Photosensitive resin composition for light-shielding films, and light-shielding films, color filters, and display devices using the same.

Abstract

To provide a photosensitive resin composition for a light-shielding film from which a light-shielding film that can achieve both high light-shielding property and high resistance, and is excellent in development adhesion when a thin line is formed can be obtained.SOLUTION: A photosensitive resin composition for a light-shielding film contains (A) an epoxy compound, (B) a polymerizable unsaturated group-containing alkali-soluble resin, (C) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (D) a light-shielding component containing a carbon black as a light-shielding material, (E) a polymerization initiator, and (F) a solvent, as essential components, wherein the component (A) has an aromatic ring in a main chain, the number of aromatic rings to the number of glycidyl groups occupying in the component (A) is 0.5-10, and an epoxy equivalent is 100-400 g / eq.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition for light-shielding films suitable for forming a black matrix with a fine-line pattern that provides high light shielding and high resistance. [Background technology]

[0002] Color filters are one of the important components that affect the visibility of liquid crystal display devices. To improve visibility, that is, to obtain a clear image, it is necessary to increase the color purity of the red (R), green (G), and blue (B) pixels that make up the color filter, and to achieve high light shielding in the black matrix. To achieve this, a larger amount of colorant must be added to the photosensitive resin composition than before.

[0003] Carbon black is generally known as a light-shielding material for resin black matrices. However, while carbon black offers excellent light-shielding properties, its low electrical resistance can sometimes cause malfunctions in display devices. Therefore, methods have been proposed to increase the electrical resistance of the black matrix using carbon black, such as reducing the proportion of conductive carbon black or applying a material with a resin coating on the carbon black surface. However, there are limitations to the degree of light-shielding that can be achieved while maintaining sufficient patternability, making it difficult to achieve the required high level of light-shielding.

[0004] Furthermore, in light of the above-mentioned prior art, the applicant of this application has proposed a method for formulating an alkali-soluble resin containing polymerizable unsaturated groups having a specific structure and acid value as a photosensitive resin composition for light-shielding films that maintains optical density (OD) and volume resistivity while also providing excellent developability and sufficient adhesion to glass substrates even when forming fine lines of 10 μm or less (see Patent Document 1). However, even with this method, as the performance of display devices increases, the characteristics required of black matrices are also becoming increasingly demanding, leaving room for further improvement in achieving both high light shielding and high resistance. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2015-200881 [Patent Document 2] Japanese Patent Publication No. 2014-145821 [Patent Document 3] Japanese Patent Publication No. 2019-070720 [Overview of the project] [Problems that the invention aims to solve]

[0006] Therefore, in response to the above-mentioned conventional attempts, the inventors of this application further investigated photosensitive resin compositions for light-shielding films that can achieve both high light shielding and high resistance, and arrived at the following idea. In other words, while incorporating a large amount of carbon black, a light-shielding material, to achieve high light shielding, it was thought that reducing the probability of contact between carbon black particles, that is, suppressing thermal shrinkage during the heat curing of the light-shielding film, would prevent contact between carbon black particles. Furthermore, it was known that ordinary carbon black, whether untreated or oxidized, has many acidic functional groups on its surface, and it was thought that incorporating other compounds with functional groups that can preferentially react with it during the heat curing process of the light-shielding film would be beneficial, thus creating the presence of such other resins near the surface of the carbon black.

[0007] Based on this idea, we diligently investigated compounds that possess high heat resistance to suppress thermal shrinkage during heat curing, and that have functional groups that preferentially react with the acidic functional groups of carbon black during heat curing. As a result, we newly discovered that by incorporating a predetermined amount of a specific epoxy compound into a photosensitive resin composition, which has an aromatic ring in its main chain and a rigid skeleton, as well as glycidyl groups that can react with carbon black during heat curing, it is possible to achieve both high light shielding and high resistance, and to obtain a cured product (light-shielding film) that exhibits excellent developability even when forming fine lines of, for example, 3 to 8 μm in diameter.

[0008] While the applicants of this application have already proposed techniques for incorporating epoxy compounds into photosensitive resin compositions (see Patent Documents 2 and 3), the technique described in Patent Document 2 relates to a black photosensitive resin composition for touch panel applications and discloses the inclusion of a relatively large amount of epoxy compound, particularly to meet the requirement for high chemical resistance to chemicals used in the processing. Furthermore, Patent Document 3 is characterized by the essential inclusion of a curing agent and / or curing accelerator in a photosensitive resin composition for forming a resin film pattern on a plastic substrate with a heat resistance of at most 140°C, and by setting the total amount of these and the epoxy compound within a specific range. It only discloses components that are particularly essential when low-temperature curing is the goal. In other words, the compositions described in Patent Documents 2 and 3 require the above-mentioned formulation, which made it difficult to satisfy all three requirements: high light shielding, high resistance, and thinning of the wire.

[0009] Therefore, the present invention was made based on the above-mentioned findings, and its objective is to provide a photosensitive resin composition for light-shielding films that provides a cured product (light-shielding film) that achieves both high light-shielding and high resistance, and also exhibits excellent developability even when fine lines are formed.

[0010] Another object of the present application is to provide a light-shielding film formed by curing such a photosensitive resin composition for light-shielding films, and furthermore, to provide a color filter equipped with the light-shielding film and a display device equipped with the color filter. [Means for solving the problem]

[0011] In other words, the gist of this invention is as follows: [1] The following components (A) to (F), (A) Epoxy compound, (B) Alkali-soluble resin containing polymerizable unsaturated groups, (C) A photopolymerizable monomer having at least one ethylenically unsaturated bond, (D) Light-shielding components containing carbon black as a light-shielding material, (E) Photopolymerization initiator, and (F) Solvent In a photosensitive resin composition for light-shielding films containing as an essential component, The photosensitive resin composition for light-shielding films is characterized in that component (A) has an aromatic ring in its main chain, the number of aromatic rings relative to the number of glycidyl groups in component (A) is 0.5 to 10, and the epoxy equivalent is 100 to 400 g / eq. [2] The photosensitive resin composition for light-shielding films according to claim 1, characterized in that the mass ratio (B) / (C) of component (B) to component (C) is 50 / 50 to 90 / 10, component (A) is contained in parts 0.5 to 15 parts by mass per 100 parts by mass of component (D), and component (D) is contained in 40 to 70% by mass of the solid content of the photosensitive resin composition for light-shielding films. A light-shielding film characterized by being formed by curing the photosensitive resin composition for light-shielding films described in [3], [1], or [2]. A color filter characterized by having the light-shielding film described in [4] and [3]. A display device having the color filter described in [5] and [4]. [Effects of the Invention]

[0012] According to the present invention, it is possible to achieve both high light shielding and high resistance, and a photosensitive resin composition for a light shielding film can be provided that can obtain a cured product (light shielding film) having excellent development adhesion even when forming fine lines up to 3 to 8 μm, for example.

Embodiments for Carrying Out the Invention

[0013] As described above, the photosensitive resin composition for a light shielding film of the present invention contains at least (A) an epoxy compound, (B) an alkali-soluble resin containing a polymerizable unsaturated group, (C) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (D) a light shielding component using carbon black as a light shielding material, (E) a photopolymerization initiator, and (F) a solvent as essential components. Hereinafter, these components will be described in detail.

[0014] <(A) Epoxy Compound> The (A) epoxy compound in the photosensitive resin composition for a light shielding film of the present invention needs to have an aromatic ring in the main chain. By having an aromatic ring in the main chain, it becomes possible to have excellent heat resistance and mechanical properties, and it is preferable in that it can suppress heat shrinkage that occurs when forming a light shielding film by heat-curing the photosensitive resin composition for a light shielding film of the present invention using this. Here, having in the main chain means having at least one aromatic ring in the structure that becomes the skeleton of the molecule having the largest number of carbon atoms, as commonly used in the art. Further, examples of the aromatic ring include a benzene ring, a naphthalene ring, a biphenyl ring, a bisphenol ring, etc., and their structures may be unsubstituted, or may each independently have one or more substituents. The substituent may be an alkyl group or an aryl group having 1 to 10 carbon atoms, and is not particularly limited within the scope of the object of the present invention.

[0015] Here, as the component (A), it is preferable to use one having an epoxy equivalent of 100 to 400 g / eq, preferably 120 to 380 g / eq, more preferably 150 to 360 g / eq. When the epoxy equivalent is less than 100 g / eq, the reaction with the acidic functional group responsible for developing solubility contained in the component (B) may proceed, and the developability may decrease. On the contrary, when it exceeds 400 g / eq, the control of the distance between carbon blacks becomes poor, and there is a possibility that the resistance cannot be improved.

[0016] Also, for the component (A), the number of aromatic rings, as the number with respect to the glycidyl group, the number of aromatic rings / the number of glycidyl groups is 0.5 to 10, preferably 1.1 to 4, more preferably 1.3 to 4, particularly preferably 2 to 4. The number of aromatic rings here refers to the number of benzene rings. For example, for a naphthalene ring, it is 2, for biphenyl it is 2, for anthracene it is 3, and for a bisphenol fluorene ring it is 4. As the aromatic ring, a bulky one (with a large number of aromatic rings) is preferable, and those having a condensed ring structure such as a bisphenol fluorene ring or naphthalene are more preferable. When the number of aromatic rings / the number of glycidyl groups is less than 0.5, the resistance may decrease due to a decrease in heat resistance resulting from a small number of aromatic rings, or the reaction with the acidic functional group responsible for developing solubility contained in the component (B) may proceed due to a large number of glycidyl groups, and the developability may decrease. On the contrary, when the number of aromatic rings / the number of glycidyl groups exceeds 10, the control of the distance between carbon blacks becomes poor due to a small number of glycidyl groups, and there is a possibility that the resistance cannot be improved.

[0017] Here, the aforementioned aromatic ring number / glycidyl group number can be calculated from the epoxy equivalent based on the proportional relationship between the aromatic ring number / glycidyl group number and the epoxy equivalent when considering the repeating units of the epoxy compound, as shown below. In other words, although the aromatic ring number and glycidyl group number change depending on the chemical structure and repeating units of each epoxy compound, by specifically substituting some of the repeating units and understanding the relationship with the epoxy equivalent in advance, it becomes possible to calculate the aromatic ring number / glycidyl group number according to the measured epoxy equivalent. Here, as a specific example, we show the compounds listed in chemical formulas (1) to (4) below, but it is possible to determine other epoxy compounds in the same way. • Bisphenol fluorene type epoxy compound [ka] In the case of formula (1) above, the number of aromatic rings / number of glycidyl groups = (4m1+4) / 2, and for example, when m1=1, it is 4. In this case, the epoxy equivalent is 435. Similarly, when m1=2, the number of aromatic rings / number of glycidyl groups is 6, and the epoxy equivalent is 638. From this relationship, (epoxy equivalent) = 102 × (number of aromatic rings / number of glycidyl groups) + 28, so it is possible to calculate the number of aromatic rings / number of glycidyl groups from the epoxy equivalent.

[0018] • 1,6-Naphthalenediol aralkyl type epoxy compound [ka] In the case of equation (2) above, the number of aromatic rings / number of glycidyl groups = (3m2+2) / (2m2+2), and for example, when m2=1, it is 1.25. In this case, the epoxy equivalent is 162. Similarly, when m2=2, the number of aromatic rings / number of glycidyl groups is 1.33, and the epoxy equivalent is 170. From this relationship, (epoxy equivalent) = 102 × (number of aromatic rings / number of glycidyl groups) + 34.

[0019] • 1-Naphthol Aralkyl-type epoxy compound [ka] In the case of equation (3) above, the number of aromatic rings / number of glycidyl groups = (3m3+2) / (m3+1), and for example, when m3=1, it is 2.5. In this case, the epoxy equivalent is 252. Similarly, when m3=2, the number of aromatic rings / number of glycidyl groups is 2.67, and the epoxy equivalent is 269. From this relationship, (epoxy equivalent) = 102 × (number of aromatic rings / number of glycidyl groups) - 3.

[0020] • Phenol novolac type epoxy compound [ka] In the case of equation (4) above, the number of aromatic rings / number of glycidyl groups = (m4+2) / (m4+2), and regardless of the epoxy equivalent, (number of aromatic rings / number of glycidyl groups) = 1.

[0021] For component (A), it is preferable to use one with a weight-average molecular weight of 300 to 10000.

[0022] Such (A) epoxy compounds are not particularly limited as long as they have an aromatic ring in their main chain, but examples include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds, tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polyhydric carboxylic acids, copolymers of monomers having a (meth)acrylic group containing (meth)acrylic acid glycidyl as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, and epoxy compounds having a silicone skeleton. Of these, polycyclic aromatic epoxy compounds are preferred from the viewpoint of good affinity with carbon black. Furthermore, component (A) may be a single compound or a combination of multiple compounds.

[0023] The amount of component (A) to be blended is preferably 1 to 25 parts by mass, more preferably 1 to 18 parts by mass, and even more preferably 1.5 to 16 parts by mass, relative to 100 parts by mass of the total of components (B) and (C) described later. This blending ratio relative to components (B) and (C) is preferable because it allows for obtaining good patterning characteristics. Furthermore, it is preferable to blend component (A) in an amount of 0.5 to 15 parts by mass, more preferably 1 to 13 parts by mass, and even more preferably 1.0 to 9.0 parts by mass, per 100 parts by mass of component (D), which will be described later. By optimizing the amount relative to the carbon black in this way, it is possible to achieve both sufficient light shielding and resistance while maintaining good affinity with the carbon black, which is preferable.

[0024] <(B) Alkali-soluble resin containing polymerizable unsaturated groups> In the photosensitive resin composition for light-shielding films of the present invention, (B) the alkali-soluble resin containing polymerizable unsaturated groups can be used without particular limitations as long as it is a resin having polymerizable unsaturated groups and acidic groups in its molecule. However, a preferred first example is an epoxy (meth)acrylate adduct obtained by reacting a compound having two or more epoxy groups with (meth)acrylic acid (this means acrylic acid and / or methacrylic acid), and then reacting the resulting epoxy (meth)acrylate compound having hydroxyl groups with (a) dicarboxylic acid or tricarboxylic acid or its acid monoanhydride and / or (b) tetracarboxylic acid or its acid dianhydride. Examples of compounds having two or more epoxy groups that can be converted into epoxy (meth)acrylate adducts include bisphenol-type epoxy compounds and novolac-type epoxy compounds. Specifically, bisphenol-type epoxy compounds represented by the following general formula (I) can be preferred. [ka]

[0025] In general formula (I), R1, R2, R3, and R4 each independently represent a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group, and A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond. l is an integer from 0 to 10. Preferred R1, R2, R3, and R4 are hydrogen atoms, and preferred A is a fluorene-9,9-diyl group. Also, since l usually has multiple values, the average value is 0 to 10 (not necessarily an integer), but the preferred average value of l is 0 to 3.

[0026] Bisphenol-type epoxy compounds are epoxy compounds having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. This reaction generally involves oligomerization of the diglycidyl ether compound, and therefore includes epoxy compounds containing two or more bisphenol skeletons. Bisphenols used in this reaction include 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-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl) Nyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3- Chlorophenyl)propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,Examples include 9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 4,4'-biphenol, and 3,3'-biphenol. Among these, bisphenols having a fluorene-9,9-diyl group are particularly preferred.

[0027] (a) As the acid monoanhydride of a dicarboxylic acid or tricarboxylic acid to be reacted with epoxy (meth)acrylate, acid monoanhydrides of chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, or acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids can be used. Here, as the acid monoanhydrides of chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids, for example, there are acid monoanhydrides such as succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and furthermore, acid monoanhydrides of dicarboxylic acids or tricarboxylic acids to which any substituent has been introduced may also be used. Furthermore, examples of alicyclic dicarboxylic acid or tricarboxylic acid acid monoanhydrides include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chloridenic acid, hexahydrotrimellitic acid, norbornanedicarboxylic acid, and may also be acid monoanhydrides of dicarboxylic acid or tricarboxylic acid to which any substituent has been introduced. Furthermore, examples of aromatic dicarboxylic acid or tricarboxylic acid acid monoanhydrides include phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and may also be acid monoanhydrides of dicarboxylic acid or tricarboxylic acid to which any substituent has been introduced.

[0028] Furthermore, as the (b) tetracarboxylic acid dianhydride to be reacted with epoxy (meth)acrylate, a dianhydride of a chain-type hydrocarbon tetracarboxylic acid, a dianhydride of an alicyclic tetracarboxylic acid, or a dianhydride of an aromatic tetracarboxylic acid can be used. Here, as the dianhydride of a chain-type hydrocarbon tetracarboxylic acid, for example, there are dianhydrides of butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc., and furthermore, dianhydrides of tetracarboxylic acids to which any substituent has been introduced may also be used. As the dianhydride of an alicyclic tetracarboxylic acid, for example, there are dianhydrides of cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, etc., and furthermore, dianhydrides of tetracarboxylic acids to which any substituent has been introduced may also be used. Furthermore, examples of acidic dianhydrides of aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, and other acidic dianhydrides of tetracarboxylic acids to which any substituent has been introduced may also be used.

[0029] The molar ratio (a) / (b) of (a) dicarboxylic acid or tricarboxylic acid acid anhydride and (b) tetracarboxylic acid dianhydride reacted with epoxy (meth)acrylate is preferably 0.01 to 10.0, and more preferably 0.02 or more and less than 3.0. A molar ratio (a) / (b) within the above range is preferable because it is easier to obtain the optimal molecular weight for a photosensitive resin composition with good photopatternability, and alkali solubility is not impaired.

[0030] Epoxy(meth)acrylate adducts can be produced by known methods, such as those described in Japanese Patent Publication No. 8-278629 and Japanese Patent Publication No. 2008-9401. First, one method for reacting an epoxy compound with (meth)acrylic acid is to add an equimolar amount of (meth)acrylic acid to the epoxy group of the epoxy compound into a solvent and heat and stir at 90-120°C while blowing in air in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.) to allow the reaction to proceed. Next, one method for reacting the hydroxyl group of the reaction product, the epoxy acrylate compound, with an acid anhydride is to add predetermined amounts of the epoxy acrylate compound, a dianhydride, and a monoanhydride to a solvent and heat and stir at 90-130°C in the presence of a catalyst (tetraethylammonium bromide, triphenylphosphine, etc.) to allow the reaction to proceed. The epoxy acrylate adduct obtained by this method has a skeleton of general formula (II). [ka] [In formula (II), R1, R2, R3, and R4 each independently represent a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group; A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; X represents a tetravalent carboxylic acid residue; Y1 and Y2 each independently represent a hydrogen atom or -OC-Z-(COOH)m (where Z represents a divalent or trivalent carboxylic acid residue, and m represents a number from 1 to 2); and n represents an integer from 1 to 20.]

[0031] (B) Another example of component (B) is a polymer of (meth)acrylic acid, (meth)acrylic acid esters, etc., which is a polymer of a polymer containing an alkali-soluble polymeric unsaturated group obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent as the first step, reacting the copolymer with (meth)acrylic acid as the second step, and reacting it with an anhydride of a dicarboxylic acid or tricarboxylic acid as the third step.

[0032] Another example of component (B) is a urethane compound obtained by reacting a polyol compound having an ethylenically unsaturated bond in its molecule as the first component, a diol compound having a carboxyl group in its molecule as the second component, and a diisocyanate compound as the third component. For resins of this type, refer to those shown in Japanese Patent Publication No. 2017-76071.

[0033] The polymerizable unsaturated group-containing alkali-soluble resin of component (B) is preferably blended in an amount of 10 to 40% by mass in the solid content of the photosensitive resin composition for light-shielding films of the present invention, and more preferably 20 to 40% by mass. Furthermore, its weight-average molecular weight (Mw) is usually preferably between 2000 and 10000, and more preferably between 3000 and 7000. If the weight-average molecular weight (Mw) is less than 2000, the adhesion of the pattern during development cannot be maintained, and pattern peeling occurs. If the weight-average molecular weight (Mw) exceeds 10000, development residue and residual film in unexposed areas are more likely to remain. In addition, the acid value of component (B) is preferably in the range of 30 to 200 KOH mg / g. If this value is less than 30 KOH mg / g, alkaline development may not be successful, or special development conditions such as strong alkali may be required. If it exceeds 200 KOH mg / g, the penetration of the alkaline developer becomes too fast, and peeling development is more likely to occur. Furthermore, for the alkali-soluble resin containing polymerizable unsaturated groups in (A), either one type may be used, or a mixture of two or more types may be used.

[0034] <(C) Photopolymerizable monomer having at least one ethylenically unsaturated bond> In the photosensitive resin composition for light-shielding films of the present invention, (C) photopolymerizable monomer having at least one ethylenically unsaturated bond is, for example, (meth)acrylic acid esters having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri Examples of (meth)acrylic acid esters such as (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, dendritic polymers having (meth)acroyl groups, etc., can be used, and one or more of these can be used. Examples of dendritic polymers having (meth)acroyl groups include known dendritic polymers obtained by adding thiol groups from a polyvalent mercapto compound to some of the carbon-carbon double bonds in the (meth)acroyl group of a polyfunctional (meth)acrylate compound.

[0035] The component (C) can crosslink molecules of alkali-soluble resins, and to achieve this function, it is preferable to use a component having two or more ethylenically unsaturated bonds. Furthermore, the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth)acroyl groups in one molecule should be between 50 and 300.

[0036] Regarding the amount of component (C), the mixing ratio with component (B) is 50 / 50 to 90 / 10 by mass ratio (B) / (C), preferably 60 / 40 to 80 / 20. If the mixing ratio of component (B) is less than 50 / 50, the cured product after photocuring will become brittle, and the acid value of the coating film in the unexposed areas will be low, reducing its solubility in alkaline developer and potentially resulting in jagged and less sharp pattern edges. Furthermore, if the mixing ratio of component (B) is more than 90 / 10, the proportion of photoreactive functional groups in the resin will be low, resulting in insufficient cross-linking structure formation. Additionally, the acid value of the resin component may be too high, potentially increasing solubility in alkaline developer in the exposed areas, which could lead to problems such as the formed pattern being thinner than the target line width or the pattern being prone to gaps.

[0037] <(D) Light-blocking component containing carbon black as a light-blocking material> The light-shielding component (D) in the photosensitive resin composition for light-shielding films of the present invention essentially contains untreated or oxidized carbon black. Here, "untreated" means that no special surface treatment such as oxidation treatment or resin coating treatment is applied, and "oxidized treatment" means that the surface of the carbon black is treated with some kind of oxidizing agent before the dispersion process. Since such untreated or oxidized carbon black has many acidic functional groups on its surface, it is important to have a large amount of component (A) near the carbon black by reacting with the glycidyl groups of component (A) during the thermal curing process when obtaining the light-shielding film. Furthermore, if it is desired to further increase the resistance value of the light-shielding film using carbon black, surface-coated carbon black, in which the surface of the carbon black is coated with a dye, pigment, resin, etc., may be used. However, it is preferable to blend carbon black in component (D) at a concentration of 80% by mass or more. As light-shielding components other than carbon black, light-shielding components selected from black organic pigments, mixed organic pigments, or light-shielding materials can be used, and it is preferable that they have excellent heat resistance, light resistance, and solvent resistance. Examples of black organic pigments include perylene black, aniline black, cyanine black, and lactam black. Examples of mixed organic pigments include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc., to create a pseudo-black color. Examples of light-shielding materials include chromium oxide, iron oxide, and titanium black. Two or more of these other light-shielding components can also be used by appropriately selecting them.

[0038] Furthermore, the light-shielding component is preferably dispersed in solvent (F) together with a dispersant beforehand to form a light-shielding dispersion, which is then incorporated into the photosensitive resin composition for the light-shielding film. Here, the solvent used for dispersion becomes part of component (F) described later, so any of the solvents listed in component (F) above can be used, but for example, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are preferably used. The blending ratio of component (D) that forms the light-shielding dispersion is preferably in the range of 40 to 70% by mass relative to the total solid content of the photosensitive resin composition for the light-shielding film of the present invention, and is particularly preferably in the range of 40 to 60% by mass.

[0039] Furthermore, known dispersants such as various polymer dispersants can be used as the dispersant. Examples of dispersants include known compounds conventionally used for pigment dispersion (compounds commercially available under names such as dispersants, dispersion wetting agents, and dispersion accelerators), which can be used without particular limitation. Examples include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative type dispersants (dispersion aids). In particular, cationic polymer dispersants having cationic functional groups such as imidazolyl groups, pyrrolyl groups, pyridyl groups, and primary, secondary, or tertiary amino groups as adsorption sites to pigments, with an amine value of 1 to 100 mg KOH / g and a number average molecular weight in the range of 1,000 to 100,000 are preferred. The amount of this dispersant to be blended is preferably 1 to 30% by mass relative to the (D) light-shielding component.

[0040] <(E) Photopolymerization initiator> (E) Photopolymerization initiators in the photosensitive resin composition for light-shielding films of the present invention include, for example, acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and benzyldimethylketal; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdimethylaminobenzophenone (Michler ketone), and 4-phenylbenzophenone. Benzophenones such as 4,4'-dichlorobenzophenone, hydroxybenzophenone, and 4,4'-diethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 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- Biimidazole compounds such as diphenylbiimidazole, 2,4,5-triarylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole; halomethyldiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1, 3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3Halomethyl-s-triazine compounds such as 5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-bicycloheptyl-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantilmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-adamantilmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-one Oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-onoxime-O-bicycloheptane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-onoxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-onoxime-O-adamantane carboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-Dione=2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]ethanone-O-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethanone,1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyl oxime), ethanone,1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetyl oxime O-acyloxime compounds such as ethyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone; 2-ethyl Anthraquinones such as ruanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3- Mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 3,Examples include thiol compounds such as 3'-thiodipropionic acid, dithiodipropionic acid, and laurylthiopropionic acid. Among these, O-acyloxime compounds are preferred from the viewpoint of easily obtaining a highly sensitive photosensitive resin composition for light-shielding films. Furthermore, two or more of these photopolymerization initiators can also be used. In this invention, the term "photopolymerization initiator" includes sensitizers.

[0041] Furthermore, compounds that do not act as photoinitiators or sensitizers on their own but can increase the photoinitiator or sensitizer capacity when used in combination with the above-mentioned compounds may be added. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of the above-mentioned amine compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone.

[0042] The amount of component (E) is preferably 2 to 40 parts by mass, and more preferably 3 to 30 parts by mass, relative to 100 parts by mass of the total of components (B) and (C).

[0043] <(F) Solvent> The (F) solvent in the photosensitive resin composition for light-shielding films of the present invention may be, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples include glycol ethers such as ethyl acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing these, a homogeneous solution-like composition can be obtained.

[0044] <Other ingredients> Furthermore, the photosensitive resin composition for light-shielding films of the present invention may optionally contain additives such as thermal polymerization inhibitors, antioxidants, plasticizers, fillers, leveling agents, defoamers, coupling agents, surfactants, and viscosity modifiers. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina. Examples of defoamers and leveling agents include silicone-based, fluorine-based, and acrylic compounds. Furthermore, examples of surfactants include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, amphoteric surfactants such as lauryldimethylamine oxide and laurylcarboxymethylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate, silicone-based surfactants with polydimethylsiloxane as the main skeleton, and fluorine-based surfactants. Examples of coupling agents include silane coupling agents such as 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0045] <Solid content> The photosensitive resin composition for light-shielding films of the present invention mainly contains the above components (A) to (F). The solid content excluding the solvent (the solid content includes monomers that become solid after curing) preferably contains a total of 70% by mass of components (A) to (E), more preferably 80% by mass or more, and even more preferably 90% by mass or more. The amount of solvent (F) varies depending on the target viscosity, but it is preferable that it be included in the photosensitive resin composition for light-shielding films of the present invention in the range of 60 to 90% by mass.

[0046] <Method for forming a light-shielding film> The photosensitive resin composition for light-shielding films in the present invention is excellent, for example, as a photosensitive resin composition for forming color filter light-shielding films. A photolithography method is used to form the light-shielding film as follows: First, the photosensitive resin composition is applied to a transparent substrate, then the solvent is dried (pre-bake), a photomask is placed on the resulting film, ultraviolet light is irradiated to harden the exposed areas, and then development is performed using an alkaline aqueous solution to dissolve the unexposed areas and form a pattern, followed by post-bake (heat firing) as a post-drying step.

[0047] Examples of transparent substrates to which the photosensitive resin composition is applied include glass substrates, as well as transparent films (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) on which transparent electrodes such as ITO or gold are deposited or patterned. Methods for applying the photosensitive resin composition solution to the transparent substrate include the known solution immersion method, spray method, and methods using roller coaters, land coaters, slit coaters, or spinner machines. After applying the solution to the desired thickness using these methods, the solvent is removed (pre-baked) to form a film. Pre-baking is performed by heating in an oven, hot plate, etc. The heating temperature and time during pre-baking are appropriately selected depending on the solvent used; for example, it is performed at a temperature of 60-110°C for 1-3 minutes.

[0048] The exposure performed after pre-baking is carried out using an ultraviolet exposure apparatus, and by exposing the resist only to the parts corresponding to the pattern through a photomask, only the resist is exposed. The exposure apparatus and its exposure irradiation conditions are selected as appropriate, and exposure is performed using light sources such as ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and far-ultraviolet lamps to photo-cure the photosensitive resin composition in the coating film.

[0049] Alkaline development after exposure is performed to remove the resist from the unexposed areas, and this development forms the desired pattern. Suitable developers for this alkaline development include aqueous solutions of alkali metal or alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, etc. In particular, it is preferable to develop at a temperature of 23 to 28°C using a weakly alkaline aqueous solution containing 0.05 to 3% by mass of carbonates such as sodium carbonate, potassium carbonate, or lithium carbonate, and to precisely form fine images using commercially available developing machines or ultrasonic cleaners.

[0050] After development, heat treatment (post-bake) is preferably performed at a temperature of 180-250°C for 20-60 minutes. This post-bake is performed to improve the adhesion between the patterned light-shielding film and the substrate, among other purposes. This is done by heating using an oven, hot plate, etc., similar to the pre-bake. The patterned light-shielding film of the present invention is formed through the above steps of the photolithography method.

[0051] As described above, the photosensitive resin composition for light-shielding films of the present invention is suitable for forming fine patterns by operations such as exposure and alkaline development. Furthermore, the photosensitive resin composition for light-shielding films of the present invention can be suitably used as a coating material, and is particularly suitable as an ink for color filters used in liquid crystal display devices or image sensors. The light-shielding film formed therefrom is useful as a color filter, a black matrix for liquid crystal projection, a light-shielding film, a light-shielding film for touch panels, and the like.

[0052] The highly light-shielding, high-resistance light-shielding film obtained in this invention exhibits a resistance of 1 × 10⁻¹⁶ when an applied voltage of 10V is applied, with an OD of 3.9 / μm or higher. 8 It is possible to ensure a volume resistivity of Ω·cm or more. Furthermore, the photosensitive resin composition of the present invention is suitable for forming light-shielding film patterns that exhibit excellent developability even when forming fine lines of, for example, 3 to 8 μm in diameter. [Examples]

[0053] The embodiments of the present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited thereto. Examples 4, 11, and 34 are provided for reference only.

[0054] First, we present an example of the synthesis of a polymerizable unsaturated group-containing alkali-soluble resin, which corresponds to component (B) of the present invention. The resin in the synthesis example was evaluated as follows.

[0055] [Solid content concentration] The mass of the resin solution obtained in the synthesis example (1 g) was impregnated into a glass filter (mass: W0 (g)) and weighed (W1 (g)), and the mass after heating at 160°C for 2 hours (W2 (g)) was calculated using the following formula. Solid content concentration (mass%) = 100 × (W2-W0) / (W1-W0)

[0056] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator (product name COM-1600, manufactured by Hiranuma Seisakusho Co., Ltd.) to determine the result.

[0057] [Molecular weight] The molecular weight was measured using gel permulation chromatography (GPC) [product name HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 (1) manufactured by Tosoh Corporation, temperature: 40°C, rate: 0.6 ml / min], and the weight-average molecular weight (Mw) was determined as a value converted to standard polystyrene [PS-oligomer kit manufactured by Tosoh Corporation].

[0058] [Epoxy equivalent] The epoxy compound to be measured was dissolved in dioxane, then an acetic acid solution of tetraethylammonium bromide was added, and the result was determined by titration with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0059] The abbreviations used in the synthesis examples are as follows: AA: Acrylic acid BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. In compounds of general formula (I), A is a fluorene-9,9-diyl group and R1 to R4 are hydrogen atoms. BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride THPA:1,2,3,6-tetrahydrophthalic anhydride TPP: Triphenylphosphine PGMEA: Propylene glycol monomethyl ether acetate TEAB: Tetraethylammonium bromide

[0060] [Synthesis Example 1] 114.4 g (0.23 mol) of BPFE, 33.2 g (0.46 mol) of AA, 157 g of PGMEA, and 0.48 g of TEAB were charged into a 500 ml four-necked flask equipped with a reflux condenser, and the mixture was stirred under heating at 100-105°C for 20 hours to allow it to react. Next, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were charged into the flask, and the mixture was stirred under heating at 120-125°C for 6 hours to obtain an alkali-soluble resin solution containing polymerizable unsaturated groups. The solid content concentration of the obtained resin solution was 56.5% by mass, the acid value (based on solid content) was 103 mg KOH / g, and the Mw value determined by GPC analysis was 3600.

[0061] [Preparation of photosensitive resin composition for light-shielding film] Photosensitive resin compositions for Examples 1-34, Comparative Examples 1-9, and Reference Comparative Examples 1-5 were prepared by compounding according to the compositions shown in Tables 1 to 4. The amounts of each component used in the compounding are as follows, and all values ​​in the table are in parts by mass.

[0062] (A) Epoxy compound: (A)-1: Bisphenol fluorene type epoxy compound [ESF-300C, manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 240, number of aromatic rings relative to the number of glycidyl groups: 2.09] (A)-2: 1,6-Naphthalenediol aralkyl type epoxy compound [Compound represented by formula (2) above, epoxy equivalent 167, number of aromatic rings relative to the number of glycidyl groups: 1.30] (A)-3: 1-Naphthol Aralkyl type epoxy compound [Compound represented by formula (3) above, epoxy equivalent 317, number of aromatic rings relative to the number of glycidyl groups: 3.13] (A)-4: Phenol novolac type epoxy compound [YDPN-6300, manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 175, number of aromatic rings relative to the number of glycidyl groups: 1] (A)-5: Alicyclic epoxy compound [ZX-1658GS, manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 132, number of aromatic rings relative to the number of glycidyl groups: 0]

[0063] (B) Alkali-soluble resin containing polymerizable unsaturated groups: The alkali-soluble resin solution containing polymerizable unsaturated groups obtained in Synthesis Example 1.

[0064] (C) Photopolymerizable monomer: A mixture of dipentaerythritol pentaacrylate and hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., DPHA, acrylic equivalent 96-115]

[0065] (D) Pigment dispersion containing light-shielding components: (D)-1: Pigment dispersion in propylene glycol monomethyl ether acetate solvent containing 25.0% by mass of carbon black, 5.0% by mass of dispersion resin, and 3.5% by mass of polymer dispersant. (D)-2: Pigment dispersion in propylene glycol monomethyl ether acetate solvent containing 25.0% by mass of carbon black and 6.3% by mass of polymer dispersant. (D)-3: Pigment dispersion in propylene glycol monomethyl ether acetate solvent containing 16.0% by mass of organic black pigment and 4.8% by mass of polymer dispersant. (D)-4: Pigment dispersion in propylene glycol monomethyl ether acetate solvent containing 15.0% by mass of titanium black and 4.0% by mass of polymer dispersant. (D)-5: Pigment dispersion in propylene glycol monomethyl ether acetate solvent containing 25.0% by mass of dye-coated carbon black, 8.1% by mass of dispersion resin (alkali-soluble resin (using component (B) above)), and 2.0% of polymer dispersant.

[0066] (E) Photopolymerization initiator: Oxime ester-based photopolymerization initiator [(Manufactured by ADEKA Corporation, NCI-831)]

[0067] (F) Solvent: (F)-1: Propylene glycol monomethyl ether acetate (F)-2: Diethylene glycol dimethyl ether (F)-3: Diethylene glycol ethyl methyl ether (F)-4: Diethylene glycol dibutyl ether

[0068] (G) Silane coupling agent: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.

[0069] (H) Surfactant: BYK-330 manufactured by BIC Chemie Japan Co., Ltd.

[0070] [Table 1]

[0071] [Table 2]

[0072] [Table 3]

[0073] [Table 4]

[0074] [evaluation] Using the photosensitive resin compositions of Examples 1 to 34, Comparative Examples 1 to 9, and Reference Comparative Examples 1 to 5, the evaluations described below were conducted. The results of these evaluations are shown in Tables 5 to 8.

[0075] <Evaluation of OD / μm> Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.0 μm, and pre-baked at 90°C for 1 minute. Then, without covering with a negative photomask, ultraviolet light of 40 mJ / cm 2 was irradiated with an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm 2 to perform a photocuring reaction.

[0076] Next, this exposed coated plate was developed for 80 seconds at a shower pressure of 1 kgf / cm 2 using a 0.04% aqueous potassium hydroxide solution at 23°C, and then spray water-washed at a pressure of 5 kgf / cm 2 . Thereafter, it was thermally post-baked at 230°C for 30 minutes using a hot air dryer. The OD value of this coated plate was evaluated using a transmission densitometer. Also, the film thickness of the light-shielding film formed on the coated plate was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD / μm.

[0077] <Evaluation of residual film rate after heat curing> Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 3.0 μm, and after pre-baking at 90°C for 1 minute, the film thickness of the light-shielding film formed on the coated plate was measured. Then, after thermally post-baking at 230°C for 180 minutes using a hot air dryer, the film thickness of the light-shielding film formed on the coated plate was measured again, and it was calculated based on the following formula from the film thicknesses before and after post-baking. Residual film rate (%) = 100 × film thickness after post-baking (μm) / film thickness before post-baking (μm)

[0078] <Evaluation of increase in volume resistivity> Each of the photosensitive resin compositions obtained above was coated onto a 100 mm × 100 mm chromium-deposited glass substrate (Corning 1737) using a spin coater to a post-baking thickness of 3.0 μm, and pre-baked at 90°C for 1 minute. Subsequently, after thermal post-baking at 230°C for 180 minutes using a hot air dryer, the volume resistivity was measured at applied voltages from 1V to 10V using an electrometer (Keithley, "Model 6517A"), with the voltage held for 60 seconds at each applied voltage in 1V steps. The following calculations were performed based on the following formulas to determine the percentage increase in volume resistivity when 10V is applied: for Examples 1-11 and Comparative Examples 1-3 relative to Reference Comparative Example 1 (without component A), for Examples 12-24 relative to Reference Comparative Example 2 (without component A), for Comparative Examples 4-6 relative to Reference Comparative Example 3 (without component A), for Comparative Examples 7-9 relative to Reference Comparative Example 4 (without component A), and for Examples 25-33 relative to Reference Comparative Example 5 (without component A). The reference is indicated as "Ref." in the table below. Increase = Volume resistivity of each example or comparative example (Ω·cm) / Volume resistivity of each reference comparative example (Ω·cm) The calculated increase in volume resistivity was evaluated based on the following criteria. ○: 100≦ Increase in volume resistivity △: 10 ≤ Volume Resistivity Increase < 100 ×: Increase in volume resistivity < 10

[0079] <Evaluation of development characteristics (minimum resolution linewidth)> Each of the photosensitive resin compositions obtained above was coated onto a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater to a post-baking film thickness of 1.2 μm, and pre-baked at 90°C for 1 minute. Then, a negative-type photomask with a line pattern having an aperture width of 1 to 20 μm was placed in close contact with the dried coating, and the i-line illuminance was 30 mW / cm². 2 40 mJ / cm² with an ultra-high pressure mercury lamp 2 The photosensitive portion was irradiated with ultraviolet light to induce a photocuring reaction.

[0080] Next, this exposed coated plate was placed in an aqueous solution of 0.04% potassium hydroxide at 23°C, and at a shower development pressure of 1 kgf / cm 2 From the development time (break time = BT) when the pattern began to appear at the shower development pressure, after 60 seconds of development, spray water washing was performed at a pressure of 5 kgf / cm 2 to remove the unexposed portion of the coating film and form a line pattern on the glass substrate. Then, after heat post-baking at 230°C for 30 minutes using a hot air dryer, the minimum opening line where no pattern peeling occurred in the obtained line pattern was defined as the minimum resolution line width. ◎: 2 μm or more and less than 5 μm 〇: 5 μm or more and less than 9 μm △: 9 μm or more and less than 11 μm ×: 11 μ or more

[0081] <Evaluation of volume resistivity decrease rate (heat resistance)> Each photosensitive resin composition obtained in Examples 15 to 17 and 34 and Reference Comparative Example 2 was applied onto a 100 mm × 100 mm chromium-evaporated glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 3.0 μm, and pre-baked at 90°C for 1 minute. Then, after heat post-baking at 230°C for 180 minutes using a hot air dryer, an electrometer (manufactured by Keithley Instruments, Inc., "6517A型") was used to measure the volume resistivity at each applied voltage from 1 V to 10 V under the condition of holding the voltage for 60 seconds at each applied voltage in 1 V steps. Separately from these, the temperature of the heat post-baking was changed to 270°C, and the same procedure was carried out for each photosensitive resin composition of Examples 15 to 17 and 34 and Reference Comparative Example 2 to measure the volume resistivity. Regarding the volume resistivity at 10 V application, the decrease rate (absolute value) of the volume resistivity when the temperature of the heat post-baking changed from 230°C to 270°C was calculated based on the following calculation formula. Also, when the decrease rate in the case of Reference Comparative Example 2 was regarded as 1, the relative value [relative value (x) of the decrease rate] of Examples 15 to 17 and 34 with respect to Reference Comparative Example 2 was calculated based on the following calculation formula. Note that Reference Comparative Example 2 is denoted as "Ref." in the subsequent table. Rate of decrease (absolute value) = 100 × (logA - logB) / logB (Here, A is the measured volume resistivity (Ω·cm) when the post-heat baking temperature is 270°C, and B is the measured volume resistivity (Ω·cm) when the post-heat baking temperature is 230°C.) Relative value of the rate of decrease (x) = Rate of decrease for each of Examples 15, 16, 17, or 34 / Rate of decrease for the reference comparative example 2 The relative values ​​of the calculated rate of decrease were used as the heat resistance and evaluated based on the following criteria. ◎: 0≦x<0.5 ○: 0.5 ≤ x < 0.8 △: 0.8 ≤ x < 1.0 ×: 1.0 ≤ x

[0082] [Table 5]

[0083] [Table 6]

[0084] [Table 7]

[0085] [Table 8]

[0086] From the results of Examples 1-34, Comparative Examples 1-9, and Reference Comparative Examples 1-5, it is clear that the volume resistivity is improved by adding an epoxy compound, which is component (A), to a photosensitive resin composition containing a light-shielding component using carbon black as a light-shielding material. In particular, Examples 15-17, 21-24, and 28-30 showed a very high increase in volume resistivity and also exhibited excellent development adhesion due to their narrow minimum resolution linewidth, making them photosensitive resin compositions for light-shielding films that achieve both high light-shielding, high resistance, and high resolution. Furthermore, it was found that Examples 15-17, which used epoxy compounds (A)-1 to (A)-3 of component (A), exhibited excellent heat resistance, and in particular, (A)-1 and (A)-2 showed even better heat resistance.

Claims

1. The following components (A) to (F), (A) Epoxy compounds, (B) Alkali-soluble resin containing polymerizable unsaturated groups, (C) A photopolymerizable monomer having at least one ethylenically unsaturated bond, (D) Light-shielding component containing carbon black as a light-shielding material, (E) Photopolymerization initiator, and (F) solvent In a photosensitive resin composition for light-shielding films containing as an essential component, The photosensitive resin composition for light-shielding films is characterized in that component (A) has an aromatic ring in its main chain, the number of aromatic rings relative to the number of glycidyl groups in component (A) is 0.5 to 10, and the epoxy equivalent is 100 to 400 g / eq, and component (A) is one or more compounds selected from the group consisting of compounds represented by the following chemical formulas (1) to (3). 【Chemistry 1】 【Chemistry 2】 【Transformation 3】

2. The photosensitive resin composition for light-shielding films according to Claim 1, characterized in that the component (A) is one or more selected from the group consisting of compounds represented by the chemical formulas (1) and (3).

3. The photosensitive resin composition for light-shielding films according to Claim 1, characterized in that the component (A) is a compound represented by the chemical formula (1).

4. The photosensitive resin composition for light-shielding films according to any one of claims 1 to 3, characterized in that the mass ratio (B) / (C) of component (B) to component (C) is 50 / 50 to 90 / 10, component (A) is contained in parts 0.5 to 15 parts by mass per 100 parts by mass of component (D), and component (D) is contained in 40 to 70% by mass of the solid content of the photosensitive resin composition for light-shielding films.

5. A light-shielding film characterized by being formed by curing a photosensitive resin composition for light-shielding films according to any one of claims 1 to 4.

6. A color filter characterized by comprising the light-shielding film described in claim 5.

7. A display device having a color filter as described in claim 6.

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