JP4555988B2 - Photosensitive element - Google Patents

Description

  The present invention relates to a photosensitive element suitable for forming a black matrix and a spacer of a color filter used for a color liquid crystal display device or the like.

  Conventionally, a black matrix or a spacer of a color filter used in a color liquid crystal display device or the like is formed by the following procedure, for example, when formed using a photosensitive resin composition. That is, a black photosensitive resin composition in which a black colorant is dispersed is applied onto a substrate, dried, and then irradiated with actinic rays such as ultraviolet rays through a photomask (hereinafter referred to as “exposure”). And a black matrix or spacer having a desired pattern is formed by development (for example, see Patent Document 1).

  However, in such a black photosensitive resin composition, it is necessary to use a considerable amount of a black colorant in order to sufficiently enhance the light shielding property of the black matrix or spacer. Therefore, the actinic rays irradiated during the exposure are absorbed by the colorant, and the effective intensity of the actinic rays in the coating film inevitably decreases from the coating surface to the bottom (near the substrate surface). Will occur. As a result, the curing reaction inside the coating film tends to become insufficient gradually from the coating film surface toward the bottom, resulting in a problem that the adhesion of the formed pattern to the substrate is lowered. For this reason, when a black matrix or spacer is formed using a conventional black photosensitive resin composition, the pattern after the development peels off, lacks, lacks, or the like, or the coating film physical properties of the pattern heat-treated after development are inferior. There was a problem.

In addition, when the amount of the black colorant in the black photosensitive resin composition is reduced, absorption of visible light tends to be reduced, a desired black color cannot be obtained, and functions as a black matrix, a spacer, and the like. There was a problem that it could not be obtained sufficiently. Therefore, when a display panel is manufactured, there is a problem that display defects such as image sticking occur.
Japanese Patent Laid-Open No. 6-1938

  The present invention has been made in view of the above-described problems of the prior art, and has excellent adhesion to a substrate of a pattern during development, and is used for forming a black matrix, a spacer, and the like of a color filter. It is an object of the present invention to provide a photosensitive element capable of sufficiently suppressing the occurrence of display defects such as image sticking when a display panel such as the above is manufactured.

In order to achieve the above object, the present invention is a photosensitive element comprising a support and a photosensitive layer having a thickness of 1 to 100 μm formed of the photosensitive resin composition formed on the support. The photosensitive resin composition comprises: (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, (C) a photopolymerization initiator , ( D ) Colorant and malachite green as a dye, and the component (D) contains two or more organic pigments in an amount of 0.001 part by weight relative to 100 parts by mass of the total amount of the component (A) and the component (B). The photosensitive layer contains 01 to 10 parts by mass, does not contain a black inorganic pigment, and the photosensitive layer has a minimum light transmittance of 50% or more in a wavelength region of 350 to 370 nm and a maximum light transmission in a wavelength region of 400 to 700 nm. Rate is 20% Provided is a photosensitive element characterized by:

  Such a photosensitive element can be suitably used as a black resist photosensitive element for forming a black matrix and a spacer of a color filter. According to this photosensitive element, in the photosensitive layer having the above composition, the minimum light transmittance in the wavelength region of 350 to 370 nm is 50% or more, so that the photosensitive layer can be sufficiently cured by actinic rays such as ultraviolet rays. It can be performed uniformly. Thereby, the adhesion of the pattern to the substrate during development can be made sufficient. Further, when the maximum light transmittance of the photosensitive layer in the wavelength region of 400 to 700 nm is 20% or less, a function as a black matrix, a spacer, or the like can be sufficiently obtained. Thereby, when a display panel is produced, it is possible to sufficiently suppress the occurrence of display defects such as image sticking.

  Further, in the photosensitive element, the component (A) includes a copolymer of a monomer having a carboxyl group and a monomer copolymerizable therewith, and the copolymer is based on the total amount of monomers constituting the copolymer. It is preferable that the ratio of the monomer which has the said carboxyl group was 5-30 mass%.

  According to such a photosensitive element, the photosensitive layer can be cured more sufficiently and more uniformly by actinic rays such as ultraviolet rays, and the adhesion of the pattern to the substrate during development can be further improved. it can.

  Furthermore, in the photosensitive element, the component (C) preferably contains a 2,4,5-triarylimidazole dimer.

  According to such a photosensitive element, the photosensitive layer can be cured more sufficiently and more uniformly by actinic rays such as ultraviolet rays, and the adhesion of the pattern to the substrate during development can be further improved. it can.

  The photosensitive element preferably further includes a support, and the photosensitive layer is formed on the support. By having such a configuration, the manufacturing process of the black matrix and the spacer using the photosensitive element is facilitated.

  Moreover, in the said photosensitive element, it is preferable that (D) component contains an organic pigment. As a result, the minimum light transmittance of the photosensitive layer in the wavelength range of 350 to 370 nm can be easily set to 50% or more, and the maximum light transmittance in the wavelength range of 400 to 700 nm can be easily set to 20% or less. There is. Therefore, according to the photosensitive element, the adhesion of the pattern to the substrate at the time of development can be made more satisfactory, and the occurrence of display defects such as burn-in can be more sufficiently caused when a display panel is produced. There is a tendency to be able to suppress.

  Further, in the photosensitive element, it is preferable that the component (D) does not contain carbon black. As a result, the minimum light transmittance of the photosensitive layer in the wavelength range of 350 to 370 nm can be easily set to 50% or more, and the maximum light transmittance in the wavelength range of 400 to 700 nm can be easily set to 20% or less. There is. In particular, the minimum light transmittance in the wavelength range of 350 to 370 nm of the photosensitive layer can be easily set to 50% or more, and the adhesion of the pattern to the substrate during development tends to be more sufficient. is there.

  According to the present invention, the adhesion of the pattern to the substrate during development is excellent, and when a display panel is produced for use in forming a black matrix or a spacer of a color filter, display defects such as burn-in are sufficiently generated. It is possible to provide a photosensitive element that can be suppressed.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant.

  The photosensitive element of the present invention comprises (A) a binder polymer (hereinafter sometimes referred to as “component (A)”), (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule. (Hereinafter referred to as “component (B)” in some cases), (C) photopolymerization initiator (hereinafter referred to as “component (C)” in some cases), and (D) colorant (hereinafter referred to as “(D And a photosensitive layer composed of a colored photosensitive resin composition containing a component “)”, and the photosensitive layer has a minimum light transmittance of 50% or more in a wavelength region of 350 to 370 nm and 400 to 700 nm. The maximum light transmittance in the wavelength region is 20% or less.

  First, the components (A) to (D) constituting the colored photosensitive resin composition will be described.

((A) component)
The (A) binder polymer that is the component (A) is not particularly limited, and examples thereof include acrylic resins, methacrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenols. Based resins and the like. From the viewpoint of alkali developability, an acrylic resin or a methacrylic resin is preferable. These can be used alone or in combination of two or more.

  Such a (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyl toluene, α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, vinyl, and the like. -Esters of vinyl alcohol such as n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, ( (Meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acryl Acid, α-chloro ( T) Acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and the like, Examples include fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.

As said (meth) acrylic-acid alkylester, the compound etc. which the hydroxyl group, the epoxy group, the halogen group, etc. substituted the compound represented by the following general formula (I), the alkyl group of these compounds, etc. are mentioned, for example.
^{_{CH 2 = C (R 1)}} -COOR 2 (I)
[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 12 carbon atoms. ]

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ² in the general formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof can be mentioned.

  Examples of the monomer represented by the general formula (I) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (Meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (Meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester and the like. These can be used alone or in combination of two or more.

  In addition, the (A) binder polymer is preferably a polymer containing a carboxyl group from the viewpoint of alkali developability and more fully obtaining the effects of the present invention, for example, a polymerizable monomer having a carboxyl group. It can be produced by radical polymerization of a monomer and another polymerizable monomer. Here, it is preferable that the ratio of the polymerizable monomer having a carboxyl group based on the total amount of the polymerizable monomer constituting the (A) binder polymer is 5 to 30% by mass.

  (A) The binder polymer preferably has a dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 6.0, and more preferably 1.0 to 3.0. When the degree of dispersion exceeds 6.0, the adhesion and resolution tend to decrease. In addition, the weight average molecular weight and number average molecular weight in this invention are measured by gel permeation chromatography, and the value converted into standard polystyrene is used.

  (A) The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, and more preferably 40,000 to 150,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

  (A) The acid value of the binder polymer is preferably 100 to 500 mgKOH / g, and more preferably 100 to 300 mgKOH / g. When the acid value is less than 100 mgKOH / g, the development time tends to be long, and when it exceeds 500 mgKOH / g, the developer resistance of the photocured resist tends to be lowered.

  These (A) binder polymers are used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, two or more types of binder polymers having different degrees of dispersion are used. Examples thereof include a binder polymer.

((B) component)
Examples of the photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond as component (B) include compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. , 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, a urethane monomer, nonylphenyldioxylene (Meth) acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxy Propyl-β '-(meth) acryloyloxyethyl-o-phthalate, (meth) acrylic acid alkyl ester, etc. Is mentioned.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. It is done.

  Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxydecaethoxy) phenyl), etc., and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.). Are available.

  Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy) phenyl, and the like.

  Examples of the urethane monomer include addition of a (meth) acryl monomer having an OH group at the β-position and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, and the like. Examples include reactants, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.

  Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and the like. .

  These may be used alone or in combination of two or more.

  In the present invention, the blending amount of the (A) binder polymer in the colored photosensitive resin composition is preferably 40 to 80 parts by mass, with the total amount of the (A) component and the (B) component being 100 parts by mass, It is more preferable that it is 45-70 mass parts. If the blending amount is less than 40 parts by mass, the photocured product tends to be brittle, and when used as a photosensitive element, the coating property tends to be inferior, and if it exceeds 80 parts by mass, the photosensitivity tends to be insufficient. is there.

  Moreover, the compounding amount of the component (B) is preferably 20 to 60 parts by mass, more preferably 30 to 55 parts by mass, with the total amount of the component (A) and the component (B) being 100 parts by mass. . If this amount is less than 20 parts by mass, the photosensitivity tends to be insufficient, and if it exceeds 60 parts by mass, the photocured product tends to be brittle.

((C) component)
The (C) photopolymerization initiator, which is the component (C), generates active species such as radicals by irradiation with light (actinic rays such as ultraviolet rays and electron beams), and a polymerization reaction between the components (A) and (B). It is a component that starts.

  Examples of such (C) photopolymerization initiator include N, N′-tetraalkyl-4,4′-, such as benzophenone and N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone). Fragrances such as diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino-propanone-1 Quinones such as aromatic ketones, alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole Dimer, 2- (o-chlorophenyl) -4,5- (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- ( 2,4,5-triarylimidazole dimer such as p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc. And oxime compounds such as N-phenylglycine, N-phenylglycine derivatives, coumarin compounds, and O-acyl-α-oxooximes. Also, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may give the same and symmetric compounds, or differently give asymmetric compounds. Among these, 2,4,5-triarylimidazole dimer, N, N′-tetraalkyl-4,4′-diaminobenzophenone, and coumarin compounds are preferable from the viewpoint of adhesion and photosensitivity. These (C) photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  The amount of component (C) is preferably 0.1 to 20 parts by weight, and preferably 0.2 to 10 parts by weight with respect to 100 parts by weight as the total of component (A) and component (B). Is more preferable. If the blending amount is less than 0.1 parts by mass, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by mass, the light absorption on the surface of the photosensitive resin composition increases during exposure, and the internal light is increased. There is a tendency for curing to be insufficient.

((D) component)
The (D) colorant as the component (D) is not particularly limited as long as it is a pigment capable of coloring the photosensitive layer in the photosensitive element to such an extent that the photosensitive element can be applied to the formation of a black matrix, a spacer or the like. It is not always necessary to use a black pigment. Such a colorant (D) can be appropriately selected according to the use of the photosensitive element, and may be an inorganic pigment or an organic pigment, or a single pigment or a mixture of two or more pigments. Although it is good, in the present invention, a pigment having high color developability is preferred.

  Examples of the inorganic pigment include black inorganic pigments such as carbon black, titanium black, Cu—Fe—Mn-based oxides, and metal oxides such as synthetic iron black.

  Examples of the carbon black include SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HS, HAF, HAF-LS, HAF-HS, NAF, FEF, FEF-HS, SRF, SRF-LM, and SRF-. Furnace black such as LS, GPF, ECF, N-339 and N-351; Thermal black such as FT and MT; Acetylene black and the like.

  These inorganic pigments can be used alone or in admixture of two or more.

  Examples of the organic pigment include MHI Red # 4828M (trade name, manufactured by Mikuni Color Co., Ltd.), MHI Yellow # 4973M (trade name, manufactured by Mikuni Color Co., Ltd.), MHI Cyan # 4793M (trade name, manufactured by Mikuni Color Co., Ltd.), Examples include phthalocyanine blue, chromophthaled red, pyrazolone orange, and viridian. These organic pigments can be appropriately selected and used so as to obtain a desired hue. For example, two or more kinds of organic pigments can be mixed and used so that black or a hue close thereto can be obtained.

  In addition, an extender pigment may be added to the colorant (D) in the present invention as necessary. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, satan white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more.

  These (D) colorants can be used by modifying the surface with a polymer as required.

  Moreover, it is preferable that (D) a coloring agent contains the said organic pigment at least. As a result, the minimum light transmittance of the photosensitive layer in the wavelength range of 350 to 370 nm can be easily set to 50% or more, and the maximum light transmittance in the wavelength range of 400 to 700 nm can be easily set to 20% or less. There is.

  Furthermore, (D) the colorant preferably does not contain the carbon black, and more preferably does not contain the inorganic pigment. That is, (D) the colorant is preferably composed of the organic pigment and an extender pigment used as necessary. Thereby, there exists a tendency which the minimum light transmittance especially in the 350-370 nm wavelength range of a photosensitive layer can be easily 50% or more. In addition, carbon black and an inorganic pigment are not included as long as these are not substantially contained, and a small amount may be contained as an inevitable component.

  The blending amount of the component (D) is preferably 0.01 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). Is more preferable. If the blending amount is less than 0.01 parts by mass, desired coloration tends not to be obtained, and if it exceeds 10 parts by mass, the adhesion between the photosensitive layer and the substrate tends to decrease.

  In addition, when the extender is used as the component (D), the blending amount is usually 100 parts by mass or less, preferably 5 with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment other than the extender pigment. It is -50 mass parts, More preferably, it is 10-40 mass parts.

  Furthermore, when the inorganic pigment is used as the component (D), the blending amount is usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 1 with respect to 100 parts by mass of the organic pigment. It is below mass parts.

  In the photosensitive element of the present invention, the colored photosensitive resin composition constituting the photosensitive layer contains the above-described components (A) to (D) as essential components. D) An additive other than the component may be contained. Examples of such additives include dyes such as malachite green, photochromic agents such as tribromophenyl sulfone and leuco crystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, fillers, antifoaming agents, flame retardants , Stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents and the like. These additives can be blended in an amount of about 0.01 to 20 parts by mass per 100 parts by mass of the total amount of the component (A) and the component (B). These are used alone or in combination of two or more.

  Next, the photosensitive element of the present invention will be described.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 has a structure in which a photosensitive layer 14 is laminated on a support 10. Here, the photosensitive layer 14 is a layer made of the above-described colored photosensitive resin composition.

  Examples of the support 10 include metal plates of copper, copper alloys, nickel alloys, chromium alloys, iron alloys such as stainless steel (preferably copper, copper alloys, iron alloys), polyethylene terephthalate, polypropylene, Polymer films such as polyethylene and polyester can be used.

  The support 10 preferably has a thickness of 5 to 25 μm, more preferably 8 to 20 μm, and particularly preferably 10 to 16 μm. If this thickness is less than 5 μm, it tends to be easily broken when the support is peeled off before development, and if it exceeds 25 μm, the resolution tends to decrease.

  When the support 10 is made of the polymer film, the haze of the support 10 is preferably 0.001 to 5.0, more preferably 0.001 to 2.0, It is especially preferable that it is 0.01-1.8. When this haze exceeds 5.0, the resolution tends to decrease. In addition, the haze in this invention means the value measured based on JISK7105, for example with commercially available turbidimeters, such as NDH-1001DP (brand name, Nippon Denshoku Industries Co., Ltd.). Measurement is possible.

  The photosensitive layer 14 can be formed by, for example, applying the above-described colored photosensitive resin composition on the support 10 as a liquid resist.

  When the colored photosensitive resin composition is applied onto the support 10, the colored photosensitive resin composition is dissolved in a predetermined solvent as necessary to obtain a solution having a solid content of 30 to 60% by mass. Can be used as a coating solution. Examples of the solvent include organic solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, and mixed solvents thereof.

  Examples of the coating method include a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. The solvent can be removed, for example, by heating. In this case, the heating temperature is preferably about 70 to 150 ° C., and the heating time is preferably about 5 to 30 minutes.

  Moreover, although the thickness of the photosensitive layer 14 changes with uses, it is preferable that it is 1-100 micrometers in thickness after drying, and it is more preferable that it is 1-50 micrometers. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the adhesive strength and resolution tend to decrease.

  The photosensitive layer 14 constituting the photosensitive element 1 has a minimum light transmittance in the wavelength range of 350 to 370 nm of 50% or more and a maximum light transmittance in the wavelength range of 400 to 700 nm of 20% or less. is required. The photosensitive layer 14 more preferably has a maximum light transmittance of 5% or less in a wavelength range of 400 to 700 nm.

  Here, the light transmittance of the photosensitive layer 14 can be within the above range by adjusting, for example, the type and blending amount of the colorant (D), the film thickness of the photosensitive layer 14 and the like.

  In the present invention, the light transmittance of the photosensitive layer 14 is measured by using, for example, a UV spectrometer (manufactured by Hitachi, Ltd., 228A type W beam spectrophotometer, etc.) on the measurement side and the photosensitive member 14. It can be performed by placing the photosensitive element 1 composed of the layer 14, placing the support 10 on the reference side, and continuously measuring from 700 to 300 μm in the T% mode.

  According to the photosensitive element 1 having such a photosensitive layer 14, the adhesion (adhesive force) of the pattern to the substrate at the time of development can be made sufficient, and when the display panel is produced, it is seized. The occurrence of display defects can be sufficiently suppressed.

  The photosensitive element 1 may include a protective film (not shown) on the surface F1 opposite to the support side of the photosensitive layer 14 as necessary.

  Examples of the protective film include polymer films such as polyethylene and polypropylene. Further, the protective film is preferably a low fish eye film, and the adhesive force between the protective film and the photosensitive layer 14 is such that the protective layer 14 and the support can be easily peeled off from the photosensitive layer 14. It is preferable that it is smaller than the adhesive force between 10.

  The protective film preferably has a thickness of 5 to 30 μm, more preferably 10 to 28 μm, and particularly preferably 15 to 25 μm. If this thickness is less than 5 μm, the protective film tends to be easily broken during lamination, and if it exceeds 30 μm, the cost tends to be inferior.

  Further, the protective film preferably has a tensile strength in the film longitudinal direction of 13 MPa or more and a tensile strength in the film width direction of 9 MPa or more.

  The tensile strength in the film longitudinal direction is more preferably 13 to 100 MPa, further preferably 14 to 100 MPa, particularly preferably 15 to 100 MPa, and most preferably 16 to 100 MPa. If the tensile strength is less than 13 MPa, the protective film tends to be easily broken during lamination.

  The tensile strength in the film width direction is more preferably 9 to 100 MPa, further preferably 10 to 100 MPa, particularly preferably 11 to 100 MPa, and most preferably 12 to 100 MPa. If the tensile strength is less than 9 MPa, the protective film tends to be easily broken during lamination.

  In addition, the tensile strength in this invention means the value measured based on JISC2318-1997 (53.3), for example, Toyo Baldwin Co., Ltd. product name: Commercially available, such as Tensilon It can be measured with a tensile strength tester.

  Moreover, since it is necessary to remove the support 10 and the protective film from the photosensitive layer 14 later, it is preferable that the support 10 and the protective film are not subjected to a surface treatment that makes removal difficult, but the treatment is performed as necessary. It may be. Furthermore, the support 10 and the protective film may be subjected to antistatic treatment as necessary.

  The photosensitive element 1 includes a cushion layer, an adhesive layer, a light absorption layer, between the support 10 and the photosensitive resin composition layer 14 and / or between the photosensitive resin composition layer 14 and the protective film. An intermediate layer such as a gas barrier layer or a protective layer may be further provided.

  The photosensitive element 1 is, for example, in the form of a flat plate as it is or by laminating a protective film on one surface F1 of the photosensitive layer 14, wound around a cylindrical core, and stored in a roll form. be able to. The core is not particularly limited as long as it is conventionally used. For example, plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Etc. At the time of storage, it is preferable that the support is wound up so as to be the outermost side. Moreover, it is preferable to install an end face separator from the viewpoint of protecting the end face on the end face of the photosensitive element (photosensitive element roll) wound up in a roll shape, and in addition, a moisture-proof end face separator is installed from the viewpoint of edge fusion resistance. It is preferable to do. Moreover, when packaging the photosensitive element 1, it is preferable to wrap it in a black sheet with low moisture permeability.

  Next, a method for producing a black matrix and a spacer using the photosensitive element 1 of the present invention will be described.

  First, when a protective film is present on the photosensitive element 1, after removing the protective film, the photosensitive layer 14 is pressure-bonded to the substrate while heating, and the photosensitive layer 14 is laminated on the substrate. Here, it is preferable to laminate | stack under reduced pressure from a viewpoint of adhesiveness and followable | trackability.

  Examples of the material of the substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. In addition, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, or the like, if necessary.

  Next, the photosensitive layer 14 laminated on the substrate is irradiated with actinic rays in a predetermined pattern shape through a photomask to form an exposed portion. At this time, when the support 10 existing on the photosensitive layer 14 is transparent to the active light, the support 10 can be irradiated with the active light, and the support 10 can block the active light. In this case, the photosensitive layer 14 is irradiated with actinic rays after the support 10 is removed.

As the actinic ray used when producing the black matrix and the spacer, for example, visible ray, ultraviolet ray, far ultraviolet ray, electron beam, X-ray and the like can be used, but the wavelength is in the range of 190 to 450 nm. Actinic rays are preferred. Moreover, it is preferable that the energy amount of the actinic ray to irradiate shall be 10-10,000 J / m < ² >.

  As the active light source, a conventionally known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used. Further, a laser direct drawing exposure method or the like can also be used.

  Next, the exposed photosensitive layer 14 is developed. The development is performed by, for example, dissolving and removing the unexposed portion of the photosensitive layer 14 using an alkali developer, forming a black resist pattern having a predetermined pattern shape on the substrate, and completing the production of the black matrix or spacer. .

  Examples of the alkali developer used for development include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, after alkali development, the black resist pattern is usually washed with water.

  The development treatment can be performed by a method such as a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid buildup) development method, or the like. The development processing is preferably performed at room temperature for 5 to 300 seconds.

As a process after development, the black resist pattern may be further cured by performing heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² as necessary (post baking).

  The black matrix and the spacer thus produced are extremely useful for, for example, a color liquid crystal display device, a color image pickup tube element, a color sensor and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Examples 1-3 and Comparative Examples 1-3]
First, after synthesizing the component (A) in Table 1 below, the component (A) obtained was combined with the component (B), component (C) and additives shown in Table 1 and component (D) shown in Table 2 below. Were mixed to obtain solutions of colored photosensitive resin compositions corresponding to Examples 1 to 3 and Comparative Examples 1 to 3.

In Table 1, BPE-1300 ^{* 1} represents 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  The obtained colored photosensitive resin composition solution is uniformly applied onto a 25 μm-thick polyethylene terephthalate film as a support, and dried for 10 minutes in a hot air convection dryer at 100 ° C. to form a photosensitive layer. The photosensitive element of Examples 1-3 and Comparative Examples 1-3 was obtained. The film thickness after drying of the photosensitive layer was 50 μm.

  Further, using a UV spectrometer (manufactured by Hitachi, Ltd., 228A type W beam spectrophotometer), light having a wavelength of 300 to 700 μm of the photosensitive layer in the photosensitive elements of Examples 1 to 3 and Comparative Examples 1 to 3 was used. The light transmittance with respect to was measured. The light transmittance was measured by first placing a photosensitive element comprising a support film and a photosensitive layer on the measurement side, placing the support film on the reference side, and continuously measuring from 700 to 300 μm in the T% mode. Table 3 shows the maximum light transmittance in the wavelength region of 400 to 700 nm and the minimum light transmittance in the wavelength region of 350 to 370 nm.

(Evaluation of adhesion)
Using the photosensitive elements of Examples 1 to 3 and Comparative Examples 1 to 3, adhesion was evaluated according to the following procedure. First, a soda glass substrate having a silica (SiO ₂ ) film for preventing elution of sodium ions on the surface was prepared. The surface of this substrate was heated to 80 ° C., and the photosensitive element was laminated on the surface at a speed of 3 m / min using a 120 ° C. heat roll.

  Next, a phototool having a stove 21-step tablet and a phototool having a wiring pattern with a line width / space width of 10/10 to 100/100 (unit: μm) as an adhesive evaluation negative Then, exposure was performed with an energy amount such that the number of remaining steps after development of the stove 21-step tablet was 8.0. For the exposure, an exposure machine (HMW-201B manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp was used.

  Next, the polyethylene terephthalate film as a support was peeled from the photosensitive layer, and a 1% by mass sodium carbonate aqueous solution was sprayed on the photosensitive layer at 30 ° C. for 60 seconds to remove the unexposed portion, thereby producing a black matrix.

  Here, the adhesiveness is represented by the width (μm) of the minimum line remaining without being peeled off in the developer. The smaller this value is, the closer the thin line is not peeled off. (Adhesive strength) means high. The adhesion measurement results are shown in Table 4.

(Evaluation of display characteristics)
Using the photosensitive elements of Examples 1 to 3 and Comparative Examples 1 to 3, a silica (SiO ₂ ) film for preventing elution of sodium ions was formed on the surface in the same procedure as described above (adhesion evaluation). The photosensitive element was laminated on the soda glass substrate, exposed and developed to produce a black spacer on which a black dot pattern of 18 μm square was formed. At this time, the photo tool used for the exposure was one that can form the dot pattern. Next, this substrate was bonded to another glass substrate having an ITO film formed on the surface, and liquid crystal was injected between the substrates to produce a liquid crystal cell, and annealed at 100 ° C. for 1 hour. The obtained substrate was assembled into a display panel, and the presence or absence of display defects was evaluated.

Here, whether or not there is a display defect is that even if a static screen with a specific character or design is displayed for a long time (3 seconds or more) and then the static screen is turned off, the specific character or design is faint on the screen. Display defects such as burn-in afterimages and lack of information to be displayed at unspecified positions on the display panel at the pixel level were evaluated by visual observation and observation with an optical microscope (20 ×). The evaluation criteria at this time are as follows.
Display defect present: Display defects such as burn-in and missing pixel level were not recognized.
No display failure: Display failure such as burn-in and / or missing pixel level was observed.
The results are shown in Table 4.

(Observation of resist shape)
Using the photosensitive elements of Examples 1 to 3 and Comparative Examples 1 to 3, lamination, exposure and development of the photosensitive element on the soda glass substrate were performed in the same procedure as described above (adhesion evaluation). It was. The resist cross-sectional shape (cross-sectional shape cut along a plane perpendicular to the line length direction) of the resist pattern (black matrix) with a line width of 50 μm was observed with a scanning electron microscope (5000 times). The results are shown in Table 4.

  As is apparent from the results shown in Table 4, the photosensitive element (Examples 1 to 3) of the present invention has a good resist cross-sectional shape as compared with the photosensitive elements of Comparative Examples 1 to 3. In addition, it was confirmed that the adhesion of the pattern to the substrate during development was excellent and the occurrence of display defects such as image sticking could be sufficiently suppressed when a display panel was produced.

It is a schematic cross section which shows suitable one Embodiment of the photosensitive element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive layer.

Claims (5)

A photosensitive element comprising: a support; and a photosensitive layer having a thickness of 1 to 100 μm formed of the photosensitive resin composition formed on the support,
The photosensitive resin composition comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, (C) a photopolymerization initiator , and ( D) coloring. Containing malachite green as an agent and dye ,
The component (D) contains 0.01 to 10 parts by mass of two or more kinds of organic pigments with respect to 100 parts by mass of the total amount of the components (A) and (B), and does not contain a black inorganic pigment. ,
The photosensitive layer has a minimum light transmittance in a wavelength region of 350 to 370 nm of 50% or more and a maximum light transmittance in a wavelength region of 400 to 700 nm of 20% or less. .   The component (A) includes a copolymer of a monomer having a carboxyl group and a monomer copolymerizable therewith, and in the copolymer, the monomer having the carboxyl group based on the total amount of monomers constituting the copolymer The photosensitive element according to claim 1, wherein the proportion of the photosensitive element is 5 to 30% by mass.   The photosensitive element according to claim 1, wherein the component (C) contains a 2,4,5-triarylimidazole dimer. The photosensitive element according to claim 1, wherein the photosensitive resin composition further contains a photochromic agent. The photosensitive element according to claim 1, wherein the support has a thickness of 5 to 25 μm.

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