KR102392964B1 - Photosensitive resin composition for light-shielding film, display substrate having the light-shielding film obtained by curing the same, and manufacturing method of display substrate - Google Patents

Abstract

(Problem) A photosensitive resin composition for a light-shielding film that is suitable for forming a light-shielding film on a plastic substrate with heat resistance of only 160°C, etc., and can obtain a light-shielding film excellent in solvent resistance and alkali resistance, a display substrate provided with a light-shielding film obtained by curing the light-shielding film; and a manufacturing method thereof.
(Solution means) (A) Alkali-soluble resin containing a polymerizable unsaturated group 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 system A photosensitive resin composition for a light-shielding film comprising a polymerization initiator, (D) an azo polymerization initiator, and (E) at least one light-shielding component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material. A method for producing a substrate for a display in which a light-shielding film having a predetermined pattern is formed by applying to the substrate, exposing and developing through a photomask, and heating at 160° C. or lower, and a display substrate obtained thereby.

Description

A photosensitive resin composition for a light-shielding film, a substrate for a display provided with a light-shielding film obtained by curing the same, and a method for manufacturing a substrate for a display TECHNICAL FIELD METHOD OF DISPLAY SUBSTRATE}

The present invention relates to a photosensitive resin composition for a light-shielding film, a substrate for a display provided with a light-shielding film obtained by curing the same, and a method for manufacturing a substrate for a display. It is related with the photosensitive resin composition for light-shielding films, the board|substrate for displays provided with the light-shielding film which is the cured film on a board|substrate, and the manufacturing method of this board|substrate for displays.

In recent years, for the purpose of making devices flexible and one-chip, for example, a light-shielding film (light-shielding pattern) is formed directly on a plastic substrate (plastic film, resin film), such as PET (polyethylene terephthalate) or PEN (polyethylene naphthalate). Alternatively, there is a demand to directly form a light-shielding film on a device including organic EL, organic TFT, or the like on a glass substrate or a silicon wafer. However, they have low heat resistance temperature of the plastic substrate itself and heat resistance temperature as a device, and generally heat resistance is only about 160°C in many cases. For this reason, when forming a light-shielding film on a plastic substrate or device, the film strength becomes insufficient at a thermal sintering temperature of 160° C. or less, and the film decreases in subsequent steps (eg, application of each RGB resist or alkali resistance, etc.) , there is a problem that problems such as surface roughness and pattern peeling occur.

Therefore, for example, in Japanese Patent Application Laid-Open No. 2003-15288 (Patent Document 1), a photosensitive resin composition containing a thermal polymerization initiator by adding an alkali-soluble resin of an acrylic copolymer to a photoinitiator as a base is used, Although substrates that have been coated, exposed, patterned, and baked at 150°C are disclosed, adhesion to the residue and substrate (peel test) is ensured, but substrates such as pattern line width, development margin, and reliability (solvent resistance, alkali resistance) are described. There are not enough of them yet.

Japanese Patent Laid-Open No. 2003-15288

The present invention was made in view of the above problems, and its purpose is to form a light-shielding film on a plastic substrate or device having a heat resistance of only 160° C. It is to provide the photosensitive resin composition for light-shielding films which can obtain the light-shielding film excellent in alkali resistance. And, it is to provide the board|substrate for displays provided with the light-shielding film which hardened the said photosensitive resin composition for light-shielding films, and its manufacturing method.

Then, the present inventors earnestly examined the photosensitive resin composition for light-shielding film which can obtain the light-shielding film excellent in solvent resistance and alkali resistance while obtaining favorable image development adhesiveness and pattern linearity by thermosetting at 160 degrees C or less, As a result, The present invention was completed by discovering that the above problems could be solved by combining two types of specific polymerization initiators, including alkali-soluble resins containing polymerizable unsaturated groups, photopolymerizable monomers, light-shielding components, and solvents.

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

(1) following (A)-(E) component,

(A) an alkali-soluble resin containing a polymerizable unsaturated group 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 polymerization initiator;

(D) an azo polymerization initiator, and

(E) at least one light blocking component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light blocking material

A photosensitive resin composition for a light-shielding film, comprising as an essential component.

(2) The photosensitive resin composition for light-shielding films 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).

[Wherein, 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 is —CO -, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9- represents a diyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ are each independently a hydrogen atom or -OC-Z-(COOH) _m (provided that Z is divalent or trivalent represents a carboxylic acid residue, m represents the number of 1 or 2), and n represents an integer of 1 to 20]

(3) In (1) or (2), the mass ratio (A)/(B) of the component (A) and the component (B) is 50/50 to 90/10, and the component (A) and ( B) While (C)component is 2-30 mass parts with respect to a total of 100 mass parts of components, (D)component is 1-20 mass parts, The component used as solid content by photocuring of the photosensitive resin composition for light-shielding films The photosensitive resin composition for light-shielding films in which 40-70 mass % of (E)component is contained in the contained solid.

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

(5) A substrate for a display provided with a light-shielding film on a substrate having a heat resistance temperature of 160° C. or less, wherein the light-shielding film contains the following components (A) to (E)

(A) an alkali-soluble resin containing a polymerizable unsaturated group 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 polymerization initiator;

(D) an azo polymerization initiator, and

(E) at least one light blocking component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light blocking material

A display substrate obtained by curing a photosensitive resin composition for a light-shielding film containing as an essential component.

(6) A method for manufacturing a display substrate having a light-shielding film on a substrate having a heat resistance temperature of 160° C. or less, the method comprising:

The following (A) - (E) component,

(A) an alkali-soluble resin containing a polymerizable unsaturated group 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 polymerization initiator;

(D) an azo polymerization initiator, and

(E) at least one light blocking component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light blocking material

A photosensitive resin composition for a light-shielding film containing as an essential component is applied on a substrate, exposed through a photomask, the unexposed portion is removed by development, and then heated at 160° C. or less to form a light-shielding film having a predetermined pattern. A method of manufacturing a substrate for a display, characterized in that it is formed.

(Effects of the Invention)

The photosensitive resin composition for a light-shielding film of the present invention has a line width of 5 to 15 µm, especially 10 µm or less, even if the process of manufacturing the light-shielding film does not include a step of thermosetting at a temperature exceeding 160 ° C. In addition, a light-shielding film (light-shielding pattern) having good solvent resistance can be formed. Therefore, a light-shielding film can be formed on a film made of a resin such as PET or PEN having a heat resistance temperature of 160°C or less, or a device having an organic EL or organic TFT formed on a glass substrate or a silicon wafer, and the like. A display substrate having a light-shielding film having the same characteristics can be obtained.

That is, as in the present invention, an alkali-soluble resin containing a polymerizable unsaturated group having a specific structure, a polymerizable monomer having three or more ethylenically unsaturated groups, an oxime ester polymerization initiator, an azo polymerization initiator, and a light-shielding component as essential components. By using a resin composition, a desired light-shielding film can be formed with respect to the low heat resistance board|substrate whose heat resistance temperature is 160 degreeC or less, and it can be set as the board|substrate for displays provided with various functions.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Each component of the photosensitive resin composition for light-shielding films of this invention is demonstrated first.

The polymerizable unsaturated group-containing alkali-soluble resin of component (A) in the present invention has a structure of an epoxy (meth) acrylate acid adduct, specifically, a compound having two or more epoxy groups and (meth) acrylic acid (which It is a compound obtained by making polyhydric carboxylic acid or its anhydride further react with the reactant of "acrylic acid and/or methacrylic acid"). When described in detail using a preferred example, (a) dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof to a compound having a hydroxyl group obtained by reacting (meth)acrylic acid with an epoxy compound represented by the following general formula (I) and (b) an epoxy (meth)acrylate acid adduct obtained by reacting tetracarboxylic acid or its acid dianhydride. The epoxy compound represented by general formula (I) means the epoxy compound obtained by making bisphenol and epihalohydrin react, or an equivalent to this. Since component (A) has both a polymerizable unsaturated double bond and a carboxyl group, the photosensitive resin composition imparts excellent photocurability, good developability, and patterning properties, thereby improving the physical properties of the light-shielding film.

However, 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 is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl group or a direct bond , and l is an average value of 0 to 10.

As bisphenols which give the epoxy compound of general formula (I), bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5 -dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, 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-hydroxy Phenyl)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) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) flu Orene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy) Roxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)flu Orene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4' -biphenol, 3,3'-biphenol, etc. are mentioned. Among these, the bisphenol which gives the epoxy compound whose A in General formula (1) is a fluorene-9,9- diyl group can be used especially preferably.

The compound of the general formula (I) for inducing the alkali-soluble resin of (A) is an epoxy compound having two glycidyl ether groups obtained by reacting the bisphenols with epichlorohydrin. In this reaction, oligomerization of the diglycidyl ether compound is generally accompanied, and l is usually an average value of 0 to 10 (not an integer) because a plurality of values are mixed, but the preferred average value of l is 0 to 3. When the average value of l exceeds the upper limit, when a photosensitive resin composition using an alkali-soluble resin synthesized using the above epoxy compound is obtained, the viscosity of the composition becomes excessively large, so that coating is not performed well or alkali solubility cannot be sufficiently imparted, resulting in alkali phenomenon The sex becomes very bad.

As the (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride used in the epoxy (meth)acrylate acid adduct, the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride or alicyclic dicarboxyl An acid or tricarboxylic acid or an acid anhydride thereof, an aromatic dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof is used. Here, as the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, for example, succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc. or an acid anhydride thereof, and dicarboxylic acid or tricarboxylic acid introduced with an optional substituent Or the acid anhydride may be sufficient. Moreover, as alicyclic dicarboxylic acid or tricarboxylic acid, or its acid anhydride, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid etc. or an acid anhydride thereof, and may also be a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof having an arbitrary substituent introduced thereto. Examples of the aromatic dicarboxylic acid or tricarboxylic acid or acid anhydride thereof include a compound such as phthalic acid, isophthalic acid, trimellitic acid, or an acid anhydride thereof, and a dicarboxylic acid having an optional substituent introduced therein. Or tricarboxylic acid or its acid anhydride may be sufficient.

Moreover, as (b) tetracarboxylic acid or its acid dianhydride used for an epoxy (meth)acrylate acid adduct, a chain hydrocarbon tetracarboxylic acid or its acid dianhydride, or an alicyclic tetracarboxylic acid or its acid dianhydride , or an aromatic polyhydric carboxylic acid or an acid dianhydride thereof is used. Here, the chain hydrocarbon tetracarboxylic acid or its acid dianhydride includes, for example, a compound such as butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, or an acid dianhydride thereof. The tetracarboxylic acid to which a substituent was introduce|transduced, or its acid dianhydride may be sufficient. Moreover, as alicyclic tetracarboxylic acid or its acid dianhydride, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid is, for example. There may be a compound such as an acid or an acid dianhydride thereof, and tetracarboxylic acid or an acid dianhydride thereof having an arbitrary substituent introduced therein may be used. Moreover, as aromatic tetracarboxylic acid and its acid dianhydride, For example, compounds, such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, or its acid dianhydride , and tetracarboxylic acid or an acid dianhydride thereof having an arbitrary substituent introduced thereto may be used.

Molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its acid dianhydride used in the epoxy (meth)acrylate acid adduct is preferably 0.01 to 10.0, more preferably 0.02 or more and less than 3.0. When the molar ratio (a)/(b) deviates from the above range, it is not preferable because the optimum molecular weight for obtaining the photosensitive resin composition having high light-shielding and high resistance of the present invention and having good optical patterning properties is not obtained. Moreover, there exists a tendency for molecular weight to become large and to be inferior to alkali solubility, so that molar ratio (a)/(b) is small.

The epoxy (meth)acrylate acid adduct can be produced by a known method according to the above process, for example, the method described in Japanese Patent Application Laid-Open No. 8-278629 or 2008-9401. First, as a method for reacting (meth)acrylic acid with the epoxy compound of the general formula (I), for example, (meth)acrylic acid equimolar to the epoxy group of the epoxy compound is added to a solvent, and a catalyst (triethylbenzylammonium chloride, 2 ,6-diisobutylphenol, etc.), there is a method of reacting by heating and stirring at 90 to 120°C while blowing air. Next, as a method of reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound as the reaction product, predetermined amounts of the epoxy acrylate compound, acid dianhydride, and acid monoanhydride are added to a solvent, and a catalyst (tetraethylammonium bromide, triphenylphos There is a method of reacting by heating and stirring at 90 to 130°C in the presence of pins, etc.).

About the weight average molecular weight (Mw) of polymerizable unsaturated group containing alkali-soluble resin (A), it is preferable that it is the range of 2000-10000, and it is more preferable that it is between 3000-7000. If the weight average molecular weight (Mw) does not satisfy 2000, pattern adhesion cannot be maintained at the time of development of the photosensitive resin composition using (A), and pattern peeling occurs, and if the weight average molecular weight (Mw) exceeds 10000, development residue or A residual film of an unexposed part becomes easy to remain. Moreover, it is good that the acid value of (A) is the range of 80-120 mgKOH/g. When this value is smaller than 80 mgKOH/g, a residue tends to remain at the time of alkali development of the photosensitive resin composition using (A), and when it exceeds 120 mgKOH/g, alkali developer to the photosensitive resin composition using (A) It is not preferable because of the excessively rapid penetration of the peeling phenomenon. In addition, about the polymerizable unsaturated group containing alkali-soluble resin of (A), even if only 1 type is used, 2 or more types of mixtures can also be used.

Next, (B) as a photopolymerizable monomer having at least three ethylenically unsaturated bonds, for example, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate , pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphagen, and (meth)acrylic acid esters such as caprolactone-modified dipentaerythritol hexa(meth)acrylate, dendrimers Type polyfunctional acrylates, hyperbranched polyfunctional acrylates, etc. can be presented, and one type or two or more types thereof can be used. Further, (B) the photopolymerizable monomer having at least three ethylenically unsaturated bonds does not have a free carboxyl group. In the present invention, a trifunctional or higher functional photopolymerizable monomer is used in order to obtain sufficient crosslinking density only by heat treatment at 160°C or lower.

As for the compounding ratio of these (A) component and (B) component, it is good that it is 50/50-90/10 in mass ratio (A)/(B), It is good that it is preferably 60/40-80/20. (A) When the mixing ratio of the component is less than 50/50 in (A)/(B), the cured product after photocuring becomes brittle, and in the unexposed part, since the acid value of the coating film is low, the solubility in an alkali developer decreases, , a problem that the pattern edge is milled and not sharp occurs, and if it is more than 90/10 in (A)/(B), the proportion of photoreactive functional groups in the resin is small, so the formation of a crosslinked structure is not sufficient, and the resin Since the acid value of the coating film on the exposed part due to the component is too high and the solubility in the alkali developer in the exposed part is increased, the formed pattern becomes thinner than the target line width, or there is a possibility that there is a problem that the pattern is more likely to occur there is.

Moreover, as an oxime ester type polymerization initiator of (C)component, it is 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyl oxime), 1-(4), for example. -(phenylsulfanyl)phenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-(methylsulfanyl)phenyl)butane-1,2-dione-2-oxime-O -acetate, 1-(4-(methylsulfanyl)phenyl)butan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone =O-acetyloxime, (9-ethyl-6-nitrocarbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone=O-acetyloxime, ( 8-{[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl}-11-(2-ethylhexyl)-11H-benzo[a]car bazol-5-yl) (2,4,6-trimethylphenyl) methanone, (2-methylphenyl) (7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-, acetyloxime; Ethanone,1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-,1-(O-acetyloxime), ethanone,1-(-9 and 9-dibutyl-7-nitro-9H-fluoren-2-yl)-,1-O-acetyloxime. Moreover, two or more types of these oxime ester type polymerization initiators can also be used.

(C) The main function of the oxime ester polymerization initiator of component is to initiate radical photopolymerization, and the amount used is preferably 2 to 30 parts by mass based on 100 parts by mass in total of component (A) and component (B), Preferably, it is good that it is 5-25 mass parts. (C) When the blending ratio of the component is less than 2 parts by mass, the speed of photopolymerization is slowed and the sensitivity is lowered. On the other hand, when it exceeds 30 parts by mass, the sensitivity is too strong and the pattern line width becomes thick with respect to the pattern mask. There is a fear that a problem arises that a faithful line width cannot be reproduced, or the pattern edge is milled and does not become sharp.

(D) As an azo polymerization initiator of a component, azobisisobutyronitrile (10-hour half-life temperature (toluene) (hereafter T _1/2 ) 65 degreeC), 2,2'- azobis (2, 4- dimethylvalonitrile) ) (T _1/2 51 ℃), dimethyl 2,2'-azobis ( ₂ -methylpropionate) (T _{1/2 6} ℃), dimethyl 1,1'-azobis (1-cyclohexanecarboxyl) rate) (T _1/2 73° C.), 1,1′-azobis (cyclohexane-1-carbonitrile) (T _1/2 88° C.), 1,1′-azobis (1-acetoxy-1) -phenylethane) (T _1/2 61 degreeC), dimethyl 2,2'- azobisisobutyrate (T _1/2 67 _degreeC ), etc. are mentioned.

(D) The function of the azo polymerization initiator of the component is mainly to improve the thermal radical polymerizability of the photosensitive resin composition, in particular to improve the physical properties of the cured product such as the hardness of the pattern formed by thermal polymerization during post-baking after exposure and development aims to make Therefore, it is necessary to add an appropriate amount of an appropriate 10-hour half-life temperature (T _1/2 ) according to post-baking conditions or the like. A preferable 10-hour half-life temperature is 50 to 80 ° C., and the amount used is preferably 1 to 20 parts by mass, preferably 2 to 15 parts by mass, based on 100 parts by mass in total of the component (A) and component (B). .

(E) Component is a light-shielding component selected from a black organic pigment, a mixed color organic pigment, or a light-shielding material, and it is good that it is excellent in heat resistance, light resistance, and solvent resistance. Here, as a black organic pigment, perylene black, aniline black, cyanine black, lactam black etc. are mentioned, for example. Examples of the mixed color organic pigment include those obtained by mixing two or more types of pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like to obtain pseudoblackness. Examples of the light-shielding material include carbon black, chromium oxide, iron oxide, and titanium black. Although two or more types of light-shielding components can be selected and used suitably, especially carbon black is preferable at the point of light-shielding property, surface smoothness, dispersion stability, and compatibility with resin. In addition, as the carbon black to be used, a carbon black whose surface is coated with a dye, a resin, etc. is suitable for making a cured product with high resistance.

Moreover, as a solvent of (F) component, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes, such as alpha- or beta-terpineol, acetone, methyl Ketones such as ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methylcarbohydrate Bitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc. glycol ethers, 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 Acetic acid esters, such as monoethyl ether acetate, etc. are mentioned, It can be set as the composition of a uniform solution state by dissolving and mixing using these.

The light-shielding component of (E) is preferably dispersed in the solvent (F) together with the dispersing agent (G) in advance to obtain a light-shielding dispersion, and then blended as a photosensitive resin composition for a light-shielding film. Here, although the solvent to disperse|distribute can be used if it enumerates in the said (F) component, For example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are used suitably. About the blending ratio of the light-shielding component of (E) which forms the light-shielding dispersion liquid, it is preferable to use in the range of 40-70 mass % with respect to the total solid of the photosensitive resin composition for light-shielding films of this invention, The range of 40-60 mass % is particularly preferred. When it is less than 40 mass %, light-shielding property will become insufficient for high light-shielding use. When it exceeds 70 mass %, since content of the photosensitive resin used as an original binder reduces, while impairing development characteristics, the undesirable problem that film-forming ability is impaired arises. Moreover, the component used as solid content by photocuring of the photosensitive resin composition for light-shielding films is also contained in the total solid of the photosensitive resin composition for light-shielding films.

As for the dispersing agent (G) to be used, well-known dispersing agents, such as various polymer dispersing agents, can be used. Specific examples of the dispersant include known compounds (compounds marketed under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) conventionally used for dispersing pigments without particular limitation. For example, cationic polymer-based dispersants, anions A high molecular weight dispersing agent, a nonionic high molecular weight dispersing agent, a pigment derivative type dispersing agent (dispersing aid), and the like can be presented. In particular, it has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to the pigment, and has an amine value of 1 to 100 mgKOH/g, a number average molecular weight A cationic polymer-based dispersant in the range of 1000 to 100,000 is suitable. About the compounding quantity of this dispersing agent, it is good that it is 1-30 mass % with respect to a light-shielding component, It is good that it is preferably 2-25 mass %.

In addition, when preparing the light-shielding dispersion liquid, in addition to the above dispersing agent, a part of the polymerizable unsaturated group-containing alkali-soluble resin of component (A) is co-dispersed to obtain a photosensitive resin composition for a light-shielding film. , It can be set as the photosensitive resin composition with favorable adhesiveness at the time of image development, and the problem of a residue also being hard to generate|occur|produce. It is preferable that it is 2-20 mass % in light-shielding dispersion liquid, and, as for the compounding quantity of (A) component in that case, it is more preferable that it is 5-15 mass %. (A) If component is less than 2 mass %, the effect of the sensitivity improvement which is an effect co-dispersed, adhesive improvement, and residue reduction cannot be acquired. In addition, if it exceeds 20 mass %, especially when the content of the light-shielding material is large, the viscosity of the light-shielding dispersion is high, and it is difficult to uniformly disperse it, or it is very time-consuming, and it is difficult to obtain a photosensitive resin composition for obtaining a coating film of high resistance. lose And the obtained light-shielding dispersion liquid is mixed with (A) component, (B) component, (C)component, and (D) component, and (F) component is added as needed and adjusted to the viscosity suitable for film forming conditions to be used for light-shielding film It can be set as the photosensitive resin composition.

In addition, in the photosensitive resin composition of the present invention, if necessary, polymerization initiators other than oxime ester-based and azo-based polymerization initiators, chain transfer agents, sensitizers, non-photosensitive resins, curing accelerators, antioxidants, plasticizers, fillers, leveling agents, anti-foaming agents, coupling agents , surfactants, pigments for color adjustment, and additives such as dyes can be blended. Examples of polymerization initiators other than oxime esters and azos include acetophenones, benzophenones, α-hydroxyalkylphenones, α-aminoalkylphenones, benzoin ethers, biimidazole compounds, and halomethyldiazole. compounds, halomethyl-s-triazine-based compounds, and the like. As a chain transfer agent and sensitizer, a compound containing a sulfur atom is generally used, and mercapto compounds and disulfide compounds are mentioned, and 1,4 Aliphatic polyfunctional thiols, such as -bis(3-mercaptobutyryloxy)butane, can be illustrated preferably. Examples of the non-photosensitive resin include bisphenol-type epoxy resins, novolac-type epoxy resins, alicyclic epoxy resins, and epoxy silicone resins. Examples of the antioxidant include hindered phenolic antioxidants and phosphorus-based antioxidants. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate, and examples of the filler include glass fiber, silica, mica, and alumina. can be heard Moreover, as surfactant, a fluorine-type surfactant, silicone type surfactant, etc. are mentioned, As a coupling agent, 3-(glycidyloxy) propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-ureide propyl tri Silane coupling agents, such as ethoxysilane, are mentioned.

The photosensitive resin composition of this invention contains the said (A)-(F) component as a main component suitably. 80 mass % of components (A) - (E) in total in solid content (solid content contains the monomer which becomes solid content after hardening) excluding a solvent, It is preferable to contain 90 mass % or more preferably. (F) Although the quantity of a solvent changes with the target viscosity, it is good to make it contained in the range of 70-90 mass % in the photosensitive resin composition.

As a formation method of the light-shielding film using the photosensitive resin composition for light-shielding films in this invention, there exist the following photolithographic methods. First, a photosensitive resin composition is applied on a plastic substrate or device, and then the solvent is dried (pre-baking), and then the resulting film is irradiated with ultraviolet rays through a photomask to cure the exposed part, and mino using an aqueous alkali solution. A method of further performing the development of eluting the light portion to form a pattern and performing post-baking (thermal firing) as post-curing is exemplified.

As a board|substrate to which the photosensitive resin composition of this invention is apply|coated, a resin film (plastic board|substrate), such as PET and PEN whose heat-resistant temperature is 160 degrees C or less, is mentioned. Here, the heat resistance temperature is a temperature at which problems such as deformation do not occur even when the substrate is exposed in a processing process such as pattern formation of a light-shielding film on the substrate. It is necessary not to exceed the glass transition temperature (Tg). Moreover, the thing which vapor-deposited or patterned electrodes, such as ITO and gold|metal|money, on the resin film can be illustrated as a board|substrate.

In addition, other examples of the substrate to which the photosensitive resin composition of the present invention is applied include those in which a thin film having high heat resistance but low heat resistance is formed on the substrate, such as a glass substrate or a silicon wafer. As a specific example, the device which formed organic electroluminescent (OLED) or organic thin film transistor (TFT) on glass or a silicon wafer is mentioned. In addition, the heat resistance temperature of the low heat resistance substrate made into the object of this invention, such as a resin film and a device, although it changes also with the kind of resin and a device, it can be generally said 100-160 degreeC.

As a method of applying the solution of the photosensitive resin composition on these substrates, any method, such as a method using a roller coater machine, a land coater machine, a slit coater machine, or a spinner machine, in addition to the known solution immersion method and spray method, can be adopted. After coating to a desired thickness by these methods, a film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in prebaking are suitably selected according to the solvent to be used, and it is performed at the temperature of 60-110 degreeC for 1-3 minutes, for example.

The exposure performed after pre-baking is performed by an ultraviolet exposure apparatus, and only the resist of the part corresponding to a pattern is photosensitized by exposing through a photomask. An exposure apparatus and its exposure irradiation conditions are appropriately selected, exposure is performed using light sources, such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and a deep ultraviolet lamp, and the photosensitive resin composition in a coating film is photocured.

Alkali development after exposure is performed for the purpose of removing the resist in an unexposed portion, and a desired pattern is formed by this development. As a developing solution suitable for this alkali development, for example, an aqueous solution of a carbonate of an alkali metal or alkaline earth metal, an aqueous solution of an alkali metal hydroxide, etc. are mentioned, In particular, 0.05-3 mass of carbonates, such as sodium carbonate, potassium carbonate, lithium carbonate, It is preferable to develop at a temperature of 23 to 28° C. using a weakly alkaline aqueous solution containing

After development, heat treatment (post-baking) is preferably performed at a temperature of 100 to 160° C. and for 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesiveness between the patterned light-shielding film and a board|substrate. This is done by heating with an oven, a hot plate, etc. similarly to pre-baking. The patterned light-shielding film of the present invention is formed through each process by 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 up to a substrate having a low heat-resistance temperature by operations such as exposure and alkali development, and in particular, a fine light-shielding film pattern is required. It is also suitable for Specifically, when a substrate with a low heat resistance temperature is used, a black matrix or partition material for forming an organic EL pixel or a black matrix for forming an organic EL pixel (for example, when forming RGB by inkjet method), a light-shielding film, a light-shielding film for a touch panel, etc. are formed for a color filter, etc. It is useful to do this, and it is possible to make the substrate to which these light-shielding films are attached as an object for display devices such as liquid crystal or organic EL or as a member object of a photographing element (that is, they are collectively referred to as a display substrate).

Example

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is concretely described based on an Example and a comparative example, this invention is not limited to these.

First, the synthesis example of (A) polymerizable unsaturated group containing alkali-soluble resin of this invention is shown. Evaluation of resin in a synthesis example was performed as follows.

[Solid content concentration]

1 g of the resin solution obtained in the synthesis example was impregnated in a glass filter [weight: W ₀ (g)], weighed [W ₁ (g)], and heated at 160 ° C. for 2 hours [W 2 (g)] from the weight [W ₂ (g)] saved by

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

[acid value]

The resin solution was dissolved in dioxane, and titrated with a 1/10 N-KOH aqueous solution was obtained using a potentiometric titrator (trade name COM-1600 manufactured by HIRANUMA SANGYO Co., Ltd.).

[Molecular Weight]

Gel permeation chromatography (GPC) [trade name HLC-8220GPC manufactured by TOSOH CORPORATION, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 pcs.) + TSKgelSuperH-3000 (1 pc.) + TSKgelSuperH-4000 (1 pc.) + TSKgelSuper- H5000 (1 piece) [manufactured by TOSOH CORPORATION], temperature: 40°C, speed: 0.6 ml/min], the weight average molecular weight (Mw) was determined as a conversion value of standard polystyrene [PS-oligomer kit manufactured by TOSOH Corporation].

In addition, the abbreviation used by the synthesis example is as follows.

BPFE: reaction of 9,9-bis(4-hydroxyphenyl)fluorene with chloromethyloxylan.

A compound of formula (I), wherein A is fluorene-9,9-diyl, R ₁ , R ₂ , R ₃ , R ₄ is hydrogen.

AA: acrylic acid

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]

BPFE 114.4g (0.23 mol), AA 33.2g (0.46 mol), PGMEA 157g and TEAB 0.48g were injected into a 500ml four-neck flask equipped with a reflux condenser, and stirred at 100-105° C. for 20 hr under heating to react. Next, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were injected into the flask, and stirred for 6 hr under heating at 120 to 125°C to obtain alkali-soluble resin (A)-1. The solid content concentration of the obtained resin solution was 56.1 wt%, the acid value (solid content conversion) was 103 mgKOH/g, and Mw by GPC analysis was 3600.

[Synthesis Example 2]

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 g of DMDG were injected into a 1000 ml four-neck flask equipped with a nitrogen inlet tube and a reflux tube, Polymerization was carried out by stirring for 8 hours at 80-85°C under a nitrogen stream. Furthermore, GMA 39.8g (0.28mol), TPP 1.44g, and DTBC 0.055g were inject|poured in the flask, and it stirred at 80-85 degreeC for 16 hr, and polymerizable unsaturated group containing (meth)acrylate resin (A)-2 was obtained. The solid content concentration of the obtained resin solution was 35.5 mass %, the acid value (solid content conversion) was 110 mgKOH/g, and Mw by GPC analysis was 18080.

Next, although this invention is concretely demonstrated based on the Example and comparative example regarding manufacture of the photosensitive resin composition for light-shielding films, and its hardened|cured material, this invention is not limited to these. Here, the raw material and abbreviation used in manufacture of the photosensitive resin composition for light-shielding films of a subsequent Example and a comparative example, and its hardened|cured material are as follows.

(Alkali-soluble resin containing polymerizable unsaturated group)

(A)-1: Alkali-soluble resin solution obtained in Synthesis Example 1 above

(A)-2: Alkali-soluble resin solution obtained in Synthesis Example 2 above

(photopolymerizable monomer)

(B)-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by TOAGOSEI CO., LTD., trade name ARONIX M-405)

(B)-2: trimethylolpropane triacrylate (manufactured by Sartomer Company, trade name SR351S)

(B)-3: EO adduct diacrylate of bisphenol A (manufactured by Kyoeisha Chemical Co., Ltd., trade name light acrylate BP-4EAL)

(Oxime ester polymerization initiator)

(C): ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (manufactured by BASF Corp., product name IRGACURE OXE02)

(Excluding azo polymerization initiators)

(D)-1: 2,2-azobisisobutyronitrile (trade name V-60 manufactured by Wako Pure Chemical Industries, Ltd.)

(D)-2: Dimethyl 2,2-azobis 2-methylpropionate) (trade name V-601 manufactured by Wako Pure Chemical Industries, Ltd.)

(D)-3: 1,1'-azobis(1-acetoxy-1-phenylethane) (Otsuka Chemical Co., Ltd. trade name: OTAZO-15)

(D)-4: benzoyl peroxide (product name manufactured by NOF CORPORATION: NYPER BMT-K40)

(Light-shielding dispersion pigment)

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

(solvent)

(F)-1: PGMEA

(F)-2: cyclohexanone

(Silane coupling agent)

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

(Surfactants)

(I): Megafac F475 (manufactured by DIC Corporation)

The said compounding component was mix|blended in the ratio shown in Table 1, and the photosensitive resin composition of Examples 1-6 and Comparative Examples 1-4 was prepared. In addition, all the numerical values in Table 1 show a mass part. In addition, (F)-1 and (F)-2 are quantities which do not contain the solvent in (A)-1 and (A)-2, and the solvent in (E).

[evaluation]

Evaluation described below was performed using the photosensitive resin composition for black resists of Examples 1-6 and Comparative Examples 1-4. These evaluation results are shown in Table 2 and Table 3.

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

Each photosensitive resin composition obtained above was coated on a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.2 µm, and prebaked at 90°C for 1 minute. After that, the exposure gap was adjusted to 100 μm, a negative photomask of line/space = 10 μm/50 μm was put on the dry coating film, and UV rays of 50 mJ/cm 2 were irradiated with an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm 2 It was irradiated and photocuring reaction of the photosensitive part was performed.

Subsequently, the exposed plate was subjected to +10 seconds and +20 seconds from the development time (break time = BT) at which a pattern began to appear with a shower pressure of 1 kgf/cm 2 by 25° C. and 0.04% aqueous potassium hydroxide solution, followed by development of 5 kgf Spraying was performed at a pressure of /cm 2 , unexposed portions of the coating film were removed to form a light-shielding film pattern on a glass substrate, and then post-baked at 120° C. for 60 minutes using a hot air dryer. The line width with respect to the mask width of a 10 micrometer line|wire of the obtained light-shielding film pattern, and pattern linearity were evaluated.

Pattern line width: The pattern line width with a mask width of 10 µm was measured using a measuring microscope (“XD-20” manufactured by Nikon Corporation).

Pattern linearity: Observe the 10 μm mask pattern after post-baking under an optical microscope, and evaluate it as ○ if peeling to the substrate or milling of the pattern edge portion was not confirmed, △ if it was partially confirmed, and × if it was confirmed throughout. did.

In addition, evaluation of the pattern line width and pattern linearity was performed in the case of BT+10 second and the case of BT+20 second.

<Evaluation of OD/㎛>

Each photosensitive resin composition obtained above was coated on a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 µm, and pre-baked at 90°C for 1 minute. Thereafter, a photocuring reaction is performed by irradiating an ultraviolet ray of 80 mJ/cm 2 with an ultra-high pressure mercury lamp with an i-line irradiance of 30 mW/cm 2 without a negative photomask.

Next, the exposed plate was developed at 25 ° C., using a 0.05% aqueous potassium hydroxide solution for 60 seconds with a shower pressure of 1 kgf/cm 2 , followed by spray water washing at a pressure of 5 kgf/cm 2 , and then at 120 ° C. using a hot air dryer. , and heat post-baked for 60 minutes. The OD value of this conductive plate was evaluated using a Macbeth permeation densitometer. Moreover, the film thickness of the light-shielding film formed in the conductive plate was measured, and the value which divided the OD value by the film thickness was made into OD/micrometer.

<Evaluation of solvent resistance>

Solvent resistance of the coating film (light-shielding film) formed using the prepared coating plate (glass plate with a light-shielding film) similarly to the time of OD evaluation was evaluated. The surface condition was observed by continuously rubbing with a rag dipped in PGMEA or cyclohexanone (anone), and the number of rubs when the surface of the coating film was dissolved or softened and scratched was recorded. When the number of times when any one solvent was used was 20 or more times, it was set as solvent resistance (circle), and when less than 20 times, it was set as solvent resistance x.

<Stability over time>

With respect to the initial solution viscosity of the prepared photosensitive resin solution, the solution viscosity after standing at room temperature of 23°C for 5 days increased by 1.5 times or more of the initial solution viscosity, x and less than 1.5 times were defined as ○.

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

On the other hand, when a bifunctional monomer is used as a photopolymerizable monomer as in Comparative Example 1, the crosslinking density of the cured film after post-baking is not sufficiently obtained, and when the development time is slightly longer, the pattern linearity deteriorates, and the solvent resistance is also insufficient. . As in Comparative Example 2, when a peroxide polymerization initiator is used instead of an azo polymerization initiator for imparting thermal radical polymerizability, storage stability as a photosensitive resin composition solution is not sufficient. When an azo polymerization initiator is not added as in Comparative Example 3, sufficient solvent resistance is not obtained when the post-baking temperature is low. As in Comparative Example 4, when an acrylic copolymer compound, not a compound of general formula (II), is used as the polymerizable unsaturated group-containing alkali-soluble resin, crosslinking does not proceed sufficiently at a low post-baking temperature, and a pattern with sufficiently good linearity is obtained. It is not obtained, and the solvent resistance is also insufficient.

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

That is, the photosensitive resin composition for a light-shielding film of the present invention, for example, a light-shielding film such as a black matrix, a barrier rib material, a column spacer having a light-shielding function, etc. necessary for forming a color filter or organic EL pixel, with respect to a substrate having a low heat resistance temperature. It is suitable for installing or installing a light-shielding film such as a frame (bezel) part required when forming a touch panel, etc. It can be used for manufacturing a solid state imaging device such as CMOS or for manufacturing a solid state imaging device such as CMOS.

Claims (6)

The following (A) - (E) component,
(A) an alkali-soluble resin containing a polymerizable unsaturated group 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 polymerization initiator;
(D) 1,1'-azobis(1-acetoxy-1-phenylethane), which is an azo polymerization initiator, and
(E) at least one light blocking component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light blocking material
A photosensitive resin composition for a light-shielding film, comprising as an essential component. The method of claim 1,
The photosensitive resin composition for light-shielding films whose polymerizable unsaturated group containing alkali-soluble resin of the said (A) component is represented by following General formula (II).

[Wherein, 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 is -CO -, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9- represents a diyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ are each independently a hydrogen atom or -OC-Z-(COOH) _m (provided that Z is divalent or trivalent represents a carboxylic acid residue, m represents the number of 1 or 2), and n represents an integer of 1 to 20] 3. The method of claim 1 or 2,
Mass ratio (A)/(B) of said (A) component and (B) component is 50/50-90/10, (C) with respect to a total of 100 mass parts of said (A) component and (B) component While a component is 2-30 mass parts, (D)component is 1-20 mass parts, and (E)component is 40-70 mass % in solid content including the component used as solid content by photocuring of the photosensitive resin composition for light-shielding films. The photosensitive resin composition for light-shielding film contained. 3. The method of claim 1 or 2,
(E) The photosensitive resin composition for light-shielding films whose component is carbon black. A display substrate having a light-shielding film on a substrate having a heat resistance temperature of 160° C. or less, the display substrate comprising:
The substrate having a heat resistance temperature of 160° C. or less is a plastic substrate, a glass substrate on which an organic EL (OLED) or an organic thin film transistor (TFT) is formed, or a silicon wafer on which an organic EL (OLED) or an organic thin film transistor (TFT) is formed,
The said light-shielding film following (A) - (E) component,
(A) an alkali-soluble resin containing a polymerizable unsaturated group 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 polymerization initiator;
(D) 1,1'-azobis(1-acetoxy-1-phenylethane), which is an azo polymerization initiator, and
(E) at least one light blocking component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light blocking material
A display substrate obtained by curing a photosensitive resin composition for a light-shielding film containing as an essential component. A method of manufacturing a display substrate having a light-shielding film on a substrate having a heat resistance temperature of 160° C. or less, the method comprising:
The substrate having a heat resistance temperature of 160° C. or less is a plastic substrate, a glass substrate on which an organic EL (OLED) or an organic thin film transistor (TFT) is formed, or a silicon wafer on which an organic EL (OLED) or an organic thin film transistor (TFT) is formed,
The following (A) to (E) components,
(A) an alkali-soluble resin containing a polymerizable unsaturated group 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 polymerization initiator;
(D) 1,1'-azobis(1-acetoxy-1-phenylethane), which is an azo polymerization initiator, and
(E) at least one light blocking component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light blocking material
A photosensitive resin composition for a light-shielding film containing as an essential component is applied on a substrate, exposed through a photomask, the unexposed portion is removed by development, and then the light-shielding film having a predetermined pattern is heated at 160° C. or less. A method of manufacturing a substrate for a display, characterized in that it is formed.