bond of the polyfunctional (meth) acrylate compound represented by the above formula (1) is thiol/ The molar ratio of the double bond is preferably from 1/100 to 1/3.

The above component (B) is an unsaturated group obtained by reacting a reactant of an epoxy group having two epoxypropyl ether groups derived from a bisphenol and (meth)acrylic acid with a polyvalent carboxylic acid or an anhydride thereof. The epoxy group compound having two epoxypropyl ether groups is preferably an epoxy compound represented by the following formula (3).

(Wherein, R ₁₁ and R ₁₂ represents a hydrogen atom a halogen atom or an alkyl, 1 to 5 carbon atoms in any one, X represents _{-CO -, - SO 2 -,} - C (CF 3) 2 -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, a 9,9-fluorenyl group or a single bond represented by the following formula (4), n is 0 to 10 integer)

The above component (D) is a light-shielding component, preferably carbon black. Further, the component (D) is preferably blended in a proportion of 30% by weight to 50% by weight based on the solid content of the photosensitive resin composition for a black resist. Here, the solid content in the photosensitive resin composition for a black resist is a component other than a solvent, which contains a reaction component which remains as a solid after reacting after curing.

Further, the color filter light-shielding film of the present invention is characterized by being formed of the above-mentioned photosensitive resin composition for a black resist.

The photosensitive resin composition for black resist of the present invention can be suitably used as a coating material, and in particular, a color filter ink used for a liquid crystal display device or a photographic element, and a light-shielding film formed thereby are used as a filter. A color matrix, a liquid crystal projection, a black matrix, or the like. Further, the photosensitive composition for black resist of the present invention can be used as a color liquid crystal display device, a color facsimile, or an image sensor in addition to the color filter ink of the color liquid crystal display described above. It is used in various multi-color display body ink materials.

The invention is described in detail below. The photosensitive resin composition for black resists of the present invention (hereinafter, simply referred to as a photosensitive resin composition) contains the components (A) to (D) as essential components. The components (A) to (D) are explained below.

The dendrimer of the component (A) is a multi-difference type polymer having two or more ethylenic polymerizable groups at the terminal. The ethylenic polymerizable group is preferably derived from a (meth) acrylate compound, but is not limited thereto. Here, the ethylenic polymerizable group is a group having a carbon-carbon double bond, and is known as a conjugated compound such as an α,β-unsaturated carbonyl compound in which a carbon-carbon double bond is bonded with a carbonyl group. The strongest vinyl group interacting with a nucleophile such as a mercapto compound causes a Michael addition reaction. Therefore, when a compound having a plurality of ethylenic polymerizable groups such as an α,β-unsaturated carbonyl compound is reacted with a compound having a plurality of nucleophilic groups such as a polyhydrazinyl compound, the β-position carbon and the carbonyl group are reacted. When an addition reaction occurs, when there are a plurality of radicals in the addition reaction, a large number of divergence occurs to form a dendrimer. The dendrimer is known from Patent Document 2 and the like, and can be obtained by the method described in the literature.

The dendrimer as the component (A) is a Michaeline addition reaction (carbonyl group) of the polyfunctional (meth) acrylate compound represented by the formula (1) and the polyhydrazino compound represented by the formula (2). It is polymerized for the addition of a carbon-carbon double bond at the β position. Here, a preferred embodiment of the Michael addition of the polyvalent mercapto compound represented by the formula (2) to the polyfunctional (meth) acrylate compound represented by the formula (1) is as follows: The dendrimer may also be subjected to radiation polymerization based on a carbon-carbon double bond, and the carbon-carbon double bond possessed by the compound represented by the general formula (1) may remain 0.1 to 50 mol% as a whole. The scope.

For example, the fluorenyl group of the polyhydrazinyl compound represented by the formula (2) and the carbon-carbon double bond of the polyfunctional (meth) acrylate compound represented by the formula (1) (in the formula (1), CH ₂ =C(R ¹ )- represents a double bond, which is called a double bond when calculating the molar ratio. The addition ratio is preferably 1/100 to 1/3 of the molar ratio of the thiol/double bond. More preferably, it is 1/50 to 1/5, and particularly preferably 1/20 to 1/8.

Further, among the above dendrimers, it is preferred to have a sufficient amount of functional groups for radiation polymerization. Therefore, the molecular weight of the dendrimer, the molecular weight of the carbon-carbon double bond per 1 mole is preferably in the range of 100 to 10,000. Further, the weight average molecular weight (Mw) of the dendrimer is preferably from 1,000 to 20,000, more preferably from 8,000 to 15,000.

In the above formula (1), R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ² is an ester bond of n of the m hydroxyl groups of the polyol R ³ (OH) _m After the rest of the section. Preferably, R ³ (OH) _m is a polyol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a dehydration condensation of a plurality of molecules of the polyol by an alcohol and A polyol ether which is linked via an ether bond, or an ester of such a polyol or polyol ether and a hydroxy acid. In the above formula (1), m and n each represent an integer of 2 to 20, but m≧n. m and n are preferably an integer of 2 to 10, m≧n.

Preferable specific examples of the polyfunctional (meth) acrylate compound represented by the formula (1) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and three. Ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ring Ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylolethane Tris(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol hexa(meth) acrylate, tripentenol octa (meth) acrylate, triphenol tetrakis (meth) acrylate, caprolactone Neopentyl alcohol tri(meth)acrylate, caprolactone modified neopentyltetrakis(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, epichlorohydrin Alcohol (epichlorohydrin) modified six Di(meth) acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, ethylene oxide modified neopentyl glycol (Meth) acrylate, propylene oxide modified neopentyl glycol di(meth) acrylate, ethylene oxide modified trimethylolpropane tri(meth) acrylate, propylene oxide modified tris Methylpropane tri(meth)acrylate, trimethylolpropane benzoate (meth) acrylate, tris((meth) propylene methoxyethyl) trimeric isocyanate, alkoxy modified three Hydroxymethylpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, bis(trimethylolpropane) (Meth) acrylate such as tetra (meth) acrylate. These compounds may be used alone or in combination of two or more.

In the above formula (2), R ⁴ is a single bond or a 2 to 6 valent group having a hydrocarbon group of 1 to 6 carbon atoms, and when R ⁴ is a single bond, p represents 2, and when R ⁴ is 2 to 6 The base time, p represents an integer from 2 to 6. R ^{4 is} preferably a single bond, or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent or a hydrocarbon group which may further contain an oxygen atom in the hydrocarbon group skeleton, which may be a straight chain or a branched chain. Further, these hydrocarbon group-containing groups may have a carbonyloxy group bonded to a part of a thiomethyl group (HSCH ₂ -) appearing in the formula (2). Further, when an oxygen atom is contained in the hydrocarbon group skeleton, both ends thereof may be a hydrocarbon group. p represents an integer from 2 to 6, which corresponds to the valence of R ⁴ . Therefore, when R ⁴ represents a single bond, p is 2, when the carbon number of R ⁴ is 1, p is 2 to 4, and when carbon number of R ⁴ is 2 to 6, p is 2 to 6.

The polyvalent fluorenyl compound represented by the above formula (2) may, for example, be 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-didecylbutane or bis(diindenyl)ethane. Mercaptan, trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tris(mercaptoacetic acid) Ester), neopentyltetrakis(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), and the like.

When the above dendrimer is synthesized, a polymerization inhibitor may be added as needed. As the polymerization inhibitor, a hydroquinone-based compound or a phenol-based compound which is generally used for suppressing polymerization of a (meth) acrylate compound can also be used in the present invention. Specific examples of such may, for example, be hydroquinone, methoxyhydroquinone, catechol, p-tert-butyl catechol, cresol, dibutylhydroxytoluene, 2,4,6-tris-three-stage Butyl phenol (BHT) and the like, but is not limited to these examples.

It is confirmed whether or not the synthesis of the dendrimer has been completed, and it can be confirmed by liquid chromatography, gel filtration chromatography, and other general analytical instruments.

When the dendrimer is synthesized, the polyhydrazinyl compound represented by the formula (2) produces a Michael addition reaction to the double bond of the polyfunctional (meth) acrylate compound represented by the formula (1), which can be achieved by After mixing the polyfunctional (meth) acrylate compound and the polyvalent fluorenyl compound, it is carried out by adding a basic catalyst at room temperature to 100 °C. The reaction time is usually from about 30 minutes to about 20 hours, preferably from 6 to 12 hours.

The detailed mechanism in which the above dendrimer has excellent characteristics as a photosensitive resin composition for a black resist is not clear. However, it is generally considered that a dendrimer using a thiol and an acrylate is hardened by low energy due to suppression of a reaction of oxygen and a solvent in a radical polymerization, and hardening shrinkage is suppressed by a unique structure. Since the surface roughness of the coating film is deteriorated or the like, the light-shielding film has a particularly excellent property when it is formed into a thick film.

The amount of the dendrimer contained in the photosensitive resin composition for black resist of the present invention is preferably 5% by weight to 40% by weight, preferably 10% by weight based on the total amount of each component of (A) and (B). % to 40% by weight. Further, when other polymerizable component (E) is used, it is preferably 20% by weight to 35% by weight based on the total amount of the polymerizable component. When the content of the dendrimer is smaller than the range, the effect of suppressing the surface roughness of the coating film is lowered, and the surface roughness of the coating film is increased. Further, when the content of the dendrimer is larger than the range, there is a case where retardation development and pattern linearity are deteriorated.

In addition to the above components (A) and (B), the photosensitive resin composition for a black resist of the present invention may further contain a photopolymerizable or radically polymerizable compound having an ethylenically unsaturated bond as a component. (E) Use. As the above component (E), a preferred example is a polyfunctional (meth) acrylate. Further, the component (E) and the components (A) and (B) are not the same.

The difunctional (meth) acrylate as the component (E) may, for example, be 1,6-hexanediol di(meth)acrylate or 1,10-nonanediol di(meth)acrylate, new Pentyl glycol di(meth) acrylate, 2,4-dimethyl-1,5-pentanediol di(meth) acrylate, butyl ethyl propylene glycol (meth) acrylate, ethoxylated cyclohexyl Alkanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, 2-ethyl -2-butyl-butanediol di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, bisphenol F polyethoxy di(meth) acrylate or the like.

Further, examples of the trifunctional (meth) acrylate include a ring of trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and trimethylolpropane. Oxyalkane modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tris((meth)acryloquinone Oxypropyl)ether, iso-cyanuric acid alkylene oxide-modified tris(meth)acrylate, and the like.

Further, as the tetrafunctional (meth) acrylate, neopentyltetrakis (meth) acrylate, sorbitol tetra (meth) acrylate, and bis (trimethylolpropane) tetra (a) may be mentioned. Acrylate, dipentaerythritol tetra(meth)acrylate propionate, neopentyltetraol tetra(meth)acrylate, and the like.

Further, as the pentafunctional or hexafunctional (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (a) may be mentioned. Methyl) acrylate, sorbitol hexa(meth) acrylate, phosphazene alkylene oxide modified hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa ) Acrylate and the like.

When the component (E) is contained in the photosensitive resin composition for a black resist, the content is preferably 10 parts by weight to 50 parts by weight based on 100 parts by weight of each of the components (A) and (E). It is 20 parts by weight to 40 parts by weight.

The unsaturated group-containing compound of the component (B) is a reaction product of an epoxy compound having two epoxypropyl ether groups derived from a bisphenol and (meth)acrylic acid, and a polycarboxylic acid or The unsaturated group-containing compound obtained by the acid anhydride reaction is known to the epoxy compound or the unsaturated group-containing compound.

The above unsaturated group-containing compound is obtained by reacting an epoxy compound having two epoxypropyl ether groups derived from a bisphenol and (meth)acrylic acid (this means acrylic acid and/or methacrylic acid). And an epoxy (meth) acrylate acid addition product obtained by reacting the obtained compound having a hydroxyl group with a polyvalent carboxylic acid or an anhydride thereof. Then, the epoxy compound derived from bisphenols means an epoxy compound obtained by reacting a bisphenol with an epihalohydrin or an equivalent compound thereof. Since the unsaturated group-containing compound of the component (B) has both an ethylenically unsaturated double bond and a carboxyl group, it imparts excellent photocurability, good developability, and patterning to the photosensitive resin composition for a black resist. Characteristics, while improving the physical properties of the light-shielding film.

The component (B) is preferably an epoxy group compound having two epoxypropyl ether groups derived from a bisphenol, and is an epoxy compound represented by the above formula (3). In the above formula (3), R ₁₁ and R ₁₂ are any of an oxygen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and X represents -CO-, -SO ₂ -, -C (CF _{3 ). 2} -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenyl or a single bond represented by the above formula (4), n An integer from 0 to 10.

The unsaturated group-containing compound of the component (B) is preferably one derived from the epoxy compound represented by the formula (3). The epoxy compound is derived from bisphenols. Therefore, a compound containing an unsaturated group can be understood by explaining a bisphenol, and a preferred specific example will be described by a bisphenol. Preferred bisphenols which give a compound containing an unsaturated group are as exemplified below. A bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, Bis(4-hydroxyphenyl)indole, bis(4-hydroxy-3,5-dimethylphenyl)anthracene, bis(4-hydroxy-3,5-dichlorophenyl)anthracene, bis(4-hydroxyl) Phenyl) hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4- Hydroxyphenyl) dimethyl decane, bis(4-hydroxy-3,5-dimethylphenyl)dimethyl decane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyl decane, Bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-dual ( 4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane , 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis ( a compound such as 4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, and the like 9, wherein X is the 9,9-fluorenyl group 9,9 - bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9- (4-hydroxy-3-chlorophenyl)indole, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene, 9 ,9-bis(4-hydroxy-3-methoxyphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxyl -3,5-dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene, etc., and 4,4'-biphenol (4,4'-bisphenol) ), a compound such as 3,3'-biphenol.

Further, as a polyvalent carboxylic acid or an anhydride thereof which can react with a hydroxyl group in an epoxy (meth) acrylate molecule obtained by reacting such an epoxy compound and (meth)acrylic acid, for example, a cis-butyl group can be exemplified. Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrofurfuric acid, hexahydrophthalic acid, methyl endomethylenetetrahydroanthracene An acid, a chlorendic acid, a methyltetrahydrofurfuric acid, a trimellitic acid, or the like, and an acid anhydride thereof, and may also be exemplified by pyromellitic acid or diphenyl ketone tetracarboxylic acid. An aromatic polycarboxylic acid such as biphenyltetracarboxylic acid or diphenyl ether tetracarboxylic acid, or a dianhydride thereof. Then, regarding the ratio of use of the acid anhydride and the dianhydride, a ratio suitable for forming a fine pattern by exposure or alkali development operation can be selected.

The unsaturated group-containing compound of the component (B) may be used alone or in combination of two or more. Further, a reaction of the epoxy compound and (meth)acrylic acid, a reaction of the epoxy (meth) acrylate obtained by the reaction, and a polybasic acid or an acid anhydride thereof can be carried out by a known method, and is not particularly limited.

As the photopolymerization initiator of the component (C), benzophenone, Michler's ketone, N, N, N', N'-tetramethyl-4, 4 may be exemplified. '-Diaminodiphenyl ketone, 4-methoxy-4'-dimethylaminodiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, 2-ethyl fluorene Aromatic ketones such as phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other benzoin ethers, methyl benzoin, ethyl benzoin and other benzoin, 2-(o-chlorophenyl)-4,5 -Phenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl Imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-trichloromethyl- 5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halogenated methyldiazole compound such as oxadiazole, 2,4,6-tris(trichloromethyl)-1,3,5-three 2-methyl-4,6-bis(trichloromethyl)-1,3,5-three 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three 2-(4-Methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-three Halogenated methyl-S-three a compound, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-(N- 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinophenylpropanone), 2-benzyl-2-dimethylamino-1-[4-(N-morpholine) A photopolymerization initiator such as phenyl]-butanone or 1,1-hydroxy-cyclohexyl-phenyl ketone.

These photopolymerization initiators may be used singly or in combination of two or more. Further, a compound which does not have a function as a photopolymerization initiator and a sensitizer, but which can increase the ability of a photopolymerization initiator and a sensitizer by using it in combination with the above compound may be added. As such a compound, for example, a tertiary amine such as triethanolamine which is effective when used in combination with diphenylketone can be mentioned.

The amount of the photopolymerization initiator to be used in the component (C) is preferably from 3 to 30 parts by weight based on 100 parts by weight of the total of the components (A) and (B). More preferably, it is 5 to 20 parts by weight. When the proportion of the component (C) is less than 3 parts by weight, the photopolymerization rate is slowed down, and the sensitivity is lowered. On the other hand, when the amount is more than 30 parts by weight, the sensitivity is too strong, and the pattern line width is changed with respect to The pattern mask is in a thick state, and the mask may not faithfully reproduce the line width, or there may be a problem that the edge of the pattern is not clear.

The light-shielding component such as a black organic pigment, a color mixed organic pigment or a light-shielding material as the component (D) is preferably excellent in heat resistance, light resistance, and solvent resistance. Here, as the black organic pigment, for example, perylene black, cyanine black, nigrosine or the like can be exemplified. The mixed color organic pigment may, for example, be a mixture of at least two kinds of pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like, and which are intended to be blackened. The light-shielding material may, for example, be carbon black, chromium oxide, iron oxide or titanium black, and may be selected from two or more types, and is excellent in light-shielding property, surface smoothness, dispersion stability, and compatibility with a resin. In view, the best one is carbon black.

The blending ratio of the light-shielding component of the component (D) is preferably from 30% by weight to 50% by weight based on the solid content of the photosensitive resin composition for a black resist. When the amount is less than 30% by weight, in addition to the insufficient light-shielding property, the thermal curing shrinkage may be increased to increase the surface roughness of the coating film. When the amount is more than 50% by weight, the thermosetting shrinkage is small and the deterioration of the surface roughness is suppressed. However, the content of the photosensitive resin which is originally a binder is reduced, and the development characteristics are impaired and the film forming ability is also impaired. Bad problem.

The photosensitive resin composition for black resists of the present invention contains the above components (A) to (D) as essential components, and contains the above component (E) as an optional component. Here, the components (A), (B), and (E) are polymerizable components, the component (C) is a component that initiates polymerization of these polymerizable components, and the component (D) is a component that imparts light shielding properties. In the photosensitive resin composition for black resist, the ratio of the polymerizable component ((A)+(B)+(E))) in the solid component other than the solvent is preferably 40% by weight to 60% by weight, the ratio of the component (C) is preferably from 2% by weight to 12% by weight, and the ratio of the component (D) is preferably from 30% by weight to 50% by weight. Further, in the polymerizable component, the ratio of the component (A) is from 10% by weight to 50% by weight, preferably from 20% by weight to 40% by weight based on the total polymerizable component, and the ratio of the component (B) is in the total polymerization property. From 90% by weight to 50% by weight, preferably from 80% by weight to 60% by weight of the component, the proportion of the component (E) ranges from 0% by weight to 25% by weight of the total polymerizable component. Further, when the component (E) is blended, a more preferable ratio of the components (A), (B) and (E) is 20% by weight to 35% by weight of the component (A) and 75% by weight to 60% by weight of the component (B). The component (E) is 5% by weight to 15% by weight.

In the photosensitive resin composition for black resist of the present invention, in addition to the above components (A) to (D), it is preferred to adjust the viscosity using a solvent. The solvent may, for example, be an alcohol such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol or propylene glycol, or a terpene such as α- or β-terpineol, or acetone or methyl. Ketones such as ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycolosolve, ethylene glycol methyl ether (methyl cellosolve), ethylene glycol ether, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol a glycol ether such as methyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, glycol ether acetate, Ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate An acetate or the like such as propylene glycol monoethyl ether acetate can be dissolved and mixed by using such a solvent to prepare a uniform solution composition.

Further, in the resin composition for a black resist of the present invention, additives such as a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, and an antifoaming agent may be added as needed. The thermal polymerization inhibitor may, for example, be hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl quinone, or phenothiazine. (phenothiazine), etc., the plasticizer may, for example, be dibutyl phthalate, dioctyl phthalate or tricresyl phosphate, and the filler may, for example, be glass woven, cerium oxide, mica or alumina, and defoaming. The agent and the leveling agent may, for example, be a compound of an anthracene, a fluorine or an acrylic.

The resin composition for black resist of the present invention contains the above components (A) to (D) or these components and a solvent as a main component. In the solid component from which the solvent is removed, the components (A) to (D) are contained in an amount of 70% by weight or more, preferably 80% by weight, more preferably 90% by weight or more. Although the amount of the solvent varies depending on the viscosity of the target, it is preferably in the range of 10% by weight to 30% by weight.

The color filter light-shielding film of the present invention is formed by photolithography using the photosensitive resin composition for black resist of the present invention. As a manufacturing step, for example, first, the photosensitive resin composition is applied to the surface of the substrate as a solution, and then dried (pre-bake) the solvent, and then the mask is covered. The exposed film is irradiated with ultraviolet rays to cure the exposed portion, and the developed image is eluted with an alkaline aqueous solution to form a pattern, and then post-baking is performed as a method of post-drying. Here, as a substrate on which a solution of a photosensitive resin composition is applied, ITO, gold, or the like can be deposited on glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether oxime, etc.). Transparent electrode or patterned person, etc.

As a method of applying the photosensitive resin composition solution to the substrate, in addition to the known solution dipping method and spraying method, a roller coater, a land coater, and a spin coater (spinner) may be used. ) method or any other method. According to these methods, after the desired thickness is applied, the film is formed by removing (prebaking) the solvent. The prebaking is performed by heating by an oven, a hot plate, or the like. In the prebaking, the heating temperature and the heating time are appropriately selected depending on the solvent to be used, for example, at a temperature of 60 ° C to 110 ° C for 1 to 3 minutes.

The exposure performed after the prebaking is performed by an exposure machine, and only a portion of the resist of the corresponding pattern is exposed by exposure through the mask. The exposure machine and its exposure and irradiation conditions are appropriately selected, and exposure is performed with a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far ultraviolet lamp to photoharden the resin composition for a black resist in the coating film.

The alkali development after the exposure is performed for the purpose of removing the resist of the unexposed portion, and the desired pattern is formed by the development. Examples of the developing solution suitable for the alkali development include an aqueous solution of an alkali metal and an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like, and particularly preferably a carbonate containing sodium carbonate or potassium carbonate. 0.03 wt% to 1 wt% of the weakly alkaline aqueous solution is developed at a temperature of 23 ° C to 27 ° C, and a fine image can be precisely formed using a commercially available developing machine, an ultrasonic cleaner, or the like.

After the development by this, heat treatment (post-baking) was carried out at a temperature of 200 ° C to 240 ° C for 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned light-shielding film and the substrate. Like prebaking, it is carried out by heating by an oven, a hot plate or the like. The patterned light-shielding film of the present invention is formed by the respective steps of the above photolithography method.

As described above, the resin composition for a black resist of the present invention is suitable for forming a fine pattern by an operation such as exposure or alkali development. However, when a pattern is formed by conventional screen printing, the same can be obtained. A light-shielding film excellent in light-shielding property, adhesion property, electrical insulation property, heat resistance, and chemical resistance.

(Example)

Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples.

Synthesis Example 1

To a 1 L 4-neck flask was added 212 g of a mixture of neopentyltetrakis(mercaptoacetate) 20 g (mercapto-based 0.19 mol), dipentaerythritol hexaacrylate and dineopentalt penta pentoxide ( Carbon-carbon double bond 2.12 mol, propylene glycol monomethyl ether acetate 58 g, hydroquinone 0.1 g, and benzyl dimethylamine 0.01 g, reacted at 60 ° C for 12 hours to obtain dendrimer A . With respect to the obtained dendrimer A, the disappearance of the thiol group was confirmed by iodometry. The dendritic polymer A obtained had a weight average molecular weight Mw of 10,000.

The weight average molecular weight Mw is by gel filtration chromatography (HLS-8220GPC manufactured by TOSOH, solvent: tetrahydrofuran, column: TSKgel SuperH-2000 (2) + TSKgel SuperH-3000 (1) + TSKgel SuperH-4000 ( 1)) +TSKgelSuper-H5000 (1) (TOSOH (manufactured by TOSOH), temperature: 40 ° C, speed: 0.6 ml / sec) and measured with standard polystyrene (PS-OLIGOMER KIT, TOSOH (share) The value converted.

The abbreviations of the compounds used in the examples and comparative examples are shown below.

(ingredient A)

(a)-1: dendrimer A solution obtained in Synthesis Example 1

(ingredient E)

(a)-2: Trimethylolpropane triacrylate (manufactured by Sartomer Japan Co., Ltd., trade name SR351S)

(a)-3: urethane acrylate oligomer (average propylene thiol group number 15, Mw: 5000) (manufactured by Kokusai Industrial Co., Ltd., trade name UN-3320HS)

(ingredient B)

(b)-1: a propylene glycol monomethyl ether acetate solution of an acid anhydride polycondensate of an epoxy group having an anthracene skeleton (resin solid concentration = 56.1% by weight, manufactured by Nippon Steel Chemical Co., Ltd., Name V259ME)

(alkali soluble resin)

(b)-2: Mw9000, an acid-valent 80 N-phenyl maleimide/acrylic acid/styrene copolymer propylene glycol monomethyl ether acetate solution (resin solids concentration = 35.5 wt% ), (N-phenyl maleimide: acrylic acid: styrene = 19:22:59 mol%)

Further, the component (b)-2 is added to exhibit a wrinkle-reducing effect, and is an alkali-soluble resin having no photopolymerizable unsaturated bond.

(ingredient C)

(c): Ethylketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) ( BASF Japan company, product name Irgacure OXE02)

(ingredient D)

(d) a propylene glycol monomethyl ether acetate dispersion having a carbon black concentration of 25.0% by weight and a polymer dispersant concentration of 4.75 wt% (solid content: 29.75% by weight)

(solvent)

(e)-1: Propylene glycol monomethyl ether acetate

(e)-2: cyclohexanone

(surfactant)

(f): MEGAFACE F475 (DIC system)

(coupling agent)

(g): S-510 (Chisso system)

Examples 1 to 5 and Comparative Examples 1 to 5

The above components were blended in the proportions shown in Table 1, and the photosensitive resin compositions for black resists of Examples 1 to 5 and Comparative Examples 1 to 5 were prepared. In Table 1, the upper digits of (a)-1, (b)-1, (b)-2, and (d) indicate the amount (g) as a solution, and the number in the lower paragraph () relates to (a)-1, (b)-1, (b)-2 shows the amount (gram) of the solid component from which the solvent is removed, and (d) shows the amount of the light-shielding (gram) in the solution. The blending ratio is the ratio of the opacifier of the component (D) to the solid content of the photosensitive resin composition.

Further, (a)-1, (a)-2, and (a)-3 are photopolymerizable compounds, (b)-1 is a resin containing an unsaturated group, and (b)-2 is an alkali-soluble resin, (c) It is a photopolymerization initiator, (d) is a light-shielding dispersion pigment, (e)-1, (e)-2 is a solvent, (f) is a surfactant, and (g) is a decane coupling agent.

Each component was uniformly mixed at the blending ratio shown in Table 1, and the photosensitive resin compositions for black resists of Examples 1 to 5 and Comparative Examples 1 to 5 were obtained.

The photosensitive resin composition for black resist obtained above was applied to a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after baking was 2.0 μm, and was preliminarily prepared at 90 ° C. Bake for 1 minute. Then, the exposure gap was adjusted to 80 μm, a negative mask of line/space=20 μm/80 μm was covered on the dried coating film, and an ultraviolet ray of 80 mj/cm ² was irradiated with an ultrahigh pressure mercury lamp having an I illuminance of 30 mW/cm ² to perform a photosensitive portion. Light hardening reaction. Next, the exposed coated plate was subjected to a shower development pressure of 1 kgf/cm ² in a 25 ° C, 0.05% potassium hydroxide aqueous solution, and the development time (break time) at the start of the pattern = BT) After the development of +10 seconds and +20 seconds, the spray water washing was performed at a pressure of 5 kgf/cm ^{2 to} remove the unexposed portions of the coating film to form a pixel pattern on the glass substrate, and then the hot air dryer was used. After hot post-baking at 230 ° C for 30 minutes, the line width (μm) of the mask width with respect to the 20 μm line, the pattern linearity, and the surface roughness Ra of the coating film were evaluated. The results are shown in Table 2. In addition, the evaluation method is as follows.

‧ pattern line width

The pattern line width of the mask width of 20 μm was measured using a length measuring microscope (trade name XD-20 manufactured by Nikon Co., Ltd.).

‧ pattern linearity

The 20 μm mask pattern after the post-baking was observed under a microscope, and it was evaluated that the peeling of the substrate and the unevenness of the pattern edge portion were not evaluated as ○, and it was confirmed that the portion was evaluated as Δ, and all the confirmed persons were evaluated as ×.

‧ pattern profile shape

The cross-sectional shape of the 20 μm mask pattern after post-baking and post-baking was observed by a scanning electron microscope (SEM), and the trapezoidal shape before the post-baking was maintained after the post-baking evaluation was ○, and the trapezoidal shape was The state in which the shape becomes a semicircular shape in which the trapezoidal angle is rounded (fish plate type) is evaluated as ×.

‧Surface roughness

Surface roughness (Ra) was measured using P-15 manufactured by KLA-Tencor. The surface roughness (Ra) of the coating film after post-baking is less than 150 Rate is ○ and will be 150 The above evaluation is × (bad).

In Table 2, the left column of each of the examples and the comparative examples is the result of the development time BT + 10 seconds, and the right column is the example of BT + 20 seconds.

Claims (4)

A photosensitive resin composition for a black resist, which comprises the following components (A) to (D) as essential components: (A) a dendrimer having two or more ethylenic polymerizable groups at a terminal; (B) an unsaturated group-containing compound obtained by reacting a reactant of an epoxy group having two epoxypropyl ether groups derived from a bisphenol and a (meth)acrylic acid with a polyvalent carboxylic acid or an anhydride thereof (C) a photopolymerization initiator; and (D) one or more kinds of light-shielding components selected from the group consisting of a black organic pigment, a color mixed organic pigment, and a light-shielding material; wherein the component (A) is a formula (1) a part of a carbon-carbon double bond in a (meth) acrylate group of a polyfunctional (meth) acrylate compound represented by addition of a polyvalent fluorenyl compound represented by the following formula (2) a dendrimer; in the component (B), an epoxy compound having two epoxypropyl ether groups derived from a bisphenol is an epoxy compound represented by the following formula (3); The amount of the dendrimer of the component (A) is 5% by weight to 40% by weight based on the total amount of each component of (A) and (B), and photopolymerization of the component (C) When the amount of the initiator is from 3 to 30 parts by weight based on 100 parts by weight of the total of the components (A) and (B), the amount of the component is based on the solid content of the photosensitive resin composition for a black resist. The shading component of (D) is formulated in a ratio of 30% by weight to 50% by weight; In the formula, R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ² represents a portion obtained by supplying n hydroxyl groups among m hydroxyl groups of the polyol R ³ (OH) _m to the ester bond in the formula. , m and n represent integers from 2 to 20, respectively, and m≧n; Wherein R ⁴ represents a single bond or a 2 to 6 valent group having a hydrocarbon group of 1 to 6 carbon atoms; when R ⁴ is a single bond, p represents 2, and when R ⁴ is a 2 to 6 valent group, p An integer representing 2 to 6; In the formula, R ₁₁ and R ₁₂ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and X represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, - Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, a 9,9-fluorenyl group or a single bond represented by the following formula (4), n is 0 to 10 Integer The photosensitive resin composition for black resists as described in claim 1, wherein the polyvalent thiolation represented by the above formula (2) The addition ratio of the fluorenyl group of the compound to the carbon-carbon double bond of the polyfunctional (meth) acrylate compound represented by the above formula (1) is 1/100 to the molar ratio of the thiol/double bond. 1/3. The photosensitive resin composition for black resists as described in claim 1, wherein the component (D) is carbon black. A color filter light-shielding film is characterized in that the color filter light-shielding film is formed of the photosensitive resin composition for black resists according to any one of claims 1 to 3.