TW201715306A - Photosensitive resin composition for light-shielding film with the role of spacer, light-shielding film, liquid crystal display device, method for producing photosensitive resin composition for light-shielding film with the role of spacer obtain hardened substance having excellent flexible modulus, deformation and flexible recovery rate under condition of retaining shading and insulation - Google Patents

Abstract

The invention relates to a photosensitive resin composition for light-shielding film with role of spacer. The photosensitive resin composition comprises the following compounds taken as essential components: (A) alkali-soluble resins containing polymerizable unsaturated group that enables molecules to have a polyol compound (a) having ethylenic unsaturated bond, a diol compound (b) having carboxyl group in molecules, and an urethane compound obtained by reacting diisocyanate compound (c); (B) photopolymerizable monomer having at least one ethylenic unsaturated bond; (C) photopolymerization initiator; (D) one or more light-shielding compounds selected from a group consisting of black organic pigment, color-mixed organic pigment and light-shielding materials; and (E) solvent.

Description

Photosensitive resin composition for a light-shielding film having a spacer function, a light-shielding film, a liquid crystal display device, a method for producing a photosensitive resin composition for a light-shielding film having a spacer function, a method for producing a light-shielding film, and a liquid crystal display device Production method

The present invention relates to a photosensitive resin composition for a light-shielding film having a spacer function, and a light-shielding film having a spacer function, which is formed by hardening a light-shielding method. A photosensitive resin composition and a cured film of a black column spacer having a spacer function and a black matrix function in a liquid crystal display device are formed. The present invention is further directed to a liquid crystal display device using a black column spacer obtained by the hardening. Further, the present invention relates to the photosensitive resin composition, a light shielding film, and a method of producing a liquid crystal display device.

In recent years, color liquid crystal display (LCD) has been used in all fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. Among them, in order to improve the performance of the LCD, the improvement of the viewing angle, the contrast ratio, the response speed, and the like are actively carried out, and various panel structures are currently being developed in the thin film transistor (TFT)-LCD which is currently in large use. . In the TFT-LCD, an array substrate and a color filter substrate which form a conventional TFT are separately manufactured, and the two substrates are bonded together in a state in which the spacers are kept at a constant interval; however, development is also being carried out at a low cost. LCD process to improve the yield. For example, as a substrate on which a color filter is directly formed on a TFT of an array substrate, a process of bonding a glass substrate is being developed. The structure formed in the above manner is referred to as a Color Filter On Thin Film Transistor (COT) or the like on a TFT. In the COT, a black matrix which is a boundary of each of pixels such as red (R), green (G), and blue (B) which are to be formed on the TFT is formed before RGB is formed. Various methods, such as a method formed after forming RGB pixels, or a method of forming on a facing glass substrate, have been studied.

Regarding the use of one of the factors that will affect the performance of the LCD, that is, the thickness of the liquid crystal layer (if the conventional method is used, the interval between the array substrate and the color filter substrate) is fixed, and the spacer is previously used. The method of the ball spacer of the diameter. However, in this method, the dispersion state of the ball spacer becomes uneven, and there is a problem that the amount of light per aperture is not fixed. In response to this problem, a method of forming a column spacer by photolithography is employed. However, the column spacer formed by the photolithography method is mostly transparent, and such a column spacer has a problem that light incident from the oblique direction affects the electrical characteristics of the TFT and deteriorates display quality. In response to such a problem, an LCD panel structure using a light-shielding film having a spacer function, that is, a light-shielding column spacer is formed by a photolithography method (Patent Document 1). In the COT, a method of forming a so-called black column spacer (BCS) using a material similar to that of a black matrix is also studied (for example, Patent Document 2).

In order to function as a spacer, the light-blocking column spacer requires a film thickness of about 2 μm to 7 μm. Further, it is necessary to form a light-blocking column spacer having a different height at the same time as the other portion where the TFT is formed. In addition, the light-shielding column spacer is required to have an appropriate modulus of elasticity, deformation amount, elastic recovery rate, and the like as a spacer function (Patent Document 3). Further, in the light-blocking column spacer, it is required to improve the reduction of the curable component caused by the addition of the light-shielding component (colorant) to the spacer, or the loss of electrical characteristics caused by the influence of impurities or the like in the coloring agent. Etc. (Patent Document 4). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2009-0303407 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-031778 (Patent Document 4) International Publication No. 2013/062011

[Problems to be Solved by the Invention] In Patent Document 4, a mixed color organic pigment is used, but the optical density of the light-blocking column spacer is not shown. The color-mixed organic pigment has an effect on low dielectric constant compared with an inorganic pigment such as carbon black, but has a large light-shielding property. Further, since the spacer must simultaneously form spacers having different heights, mechanical properties such as elastic modulus, deformation amount, and elastic recovery rate are further required for the light-shielding column spacer. Since the shape or mechanical properties of the spacer are greatly affected by the light-shielding component, it is difficult to design the photosensitive resin composition for the light-shielding film. Therefore, the shape or mechanical properties of the spacer using carbon black or a mixed color organic pigment or the like are still not sufficient, and further improvement is required.

Further, as described above, the light-blocking column spacer is manufactured with a film thickness of about 2 μm to 7 μm. With the miniaturization of the liquid crystal display element in recent years, it is desirable to form a spacer shape which is fine even when the film thickness is about 2 μm to 7 μm.

The present invention has been made in view of the above-mentioned problems, and is a photosensitive resin composition for a light-shielding film having a spacer function which is excellent in light-shielding property and insulating property, and further excellent in elastic modulus, deformation amount, and elastic recovery rate, and use thereof. A light-shielding film having a spacer function and a liquid crystal display device having the light-shielding film as a constituent element. [Means for solving the problem]

In order to solve the problem in the photosensitive resin composition for a light-shielding film as described above, the present inventors have found that a specific coloring agent is suitable as a light-shielding component of a photosensitive resin composition for a target light-shielding film. Thus, the present invention has been completed. (1) The present invention is a photosensitive resin composition for a light-shielding film having a separator function, which comprises the following components (A) to (E) as essential components: (A) a polymerizable unsaturated group-containing An alkali-soluble resin obtained by reacting a polyol compound (a) having an ethylenically unsaturated bond in a molecule, a diol compound (b) having a carboxyl group in a molecule, and a diisocyanate compound (c) An ester compound; (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material. More than one shading component in the group; and (E) solvent. (2) The photosensitive resin composition according to (1), which comprises titanium black as the (D) light-shielding component. (3) The photosensitive resin composition according to (2), wherein the titanium black has an average secondary particle diameter of 100 nm to 300 nm. (4) The photosensitive resin composition according to any one of (1) to (3), comprising a black organic pigment and/or a mixed color organic pigment as (D) a light-shielding component, and The average secondary particle diameter of the black organic pigment and/or the mixed color organic pigment is from 20 nm to 500 nm. (5) The photosensitive resin composition according to any one of (1) to (4), which is contained in an amount of 5 parts by mass to 400 parts by mass based on 100 parts by mass of the component (A) ( The component B) contains 0.1 parts by mass to 30 parts by mass of the component (C) per 100 parts by mass of the total of the components (A) and (B), and is a solid component (B) When the component other than the component (E) is a solid component, the solid component contains 5% by mass to 80% by mass of the component (D). (6) The photosensitive resin composition according to any one of (1) to (5), which can form a light-shielding film having an optical density OD of 0.5/μm or more and 3/μm or less. Further, when the voltage of 10 V is applied, the volume resistivity is 1 × 10 ⁹ Ω·cm or more, and the dielectric constant is 2 to 10. (7) The photosensitive resin composition according to any one of (1) to (6), which can be formed in a load-load-removal test using a micro hardness tester (i) (a) a breaking strength of 200 mN or more; (ii) an elastic recovery rate of 30% or more; and (iii) a compression ratio of 40% or less. (8) The present invention is a light-shielding film having a function of a spacer, which is formed by curing the photosensitive resin composition according to any one of (1) to (7). (9) Further, the present invention is a liquid crystal display device comprising the light shielding film as described in (8) as a black column spacer (BCS). (10) Further, the present invention is the liquid crystal display device of (9), which further comprises a thin film transistor (TFT). (11) Further, the present invention provides a method for producing a photosensitive resin composition for a light-shielding film having a separator function, which is obtained by preparing a dispersion obtained by dispersing (D) a light-shielding component in (E) a solvent. Further, (A) an alkali-soluble resin containing a polymerizable unsaturated group, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator are further added to the dispersion. And (E) a solvent which is a polyol compound (a) having an ethylenically unsaturated bond in the molecule, a diol compound (b) having a carboxyl group in the molecule, and a diisocyanate. The urethane compound obtained by the reaction of the compound (c), and the (D) light-shielding component is one or more components selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material. (12) Further, the invention is the method of (11), wherein the (D) light-shielding component comprises titanium black. (13) Further, the invention is the method of (12), wherein in the dispersion, the average secondary particle of the titanium black is from 100 nm to 300 nm. (14) The method of any one of (11) to (13), wherein (D) the light-shielding component comprises a black organic pigment and/or a mixed color organic pigment, and in the dispersion, The black organic pigment and/or the mixed color organic pigment has an average secondary particle diameter of 20 nm to 500 nm. (15) The present invention is a method for producing a light-shielding film formed on a substrate, which is characterized in that the photosensitive resin composition according to any one of (1) to (7) is applied onto a substrate and irradiated with light. The photosensitive resin composition is cured. (16) The method for producing a light-shielding film according to (15), wherein a film thickness H1 for setting an optical density as a light-shielding film to 0.5/μm or more and less than 3/μm, and When the film thickness H2 of the light-shielding film which is a spacer function is 2 to 7 μm, a light-shielding film having a film thickness H1 and a film thickness H2 of ΔH=H2-H1 of 0.1 to 2.9 is simultaneously formed. (17) Further, the present invention is a method of manufacturing a liquid crystal display device which uses a light shielding film manufactured by the method according to (16) as a black column spacer. (18) Further, the present invention is the manufacturing method according to (17), wherein the liquid crystal display device comprises a thin film transistor (TFT). [Effects of the Invention]

Since the photosensitive resin composition for a light-shielding film of the present invention contains a specific coloring agent, it is possible to obtain an elastic modulus and a deformation amount while maintaining the light-shielding property and the insulating property as compared with the conventional photosensitive resin composition. A cured product with excellent elastic recovery rate. Further, the photosensitive resin composition for a light-shielding film of the present invention can be formed into a fine separator shape even when the film thickness is about 2 μm to 7 μm.

Hereinafter, the present invention will be described in detail. The polymer-soluble unsaturated group-containing alkali-soluble resin of the component (A) is a polyol compound (a) having an ethylenically unsaturated bond in the molecule, a diol compound (b) having a carboxyl group in the molecule, and a diisocyanate compound ( c) A urethane compound obtained by carrying out the reaction.

The polyol compound (a) having an ethylenically unsaturated bond in the molecule used for the production of the component (A) is, for example, an epoxy compound having two or more alcoholic hydroxyl groups and two or more epoxy groups in the molecule. An epoxy acrylate compound which is a reactant of (meth)acrylic acid (which is a meaning of "acrylic acid and/or methacrylic acid"). A typical epoxy group (meth) acrylate compound is a compound obtained by reacting (meth)acrylic acid with the epoxy compound represented by the formula (I). [Chemical 1] In the formula (I), R ₁ , R ₂ , R ₃ and R _{4 each} independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and X represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, or 茀-9,9-diyl or a single bond The average value of m is 0 to 10, preferably 0 to 4.

The bisphenols which provide the epoxy compound of the formula (I) include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl)anthracene, and bis(4-hydroxyl). Phenyl) hexafluoropropane, bis(4-hydroxyphenyl)dimethyl decane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, 2,2 - bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorobenzene Propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxy-3,5 -Dimethylphenyl)ether, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 4,4'-biphenol, 3,3'-biphenol and the like. These bisphenols may be used alone or in combination of two or more. Among them, a bisphenol in which X in the formula (I) is a propane-2,2-diyl group can be preferably used.

The compound of the formula (I) is an epoxy compound having (m + 2) or more alcoholic hydroxyl groups and two glycidyl ether groups obtained by reacting the bisphenols with epichlorohydrin. In the reaction, the oligomerization of the diglycidyl ether compound is usually carried out, and m is an integer of 0 to 10 in each molecule. Since a molecule having a plurality of values is usually mixed, the average value is 0 to 10 (not limited to an integer). However, the average value of preferred m is 0-4. When the average value of m exceeds the upper limit, when a photosensitive resin composition using an alkali-soluble resin synthesized using the epoxy compound is formed, the viscosity of the composition becomes too large, and coating cannot be smoothly performed or cannot be performed. The alkali solubility is sufficiently imparted, and the alkali developability is very poor.

Examples of the compound of the formula (I) which is an epoxy compound used in the production of an epoxy group (meth) acrylate include a hydrogenation of a benzene ring of a compound of the formula (I) to form a cyclohexane ring. A group of compounds obtained by reacting a compound group or a phenol compound having two or more phenolic hydroxyl groups in a molecule with epichlorohydrin.

The epoxy compound obtained by reacting a phenol compound having two or more phenolic hydroxyl groups in the molecule with epichlorohydrin is, for example, a compound of the formula (II). [Chemical 2] In the formula (II), Y and Z represent a benzene skeleton, a naphthalene skeleton or a biphenyl skeleton, and G represents a glycidyl group. l represents 1 or 2, and n represents a number of 1 to 5 on average.

The epoxy compound used in the epoxy group (meth) acrylate preferably has an epoxy equivalent of from 100 to 500. When the epoxy equivalent is less than 100, the molecular weight of the (A) alkali-soluble resin containing a polymerizable unsaturated group is formed. Small, film formation may become difficult, and there is a concern that the film becomes brittle. In addition, when the epoxy equivalent exceeds 500, the content ratio of the polymerizable unsaturated group per molecule becomes small, and the sensitivity as a photosensitive resin cannot be sufficiently obtained.

Further, the diol compound (b) having a carboxyl group in the molecule used in the production of the component (A) is not particularly limited as long as it has two alcoholic hydroxyl groups and one or more carboxyl groups in the molecule, and is preferably selected. Dimethylolpropionic acid, dimethylolbutanoic acid was used. Further, a reaction product of a trifunctional or higher polyhydric alcohol compound and a polybasic acid anhydride can also be mentioned. These diol compounds having a carboxyl group may be used alone or in combination of two or more.

In the case where the diisocyanate compound (c) used in the production of the component (A) is a compound having two isocyanate groups in the molecule, it is not particularly limited. However, in order to form a urethane compound excellent in flexibility and the like, Preference is given to using: phenyl diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, aryl aryl ether diisocyanate, norbornane - Methyl dicyanate or the like, among these compounds, isophorone diisocyanate or trimethylhexamethylene diisocyanate can be preferably used. These compounds may be used singly or in combination of two or more kinds.

When the component (a) is a diol compound having an ethylenically unsaturated bond, the composition of each component (a), (b), and (c) in the case of producing the component (A) is preferably a molar ratio [(a) The value of +(b)]/(c) is 1 to 5. When the molar ratio is less than 1, the isocyanate group remains at the terminal of the compound obtained by the reaction, and there is a concern of gelation, which is not preferable. In the case where the molar ratio exceeds 5, the obtained content is contained. The molecular weight of the alkali-soluble resin of the polymerizable unsaturated group is small, and when the photosensitive resin composition is formed, the sensitivity is not sufficiently obtained, or the viscosity is generated at the time of film formation.

Further, a component (A) obtained by disposing a part of the component (b) with a diol compound (d) having no ethylenically unsaturated bond or a carboxyl group in the molecule and reacting it may be formed. Examples of the component (d) include aliphatic diol compounds such as (poly)ethylene glycol, (poly)propylene glycol, 1,4-butanediol, and 1,6-hexanediol, or cyclohexane-1. An alicyclic diol such as 4,-diol or cyclohexane-1,4-dimethanol.

The reaction conditions of the component (A) are in a solvent free or a solvent having no alcoholic hydroxyl group (for example, glycol ethers produced from ethylene glycol or the like, propylene glycol monomethyl ether acetate, butyl cellosolve acetate) Adding a predetermined amount of (a), (b), and optionally (d) components to the reactor for mixing and stirring, and slowly adding the component (c), the reaction temperature is 40. The reaction is carried out at a temperature of from ° C to 120 ° C for a period of from about 5 hours to about 60 hours, whereby an alkali-soluble resin having an ethylenically unsaturated bond as the component (A) is obtained.

For example, when the component (a) is an epoxy group (meth) acrylate obtained by reacting an epoxy compound represented by the formula (I) with (meth)acrylic acid, the obtained ethylenicity is not The basic skeleton of the saturated bond alkali-soluble resin can be represented by the general formula (III) and the general formula (IV). The alkali-soluble resin obtained at this time is a resin in which the two structures are substantially randomly bonded, and may contain a part of a skeleton having a different structure. [Chemical 3] In the formula (III), R ₅ independently represents a hydrogen atom or a methyl group, J represents a residue other than the epoxy group of the epoxy compound, and L represents a residue other than the isocyanate group of the diisocyanate compound, and p represents 10 The number of ~100. [Chemical 4] In the formula (IV), L represents a residue other than the isocyanate group of the diisocyanate compound, M represents a ternary alkyl group having 1 to 5 carbon atoms, and q represents a number of 10 to 100.

Further, the acid value of the component (A) can be adjusted by reacting the terminal alcoholic hydroxyl group remaining in the ethylenically unsaturated group-containing alkali-soluble resin obtained in the reaction with the acid anhydride (e).

Examples of the acid anhydride (e) for adjusting the acid value include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. And trimellitic anhydride, tetrahydrotrimellitic anhydride, hexahydrotrimellitic anhydride, and the like.

The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (A) measured by gel permeation chromatography (GPC) is usually 2,000 to 50,000, preferably 5,000 to 20,000. When the weight average molecular weight is less than 2,000, there is a concern that the adhesion of the pattern at the time of alkali development is lowered. When the weight average molecular weight exceeds 50,000, the developability is remarkably lowered.

Further, the acid value of the alkali-soluble resin of (A) is preferably in the range of 80 mgKOH/g to 120 mgKOH/g. When the value is less than 80 mgKOH/g, the residue tends to remain during alkali development, and if it exceeds 120 mgKOH/g, the penetration of the alkali developing solution becomes too fast, causing peeling and development, which is not preferable. Further, (A) the alkali-soluble resin containing a polymerizable unsaturated group may be used alone or in combination of two or more.

Further, (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond may, for example, be 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate or (meth). a (meth) acrylate having a hydroxyl group such as 2-hydroxyhexyl acrylate, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, or triethylene glycol di(methyl) Acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane three (Meth) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (methyl) Acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene (Meth) acrylates such as alkylene oxide-modified hexa(meth) acrylate and caprolactone-modified dipentaerythritol hexa(meth) acrylate Divinyl compounds vinylbenzyl ethers of polyhydric phenol compounds, pentaerythritol, dipentaerythritol, polyhydric alcohols, phenol novolac and the like, divinylbenzene addition polymerization like. These (B) photopolymerizable monomers having at least one ethylenically unsaturated bond may be used alone or in combination of two or more. Further, (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxyl group.

The blending ratio of the component (B) is preferably from 5 parts by mass to 400 parts by mass, and preferably from 10 parts by mass to 150 parts by mass, per 100 parts by mass of the component (A). When the compounding ratio of the component (B) is more than 400 parts by mass based on 100 parts by mass of the component (A), the cured product after photocuring becomes brittle, and the acid value of the coating film in the unexposed portion is low, so The solubility of the alkali developer is lowered, causing a problem that the edges of the pattern are not jagged. On the other hand, when the proportion of the component (B) is less than 5 parts by mass based on 100 parts by mass of the component (A), the proportion of the photoreactive functional group in the resin is small, and the formation of the crosslinked structure is insufficient. Further, since the acid value of the resin component is high, the solubility of the exposed portion to the alkali developer is improved. Therefore, there is a concern that the formed pattern becomes thinner than the target line or is likely to fall off from the pattern. .

Further, examples of the photopolymerization initiator of the component (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, and Acetophenones such as chloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylammonyl Benzophenones such as benzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers, 2-(o-chlorophenyl)-4,5-phenylbiimidazole , 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(neighbor a biimidazole compound such as oxyphenyl)-4,5-diphenylbiimidazole or 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3, 4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyrene Halomethyldiazole compounds such as-1,3,4-oxadiazole, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4 ,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4 -chlorine Phenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1 ,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxybenzene Vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloro) Methyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine Base-s-triazine-based compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzhydrylhydrazine), 1-(4- Phenylnonylphenyl)butane-1,2-dione-2-indole-O-benzoate, 1-(4-methylnonylphenyl)butane-1,2-dione-2-肟-O-acetate, 1-(4-methylnonylphenyl)butan-1-one oxime-O-acetate, ethyl ketone, 1-[9-ethyl-6-(2-A Benzobenzhydryl)-9H-indazol-3-yl]-, 1-(0-ethenylhydrazine), ketone, (9-ethyl-6-nitro-9H-carbazole-3- [4-(2-methoxy-1-methylethoxy)-2-methylphenyl]-, O-ethylindenyl ketone, ketone, (2-methylphenyl) (7 -nitro-9,9-dipropyl-9H-indol-2-yl)-, acetyl hydrazine, ethyl ketone, 1-[7-(2-methylbenzhydryl)-9,9- Dipropyl-9H-indol-2-yl]-, 1-(O-acetamidine肟), ethyl ketone, 1-(-9,9-dibutyl-7-nitro-9H-indol-2-yl)-, 1-O-ethylindenyl hydrazine and other O-mercapto lanthanide compounds , benzyl dimethyl ketal, thioxanthone, 2-chlorothiazinone, 2,4-diethylthiazinone, 2-methylthiaxanone, 2-isopropylthio Sulfur compounds such as fluorenone, anthracene such as 2-ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl hydrazine, azobisisobutyronitrile, benzene An organic peroxide such as a methyl ketone peroxide or a cumene peroxide; a thiol compound such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole. Among them, from the viewpoint of easily obtaining a photosensitive resin composition for a light-shielding film having high sensitivity, it is preferred to use an O-fluorenyl compound. These (C) photopolymerization initiators may be used alone or in combination of two or more. Further, the photopolymerization initiator in the present invention is used in the meaning of containing a sensitizer.

These photopolymerization initiators or sensitizers may be used alone or in combination of two or more. Further, although it does not function as a photopolymerization initiator or a sensitizer by itself, a compound capable of increasing the ability of a photopolymerization initiator or a sensitizer can be added by being used in combination. Examples of such a compound include a tertiary amine such as triethanolamine or triethylamine which is effective when used in combination with benzophenone.

The amount of the photopolymerization initiator of the component (C) is preferably from 0.1 part by mass to 30 parts by mass, based on 100 parts by mass of the total of the component (A) and the component (B), and preferably from 1 part by mass to 25 parts by mass. It is appropriate. When the compounding ratio of the component (C) is less than 0.1 part by mass, the rate of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, when it exceeds 30 parts by mass, there is a concern that the sensitivity is too strong. In a state where the pattern line width becomes thicker with respect to the pattern mask, a faithful line width cannot be reproduced for the mask, or the pattern edges are jagged and unclear.

The component (D) is a light-shielding component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material, and is preferably excellent in insulation, heat resistance, light resistance, and solvent resistance. Here, examples of the black organic pigment include perylene black, aniline black, cyanine black, and lactam black. The mixed color organic pigment may be a mixture of two or more kinds of pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like to simulate blackening. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, and titanium black. These (D) light-shielding components may be used alone or in combination of two or more.

As a light-shielding material, titanium black is preferable in terms of light-shielding property, elastic modulus, deformation amount, and elastic recovery rate. In the case of using titanium black, a black organic pigment and/or a mixed color organic pigment may be used in combination for the purpose of further improving the insulating property. As described above, when the inorganic light-shielding material and the organic pigment are used in combination, the blending ratio of the light-shielding material/(black organic pigment and/or mixed color organic pigment) is preferably 90/10 to 10/ by mass ratio. 90 is preferably 70/30 to 30/70. According to the combination of the light-shielding material and the organic pigment and their blending ratio, a light-shielding film having a spacer function having desired properties such as light-shielding property and insulating property can be obtained. For the purpose of controlling the chromaticity of the light-shielding film to make the light-shielding film achromatic, the organic pigment other than black is not intended to be black which is obtained by analog color mixing, and may be added as a single color.

The titanium black used in the present invention is a titanium-containing black inorganic pigment represented by low-valent titanium oxide, titanium oxynitride or the like, and those exhibiting high insulating properties can be preferably used among these inorganic pigments. These titanium blacks are produced by a method in which a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing gas atmosphere (Japanese Patent Laid-Open Publication No. SHO 49-5432); A method for reducing ultrafine titanium dioxide obtained by hydrolysis in a reducing gas atmosphere containing hydrogen (Japanese Patent Laid-Open Publication No. SHO 57-205322); a method of performing high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia (Japanese Patent) JP-A-60-65069, JP-A-61-201610), a method in which a vanadium compound is adhered to titanium dioxide or titanium hydroxide, and a high-temperature reduction is carried out in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610) No.), etc.; but it is not limited to these methods.

Further, these titanium-containing black inorganic pigments may be those in which an organic compound or an inorganic compound is coated on the surface of the inorganic particles. Examples of the organic compound to be coated include a polyhydric alcohol, an alkanolamine or a derivative thereof, an organic antimony compound (polyoxane, a decane coupling agent, etc.), a higher fatty acid or a metal salt thereof, and an organometallic compound ( A titanium-based coupling agent, an aluminum-based coupling agent, or the like). On the other hand, examples of the inorganic compound to be coated include an aluminum compound, a ruthenium compound, a zirconium compound, a tin compound, a titanium compound, a ruthenium compound and the like. The method of coating the surface of the titanium-containing particles can be carried out by the method described in JP-A-2006-206891.

Examples of commercially available products of titanium black include titanium black 12S, 13M-T, 13M-C, and UF8 manufactured by Mitsubishi Materials, and Tilack D ("Tilack D" manufactured by AkoSui Chemicals Co., Ltd." The company's registered trademark) and so on.

The organic pigment used in the present invention can be used without any particular limitation, and is preferably a microparticulated process and a specific surface area obtained by the Brunauer-Emmett-Teller (BET) method. It is a compound of 50 m ² /g or more. Specific examples thereof include an azo pigment, a condensed azo pigment, an azomethine pigment, a phthalocyanine pigment, a quinacridone pigment, and an isoindolinone. ) pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketones Specific examples of the diketopyrrolopyrrole pigment and the thioindigo pigment include a pigment index (CI) compound as described below, but are not limited thereto.

CI pigments red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc.; CI pigments, oranges 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.; CI pigments, yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.; CI pigment, green 7, 36, 58 Etc.; CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.; CI Pigment, Violet 19, 23, 37, etc.

Further, examples of the solvent of the component (E) include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, and 3- Alcohols such as hydroxy-2-butanone and diacetone alcohol, terpenes such as α-terpineol or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2- Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbene Alcohol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and other glycol ethers, acetic acid B Ester, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve Acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.; These solvents are dissolved , Mixing, may form a homogeneous solution composition. These solvents may be used in combination of two or more kinds in order to provide necessary properties such as coatability.

Further, it is preferable that these light-shielding components are dispersed in a solvent together with the (F) dispersant to form a light-shielding dispersion liquid, and then it is preferably a photosensitive resin composition for a light-shielding film. Here, since the solvent to be dispersed is a part of the component (E), it can be used as described in the component (E), and for example, propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate is preferably used. Wait. The blending ratio of the (D) light-shielding component to form the light-shielding dispersion liquid is preferably from 5% by mass to 80% by mass based on the total solid content of the photosensitive resin composition for a light-shielding film of the present invention. Further, the solid component means a component other than the component (E) in the composition. The solid component also contains a component (B) which becomes a solid component after photocuring. If it is less than 5% by mass, the desired light blocking property cannot be set. When the amount is more than 80% by mass, the content of the photosensitive resin which is a binder is reduced, which causes an problem of not only impairing the development characteristics but also impairing the film forming ability.

The average particle diameter (hereinafter referred to as "average secondary particle diameter") measured by a laser diffraction/scattering particle size analyzer of the light-shielding component in the light-shielding dispersion liquid is preferably as follows. The average secondary particle diameter of titanium black in the case of using titanium black is preferably from 100 nm to 300 nm, and in the case of using a black organic pigment and/or a mixed color organic pigment, and/or a monochromatic organic pigment, the particles are dispersed. The average secondary particle diameter is preferably from 20 nm to 500 nm. Further, in the photosensitive resin composition for a light-shielding film prepared by disposing these light-shielding dispersion liquids, it is preferable that these light-shielding components have the same average secondary particle diameter.

In the light-shielding dispersion liquid, the (F) dispersant is used to stably disperse the light-shielding component. However, a known dispersant such as various polymer dispersants can be used for this purpose. As an example of the dispersing agent, a known compound (a compound sold by a name such as a dispersing agent, a dispersing wetting agent, a dispersing accelerator, etc.) which has been previously used for pigment dispersion can be used without particular limitation, and examples thereof include a cationic polymer dispersing agent. An anionic polymer dispersant, a nonionic polymer dispersant, a pigment derivative dispersant (dispersion aid), and the like. Particularly preferred is a cationic polymer-based dispersant having a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary amino group, a secondary amino group or a tertiary amino group as a point of adsorption to a pigment, and an amine value It is 1 mgKOH/g to 100 mgKOH/g, and the number average molecular weight is in the range of 1,000 to 100,000. The amount of the dispersant to be added is 1% by mass to 30% by mass, and preferably 2% by mass to 25% by mass based on the light-shielding component.

Furthermore, when a light-shielding dispersion liquid is prepared, a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is co-dispersed in addition to the dispersing agent, thereby forming a photosensitive resin for a light-shielding film. In the case of the composition, it is possible to form a photosensitive resin composition which is easy to maintain the exposure sensitivity to a high sensitivity, has good adhesion at the time of development, and is less likely to cause a problem of residue. The amount of the component (A) is preferably 2% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass in the light-shielding dispersion liquid. When the component (A) is less than 2% by mass, the effect of co-dispersion such as improvement in sensitivity, improvement in adhesion, and reduction in residue cannot be obtained. In addition, when the content of the light-shielding material is large, the viscosity of the light-shielding dispersion liquid is high, and it is difficult to uniformly disperse or it takes a long time, and it becomes difficult to obtain a coating for uniformly dispersing the light-shielding component. A photosensitive resin composition of the film.

The light-shielding dispersion liquid obtained as described above can be used as the component (A) (in the case where the component (A) is co-dispersed in the preparation of the light-shielding dispersion liquid, the residual component (A) and the component (B) The component (C) and the remaining component (E) are mixed to form a photosensitive resin composition for a light-shielding film.

Further, in the photosensitive resin composition of the present invention, a curing accelerator, a thermal polymerization inhibitor, and an antioxidant, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent, a coupling agent, and a surface may be blended as needed. Additives such as active agents. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethylether, pyrogallol, and tert-butyl catechol (tert-butyl). Catechol), phenothiazine, hindered phenol compound, etc., plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., filler Examples thereof include glass fiber, cerium oxide, mica, and alumina. Examples of the antifoaming agent and the leveling agent include an anthrone-based, fluorine-based, and acrylic-based compound. Further, examples of the surfactant include a fluorine-based surfactant and an anthrone-based surfactant. Examples of the coupling agent include 3-(glycidoxy)propyltrimethoxydecane and 3-propenyloxypropane. A decane coupling agent such as a trimethoxy decane, 3-isocyanatopropyltriethoxy decane or 3-ureidopropyltriethoxy decane.

The photosensitive resin composition of the present invention may be used in combination with other resin components which are polymerized or cured by heat. The other resin component is preferably (G) an epoxy resin or an epoxy compound having two or more epoxy groups, and examples thereof include 3,3',5,5'-tetramethyl-4,4'-biphenol type. Epoxy resin, bisphenol A epoxy resin, bisphenol fluorene epoxy resin, phenol novolak epoxy resin, 3,4-epoxycyclohexenylmethyl-3,4-epoxy ring Hexene carboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxy Ketone resin and the like. These additional components may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention contains the components (A) to (E) as a main component. It is preferable that the solid component contains a total of 70% by mass, preferably 80% by mass or more of the components (A) to (D). (E) The amount of the solvent varies depending on the intended viscosity, but is preferably contained in the photosensitive resin composition in the range of 60% by mass to 90% by mass.

The photosensitive resin composition for a light-shielding film of the present invention is excellent as a photosensitive resin composition for forming a light-shielding film having a spacer function. A method of forming a light-shielding film having a spacer function is as follows. The following method is used. First, the photosensitive resin composition for a light-shielding film of the present invention is applied onto a substrate, and then the solvent is dried (prebaked), and then a mask is placed on the film obtained in the manner described above. The exposed portion is cured by irradiation with ultraviolet rays, and development is performed by eluting the unexposed portion with an aqueous alkali solution to form a pattern, and then post-baking (thermal baking) is performed as post-drying.

The substrate may be a transparent substrate, or may be an alignment film formed on a pixel, a planarization film on a pixel, or a planarization film on a pixel after forming a pixel such as RGB. A substrate other than a transparent substrate. A light-shielding film having a spacer function is formed on which substrate, and it differs depending on the design of the liquid crystal display device.

The transparent substrate on which the photosensitive resin composition is applied may be, in addition to the glass substrate, vapor-deposited or patterned indium tin oxide on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether oxime, etc.). (indium tin oxide, ITO) or transparent electrodes such as gold. A method of applying a solution of a photosensitive resin composition on a transparent substrate may be a method using a roll coater, a land coater, a slit coater, or a rotary machine in addition to a known solution dipping method or spray method. Any one of the methods. After these methods are applied to a desired thickness, the solvent is removed (prebaking), whereby a film is formed. Prebaking is performed by heating using an oven, a hot plate, or the like. The heating temperature and the heating time in the prebaking are appropriately selected depending on the solvent to be used, and are, for example, carried out at a temperature of from 60 ° C to 110 ° C for from 1 minute to 3 minutes.

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

The alkali development after exposure is performed for the purpose of removing the resist of the unexposed portion, and the desired pattern is formed by the development. The developer suitable for the development of the alkali is, for example, an aqueous solution of an alkali metal or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, or the like, and particularly preferably contains 0.05% by mass to 3% by mass of sodium carbonate or carbonic acid. A weakly alkaline aqueous solution of a carbonate such as potassium or lithium carbonate is developed at a temperature of 23 to 28 ° C, and a fine image can be precisely formed using a commercially available developing machine or an ultrasonic cleaner.

After the development, heat treatment (post-baking) is preferably carried out at a temperature of from 180 ° C to 250 ° C and for a period of from 20 minutes to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned light-shielding film and the substrate. This is carried out by heating with an oven, a heating plate or the like as in the prebaking. The patterned light-shielding film of the present invention is formed by using the respective steps of the above photolithography method.

According to the method, a light-shielding film having an optical density (OD) of 0.5/μm to 3/μm, preferably 1.5/μm to 2.5/μm can be formed. Further, according to the above method, a light-shielding film having a volume resistivity of 1 × 10 ⁹ Ω·cm or more, preferably 1 × 10 ¹² Ω·cm or more when a voltage of 10 V is applied can be formed. Further, according to the above method, a light-shielding film having a dielectric constant of 2 to 10, preferably 2 to 8, and particularly preferably 3 to 6 can be formed. Further, according to the above method, in the mechanical property test, a light-shielding film having a breaking strength of 200 mN or more and/or an elastic recovery rate of 30% or more and/or a compression ratio of 40% or less can be formed. The light-shielding film formed by the above method can be used as a column spacer of a liquid crystal display device, and is preferably used as a black column spacer.

Further, according to the method, the film thickness H1 for setting the optical density as the light-shielding film to 0.5/μm or more and less than 3/μm, and the film thickness H2 of the light-shielding film functioning as a spacer can be simultaneously formed. When H2 is 2 μm to 7 μm, ΔH=H2-H1 is a light-shielding film having a film thickness H1 of 0.1 to 2.9 and a light-shielding film having a film thickness H2. The cured film formed by the above method can be used as a column spacer of a liquid crystal display device, and is preferably used as a black column spacer. According to the cured film having the ΔH in the above range, the black column spacer having a different height can be formed at one time from the same material, so that the liquid crystal display device can be manufactured more efficiently. In this case, for example, the cured film having the film thickness H2 functions as a spacer, and the cured film having the film thickness H1 functions as a black matrix. Further, ΔH is necessary because when the film having the black matrix function is the same film thickness as the film of the spacer function, the liquid crystal layer is divided by the respective pixels, which not only hinders the free flow of the liquid crystal layer, but also causes concern. The yield is lowered when the liquid crystal layer is filled to form a liquid crystal display device.

The liquid crystal display device including the light shielding film or the cured film is preferably a TFT-LCD provided with a thin film transistor.

The liquid crystal display device including the light-shielding film or the cured film has high light-shielding property and insulating property, and further has a spacer function which is excellent in elastic modulus, deformation amount, and elastic recovery rate, and can be formed even when the film thickness is 2 μm to 7 μm. The shape of the spacer is also fine. [Examples]

Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto.

First, a synthesis example of the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention is shown. The evaluation of the resin in the synthesis example was carried out as follows.

[Solid component concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)], and weighed [W1 (g)], and the weight after heating at 160 ° C for 2 hr [ W2(g)] is obtained by the following formula. Solid content concentration (% by weight) = 100 × (W2-W0) / (W1-W0)

[Acid value] The resin solution was dissolved in dioxane, and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus [manufactured by Hiranuma Satoshi Co., Ltd., trade name: COM-1600].

[Molecular weight] By gel permeation chromatography (GPC) [trade name HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgel SuperH-2000 (2) + TSKgel SuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgel Super-H5000 (1) [made by Tosoh (stock)], temperature: 40 ° C, speed: 0.6 ml / min] was measured with standard polystyrene [Dongcao (share) The weight average molecular weight (Mw) was determined in the form of a converted value of the produced PS-oligomer kit.

[Measurement of average secondary particle diameter] The concentration of the light-shielding component is 0.1% by mass in which the light-shielding dispersion liquid is diluted with a solvent (propylene glycol monomethyl ether acetate (PGMEA) in the present embodiment). The average secondary particle diameter was measured by the fineness distribution meter of the laser diffraction/scattering method (made by Nikkiso Co., Ltd., Microtrac MT-3000).

[Synthesis Example 1] In a 500 mL four-necked flask equipped with a reflux condenser, 105.7 g (0.29 mol) of a bisphenol A type epoxy compound (manufactured by Shin-Nippon Epoxy Manufacturing Co., Ltd., trade name YD-128) was added. , epoxy equivalent = 182), 41.8 g (0.58 mol) of acrylic acid, 1.52 g of triphenylphosphine (TPP), and 40.0 g of propylene glycol monomethyl ether acetate (PGMEA) at 100 ° C to 105 The mixture was stirred under heating at ° C for 12 hr to obtain a reaction product.

Then, 16.9 g (0.13 mol) of dimethylolpropionic acid and 96 g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 °C. Then, while paying attention to the temperature in the flask, 61.8 g (0.28 mol) of isophorone diisocyanate was added dropwise. After completion of the dropwise addition, the mixture was stirred under heating at 75 ° C to 80 ° C for 6 hr. Further, 6.2 g (0.04 mol) of tetrahydrophthalic anhydride was added, and the mixture was stirred under heating at 90 ° C to 95 ° C for 6 hr to obtain an alkali-soluble resin solution (A)-1 containing a polymerizable unsaturated group. The solid content concentration of the obtained resin solution was 63.2 wt%, the acid value (in terms of solid content) was 40 mgKOH/g, and the Mw obtained by GPC analysis was 11,540.

[Synthesis Example 2] In a 500 mL four-necked flask equipped with a reflux condenser, 104.2 g (0.29 mol) of a bisphenol A type epoxy compound (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name YD-) was added. 128, epoxy equivalent = 182), 41.2 g (0.57 mol) of acrylic acid, 1.50 g of TPP, and 40.0 g of PGMEA were stirred under heating at 100 ° C to 105 ° C for 12 hr to obtain a reaction product.

Then, 23.1 g (0.17 mol) of dimethylolpropionic acid and 98 g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 °C. Then, while paying attention to the temperature in the flask, 68.0 g (0.31 mol) of isophorone diisocyanate was added dropwise. After completion of the dropwise addition, the mixture was stirred under heating at 75 ° C to 80 ° C for 6 hr to obtain an alkali-soluble resin solution (A)-2 containing a polymerizable unsaturated group. The solid content concentration of the obtained resin solution was 63.3 wt%, the acid value (in terms of solid content) was 41 mgKOH/g, and the Mw obtained by GPC analysis was 11210.

[Synthesis Example 3] In a 500 mL four-necked flask equipped with a reflux condenser, 104.2 g (0.29 mol) of a bisphenol A type epoxy compound (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name YD-) was added. 128, epoxy equivalent = 182), 41.2 g (0.57 mol) of acrylic acid, 1.50 g of TPP, and 40.0 g of PGMEA were stirred under heating at 100 ° C to 105 ° C for 12 hr to obtain a reaction product.

Then, 17.4 g (0.13 mol) of dimethylolpropionic acid and 84 g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 °C. Then, while paying attention to the temperature in the flask, 61.8 g (0.28 mol) of isophorone diisocyanate was added dropwise. After completion of the dropwise addition, the mixture was stirred under heating at 75 ° C to 80 ° C for 6 hr. Further, 21.0 g (0.14 mol) of tetrahydrophthalic anhydride was added, and the mixture was stirred under heating at 90 ° C to 95 ° C for 6 hr to obtain an alkali-soluble resin solution (A)-3 containing a polymerizable unsaturated group. The solid content concentration of the obtained resin solution was 66.6 wt%, the acid value (in terms of solid content) was 61 mgKOH/g, and the Mw obtained by GPC analysis was 11,860.

[Synthesis Example 4] In a 500 mL four-necked flask equipped with a reflux condenser, 105.7 g (0.29 mol) of a bisphenol A type epoxy compound (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name YD-) was added. 128, epoxy equivalent = 182), 41.8 g (0.58 mol) of acrylic acid, 1.52 g of TPP, and 40.0 g of PGMEA were stirred under heating at 100 ° C to 105 ° C for 12 hr to obtain a reaction product.

Then, 16.9 g (0.13 mol) of dimethylolpropionic acid and 96 g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 °C. Then, while paying attention to the temperature in the flask, 58.5 g (0.28 mol) of trimethylhexamethylene diisocyanate was added dropwise. After completion of the dropwise addition, the mixture was stirred under heating at 75 ° C to 80 ° C for 6 hr. Further, 6.2 g (0.04 mol) of tetrahydrophthalic anhydride was added, and the mixture was stirred under heating at 90 ° C to 95 ° C for 6 hr to obtain an alkali-soluble resin solution (A)-4 containing a polymerizable unsaturated group. The solid content concentration of the obtained resin solution was 62.9 wt%, the acid value (in terms of solid content) was 41 mgKOH/g, and the Mw obtained by GPC analysis was 11950.

[Synthesis Example 5] In a 500 mL four-necked flask equipped with a reflux condenser, 104.2 g (0.29 mol) of a bisphenol A type epoxy compound (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name YD-) was added. 128, epoxy equivalent = 182), 41.2 g (0.57 mol) of acrylic acid, 1.50 g of TPP, and 40.0 g of PGMEA were stirred under heating at 100 ° C to 105 ° C for 12 hr to obtain a reaction product.

Then, 4.0 g (0.03 mol) of dimethylolpropionic acid, 11.8 g (0.10 mol) of 1,6-hexanediol, and 84 g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 °C. Then, while paying attention to the temperature in the flask, 61.8 g (0.28 mol) of isophorone diisocyanate was added dropwise. After completion of the dropwise addition, the mixture was stirred under heating at 75 ° C to 80 ° C for 6 hr. Further, 21.0 g (0.14 mol) of tetrahydrophthalic anhydride was added, and the mixture was stirred under heating at 90 ° C to 95 ° C for 6 hr to obtain an alkali-soluble resin solution (A)-5 containing a polymerizable unsaturated group. The solid content concentration of the obtained resin solution was 66.5 wt%, the acid value (in terms of solid content) was 38 mgKOH/g, and the Mw obtained by GPC analysis was 12220.

[Comparative Synthesis Example 1] In a 1000 ml four-necked flask equipped with a nitrogen introduction tube and a reflux tube, 51.65 g (0.60 mol) of methacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, 38.77 g were added. (0.22 mol) of benzyl methacrylate, 5.91 g of azobisisobutyronitrile, and 370 g of diethylene glycol dimethyl ether were polymerized by stirring at 80 ° C to 85 ° C for 8 hr under a nitrogen stream. Further, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.44 g of TPP, and 0.055 g of 2,6-di-t-butyl-p-cresol were added to the flask at 80 ° C to 85 ° C. After stirring for 16 hr, an alkali-soluble resin solution (A)-6 was obtained. The solid content concentration of the obtained resin solution was 32% by mass, the acid value (in terms of solid content) was 110 mgKOH/g, and the Mw obtained by GPC analysis was 18,100.

(Alkyl-soluble resin containing a polymerizable unsaturated group) (A)-1 component: the alkali-soluble resin solution (A)-2 component obtained in the synthesis example 1 : the alkali-soluble resin solution obtained by the said synthesis example 2 (A)-3 component: the alkali-soluble resin solution (A)-4 component obtained in the synthesis example 3: the alkali-soluble resin solution (A)-5 component obtained in the synthesis example 4: the synthesis example 5 Alkali-soluble resin solution (A)-6 component obtained in the above: the alkali-soluble resin solution obtained in Comparative Synthesis Example 1

(Photopolymerizable monomer) (B): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA)

(Photopolymerization initiator) (C): ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-, 1-(0 -Ethyl acetate (manufactured by BASF), product Irgacure OXE02 (shading disperse pigment) (D)-1: 20.0% by mass of titanium black (manufactured by Mitsubishi Materials Co., Ltd., PGMEA dispersion of product name 13M-C), 5.0% by mass of dispersant (solid content 25.0%, average diameter of titanium black is 188 nm) (D)-2: 15.0% by mass of black pigment (endoamine Black, BASF company, Irgaphor S100CF), 4.5% by mass of polymer dispersant PGMEA dispersion (solid content 19.5%, black pigment average secondary particle size 241 nm) D)-3: 7.0% by mass of CI pigment, orange 64 (manufactured by BASF), 3.0% by mass of CI pigment, Violet 23 (manufactured by Clariant), 7.0% by mass of CI pigment, blue 15:6 (manufactured by Clariant Co., Ltd.), 4.0% by mass of a polymer dispersant, 2.0% by mass of a sulfonated azo dispersing aid, and 2.0% by mass of methacryl PGMEA dispersion of benzyl ester/methacrylic acid copolymer (solid content: 25.0%) (D)-4: 20.0% by mass of carbon black, 5.0% by mass of polymer dispersant PGMEA dispersion (solid content: 25.0%) , the average secondary particle size of carbon black is 162 nm)

(solvent) (E)-1: PGMEA (E)-2: 3-methoxy-3-methyl-1-butyl acetate

(Surfactant) (H): PGMEA solution of BYK-330 (manufactured by BYK-Chemie Co., Ltd.) (solid content: 1.0%)

The compounding components described above were blended at the ratios shown in Tables 1 and 2 to prepare photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 2. In addition, the numerical values in Table 1 and Table 2 all show the mass parts. Further, (E)-1 in the column of the solvent is PGMEA (the same as (E)-1) in the resin solution (the alkali-soluble resin solution containing a polymerizable unsaturated group) containing no unsaturated group, and shading The amount of PGMEA (same as (E)-1) in the dispersion.

[Table 1]

[Table 2]

[Evaluation] The photosensitive resin compositions for the light-shielding films of Examples 1 to 11 and Comparative Examples 1 to 2 were used, and the evaluations described below were carried out. The results of these evaluations are shown in Tables 3 and 4.

<Development Characteristics> Each of the obtained photosensitive resin compositions was applied onto a glass substrate having a thickness of 1.2 mm by a spin coater so that the film thickness after the heat curing treatment was 3.0 μm, and was carried out at 90 ° C. Pre-bake in 1 minute. Then, the photomask was brought into close contact with each other, and ultraviolet rays of 100 mJ/cm ² were irradiated with an ultrahigh pressure mercury lamp having a wavelength of 365 nm and an illuminance of 30 mW/cm ² to carry out a photohardening reaction of the photosensitive portion.

Then, the exposed glass substrate was developed with a 0.05% potassium hydroxide aqueous solution at a pressure of 24 ° C and 0.1 MPa for 60 seconds to remove the unexposed portion of the coating film. Then, the film was subjected to a heat curing treatment at 230 ° C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The formation of fine lines of the obtained cured film pattern was confirmed by an optical microscope, and evaluation was performed by the following three stages. ○: A pattern having an L/S of 10 μm/10 μm or more is formed without residue. Δ: A pattern having an L/S of 30 μm/30 μm or more is formed without residue. ×: L/S is not formed to be less than 50 μm. /50 μm pattern, or the bottom of the pattern is curled or residue is significant

<Optical Density> Each of the obtained photosensitive resin compositions was applied onto a glass substrate having a thickness of 1.2 mm by a spin coater so that the film thickness after the thermosetting treatment was 1.1 μm, and the film was formed at 90° C. at 90° C. Pre-bake in 1 minute. Then, the film was subjected to a heat curing treatment at 230 ° C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Then, the optical density of the obtained cured film was measured using a Macbeth Permeation Densitometer, and evaluated by the optical density per unit film thickness.

<Volume Resistivity> The obtained photosensitive resin composition was applied onto a glass substrate having a thickness of 1.2 mm on which Cr was deposited by using a spin coater so that the film thickness after the heat curing treatment was 3.5 μm. The portion except the electrode was prebaked at 90 ° C for 1 minute. Then, the film was subjected to a heat curing treatment at 230 ° C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Then, an aluminum electrode was formed on the cured film to prepare a substrate for volume resistivity measurement. Then, using a static electricity meter ("6517A" manufactured by Keithley Co., Ltd.), the volume resistivity at an applied voltage of 1 V to 10 V was measured. The measurement was carried out under the conditions of voltage holding for 60 seconds in each of the applied voltages in the 1 V phase, and the volume resistivity when 10 V was applied is shown in Tables 3 and 4.

<Dielectric constant> Each of the obtained photosensitive resin compositions was applied onto a glass substrate having a thickness of 1.2 mm on which Cr was deposited by using a spin coater so that the film thickness after the heat curing treatment was 3.5 μm. The portion except the electrode was prebaked at 90 ° C for 1 minute. Then, the film was subjected to a heat curing treatment at 230 ° C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Then, an aluminum electrode was formed on the cured film to form a substrate for dielectric constant measurement. Then, an electrometer ("6517A" manufactured by Keithley Co., Ltd.) was used, and a capacitance at a frequency of 1 Hz to 100,000 Hz was measured, and a dielectric constant was calculated from the capacitance.

<Half tone (HT) characteristics of the spacer> Each of the obtained photosensitive resin compositions was applied to a thickness of 1.2 mm so that the film thickness after the thermosetting treatment was 3.0 μm using a spin coater. The glass substrate was prebaked at 90 ° C for 1 minute. Then, the photomask having the dot pattern is brought into close contact, and ultraviolet rays of 5 mJ/cm ² to 100 mJ/cm ² are irradiated with an ultrahigh pressure mercury lamp having a wavelength of 365 nm and an illuminance of 30 mW/cm ² to carry out photohardening reaction of the photosensitive portion. .

Then, the exposed glass substrate was developed with a 0.05% potassium hydroxide aqueous solution at a pressure of 24 ° C and 0.1 MPa for 60 seconds to remove the unexposed portion of the coating film. Then, the film was subjected to a heat curing treatment at 230 ° C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The halftone characteristic of the separator was calculated by the following four stages by calculating the difference (ΔH) between the heights of the spacers at an exposure amount of 5 mJ/cm ² and 100 mJ/cm ² . ○: When ΔH is 1.0 μm to 2.0 μm △: When ΔH is 0.1 μm to 2.9 μm ×: When ΔH is less than 0.1 μm or larger than 2.9 μm

<Compression ratio, elastic recovery rate, and breaking strength of the separator> Each of the obtained photosensitive resin compositions was applied to a thickness of 1.2 mm so that the film thickness after the heat curing treatment was 3.0 μm using a spin coater. The glass substrate was prebaked at 90 ° C for 1 minute. Then, the photomask having the dot pattern was brought into close contact with each other, and ultraviolet rays of 100 mJ/cm ² were irradiated with an ultrahigh pressure mercury lamp having a wavelength of 365 nm and an illuminance of 30 mW/cm ² to carry out a photohardening reaction of the photosensitive portion.

Then, the exposed glass substrate was developed with a 0.05% potassium hydroxide aqueous solution at a pressure of 24 ° C and 0.1 MPa for 60 seconds to remove the unexposed portion of the coating film. Then, the film was subjected to a heat curing treatment at 230 ° C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The separator characteristics of the obtained cured film pattern were evaluated using an ultra-micro hardness tester (Fischerscope HM2000Xyp, manufactured by Fisher Instruments). The plane indenter of 100 μm square was extruded at a load speed of 5.0 mN/sec, and the load was loaded up to 50 mN, and then the load was removed by a charge rate of 5.0 mN/sec.

The compression ratio is obtained by setting the displacement amount at a load of 50 mN at the time of load to L1. Compression ratio (%) = L1/the height of the spacer × 100

The elastic recovery rate is obtained by setting the displacement amount at a load of 50 mN at the time of load to L1 and the displacement amount at the time of load removal to L2. Elastic recovery rate (%) = (L1-L2) / L1 × 100

The breaking strength was evaluated using a micro-hardness tester (Fischerscope HM2000Xyp, manufactured by Fisher Instruments). The load at a load speed of 5.0 mN/sec was extruded into a 100 μm square flat head and the load was applied to a load of 300 mN to measure the load at the time of fracture of the separator, and the evaluation was performed in the following four stages. ○: When the breaking strength is 300 mN or more △: When the breaking strength is 200 mN or less ×: When the breaking strength is 100 mN or less

<Shape of Spacer> Each of the obtained photosensitive resin compositions was applied onto a glass substrate having a thickness of 1.2 mm by a spin coater so that the film thickness after the heat curing treatment was 3.0 μm, at 90 ° C. Pre-bake for 1 minute. Then, the photomask having the dot pattern was brought into close contact with each other, and ultraviolet rays of 100 mJ/cm ² were irradiated with an ultrahigh pressure mercury lamp having a wavelength of 365 nm and an illuminance of 30 mW/cm ² to carry out a photohardening reaction of the photosensitive portion.

Then, the exposed glass substrate was developed with a 0.05% potassium hydroxide aqueous solution at a pressure of 24 ° C and 0.1 MPa for 60 seconds to remove the unexposed portion of the coating film. Then, the film was subjected to a heat curing treatment at 230 ° C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The shape of the spacer was evaluated using a scanning electron microscope at the inner angle (taper angle) of the end of the spacer. The case where the taper angle is 70° or more and 90° or less is ◎, the case of 50° or more and less than 70° is ○, the case of 50° or less is Δ, and the case of 90° or more is ×.

[table 3]

[Table 4]

According to the results of Examples 1 to 11 and Comparative Examples 1 to 2, it is understood that by using titanium black for the (D) light-shielding material, the light-shielding property, the dielectric constant, and the elastic recovery can be improved while maintaining the volume resistivity. Rate equal spacer characteristics. In particular, by using titanium black together with a black organic pigment or a mixed color organic pigment, the disadvantages of various light-shielding materials can be supplemented without deteriorating the elastic recovery rate and the like, and the light-shielding property, the volume resistivity, and the The coexistence of electrical constants has an effect.

no

no

no

Claims (18)

A photosensitive resin composition for a light-shielding film having a separator function, comprising the following components (A) to (E) as essential components: (A) an alkali-soluble resin containing a polymerizable unsaturated group, a urethane compound obtained by reacting a polyol compound (a) having an ethylenically unsaturated bond in a molecule, a diol compound (b) having a carboxyl group in a molecule, and a diisocyanate compound (c); B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) one selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material The above shading component; and (E) a solvent. The photosensitive resin composition according to claim 1, which comprises titanium black as the (D) light-shielding component. The photosensitive resin composition according to claim 2, wherein the titanium black has an average secondary particle diameter of 100 nm to 300 nm. The photosensitive resin composition according to any one of claims 1 to 3, which comprises a black organic pigment and/or a mixed color organic pigment as the (D) light-shielding component, and the black organic pigment And/or the mixed color organic pigment has an average secondary particle diameter of 20 nm to 500 nm. The photosensitive resin composition according to any one of the above-mentioned items (1), wherein the (B) component contains 5 parts by mass to 400 parts by mass of the above (B) The component (C) is contained in an amount of 0.1 part by mass to 30 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B), and becomes solid when it is cured by light. When the component other than the component (E) of the component (B) of the component is a solid component, the solid component contains 5% by mass to 80% by mass of the component (D). The photosensitive resin composition according to any one of the items 1 to 3, which can form a light-shielding film having an optical density OD of 0.5/μm or more and 3/μm or less and applying 10 V. The volume resistivity at the time of voltage is 1 × 10 ⁹ Ω·cm or more, and the dielectric constant is 2 to 10. The photosensitive resin composition according to any one of the first to third aspects of the invention, which can be formed in the load-load-removal test using a micro hardness tester, which satisfies the following (i) to (iii) At least one of the light-shielding films, (i) having a breaking strength of 200 mN or more; (ii) an elastic recovery rate of 30% or more; and (iii) a compression ratio of 40% or less. A light-shielding film having a function of a spacer, which is formed by curing a photosensitive resin composition according to any one of claims 1 to 7. A liquid crystal display device comprising the light shielding film as described in claim 8 as a black column spacer (BCS). The liquid crystal display device of claim 9, which further comprises a thin film transistor (TFT). A method for producing a photosensitive resin composition for a light-shielding film having a separator function, which is prepared by dispersing a dispersion of (D) a light-shielding component in (E) a solvent, and further adding the dispersion to the dispersion ( A) an alkali-soluble resin containing a polymerizable unsaturated group, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, and (E) a solvent; Further, the (A) alkali-soluble resin is obtained by reacting a polyol compound (a) having an ethylenically unsaturated bond in a molecule, a diol compound (b) having a carboxyl group in a molecule, and a diisocyanate compound (c). The urethane compound, wherein the (D) light-shielding component is one or more components selected from the group consisting of black organic pigments, mixed color organic pigments, and light-shielding materials. The method for producing a photosensitive resin composition according to claim 11, wherein the (D) light-shielding component contains titanium black. The method for producing a photosensitive resin composition according to claim 12, wherein in the dispersion, the average secondary particles of the titanium black are from 100 nm to 300 nm. The method for producing a photosensitive resin composition according to any one of the preceding claims, wherein the (D) light-shielding component comprises a black organic pigment and/or a mixed color organic pigment, and In the dispersion, the black organic pigment and/or the mixed color organic pigment has an average secondary particle diameter of 20 nm to 500 nm. A method of producing a light-shielding film formed on a substrate, wherein the photosensitive resin composition according to any one of claims 1 to 7 is applied onto a substrate, and the photosensitive material is irradiated by light irradiation. The resin composition hardens. The method for producing a light-shielding film according to claim 15, wherein the film thickness H1 for setting the optical density as the light-shielding film to 0.5/μm or more and less than 3/μm, and the function of the spacer function The film thickness H2 of the film is simultaneously formed into a light-shielding film having a film thickness H1 and a film thickness H2 of ΔH = H2 - H1 of 0.1 to 2.9 when H2 is 2 μm to 7 μm. A method of manufacturing a liquid crystal display device, which is characterized in that a light-shielding film produced by the method for producing a light-shielding film according to claim 16 is used as a black column spacer. The method of manufacturing a liquid crystal display device according to claim 17, wherein the liquid crystal display device comprises a thin film transistor (TFT).