TWI575314B - Photosensitive black resin composition and resin black matrix substrate - Google Patents

Description

Photosensitive black resin composition and resin black matrix substrate

The present invention relates to a photosensitive black resin composition and a resin black matrix substrate.

Conventionally, a metal film using a chromium-based material has been used as a black matrix material. However, in recent years, a resin black matrix composed of a resin and a light-shielding material has been used in terms of cost or environmental pollution. In the resin black matrix, a black resin composition containing a light-shielding material such as a resin and carbon black is applied onto a substrate and dried to form a black film, and this is obtained by finely patterning the pattern by a photolithography method.

In recent years, due to the miniaturization of liquid crystal display devices and the diversification of display contents from characters to images, high performance and high definition of color filters are required, and high blackout resistance (OD value) and film are required for resin black matrix. And improve the requirements of fine line processing. Although the volume ratio of the light-shielding material is increased to achieve high OD value and thin film formation, the resin black matrix and the glass are decreased in adhesion due to a decrease in the proportion of the resin in the resin black matrix, and the resin black matrix is peeled off during alkali development. And other issues. Therefore, it is necessary to develop the resin black matrix which can be processed with a high-definition pattern with the development adhesion of the glass substrate.

Further, in the substrate for a touch panel, a light-shielding film is formed as an edge of the peripheral portion, and when the volume ratio of the light-shielding material is increased similarly to the color filter, high development adhesiveness is required, and high-definition pattern processing is required.

However, in the black matrix of the photosensitive black matrix due to its own light-shielding property, photohardening due to exposure is hard to occur in the vicinity of the interface with the substrate. Therefore, the higher the light-shielding property of the resin black matrix, the worse the adhesion to the glass substrate during development, and the light-shielding property and the development adhesive property have a mutual compensation relationship.

Further, since the black resin composition having a high optical density contains a large amount of inorganic particles as a pigment, the compatibility with the alkali developing solution is deteriorated, and there is a problem that the fine pattern falls off during development.

In order to solve such problems, the sensitivity of the resin black matrix is increased, and as an additive for causing a photopolymerization reaction in the vicinity of the interface with the substrate, a tertiary amine compound, a trivalent phosphorus compound, an epoxy decane or the like is known ( Patent Documents 1 to 3). However, it is difficult to obtain a high-definition patterned substrate.

On the other hand, among the pigment-free systems, a photosensitive resin composition containing an oxetane compound as an additive is known (Patent Documents 4 and 5). Further, in the photosensitive resin composition containing a pigment, a cured film composed of a resin containing a oxetane group as a copolymer of a structural unit is known to be effective in physical adhesion to a substrate (patent Document 6).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-282325

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-246955

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-347916

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-258460

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2001-228610

[Patent Document 6] Japanese Laid-Open Patent Publication No. 2007-316506

The inventors of the present invention firstly made it difficult to peel off the fine pattern during development as an index, and focused on development adhesiveness. In Patent Documents 1 to 3, the film having a high optical density of the resin black matrix has insufficient curing reaction at the substrate interface. It does not affect the adhesion at the time of development, but the adhesion in further development is easily affected by the base substrate, and in particular, the adhesion of the touch panel to the soda glass used in general is deteriorated, so that the consideration is high. Fine patterning of substrates has its difficulties.

Further, in the black resin composition having a high optical density of the resin black matrix and containing a large amount of pigment particles, compatibility with the developer is less sufficient, and peeling of the fine pattern during development is caused. The present inventors also focused on compatibility.

The present invention has been made in view of the disadvantages of the prior art, and an object of the invention is to provide a resin black matrix which is formed on a glass substrate, has good substrate adhesion during development, and has good compatibility with a developer. A black resin composition processed by high-definition patterning is provided with a resin black matrix substrate using the photosensitive black resin composition, and a color filter and a light shielding film for a touch panel are further provided.

In the patents 4 and 5, the oxetane compound is known, and the cured film after post-baking has excellent physical adhesion to the substrate, and is excellent in resolution and sensitivity, but adhesion to the substrate during development. It is not known, and a black resin composition containing a large amount of pigment particles suitable for a high optical density of a resin black matrix is not described.

On the other hand, Patent Document 6 discloses a post-baked cured film composed of a resin containing a copolymer of a oxetane group as a structural unit in a photosensitive resin composition containing a pigment, and a substrate. The physical adhesiveness is effective, but the use as a copolymer is not known for the adhesion of the substrate during development, and is easily manifested in a black resin composition containing a large amount of pigment particles, and is compatible with the developer. Compatibility is still unknown.

Here, the inventors of the present invention have found that the above problems can be solved by adding a specific amount of a specific oxetane compound, and the present invention has been completed.

The object of the present invention is achieved by the following constitution.

(1) A photosensitive black resin composition comprising at least a light-shielding material, an alkali-soluble resin, a photopolymerization initiator, and a solvent, and a photosensitive black resin composition characterized by having at least the following formula (A) The oxetane compound having the structure as an additive and comprising 1.5 to 10.0% by weight of the above oxetane compound with respect to the total of the light-shielding material and the alkali-soluble resin; (2) the photosensitive black resin of the above (1) A composition wherein the above oxetane compound has a mercapto group.

(3) The photosensitive black resin composition of the above (1) or (2), wherein the oxetane compound is represented by the following structural formula (B).

(4) A resin black matrix substrate obtained by applying the photosensitive black resin composition according to any one of the above (1) to (3) to a transparent substrate and patterning the same.

By using the black resin composition of the present invention, effects such as a resin black matrix substrate excellent in development adhesion and pattern processing accuracy can be obtained.

[Formation of the Invention]

The photosensitive black resin composition of the present invention must contain at least a light-shielding material, an alkali-soluble resin, a photopolymerization initiator, and a solvent, and the desired properties are shown below.

The photosensitive black resin composition of the present invention can be used for printing inks, inkjet inks, mask manufacturing materials, materials for proofing production for printing, barriers for etching, solder resist, plasma display (PDP), dielectric It is produced by a body pattern, an electrode (conductor circuit) pattern, a wiring pattern of an electronic component, a conductive paste, a conductive film, or a black matrix (hereinafter referred to as "BM"). In order to improve the display characteristics of a color filter used for a color liquid crystal display device, it is preferable to provide a light-shielding image (including BM) such as a spacer portion, a peripheral portion, and an outer light side of the TFT, or to be suitable for touch A light shielding film used in the peripheral portion of the control panel substrate.

It is particularly preferable that the liquid crystal display device, the plasma display device, the EL display device including the inorganic EL, the CRT display device, the black side of the peripheral portion of the display device having the touch panel, or the red, blue, and green colors A grid-like or linear black portion between the colored images is more preferably used as a BM for a dot-like or linear black pattern for light-shielding of the TFT.

The light-shielding material used in the present invention may, for example, be a black pigment such as carbon black, titanium black, chromium oxide, iron oxide, aniline black, an anthraquinone pigment or CI, solvent black 123, or the like. An inorganic carbon black pigment such as a composite oxide of carbon black, titanium, manganese, iron, copper or cobalt, or a combination of an organic pigment and a black pigment, but in terms of high light-shielding property, carbon black or nitriding is preferred. titanium.

The alkali-soluble resin used in the present invention may, for example, be an epoxy resin, an acrylic resin, a decane polymer resin or a polyimide resin, but the storage stability of the composition and the heat resistance of the coating film. In an excellent aspect, an acrylic resin or a polyimide resin is preferred.

As the acrylic resin, an acrylic resin having a carboxyl group is preferably used. The acrylic resin having a carboxyl group is preferably a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound. The unsaturated carboxylic acid may, for example, be acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid or ethylene acetic acid. These may be used singly or in combination with other copolymerizable ethylenically unsaturated compounds.

Examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, and A. Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl acrylate, methacrylic acid Dibutyl acrylate, isobutyl acrylate, isobutyl methacrylate, butyl acrylate, butyl methacrylate, n-amyl acrylate, n-amyl methacrylate, 2-hydroxyethyl acrylate, An unsaturated carboxylic acid alkyl ester such as 2-hydroxyethyl methacrylate, benzyl acrylate or benzyl methacrylate, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene Or an aromatic vinyl compound such as α-methylstyrene, an amine alkyl ester of an unsaturated carboxylic acid such as aminoethyl acrylate, an unsaturated carboxylic acid glycidyl ester such as glycidyl acrylate or glycidyl methacrylate, or vinyl acetate. Ethyl vinyl carboxylate such as ester or vinyl propionate, vinyl cyanide compound such as acrylonitrile, methacrylonitrile or α-chloroacrylonitrile, or aliphatic conjugated diene such as 1,3-butadiene or isoprene , having a propylene fluorenyl group or a methacryl fluorenyl group at the terminal Polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate or polybutyl methacrylate, but from the viewpoint of solubility in an alkali developer, it is preferably selected from methacrylic acid. 2,4 copolymer of acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate or styrene, average molecular weight (Mw) 2,000 to 100,000, acid value 70~150 (mgKOH/g) polymer. If it is outside this range, the dissolution rate for the alkali developer is lowered or becomes too fast.

Further, when an acrylic resin having an ethylenically unsaturated group in its side chain is used, the sensitivity at the time of exposure and development becomes good, which is more preferable. The ethylenically unsaturated group is preferably an acrylic group or a methacryl group. Such an acrylic resin can be an acrylic resin having a carboxyl group. The carboxyl group of the copolymer is obtained by addition reaction with an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group.

For example, the acrylic resin described in the above-mentioned publication (Japanese Patent No. 3120476 and Japanese Patent Application Laid-Open No. Hei No. 8-262221), and a commercially available acrylic resin, are exemplified as the acrylic resin having an ethylenic unsaturated group in the side chain. Photocurable resin "Cyclomer (registered trademark) P" (DAICEL Chemical Industry Co., Ltd.) or alkali-soluble cardo resin. Among them, from the viewpoints of photosensitivity, solubility in an ester solvent, and solubility in an alkali developer, an acrylic resin having an ethylenically unsaturated group in a side chain is preferred, and an average molecular weight (Mw) is 2,000. ~100,000 (acrylic resin having an acid value of 70 to 150 (mgKOH/g) by using tetrahydrofuran as a carrier and measuring by gel permeation chromatography using a standard polystyrene calibration line).

Further, a monomer of the photosensitive black resin composition of the present invention may be added. The monomer may, for example, be a polyfunctional or monofunctional acrylic monomer or oligomer. Examples of the polyfunctional acrylic monomer include bisphenol A diglycidyl ether methacrylate, polymethacrylic acid urethane, modified bisphenol A epoxy methacrylate, and adipic acid. 1,6-hexanediol methacrylate, phthalic anhydride propylene oxide methacrylate, 1,2,4-benzenetricarboxylic acid diethylene glycol methacrylate, rosin modified epoxy dimethyl An acrylate diacrylate oligoacrylate or a tripropylene glycol dimethacrylate described in the acryl-ester, the alkyd-modified methacrylate, and the known document (Japanese Patent No. 3621533 and JP-A No. 8-278630) Ester, 1,6-hexanediol dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, trimethylolpropane trimethacrylate Ester, neopentyl alcohol trimethacrylate, triacrylformal, neopentyl alcohol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol penta methacrylate 2,2-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]propane) , bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]methane, bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]indole, double [4-(3-Propyloxy-2-hydroxypropoxy)phenyl]ether, 4,4'-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl] Cyclohexane, 9,9-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]anthracene, 9,9-bis[3-methyl-4-(3-propene oxime) Oxy-2-hydroxypropoxy)phenyl]anthracene, 9,9-bis[3-chloro-4-(3-propenyloxy-2-hydroxypropoxy)phenyl]anthracene, bisphenyloxy Bis-phenoxyethanol fluorenediacrylate, bisphenoxyethanol oxime dimethacrylate, bis-cresol fluorene diacrylate or biscresol oxime dimethacrylate. These may be used singly or in combination.

The properties of the resist's sensitivity or processability can be controlled by selecting and combining such polyfunctional or monofunctional acrylic monomers or oligomers. In particular, in order to increase the sensitivity, a compound having a functional group of 3 or more is preferred, a compound having a functional group of 5 or more is more preferred, and more preferably dipentaerythritol hexamethacrylate or dipentaerythritol. Methacrylate.

When using a pigment such as a black pigment for photocrosslinking to absorb an effective ultraviolet ray, dipentaerythritol hexamethacrylate or dipentaerythritol pentamethyl acrylate is added, and the combined use has a large amount in the molecule. It is preferred to use a high degree of water-repellent ring of methacrylate in the aromatic ring and control the pattern to a desired shape during development. Among them, a mixture of 10 to 60 parts by weight of dipentaerythritol hexamethacrylate and/or dipentaerythritol penta methacrylate and 90 to 40 parts by weight of a methacrylate having an anthracene ring is preferred. Used as a monomer.

The photopolymerization initiator may, for example, be a diphenylketone compound or an acetophenone compound. Oxoxanthene compound, imidazole compound, benzothiazole compound, benzo An azole compound, an oxime ester compound, an oxazole compound, and three An inorganic photopolymerization initiator such as a compound, a phosphorus compound or a titanate.

More specifically, for example, diphenyl ketone, N, N'-tetraethyl-4,4'-diaminodiphenyl ketone, 4-methoxy-4'-dimethyl group Aminodiphenyl ketone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzoyl imethylketal, α-hydroxyisobutyl Alpha-hydroxyisobutyl phenon, 9-oxosulfur (thioxanthone), 2-chlorothioxanthone, hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]- 2- Phenyl-1-propanone, "IRGACURE (registered trademark)" 369 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone (manufactured by Ciba‧Specialty‧Chemicals), "IRGACURE (registered trademark)" 379 2-(dimethylamino)-2-[4-(methylphenyl)methyl] -1-[4-(4- Phenyl)phenyl]-1-butanone (manufactured by Ciba‧Specialty‧Chemicals), 2-[4-methylbenzyl]-2-dimethylamino-1-(4-) of CGI-113 Phenanylphenyl)-butanone (manufactured by Ciba‧Specialty‧Chemicals), tertiary butyl hydrazine, 1-chloroindole, 2,3-dichloropurine, 3-chloro-2-methylindole Bismuth, 2-ethyl hydrazine, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzopyrene (Benzanthraquinone), 1,4-dimethylhydrazine, 2-phenylindole , 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoene Azole, "IRGACURE (registered trademark)" OXE01 1,2-octanedione, 1-[4-(phenylthio)-2-((O-benzamide)] (Ciba‧Specialty ‧Chemicals()), "IRGACURE(registered trademark)" ketone of OXE02, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]- , 1-(O-acetamidine), ethyl ketone of CGI-242, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine), 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-three ("Ciba‧Specialty ‧ Chemicals") or EZZ-based compound "ADEKA (registered trademark) OPTMER" N-1818, N-1919 or "ADEKA (registered trademark) CRUISE" NCI-831 (above, Asahi Chemical Industry (share) system).

These photopolymerization initiators may be used in combination of two or more kinds, and if used in combination, are selected from "IRGACURE (registered trademark)" 379, "IRGACURE (registered trademark)" OXE02, "ADEKA (registered trademark) OPTMER" N- In the case of two types of groups of 1919 and "ADEKA (registered trademark) CRUISE" NCI-831, a photosensitive black resin composition having a high sensitivity pattern shape is obtained, which is preferable.

Further, an adhesion improver may be added for the purpose of improving the adhesion to an inorganic material such as a glass plate or a tantalum wafer. As the adhesion improving agent, for example, a decane coupling agent or a titanium coupling agent can be used. The amount of the adhesion improver to be added is usually about 0.2 to 20% by weight based on the weight of the polyimide resin or the acrylic resin.

Further, in the photosensitive black resin composition of the present invention, a polymer dispersant may be added for the purpose of improving the dispersion stability of the light shielding material. The polymer dispersant may, for example, be a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant or a polyacrylamide polymer dispersant. These polymer dispersing agents are added so as not to reduce the photosensitivity or adhesion, and the amount thereof is usually about 1 to 40% by weight based on the light-shielding material.

In the photosensitive black resin composition of the present invention, the weight composition ratio of the light shielding material/resin component is preferably in the range of 80/20 to 40/60, and the adhesion, pattern processability, and OD value balance are in terms of balance. More preferably, it is in the range of 75/25~50/50. Here, the resin component means a total of a polymer, a monomer, an oligomer, and a polymer dispersant. When the amount of the resin component is too small, the adhesion to the substrate of the black film is deteriorated. Conversely, when the amount of the light shielding material is too small, the optical density (OD value/μm) of each thickness becomes low.

The solvent used for the black resin composition of the present invention may be water or an organic solvent by combining the dispersion stability of the dispersed pigment and the solubility of the added resin. The organic solvent may, for example, be an ester, an aliphatic alcohol, a polyalkylene ether ether solvent, a ketone, a guanamine-based polar solvent or a lactone-based polar solvent, but two or more of these may be mixed. Mixed solvents are also preferred. Moreover, it is also preferable to mix with an organic solvent other than these.

As the alkali-soluble resin, it is preferred to use an acrylic resin, and as the organic solvent, an organic solvent in which an acrylic resin is dissolved is preferable. More specifically, for example, benzyl acetate (boiling point: 214 ° C), Ethyl benzoate (boiling point 213 ° C), methyl benzoate (boiling point 200 ° C), diethyl malonate (boiling point 199 ° C), 2-ethylhexyl acetate (boiling point 199 ° C), 2-butoxy 2-butoxy ethyl acetate (boiling point 192 ° C), propylene glycol monoethyl ether acetate (boiling point 188 ° C), diethyl oxalate (boiling point 185 ° C), ethyl acetate Ester (boiling point 181 ° C), cyclohexyl acetate (boiling point 174 ° C), 3-methoxy-butyl acetate (boiling point 173 ° C), ethyl acetate methyl acetate (boiling point 172 ° C), 3-ethoxypropionic acid Ethyl 3-ethyl ester propionate (boiling point 170 ° C), 2-ethyl acetate butyl ester (boiling point 162 ° C), isoamyl propionate (boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C ), propylene glycol monoethyl ether acetate (boiling point 158 ° C), amyl acetate (boiling point 150 ° C) or propylene glycol monomethyl ether acetate (boiling point 146 ° C).

Further, examples of the solvent other than the above include ethylene glycol monomethyl ether (boiling point: 124 ° C), ethylene glycol monoethyl ether (boiling point: 135 ° C), propylene glycol monoethyl ether (boiling point: 133 ° C), and diethylene glycol alone. Methyl ether (boiling point 193 ° C), monoethyl ether (boiling point 135 ° C), methyl carbitol (boiling point 194 ° C), ethyl carbitol (boiling point 202 ° C), propylene glycol monomethyl ether (boiling point 120 ° C), propylene glycol single Polyalkylene ether ether solvent such as diethyl ether (boiling point 133 ° C), propylene glycol tertiary butyl ether (boiling point 153 ° C) or dipropylene glycol monomethyl ether (boiling point 188 ° C), ethyl acetate (boiling point 77 ° C), butyl acetate Aliphatic esters (boiling point 126 ° C) or isoamyl acetate (boiling point 142 ° C), butanol (boiling point 118 ° C), 3-methyl-2-butanol (boiling point 112 ° C) or 3-methyl-3 An aliphatic alcohol such as methoxybutanol (boiling point 174 ° C), a ketone such as cyclopentanone or cyclohexanone, xylene (boiling point 144 ° C), ethylbenzene (boiling point 136 ° C) or solvent oil (solvent naphtha) (Petroleum fraction: boiling point 165 ~ 178 ° C).

In order to increase the size of the substrate, it is preferably applied by a die-casting coating device, and in order to achieve appropriate volatility and drying properties, a mixed solvent of two or more components is preferable. When the boiling point of the total solvent constituting the mixed solvent is 150° C. or lower, it is difficult to obtain film thickness uniformity, and the film thickness after the application is completed is increased, and agglomeration of the pigment is generated in the nozzle portion from which the coating liquid is discharged from the slit. There are many problems such as streaks in the coating film. On the other hand, when a solvent having a boiling point of 200 ° C or more is contained in a large amount of the mixed solvent, the surface of the coating film becomes adhesive and adheres. Therefore, it is preferably a mixed solvent containing 30 to 75% by weight of a solvent having a boiling point of 150 to 200 °C.

The oxetane compound which is an additive in the present invention has a structure of the following formula (A).

(wherein R ¹ and R ² may be the same or different, respectively, R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may further have a substituent; further, R ² represents hydrogen, fluorenyl group Or an alkyl group having 1 to 10 carbon atoms, and the mercapto group and the alkyl group may further have a substituent.)

In the above formula (A), examples of the substituent in the case where the alkyl group further has a substituent include an alkoxy group, an acryloyl group, an ethoxy group or a fluorenyl group, and R ² is a carbon number of 1 to 10. In the case of an alkyl group, R ² preferably contains an oxetanyl group. Further, when the thiol group further has a substituent, for example, an alkyl group, an alkoxy group, an acryloyl group or an ethoxy group is mentioned, but among these, an oxetane group is preferable.

Further, in order to sufficiently obtain the effects of the invention, it is preferable that R ² has a mercapto group, and more preferably an oxetane compound represented by the following structural formula (B).

(wherein, X represents the following oxetene compound, and n represents a natural number of 10 or less.)

(wherein * represents a linking moiety, and R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may further have a substituent.)

The oxetane compound represented by the above formula (B) is preferably an oxetane compound in the range of n = 3 to 6. In the above structural formula (B), examples of the substituent in the case where the alkyl group further has a substituent include an alkoxy group, an acryloyl group or an ethoxy group.

The amount of the oxetane compound to be added is preferably from 1.5 to 10.0% by weight based on the total of the light-shielding material and the alkali-soluble resin, and is used in a range in which the solubility in the alkali developer is not excessively high. More preferably, it is 1.5 to 5.0% by weight.

The oxetane compound which does not have a hydrazine atom is "Aron Oxetane (registered trademark)" represented by the following general formula (C). OXT-101 (3-ethyl-3-hydroxymethyloxetane), "Aron Oxetane (registered trademark)" OXT-221 (3-ethyl-3) represented by the following formula (D) [(3-Ethyloxetane-3-yl)methoxy]methyl}oxetane) or "Aron Oxetane (registered trademark)" OXT-121 (main component 1,4-double [ [(3-ethyl-3-oxetanyl)methoxy]methyl]benzene) (above, East Asia Synthetic Co., Ltd.), "ETERNACOLL (registered trademark)" OXBP (double [(3-B) 3-oxo-oxetane)methyl]biphenyl-4,4'-dicarboxylate) or "ETERNACOLL" OXTP (bis[(3-ethyl-3-oxetane)) Base] phthalate) (above, Ube Industries (stock) system).

The oxetane compound having a mercapto group, for example, "Aron Oxetane (registered trademark)" having the average of n = 5 in the above structural formula (B) and having the following general formula (E) OXT-191 (a condensation reaction product of 3-ethyloxetane-3-ylmethanol with silanetetrol polycondensate; East Asian synthesis), as shown in the following structural formula (F1) or An oxetane compound having a sesquisesquioxane structure as shown in F2) (for example, OX-SQ TX-100 or the same as SI-20; above, manufactured by East Asia Synthetic Co., Ltd.), the following general formula (G) ) "Aron Oxetane (registered trademark)" TMSOX (3-ethyl-3-((3-(trimethoxymethyl)propyloxy)methyl) oxetane) (East Asia Synthetic Co., Ltd.), (oxetane-3-yl)methyltrimethoxydecane, (oxetane-3-yl)methyltriethoxydecane, (oxalate) Cyclobutane-3-yl)methyltriethoxypropane, [(oxetan-3-yl)methyl]methyldimethoxydecane, [(oxetane-3- Methyl]methyldiethoxydecane, [(oxetan-3-yl)methyl]methyldiethoxydecane, [(oxetan-3-yl) A Ethyldimethoxydecane, [(oxetan-3-yl)methyl]ethyldiethoxydecane, [(oxetan-3-yl)methyl]ethyl Diethoxydecane, [(oxetane-3-yl)methyl]phenyldimethoxydecane, [(oxetan-3-yl)methyl]phenyldiethoxylate Basearane, [(oxetan-3-yl)methyl]phenyldiethoxydecane, bis[(oxetane-3-yl)methyl]dimethoxydecane, two [oxetan-3-yl)methyl]diethoxydecane, bis[(oxetan-3-yl)methyl]diethoxypropane, bis[(oxetane) Alkyl-3-yl)methyl]methylmethoxydecane, bis[(oxetan-3-yl)methyl]methylethoxydecane, two [( Heterocyclobutane-3-yl)methyl]methylethoxydecane, bis[(oxetane-3-yl)methyl]ethylmethoxydecane, bis[(oxetane) Alkyl-3-yl)methyl]ethyl ethoxy decane, bis[(oxetan-3-yl)methyl]ethyl ethoxy decane, bis[(oxetane-3) -yl)methyl]phenylmethoxydecane, bis[(oxetan-3-yl)methyl]phenylethoxy decane, bis[(oxetane-3-yl)-methyl Phenyl ethoxy decane, tris[(oxetan-3-yl)methyl]methoxy decane, tris[(oxetane-3-yl)methyl]ethoxy Decane or tris[(oxetan-3-yl)methyl]ethoxypropane. In the present invention, two or more kinds of the oxetane compounds are mixed and used.

In addition, a surfactant may be added to the photosensitive black resin composition of the present invention for the purpose of preventing the beard cells from improving the smoothness of the coating property and the coloring film. The amount of the surfactant added is preferably 0.001 to 10% by weight, more preferably 0.01 to 1% by weight based on the pigment. When the amount added is too small, there is no effect of improving the smoothness of the coating property and the coloring film, or the effect of preventing the Pena cells; if it is too large, the coating property may be adversely affected. Examples of the surfactant include ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine. Cationic surfactants such as anionic surfactants, octadecylamine acetate or dodecyltrimethylammonium chloride, lauryl dimethylamine oxide or dodecyl carboxymethyl An amphoteric surfactant such as laurylcarboxymethyl hydroxyethylimidazolium betaine, a polyoxyethylene lauryl ether, a polyoxyethylene stearyl ether or a nonionic surfactant such as sorbitan monostearate, A polyfluorene-based surfactant or a fluorine-based surfactant having a polydimethylsiloxane or the like as a main skeleton. One or two or more kinds of these surfactants can be used in the present invention.

In the photosensitive black resin composition of the present invention, a combination of a resin component (including an additive such as a monomer or an oligomer and a photopolymerization initiator) and a solid of a light-shielding material is used as a coating property and a drying property. The concentration of the component is preferably from 2 to 30%, more preferably from 5 to 20%. Therefore, the photosensitive black resin composition of the present invention preferably has a solvent, a resin component, and a light-shielding material, and the total amount of the resin component and the light-shielding material is preferably 2 to 30%, more preferably 5 to 20%. The solid component is removed and the residual portion is a solvent, and as described above, a surfactant may be further contained.

The method for producing the photosensitive black resin composition of the present invention includes, for example, a method of directly dispersing a pigment in a resin solution using a disperser, or dispersing a pigment in water or an organic solvent using a disperser to prepare a pigment. After the dispersion, the method of mixing with the resin solution. Examples of the method of dispersing the pigment include a ball mill, a sand mill, a three-roll mill, and a high-speed impact machine. However, from the viewpoint of dispersion efficiency and micro-dispersion, a bead mill is preferred. As the bead mill, for example, a co-ball mill, a basket mill, and a column mill (pin) Mill) or dyno mill. Examples of the beads of the bead mill include titanium oxide beads, zirconium dioxide beads or zircon beads. The particle diameter used as the dispersion is preferably from 0.01 to 5.0 mm, more preferably from 0.03 to 1.0 mm. When the primary particle diameter of the pigment and the secondary particle obtained by aggregating the primary particle are small, it is preferable to use a minute dispersion bead such as 0.03 to 0.10 mm. At this time, it is preferred to use a bead mill to disperse minute dispersed beads and a dispersion using a telecentric separation method. On the other hand, when a pigment containing coarse particles of a size of about micrometers is dispersed, it is preferable to use a dispersion bead of 0.10 mm or more to obtain a sufficient pulverization force and to finely disperse the pigment.

A production example of the resin BM substrate of the present invention is shown below. As a method of applying a photosensitive black resin composition on a transparent substrate, for example, a transparent substrate is immersed in a photosensitive method by a dip coating method, a roll coating method, a spin method, a die-casting method, or a wire bar method. A method in a solution of a black resin composition or a method of spraying a solution of a photosensitive black resin composition on a transparent substrate. Examples of the transparent substrate include quartz glass, borosilicate glass, aluminosilicate glass, or inorganic glass such as soda lime glass coated with cerium oxide, or an organic plastic film or sheet. Further, when the substrate is coated on a substrate, the adhesion of the BM film to the substrate can be improved by previously treating the surface of the substrate with a bonding aid such as a decane coupling agent, an aluminum chelating agent or a titanium chelating agent.

After the photosensitive black resin composition is applied onto a transparent substrate, it is dried by heating, dried by air drying, heat drying or vacuum drying, and cured to form a dried film. In order to suppress uneven drying or uneven conveyance when forming a film, it is preferred to use a transparent substrate coated with a coating liquid. The vacuum dryer having a heating device is dried under reduced pressure, and then dried by heating and hardened.

The dried film thus obtained is usually subjected to pattern processing using a method such as photolithography. The dried film obtained from the photosensitive resin, after forming an oxygen blocking film on the surface thereof, is subjected to exposure development to form a desired pattern. Thereafter, the oxygen barrier film may be removed as needed, and then heat-hardened to obtain a resin BM substrate. The heat curing conditions vary depending on the resin. However, when an acrylic resin is used, it is usually heated at 200 to 250 ° C for 1 to 60 minutes.

By using the resin BM substrate of the present invention, a color filter substrate for a liquid crystal display or a light-shielding film for a touch panel can be manufactured. In other words, the present invention provides a color filter substrate for a liquid crystal display or a light-shielding film for a touch panel including the resin BM substrate of the present invention. The color filter is provided with at least a resin BM substrate on which a resin BM is formed in a partial region of a transparent substrate, and a color filter in which a pixel is formed on a transparent substrate without forming a resin BM region, and the resin BM substrate is a resin BM of the present invention. Substrate.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples and comparative examples, but the invention is not limited thereto. Among them, Examples 5 and 6 are reference examples.

Example 1

As a titanium nitride particle (manufactured by Nissin Engineering Co., Ltd.; 400 g), an acrylic resin produced by a thermo-plasma method, methyl methacrylate/methyl was synthesized by the method described in the Japanese Patent Publication No. 3120476. After the acrylic acid/styrene copolymer (weight composition ratio: 30/40/30), it is added to 40 parts by weight of glycidyl methacrylate, and re-precipitated with purified water, filtered and dried to obtain an average molecular weight (Mw). ) 15,000 and an acrylic resin (P-1) having an acid value of 110 (mgKOH/g). A 40% by weight solution of propylene glycol monomethyl ether acetate (187.5 g) of the obtained acrylic resin (P-1), a polymer dispersant (BYK21116; manufactured by BYK Co., Ltd.; 62.5 g), and propylene glycol monoethyl ether acetate ( 890 g) was placed in a tank, and stirred by a homogenizer (special machine) for 1 hour to obtain a preliminary dispersion 1. Thereafter, the preliminary dispersion 1 is supplied to have a 70% filling of 0.10 mm. An ultra-apex mill (manufactured by Shou Industrial Co., Ltd.) of a telecentric separation separator of zirconium dioxide beads (manufactured by Toray Industries, Inc.) was dispersed at a rotation speed of 8 m/s for 2 hours to obtain a solid content concentration of 25% by weight. Pigment/resin (weight ratio) = 80/20 titanium black pigment dispersion TB-1.

40% by weight (187.5 g) of propylene glycol monomethyl ether acetate of acrylic resin (P-1), polymer dispersant (BYK21116; 62.5 g) and propylene glycol monoethyl ether B were added to carbon black (TPX1291; CABOT; 400 g) The acid ester (890 g) was placed in a tank, and stirred by a homogenizer for 1 hour to obtain a preliminary dispersion 2. Thereafter, the preliminary dispersion 2 is supplied to have a 70% filling of 0.10 mm. A nanomill of a telecentric separation separator of zirconium dioxide beads was dispersed at a rotation speed of 8 m/s for 2 hours to obtain a carbon black having a solid content concentration of 20% by weight and a pigment/resin (weight ratio) = 80/20. Pigment dispersion CB-1.

"ADEKA (registered trademark) CRUISE" NCI-831 (1.69 g) as a photopolymerization initiator was added to propylene glycol monoethyl ether acetate (14.31 g), and stirred until the solid component was dissolved.

Further, a 40% by weight solution of propylene glycol monomethyl ether acetate (5.50 g) of an acrylic polymer (P-1) was added as a polyfunctional monomer dipentane A propylene glycol monoethyl ether acetate 50% by weight solution (3.61 g) of tetraol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) and "Aron Oxetane" OXT-191 as an adhesion modifier oxetane compound ( In the following, "oxyxetane compound 1"; propylene glycol monoethyl ether acetate 50% by weight solution (0.41 g), KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.; 0.41 g) and interface A 10 wt% solution of propylene glycol monoethyl ether acetate (0.24 g) of the active agent polyfluorene surfactant BYK333 was stirred at room temperature for 1 hour to obtain a photosensitive resist. To the photosensitive resist, 13.93 g of the above pigment dispersion liquid 1 and 19.90 g of the pigment dispersion liquid 2 were added, whereby a photosensitive black resin having a total solid content concentration of 23% and a pigment/resin (weight ratio) = 46/54 was prepared. Matter 1.

The prepared photosensitive black resin composition 1 was filtered through a 2 μm Teflon (registered trademark) filter, and then a spin coating apparatus was used on a soda lime glass substrate at a film thickness of 1 μm (post-bake). (1H-DS; manufactured by Mikasa Co., Ltd.) was applied, and the coated substrate was subjected to heat treatment for 2 minutes on a hot plate at 90 ° C for 2 minutes, and further, the substrate was directly placed on a hot plate for 2 minutes. Pre-baked. The coating film was exposed using an illuminating exposure machine (PEM-6M; manufactured by UNION Optics Co., Ltd.) through a spectroscopic test reticle with an exposure amount of ultraviolet rays of 200 mJ/cm ² .

Next, development was carried out using an alkali developing solution of a 0.1% by weight aqueous solution of TMAH, and washing with pure water was continued to obtain a patterned substrate. The obtained patterned substrate was post-baked in a hot air oven at 230 ° C for 30 minutes to obtain a resin BM substrate 1.

Example 2

As the adhesion improving agent to be used, OX-SQ TX-100 (hereinafter, "oxetane compound 2") having an oxetane compound having a sesquisesquioxane structure is used, and manufactured by Toagosei Co., Ltd. The photosensitive black resin composition 2 was obtained in the same manner as in Example 1 except that the oxetane compound 1 was replaced. Moreover, the resin BM substrate 2 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 2.

Example 3

As the adhesion improving agent to be used, OX-SQ SI-20 (hereinafter, "oxetane compound 3") which is an oxetane compound having a sesquiterpene oxide structure (manufactured by Toagosei Co., Ltd.) is used. The photosensitive black resin composition 3 was obtained in the same manner as in Example 1 except that the oxetane compound 1 was replaced. Moreover, the resin BM substrate 3 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 3.

Example 4

In addition to the oxetane compound 1 except "Aron Oxetane (registered trademark)" TMSOX (hereinafter, "oxetane compound 4"; manufactured by Toagosei Co., Ltd.) is used as the adhesion improving agent to be used. The photosensitive black resin composition 4 was obtained in the same manner as in Example 1. Moreover, the resin BM substrate 4 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 4.

Example 5

In place of the oxetane compound 1, "Aron Oxetane (registered trademark)" OXT-101 (hereinafter, "oxetane compound 5"; manufactured by Toagosei Co., Ltd.) is used as the adhesion improving agent to be used. A photosensitive black resin composition was obtained in the same manner as in Example 1 except that the photosensitive black resin composition was obtained. 5. Moreover, the resin BM substrate 5 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 5.

Example 6

In place of the oxetane compound 1, "Aron Oxetane (registered trademark)" OXT-221 (hereinafter, "oxetane compound 6"; manufactured by Toagosei Co., Ltd.) is used as the adhesion improving agent to be used. The photosensitive black resin composition 6 was obtained in the same manner as in Example 1. Moreover, the resin BM substrate 6 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 6.

Example 7

The photosensitive black resin composition 7 was obtained in the same manner as in Example 1 except that the amount of the oxetane compound 1 added was 3.0%. Moreover, the resin BM substrate 7 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 7.

Example 8

The photosensitive black resin composition 8 was obtained in the same manner as in Example 1 except that the amount of the oxetane compound 1 added was 5.0%. Moreover, the resin BM substrate 8 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 8.

Example 9

The photosensitive black resin composition 9 was obtained in the same manner as in Example 1 except that the amount of the oxetane compound 1 added was 7.0%. Moreover, the resin BM substrate 9 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 9.

Example 10

The photosensitive black resin composition 10 was obtained in the same manner as in Example 1 except that the amount of the oxetane compound 1 added was changed to 10.0%. Moreover, the resin BM substrate 10 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 10.

Example 11

Propylene glycol monoethyl ether acetate (19.05 g) was added as a photopolymerization initiator "ADEKA (registered trademark) CRUISE" NCI-831 (1.69 g), and stirred until the solid component was dissolved. Further, a 40% by weight solution of propylene glycol monomethyl ether acetate (6.73 g) of the acrylic polymer (P-1) was added, and the polyfunctional monomer, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) was added. 50% by weight solution of propylene glycol monoethyl ether acetate (3.62 g), propylene glycol monoethyl ether acetate 50% by weight solution of OXT-191 (manufactured by Toagosei Co., Ltd.) as an adhesion modifier oxetane compound (0.41g) and KBM5103 (0.41g) manufactured by Shin-Etsu Chemical Co., Ltd., a 10% by weight solution (0.24 g) of propylene glycol monoethyl ether acetate as a surfactant polyfluorene surfactant BYK333, stirred at room temperature One hour, thereby obtaining a photosensitive resist. To the photosensitive resist, 27.84 g of the above titanium black pigment dispersion TB-1 was added, whereby a photosensitive black resin composition 11 having a total solid content concentration of 23% and a pigment/resin (weight ratio) = 46/54 was prepared. Moreover, the resin BM substrate 11 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 11.

Example 12

Propylene glycol monoethyl ether acetate (9.57 g) was added as a photopolymerization initiator "ADEKA (registered trademark) CRUISE" NCI-831 (1.69 g), and stirred until the solid component was dissolved. Further, adding acrylic resin (P-1) to C a 40% by weight solution of diol monomethyl ether acetate (4.28 g) and a 50% by weight solution of propylene glycol monoethyl ether acetate as a polyfunctional monomer, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) (3.60 g), a propylene glycol monoethyl ether acetate 50% by weight solution (0.41 g) and KBM 5103 (0.41 g) as OXT-191 (manufactured by Toagosei Co., Ltd.) as an adhesion modifier oxetane compound. And a 10 wt% solution of propylene glycol monoethyl ether acetate (0.24 g) as a surfactant polyfluorinated surfactant BYK333, and stirred at room temperature for 1 hour, thereby obtaining a photosensitive resist. To the photosensitive resist, 19.9 g of a carbon black pigment dispersion liquid CB-1 was added, whereby a photosensitive black resin composition 12 having a total solid content concentration of 23% and a pigment/resin (weight ratio) = 46/54 was prepared. Moreover, the resin BM substrate 12 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 12.

Comparative example 1

The photosensitive black resin composition 13 was obtained in the same manner as in Example 1 except that the oxetane compound 1 was replaced with Tetramethyl orthosilicate. Moreover, the resin BM substrate 13 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 13.

Comparative example 2

The photosensitive black resin composition 14 was obtained in the same manner as in Example 1 except that the oxetane compound was not added. Moreover, the resin BM substrate 14 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 14.

Comparative example 3

As the adhesion modifier used, in addition to the oxetane compound 1 The photosensitive black resin composition 15 was obtained in the same manner as in Example 1 except that the amount of addition was 0.5%. Moreover, the resin BM substrate 15 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 15.

Comparative example 4

The photosensitive black resin composition 16 was obtained in the same manner as in Example 1 except that the amount of the oxetane compound 1 added was changed to 13.0%. Moreover, the resin BM substrate 16 was obtained in the same manner as in Example 1 using the photosensitive black resin composition 16. The obtained resin BM substrate 16 was evaluated by the following method regarding the pattern shape, development adhesion, and OD value. The results are shown in Table 1.

[developing adhesion]

In the same manner as the above method, the resin BM having a different line width was formed, and the presence or absence of occurrence of peeling or chipping of the pattern in each line width was visually determined. Further, it was judged as ○: no defect or peeling, and ×: there was a defect peeling.

[pattern linearity]

The linearity of the pattern-worked portion was evaluated using BH-C1410 (manufactured by OLYMPUS Co., Ltd.). For the judgment system, the linearity is good, and the degree of visibility of the snake or the shape end defect is Δ, ×.

[OD value]

Using the X-rite 361T (visual) densitometer, the following relationship was obtained.

OD value = log10 (I ₀ /I)

Here, I ₀ is the incident light intensity, and I is the transmitted light intensity. Further, since the OD value is a film thickness ratio, and the light shielding property is a film thickness ratio, it is expressed as an OD value per 1.0 μm in the present invention.

As a result shown in Table 1, by adding an oxetane compound as an adhesion improver, it was found that the linearity of the pattern was improved depending on the type of the substituent of the side chain. In addition, by adding an oxetane group containing a mercapto group, a photosensitive black resin composition excellent in development adhesiveness and pattern linearity can be obtained.

When the amount of the oxetane compound added is 1.5% or less or 10.0% or more with respect to the paste solid content, the development adhesiveness is deteriorated, and the amount is appropriately added in an amount of 1.5 to 10.0%.

As Comparative Example 1, tetramethyl decanoate having no oxetane ring and having only a mercapto group was added, and development developability and pattern linearity were not improved, and as a result, it was found to be a component of the present invention. The base oxetane compound can improve the developability and pattern linearity of the photosensitive black resin composition.

Claims (3)

A photosensitive black resin composition comprising at least a light-shielding material, an alkali-soluble resin, a photopolymerization initiator, and a solvent, and a photosensitive black resin composition characterized by comprising at least a structure having the following formula (A) An oxetane compound as an additive, comprising 1.5 to 10.0% by weight of the oxetane compound, based on the total of the light-shielding material and the alkali-soluble resin, and the oxetane compound has a mercapto group; (wherein R ¹ and R ² may be the same or different, respectively, and R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may further have a substituent; further, R ² represents a hydrogen atom, ruthenium A group or an alkyl group having 1 to 10 carbon atoms, and the fluorenyl group and the alkyl group may further have a substituent). The photosensitive black resin composition of claim 1, wherein the oxetane compound is represented by the following structural formula (B), (wherein, X represents the following oxetane group, and n represents a positive integer of 10 or less); (wherein * represents a linking moiety, and R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may further have a substituent). A resin black matrix substrate obtained by applying a photosensitive black resin composition according to claim 1 or 2 to a transparent substrate and forming a pattern.