TW201531804A - Photosensitive resin composition for light shielding film and cured product using the same - Google Patents

Abstract

An objective of this invention is to provide a photosensitive resin composition for light shielding film capable of obtaining a coating film having high fineness, high light shielding, and sufficiently secured development adhesion property even formed in fine line so as to have an excellent adhesion with glass substrate. Provided is a photosensitive resin composition for light shielding film comprising: (A) an alkali soluble resin contains predetermined polymerizable unsaturated group, (B) a photo polymerizable monomer having at least one ethylene unsaturated bond, (C) a photo polymerization initiator, and (D) a shielding component, wherein, the composition comprises (A)/(B) in weight ratio is 50/50 to 90/10, contains 2 to 30 part by weight of (C) component with resects to 100 part by weight of total amount of (A) component and (B) component, and contains a compound represented by the following general formula (I) as the photo polymerization initiator of component (C).

Description

Photosensitive resin composition for light-shielding film and cured product thereof

The present invention relates to a photosensitive resin composition for a light-shielding film and a cured product thereof, and more particularly to a photosensitive resin composition for a light-shielding film of an alkali aqueous solution development type which is suitable for forming a fine light-shielding film on a transparent substrate and hardening thereof The hardened film is suitable for use in forming a color filter or a touch panel.

The color liquid crystal display device uses a liquid crystal portion and a color filter for controlling the amount of light penetration or reflection as constituent elements, and the method for manufacturing the color filter is usually formed on the surface of a transparent substrate such as glass or plastic sheet. A black matrix, followed by a method of forming a color pattern of red, green, and blue in a streak or mosaic pattern.

In recent years, color liquid crystal display devices have begun to be used in various fields such as liquid crystal televisions, liquid crystal screens, and color liquid crystal mobile phones. A color filter is one of important components that affects the visibility of a color liquid crystal display device. In order to improve visibility, that is, in order to obtain a clear image, It is necessary to make the color of red (R), green (G), and blue (B) constituting the color filter high in purity beyond the current state, and at the same time, it is necessary to achieve high light-shielding in the black matrix, and therefore, it is necessary to be photosensitive. The resin composition is added with more coloring agents than before.

In addition, in recent years, small and medium-sized panels such as smart mobile phones require ultra-high definition (Pixel Per Inch 400 or more) technology for obtaining full HD (Full HD) resolution. High definition has become a necessary technology trend. In order to achieve high definition, it is necessary to make the size of each of the red, green, and blue pixels finer. However, in terms of high brightness, it is necessary to prevent the aperture ratio of the color filter (the RGB pixel penetrated by the backlight). The area ratio is reduced, and at the same time, the refinement of the black matrix is also pursued. That is, the line width of the black matrix has been mainly 6 to 8 μm in the past, but recently it has been required to be 4 to 5 μm.

Further, in order to increase the brightness, there is a tendency to improve the backlight intensity. Accordingly, in order to prevent light leakage from the black matrix, it is necessary to make the black matrix around RGB high in light shielding. In order to ensure high light shielding, the film thickness of the black matrix may be increased. However, if the film thickness is increased, the thickness of the black matrix in the surface of the mother glass is easily affected by the development process. The stagger will become bigger. In particular, in the case of a thin line of 4 to 5 μm, the variation in line width greatly affects the display performance such as generation of a stain. Therefore, in order to ensure the opacity of the target with a thin film thickness as much as possible, it is necessary to increase the light-shielding property per unit film thickness. However, in general, the content of the black pigment in the resin composition is increased. As a result, the proportion of the binder resin or the acrylate component which contributes to the hardenability is relatively small, and the coating film becomes difficult. Fully hardened, the adhesion between the coating film and the glass substrate is reduced, and it becomes easy to occur Peeling and other issues.

However, as a durability test (reliability test) of a liquid crystal panel, a PCT (Pressure Cooker Test) is generally used. This test method is carried out under the so-called severe conditions of a temperature of 121 ° C, a humidity of 100%, and a gas pressure of 2 atm. The liquid crystal panel was left for several hours, and it was confirmed whether or not the sealed liquid crystal leaked out between the color filter substrate and the TFT substrate of the liquid crystal panel. The black matrix exists between the red, green and blue colors. In addition to the effect of improving contrast, it also functions as a light-shielding film outside the color filter. One part of the outer frame light-shielding film is via a sealing material. The opposite substrates are attached to each other. Therefore, it is also required that the black matrix has a high adhesion strength such as peeling off from the glass substrate even under severe conditions such as PCT. In particular, in recent years, in order to improve the visibility of the liquid crystal panel, the frame light-shielding film has a high demand for high light-shielding.

As described above, it is required that the photosensitive resin composition having a large content ratio of the light-shielding material and being difficult to be photo-cured is required to obtain a pattern size stability and pattern adhesion at a low exposure amount with a wide development margin. The fine line pattern having good sharpness and the sharpness of the edge shape of the pattern, and the black matrix and the outer frame light-shielding film having high adhesion to the glass substrate and good quality even in a durability test such as PCT. Further, for the same purpose as the color filter outer frame light-shielding film, the demand for forming a light-shielding film on the outer frame of the touch panel or the like is also increased.

Then, for example, Patent Documents 1 to 3 have proposed a photosensitive resin composition for a black matrix containing an oxime ester-based compound as a high-sensitivity photopolymerization initiator. However, it is more widely developed When the margin is obtained at a low exposure amount, which is excellent in pattern dimensional stability, pattern adhesion, and sharpness of the edge shape of the pattern, it is difficult to express sufficient performance, and there is no such thing as in the PCT. Specific description of the adhesion in the durability test.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-242279

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2006-53569

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-100955

The present invention has been made in view of the above-mentioned problems, and an object of the invention is to provide a photosensitive resin composition for a light-shielding film which maintains high definition and high light-shielding in a photosensitive resin composition, and even when a fine line of, for example, 5 μm is formed. It also ensures sufficient development adhesion and excellent adhesion to a glass substrate. The present invention provides a cured product of a light-shielding film pattern formed by photolithography using the photosensitive resin composition, and further provides a color filter and a touch panel including the cured product.

In order to solve the above-mentioned problems, the present inventors have found that an oxime-based photopolymerization initiator having a specific chemical structure is formulated as an alkali-soluble resin containing a polymerizable unsaturated group, and photopolymerization is carried out. The photopolymerization initiator of the photosensitive resin composition of the monomer, the photopolymerization initiator, and the light-shielding component can maintain high definition and high light-shielding, and can sufficiently ensure development adhesion when forming a fine line. The present invention is completed by a light-shielding film which is excellent in adhesion to a glass substrate.

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

(1) A photosensitive resin composition for a light-shielding film comprising the following (A) to (D) as essential components: (A) an alkali-soluble resin containing a polymerizable unsaturated group, which has two or more a reaction of a compound of an epoxy group and a reaction of (meth)acrylic acid with a polycarboxylic acid or an anhydride thereof, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (C) photopolymerization a starter, and (D) one or more light-shielding components selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material; wherein the weight ratio of the component (A) to the component (B) is (A) / (B) is 50/50 to 90/10, and contains 100 parts by weight of the component (A) and (B), and contains 2 to 30 parts by weight of the component (C), and contains the following general formula (I) The compound represented as a photopolymerization initiator of the component (C) However, in the formula (I), R ₁ and R _{2 each} represent an alkyl group having 1 to 20 carbon atoms C or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group may further contain an ether bond. Further, a part of the hydrogen atom in the alkyl group or the aryl group may be substituted with a substituent represented by a substituent having a carbon atom C of 2 to 12 alkenyl groups and a carbon atom C of 4 to 8 a cycloalkenyl group, an alkynyl group having 2 to 12 carbon atoms C, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, an alkoxy group having a carbon atom C of 1 to 5 which may be substituted by halogen Or a halogen; R ₃ represents an aryl group having 6 to 20 carbon atoms C or a heteroaryl group having 5 to 20 carbon atoms C.

(2) The photosensitive resin composition for a light-shielding film according to (1), wherein the photopolymerization initiator of the component (C) contains a compound represented by the following formula (II) However, in the formula (II), R ₁ and R _{2 each} represent an alkyl group having 1 to 20 carbon atoms C or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group may further contain an ether bond. Further, a part of the hydrogen atom in the alkyl group or the aryl group may be substituted with a substituent represented by a substituent having a carbon atom C of 2 to 12 alkenyl groups and a carbon atom C of 4 to 8 a cycloalkenyl group, an alkynyl group having 2 to 12 carbon atoms C, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, an alkoxy group having a carbon atom C of 1 to 5 which may be substituted by halogen Base or halogen.

(3) The photosensitive resin composition for a light-shielding film according to (1), wherein the photopolymerization initiator of the component (C) contains a compound represented by the following formula (III) However, in the formula (III), R ₄ and R ₅ independently represent a hydrogen atom, -O-CH ₃ , -O-CH ₂ CH ₃ , -O-(CH ₂ ) _n+1 CH ₃ , -O -CH ₂ CF ₃ or -O-CH ₂ (CF ₂ ) _n CHF ₂ ; however, either R ₄ or R ₅ is a hydrogen atom; n is an integer from 1 to 3.

(4) The photosensitive resin composition for a light-shielding film according to (1), wherein the photopolymerization initiator of the component (C) contains a compound represented by the following formula (IV)

(5) The photosensitive resin composition for a light-shielding film according to any one of (1) to (4), wherein a compound represented by the following formula (V) and (meth)acrylic acid are used. The alkali-soluble resin containing a polymerizable unsaturated group obtained by further reacting a reactant with a polyvalent carboxylic acid or an anhydride thereof as the component (A) However, in the general formula (V), R ₆ and R ₇ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents -CO-, -SO ₂ -, -C(CF). ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 茀-9,9-diyl, or a single bond, l is 0 to 10 figures.

(6) The photosensitive resin composition for a light-shielding film according to any one of (1) to (5), wherein the solid component in the photosensitive resin composition for a light-shielding film is in the component (D) The content of the light-shielding component is 40 to 70% by mass.

(7) The photosensitive resin composition for a light-shielding film according to any one of (1), wherein (D) the light-shielding component is carbon black.

(8) A coating film formed by curing the light-shielding film according to any one of (1) to (7).

(9) A color filter comprising: the photosensitive resin composition for a light-shielding film according to any one of (1) to (7), which is applied onto a transparent substrate, and pre-bake Thereafter, a light-shielding film produced by exposure by an ultraviolet exposure apparatus, development by an aqueous alkali solution, and post-bake was performed.

(10) A touch panel comprising: the photosensitive resin composition for a light-shielding film according to any one of (1) to (7), which is applied onto a transparent substrate, and after pre-baking, A light-shielding film which is formed by exposure by an ultraviolet exposure apparatus, development by an aqueous alkali solution, and post-baking is performed.

The invention is described in detail below.

The alkali-soluble resin containing a polymerizable unsaturated group as the component (A) is preferably an epoxy compound having two epoxypropyl ether groups derived from bisphenol and (meth)acrylic acid ( Here, the reaction is referred to as "acrylic acid and/or methacrylic acid", and the obtained compound having a hydroxyl group is reacted with a polyvalent carboxylic acid or an anhydride thereof to obtain an acid addition product of an epoxy (meth) acrylate. The epoxy compound derived from bisphenols refers to an epoxy compound obtained by reacting bisphenols with epihalohydrin or the like. Since the component (A) has a polymerizable unsaturated double bond and a carboxyl group, it provides excellent photocurability, good developability, and patterning properties to the photosensitive resin composition, and the physical properties of the light-shielding film are improved.

A preferred example of the component (A) is derived from an epoxy compound represented by the formula (V). This epoxy compound is derived from a bisphenol, and first, a monocarboxylic acid containing an unsaturated group is reacted. And (a) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof, and a reaction product of the epoxy compound and a monocarboxylic acid containing an unsaturated group, thereby obtaining a content An alkali-soluble resin of a polymerizable unsaturated group. Hereinafter, the case where the component (A) is obtained by using the compound of the formula (V) will be described.

Examples of the bisphenol which provides the epoxy compound of the formula (V) include bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, and bis. (4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxy-3,5-dimethylphenyl)anthracene, bis(4-hydroxy- 3,5-dichlorophenyl) hydrazine, Bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane , bis(4-hydroxyphenyl)dimethyl decane, bis(4-hydroxy-3,5-dimethylphenyl)dimethyl decane, bis(4-hydroxy-3,5-dichlorophenyl) Dimethyldecane, 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-di Chlorophenyl)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) Indole, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-bis(4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3) -Bromophenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene, 9,9-bis(4-hydroxy-3-methoxyphenyl)anthracene, 9,9-double (4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3, 5-dibromophenyl) , 4,4'-biphenol, 3,3'-biphenol and the like. Among them, it is particularly preferable to use a bisphenol of the formula (V) wherein X is a -9,9-diyl group.

In order to obtain the alkali-soluble resin of (A), it is suitable to obtain an epoxy compound having two epoxypropyl ether groups by reacting the above bisphenols with epichlorohydrin. In the case of this reaction, the oligomerization of the diglycidyl ether compound is usually accompanied, so that the epoxy compound of the formula (V) is obtained. l Usually there are a plurality of values mixed, so the average value is 0 to 10 (not limited to an integer), and it is preferable that the average value of l is 0 to 3. If the value of l exceeds the upper limit, an alkali-soluble resin synthesized using the epoxy compound is used as the photosensitive resin group. When the product is formed, the viscosity of the composition becomes too large to be applied smoothly, and sufficient alkali solubility cannot be imparted, and the alkali developability is extremely poor.

Further, the alkali-soluble resin containing a polymerizable unsaturated group of the present invention may be obtained from an epoxy compound derived from the above-mentioned bisphenol, and in addition to the epoxy compound, for example, a phenol novolak type may be used. An epoxy compound having two epoxypropyl ether groups such as an epoxy compound or a cresol novolak type epoxy compound.

Next, for example, a compound of the formula (V) is reacted with acrylic acid or methacrylic acid as a monocarboxylic acid containing an unsaturated group or both, and a reactant having a hydroxyl group and (a) a dicarboxylic acid are obtained therefrom. The acid or tricarboxylic acid or anhydride thereof, and (b) the tetracarboxylic acid or its acid dianhydride are reacted. At this time, it is preferred that the molar ratio of (a)/(b) is in the range of 0.01 to 10. By this reaction, an alkali-soluble resin containing a polymerizable unsaturated group having a structure of an epoxy (meth) acrylate acid addition product is obtained.

As the (a) dicarboxylic acid or tricarboxylic acid or an anhydride thereof used in the epoxy group (meth) acrylate acid adduct, a chain hydrocarbon dicarboxylic acid or a tricarboxylic acid or an anhydride thereof and An alicyclic dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, an aromatic dicarboxylic acid or a tricarboxylic acid or an anhydride thereof. Wherein, in the case of a chain hydrocarbon dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, sebacic acid, citramalic acid ( Citramalic acid), malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc. It may also be a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof to which an arbitrary substituent is introduced. Alicyclic dicarboxylic acid Or a tricarboxylic acid or an acid anhydride thereof, for example, a compound such as cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrononanoic acid, tetrahydrofurfuric acid or norbornane dicarboxylic acid, or A dicarboxylic acid or a tricarboxylic acid or an anhydride thereof having an arbitrary substituent is introduced. Further, in the case of an aromatic dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, for example, a compound such as citric acid, isophthalic acid or trimellitic acid may be introduced. A dicarboxylic acid or a tricarboxylic acid having an optional substituent or an anhydride thereof.

Further, as the (b) tetracarboxylic acid or its acid dianhydride used in the epoxy group (meth) acrylate acid adduct, a chain hydrocarbon tetracarboxylic acid or an acid dianhydride thereof and an alicyclic ring type can be used. a tetracarboxylic acid or an acid dianhydride thereof, or an aromatic polycarboxylic acid or an acid dianhydride thereof. Wherein, in the case of a chain hydrocarbon tetracarboxylic acid or an acid dianhydride thereof, for example, butane tetracarboxylic acid, pentane tetracarboxylic acid, hexanetetracarboxylic acid, etc., and further, four may be introduced with any substituent. A carboxylic acid or its acid dianhydride. Further, in the case of an alicyclic tetracarboxylic acid or an acid dianhydride thereof, for example, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornane IV Further, a carboxylic acid or the like may be a tetracarboxylic acid or an acid dianhydride to which an arbitrary substituent is introduced. Further, examples of the aromatic tetracarboxylic acid or the acid dianhydride thereof include, for example, pyrogal acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid or acid dianhydride thereof. Further, it may be a tetracarboxylic acid or an acid dianhydride to which an arbitrary substituent is introduced.

The molar ratio (a)/(a) of the (a) dicarboxylic acid or tricarboxylic acid or anhydride thereof to (b) the tetracarboxylic acid or its acid dianhydride used in the epoxy (meth) acrylate acid adduct. b) is preferably 0.01 to 10 as described above. When the molar ratio (a)/(b) is out of the above range, the most suitable molecular weight cannot be obtained, and in the photosensitive resin composition using (A), alkali developability, heat resistance, solvent resistance, The shape of the graphic or the like deteriorates, so it is not preferable. Further, the smaller the molar ratio (a)/(b), the larger the alkali solubility and the higher the molecular weight.

The epoxy (meth) acrylate acid addition system can be obtained by a known method, for example, by the method described in JP-A-H08-278629 or JP-A-2008-9401. Manufacturing. First, as a method of reacting a monocarboxylic acid containing an unsaturated group with an epoxy compound of the formula (V), for example, a monocarboxylic acid containing a molar unsaturated group such as an epoxy group with an epoxy compound Adding to a solvent, heating to 90 to 120 ° C while blowing air in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.), stirring and reacting The method. Next, as a method of reacting a hydroxyl group of an epoxy acrylate compound of a reaction product with an acid anhydride, a predetermined amount of an epoxy acrylate compound, an acid dianhydride, and an acid anhydride are added to a solvent to cause a catalyst (bromine tetra A method of heating to 90 to 130 ° C in the presence of ethylammonium, triphenylphosphine or the like and stirring to cause a reaction.

The weight average molecular weight (Mw) of the alkali-soluble resin (A) containing a polymerizable unsaturated group is preferably in the range of from 2,000 to 50,000, more preferably from 2,000 to 7,000. When the weight average molecular weight (Mw) is less than 2,000, the adhesion of the photosensitive resin composition of (A) to the pattern at the time of development cannot be maintained, and pattern peeling occurs, and if the weight average molecular weight (Mw) exceeds 50,000. Then, the residue of the developing residue or the unexposed portion may become easily left. Further, the acid value of (A) is preferably in the range of 30 to 200 mgKOH/g. When the value is smaller than 30 mgKOH/g, alkali development using the photosensitive resin composition of (A) or special development conditions such as strong alkali is not required, and if it exceeds 200 mgKOH/g, it is used (A) Sensitivity The penetration of the alkali developer of the resin composition becomes too fast and causes peeling, which is not preferable. In addition, the alkali-soluble resin containing a polymerizable unsaturated group of (A) may be used alone or in combination of two or more.

Next, (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond may, for example, be 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. a (meth) acrylate having a hydroxyl group such as 2-ethylhexyl (meth)acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol Di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, three Hydroxymethylethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, two Pentaerythritol tetra (meth) acrylate, glyceryl (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol (Meth) acrylate, sorbitol hexa(meth) acrylate, phosphazene alkylene oxide modified hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa(methyl) Propylene Esters of (meth) acrylates may be used or two or more of these. Further, (B) the photopolymerizable single system having at least one ethylenically unsaturated bond does not have a free carboxyl group.

The blending ratio of the components (A) and (B) is preferably 50/50 to 90/10 by weight ratio (A)/(B), and preferably 60/40 to 80/20. If the blending ratio of the component (A) and the component (B) is less than 50/50, the cured product after photohardening becomes brittle, and the acid value of the coating film in the unexposed portion is low, so The solubility of the alkali developing solution is lowered, and there is a problem that the edge of the pattern may be staggered and cannot be clearly displayed, and if it is more than 90/10, the proportion of the photoreactive functional group of the resin is small and the crosslinked structure is small. The formation of the resin component is insufficient, and the acidity of the resin component is too high, and the solubility of the exposed portion to the alkali developer becomes high. Therefore, the pattern formed by the so-called occurrence is thinner than the target line width, and pattern defects are likely to occur. The problem is the problem.

In addition, the photopolymerization initiator of the component (C) contains a compound represented by the above formula (I) as an essential component, and generates a radical species by irradiation with ultraviolet light or the like, and is added to a photopolymerizable compound. The free radicals begin to polymerize and the composition hardens. Among them, those having a general formula (II), more preferably those having the general formula (III), further considering the point at which high sensitivity can be achieved, further 1-[11- represented by the general formula (IV). (2-ethylhexyl)-8-(2,4,6-trimethylbenzylidene)-11H-benzo[a]indazol-5-yl]-[4-(2,2,3 , 3-tetrafluoropropoxy)-phenyl]-methanone O-acetate is particularly preferred. The production of the general formula (I) is described in, for example, International Publication No. WO 2012/045736 A1.

Further, in the present invention, one or more other photopolymerization initiators or sensitizers may be used in combination with the photopolymerization initiator represented by the formula (I). Among them, as other photopolymerization initiators or sensitizers, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethyl group Acetophenones such as amphetamine, dichloroacetophenone, trichloroacetophenone, p-t-butylacetophenone, benzophenone, 2-chlorobenzophenone, p,p'- Benzophenones such as bis-dimethylaminobenzophenone; benzophenone, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Acryl ethers; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole , 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triaryl Biimidazole-based compounds such as imidazole; 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halodimethyldiazole compounds such as oxadiazoles; 2,4,6-paraxyl (trichloromethyl)-1,3,5-three 2-methyl-4,6-bis(trichloromethyl)-1,3,5-three 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-three Isohalomethyl-S-three Compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzylidene fluorene), 1-(4-phenylmercaptobenzene) Butane-1,2-dione-2-indole-o-benzoate, 1-(4-methylnonylphenyl)butane-1,2-dione-2-indole-o- Acetate, o-nonyl fluorene compounds such as 1-(4-methylnonylphenyl)butan-1-one oxime-o-acetate; benzyl dimethyl ketal, oxythiazepine Sulfur compounds such as anthrone, 2-chlorooxazepinone, 2,4-diethyloxythiazinone, 2-methyloxazepinone, 2-isopropyloxythiazolone; - anthracene such as ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl hydrazine; azobisisobutyronitrile, benzammonium peroxide, Organic peroxides such as cumene oxide; 2-mercaptobenzimidazole, 2-mercaptobenzoene a thiol compound such as azole or 2-mercaptobenzothiazole.

In addition to the photopolymerization initiator or the sensitizer, the photopolymerization initiator or the sensitizer may be used alone or in combination of two or more. Further, a compound which does not function as a photopolymerization initiator or a sensitizer itself, but which can increase the ability of a photopolymerization initiator or a sensitizer by a combination can be added. Such a compound may, for example, be a tertiary amine such as triethanolamine or triethylamine which is effective in combination with diphenylketone.

The photopolymerization initiator of the component (C) is used in an amount of 2 to 30 parts by mass, preferably 5 to 25 parts by mass, based on 100 parts by mass based on the total of the components (A) and (B). 20 parts by mass is preferred. If the proportion of the component (C) is less than 2 parts by mass, the speed of photopolymerization will be slower and the sensitivity will be lowered. On the other hand, if it exceeds 30 parts by mass, the sensitivity is too strong, and the pattern line width is relatively large. The graphic mask becomes inflated, and the line width cannot be faithfully reproduced to the mask, or the edge of the graphic may have a staggered nick and cannot be clearly presented. The photopolymerization initiator of the component (C) contains, as an essential component, a photopolymerization initiator represented by the formula (I), preferably in an amount as a photopolymerization initiation even if no other component (C) is added. The amount of the photopolymerization initiator represented by the formula (I) is preferably from 70 to 100% by mass based on the total amount of the component (C).

Among the components (D), a light-shielding component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material is preferred because it is excellent in heat resistance, light resistance, and solvent resistance. Among them, the black organic pigment may, for example, be perylene black, cyanine black, aniline black or the like. Mixed color organic pigments may be selected from: red, blue, green, purple, Two or more kinds of pigments such as yellow, cyanine, and magenta are mixed to simulate black. The light-shielding material may be an inorganic black pigment such as carbon black, chromium oxide, iron oxide or titanium black, and may be appropriately selected from two or more types, and the light-shielding property, surface smoothness, dispersion stability, and In terms of good compatibility with the resin, carbon black is preferred.

In addition, it is preferable that the light-shielding component is prepared by dispersing the dispersion medium in advance to form a light-shielding dispersion liquid, and then to prepare a photosensitive resin composition for a light-shielding film. The dispersion medium may, for example, be propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate. The blending ratio of the light-shielding component (D) in the light-shielding dispersion is 20 to 80% by mass, and preferably 40 to 70% by mass, based on the total solid content of the composition of the present invention. In this case, when an organic pigment such as aniline black or cyanine black or a carbon-based light-shielding component such as carbon black is used, it is preferably in the range of 40 to 60% by mass. When the amount is less than 20% by mass, the light shielding property may be insufficient. When the amount is more than 80% by mass, the content of the photosensitive resin which is originally a binder is reduced, which causes a problem of impairing the developing property and impairing the film forming ability.

In the photosensitive resin composition of the present invention, it is preferred to use a solvent to adjust the viscosity in addition to the above (A) to (D). Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; and acetone and methyl ethyl Ketones such as ketone, cyclohexanone and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; 赛 璐, methyl 赛 璐, ethyl 赛 璐, carbitol, methyl carbitol, ethyl carbitol, butyl carbene Alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and other glycol ethers Ethyl acetate, butyl acetate, celecoxib acetate, ethyl cyproterone acetate, butyl cyproterone acetate, carbitol acetate, ethyl carbitol acetate, Acetate such as butyl carbitol acetate, propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate can be used by dissolving and mixing to form a uniform solution-like composition.

Further, in the photosensitive resin composition of the present invention, an additive such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant may be blended as needed. . Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, gallic phenol, tert-butylcatechol, and thiophene Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate; and examples of the filler include glass fiber, cerium oxide, mica, alumina, and the like. Examples of the antifoaming agent or the leveling agent include polyfluorene-based, fluorine-based, and acrylic-based compounds. Further, examples of the surfactant include a fluorine-based surfactant and a polyfluorene-based surfactant; and as the coupling agent, 3-(epoxypropyloxy)propyltrimethoxy A decane coupling agent such as decane, 3-isocyanatopropyltriethoxy decane or 3-ureidopropyltriethoxy decane.

The photosensitive resin composition of the present invention contains the above components (A) to (D) or contains such a solvent as a main component. In the case where the solid content of the solvent is removed (the solid component includes a monomer which becomes a solid component after hardening), the total content of the components (A) to (D) is preferably 80% by mass, preferably 90% by mass or more. The amount of solvent varies depending on the target viscosity, but it becomes a photosensitive resin. The composition preferably contains a range of 70 to 90% by mass.

The photosensitive resin composition for a light-shielding film of the present invention is excellent in, for example, a resin composition for forming a color filter light-shielding film, and the light-shielding film is formed by the following photo-etching method. First, the photosensitive resin composition is applied onto a transparent substrate, and then the solvent is dried (pre-baked), and then a mask is placed on the film obtained in this manner, and the ultraviolet ray is irradiated to expose the exposed portion. After hardening, the unexposed part is further eluted by using an aqueous alkali solution to develop, form a pattern, and further post-baking (hot baking) is used as a method of post-drying.

The transparent substrate on which the photosensitive resin composition is applied may be, for example, vapor-deposited or patterned on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether oxime, etc.) in addition to the glass substrate. Transparent electrode such as ITO or gold. A method of coating a solution of a photosensitive resin composition on a transparent substrate may be a roll coater or a Land Coater coater, in addition to a conventional solution dipping method or a spray method. Any method such as a slit coater or a spinner. After the desired thickness is applied by such a method, the solvent (prebaking) is removed, thereby forming a film. The pre-baking is carried out by heating with an oven, a hot plate or the like. The preheating heating temperature and heating time are appropriately selected depending on the solvent to be used, for example, at a temperature of 60 to 110 ° C for 1 to 3 minutes.

The exposure performed after the prebaking is performed by an ultraviolet exposure device, and the resist which is only corresponding to the portion of the pattern is exposed by exposure through the photomask. The exposure device and its exposure illumination conditions can be appropriately selected, and an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a far ultraviolet lamp are used. The light source is exposed to light to cure the photosensitive resin composition in the coating film.

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

After the development, heat treatment (post-baking) is preferably carried out at a temperature of 180 to 250 ° C and a condition of 20 to 60 minutes. Thereafter, the baking is performed in order to improve the adhesion of the patterned light-shielding film to the substrate. This is the same as prebaking, and is performed by heating by an oven, a heating plate, or the like. The patterned light-shielding film of the present invention is formed through each step of the photolithography method.

The photosensitive resin composition of the present invention is suitable for forming a fine pattern by an operation such as exposure or alkali development as described above. Further, the photosensitive resin composition for a light-shielding film of the present invention can be suitably used as a coating material, and is particularly suitable for use in a color filter ink for a liquid crystal display device or a photographic element, whereby a light-shielding film formed is useful. It is used as a color filter, a black matrix for liquid crystal projection, a light-shielding film, and a light-shielding film for a touch panel.

In the photosensitive resin composition for a light-shielding film of the present invention, high-definition and high light-shielding are maintained, and when a fine line having a line width of about 5 μm is formed, for example, development adhesion can be sufficiently ensured, and adhesion to a glass substrate is also excellent.

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

(Example)

First, Synthesis Example 1 of the (A) alkali-soluble resin containing a polymerizable unsaturated group of the present invention will be described. The evaluation of the resin in the synthesis example was carried out in the following manner.

[solid component concentration]

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

Solid component concentration (% by weight) = 100 × (W _{2 -} W ₀ ) / (W _{1 -} W ₀ ).

[acid price]

Dissolve the resin solution in two The alkane was obtained by titration with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus [trade name: COM-1600, manufactured by Hiroshima Seisakusho Co., Ltd.].

[molecular weight]

By gel permeation chromatography (GPC) [Tosoh Corporation, trade name HLC-8220GPC, solvent: tetrahydrofuran, column: TSKgel SuperH-2000 (2 pieces) + TSKgel SuperH-3000 (1 piece) + TSKgel SuperH-4000 (1 piece) + TSKgel Super-H5000 (1 piece) [Tosoh Co., Ltd.], temperature: 40 ° C, speed: 0.6 ml / minute The measurement was carried out to obtain a weight average molecular weight (Mw) in terms of a standard polystyrene [PS-Eligomer Set made by Tosoh Co., Ltd.].

Further, the abbreviations used in the synthesis examples and the comparative synthesis examples are as follows.

BPFE: a reaction of 9,9-bis(4-hydroxyphenyl)fluorene with 1-chloro-2,3-1 chloromethyloxirane. Among the compounds of the formula (V), a compound wherein X is a hydrazone-9,9-diyl group, and R ₆ and R ₇ are a hydrogen atom.

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

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

TPP: triphenylphosphine

PGMEA: propylene glycol monomethyl ether acetate

[Synthesis Example 1]

In a 500 ml four-necked flask equipped with a reflux condenser, 78.63 g (0.17 mol) of BPFE, 24.50 g (0.34 mol) of acrylic acid, 0.45 g of TPP and 114 g of PGMEA were added, and the mixture was stirred under heating at 100 to 105 ° C for 12 hours. Reaction product.

Next, BPDA 25.01 g (0.085 mol) and THPA 12.93 g (0.085 mol) were added to the obtained reaction product, and the mixture was stirred under heating at 120 to 125 ° C for 6 hours to obtain an alkali-soluble resin solution containing a polymerizable unsaturated group ( A)-1. Solid component concentration system of the obtained resin solution 55.8 wt%, the acid value (calculated as solid content) was 103 mgKOH/g, and the Mw system obtained by GPC analysis was 2600.

[Comparative Synthesis Example 1]

51.65 g (0.60 mol) of methacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, and 36.33 g (0.22 mol) of cyclohexyl methacrylate were added to a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube. AIBN 5.91g and DMDG 368g were stirred under a nitrogen gas flow of 80 to 85 ° C for 8 hours to polymerize. Further, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.42 g of TPP, and 2,6-di-tert-butyl-p-cresol (2,6-di-tert-butyl-p) were added to the flask. -cresol) 0.055 g, and stirred at 80 to 85 ° C for 16 hours to obtain an alkali-soluble resin solution (A)-2 containing a polymerizable unsaturated group. The solid content concentration of the obtained alkali-soluble resin containing a polymerizable unsaturated group was 32% by mass, the acid value (in terms of solid content) was 110 mgKOH/g, and the Mw system obtained by GPC analysis was 18080.

Next, (C) Synthesis Examples 2 to 4 of the photopolymerization initiator represented by the formula (I) will be explained.

[Synthesis Example 2]

The reaction of the following six steps is carried out to synthesize a compound of the formula (IV).

Step 1:11 Synthesis of H-benzo[a]carbazole (Structure (VI))

16.22 g (0.18 mol) of phenylhydrazine and 26.89 g (0.18 mol) of α-tetralone were heated in 400 ml of ethanol in 18 ml of concentrated hydrochloric acid, and reacted under reflux for 4 hours. The reaction solution was removed by ethanol in an evaporator, and recrystallized from cyclohexane/toluene (50/50), whereby 38.25 g of a reaction product was obtained. 30.82 g (0.14 mol) of this reaction product was dissolved in 240 ml of xylene, and 9.23 g of 5% Pd/C was added as a catalyst, and it heated, and it was set on the refluxing state for 1 hour. The reaction liquid was cooled, and 240 ml of ethyl acetate was added thereto, and the catalyst was filtered with diatomaceous earth, and then the solvent was distilled off by an evaporator to precipitate crystals. This was filtered to give 24.64 g of a white solid compound. The obtained compound was confirmed by 1 H-NMR to be a compound of the formula (VI).

1H-NMR spectrum (in CDCl3): δ (ppm) = 7.30-7.70 (m, 6H), 8.00-8.20 (m, 4H), 8.80 (br, 1H)

Step 2: Synthesis of 11-(2-ethylhexyl)-11H-benzo[a]carbazole (Structure (VII))

11H-benzo[a]carbazole (structural formula (VI)) 21.72 g (0.10 mol) was dissolved in DMF 100 mL, and cooled to 0 ° C in an ice bath, then sodium hydride 4.04 g (0.101 mol) was added and kept for 1 hour. . Thereafter, 27.04 g (0.14 mol) of 1-bromo-2-ethylhexane was added, and after maintaining for 30 minutes, the ice bath was removed and the temperature was returned to room temperature, and then allowed to react overnight. The reaction solution was poured into ice water to stop the reaction, and the mixture was extracted twice with ethyl acetate. The organic phase was collected, washed with pure water and saturated brine, and then dried over magnesium sulfate. Thus, 33.23 g of a crude product in the form of a yellow liquid was obtained. The obtained crude product was not purified and used in the next reaction. The obtained crude product was identified by 1H-NMR to confirm the compound of the formula (VII).

1H-NMR spectrum (CDCl3): δ (ppm) = 0.80-0.92 (m, 6H), 1.16-1.47 (m, 8H), 2.27 (m, 1H), 4.65-4.69 (m, 2H), 7.27 (td) , 1H), 7.44 - 7.59 (m, 4H), 7.66 (d, 1H), 8.02 (d, 1H), 8.14 (d, 1H), 8.18 (d, 1H), 8.54 (d, 1H)

Step 3: 1-[11-(2-Ethylhexyl)-8-(2-fluorobenzhydryl)-11H-benzo[a]oxazol-5-yl]-(2,4,6- Synthesis of trimethylbenzene)-methanone (structural formula (VIII))

19.83 g (60 mmol) of the compound of the formula (VII) was dissolved in dichloromethane (200 mL), cooled to 0 ° C in an ice bath, and kept for a period of 30 minutes, then added 2,4,6-trimethylbenzhydryl chloride 11.51 g (63 mmol) and 8.4 g (63 mmol) of aluminum chloride were then removed from the ice bath and allowed to react to room temperature for 2 hours. After cooling to 0 ° C again in an ice bath after 2 hours, 8.4 g (63 mmol) of aluminum chloride was added, and 9.3 g (63 mmol) of 2-fluorobenzhydryl chloride was added dropwise over 2 hours through a titration funnel. After the completion of the dropwise addition, the ice bath was removed, returned to room temperature, and allowed to react at room temperature for 3 hours. The reaction solution was poured into ice water, and after the reaction was stopped, the mixture was extracted twice with dichloromethane, and the organic phase was collected, washed with pure water and saturated brine, and dried over magnesium sulfate. Thereafter, 800 mL of n-hexane was added and simultaneously removed/concentrated with dichloromethane to precipitate a white solid substance. This was filtered, washed with n-hexane and dried to give a white solid. The obtained compound was identified by 1H- and 19F-NMR to confirm the compound of the formula (VIII).

1H-NMR spectrum (CDCl3): δ (ppm) = 0.84 (t), 0.89 (t), 1.18-1.42 (m), 2.20 (s), 2.28-2.31 (m), 2.40 (s), 4.72-4.76 (m), 6.96(s), 7.19(t), 7.29(t), 7.52-7.60(m), 7.70-7.84(m), 8.38(s), 8.63-8.66(m), 9.56(d)

19F-NMR spectrum (CDCl3): δ (ppm) = -111.58

Step 4: 1-[11-(2-Ethylhexyl)-8-(2,4,6-trimethylbenzylidene)-11H-benzo[a]indazol-5-yl]-[ Synthesis of 4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone (Structure (IX))

29.94 g (50 mmol) of the compound of the formula (VIII) was dissolved in pyridine (100 mL), and 2.9 g (75 mmol) of 2,2,3,3-tetrafluoro 1-propanol and 3.0 g (75 mmol) of sodium hydroxide were added. Stir at 70 ° C for one night. After the predetermined reaction time, it was cooled to room temperature, poured into pure water, extracted with ethyl acetate, and washed with pure water and saturated brine. After adding magnesium sulfate, drying, and concentrating, the obtained crude product was purified by a silica gel column chromatography using methylene chloride as a solvent, whereby 18.13 g of a white solid was obtained. The obtained compound was identified by 1H- and 19F-NMR to confirm the compound of the formula (IX).

1H-NMR spectrum (CDCl3): δ (ppm) = 0.82 (t), 0.87 (t), 1.16-1.56(m), 2.19(s), 2.26-2.29(m), 2.39(s), 4.30-4.34(t), 4.65-4.77(m), 5.35-5.60(m), 6.95(s), 7.15-7.20(m), 7.29(t), 7.52-7.60(m), 7.70-7.77(m), 8.63-8.66(m), 9.56(d)

19F-NMR spectrum (CDCl3): δ (ppm) = -140.92, -126.30

Step 5: 1-[11-(2-Ethylhexyl)-8-(2,4,6-trimethylbenzylidene)-11H-benzo[a]indazol-5-yl]-[ Synthesis of 4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone oxime (Structure (X))

After dissolving 14.22 g (20 mmol) of the compound of the formula (IX) in pyridine (100 mL), 0.67 g (21 mmol) of hydroxylamine hydrochloride was added. Thereafter, the temperature was raised to 130 ° C to carry out a reaction for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction mixture was poured into pure water and extracted with dichloromethane. The organic phase was collected, washed with purified water and saturated brine, and then dried over magnesium sulfate. Thereafter, 13.06 g of a pale yellow solid was obtained by concentration with an evaporator. The obtained compound was identified by 1H- and 19F-NMR to confirm the compound of the formula (X).

1H-NMR spectrum (CDCl3): δ (ppm) = 0.82 (t), 0.87 (t), 1.16-1.56(m), 2.19(s), 2.26-2.29(m), 2.39(s), 4.25-4.30(t), 4.65-4.77(m), 5.30-5.55(m), 6.95(s), 7.10(d), 7.15-7.20(m), 7.45-7.60(m), 7.70-7.77(m), 8.42-8.66(m), 9.56(d)

19F-NMR spectrum (CDCl3): δ (ppm) = -140.92, -126.30

Step 6: 1-[11-(2-Ethylhexyl)-8-(2,4,6-trimethylbenzylidene)-11H-benzo[a]indazol-5-yl]-[ Synthesis of 4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone O-acetate (Structure (IV))

After dissolving 7.26 g (10 mmol) of the compound of the formula (X) in ethyl acetate (150 mL), the mixture was cooled to 0 ° C in an ice bath, and then, to the mixture, triethylamine 3.04 g (30 mmol) and acetonitrile chloride 2.35 g (30 mmol). ). After the addition, the reaction mixture was poured into pure water, and extracted with ethyl acetate. The organic phase was collected, washed with pure water and saturated brine, and then dried over magnesium sulfate. After drying, the solvent was removed to give a pale yellow to white solid, 7.03 g. The obtained compound was identified by 1H- and 19F-NMR to confirm the compound of the formula (IV).

1H-NMR spectrum (CDCl3): δ (ppm) = 0.82 (t), 0.87 (t), 1.16-1.56 (m), 2.05 (s), 2.19 (s), 2.26-2.29 (m), 2.39 (s) ), 4.30-4.34(t), 4.65-4.77(m), 5.39-5.65(tt), 6.95(s), 7.01(d), 7.15-7.20(m), 7.39(d), 7.46-7.53(m) ), 7.70-7.77(m), 8.35(s), 8.42(s), 8.63(d), 9.56(d)

19F-NMR spectrum (CDCl3): δ (ppm) = -140.66, -126.32

[Synthesis Example 3]

Using the compound of the formula (VII) obtained in the second step of Synthesis Example 2, the reaction of the following step 3 and subsequent steps is carried out to synthesize a compound of the formula (XII) which is one of the compounds of the formula (I).

Step 3: 1-[11-(2-Ethylhexyl)-5-(2,4,6-trimethylbenzylidene)-11H-benzo[a]carbazole-8-yl]-ethanone Synthesis of (Structure (XI))

The compound of the formula (VII) (4.18 g; 12.6 mmol) was dissolved in dichloromethane (40 mL) and cooled to 0 ° C in an ice bath, and then, after being kept for 30 minutes, 2,4,6-trimethylbenzhydrazide was added. Chlorine (2.38 g; 13.0 mmol) and aluminum chloride (1.77 g; 13.3 mmol) were added, and then the ice bath was removed and returned to room temperature, and allowed to react for 2 hours. Thereafter, after cooling again to 0 ° C in an ice bath, aluminum chloride (1.77 g; 13.3 mmol) was added, and toluene chloride (1.02 g; 13.0 mmol) was added dropwise over 30 minutes through a titration funnel. After the completion of the dropwise addition, the ice bath was removed and returned to room temperature, and allowed to react at room temperature for 3 hours.

The reaction solution was poured into ice water to stop the reaction, and the mixture was extracted twice with dichloromethane. The organic layer was collected, washed with purified water and brine, and dried over magnesium sulfate. Thereafter, 230 mL of n-hexane was added and simultaneously removed/concentrated with dichloromethane to precipitate a white solid substance.

This was filtered, washed with n-hexane and dried to give a white solid material (yield: 4.91 g; yield: 75.0%).

The obtained compound was identified by ¹ H-NMR.

¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.82 (t), 0.90 (t), 1.18-1.45 (m), 2.20 (s), 2.29-2.30 (m), 2.41 (s), 2.72 ( s), 4.74 - 4.77 (m), 6.98 (s), 7.58 (d), 7.70 - 7.79 (m), 8.10 (dd), 8.39 (s), 8.60 (d), 8.64 (d), 9.53 (d) ).

Step 4: 1-[11-(2-Ethylhexyl)-5-(2,4,6-trimethylbenzylidene)-11H-benzo[a]carbazol-8-yl]-B Synthesis of ketooxime O-acetate (structural formula (XII))

After dissolving the compound of the formula (X1) (4.91 g; 9.49 mmol) in toluene (10 mL) and pyridine (2 mL), the mixture was heated to 80 ° C, and sodium acetate (0.82 g; 10.0 mmol) and hydroxylamine hydrochloride (0.69 g; 10.0 mmol), stirred at 100 ° C for one night. Thereafter, the mixture was cooled to 0 ° C in an ice bath, and then triethylamine (2.88 g; 28.5 mmol) and acetonitrile (0.77 g; 9.8 mmol) were added, and the mixture was allowed to react at room temperature for 2 hours. Thereafter, the reaction solution was poured into pure water, extracted with toluene, and organic was collected. After washing, wash with pure water and saturated saline. The washing liquid was dried over magnesium sulfate and concentrated, and the crude product was washed with tri-butyl butyl ether to give a white solid (yield: 3.30 g, yield: 60.5%).

The obtained compound was identified by ¹ H-NMR.

¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.82 (t), 0.87 (t), 1.19-1.39 (m), 2.26 (s), 2.27-2.30 (m), 2.29 (s), 2.39 ( s), 2.50 (s), 4.72-4.76 (m), 6.96 (s), 7.16-7.18 (m), 7.24-7.27 (m), 7.57 (d), 7.69-7.77 (m), 7.87 (dd) , 8.31(s), 8.38(s), 8.64(d), 9.53(d).

[Synthesis Example 4]

The compound of the formula (VII) obtained in the second step of Synthesis Example 2 is subjected to the reaction of the following step 3 to synthesize a compound of the formula (XV) which is one of the compounds of the formula (I).

Step 3: 1-[11-(2-Ethylhexyl)-8-(2-ethoxybenzhydryl)-11H-benzo[a]oxazol-5-yl]-(2,4, Synthesis of 6-trimethylbenzene)-methanone (structural formula (XIII))

The compound of formula (VII) (4.18 g; 12.6 mmol) was dissolved in dichloro Methane (40 mL) was cooled to 0 ° C in an ice-bath, and then, for 30 minutes, 2,4,6-trimethylbenzhydrin chloride (2.38 g; 13.0 mmol) and aluminum chloride (1.77 g; 13.3 mmol) were added. Thereafter, after removing the ice bath and returning to room temperature, it was allowed to react for 2 hours. Thereafter, after cooling again to 0 ° C in an ice bath, aluminum chloride (1.77 g; 13.3 mmol) was added, and 2-ethoxybenzylguanidinium chloride (2.41 g; 13.0 mmol) was added dropwise thereto over 30 minutes through a titration funnel. . After the completion of the dropwise addition, the ice bath was removed and returned to room temperature, and allowed to react at room temperature for 3 hours.

The reaction solution was poured into ice water to stop the reaction, and the mixture was extracted twice with dichloromethane. The organic layer was collected, washed with purified water and brine, and dried over magnesium sulfate. Thereafter, 230 mL of n-hexane was added and simultaneously removed/concentrated with dichloromethane to precipitate a white solid substance.

This was filtered, washed with n-hexane and dried to give a white solid material (yield: 4.71 g; yield: 72.0%).

The obtained compound was identified by ¹ H-NMR.

¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.78-0.90 (m), 1.15 - 1.42 (m), 2.06 (s) 2.07 (s), 2.18 (s), 2.19 (s), 2.22 - 2.32 (m), 2.38(s), 2.39(s), 3.74(q), 4.00(q), 4.69-4.76(m), 6.84(d), 6.94(s), 7.00-7.05(m),7.42- 7.51(m), 7.28(d), 7.67-7.76(m), 8.20(s), 8.30(s), 8.36-8.40(m), 8.62(d), 9.54(d), 9.60(d).

Step 4: 1-[11-(2-Ethylhexyl)-8-(2-ethoxybenzhydryl)-11H-benzo[a]oxazol-5-yl]-(2,4, Synthesis of 6-trimethylbenzene)-methanone (Structure (XIV))

After dissolving the compound of the formula (XIII) (4.71 g; 9.11 mmol) in pyridine (5 mL), hydroxylamine hydrochloride (0.76 g; 10.9 mmol) was added and allowed to react at 130 ° C for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction mixture was poured into pure water, and extracted with dichloromethane. The organic phase was collected, washed with purified water and saturated brine, and dried over magnesium sulfate. Thereafter, it was concentrated by an evaporator, whereby a pale yellow solid (yield: 4.85 g, yield: 90.6%) was obtained.

The obtained compound was identified by ¹ H-NMR.

¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.78-0.90 (m), 1.15 - 1.42 (m), 2.06 (s) 2.07 (s), 2.18 (s), 2.19 (s), 2.22 - 2.32 (m), 2.38(s), 2.39(s), 3.74(q), 4.00(q), 4.69-4.76(m), 6.84(d), 6.94(s), 7.00-7.05(m),7.42- 7.51(m), 7.44(d), 7.67-7.76(m), 8.20(s), 8.30(s), 8.36(s), 8.52(s), 8.62(d), 9.54(d), 9.60(d) ).

Step 5: 1-[11-(2-Ethylhexyl)-8-(2-ethoxybenzhydryl)-11H-benzo[a]oxazol-5-yl]-(2,4, Synthesis of 6-trimethylbenzene)-methanone O-acetate (structural formula (XV))

After dissolving the compound of the formula (XIV) (4.85 g; 9.11 mmol) in dichloromethane (50 mL), the mixture was cooled to 0 ° C in an ice bath, and then triethylamine (2.76 g; 27.3 mmol) (0.74 g; 9.38 mmol). After the reaction, the reaction mixture was poured into pure water and extracted with ethyl acetate. The organic phase was collected, washed with purified water and saturated brine, and dried over magnesium sulfate. After drying, the solvent was evaporated to give a pale yellow to white solid (yield: 5.02 g, yield: 96.0%).

The obtained compound was identified by ¹ H-NMR.

¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.78-0.90 (m), 1.15 - 1.42 (m), 2.06 (s) 2.07 (s), 2.18 (s), 2.19 (s), 2.22 - 2.32 (m), 2.38(s), 2.39(s), 3.74(q), 4.00(q), 4.69-4.76(m), 6.84(d), 6.94(s), 7.00-7.05(m),7.42- 7.51(m), 7.60(d), 7.67-7.76(m), 8.20(s), 8.30(s), 8.36(s), 8.45(s), 8.62(d), 9.54(d), 9.60(d) ).

(Examples 1 to 4, Comparative Examples 1 to 6)

Next, the present invention will be specifically described based on examples and comparative examples in which a photosensitive resin composition and a cured product thereof are produced, but the present invention is not limited thereto. The raw materials and abbreviations used for the production of the photosensitive resin composition and the cured product of the examples and comparative examples described later are as follows.

(alkali-soluble resin containing a polymerizable unsaturated group)

(A)-1 component: the alkali-soluble resin solution obtained in the above Synthesis Example 1.

(A)-2 component: the alkali-soluble resin solution obtained in the above Comparative Synthesis Example 1

(photopolymerizable monomer)

(B): Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Industrial Co., Ltd., trade name A-TMMT)

(photopolymerization initiator)

(C)-1: a compound represented by the formula (IV) obtained in the above Synthesis Example 2

(C)-2: a compound represented by the formula (XII) obtained in the above Synthesis Example 3

(C)-3: a compound represented by the formula (XV) obtained in the above Synthesis Example 4

(C)-4: Ethylketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3- Base]-, 1-(0-ethenylhydrazine) (manufactured by BASF Japan, product name IRGACURE OXE02)

(light-shielding disperse pigment)

(D): a propylene glycol monomethyl ether acetate dispersion having a carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 5.0% by mass (solid content: 30.0%)

(decane coupling agent)

(E): 3-thiol propyl trimethoxy decane (trade name: KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.)

(solvent)

(F)-1: propylene glycol monomethyl ether acetate (F)-2: cyclohexanone

(surfactant)

(G): BYK-330 (BYK-Chemie)

The above-mentioned compounding components were blended at a ratio shown in Table 1, and the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 6 were prepared. Furthermore, the numerical values in Table 1 represent parts by mass.

[assessment]

Using the photosensitive resin compositions of the black resists of Examples 1 to 4 and Comparative Examples 1 to 6, the following evaluations were carried out. Put this The results of the evaluation are shown in Table 2.

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

Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater, and prebaked at 90 ° C for 1 minute so that the film thickness after post-baking was 1.1 μm. . Thereafter, the exposure slit was adjusted to 100 μm, a 5 μm negative mask was placed on the dried coating film, and a short-wavelength cut filter was placed on the mask (model LU0350, manufactured by Asahi Seisakusho Co., Ltd. (blocking 340 nm or less) In the case of the mercury lamp wavelength)) (Example 1, Comparative Examples 1 to 4) and the case where it was not placed (Examples 2 to 4, Comparative Examples 5 and 6), the i-line illuminance was 30 mW/cm ² . The high-pressure mercury lamp was irradiated with ultraviolet rays of 80 mJ/cm ^{2 to} carry out a photohardening reaction of the photosensitive portion.

Next, the exposed plate was applied to a 25 ° C, 0.08% potassium hydroxide aqueous solution, and developed at a pressure of 1 kgf/cm ² , and the development time (break time = BT) from the beginning of the pattern was +10 seconds, + After 15 seconds of development, a spray washing with a pressure of 5 kgf/cm ^{2 was} performed, and the unexposed portion of the coating film was removed to form a pixel pattern on the glass substrate, and thereafter, hot-drying was performed at 230 ° C for 30 minutes using a hot air dryer. Thereafter, the line width and the linearity of the pattern for the mask of the 5 μm line were evaluated. It is considered that the development is not possible even if the development time exceeds 80 seconds. Furthermore, each evaluation method is as follows.

Graphic line width: Using a length measuring microscope ("XD-20" manufactured by Nikon Corporation), the line width of the mask width of 5 μm was measured.

Linearity of the pattern: a 5 μm mask pattern after observation by a microscope, and a nicker who was not confirmed to be uneven with respect to the peeling of the substrate or the edge portion of the pattern was evaluated as ○, and it was confirmed that some of the evaluators were evaluated as Δ, and the whole was evaluated by the finder. For ×.

<OD/μm evaluation>

Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) by a spin coater, and prebaked at 90 ° C for 1 minute so that the film thickness after post-baking became 1.1 μm. . Thereafter, a short-wavelength cut filter (model LU0350, manufactured by Asahi Seiki Co., Ltd. (blocking the mercury lamp wavelength of 340 nm or less)) was placed on the dried coating film without a negative mask (Example 1, In Comparative Examples 1 to 4) and in the case where the short-wavelength cut filter was not placed (Example 2, Comparative Examples 5 and 6), ultraviolet rays of 80 mJ/cm ^{2 were} irradiated with an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW/cm ² . A photohardening reaction of the photosensitive portion is carried out.

Next, the exposed coated plate was developed in a 0.08% potassium hydroxide aqueous solution at 25 ° C in a developing pressure of 1 kgf/cm ² for 60 seconds, and then subjected to a spray washing with a pressure of 5 kgf/cm ² , and thereafter, used. After hot-drying at 230 ° C for 30 minutes in a hot air dryer, the OD of the light-irradiating portion was evaluated using a Macbeth penetration densitometer. Further, the film thickness of the light-irradiating portion was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD/μm.

<Evaluation of adhesion>

Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) by a spin coater, and prebaked at 90 ° C for 1 minute so that the film thickness after post-baking became 1.1 μm. . Thereafter, a short-wavelength cut filter (model LU0350 manufactured by Asahi Seiko Co., Ltd. (blocking the wavelength of mercury lamps below 340 nm)) was placed on the coating film without using a negative mask (Example 1, Comparison) In the cases of Examples 1 to 4) and the case where the short-wavelength cut filter was not placed (Examples 2 to 4, Comparative Examples 5 and 6), the ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW/cm ² was used for 80 mJ/cm ² . After the surface exposure, heat-drying was performed at 230 ° C for 30 minutes using a hot air dryer. Thereafter, with respect to the above-obtained post-bake substrate, the adhesion strength to the sealing glass substrate was evaluated in the following manner in accordance with the evaluation method of the 3-point bending adhesion test method of JIS K6856-1994.

The post-bake substrate and the glass substrate (Corning 1737) to which the resin composition was not applied were each cut into a short mark of 20 mm × 63 mm to prepare a test piece. The post-baking coating film and the glass substrate not coated with the photosensitive resin composition were passed through a certain amount of a sealant epoxy-based adhesive (Strike lacto bond XN-21s (manufactured by Mitsui Chemicals, Inc.)) so that the overlap width became 8 mm. In this way, the substrates (test pieces) of both sides are bonded together. The sealant epoxy adhesive in the form of a coincidence is circular and has a diameter of about 5 mm. Thereafter, the test pieces which were superposed were each subjected to prebaking at 90 ° C for 20 minutes, and then baked at 150 ° C for 2 hours, respectively, to prepare a three-point bending test piece. Further, a test sample for comparison test was prepared in the same manner as described above for the uncoated glass sheets of 20 mm × 63 mm.

In the test piece obtained as described above, the coated plate and the opposite substrate (substrate without coating) or the glass substrate for comparison test without coating were placed at two points as a center. Support (the length of the support at 2 o'clock is 3 cm), and the load was applied from the top right of the overlapping portion to the directly below at a speed of 1 mm/min using a UCT-100 manufactured by Orientec Co., Ltd. to observe the peeling surface and read the time. The load is divided by the coating area of the sealant epoxy-based adhesive, and the load per unit area is taken as the adhesion strength. Further, after performing a PCT (pressure cooker test) at 121 ° C, 100% RH, 2 atm, and 5 hours, the same adhesion strength test was carried out to evaluate the adhesion strength before and after the PCT. The adhesion strength of each composition when the adhesion strength of the glass of the uncoated resist before and after PCT was set to 100 was shown by the relative value. The evaluation of 60 or more before and after the PCT is ○, and the evaluation of less than 60 is ×.

As a result of the above, the coating film obtained from the photosensitive resin compositions of Examples 1 to 4 had good line width, pattern linearity, and adhesion strength. On the other hand, all of the coating film line widths, pattern linearities, and adhesion strengths obtained from the photosensitive resin compositions for black resists of Comparative Examples 1 to 6 were not satisfactory. Therefore, for example, even in Comparative Example 3 and Comparative Example 6, the composition having good adhesion strength is likely to be thinner in developability, and the edge of the pattern is liable to be staggered, and the linearity of the pattern is liable to be deteriorated. In particular, it is difficult to stably form a thin wire of 5 μm or less.

Claims (10)

A photosensitive resin composition for a light-shielding film comprising the following (A) to (D) as essential components: (A) an alkali-soluble resin containing a polymerizable unsaturated group, which has two or more epoxy groups a compound obtained by reacting a compound and (meth)acrylic acid with a polyvalent carboxylic acid or an anhydride thereof, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator And (D) one or more kinds of light-shielding components selected from the group consisting of black organic pigments, mixed color organic pigments, and light-shielding materials; wherein the weight ratio of (A) component to (B) component (A)/(B) And 50 to 50 to 90/10, containing 2 to 30 parts by weight of the component (C) with respect to 100 parts by weight of the total of the components (A) and (B), and containing the compound represented by the following formula (I) As a photopolymerization initiator of the component (C), However, in the formula (I), R ₁ and R _{2 each} represent an alkyl group having 1 to 20 carbon atoms C or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group may further contain an ether bond. Further, a part of the hydrogen atom in the alkyl group or the aryl group may be substituted with a substituent represented by a substituent having a carbon atom C of 2 to 12 alkenyl groups and a carbon atom C of 4 to 8 a cycloalkenyl group, an alkynyl group having 2 to 12 carbon atoms C, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, an alkoxy group having a carbon atom C of 1 to 5 which may be substituted by halogen Or a halogen; R ₃ represents an aryl group having 6 to 20 carbon atoms C or a heteroaryl group having 5 to 20 carbon atoms C. The photosensitive resin composition for a light-shielding film according to the first aspect of the invention, wherein the photopolymerization initiator of the component (C) contains a compound represented by the following formula (II). However, in the formula (II), R ₁ and R _{2 each} represent an alkyl group having 1 to 20 carbon atoms C or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group may further contain an ether bond. Further, a part of the hydrogen atom in the alkyl group or the aryl group may be substituted with a substituent represented by a substituent having a carbon atom C of 2 to 12 alkenyl groups and a carbon atom C of 4 to 8 a cycloalkenyl group, an alkynyl group having 2 to 12 carbon atoms C, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, an alkoxy group having a carbon atom C of 1 to 5 which may be substituted by halogen Base or halogen. The photosensitive resin composition for a light-shielding film according to the first aspect of the invention, wherein the photopolymerization initiator of the component (C) contains a compound represented by the following formula (III). However, in the formula (III), R ₄ and R ₅ independently represent a hydrogen atom, -O-CH ₂ CH ₃ , -O-(CH ₂ ) _n+1 CH ₃ , -O-CH ₂ CF ₃ or -O-CH ₂ (CF ₂ ) _n CHF ₂ ; however, either R ₄ or R ₅ is a hydrogen atom; n is an integer from 1 to 3. The photosensitive resin composition for a light-shielding film according to the first aspect of the invention, wherein the photopolymerization initiator of the component (C) contains a compound represented by the following formula (IV). The photosensitive resin composition for a light-shielding film according to any one of the first aspect of the invention, wherein the compound represented by the following formula (V) is used as the component (A). An alkali-soluble resin containing a polymerizable unsaturated group obtained by further reacting a reaction product of a methyl methacrylate with a polyvalent carboxylic acid or an anhydride thereof, However, in the general formula (V), R ₆ and R ₇ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and X represents -CO-, -SO ₂ -, -C(CF _{3 ). 2} -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 茀-9,9-diyl or a single bond, l is 0 to 10 digital. The photosensitive resin composition for a light-shielding film according to any one of the first aspect of the invention, wherein the light-shielding component in the component (D) is a solid component in the photosensitive resin composition for a light-shielding film. The content is 40 to 70% by mass. The photosensitive resin composition for a light-shielding film according to any one of the first aspect of the invention, wherein the (D) light-shielding component is carbon black. A coating film which is formed by curing a photosensitive resin composition for a light-shielding film according to any one of the first to seventh aspects of the invention. A color filter comprising a photosensitive resin composition for a light-shielding film according to any one of the first to seventh aspects of the invention, which is coated on a transparent substrate, pre-baked, and exposed to ultraviolet light. A light-shielding film produced by exposure of the device, development through an aqueous alkali solution, and post-baking. A touch panel having the patent application scope 1 to 7 The photosensitive resin composition for a light-shielding film according to any one of the above-mentioned items is applied onto a transparent substrate, and after pre-baking, a light-shielding film which is formed by exposure by an ultraviolet exposure apparatus, development by an aqueous alkali solution, and post-baking is performed.