TWI736601B - Photosensitive resin composition for light-sielding film, display substrate and manufacturing method thereof - Google Patents

Abstract

The present invention provides a photosensitive resin composition for a light-shielding film, a substrate for a display, and a manufacturing method thereof. The composition is suitable for forming a light-shielding film on a plastic substrate with heat resistance of at most 160°C, and can obtain solvent resistance or alkali resistance. A light-shielding film with excellent performance. The photosensitive resin composition for a light-shielding film of the present invention contains (A) a polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth)acrylate acid adduct, and (B) having at least three ethylene A photopolymerizable monomer with an unsaturated bond, (C) an oxime ester polymerization initiator, (D) an azo polymerization initiator, and (E) are selected from the group consisting of black organic pigments, color-mixing organic pigments and light-shielding materials One or more shading components in the group.

Description

Photosensitive resin composition for light-shielding film, substrate for display, and manufacturing method thereof

The present invention relates to a photosensitive resin composition for a light-shielding film, a substrate for a display including a light-shielding film formed by curing the photosensitive resin composition for a light-shielding film, and a method for manufacturing the substrate for a display. In detail, the present invention It relates to a photosensitive resin composition for a light-shielding film suitable for forming a light-shielding film on a substrate having a heat-resistant temperature of 160° C. or less, and a display provided with a light-shielding film as a cured film of the photosensitive resin composition for the light-shielding film on the substrate A substrate and a method for manufacturing the substrate for a display.

Recently, for the purpose of making components flexible or one-chip (one chip), for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is required Light-shielding film (light-shielding pattern) is directly formed on plastic substrates (plastic film, resin film), or organic electroluminescent (EL) or organic thin film transistors (Thin Film Transistor, TFT) are formed on glass substrates or silicon wafers. ) Directly form a light-shielding film on the components. However, in these cases, the heat resistance temperature of the plastic substrate itself or the heat resistance temperature as a component is low, and the heat resistance is usually only about 160°C at most in most cases. Therefore, when forming a light-shielding film on a plastic substrate or component, the film strength becomes insufficient at a sintering temperature below 160°C, and the subsequent steps (such as red, green, blue, RGB) resist There are problems such as film thinning of the coating film, surface roughness, pattern peeling, etc.) in the case of agent coating, alkali resistance, etc.).

Therefore, for example, Japanese Patent Laid-Open No. 2003-15288 (Patent Document 1) discloses a substrate obtained by coating, exposing, patterning, and sintering at 150°C on a plastic substrate using a photosensitive resin composition. The photosensitive resin composition is based on an alkali-soluble resin of an acrylic copolymer and contains a thermal polymerization initiator in addition to the photopolymerization initiator. Although the residue and adhesion to the substrate (peel test) are ensured, The pattern line width, development tolerance, reliability (solvent resistance, alkali resistance), etc. are not described, and these characteristics are not yet sufficient.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-15288

[The problem to be solved by the invention]

The present invention was made in view of the aforementioned problems, and its object is to provide a photosensitive resin composition for a light-shielding film suitable for forming on a plastic substrate or element having a heat resistance of at most 160°C As the light-shielding film, a light-shielding film excellent in solvent resistance or alkali resistance can also be obtained for these plastic substrates or elements with low heat resistance. Furthermore, this invention provides the board|substrate for a display provided with the light-shielding film which hardened this photosensitive resin composition for light-shielding films, and its manufacturing method.

[Technical means to solve the problem]

Therefore, the inventors of the present invention are concerned with a photosensitive resin combination for a light-shielding film that obtains good development adhesion or pattern linearity by thermosetting at 160°C or less, and obtains a light-shielding film excellent in solvent resistance or alkali resistance After conducting diligent research on the material, it was found that the above can be solved by containing a predetermined polymerizable unsaturated group-containing alkali-soluble resin, photopolymerizable monomer, light-shielding component, and solvent, and combining two specific polymerization initiators. With the above-mentioned problems, the present invention has been completed.

That is, the gist of the present invention is as follows.

(1) A photosensitive resin composition for a light-shielding film characterized by containing the following (A) components to (E) components as essential components, (A) having a structure of an epoxy (meth)acrylate acid adduct Alkali-soluble resins containing polymerizable unsaturated groups, (B) photopolymerizable monomers with at least three ethylenically unsaturated bonds, (C) oxime ester-based polymerization initiators, (D) azo-based polymerization initiators , And (E) one or more light-shielding components selected from the group consisting of black organic pigments, color-mixing organic pigments, and light-shielding materials.

(2) The photosensitive resin composition for a light-shielding film as described in (1), wherein the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is represented by the following general formula (II),

[化1]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, and A represents -CO -, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9, 9-diyl group or direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z-(COOH) _m (where Z represents a divalent carboxylic acid residue Or trivalent carboxylic acid residue, m represents the number of 1 or 2), n represents an integer of 1 to 20).

(3) The photosensitive resin composition for a light-shielding film according to (1) or (2), wherein the mass ratio (A)/(B) of the (A) component to the (B) component is 50/50 to 90/10, with respect to the total of 100 parts by mass of the (A) component and (B) component, the (C) component is 2 parts by mass to 30 parts by mass, and the (D) component is 1 part by mass to 20 parts by mass, in The solid content containing the component which becomes a solid content by photohardening of the photosensitive resin composition for light-shielding films contains 40 mass%-70 mass% of (E) component.

(4) The photosensitive resin composition for light-shielding films as described in any one of (1)-(3) whose (E) component is carbon black.

(5) A substrate for a display, which is a substrate for a display having a light-shielding film on a substrate having a heat-resistant temperature of 160° C. or less, and is characterized in that the light-shielding film contains the following components (A) to (E) A light-shielding film with a component as an essential component is cured by a photosensitive resin composition, (A) a polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth)acrylate acid adduct, (B) A photopolymerizable monomer having at least three ethylenically unsaturated bonds, (C) an oxime ester-based polymerization initiator, (D) an azo-based polymerization initiator, and (E) selected from black organic pigments, color-mixing organic pigments and One or more light-shielding components in the group of light-shielding materials.

(6) A method for manufacturing a substrate for a display, comprising: manufacturing a substrate for a display having a light-shielding film on a substrate having a heat-resistant temperature of 160° C. or less, and the method for manufacturing the substrate for a display is characterized in that it contains the following (A) Component ~ (E) The photosensitive resin composition for a light-shielding film, which is an essential component, is applied to a substrate, exposed through a photomask, and unexposed areas are removed by development, and then heated at 160°C or less to form a predetermined pattern (A) Alkali-soluble polymerizable unsaturated group-containing resin with the structure of epoxy (meth)acrylate acid adduct, (B) Photopolymerizable resin with at least three ethylenically unsaturated bonds Monomer, (C) oxime ester-based polymerization initiator, (D) azo-based polymerization initiator, and (E) one or more light-shielding selected from the group consisting of black organic pigments, mixed color organic pigments and light-shielding materials Element.

[Effects of the invention]

For the photosensitive resin composition for a light-shielding film of the present invention, even if the process of manufacturing the light-shielding film does not include a step of thermal curing at a temperature exceeding 160° C., it can be formed with a line width of 5 μm～ A light-shielding film (light-shielding pattern) that has excellent development adhesion and linearity at 15 μm, especially 10 μm or less, and good solvent resistance. Therefore, it is possible to form a light-shielding film for resin films such as PET, PEN, etc., with a heat-resistant temperature of 160°C or less, or elements with organic EL or organic TFT formed on a glass substrate or silicon wafer. The characteristic of the light-shielding film is a substrate for displays.

That is, by using a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure, a polymerizable monomer having three or more ethylenically unsaturated groups, an oxime ester-based polymerization initiator, and an azo-based The photosensitive resin composition in which a polymerization initiator and a light-shielding component are essential components can form a required light-shielding film on a low-heat-resistant substrate with a heat-resistant temperature of 160° C. or less to produce a display substrate with various functions.

In order to make the above-mentioned features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail in conjunction with the accompanying drawings.

Hereinafter, the present invention will be described in detail.

First, each component of the photosensitive resin composition for light-shielding films of this invention is demonstrated.

The polymerizable unsaturated group-containing alkali-soluble resin of the component (A) of the present invention has a structure of an epoxy (meth)acrylate acid adduct, and in detail, it is a compound having two or more epoxy groups A compound obtained by further reacting a reactant of a compound and (meth)acrylic acid (which means "acrylic acid and/or methacrylic acid") with a polycarboxylic acid or an anhydride thereof. If a preferred example is used for detailed description, the epoxy compound represented by the following general formula (I) is reacted with (meth)acrylic acid, and the obtained compound having a hydroxyl group is reacted with (a) dicarboxylic acid or tricarboxylic acid Or its acid anhydride, and (b) the epoxy (meth)acrylate acid adduct obtained by reacting tetracarboxylic acid or its acid dianhydride. The epoxy compound represented by the general formula (I) refers to an epoxy compound obtained by reacting bisphenols with epihalohydrin or its equivalent. (A) The component has both a polymerizable unsaturated double bond and a carboxyl group, so it imparts excellent photocurability, good developability, and patterning characteristics to the photosensitive resin composition, and improves the physical properties of the light-shielding film.

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，A表示-CO-、-SO₂ -、-C(CF₃ )₂ -、-Si(CH₃ )₂ -、-CH₂ -、-C(CH₃ )₂ -、-O-、茀-9,9-二基或直接鍵合，l表示0～10的平均值。[化2]

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 A represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 茀-9,9-diyl or direct bond , L represents the average value of 0-10.

The bisphenols forming the epoxy compound of the general formula (I) include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4- Hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl) bis(4-hydroxyphenyl) bis(4-hydroxy-3,5-dimethylphenyl) bis(4-hydroxy-3,5-dimethylphenyl) bis(4-hydroxy-3,5) -Dichlorophenyl) hexafluoropropane, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5- Dichlorophenyl) hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3) ,5-Dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5- Dibromophenyl) methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4 -Hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane , Bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9- Bis (4-hydroxyphenyl) quince, 9,9-bis(4-hydroxy-3-methylphenyl) quince, 9,9-bis(4-hydroxy-3-chlorophenyl) quince, 9,9 -Bis(4-hydroxy-3-bromophenyl)sulfurium, 9,9-bis(4-hydroxy-3-fluorophenyl)sulfuron, 9,9-bis(4-hydroxy-3-methoxyphenyl) )茀, 9,9-bis(4-hydroxy-3,5-dimethylphenyl) 茀, 9,9-bis(4-hydroxy-3,5-dichlorophenyl) 茀, 9,9- Bis(4-hydroxy-3,5-dibromophenyl) pyrene, 4,4'-bisphenol, 3,3'-bisphenol, etc. Among them, bisphenols forming an epoxy compound in which A in the general formula (I) is a -9,9-diyl group can be particularly preferably used.

The compound of general formula (I) used to derive the alkali-soluble resin of (A) is an epoxy compound having two glycidyl ether groups obtained by reacting the bisphenols with epichlorohydrin. During this reaction, l is usually mixed with a plurality of values accompanying the oligomerization of the diglycidyl ether compound. Therefore, it becomes an average value of 0-10 (not limited to an integer), and a preferable average value of l is 0-3. If the average value of l exceeds the upper limit, when the alkali-soluble resin synthesized using the epoxy compound is used to prepare a photosensitive resin composition, the viscosity of the composition becomes too large to be applied smoothly or insufficiently The alkali solubility is imparted, and the alkali developability becomes very poor.

The (a) dicarboxylic acid or tricarboxylic acid or its anhydride used in the epoxy (meth)acrylate acid adduct can be chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its anhydride or alicyclic dicarboxylic acid Or tricarboxylic acid or its anhydride, aromatic dicarboxylic acid or tricarboxylic acid or its anhydride. Here, the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its anhydride includes, for example, succinic acid, acetosuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, Malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid (oxoglutaric acid), pimelic acid, sebacic acid, suberic acid, diglycolic acid and other compounds or their anhydrides, can also be further introduced An optionally substituted dicarboxylic acid or tricarboxylic acid or its anhydride. In addition, alicyclic dicarboxylic acid or tricarboxylic acid or its anhydride includes, for example, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid. The compound such as an acid or its anhydride may be a dicarboxylic acid or tricarboxylic acid or its anhydride further introduced with any substituent. Furthermore, the aromatic dicarboxylic acid or tricarboxylic acid or its anhydride includes, for example, compounds such as phthalic acid, isophthalic acid, trimellitic acid, or its anhydride, and may be a dicarboxylic acid further introduced with arbitrary substituents. Or tricarboxylic acid or its anhydride.

In addition, the (b) tetracarboxylic acid or its acid dianhydride used in the epoxy (meth)acrylate acid adduct can be chain hydrocarbon tetracarboxylic acid or its acid dianhydride or alicyclic tetracarboxylic acid or its Acid dianhydride, or aromatic polycarboxylic acid or its acid dianhydride. Here, the chain hydrocarbon tetracarboxylic acid or its acid dianhydride includes compounds such as butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and the like or its acid dianhydride, and may be further introduced with arbitrary substituents. The tetracarboxylic acid or its acid dianhydride. In addition, alicyclic tetracarboxylic acid or its acid dianhydride includes, for example, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cyclopentane tetracarboxylic acid, norbornane tetracarboxylic acid, etc. The compound or its acid dianhydride may be tetracarboxylic acid or its acid dianhydride into which an arbitrary substituent is further introduced. Furthermore, the aromatic tetracarboxylic acid or its acid dianhydride includes, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid and other compounds or their acid dianhydrides. It may be a tetracarboxylic acid or its acid dianhydride into which an arbitrary substituent is further introduced.

The molar ratio of (a) dicarboxylic acid or tricarboxylic acid or its anhydride to (b) tetracarboxylic acid or its acid dianhydride used in epoxy (meth)acrylate acid adduct (a)/(b) It is preferably 0.01 to 10.0, more preferably 0.02 or more and less than 3.0. If the molar ratio (a)/(b) deviates from the above range, the optimal molecular weight for the photosensitive resin composition of the present invention with high light-shielding, high impedance, and good photopatternability cannot be obtained, which is undesirable . In addition, the smaller the molar ratio (a)/(b), the larger the molecular weight, and there is a tendency for alkali solubility to deteriorate.

The epoxy (meth)acrylate acid adduct can be produced by the steps described in a known method, such as the method described in Japanese Patent Laid-Open No. 8-278629 or Japanese Patent Laid-Open No. 2008-9401, etc. . First, the method of reacting (meth)acrylic acid with the epoxy compound of the general formula (I) includes, for example, the following method: adding (meth)acrylic acid in equimolar to the epoxy group of the epoxy compound to the solvent, In the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.), while blowing in air, it is heated and stirred at 90°C to 120°C to react. Then, the method of reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound as the reaction product includes the following method: the epoxy acrylate compound and a predetermined amount of acid dianhydride and acid monoanhydride are added to the solvent, and the catalyst (brominated In the presence of tetraethylammonium, triphenylphosphine, etc.), it is reacted by heating and stirring at 90°C to 130°C.

The weight average molecular weight (Mw) of the polymerizable unsaturated group-containing alkali-soluble resin (A) is preferably in the range of 2,000 to 10,000, and more preferably in the range of 3,000 to 7,000. If the weight average molecular weight (Mw) is less than 2000, the pattern adhesion during development of the photosensitive resin composition using (A) cannot be maintained, and pattern peeling occurs. In addition, if the weight average molecular weight (Mw) exceeds 10,000, development residue Or the residual film in the unexposed area is likely to remain. Furthermore, (A) preferably has an acid value in the range of 80 mgKOH/g to 120 mgKOH/g. If the value is less than 80 mgKOH/g, the residue is likely to remain during alkaline development of the photosensitive resin composition using (A), and if it exceeds 120 mgKOH/g, the alkaline developer will be used for the photosensitive resin composition (A) Penetration in the medium became too fast, peeling and development occurred, and therefore all were unsatisfactory. In addition, regarding (A) the polymerizable unsaturated group-containing alkali-soluble resin, only one type may be used, or a mixture of two or more types may be used.

Next, (B) photopolymerizable monomers having at least three ethylenically unsaturated bonds include, for example, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylic acid Ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, two Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene (phosphazene) alkylene oxide modified hexa(meth)acrylate, caprolone Ester modified dipentaerythritol hexa(meth)acrylate and other (meth)acrylates, dendrimer type polyfunctional acrylates, hyperbranch type polyfunctional acrylates, etc., can be used One or two or more of these compounds. In addition, (B) the photopolymerizable monomer having at least three ethylenically unsaturated bonds does not have a free carboxyl group. In the present invention, in order to obtain a sufficient crosslinking density only by heat treatment at 160°C or lower, a trifunctional or higher photopolymerizable monomer is used.

The blending ratio of these (A) components and (B) components is preferably 50/50 to 90/10 in terms of mass ratio (A)/(B), preferably 60/40 to 80/20. If the blending ratio of (A) component is less than 50/50 in terms of (A)/(B), the following problems will occur: the cured product after light curing becomes brittle, and the acid value of the coating film in the unexposed area is low, so The solubility to the alkali developer is reduced, and the pattern edges become rough and uneven. In addition, if it is more than 90/10 in terms of (A)/(B), the following problems may occur: photoreactive functional groups in the resin The proportion is small and the cross-linked structure is not sufficiently formed. Furthermore, the acid value of the coating film of the exposed part due to the resin component is too high, and the solubility of the exposed part to the alkali developer is improved, so the formed pattern is better than the target The line width is thinner, or pattern omissions are likely to occur.

In addition, the oxime ester-based polymerization initiator of the component (C) includes, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzyl Oxime), 1-(4-(phenylsulfonyl)phenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-(methylsulfonyl) )Phenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-(methylsulfonyl)phenyl)butane-1-ketoxime-O-ethyl Ester, 1-[9-ethyl-6-(2-methylbenzyl) azol-3-yl] ethyl ketone=O-acetoxime, (9-ethyl-6-nitro Azol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone=O-acetyloxime, (8-{[(乙(Alkoxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl)-11-(2-ethylhexyl)-11H-benzo[a]哢Azol-5-yl)(2,4,6-trimethylphenyl)methanone, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-茀-2- Yl)-, acetyloxime, ethyl ketone, 1-[7-(2-methylbenzyl)-9,9-dipropyl-9H-茀-2-yl)-,1-(O -Acetyl oxime), ethyl ketone, 1-(-9,9-dibutyl-7-nitro-9H-茀-2-yl)-, 1-O-acetyl oxime, etc. In addition, two or more of these oxime ester-based polymerization initiators can also be used.

The main function of the oxime ester-based polymerization initiator of component (C) is to initiate photoradical polymerization. Regarding the amount used, the total amount of component (A) and component (B) is 100 parts by mass based on 2 parts by mass to 30 Parts by mass are suitable, preferably 5 parts by mass to 25 parts by mass. When the blending ratio of (C) component is less than 2 parts by mass, the speed of photopolymerization becomes slow and the sensitivity decreases. On the other hand, when it exceeds 30 parts by mass, the following problem may occur: the sensitivity is too strong and it becomes a pattern When the line width is thicker than the pattern mask, the line width cannot be reproduced faithfully to the mask, or the pattern edge becomes rough and uneven.

The azo-based polymerization initiator of component (D) includes: azobisisobutyronitrile (10-hour half-life temperature (toluene) (hereinafter referred to as T _1/2 ) is 65°C), 2,2'-azo Bis(2,4-dimethylvaleronitrile) (T _1/2 is 51°C), dimethyl 2,2'-azobis(2-methyl propionate) (T _1/2 is 66°C) ), dimethyl 1,1'-azobis(1-cyclohexane carboxylate) (T _1/2 is 73℃), 1,1'-azobis(cyclohexane-1-carbonitrile) ) (T _1/2 is 88°C), 1,1'-azobis(1-acetoxy-1-phenylethane) (T _1/2 is 61°C), dimethyl 2,2 '-Azobisisobutyrate (T _1/2 is 67°C) and so on.

Regarding the function of the azo polymerization initiator of component (D), it is mainly to improve the thermal radical polymerizability of the photosensitive resin composition, especially to improve the formation of thermal polymerization during post-baking after exposure and development. The physical properties of the hardened product such as the hardness of the pattern. Therefore, it is necessary to add an appropriate amount of an azo-based polymerization initiator _{with an appropriate 10-hour half-life temperature (T 1/2) according to post-baking conditions and the like.} The preferred 10-hour half-life temperature is 50°C to 80°C, and the amount used is preferably 1 part by mass to 20 parts by mass based on 100 parts by mass of the total of component (A) and component (B), preferably 2 Parts by mass to 15 parts by mass are suitable.

The component (E) is a light-shielding component selected from black organic pigments, color-mixed organic pigments, or light-shielding materials, and is preferably excellent in heat resistance, light resistance, and solvent resistance. Here, black organic pigments include, for example, perylene black, aniline black, cyanine black, and internal amide black. Examples of the mixed-color organic pigments include pigments that simulate blackening of two or more pigments selected from the group consisting of red, blue, green, purple, yellow, cyan, magenta, and the like. Examples of the light-shielding material include carbon black, chromium oxide, iron oxide, and titanium black. Two or more types of light-shielding components can be appropriately selected and used, and carbon black is particularly preferable in terms of light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins. In addition, if the carbon black used is carbon black whose surface is coated with a dye, resin, etc., it is suitable for the case where a high-resistance hardened product is used.

In addition, the solvent of component (F) includes, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, and terpenes such as α-terpineol or β-terpineol. , Ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve Agent, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Glycol ethers such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, 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 acetates, etc., by using these solvents Dissolving and mixing can be made into a homogeneous solution-like composition.

The light-shielding component of (E) is preferably dispersed in the solvent (F) together with the (G) dispersant in advance to prepare a light-shielding dispersion, and then it is preferable to prepare the photosensitive resin composition for a light-shielding film. Here, the solvent for dispersing can be used as long as it is the solvent exemplified in the component (F). For example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are suitably used. Regarding the blending ratio of the light-shielding component (E) forming the light-shielding dispersion liquid, it is preferable to use it in the range of 40% by mass to 70% by mass relative to the total solid content of the photosensitive resin composition for a light-shielding film of the present invention. The range of 40% by mass to 60% by mass is particularly preferable. If it is less than 40% by mass, the light-shielding properties become insufficient for high light-shielding. If it exceeds 70% by mass, the following problems occur: the content of the photosensitive resin originally used as the binder decreases, and therefore the development characteristics are impaired and the film forming ability is impaired. In addition, the total solid content of the photosensitive resin composition for a light-shielding film also includes a component that becomes a solid content by photocuring the photosensitive resin composition for a light-shielding film.

Regarding the dispersant (G) to be used, well-known dispersants such as various polymer dispersants can be used. Specific examples of the dispersing agent can be used without particular limitation of well-known compounds (commercially available under the names of dispersing agents, dispersion wetting agents, dispersion accelerators, etc.) used for pigment dispersion, for example, cationic polymers Dispersant, anionic polymer dispersant, nonionic polymer dispersant, pigment derivative type dispersant (dispersion aid), etc. It is particularly suitable to have cationic functional groups such as imidazole group, pyrrolyl group, pyridyl group, primary amino group, secondary amino group or tertiary amino group as the adsorption point for the pigment, and the amine value is 1 mgKOH/g～100 mgKOH/g A cationic polymer-based dispersant with a number average molecular weight in the range of 1,000 to 100,000. The blending amount of the dispersant is preferably 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, by co-dispersing a part of the polymerizable unsaturated group-containing alkali-soluble resin of component (A) in addition to the dispersant, when the photosensitive resin composition for a light-shielding film is prepared It is easy to maintain the exposure sensitivity at a high sensitivity, and it can be made into a photosensitive resin composition that has good adhesion during development and does not easily cause the problem of residue. The compounding amount of the (A) component at this time 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, effects such as improvement in sensitivity, improvement in adhesion, and reduction in residues as a co-dispersion effect cannot be obtained. In addition, if it exceeds 20% by mass, especially when the content of the light-shielding material is large, the viscosity of the light-shielding dispersion liquid is high, it is difficult to uniformly disperse, or it takes a lot of time, and it is difficult to obtain a photosensitive resin combination for obtaining a high-resistance coating film. Things. Furthermore, the obtained light-shielding dispersion is mixed with (A) component, (B) component, (C) component and (D) component, and (F) component is added as necessary and adjusted to a viscosity suitable for film forming conditions. The photosensitive resin composition for light-shielding films was prepared.

In addition, in the photosensitive resin composition of the present invention, polymerization initiators other than oxime ester series and azo series, chain transfer agents, sensitizers, non-photosensitive resins, curing accelerators, antioxidants, plastic Additives such as chemical agents, fillers, leveling agents, defoamers, coupling agents, surfactants, pigments and dyes for color adjustment. Examples of polymerization initiators other than oxime ester series and azo series include: acetophenones, benzophenones, α-hydroxyalkylphenones, α-aminoalkylphenones, benzoin ethers, and Imidazole compounds, halogenated methyl diazole compounds, halogenated methyl s-triazine compounds, etc., chain transfer agents and sensitizers generally can use sulfur atom-containing compounds, including thiol compounds, As disulfide compounds and the like, aliphatic polyfunctional thiols such as 1,4-bis(3-mercaptobutoxy)butane and the like can be preferably exemplified. Examples of non-photosensitive resins include bisphenol type epoxy resins, novolac type epoxy resins, alicyclic epoxy resins, epoxy silicone resins, and the like. Examples of antioxidants include hindered phenol type antioxidants. , Phosphorus-based antioxidants, etc. Plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., and fillers include glass fiber, silica, mica, oxide Examples of aluminum and the like, antifoaming agent or leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. In addition, surfactants include fluorine-based surfactants, silicone-based surfactants, and the like. Coupling agents include 3-(glycidoxy)propyltrimethoxysilane, 3-isocyanatopropyltriethyl Silane coupling agents such as oxysilane and 3-ureidopropyltriethoxysilane.

The photosensitive resin composition of this invention suitably contains the said (A) component-(F) component as a main component. It is desirable to contain the (A) component to (E) component in a total of 80% by mass, preferably 90% by mass or more, in the solid content other than the solvent (the solid content includes the monomer that becomes the solid content after curing) . (F) The amount of the solvent changes according to the target viscosity, and it is preferably contained in the photosensitive resin composition in the range of 70% by mass to 90% by mass.

The method for forming a light-shielding film using the photosensitive resin composition for a light-shielding film of the present invention includes the following photolithography method. The following method can be mentioned: firstly, the photosensitive resin composition is coated on a plastic substrate or element, and then the solvent is dried (pre-baked), and then the obtained film is irradiated with ultraviolet light through a photomask to harden the exposed part, Furthermore, development of elution of the unexposed part using an alkaline aqueous solution is performed to form a pattern, and then post-baking (thermal sintering) is performed as post-curing.

The substrate to which the photosensitive resin composition of the present invention is applied includes resin films (plastic substrates) such as PET and PEN having a heat-resistant temperature of 160° C. or less. The so-called heat-resistant temperature here is a temperature that does not cause problems such as deformation even when the substrate is exposed to the patterning of the light-shielding film formed on the substrate. The temperature varies depending on the degree of stretching of the resin film, but it must be at least not more than Glass transition temperature (Tg). In addition, a substrate on which an electrode such as indium tin oxide (ITO) or gold is vapor-deposited or patterned on a resin film can also be exemplified as the substrate.

In addition, other examples of the substrate to which the photosensitive resin composition of the present invention is applied also include a substrate in which a low-heat-resistant thin film or the like is formed on a high-heat-resistant substrate such as a glass substrate or a silicon wafer. Specific examples include elements in which organic EL (Organic Light Emitting Diode (OLED)) or organic thin film transistors (TFT) are formed on glass or silicon wafers. In addition, the heat resistance temperature of the substrate with low heat resistance in the present invention, such as a resin film or element, also differs depending on the type of resin or element, but it can be said that it is usually 100°C to 160°C.

In addition to the well-known solution dipping method and spray method, the method of applying the photosensitive resin composition solution on these substrates can be a method using a roll coater, a land coater, a slit coater, or a rotary machine. And so on any method. After coating to a desired thickness by these methods, the solvent is removed (pre-baking), thereby forming a film. The pre-baking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time of the pre-baking are appropriately selected according to the solvent used, 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 pre-baking is performed by an ultraviolet exposure device, and the exposure is performed through a photomask, and 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 an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and a far ultraviolet lamp are used for exposure, and the photosensitive resin composition in the coating film is photocured.

The alkali development after exposure is performed to remove the resist of the unexposed part, and a desired pattern is formed by this development. The developer suitable for the alkaline development includes, for example, an aqueous solution of alkali metal or alkaline earth metal carbonate, an aqueous solution of alkali metal hydroxide, etc., and in particular, sodium carbonate and potassium carbonate containing 0.05% by mass to 3% by mass are used. , Lithium carbonate and other carbonate weakly alkaline aqueous solutions are preferably 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 100° C. to 160° C. and conditions of 20 minutes to 60 minutes. This post-baking is performed in order to improve the adhesion of the patterned light-shielding film and the substrate, etc. This is performed by heating with an oven, a hot plate, etc. similarly to the pre-baking. The patterned light-shielding film of the present invention is formed through the steps of the above photolithography method.

As described above, the photosensitive resin composition of the present invention can be suitably used to form a light-shielding film on a substrate with a low heat resistance temperature by exposure, alkali development, etc., and is particularly suitable for a fine light-shielding film. The pattern of the situation. Specifically, in the case of using a substrate with a low heat-resistant temperature, etc., it can be used to form a black matrix for color filters, a black matrix for forming organic EL pixels, or a partition wall material (used to pass through Inkjet method to form RGB, etc.), light-shielding films, light-shielding films for touch screens, etc., substrates with light-shielding films can also be used for liquid crystal or organic EL and other display devices or imaging elements (ie , These are collectively referred to as display substrates).

[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 examples.

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 of 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 screen [weight: W ₀ (g)] and weighed [W ₁ (g)], based on the weight after heating at 160°C for 2 hours [ W ₂ (g)] The solid content concentration is obtained from the following formula.

Solid content concentration (weight%) = 100×(W ₂ －W ₀ )/(W ₁ －W ₀ )

[Acid value]

The resin solution was dissolved in dioxane, and the acid value was determined by titration with a 1/10 N-KOH aqueous solution using a potential difference titration device [trade name COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.].

[Molecular Weight]

Gel Permeation Chromatography (GPC) [trade name HLC-8220GPC manufactured by Tosoh Co., Ltd., solvent: tetrahydrofuran, column: TSK gel Super H-2000 (2) + TSK gel Super H-3000 (1 piece) + TSK gel Super H-4000 (1 piece) + TSK gel Super-H 5000 (1 piece) [manufactured by Tosoh (stock)], temperature: 40°C, speed: 0.6 ml/min ] Was measured, and the weight average molecular weight (Mw) was calculated as a conversion value of standard polystyrene [PS-oligomer set manufactured by Tosoh Co., Ltd.].

In addition, the abbreviations used in the synthesis examples are as follows.

BPFE: the reactant of 9,9-bis(4-hydroxyphenyl) pyrene and chloromethyl oxirane. Among the compounds of the general formula (I), A is a compound having a -9,9-diyl group and R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen.

AA: Acrylic

BPDA: 3,3,4,4-biphenyltetracarboxylic dianhydride

THPA: 1,2,3,6-tetrahydrophthalic anhydride

MAA: Methacrylic acid

MMA: methyl methacrylate

CHMA: Cyclohexyl methacrylate

GMA: Glycidyl methacrylate

TEAB: Tetraethylammonium bromide

AIBN: Azobisisobutyronitrile

TPP: Triphenylphosphine

DTBC: 2,6-Di-tert-butyl p-cresol

PGMEA: Propylene Glycol Monomethyl Ether Acetate

DMDG: Diethylene glycol dimethyl ether

[Synthesis Example 1]

Put 114.4 g (0.23 mol) of BPFE, 33.2 g (0.46 mol) of AA, 157 g of PGMEA and 0.48 g of TEAB into a 500 ml four-necked flask with reflux condenser, and heat at 100℃～105℃ It was stirred for 20 hours and reacted. Then, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were added to the flask, and stirred under heating at 120°C to 125°C for 6 hours to obtain alkali-soluble resin (A)-1. The solid content concentration of the obtained resin solution was 56.1 wt%, the acid value (in terms of solid content) was 103 mgKOH/g, and the Mw obtained by GPC analysis was 3,600.

[Synthesis Example 2]

Add 51.7 g (0.60 mol) of MAA, 38.0 g (0.38 mol) of MMA, 37.0 g (0.22 mol) of CHMA, 5.91 g of AIBN and 295 to a 1000 ml four-necked flask with a nitrogen inlet tube and a reflux tube. g of DMDG was stirred at 80°C to 85°C for 8 hours under a nitrogen stream to polymerize. Furthermore, 39.8 g (0.28 mol) of GMA, 1.44 g of TPP, and 0.055 g of DTBC were added to the flask, and the mixture was stirred at 80°C to 85°C for 16 hours to obtain a (meth)acrylate containing a polymerizable unsaturated group Resin (A)-2. The solid content concentration of the obtained resin solution was 35.5% by mass, the acid value (in terms of solid content) was 110 mgKOH/g, and the Mw obtained by GPC analysis was 18080.

Next, the present invention will be specifically described based on examples and comparative examples related to the production of the photosensitive resin composition for a light-shielding film and its cured product, but the present invention is not limited to these examples. Here, the raw materials and abbreviations used in the production of the photosensitive resin composition for a light-shielding film of the following Examples and Comparative Examples and a cured product thereof are as follows.

(Alkali-soluble resin containing polymerizable unsaturated groups) (A)-1: Alkali-soluble resin solution obtained in Synthesis Example 1 (A)-2: Alkali-soluble resin solution obtained in Synthesis Example 2

(Photopolymerizable monomer) (B)-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Toagosei Co., Ltd., trade name Aronix M-405) (B)-2: Trimethylolpropane triacrylate (manufactured by Sartomer Japan (stock), trade name SR351S) (B)-3: Ethylene Oxide (EO) adduct of bisphenol A II Acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name Light Acrylate BP-4EAL)

(Oxime ester polymerization initiator)

(C): Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-oxazol-3-yl]-,1-(O-acetyloxime) ( Made by BASF Japan, the product name is Irgacure OXE02)

(Other than azo polymerization initiators) (D) -1: 2,2-Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-60) (D)-2: Dimethyl 2, 2-Azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-601) (D)-3:1,1'-azobis(1-acetoxy- 1-Phenylethane) (manufactured by Otsuka Chemical Company, trade name: OTAZO-15) (D)-4: Benzyl peroxide (manufactured by NOF Corporation, trade name: Nyper BMT-K40)

(Shading disperse pigment)

(E): PGMEA dispersion with a carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 4.75% by mass (solid content is 29.75%)

(Solvent) (F)-1: PGMEA (F)-2: Cyclohexanone

(Silane coupling agent)

(H): S-510 (manufactured by JNC)

(Surfactant) (I): Megaface F475 (manufactured by DIC)

The said compounding component was compounded in the ratio shown in Table 1, and the photosensitive resin composition of Example 1-Example 6 and Comparative Example 1-Comparative Example 4 was prepared. In addition, all the numerical values in Table 1 represent parts by mass. In addition, (F)-1 and (F)-2 are amounts that do not contain the solvent in (A)-1 and (A)-2 and the solvent in (E).

[Table 1]

[Evaluation]

Using the photosensitive resin composition for black resists of Example 1-Example 6 and Comparative Example 1-Comparative Example 4, the evaluation described below was performed. The evaluation results of these evaluations are shown in Table 2 and Table 3.

<Evaluation of development characteristics (pattern line width, pattern linearity)>

Using a spin coater, apply the obtained photosensitive resin composition to a 125 mm×125 mm glass substrate (Corning 1737) so that the film thickness after baking becomes 1.2 μm, at 90°C Pre-bake for 1 minute. Then, the exposure gap adjusted to 100 μm, the line / space = 10 μm / 50 μm of negative type dry coating film coated on the mask, using an ultrahigh pressure mercury lamp i-line irradiation illuminance of 30 mW / cm ² to 50 mJ / cm ² of ultraviolet light, the photohardening reaction of the photosensitive part is carried out.

Then, use 25°C, 0.04% potassium hydroxide aqueous solution to the exposed coating plate at ^{a spray pressure of 1 kgf/cm 2} from the development time (break time = BT) when the pattern begins to appear +10 seconds And +20 seconds after development, perform ^{spray washing at a pressure of 5 kgf/cm 2 to} remove the unexposed parts of the coating film to form a light-shielding film pattern on the glass substrate, and then use a hot air dryer at 120°C for 60 minutes Bake after heating. The line width with respect to the mask width of the 10 μm line of the obtained light-shielding film pattern and the pattern linearity were evaluated.

Pattern line width: A length measuring microscope (manufactured by Nikon, "XD-20") was used to measure the pattern line width of a mask with a width of 10 μm.

Pattern linearity: The 10 μm mask pattern after post-baking was observed with an optical microscope, and the case where peeling of the substrate or the roughness of the pattern edge part was not confirmed was evaluated as ○, and the case where partially confirmed was evaluated as △. All confirmed cases are evaluated as ×.

In addition, the pattern line width and pattern linearity were evaluated in the case of BT+10 seconds and BT+20 seconds.

＜Evaluation of OD/μm＞

Using a spin coater, apply the obtained photosensitive resin composition to a glass substrate (Corning 1737) of 125 mm×125 mm in such a way that the film thickness after baking becomes 1.1 μm, at 90°C Pre-bake for 1 minute. Then, without covering the negative mask, an ultra-high pressure mercury lamp with an i-ray illuminance of 30 mW/cm ^{2 was used to irradiate ultraviolet rays of 80 mJ/cm 2} to perform a photohardening reaction.

Then, the exposed coated plate was developed with ^{a spray pressure of 1 kgf/cm 2} at a spray pressure of 1 kgf/cm 2 at 25° C. for 60 seconds, and then spray-washed at a pressure of ^{5 kgf/cm 2 with hot air drying.} The machine is post-baked at 120°C for 60 minutes. A Macbeth transmission densitometer was used to evaluate the OD value of the coated plate. In addition, the film thickness of the light-shielding film formed on the coated plate was measured, and the value obtained by dividing the OD value by the film thickness was taken as OD/μm.

＜Evaluation of solvent resistance＞

Using the coated plate (glass plate with light-shielding film) produced in the same manner as in the OD evaluation, the solvent resistance of the formed coating film (light-shielding film) was evaluated. Use rags immersed in PGMEA or cyclohexanone (anone) to rub continuously to observe the surface state, and record the number of rubbing times when the coating film surface is dissolved or softened and damaged. The case where the number of times when any solvent is used is 20 times or more is regarded as solvent resistance ○, and the case of less than 20 times is regarded as solvent resistance ×.

＜Stability with time＞

Relative to the initial solution viscosity of the prepared photosensitive resin solution, the case where the viscosity of the solution after being left at room temperature 23°C for 5 days increased by more than 1.5 times the initial solution viscosity was regarded as ×, and the case where it was less than 1.5 times was regarded as 〇.

※關於圖案線寬及圖案直線性的評價，左欄以BT＋10秒實施評價，右欄以BT＋20秒實施評價[Table 2]

※As for the evaluation of pattern line width and pattern linearity, the left column will be evaluated by BT + 10 seconds, and the right column will be evaluated by BT + 20 seconds.

※關於圖案線寬及圖案直線性的評價，左欄以BT＋10秒實施評價，右欄以BT＋20秒實施評價[table 3]

※As for the evaluation of pattern line width and pattern linearity, the left column will be evaluated by BT + 10 seconds, and the right column will be evaluated by BT + 20 seconds.

If the photosensitive resin composition solution for a light-shielding film of the present invention is used, as shown in Examples 1 to 6, even when post-baking is performed at a low temperature of 120° C., the linearity of the pattern is maintained, and the PGMEA can be formed. Or a light-shielding film pattern with sufficient solvent resistance of cyclohexanone, and also sufficient storage stability as a photosensitive resin composition solution.

On the other hand, as in Comparative Example 1, if a difunctional monomer is used as the photopolymerizable monomer, the crosslink density of the cured film after post-baking cannot be sufficiently obtained, and the pattern is straight when the development time is slightly extended. The performance deteriorates and the solvent resistance is also insufficient. As in Comparative Example 2, if a peroxide-based polymerization initiator is used instead of an azo-based polymerization initiator in order to impart thermal radical polymerizability, the storage stability as a photosensitive resin composition solution is insufficient. Like Comparative Example 3, when the azo polymerization initiator is not added, when the post-baking temperature is low, sufficient solvent resistance cannot be obtained. Like Comparative Example 4, if an acrylic copolymerized compound instead of the compound of the general formula (II) is used as the polymerizable unsaturated group-containing alkali-soluble resin, the crosslinking is not sufficiently performed at a low post-baking temperature , A pattern with sufficiently good linearity cannot be obtained, and solvent resistance is also insufficient.

[Industrial availability]

The photosensitive resin composition for a light-shielding film of the present invention can be formed with a line width of 5 μm to 15 μm, especially 10 μm, even if the process of manufacturing the light-shielding film does not include a step of thermosetting at a temperature exceeding 160°C. A light-shielding film (light-shielding pattern) that is excellent in developing adhesiveness or linearity and good solvent resistance in the following cases. Therefore, it is possible to form a light-shielding film having such characteristics as a resin film made of PET, PEN, etc., having a heat-resistant temperature of 160° C. or less, or an element including an organic EL or organic TFT on a glass substrate or a silicon wafer.

That is, the photosensitive resin composition for a light-shielding film of the present invention is suitable for providing a black matrix, a partition material, and a spacer having a light-shielding function, which are necessary for forming a color filter or an organic EL picture element, on a substrate with a low heat resistance temperature, for example. A light-shielding film such as a column spacer, or a light-shielding film such as a bezel part necessary for forming a touch screen. These substrates with a light-shielding film (ie, display substrates) can be used to manufacture liquid crystals Or display devices such as organic EL, or used to manufacture solid-state imaging elements such as Complementary Metal Oxide Semiconductor (CMOS).

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the relevant technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be subject to those defined by the attached patent application scope.

without

without

Claims (6)

A photosensitive resin composition for a light-shielding film characterized by containing the following (A) components to (E) components as essential components, and (A) a polymer-containing polymer having a structure of an epoxy (meth)acrylate acid adduct Alkali-soluble resins with sexual unsaturated groups; (B) photopolymerizable monomers with at least three ethylenically unsaturated bonds; (C) oxime ester-based polymerization initiators; (D) azo-based polymerization initiators, wherein The azo-based polymerization initiator is 1,1'-azobis(1-acetoxy-1-phenylethane); and (E) is selected from black organic pigments, mixed color organic pigments and light-shielding materials. One or more shading components in the group. The photosensitive resin composition for a light-shielding film as described in claim 1, wherein the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is represented by the following general formula (II),

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, and A represents -CO- , -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 茀-9,9-diyl Or directly bonded, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z-(COOH) _m , where the Z of -OC-Z-(COOH) _m represents For divalent carboxylic acid residues or trivalent carboxylic acid residues, m represents the number of 1 or 2, and n represents an integer of 1-20. The photosensitive resin composition for a light-shielding film as described in item 1 or item 2 of the scope of patent application, wherein the mass ratio (A)/(B) of the component (A) to the component (B) is 50/50~ 90/10, relative to the total of 100 parts by mass of the (A) component and (B) component, the (C) component is 2 parts by mass to 30 parts by mass, and the (D) component is 1 part by mass to 20 parts by mass, in The solid content containing the component which becomes a solid content by the photohardening of the photosensitive resin composition for light-shielding films contains 40 mass%-70 mass% of (E) component. The photosensitive resin composition for a light-shielding film as described in the 1st or 2nd patent application range whose (E) component is carbon black. A substrate for a display, which is a substrate for a display having a light-shielding film on a substrate with a heat-resistant temperature of 160°C or less, the light-shielding film being used for a light-shielding film containing the following components (A) to (E) as essential components The photosensitive resin composition is cured, (A) a polymerizable unsaturated group-containing alkali-soluble resin having the structure of an epoxy (meth)acrylate acid adduct; (B) having at least three ethylenic unsaturations Bond photopolymerizable monomer; (C) oxime ester-based polymerization initiator; (D) azo-based polymerization initiator, wherein the azo-based polymerization initiator is 1,1'-azobis(1-ethyl (Ethoxy-1-phenylethane); and (E) one or more light-shielding components selected from the group consisting of black organic pigments, color-mixed organic pigments, and light-shielding materials. A method for manufacturing a substrate for a display, which is a method for manufacturing a substrate for a display having a light-shielding film on a substrate with a heat-resistant temperature of 160°C or less, and a light-shielding film containing the following components (A) to (E) as essential components The photosensitive resin composition is applied to the substrate, exposed through a photomask, and the unexposed area is removed by development, and then heated at 160°C or less to form a light-shielding film with a predetermined pattern, (A) has epoxy (former Base) Alkali-soluble resins containing polymerizable unsaturated groups with the structure of acrylate acid adducts; (B) photopolymerizable monomers having at least three ethylenically unsaturated bonds; (C) oxime ester-based polymerization initiators (D) An azo-based polymerization initiator, wherein the azo-based polymerization initiator is 1,1'-azobis(1-acetoxy-1-phenylethane); and (E) One or more light-shielding components in the group consisting of free black organic pigments, mixed-color organic pigments, and light-shielding materials.