TWI709818B - Photosensitive resin composition for light-sielding film with the role of spacer, light-sielding film, liquid crystal display device, method for producing photosensitive resin composition for light-sielding film with the role of spacer, method for producing light-sielding film and method for producing liquid crystal display device - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for a light-shielding film having a spacer function. The photosensitive resin composition of the present invention contains the following components as essential components: (A) an alkali-soluble resin containing a polymerizable unsaturated group, which is a polyol compound (a) having an ethylenically unsaturated bond in the molecule, A urethane compound obtained by reacting a diol compound (b) having a carboxyl group and a diisocyanate compound (c); (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) Photopolymerization initiator; (D) one or more light-shielding components selected from the group consisting of black organic pigments, color-mixing organic pigments and light-shielding materials; and (E) solvent.

Description

Photosensitive resin composition for light-shielding film with spacer function, light-shielding film, liquid crystal display device, method for manufacturing photosensitive resin composition for light-shielding film with spacer function, method for manufacturing light-shielding film, and liquid crystal display device Manufacturing 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 formed by curing the photosensitive resin composition. In detail, it relates to a photolithography method that can be used The photosensitive resin composition and the cured film thereof are formed to form a black column spacer having a spacer function and a black matrix function in a liquid crystal display device. The present invention further relates to a liquid crystal display device using the black column spacer obtained by curing. This invention further relates to the manufacturing method of the said photosensitive resin composition, a light-shielding film, and a liquid crystal display device.

In recent years, color liquid crystal displays (LCD) have 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 LCD, the improvement aimed at improving the viewing angle, contrast, response speed and other characteristics is actively carried out. At present, the thin film transistor (Thin Film Transistor, TFT)-LCD is also developing various panel structures. . Regarding TFT-LCD, the following methods are mainly used: the array substrate and the color filter substrate forming the existing TFT are separately manufactured, and the two substrates are bonded with a fixed interval maintained by spacers; however, they are also being developed at low cost. The LCD manufacturing process for the purpose of improving the yield rate. For example, as a substrate facing the color filter directly formed on the TFT of the array substrate, a process for bonding glass substrates is being developed. The structure formed in this manner is called a color filter on TFT (Color Filter On Thin Film Transistor, COT) or the like. In this COT, the black matrix that will be the boundary of the red (R), green (G), and blue (B) pixels of the color filter layer formed on the TFT is also being formed before the RGB is formed. Various LCD panel structures such as methods, methods of forming after RGB pixels are formed, or methods of forming on opposing glass substrates, have been studied.

Regarding spacers that have the function of keeping one of the factors that affect the performance of the LCD, that is, the thickness of the liquid crystal layer (or the distance between the array substrate and the color filter substrate in the existing method), the spacer has been adopted to hold fixed particles. Diameter ball spacer method. However, in this method, the dispersion state of the ball spacer becomes uneven, and there is a problem that the amount of light transmitted per pixel becomes unstable. In response to this problem, a method of forming column spacers by photolithography is adopted. However, most of the column spacers formed by the photolithography method are transparent. Such column spacers have the following problem: the light incident from an oblique direction affects the electrical characteristics of the TFT and deteriorates the display quality. In response to this problem, a light-shielding film having a spacer function formed by a photolithography method, that is, an LCD panel structure using a light-shielding column spacer has been proposed (Patent Document 1). In COT, a method of forming a so-called black column spacer (BCS) in which column spacers are formed using the same material as the black matrix has also been studied (for example, Patent Document 2).

In order for the light-shielding column spacer to function as a spacer, a film thickness of about 2 μm to 7 μm is required. In addition, it is necessary to be able to form light-shielding post spacers with different heights at the same time at the location where the TFT is formed and other locations. In addition, for the light-shielding column spacer, the elastic modulus, the amount of deformation, the elastic recovery rate, etc., which function as the spacer, are required to be in an appropriate range (Patent Document 3). Furthermore, for light-shielding column spacers, it is required to improve the reduction of curable components caused by the addition of light-shielding components (colorants) to the spacers, or the loss of electrical characteristics caused by the influence of impurities in the coloring agent. Etc. (Patent Document 4). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 08-234212 [Patent Document 2] US Patent Application Publication No. 2009/0303407 [Patent Document 3] Japanese Patent Laid-Open No. 2009-031778 [Patent Document 4] International Publication No. 2013/062011

[Problem to be Solved by the Invention] Although Patent Document 4 uses mixed color organic pigments, the optical density of the light-shielding column spacer is not shown. Compared with inorganic pigments such as carbon black, mixed-color organic pigments are effective for lowering the dielectric constant, but often have low light-shielding properties. In addition, the spacers must be formed at the same time as spacers with different heights. Therefore, the light-shielding column spacers also require mechanical properties such as elastic modulus, deformation amount, and elastic recovery rate. The shape and mechanical properties of the spacer are greatly affected by the light-shielding component, which makes it difficult to design the photosensitive resin composition for the light-shielding film. Therefore, the shape or mechanical properties of spacers using carbon black or mixed-color organic pigments are still insufficient, and further improvement is required.

In addition, as described above, the light-shielding column spacer is manufactured with a film thickness of about 2 μm to 7 μm. With the miniaturization of liquid crystal display elements in recent years, it is desirable for the light-shielding column spacer to be able to form a fine spacer shape even if the film thickness is about 2 μm to 7 μm.

The present invention is formed in view of the above-mentioned problems, and is to provide a photosensitive resin composition for a light-shielding film having a spacer function, which has high light-shielding and insulation properties, and excellent elastic modulus, deformation amount, and elastic recovery rate, and use thereof A light-shielding film having a spacer function formed therefrom and a liquid crystal display device using the light-shielding film as a constituent element. [Means to solve the problem]

The inventors of the present invention conducted studies in order to solve the above-mentioned problems in the photosensitive resin composition for light-shielding films, and found that a specific coloring agent is suitable as the light-shielding component of the photosensitive resin composition for the light-shielding film. , Thereby completing the present invention. (1) The present invention is a photosensitive resin composition for a light-shielding film having a spacer function, which is characterized by containing the following (A) to (E) components as essential components: (A) containing a polymerizable unsaturated group Alkali-soluble resin, which is a urethane obtained by reacting a polyol compound (a) having an ethylenically unsaturated bond in the molecule, a diol compound having a carboxyl group in the molecule (b), and a diisocyanate compound (c) Ester compound; (B) photopolymerizable monomer with at least one ethylenically unsaturated bond; (C) photopolymerization initiator; (D) selected from black organic pigments, color-mixing organic pigments and light-shielding materials One or more light-shielding components in the group; and (E) solvent. (2) Moreover, this invention is the photosensitive resin composition as described in (1) which contains titanium black as (D) light-shielding component. (3) In addition, the present invention is the photosensitive resin composition as described in (2), wherein the average secondary particle size of the titanium black is 100 nm to 300 nm. (4) In addition, the present invention is the photosensitive resin composition according to any one of (1) to (3), which contains a black organic pigment and/or a color-mixing organic pigment as (D) a light-shielding component, and The average secondary particle size of the black organic pigment and/or the mixed color organic pigment is 20 nm to 500 nm. (5) In addition, the present invention is the photosensitive resin composition according to any one of (1) to (4), which contains 5 parts by mass to 400 parts by mass with respect to 100 parts by mass of (A) component ( B) component, (B) which contains 0.1 to 30 parts by mass of component (C) with respect to 100 parts by mass of the total amount of component (A) and component (B), and which becomes a solid component after light curing When the components other than the (E) component of the component are used as the solid content, the solid content contains 5 mass% to 80 mass% of the (D) component. (6) In addition, the present invention is the photosensitive resin composition according to any one of (1) to (5), which can form a light-shielding film: an optical density OD of 0.5/μm or more and 3/μm or less, And when a voltage of 10 V is applied, the volume resistivity is 1×10 ⁹ Ω·cm or more, and the dielectric constant is 2-10. (7) In addition, the present invention is the photosensitive resin composition according to any one of (1) to (6), which can be formed to satisfy the following (i) in a load-unloading test using a microhardness meter ) To (iii) at least one light-shielding film, (i) breaking strength of 200 mN or more; (ii) elastic recovery rate of 30% or more; (iii) compression rate of 40% or less. (8) In addition, the present invention is a light-shielding film having a spacer function, which is formed by curing the photosensitive resin composition according to any one of (1) to (7). (9) In addition, the present invention is a liquid crystal display device including the light-shielding film as described in (8) as a black column spacer (BCS). (10) In addition, the present invention is the liquid crystal display device as described in (9), which further includes a thin film transistor (TFT). (11) In addition, the present invention is a method for producing a photosensitive resin composition for a light-shielding film having a spacer function, which comprises preparing a dispersion in which (D) a light-shielding component is dispersed in a solvent (E), To the dispersion, (A) an alkali-soluble resin containing polymerizable unsaturated groups, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, And (E) a solvent, mixed; the (A) alkali-soluble resin is a polyol compound (a) having an ethylenically unsaturated bond in the molecule, a diol compound having a carboxyl group in the molecule (b), and a diisocyanate Compound (c) is a urethane compound obtained by reacting, and (D) the light-shielding component is one or more components selected from the group consisting of black organic pigments, color-mixing organic pigments, and light-shielding materials. (12) In addition, the present invention is the method described in (11), wherein the (D) light-shielding component contains titanium black. (13) In addition, the present invention is the method according to (12), wherein in the dispersion, the average secondary particles of the titanium black are 100 nm to 300 nm. (14) In addition, the present invention is the method according to any one of (11) to (13), wherein (D) the light-shielding component contains a black organic pigment and/or a color-mixing organic pigment, and in the dispersion, The average secondary particle size of the black organic pigment and/or the color-mixing organic pigment is 20 nm to 500 nm. (15) In addition, the present invention is a method of manufacturing a light-shielding film formed on a substrate, which coats the photosensitive resin composition as described in any one of (1) to (7) on the substrate, and irradiates it with light. The photosensitive resin composition is cured. (16) In addition, the present invention is a method of manufacturing a light-shielding film as described in (15), wherein the optical density of the light-shielding film is set to 0.5/μm or more and a film thickness H1 of less than 3/μm, and When the thickness H2 of the light-shielding film that is responsible for the spacer function is 2 μm to 7 μm, a light-shielding film with a film thickness H1 and a film thickness H2 of 0.1-2.9 ΔH=H2-H1 is formed at the same time. (17) In addition, the present invention is a method of manufacturing a liquid crystal display device that uses a light-shielding film manufactured by the method described in (16) as a black column spacer. (18) In addition, the present invention is the manufacturing method described in (17), wherein the liquid crystal display device includes a thin film transistor (TFT). [Effects of the invention]

Since the photosensitive resin composition for the light-shielding film of the present invention contains a specific coloring agent, compared with the conventional photosensitive resin composition, the elastic modulus, the amount of deformation, and the amount of deformation can be obtained while maintaining light-shielding and insulating properties. A cured product with excellent elastic recovery rate. Furthermore, the photosensitive resin composition for a light-shielding film of the present invention can be formed into a fine spacer shape even if the film thickness is about 2 μm to 7 μm.

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

其中，通式（I）中，R₁ 、R₂ 、R₃ 及R₄ 獨立地表示氫原子、碳數1～5的烷基、鹵素原子或苯基，X表示-CO-、-SO₂ -、-C(CF₃ )₂ -、-Si(CH₃ )₂ -、-CH₂ -、-C(CH₃ )₂ -、-O-、或者茀-9,9-二基或單鍵，m的平均值為0～10、優選為0～4的範圍。The polyol compound (a) having an ethylenically unsaturated bond in the molecule used in the production of the component (A) includes, for example, epoxy compounds having two or more alcoholic hydroxyl groups and two or more epoxy groups in the molecule, and The reactant of (meth)acrylic acid (which means "acrylic acid and/or methacrylic acid") is an epoxy acrylate compound. A representative epoxy (meth)acrylate compound can exemplify a compound obtained by reacting (meth)acrylic acid with an epoxy compound represented by the general formula (I). [化1]

Among them, in the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ 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 -9,9-diyl or single bond The average value of m is 0-10, preferably 0-4.

The bisphenols that provide the epoxy compound of the general formula (I) include: bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) sulfide, bis(4-hydroxy) Phenyl) hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, 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) Yl)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) sulfone, 9,9-bis(4-hydroxy-3-methylphenyl) sulfone, 4,4'-biphenol, 3,3'-Biphenol, etc. These bisphenols may use only one kind of compound, and may also use multiple types in combination. Among them, bisphenols in which X in the general formula (I) is propane-2,2-diyl can be preferably used.

The compound of the general 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. This reaction is usually accompanied by oligomerization of the diglycidyl ether compound, and m is an integer of 0-10 in each molecule. Since it is usually mixed in molecules of multiple values, the average value becomes 0-10 (not limited to integers). ), but the preferred average value of m is 0-4. If the average value of m exceeds the upper limit, when a photosensitive resin composition is formed using an alkali-soluble resin synthesized using the epoxy compound, the viscosity of the composition becomes too large, and the coating cannot be smoothly applied or cannot The alkali solubility is sufficiently imparted, and the alkali developability becomes very poor.

Examples of epoxy compounds used in the production of epoxy (meth)acrylates other than the compound of general formula (I) include: the benzene ring of the compound of general formula (I) is hydrogenated to become a cyclohexane ring A compound group or an epoxy compound group obtained by reacting a phenol compound having two or more phenolic hydroxyl groups in the molecule with epichlorohydrin.

其中，通式（II）中，Y及Z表示苯骨架、萘骨架、或者聯苯骨架，G表示縮水甘油基。l表示1或2，n表示以平均值計為1～5的數。Regarding the epoxy compound obtained by reacting a phenol compound having two or more phenolic hydroxyl groups in the molecule with epichlorohydrin, for example, a compound of the general formula (II) can be cited. [化2]

Among them, in the general 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 from 1 to 5 on average.

The epoxy equivalent of the epoxy compound used in the epoxy (meth)acrylate is preferably 100 to 500. If the epoxy equivalent is less than 100, the molecular weight when (A) an alkali soluble resin containing polymerizable unsaturated groups 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 rate of the polymerizable unsaturated group per molecule becomes small, and the sensitivity as a photosensitive resin cannot be sufficiently obtained.

Furthermore, 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 is a compound having two alcoholic hydroxyl groups and one or more carboxyl groups in the molecule. Use dimethylol propionic acid and dimethylol butyric acid. In addition, a reaction product of a trifunctional or higher polyol compound and a polybasic acid anhydride can also be cited. These diol compounds having a carboxyl group may be used alone or in combination of multiple types.

Next, the diisocyanate compound (c) used in the production of the component (A) is not particularly limited as long as it is a compound having two isocyanate groups in the molecule, but in order to form a urethane compound excellent in flexibility, etc. Preferably used: phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, aryl ether diisocyanate, norbornane -Methyl dicyanate, etc. Among these compounds, isophorone diisocyanate or trimethylhexamethylene diisocyanate can be preferably used. These compounds may be used alone, or two or more compounds may be used at the same time.

When the component (a) is a diol compound having an ethylenically unsaturated bond, the composition of each component (a), (b), and (c) when the component (A) is produced is preferably molar ratio [(a )+(b)]/(c) is 1～5. When the molar ratio is less than 1, the isocyanate group may remain at the end of the compound obtained by the reaction, which may cause gelation. Therefore, it is not preferable. When the molar ratio exceeds 5, the obtained content The molecular weight of the alkali-soluble resin of the polymerizable unsaturated group becomes small, and sufficient sensitivity cannot be obtained when forming a photosensitive resin composition, or a problem of viscosity occurs during film formation.

In addition, it is also possible to form the component (A) obtained by substituting a part of the component (b) with a diol compound (d) that does not have an ethylenically unsaturated bond or a carboxyl group in the molecule and reacting. (D) Examples of components include: (poly)ethylene glycol, (poly)propylene glycol, 1,4-butanediol, 1,6-hexanediol, and other aliphatic diol compounds, or cyclohexane-1, Alicyclic diols such as 4,-diol, cyclohexane-1,4-dimethanol, etc.

The reaction conditions for component (A) are in a solvent-free or non-alcoholic solvent (for example, glycol ethers made from ethylene glycol, etc., propylene glycol monomethyl ether acetate, butyl cellosolve acetate In the reactor where a predetermined amount of (a), (b), and (d) components are added as necessary to mix and stir, slowly add (c) component, and the reaction temperature is 40 A reaction at a temperature of about 5 to 60 hours at a temperature of 120° C. and a reaction time of about 5 hours to 60 hours yields an alkali-soluble resin having an ethylenically unsaturated bond as the component (A).

其中，通式（III）中，R₅ 獨立地表示氫原子或者甲基，J表示環氧化合物的環氧基除外的殘基，L表示二異氰酸酯化合物的異氰酸酯基除外的殘基，p表示10～100的數。 [化4]

其中，通式（IV）中，L表示二異氰酸酯化合物的異氰酸酯基除外的殘基，M表示碳數1～5的三元烷基，q表示10～100的數。For example, when the (a) component is an epoxy (meth)acrylate obtained by reacting an epoxy compound represented by the general formula (I) with (meth)acrylic acid, the obtained has an ethylenic non- 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 basically randomly bonded, and may include a part of skeletons with different structures. [化3]

Among them, in the general 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, L represents a residue other than the isocyanate group of the diisocyanate compound, and p represents 10 The number of ~100. [化4]

However, in the general formula (IV), L represents a residue other than the isocyanate group of the diisocyanate compound, M represents a trivalent alkyl group with 1 to 5 carbon atoms, and q represents a number from 10 to 100.

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

The acid anhydride (e) for adjusting the acid value includes, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride , Trimellitic anhydride, tetrahydrotrimellitic anhydride, hexahydrotrimellitic anhydride, etc.

The weight average molecular weight (Mw) in terms of polystyrene of the alkali-soluble resin of (A) measured by Gel Permeation Chromatography (GPC) is usually 2,000 to 50,000, and preferably 5,000 to 20,000. When the weight average molecular weight is less than 2000, there is a concern that the adhesion of the pattern during alkali development may decrease, and when the weight average molecular weight exceeds 50,000, there is a concern that the developability is significantly reduced.

Moreover, the preferable range of the acid value of the alkali-soluble resin of (A) is 80 mgKOH/g-120 mgKOH/g. If the value is less than 80 mgKOH/g, residues are likely to remain during alkali development, and if it exceeds 120 mgKOH/g, the penetration of the alkali developer becomes too fast, causing peeling and development, which is not preferable. In addition, (A) the polymerizable unsaturated group-containing alkali-soluble resin may use only one kind of these, or may use a mixture of two or more kinds.

Then, (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond includes, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth) (Meth)acrylates having hydroxyl groups such as 2-hydroxyhexyl acrylate, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth) ) Acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri (Meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate ) Acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene Alkylene oxide modified hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate and other (meth)acrylates, pentaerythritol, dipentaerythritol and other polyols, phenol novolac, etc. Vinyl benzyl ether compounds of phenols, addition polymers of divinyl compounds such as divinylbenzene, etc. These (B) photopolymerizable monomers having at least one ethylenically unsaturated bond may use only one kind of compound or a combination of multiple kinds. In addition, (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 5 parts by mass to 400 parts by mass, and preferably 10 parts by mass to 150 parts by mass relative to 100 parts by mass of the component (A). If the blending ratio of (B) component is more than 400 parts by mass relative to 100 parts by mass of (A) component, the cured product after photocuring becomes brittle, and the acid value of the coating film in the unexposed area is low. The solubility of the alkaline developer decreases, causing the problem of jagged edges of the pattern and unclearness. On the other hand, if the blending ratio of component (B) is less than 5 parts by mass relative to 100 parts by mass of component (A), the proportion of photoreactive functional groups in the resin is small, and the formation of a crosslinked structure is insufficient Furthermore, since the acid value of the resin component is high, the solubility of the exposed part in the alkali developer is improved, so there is a concern that the formed pattern becomes thinner than the target line width, or the pattern is likely to fall off .

In addition, the photopolymerization initiator of the component (C) includes, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, and two Acetophenones such as chloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylamino two 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-bis(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methyl (Oxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds, 2-trichloromethyl-5-styryl-1,3, 4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyrene Yl)-1,3,4-oxadiazole and other halomethyl diazole compounds, 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 -Chlorophenyl)-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-methoxy Styryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis( Trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, etc. Halomethyl-s-triazine compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzyloxime), 1-( 4-Phenylmercaptophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylmercaptophenyl)butane-1,2-dione- 2-oxime-O-acetate, 1-(4-methylmercaptophenyl)butane-1-one oxime-O-acetate, ethyl ketone, 1-[9-ethyl-6-(2 -Methylbenzyl)-9H-carbazol-3-yl)-,1-(0-acetoxyoxime), ketone, (9-ethyl-6-nitro-9H-carbazole- 3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]-,O-acetyloxime, ketone, (2-methylphenyl) (7-nitro-9,9-dipropyl-9H-茀-2-yl)-, acetoxime, ethyl ketone, 1-[7-(2-methylbenzyl)-9, 9-Dipropyl-9H-茀-2-yl)-,1-(O-acetyloxime), ethyl ketone, 1-(-9,9-dibutyl-7-nitro-9H-茀-2-base)- ,1-O-Acetyl oxime and other O-acyl oxime compounds, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone Sulfur compounds such as ketone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3- Anthraquinones such as diphenylanthraquinone, organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole , 2-mercaptobenzothiazole and other mercaptan compounds. Among them, from the viewpoint of easily obtaining a photosensitive resin composition for a high-sensitivity light-shielding film, it is preferable to use O-acetoxime-based compounds. These (C) photopolymerization initiators may use only one type of compound, or may use multiple types in combination. In addition, the photopolymerization initiator in the present invention is used in the meaning of including a sensitizer.

These photopolymerization initiators or sensitizers may be used alone or in combination of two or more kinds. In addition, although it does not function as a photopolymerization initiator or sensitizer by itself, it is also possible to add a compound capable of increasing the ability of the photopolymerization initiator or sensitizer by using in combination. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.

Based on 100 parts by mass of the total of (A) component and (B) component, the usage amount of the photopolymerization initiator of (C) component is preferably 0.1 to 30 parts by mass, preferably 1 to 25 parts by mass Appropriate. When the blending ratio of (C) component is less than 0.1 parts by mass, the speed of photopolymerization becomes slow and sensitivity decreases. On the other hand, when it exceeds 30 parts by mass, there is a concern that the following problems may occur: too strong sensitivity , The pattern line width becomes thicker relative to the pattern mask, and the 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 black organic pigments, mixed-color organic pigments, and light-shielding materials, and is preferably one having excellent insulation, heat resistance, light resistance, and solvent resistance. Here, black organic pigments include, for example, perylene black, aniline black, cyanine black, lactam black, and the like. Examples of the mixed-color organic pigments include those that mix 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 use only one compound, and may use multiple types in combination.

As the light-shielding material, titanium black is preferable in terms of good light-shielding properties, elastic modulus, deformation amount, and elastic recovery rate. In the case of using titanium black, for the purpose of further improving insulation, black organic pigments and/or mixed color organic pigments may be used in combination. As described above, when an inorganic light-shielding material is used in combination with an organic pigment, the blending ratio of [light-shielding material/(black organic pigment and/or mixed-color organic pigment)] should be 90/10 to 10/ in mass ratio. 90, 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 with required properties such as light-shielding and insulation can be obtained. For the purpose of controlling the chromaticity of the light-shielding film in order to make the light-shielding film achromatic, it is not the purpose of making organic pigments other than black black obtained by pseudo-color mixing, but may be added as a single color.

The titanium black used in the present invention is a titanium-containing black inorganic pigment represented by titanium suboxide, titanium oxynitride, and the like. Among these inorganic pigments, those exhibiting high insulation can be preferably used. The production methods of these titanium blacks include: heating a mixture of titanium dioxide and metallic titanium in a reducing gas environment to reduce it (Japanese Patent Laid-Open No. 49-5432); and passing the high temperature of titanium tetrachloride A method of reducing the ultrafine titanium dioxide obtained by hydrolysis in a reducing gas atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322); a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Japanese Patent Laid-Open No. 60-65069 and Japanese Patent Laid-Open No. 61-201610); a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and performing high-temperature reduction in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610 No. Bulletin) etc.; but not limited to these methods.

In addition, these titanium-containing black inorganic pigments may be those coated with an organic compound or an inorganic compound on the surface of the inorganic particles. Examples of organic compounds used for coating include: polyols, alkanolamines or their derivatives, organosilicon compounds (polysiloxanes, silane coupling agents, etc.), higher fatty acids or their metal salts, organometallic compounds ( Titanium coupling agent, aluminum coupling agent, etc.) etc. On the other hand, examples of inorganic compounds used for coating include aluminum compounds, silicon compounds, zirconium compounds, tin compounds, titanium compounds, and antimony compounds. As a method of coating the surface of the titanium-containing particles, the method described in JP 2006-206891 and the like can be used.

Examples of commercially available titanium black products include: Titanium Black 12S, 13M-T, 13M-C, UF8 manufactured by Mitsubishi Materials, and Tilack D manufactured by Ako Chemicals ("Tilack D" is The company’s registered trademark), etc.

The organic pigment used in the present invention can be any known compound without particular limitation, and preferably is a specific surface area obtained by a micronization process and a Brunauer-Emmett-Teller (Brunauer-Emmett-Teller, BET) method It is a compound of 50 m ² /g or more. Specific examples include: azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone ) Pigments, isoindoline (isoindoline) pigments, dioxazine (dioxazine) pigments, reduction (threne) pigments, perylene (perylene) pigments, perinone pigments, quinophthalone pigments, diketones Specific examples of diketopyrrolopyrrole (diketopyrrolopyrrole) pigments, thioindigo (thioindigo) pigments, and the like include compounds with the following color index (CI) names, but are not limited to these compounds.

CI Pigment・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 Pigment·Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.; CI Pigment·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.

In addition, the solvent of (E) component includes, for example, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3- Alcohols such as hydroxy-2-butanone and diacetone alcohol, terpenes such as α-terpineol or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2- Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol 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, ethyl acetate 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 and other esters; by use These solvents can be dissolved and mixed to form a homogeneous solution-like composition. In order to provide essential characteristics such as coatability, two or more of these solvents may be used.

Furthermore, it is preferable that these light-shielding components are dispersed in a solvent together with the (F) dispersant in advance to form a light-shielding dispersion liquid, and then formulated as a photosensitive resin composition for a light-shielding film. Here, the dispersed solvent becomes a part of (E) component, so if it is listed in the above (E) component, it can be used. For example, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are suitably used. Wait. Regarding the blending ratio of the (D) light-shielding component forming the light-shielding dispersion liquid, it is preferable to use it in the range of 5 mass% to 80 mass% with respect to the total solid content of the photosensitive resin composition for the light-shielding film of the present invention. In addition, the said solid content means the component except (E) component in a composition. The solid component also includes the component (B) which becomes a solid component after photocuring. If it is less than 5% by mass, it cannot be set to the required light-shielding property. If it exceeds 80% by mass, the content of the photosensitive resin originally used as the binder decreases, and therefore, not only the development characteristics are impaired, but also the film forming ability is impaired.

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

In addition, in the light-shielding dispersion liquid, the (F) dispersant is used in order to stably disperse the light-shielding component, but for this purpose, various known dispersants such as various polymer dispersants can be used. Examples of the dispersant can be used without particular limitation of the well-known compounds previously used for pigment dispersion (compounds sold under the names of dispersant, dispersion wetting agent, dispersion accelerator, etc.), for example: cationic polymer dispersant , Anionic polymer dispersant, nonionic polymer dispersant, pigment derivative dispersant (dispersion aid), etc. Particularly preferred is a cationic polymer dispersant, which has cationic functional groups such as imidazole groups, pyrrolyl groups, pyridyl groups, primary amine groups, secondary amine groups, or tertiary amine groups as adsorption points for pigments, and has an amine value It is 1 mgKOH/g～100 mgKOH/g, and the number average molecular weight is in the range of 1,000～100,000. The blending amount of the dispersant is 1% by mass to 30% by mass, preferably 2% by mass to 25% by mass relative to the light-shielding component.

Furthermore, when preparing a light-shielding dispersion, in addition to the dispersant, a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is co-dispersed to form a photosensitive resin for a light-shielding film In the case of a composition, it is possible to form a photosensitive resin composition that is easy to maintain the exposure sensitivity at high sensitivity, has good adhesion during development, and is hard to cause residue problems. (A) The compounding amount of the component is preferably 2% by mass to 20% by mass in the light-shielding dispersion liquid, and more preferably 5% by mass to 15% by mass. If the (A) component is less than 2% by mass, the effects of co-dispersion such as improved sensitivity, improved adhesion, and reduced residue cannot be obtained. In addition, if it is 20% by mass or more, especially when the content of the light-shielding material is large, the viscosity of the light-shielding dispersion liquid is high, uniform dispersion is difficult or takes a lot of time, and it becomes difficult to obtain a coating with uniformly dispersed light-shielding components. The photosensitive resin composition of the film.

The light-shielding dispersion liquid obtained in the above-mentioned manner can be combined with the component (A) (when the component (A) is co-dispersed during the preparation of the light-shielding dispersion liquid, the remaining component (A)) and the component (B) , (C) component and residual (E) component are mixed, and the photosensitive resin composition for light-shielding films is formed.

In addition, in the photosensitive resin composition of the present invention, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a solvent, a leveling agent, a defoamer, a coupling agent, and a surface may be blended as necessary. Additives such as active agents. Thermal polymerization inhibitors and antioxidants include: hydroquinone, hydroquinone monomethylether, pyrogallol, tert-butyl catechol (tert-butyl) catechol), phenothiazine, hindered phenol compounds, etc. Plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., filler Examples include glass fiber, silica, mica, alumina, etc., and examples of defoaming agents or leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. In addition, surfactants include fluorine-based surfactants, silicone-based surfactants, etc., and coupling agents include 3-(glycidoxy)propyltrimethoxysilane, 3-propenoxypropyl Silane coupling agents such as trimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.

The photosensitive resin composition of the present invention may also use other resin components that are polymerized or cured by heat in combination. Other resin components are preferably (G) epoxy resins or epoxy compounds having two or more epoxy groups, and examples include: 3,3',5,5'-tetramethyl-4,4'-biphenol type Epoxy resin, bisphenol A type epoxy resin, bisphenol phenol type epoxy resin, phenol novolac type 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 Base silicone resin, etc. For these additional components, only one compound may be used, or multiple types may be used in combination.

The photosensitive resin composition of this invention contains the said (A)-(E) component as a main component. It is desirable to include (A) to (D) components in a total of 70% by mass, preferably 80% by mass or more in the solid content. (E) The amount of the solvent changes according to the target viscosity, but it 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, for example. The method of forming a light shielding film having a spacer function includes the photolithography method described below. The following methods can be cited: first, the photosensitive resin composition for the light-shielding film of the present invention is coated on a substrate, and then the solvent is dried (pre-baked), and then a photomask is placed on the film obtained in the manner described above , The exposed part is irradiated with ultraviolet rays to harden the exposed part, the unexposed part is further eluted using an aqueous alkali solution to form a pattern, and then post-baking (thermal calcination) is performed as post-drying.

The substrate may be a transparent substrate, or an alignment film formed on the pixel, or on the flattening film on the pixel, or on the flattening film on the pixel after pixels such as RGB are formed Base materials other than transparent substrates. The type of substrate on which the light-shielding film with the spacer function is formed depends on the design of the liquid crystal display device.

In addition to the glass substrate, the transparent substrate coated with the photosensitive resin composition can also be exemplified by vapor-deposited or patterned indium tin oxide on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether oxide, etc.) (Indium tin oxide, ITO) or transparent electrodes such as gold. In addition to the well-known solution immersion method and spray method, the method of coating the solution of the photosensitive resin composition on the transparent substrate can also be a method using a roll coater, a land coater, a slit coater, or a rotary machine. Wait for either method. Using these methods, after coating to a desired thickness, the solvent is removed (pre-baking) to form a film. Pre-baking is performed by heating with an oven, a hot plate, etc. The heating temperature and heating time in the prebaking are appropriately selected according to the solvent to be used, and for example, it is performed at a temperature of 60°C to 110°C for 1 minute to 3 minutes.

The exposure performed after the prebaking is performed using an ultraviolet exposure device, and by performing exposure through a photomask, only the portion of the resist corresponding to the pattern is exposed to light. The exposure device and its exposure and irradiation conditions are appropriately selected, and light sources such as ultra-high-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and far-ultraviolet lamps are used for exposure, and the photosensitive resin composition in the coating film is photocured.

The alkali development after exposure is performed for the purpose of removing the resist of the unexposed part, and a desired pattern is formed by this development. Examples of developing solutions suitable for the alkaline development include aqueous solutions of carbonates of alkali metals or alkaline earth metals, aqueous solutions of hydroxides of alkali metals, and the like. It is particularly preferable to use sodium carbonate or carbonic acid containing 0.05% to 3% by mass. A weakly alkaline aqueous solution of carbonates such as potassium and lithium carbonate is developed at a temperature of 23°C to 28°C, and a commercially available developing machine or ultrasonic cleaner can be used to precisely form a fine image.

After development, it is preferable to perform heat treatment (post-baking) at a temperature of 180°C to 250°C and conditions of 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 performed by heating with an oven, hot plate, etc., similarly to pre-baking. The patterned light-shielding film of the present invention is formed through each step using 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. In addition, according to the 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. In addition, according to the method, a light-shielding film having a dielectric constant of 2-10, preferably 2-8, and particularly preferably 3-6 can be formed. In addition, according to the above method, in a mechanical property test, a light-shielding film having a breaking strength of 200 mN or more, an elastic recovery rate of 30% or more, and/or a compression rate of 40% or less can be formed. The light-shielding film formed by the method can be used as a column spacer of a liquid crystal display device, and preferably can be used as a black column spacer.

In addition, according to the method described above, the film thickness H1 for setting the optical density of 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 with a film thickness of H1 and a light-shielding film with a film thickness of H2 of 0.1 to 2.9. The cured film formed by the above method can be used as a column spacer of a liquid crystal display device, and preferably can be used as a black column spacer. According to the cured film whose ΔH is in the above-mentioned range, black column spacers with different heights 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 of film thickness H2 may function as a spacer, and the cured film of film thickness H1 may function as a black matrix. In addition, the reason why ΔH is necessary is that if the black matrix function film is set to the same film thickness as the spacer function film, the liquid crystal layer is divided by pixels, which not only hinders the free flow of the liquid crystal layer, but also concerns that When the liquid crystal layer is filled to form a liquid crystal display device, the yield rate decreases.

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 and insulating properties, and further has a spacer function with excellent elastic modulus, deformation amount, and elastic recovery rate, and can be formed even with a film thickness of 2 μm-7 μm The shape of the spacer is fine on the left and right. [Example]

Hereinafter, the embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these.

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 performed as follows.

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

[Acid value] The resin solution was dissolved in dioxane, and the potentiometric titration device [manufactured by Hiranuma Sangyo Co., Ltd., trade name COM-1600] was used to titrate with 1/10 N-KOH aqueous solution.

[Molecular weight] Gel permeation chromatography (GPC) [trade name HLC-8220GPC manufactured by Tosoh Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1 piece) + TSKgelSuper-H5000 (1 piece) [manufactured by Tosoh Co., Ltd.], temperature: 40°C, speed: 0.6 ml/min], measured with standard polystyrene [Tosoh Co., Ltd. Manufactured PS-oligomer set] The weight average molecular weight (Mw) is calculated as the converted value.

[Average secondary particle size measurement] The light-shielding dispersion is diluted with a solvent (propylene glycol monomethyl ether acetate (PGMEA) in this example), and the concentration of the light-shielding component is 0.1% by mass For the left and right solutions, the average secondary particle size is measured using a fineness distribution meter (manufactured by Nikkiso Co., Ltd., Microtrac MT-3000) by the laser diffraction and scattering method.

[Synthesis example 1] In a 500 mL four-necked flask equipped with a reflux cooler, 105.7 g (0.29 mol) of bisphenol A epoxy compound (manufactured by Shinichi Ka Epoxy Co., Ltd., trade name YD-128) was added , Epoxy equivalent = 182), 41.8 g (0.58 mol) acrylic acid, 1.52 g triphenylphosphine (TPP), and 40.0 g propylene glycol monomethyl ether acetate (PGMEA), at 100℃～105 Stir under heating at ℃ for 12 hr to obtain the 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 the dropwise addition, the mixture was stirred under heating at 75°C to 80°C for 6 hr. Furthermore, 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-1. 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 cooler, 104.2 g (0.29 mol) of bisphenol A epoxy compound (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name YD- 128, epoxy equivalent = 182), 41.2 g (0.57 mol) of acrylic acid, 1.50 g of TPP, and 40.0 g of PGMEA, stir under heating at 100°C to 105°C for 12 hours 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 the dropwise addition, the mixture was stirred under heating at 75° C. to 80° C. for 6 hr to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-2. 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 by GPC analysis was 11210.

[Synthesis Example 3] In a 500 mL four-necked flask equipped with a reflux cooler, 104.2 g (0.29 mol) of bisphenol A epoxy compound (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name YD- 128, epoxy equivalent = 182), 41.2 g (0.57 mol) of acrylic acid, 1.50 g of TPP, and 40.0 g of PGMEA, stir under heating at 100°C to 105°C for 12 hours 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 the dropwise addition, the mixture was stirred under heating at 75°C to 80°C for 6 hr. Furthermore, 21.0 g (0.14 mol) of tetrahydrophthalic anhydride was added, and it stirred under heating of 90-95 degreeC for 6 hours, and obtained the 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 11860.

[Synthesis Example 4] In a 500 mL four-necked flask with a reflux cooler, 105.7 g (0.29 mol) of bisphenol A epoxy compound (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name YD- 128, epoxy equivalent = 182), 41.8 g (0.58 mol) of acrylic acid, 1.52 g of TPP, and 40.0 g of PGMEA, stir for 12 hr under heating at 100°C to 105°C 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 the dropwise addition, the mixture was stirred under heating at 75°C to 80°C for 6 hr. Furthermore, 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-4. 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 with a reflux cooler, 104.2 g (0.29 mol) of bisphenol A epoxy compound (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name YD- 128, epoxy equivalent = 182), 41.2 g (0.57 mol) of acrylic acid, 1.50 g of TPP, and 40.0 g of PGMEA, stir under heating at 100°C to 105°C for 12 hours 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 the dropwise addition, the mixture was stirred under heating at 75°C to 80°C for 6 hr. Furthermore, 21.0 g (0.14 mol) of tetrahydrophthalic anhydride was added, and it stirred under heating of 90-95 degreeC for 6 hours, and obtained the 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-neck 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, and 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 for 8 hr under a nitrogen stream at 80°C to 85°C. Furthermore, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.44 g of TPP, and 0.055 g of 2,6-di-tert-butyl-p-cresol were added to the flask at 80°C to 85°C Stir for 16 hr to obtain alkali-soluble resin solution (A)-6. 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.

(Alkali-soluble resin containing polymerizable unsaturated groups) (A)-1 component: the alkali-soluble resin solution obtained in the synthesis example 1 (A)-2 component: the alkali-soluble resin solution obtained in the synthesis example 2 (A)-3 component: the alkali-soluble resin solution obtained in the synthesis example 3 (A)-4 component: the alkali-soluble resin solution obtained in the synthesis example 4 (A)-5 component: the synthesis example 5 Alkali-soluble resin solution obtained in (A)-6 components: the alkali-soluble resin solution obtained in Comparative Synthesis Example 1

(Photopolymerizable monomer) (B): 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-methylbenzyl)-9H-carbazol-3-yl]-,1-(0 -Acetyl oxime) (manufactured by BASF, product name Irgacure OXE02) (light-shielding dispersed pigment) (D)-1: 20.0% by mass titanium black (manufactured by Mitsubishi Materials Co., Ltd., Product name 13M-C), 5.0% by mass dispersant PGMEA dispersion (solid content is 25.0%, the average particle size of titanium black is 188 nm) (D)-2: 15.0% by mass black pigment (endoamide Black, made by BASF, Irgaphor S100CF), 4.5 mass% polymer dispersant PGMEA dispersion (solid content 19.5%, average secondary particle size of black pigment is 241 nm) ( D) -3: 7.0% by mass CI pigment, orange 64 (manufactured by BASF), 3.0% by mass CI pigment, purple 23 (manufactured by Clariant), 7.0% by mass CI pigment, blue 15: 6 (manufactured by Clariant), 4.0% by mass polymer dispersant, 2.0% by mass sulfonated azo-based dispersing aid, 2.0% by mass benzyl methacrylate/methacrylic acid copolymer PGMEA dispersion (solid content of 25.0%) (D)-4: 20.0% by mass of carbon black, 5.0% by mass of polymer dispersant PGMEA dispersion (solid content of 25.0%, average secondary particles of carbon black Diameter 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) (solid content 1.0%)

The said compounding component was compounded in the ratio shown in Table 1 and Table 2, and the photosensitive resin composition of Example 1-Example 11 and Comparative Example 1-Comparative Example 2 was prepared. In addition, all the numerical values in Table 1 and Table 2 represent parts by mass. In addition, (E)-1 in the column of solvents does not include PGMEA (same as (E)-1) in the unsaturated group-containing resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution) and shading The amount of PGMEA (same as (E)-1) in the aqueous dispersion.

[Table 1]

[Table 2]

[Evaluation] Using the photosensitive resin composition for the light-shielding film of Example 1 to Example 11 and Comparative Example 1 to Comparative Example 2, the evaluation described below was performed. These evaluation results are shown in Table 3 and Table 4.

<Development characteristics> Using a spin coater, each photosensitive resin composition obtained as described above was applied to a glass substrate with a thickness of 1.2 mm so that the film thickness after the thermosetting treatment became 3.0 μm, and it was carried out at 90°C 1 minute pre-bake. Then, the photomask was tightly attached, and 100 mJ/cm ² ultraviolet rays were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction on the photosensitive part.

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

The thin line formation of the obtained cured film pattern was confirmed by an optical microscope, and it evaluated by the following 3 stages. ○: There is no residue and a pattern with L/S of 10 μm/10 μm or more is formed △: There is no residue and a pattern with L/S of 30 μm/30 μm or more is formed ×: No L/S is less than 50 μm /50 μm pattern, or the bottom curl or residue of the pattern is significant

<Optical Density> Using a spin coater, each photosensitive resin composition obtained as described above was coated on a glass substrate with a thickness of 1.2 mm so that the film thickness after the thermosetting treatment became 1.1 μm, at 90°C 1 minute pre-bake. Then, using a hot air dryer, heat curing treatment was performed at 230°C for 30 minutes to obtain a cured film of the photosensitive resin composition. Then, the optical density of the obtained cured film was measured using a Macbeth transmission densitometer, and it evaluated by the optical density per unit film thickness.

<Volume resistivity> Using a spin coater, each photosensitive resin composition obtained as described above was coated on a glass substrate with a thickness of 1.2 mm on which Cr was vapor-deposited so that the film thickness after the thermosetting treatment became 3.5 μm The part except the electrode is pre-baked at 90°C for 1 minute. Then, a hot-air dryer was used to perform heat curing treatment at 230°C for 30 minutes to obtain a cured film of the photosensitive resin composition. Then, an aluminum electrode was formed on the cured film to produce a substrate for volume resistivity measurement. Then, using an electrometer (produced by Keithley, "Model 6517A"), the volume resistivity under an applied voltage of 1 V to 10 V was measured. The measurement was performed under the conditions of voltage holding for 60 seconds at each applied voltage in the 1 V stage, and the volume resistivity when 10 V was applied is shown in Tables 3 and 4.

<Dielectric constant> Using a spin coater, each photosensitive resin composition obtained as described above was applied to a glass substrate with a thickness of 1.2 mm on which Cr was vapor-deposited so that the film thickness after the thermosetting treatment became 3.5 μm The part except the electrode is pre-baked at 90°C for 1 minute. Then, a hot-air dryer was used to perform heat curing treatment at 230°C for 30 minutes to obtain a cured film of the photosensitive resin composition. Then, an aluminum electrode was formed on the cured film to produce a substrate for dielectric constant measurement. Then, using an electrometer (made by Keithley, "Type 6517A"), the capacitance at a frequency of 1 Hz to 100,000 Hz was measured, and the dielectric constant was calculated from the capacitance.

<Half tone (HT) characteristics of the spacer> Using a spin coater, each photosensitive resin composition obtained as described above was applied to a thickness of 1.2 mm so that the film thickness after the thermal curing treatment became 3.0 μm On the glass substrate, pre-baked at 90°C for 1 minute. Then, a photomask with a dot pattern is closely attached, and an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² is used to irradiate ultraviolet rays of 5 mJ/cm ² to 100 mJ/cm ² to perform the photohardening reaction of the photosensitive part .

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

The halftone characteristic of the spacer is calculated by calculating the difference (ΔH) between the height of the spacer at an exposure amount of 5 mJ/cm ² and 100 mJ/cm ² , and evaluated in the following four stages. ○: 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 greater than 2.9 μm

<Compression rate, elastic recovery rate, and breaking strength of the spacer> Using a spin coater, each photosensitive resin composition obtained as described above was applied to a thickness of 1.2 mm so that the film thickness after the thermosetting treatment became 3.0 μm On the glass substrate, pre-baked at 90°C for 1 minute. Then, a photomask with a dot pattern was closely attached, and 100 mJ/cm ² of ultraviolet rays were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction on the photosensitive part.

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

The spacer characteristics of the obtained cured film pattern were evaluated using an ultra-micro hardness tester (manufactured by Fisher Instruments, Fischer scope HM2000Xyp). Squeeze a 100 μm square flat indenter at a load speed of 5.0 mN/sec. After the load reaches a load of 50 mN, remove the load at a load removal speed of 5.0 mN/sec to create a displacement curve.

The compressibility is calculated by the following formula, assuming that the displacement under a load of 50 mN is L1. Compression rate (%)=L1/height of spacer×100

The elastic recovery rate is calculated by the following formula, assuming that the displacement under a load of 50 mN under load is L1 and the displacement during unloading is L2. Elastic recovery rate (%)=(L1-L2)/L1×100

The breaking strength was evaluated using an ultra-micro hardness tester (manufactured by Fisher Instruments, Fischer scope HM2000Xyp). A 100 μm square flat indenter was squeezed at a load speed of 5.0 mN/sec, and the load up to 300 mN was used to measure the load when the spacer broke, and the following 4 stages were used for evaluation. ○: 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> Using a spin coater, each photosensitive resin composition obtained as described above was applied to a glass substrate with a thickness of 1.2 mm so that the film thickness after the thermosetting treatment became 3.0 μm, at 90°C Pre-bake for 1 minute. Then, a photomask with a dot pattern was closely attached, and 100 mJ/cm ² of ultraviolet rays were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction on the photosensitive part.

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

The shape of the spacer was evaluated by the internal angle (taper angle) of the end of the spacer using a scanning electron microscope. When the taper angle is 70° or more and 90° or less, it is ⊚, if it is 50° or more and less than 70°, it is ○, if it is 50° or less, it is △, and if it is 90° or more, it is ×.

[table 3]

[Table 4]

According to the results of Example 1 to Example 11 and Comparative Example 1 to Comparative Example 2, it can be seen that by using titanium black for the (D) light shielding material, the light shielding property, dielectric constant, and elastic recovery can be improved while maintaining the volume resistivity. Rate and other spacer characteristics. In particular, by using titanium black together with black organic pigments or mixed-color organic pigments, it is possible to supplement the shortcomings of various light-shielding materials without degrading the characteristics of the spacer such as elastic recovery rate, and improve light-shielding, volume resistivity, dielectric The coexistence of the electrical constant has an effect.

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Claims (14)

A photosensitive resin composition for a light-shielding film having a spacer function, characterized by containing the following (A) to (E) components as essential components: (A) an alkali-soluble resin containing polymerizable unsaturated groups, which A urethane compound obtained by reacting a polyol compound (a) having an ethylenically unsaturated bond in the molecule, a diol compound having a carboxyl group in the molecule (b), and a diisocyanate compound (c); B) A photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) a light-shielding component containing internal amido black; and (E) a solvent. The photosensitive resin composition according to the first item of the scope of patent application, which further contains a color-mixed organic pigment as the light-shielding component (D), and the average secondary particle size of the internal amide black and/or the color-mixed organic pigment It is 20nm~500nm. The photosensitive resin composition according to claim 1, wherein 5 parts by mass to 400 parts by mass of the component (B) are contained relative to 100 parts by mass of the component (A), relative to the ( The total amount of the A) component and the (B) component is 100 parts by mass, and 0.1 to 30 parts by mass of the (C) component is contained, and the (B) component that becomes a solid content after light curing is included When the component except for the component (E) is a solid component, the solid component contains 5 mass% to 80 mass% of the component (D). The photosensitive resin composition described in the first item of the scope of patent application can form a light-shielding film: the optical density OD is 0.5/μm or more and 3/μm or less, and the volume resistivity when a voltage of 10V is applied is 1× 10 ⁹ Ω‧cm or more, and the dielectric constant is 2~10. The photosensitive resin composition described in the first item of the patent application can form a light-shielding film that satisfies at least one of the following (i) to (iii) in a load-unloading test using a microhardness meter, ( i) Breaking strength of 200mN or more; (ii) Elastic recovery rate of 30% or more; (iii) Compression rate of 40% or less. A light-shielding film having a spacer function, characterized by being formed by curing the photosensitive resin composition described in any one of items 1 to 5 in the scope of the patent application. A liquid crystal display device includes the light-shielding film as described in item 6 of the scope of patent application as a black column spacer (BCS). The liquid crystal display device described in item 7 of the scope of patent application further includes a thin film transistor (TFT). A method for producing a photosensitive resin composition for a light-shielding film with a spacer function, which prepares a dispersion in which (D) a light-shielding component is dispersed in a solvent (E), and then adds to the dispersion ( A) 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 are mixed; and The (A) alkali-soluble resin is obtained by reacting a polyol compound (a) having an ethylenically unsaturated bond in the molecule, a diol compound having a carboxyl group in the molecule (b), and a diisocyanate compound (c) In the urethane compound, the (D) light-shielding component includes an internal amide black component. The method for producing a photosensitive resin composition according to claim 9, wherein the (D) light-shielding component further contains a color-mixing organic pigment, and in the dispersion, the internal amide black and/or The average secondary particle size of the mixed color organic pigment is 20nm~500nm. A method for manufacturing a light-shielding film formed on a substrate, which coats the photosensitive resin composition as described in any one of items 1 to 5 in the scope of the patent application on the substrate, and irradiates the light with the photosensitive resin composition. The resin composition hardens. The method for manufacturing a light-shielding film as described in the scope of patent application, wherein the light-shielding film is used to set the optical density of the light-shielding film to a film thickness H1 of 0.5/μm or more and less than 3/μm, and the light-shielding function of the spacer The film thickness of the film is H2, and when H2 is 2 μm to 7 μm, a light-shielding film with a film thickness H1 and a film thickness H2 of 0.1 to 2.9 △H=H2-H1 is formed at the same time. A method for manufacturing a liquid crystal display device is characterized in that a light shielding film manufactured by the method for manufacturing a light shielding film as described in the scope of patent application is used as a black column spacer. The method for manufacturing a liquid crystal display device according to item 13 of the scope of patent application is characterized in that the liquid crystal display device includes a thin film transistor (TFT).