JP2013242555A - Method of producing photosensitive base material composition for forming light shielding layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive base material composition for forming a light shielding layer, which causes no pin hole and is high quality.SOLUTION: In a method of producing a photosensitive base material composition for forming a light shielding layer, a surfactant component (H) that is a polymer with a mass average molecular weight of 10000-50000 is diluted to 2.5-10 mass%, and then filtered. The filtered surfactant component (H), a photosensitive base material component (A), a pigment component (G), and an organic solvent component (S) are dispersed. Preferably, the filtering is conducted with a PTFE film whose pore size is equal to or less than 1 μm.

Description

  The present invention relates to a method for producing a photosensitive substrate composition for forming a light shielding layer.

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 of manufacturing such a color filter, a method of forming a colored layer of a color filter by an inkjet 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 lithography using, for example, a resist composition containing a black pigment. Carbon black is generally used as the black pigment (for example, Patent Document 1).

  By the way, impurities and foreign substances present in the resist composition cause defects (surface defects) and pinholes in the resist pattern. Patent Document 2 describes a method for producing a resist composition having a step of filtering the resist composition using a filter having a specific potential in order to remove fine particles generated during storage of the resist solution.

  In addition, in the process of manufacturing a color filter, it is important to make the film thickness uniform after application, and therefore it is generally performed to add a surfactant having a leveling effect to the photosensitive substrate composition. (For example, Patent Document 3).

  In the method for producing a resist composition including the filtration step as described above, it is usual to pass the filtration step after mixing all the base material components and the like.

JP 2004-325736 A JP 2004-221975 A JP 2010-107957 A

When manufacturing a black matrix, impurities, foreign matters, and the like present in the photosensitive substrate and the organic solvent cause pinholes and the like on the surface of the black matrix, resulting in pattern nonuniformity.
In order to produce a high-quality black matrix that does not generate pinholes or the like, it is necessary to remove impurities, foreign matters, and the like in the photosensitive substrate and the organic solvent.

  In view of the above circumstances, when manufacturing the black matrix, the present inventors diluted the surfactant that is a polymer added to the resist composition, and then filtered to produce a resist composition. The present inventors have found a method capable of producing a high quality black matrix that does not generate pinholes.

  In the present invention, the surfactant component (H), which is a polymer having a mass average molecular weight of 10,000 to 50,000, is diluted to 2.5 to 10% by mass, filtered, and the surfactant component (H) after filtration. And a photosensitive substrate component (A), a pigment component (G), and an organic solvent component (S) are dispersed.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the high quality photosensitive base material composition for light shielding layer formation which does not generate | occur | produce a pinhole etc. can be provided.

FIG. 1 is an explanatory diagram for explaining uneven width evaluation.

≪Method for producing photosensitive substrate composition for light shielding layer formation≫
The manufacturing method of the photosensitive base material composition for light-shielding layer formation of this invention is after diluting surfactant component (H) which is a polymer of mass average molecular weights 10000-50000 to 2.5-10 mass%, The surfactant component (H), the photosensitive base material component (A), the pigment component (G), and the organic solvent component (S) after filtration are dispersed.

  The photosensitive substrate composition for forming a light shielding layer (hereinafter sometimes referred to as a photosensitive substrate composition) produced by the production method of the present invention comprises a diluted surfactant component (H) (hereinafter referred to as (H ) Component)) passes through a filtration step, so that aggregates produced during dilution are removed, and no pinholes or the like are generated when a light shielding layer is formed.

  As the component (H), commercially available products having a concentration of 40 to 50% by mass or those prepared by synthesis are generally used, and the final concentration of the component (H) in the composition is 2.5 to 10%. It mix | blends in the photosensitive base material composition so that it may become the mass%. At this time, the method may be such that the (H) component itself having a concentration of 40 to 50% by mass is directly added to the composition, and the (H) component having a concentration of 2.5 to 10% by mass is diluted in advance. The product may be prepared but requires a step of dilution. The present inventors have newly found that a part of the surfactant can be aggregated for some reason by diluting the surfactant having a relatively high concentration of 40 to 50% by mass. And it discovered together that generation | occurrence | production of a pinhole etc. can be suppressed by removing this aggregate beforehand, and completed this invention.

(H) component (H) component contained in the photosensitive base material composition in this invention is a C1-C20 fluorinated alkyl group (however, an ether bond, an ester bond, a carbonyl group, a urethane bond). And a polymer having a philic group in the side chain.

The fluorinated alkyl group is not particularly limited as long as it has 1 to 20 carbon atoms, and is an ether bond (—O—), an ester bond (—CO—O—), a carbonyl group (—CO—), a urethane bond (— NH-CO-O-) may be interrupted by, but shall not be interrupted by these groups, i.e. _-C k _H l _F m (k is an integer of from 1 to 20, l is 0 to 40 In which m represents an integer of 1 to 41, and 1 + m = 2k + 1.

  Here, in recent years, it has been reported that compounds having a perfluoroalkyl group having 7 or more fluorinated carbon atoms have ecological effects such as carcinogenicity. It can also be subject to rules (SNUR). Therefore, as a fluorinated alkyl group, a C1-C5 perfluoroalkyl group is preferable, and the remaining carbon atoms are not fluorinated. More preferably, the perfluoroalkyl group has 3 to 5 carbon atoms.

  On the other hand, examples of the amphiphilic group include those contained in conventionally known nonionic surfactants, and those containing an alkylene group interrupted by an ether bond, an ester bond, or a carbonyl group are preferable. Among these, those containing a polyalkyleneoxy group (polyethyleneoxy group, polypropyleneoxy group, polybutyleneoxy group, etc.) are preferable.

  The molar ratio between the fluorinated alkyl group and the amphiphilic group varies depending on the composition of the photosensitive substrate composition, but is preferably 4: 6 to 9: 1, and is 4: 6 to 8: 2. It is more preferable that the ratio is 5: 5 to 7: 3.

  Such a surfactant can be obtained by polymerizing at least the monomer having the fluorinated alkyl group and the monomer having the philic group. As the monomer having a fluorinated alkyl group and the monomer having an amphiphilic group, monomers represented by the following formulas (h1) and (h2) are preferable, respectively.

In the above formula (h1), R ^1h represents a hydrogen atom or a methyl group, and R ^2h represents a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. ^Rf represents a perfluoroalkyl group having 1 to 5 carbon atoms, preferably 3 to 5 carbon atoms.

In the above formula (h2), R ^3h represents a hydrogen atom or a methyl group, R ^4h represents an alkylene group having 2 to 4 carbon atoms, and R ^5h represents a hydrogen atom or 1 to 15 carbon atoms, preferably carbon. The alkyl group of number 1-10 is shown.
Moreover, in said formula (h2), p shows the integer of 1-50.

  Specific examples of the monomer represented by the formula (h1) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (Perfluorobutyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate and the like.

  Specific examples of the monomer represented by the formula (h2) include (meth) acrylic acid methoxypolyethylene glycol ester [for example, those having 1 to 50 ethylene glycol repeating units (r)], (meth) Acrylic acid methoxypolypropylene glycol ester [for example, one having 1 to 50 propylene glycol repeating units (r)], (meth) acrylic acid methoxypoly (ethylene-propylene) glycol ester [for example, ethylene glycol repeating unit number and propylene The total number of glycol repeating units (r) is 2 to 50], (meth) acrylic acid methoxy poly (ethylene-tetramethylene) glycol ester [for example, the number of ethylene glycol repeating units and the number of tetramethylene glycol repeating units And the sum (r) is ˜50], (meth) acrylic acid butoxy poly (ethylene-propylene) glycol ester [for example, the sum of the number of ethylene glycol repeating units and the number of propylene glycol repeating units (r) is 2 to 50], ( (Meth) acrylic acid octoxy poly (ethylene-propylene) glycol ester [for example, one having a total (r) of 2 to 50 ethylene glycol repeating units and propylene glycol repeating units), (meth) acrylic acid lauroxy polyethylene Glycol esters [for example, those having 2 to 50 ethylene glycol repeating units (r)], (meth) acrylic acid lauroxy poly (ethylene-propylene) glycol esters [for example, the number of ethylene glycol repeating units and propylene glycol repeating units number In which the total (r) is 2 to 50], polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyryl Examples include ethyl (meth) acrylate, Kyoeisha Chemical Co., Ltd. light ester HOA-MS, light ester HOMS, and the like.

  The molar ratio when polymerizing the monomer represented by the formula (h1) and the monomer represented by the formula (h2) is preferably 4: 6 to 9: 1. 2 is more preferable, and 5: 5 to 7: 3 is more preferable.

  In addition to the monomer represented by the above formula (h1) and the monomer represented by the above formula (h2), the component (H) contains (meth) acrylic acid alkyl ester as long as the effects of the present invention are not impaired. It may be polymerized. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, i-nonyl (meth) acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (Meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, etc. are mentioned.

  The surfactant may be either a random polymer or a graft polymer, but is preferably a graft polymer. By using a graft polymer, the leveling effect can be further enhanced while maintaining compatibility with (A) the alkali-soluble substrate. Moreover, in the case of a graft polymer, there is little possibility of becoming cloudy even if content is increased.

The sp value of the surfactant is preferably 8.0 to 9.5 (cal / cm ³ ) ^1/2 . By setting it as said range, compatibility with a base-material component and a solvent can be improved and the effect as surfactant can be improved. In addition, sp value can be measured by the method of Unexamined-Japanese-Patent No. 2005-290128, for example.

  Moreover, the mass average molecular weight of the base material contained in the surfactant is 10,000 to 50,000, and preferably 10,000 to 30,000. In general, a surfactant made of a compound having a small number of carbon atoms in the fluorinated alkyl group has a low leveling effect. Even if it exists, sufficient leveling effect can be acquired. Moreover, the photosensitive base material layer excellent in application | coating uniformity and flatness can be obtained by making a mass mean molecular weight into said range.

That is, in general, a surfactant exhibits a surface active effect by having an insoluble part and a soluble part in a solvent. However, in a low molecular weight surfactant, when a fluorinated alkyl group having a small number of carbon atoms is used as an insoluble site, the effect as an insoluble site is too small, so that a sufficient surfactant effect cannot be obtained. Further, when the proportion of the insoluble part is increased, the soluble part is decreased, so that sufficient solubility cannot be obtained. In contrast, when a fluorinated alkyl group having a small number of carbon atoms is used, by setting the mass average molecular weight of the surfactant to 10,000 or more, the insoluble portion (fluorinated alkyl group) in one molecule of the surfactant is reduced. Since the amount can be increased, the solubility in a solvent can be lowered, and the surface active effect can be ensured. Moreover, since the ratio of a soluble site | part can also be taken large, crowding of a fluorinated alkyl group can be prevented by the steric hindrance by this soluble site | part. Moreover, since the solubility with respect to a solvent can be ensured, even if it increases the addition amount of surfactant, it can become difficult to become cloudy.
Moreover, when spin-coating the photosensitive base material composition, the photosensitive base material composition is dropped onto the substrate, and the substrate is rotated and applied. When a conventional low molecular weight surfactant is used, striation can be eliminated, but a liquid puddle of the photosensitive base material composition is generated at the edge of the substrate. A raised part of the conductive base material composition is formed. That is, the coating uniformity and flatness are poor. On the other hand, in the photosensitive base material composition in the present invention, since the surfactant having a mass average molecular weight of 10,000 or more is used, the bulge of the end portion can be eliminated even in spin coating. In particular, when the solid content concentration in the photosensitive base material composition is 30% by mass or more, there is a great effect in eliminating the bulge at the end.
Furthermore, when apply | coating with a slit coater, it exists in the tendency which makes the solid content density | concentration of a photosensitive base material composition low generally. When the solid content concentration of the photosensitive substrate composition is lowered, the flowability of the photosensitive substrate composition is increased, so that the thickness of the applied photosensitive substrate composition tends to be uneven. In addition, there is a step of drying the applied photosensitive substrate composition, but due to the influence of surface tension, temperature, concentration change during drying, etc. once applied to the photosensitive substrate composition, the edge of the substrate during the drying step The liquid returns from the center to the center, and the uniformity of the film thickness tends to be worse. In particular, when a large substrate was used, the film thickness uniformity was greatly affected. On the other hand, since the photosensitive base material composition according to the present invention uses a surfactant having a mass average molecular weight of 10,000 or more, the film thickness uniformity can be improved.

  In the present invention, the component (H) which is a polymer is usually adjusted at a concentration of 40 to 50% by mass in the solvent. As this solvent, the same thing as the organic solvent component (S) (henceforth (S) component) mentioned later is mentioned, for example, The same thing as what is used as (S) component is preferable.

  In the manufacturing method of the photosensitive base material composition for light shielding layer formation of this invention, (H) component is diluted to 2.5-20 mass% with a solvent, and the solution after dilution is filtered with a filter. As the solvent, for example, the same solvent as the stock solution or the same as the component (S) is preferable.

  The filter used in the filtration step is not particularly limited, and a known filter can be used. It is preferable to use a PTFE film (polytetrafluoroethylene film), a PP film (polypropylene film), and a PE film (polyethylene film), and it is particularly preferable to use a PTFE film (polytetrafluoroethylene film).

  The filter has a pore diameter of preferably 0.01 to 0.9 μm, more preferably 0.02 to 0.6 μm, and 0.05 to 0.3 μm in order to remove aggregates generated in the diluted solution. Is particularly preferred.

  In the filtration step, a filtration device and a filtration method are not particularly limited, and known ones can be used.

  The surfactant component (H) after filtration, the photosensitive substrate component (A), the pigment component (G), and the organic solvent component (S) are dispersed to form a photosensitive substrate composition for forming a light shielding layer. Things are manufactured.

(A) component (A) component used for the manufacturing method of the photosensitive base material composition for light shielding layer formation of this invention is not specifically limited, What is conventionally well-known can be used. For example, an alkali-soluble substrate (A1) (hereinafter referred to as (A1) component), a photopolymerizable compound (A2) (hereinafter referred to as (A2) component), and a photopolymerization initiator (A3) (hereinafter referred to as “component”). (A3) component)), and those that are cured by irradiation with light such as ultraviolet rays. A pattern having a desired shape can be obtained by curing the portion irradiated with light.

(A1) component In this invention, (A1) component is an alkali-soluble base material (A1-) which has the following alkali-soluble base material (A1-1) (henceforth (A1-1) component) or the following photocurability. 2) (hereinafter referred to as component (A1-2)) can be applied.

(A1-1) Component As the component (A1-1), one or more 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 A copolymer with at least one selected from acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, acrylamide, acrylonitrile and the like;
Groups such as phenol novolac type epoxy acrylate polymer, phenol novolak 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 Materials.
Since these acryloyl groups or methacryloyl groups are introduced into these base materials, the crosslinking efficiency is enhanced, and the light resistance and chemical resistance of the coating film are excellent.
Among the monomer components constituting the component (A1-1), the content of the monomer component having a carboxy group such as acrylic acid or methacrylic acid is preferably in the range of 5 to 40% by mass.

(A1-2) Component Examples of the (A1-2) component include polymers represented by the following general formula (1). Since the compound represented by the general formula (1) itself has photopolymerizability (photocurability), in the photosensitive substrate for forming a light-shielding film containing the compound, by increasing the transmittance of ultraviolet rays, Sensitivity can be further 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.

As the component (A1), one type may be used alone, or two or more types may be used in combination. Further, only the component (A1-1) may be used, only the component (A1-2) may be used, or both may be used in combination.
The mass average molecular weight (Mw) of the component (A1) 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, 5000 to 15000 is most preferred. 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.

(A2) component
As the component (A2) in the present invention, 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, pen Erythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1 , 6-hexanediol diacrylate, benzyl acrylate, benzyl methacrylate, cardoepoxy diacrylate, acrylic acid, methacrylic acid, and the like, but are not limited thereto.
(A2) A component may be used individually by 1 type and may use 2 or more types together.
In the present invention, a photopolymerizable alkali-soluble polymer is included in the component (A1), and a photopolymerizable monomer is included in the component (A2).

When the component (A2) is used, the component (A2) is preferably in the range of 5 to 500 parts by mass with respect to 100 parts by mass of the component (A1-1). A more preferable range is 20 to 300 parts by mass.
By setting the blending amount of the component (A2) to be equal to or more than the lower limit of the above range, poor curing at the time of exposure hardly occurs, 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.

(A3) Component The (A3) component in the present invention is not particularly limited, and those that have been proposed as photopolymerization initiators for photosensitive compositions can be used. For example, 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-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,4,6-trimethylbenzoy Diphenylphosphine 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-diethylthio Santen, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chloro Benzophenone, p, p′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, Nzoin 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-dimethylaminobenzo , 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) ethenyl]- , 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-triazine And so on.

  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, a plurality of types may be used in combination as the component (A3).
In the method for producing a photosensitive base composition for forming a light shielding layer of the present invention, the blending amount of the component (A3) is preferably in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A1). .

(S) component In the manufacturing method of the photosensitive base material composition for light shielding layer formation of this invention, (A) component is dissolved in (S) component for the improvement of applicability | paintability and viscosity adjustment.
As component (S), 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 model 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 base composition for forming the light shielding layer but also improves dispersibility of insoluble components such as pigments. It is.

  Although the usage-amount of (S) component 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 substrate 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%.

  The production method of the present invention preferably includes a step of dissolving the component (A) in the component (S) and filtering the obtained substrate solution with a filter having a pore size of 1 μm or less.

  In the case where the production method of the present invention has a base material solution filtration step, as a specific embodiment, for example, the (A) component is dissolved in the (S) component, and the diluted (H) component is filtered. Is separately added to the base solution, and the base solution containing the component (H) is filtered.

  The filter used in the filtration step of the base material solution is not particularly limited, and a known filter can be used. It is preferable to use a PTFE film (polytetrafluoroethylene film), a PP film (polypropylene film), and a PE film (polyethylene film), and it is particularly preferable to use a PTFE film (polytetrafluoroethylene film).

  Since it is necessary to remove fine impurities and foreign matters as the filter, the pore size is preferably 0.01 to 0.9 μm, more preferably 0.05 to 0.6 μm, and 0.1 to 0.3 μm. Particularly preferred.

  In the present invention, as described above, the (H) component and (A) component after filtration are dissolved in the (S) component, and the obtained base solution is filtered, and then dispersed with the (G) component. It is preferable. Although the method to disperse | distribute (G) component is not specifically limited, It can carry out by methods, such as adding and stirring (G) component to a base material solution.

(G) Component In the present invention, a black pigment such as carbon black can be used as the (G) component. Further, it is also possible to use those in which the color tone or the like is adjusted by using black, red, blue, green, yellow and purple pigments together. A well-known thing can be used suitably for a pigment | dye.
In particular, when carbon black and other pigments are used in combination as the pigment, the sensitivity of the light-sensitive layer-forming photosensitive substrate composition is lowered when the carbon black is less than 15% by mass in the total pigment. Therefore, the light shielding rate can be improved.

  In the present invention, a perylene black pigment (hereinafter simply referred to as a perylene pigment) is preferably used as the component (G). 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 an amine are used as raw materials, and a heating reaction is performed in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained crude product in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

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 base material 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 base material composition for light-shielding layer formation of this invention, 5-250 mass parts is preferable with respect to 100 mass parts of (A1) component. 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.

When the perylene pigment is used in combination with the above-described pigment or dye, the amount of the other pigment or dye used is 85% of the total dye, that is, the ratio of the perylene pigment to the total of the perylene pigment and the other dye. It is preferable to set so that it may become 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 substrate composition for forming a light shielding layer, and to obtain a good light shielding rate of the light shielding film. Can be achieved.

  In addition, in the manufacturing method of the photosensitive base material composition for light shielding layer formation of this invention, after dispersing (G) component, it is preferable to pass through the process filtered again. At that time, in order to prevent the dispersed component (G) from being removed, it is preferable to use a filter having a large pore diameter, for example, a filter having a pore diameter of 0.6 to 1.5 μm. The filter used in the second filtration step is not particularly limited as long as the pigment is not removed, and a known filter can be used. Preferably, a PTFE film (polytetrafluoroethylene film), a PP film (polypropylene film), or a PE film (polyethylene film) can be used.

Moreover, you may add a thermal-polymerization inhibitor and an antifoamer to the photosensitive base material composition for light shielding layer formation.
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.

<Method for forming light shielding layer>
Hereinafter, an example of a method of forming a black matrix will be described as an embodiment of a method of forming a light shielding layer using the photosensitive substrate composition for forming a light shielding layer.
First, a photosensitive base material composition for forming a light shielding layer is applied onto a substrate, such as 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 curtain flow coater. Apply using. 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 light-sensitive layer-forming photosensitive base material composition, 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 base material 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 substrate 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 light-sensitive substrate composition for forming a light-shielding layer obtained by the production method of the present invention, a good pattern can be formed by photolithography 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 the light-shielding dye, so that the base material composition can transmit exposure light and shield visible light.

<Spacer>
Further, the light-shielding layer having a constant film thickness formed by using the photosensitive substrate 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 two substrates constant, it can also serve as a spacer provided in a state of being sandwiched 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 base material 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 substrate composition as described above is used, 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 of the display 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 substrate composition for forming a light shielding layer of the present invention is particularly suitable for forming a black matrix in a method of forming a color filter by forming a colored layer in an opening of a previously formed black matrix by an ink jet method. It is. 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 for forming a black matrix as a partition (bank) using the photosensitive substrate composition for forming a light shielding layer produced by the production method 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.

<Examples 1-3, Reference Examples 1-6, Comparative Examples 1-10>
[(A) Synthesis of alkali-soluble resin]
First, 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-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was 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. At this time, 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 value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula (a4) of colorless and transparent solid.

  Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming 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 Resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectrum. The weight average molecular weight was 3400.

[Preparation of photosensitive resin composition for forming light shielding layer]
As shown in Table 1 below, (S) a solvent is added to (A) an alkali-soluble resin, (E) a photopolymerizable monomer, (H) a surfactant, and (D) a colorant to obtain a solid concentration of 15 It adjusted to mass% or 17 mass%, and it mixed for 2 hours with the agitator, and prepared the photosensitive base material composition for light shielding layer formation. In addition, the compounding quantity of each component in Table 1 is a "mass part".

Details of (A) alkali-soluble resin, (E) photopolymerizable monomer, (B) photosensitizer, (D) colorant, and (S) organic solvent used in Table 1 are as follows.
(A) -1: Preparation liquid (E) -1: dipentaerythritol hexaacrylate (B) -1: IRGACURE prepared by adding 3-methoxybutyl acetate to resin (A-1) to adjust the solid content concentration to 50% by mass OXE 02 (Ciba Specialty Chemicals)
(B) -2: IRGACURE 369 (Ciba Specialty Chemicals)
(D) -1: Carbon black (manufactured by Mikuni Color Co., Ltd., carbon concentration: 55%, solvent: 3-methoxybutyl acetate)
(S) -1: 3-methoxybutyl acetate / cyclohexanone / propylene glycol monomethyl ether acetate = 60/20/20 (mass ratio)

  The details of the (H) surfactant used in Table 1 are as shown in Table 2 below. In Table 2, the numbers in parentheses in the copolymers of (H) -1 to (H) -7 are the charged amounts of each monomer when the total amount of monomers when synthesizing the copolymer is 100 parts by mass. Indicates the percentage.

[Evaluation of uneven width]
Using the spin coater (manufactured by MIKASA), the glass substrate (1737 glass) of 100 mm × 100 mm using the photosensitive base composition for forming the light shielding layer of Reference Examples 1 to 6 and Comparative Examples 1 to 4 obtained above. After each coating on top, it was placed on a 5 mm wide glass piece placed on a hot plate and prebaked at 90 ° C. for 120 seconds. The unevenness width at that time was measured using a surface roughness measuring machine Surfcorder SE-2300 (manufactured by Kosaka Laboratory Ltd.). The results are also shown in Table 1.
The unevenness width is the unevenness width (nm) measured at the location shown in FIG. Since heat is transmitted to the glass substrate only from the glass piece, convection occurs from the heated place and the light-shielding resin composition is repelled, and this repelling becomes a bead. The smaller the repelling, that is, the smaller the portion where the film thickness is extremely thin, the better the coating uniformity and flatness.

  As can be seen from Table 1, in Reference Examples 1 to 6 using a specific surfactant having a molecular weight of 10,000 or more, a photosensitive substrate composition for forming a light shielding layer having a small unevenness width and excellent coating uniformity and flatness. Could get. On the other hand, in Comparative Examples 1 to 4 using other surfactants having a molecular weight of less than 10,000, the unevenness width was large, and the coating uniformity and flatness were poor.

Example 1
When the composition of Reference Example 1 was prepared, the component (H) ((H) -2) was diluted with 3-methoxybutyl acetate so that the concentration became 10% by mass from the stock solution (40% by mass), and then the pore size. Was obtained by the same method as in Reference Example 1 except that filtration was performed using a PTFE membrane (manufactured by PALL) having a thickness of 0.05 μm.
The obtained light-sensitive layer-forming photosensitive base material composition has a dry film thickness of 1.2 μm on a glass substrate having a clean surface of 1 mm thickness using a spin coater (TR25000: manufactured by Tokyo Ohka Kogyo Co., Ltd.). And dried at 90 ° C. for 2 minutes to form a light-sensitive layer-forming photosensitive substrate composition film (photosensitive layer).
Subsequently, it exposed with the exposure machine (EXM-1066-E01: product made by 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 1.0 μm.
When the obtained black matrix was visually checked for pinholes, no pinholes were observed, and a good black matrix could be obtained.

(Comparative Example 5)
A photosensitive substrate composition for forming a light shielding layer was obtained in the same manner as in Example 1 except that the component (H) was not filtered. Furthermore, a photosensitive layer and a black matrix were formed in the same manner as in Example 1 using the obtained photosensitive substrate composition for forming a light shielding layer. When the presence or absence of black matrix pinholes was visually confirmed, dozens of pinholes were confirmed.
(Comparative Example 6)
(H) The light-sensitive layer forming photosensitive substrate composition was obtained in the same manner as in Example 1 except that the component was not diluted and filtered. However, a solvent was separately added so that the final concentration of the component (H) with respect to the light-sensitive layer-forming photosensitive substrate composition was 10% by mass as in Example 1. Furthermore, a photosensitive layer and a black matrix were formed in the same manner as in Example 1 using the obtained photosensitive substrate composition for forming a light shielding layer. When the presence or absence of black matrix pinholes was visually confirmed, dozens of pinholes were confirmed.

(Example 2)
A light-sensitive layer-forming photosensitive substrate composition was obtained in the same manner as in Example 1 except that the composition was changed to the composition of Reference Example 2. Furthermore, a photosensitive layer and a black matrix were formed in the same manner as in Example 1 using the obtained photosensitive substrate composition for forming a light shielding layer.
When the obtained black matrix was visually checked for pinholes, no pinholes were observed, and a good black matrix could be obtained.

(Comparative Example 7)
A photosensitive substrate composition for forming a light shielding layer was obtained in the same manner as in Example 2 except that the component (H) was not filtered. Further, a photosensitive layer and a black matrix were formed in the same manner as in Example 2 using the obtained photosensitive substrate composition for forming a light shielding layer. When the presence or absence of black matrix pinholes was visually confirmed, dozens of pinholes were confirmed.

(Comparative Example 8)
A photosensitive base material composition for forming a light shielding layer was obtained in the same manner as in Example 2 except that the (H) component was not diluted and filtered. However, a solvent was separately added so that the final concentration of the component (H) with respect to the light-sensitive layer forming photosensitive substrate composition was 10% by mass as in Example 2. Further, a photosensitive layer and a black matrix were formed in the same manner as in Example 2 using the obtained photosensitive substrate composition for forming a light shielding layer. When the presence or absence of black matrix pinholes was visually confirmed, dozens of pinholes were confirmed.

(Example 3)
A light-sensitive layer forming photosensitive substrate composition was obtained in the same manner as in Example 1 except that the composition was changed to the composition of Reference Example 6. Furthermore, a photosensitive layer and a black matrix were formed in the same manner as in Example 1 using the obtained photosensitive substrate composition for forming a light shielding layer.
When the obtained black matrix was visually checked for pinholes, no pinholes were observed, and a good black matrix could be obtained.

(Comparative Example 9)
The photosensitive base material composition for light shielding layer formation was obtained by the method similar to Example 3 except not having filtered (H) component. Further, a photosensitive layer and a black matrix were formed in the same manner as in Example 3 using the obtained photosensitive substrate composition for forming a light shielding layer. When the presence or absence of black matrix pinholes was visually confirmed, dozens of pinholes were confirmed.

(Comparative Example 10)
A photosensitive substrate composition for forming a light shielding layer was obtained in the same manner as in Example 3 except that the (H) component was not diluted and filtered. However, a solvent was separately added so that the final concentration of the component (H) with respect to the light-sensitive layer-forming photosensitive substrate composition was 10% by mass as in Example 3. Further, a photosensitive layer and a black matrix were formed in the same manner as in Example 3 using the obtained photosensitive substrate composition for forming a light shielding layer. When the presence or absence of black matrix pinholes was visually confirmed, dozens of pinholes were confirmed.

  As can be seen from the results of Examples 1 to 3 and Comparative Examples 5 to 10, pinholes are generated even when the molecular weight of component (H) is 10,000 or more by filtering component (H) after dilution. No high quality black matrix could be obtained.

  From the above results, it was shown that in the method for producing a light-sensitive layer-forming photosensitive substrate composition according to the present invention, a high-quality black matrix that does not generate pinholes can be obtained.

Claims (5)

The surfactant component (H), which is a polymer having a mass average molecular weight of 10,000 to 50,000, is diluted to 2.5 to 10% by mass, and then filtered.
The photosensitive component for forming a light shielding layer, wherein the surfactant component (H) after filtration, the photosensitive substrate component (A), the pigment component (G), and the organic solvent component (S) are dispersed. For producing a conductive substrate composition.   The said filtration is a manufacturing method of the photosensitive base composition for light shielding layer formation of Claim 1 which filters with a PTFE film | membrane with a hole diameter of 1 micrometer or less.   The manufacturing method of the photosensitive base material composition for light shielding layer formation of Claim 1 or 2 in which the said photosensitive base material component (A) contains an alkali-soluble base material (A1).   The manufacturing method of the photosensitive base material composition for light shielding layer formation in any one of Claims 1-3 in which the said photosensitive base material component (A) contains a photopolymerizable compound (A2).   The manufacturing method of the photosensitive base material composition for light shielding layer formation of Claim 4 in which the said photosensitive base material component (A) contains a photoinitiator (A3).

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