Photosensitive resin composition for black resist, method for manufacturing the same, light-shielding film, color filter, touch panel and display device.

Abstract

To provide a photosensitive resin composition for black resist that can reduce the reflectivity of the glass substrate side of the black resist, suppress aggregated foreign matter, and improve adhesion to the substrate after patterning, and a method for manufacturing the photosensitive resin composition. [Solution] The photosensitive resin composition for black resist comprises (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable compound having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) a pigment disperse containing at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments and light-shielding materials, (E) a silica disperse containing silica particles, and (F) a solvent, wherein component (A) includes component (A1) having a specific structure, a portion of component (A1) is included dissolved in component (F), and a portion of component (A1) is included in component (D).

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition for black resist, a method for producing the photosensitive resin composition, a light-shielding film obtained by curing the same, a color filter and a touch panel having the light-shielding film, and a display device having the color filter or touch panel. [Background technology]

[0002] In recent years, with the development of mobile devices, there has been an increase in display devices having touch panels or liquid crystal panels for use outdoors or in vehicles. In the above-mentioned display devices, a light-shielding film is provided on the outer frame of the touch panel to block light leakage from the area around the liquid crystal panel on the back, and a light-shielding film (black matrix) is provided on the liquid crystal panel to suppress light leakage from the screen when displaying black and to suppress color mixing between adjacent color resists.

[0003] Black matrices are required to have both high light-blocking properties and low reflectivity. For example, Patent Document 1 states that by using hydrophobic silica fine particles dispersed in a specific urethane-based dispersant, it is possible to achieve both high light-blocking and low reflectivity in the black matrix. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2015-161815 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, according to the inventors' findings, when a black resist is formed on a glass substrate using a photosensitive resin composition such as that described in Patent Document 1, there are problems such as high reflectivity on the glass surface side, generation of aggregated foreign matter, and deterioration of adhesion to the substrate after patterning.

[0006] The present invention has been made in view of the above, and aims to provide a photosensitive resin composition for black resist that can reduce the reflectivity of the glass substrate side of the black resist, suppress aggregated foreign matter, and improve adhesion to the substrate after patterning, a method for producing the photosensitive resin composition, a light-shielding film obtained by curing the same, a color filter and a touch panel having the light-shielding film, and a display device having the color filter or touch panel. [Means for solving the problem]

[0007] One aspect of the present invention for solving the above problems relates to the following photosensitive resin compositions for black resists [1] to [8].

[0008] [1] (A) Photosensitive resin containing unsaturated groups, (B) A photopolymerizable compound having at least two or more unsaturated bonds, (C) Photopolymerization initiator and (D) A pigment dispersion containing at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments, and light-shielding materials, (E) A silica dispersed powder containing silica particles, (F) Solvent and A photosensitive resin composition for black resist, comprising: The component (A) contains an unsaturated group-containing photosensitive resin obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (1) and (meth)acrylic acid with a polybasic carboxylic acid or its anhydride, and reacting the polybasic carboxylic acid or its anhydride with (a) a dicarboxylic acid, a tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dianhydride in a range where the molar ratio of (a) / (b) is 0.01 or more and less than 2.0. A part of the component (A1) is contained in a dissolved state in the component (F). A part of the component (A1) is contained in the component (D). A photosensitive resin composition for black resist.

[0009] [Chemical formula]

[0010] In general formula (1), R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group represented by general formula (2) or a single bond, and l is an integer of 0 to 10.

[0011] [Chemical formula]

[0012] In general formula (2), * indicates the bonding site with the structure represented by general formula (1).

[0013] [2] A part of the component (A1) is contained in the component (E). The photosensitive resin composition for black resist according to [1].

[0014] [3] The total mass of the component (A1) contained in the photosensitive resin composition for black resist is 51% to 100% with respect to the total mass of the component (A) contained in the photosensitive resin composition for black resist. [1] or [2] The photosensitive resin composition for black resist according to any one of the above.

[0015] [4] The component (A) substantially does not contain components other than the component (A1). [1] to [3] The photosensitive resin composition for black resist according to any one of the above.

[0016] [5] The ratio (mE1 / mD1) of the total mass (mE1) of the silica particles to the total mass (mD1) of at least one light-shielding component selected from the group consisting of the black pigment, the mixed-color pigment, and the light-shielding material contained in the photosensitive resin composition for black resist is 0.01 to 0.20. [1] to [4] The photosensitive resin composition for black resist according to any one of the above.

[0017] [6] The (mE1 / mD1) is 0.06 to 0.12. [5] The photosensitive resin composition for black resist according to [5].

[0018] [7] The average particle diameter of the silica particles contained in the component (E) is 20 nm to 150 nm. [1] to [6] The photosensitive resin composition for black resist according to any one of the above.

[0019] [8] The average particle diameter of the silica particles contained in the component (E) is 60 nm to 100 nm. [7] The photosensitive resin composition for black resist according to [7].

[0020] One aspect of the present invention for solving the above problems relates to a method for producing a photosensitive resin composition for black resist according to the following [9] or

[10] .

[0021] [9] (A) An unsaturated group-containing photosensitive resin, (B) A photopolymerizable compound having at least two or more unsaturated bonds, (C) Photopolymerization initiator and (D) A pigment dispersion containing at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments, and light-shielding materials, (E) A silica dispersed powder containing silica particles, (F) containing a solvent, A method for producing a photosensitive resin composition for black resist, wherein the (A) component is obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (1) with (meth)acrylic acid, and further reacting this product with a polybasic carboxylic acid or its anhydride, wherein the polybasic carboxylic acid or its anhydride is (a) a dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dianhydride, in a range where the molar ratio of (a) / (b) is 0.01 or more and less than 2.0, and contains an unsaturated group-containing photosensitive resin. A step of preparing a pigment dispersion containing the component (D) containing the component (A1) and a solvent, A step of preparing a silica dispersion containing the aforementioned component (E) and a solvent, A step of mixing component (A) containing component (A1), component (B), component (C), the pigment dispersion, the silica dispersion, and a solvent. A method for producing a photosensitive resin composition for black resist, including the following.

[0022] [ka]

[0023] In general formula (1), R1, R2, R3, and R4 are each independently a hydrogen atom, a C1-C5 alkyl group, or a halogen atom, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group represented by general formula (2), or a single bond, and l is an integer from 0 to 10.

[0024] [ka]

[0025] In general formula (2), * indicates a bonding site with the structure represented by general formula (1).

[0026]

[10] The step of preparing the silica dispersion is The step is to prepare a silica dispersion containing component (E) which contains component (A1), and a solvent. A method for producing the photosensitive resin composition for black resist described in [9].

[0027] One aspect of the present invention for solving the above problems relates to the light-shielding film described below

[11] .

[0028]

[11] A light-shielding film obtained by curing a photosensitive resin composition for black resist described in any one of items [1] to [8].

[0029] One aspect of the present invention for solving the above problems relates to the following color filter

[12] .

[0030] A color filter having the light-shielding film described in

[12]

[11] as a black matrix.

[0031] One aspect of the present invention for solving the above problems relates to the touch panel described in

[13] below.

[0032]

[13] A touch panel having the light-shielding film described in

[11] .

[0033] One aspect of the present invention for solving the above problems relates to a display device as described in

[14] or

[15] below.

[0034] A display device having the color filter described in

[14]

[12] .

[0035] A display device having the touch panel described in

[15]

[13] . [Effects of the Invention]

[0036] The present invention provides a photosensitive resin composition for black resist that can reduce the reflectivity of the black resist on the glass substrate side, suppress aggregated foreign matter, and improve adhesion to the substrate after patterning, a method for producing the photosensitive resin composition, a light-shielding film obtained by curing the same, a color filter and a touch panel having the light-shielding film, and a display device having the color filter or touch panel. [Modes for carrying out the invention]

[0037] The embodiments of the present invention will be described below, but the present invention is not limited to the embodiments described below. In this specification, when the first decimal place of the content of each component is 0, the decimal part may be omitted. Furthermore, unless otherwise specified, only one of the exemplified compounds, functional groups, or structures may be used, or multiple types may be used in combination.

[0038] In this specification, "(meth)acrylic" is a general term for acrylic and methacrylic, and "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, meaning one or both of these.

[0039] 1. Photosensitive resin composition for black resist The photosensitive resin composition for black resist according to this embodiment (hereinafter also referred to as the "photosensitive resin composition") is (A) A photosensitive resin containing unsaturated groups (hereinafter also referred to as "component (A)"), (B) A photopolymerizable compound having at least two or more unsaturated bonds (hereinafter also referred to as "component (B)"), (C) Photopolymerization initiator (hereinafter also referred to as "component (C)"), (D) A pigment disperse (hereinafter also referred to as "component (D)") containing at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments, and light-shielding materials, (E) A silica dispersed substance containing silica particles (hereinafter also referred to as "component (E)"), (F) Solvent (hereinafter also referred to as "component (F)") and Includes, The aforementioned component (A) includes component (A1) described later, A portion of component (A1) is included in a dissolved state in component (F), A portion of the aforementioned component (A1) is included in the aforementioned component (D), This is a photosensitive resin composition for black resist.

[0040] Here, component (A1) is obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (1) with (meth)acrylic acid, and further reacting the product with a polybasic carboxylic acid or its anhydride, wherein the polybasic carboxylic acid or its anhydride is (a) a dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dianhydride, in a range where the molar ratio of (a) / (b) is 0.01 or more and less than 2.0, resulting in an unsaturated group-containing photosensitive resin.

[0041] [ka]

[0042] In general formula (1), R1, R2, R3, and R4 are each independently a hydrogen atom, a C1-C5 alkyl group, or a halogen atom, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group represented by general formula (2), or a single bond, and l is an integer from 0 to 10.

[0043] [ka]

[0044] In general formula (2), * indicates a bonding site with the structure represented by general formula (1).

[0045] Furthermore, "a portion of component (A1) is included in a dissolved state in component (F)" refers to a state in which component (F) and component (A1) are mixed to form a uniform phase.

[0046] Furthermore, in this application, "dispersed phase" refers to a phase that is different from component (F) (dispersion medium), and contains at least light-shielding components or silica particles, and if they contain a dispersant, they contain a dispersant. And, "a portion of component (A1) is included in component (D)" refers to a state in which component (A1) and the light-shielding component interact, and component (A1) is adsorbed onto the light-shielding component to form a dispersed phase containing component (A1), or, if component (D) contains a dispersant other than (A1), a state in which component (A1) interacts with the dispersant other than (A1) or the light-shielding component adsorbed onto the light-shielding component, and exists in close proximity to the dispersant other than (A1) or the light-shielding component to form a dispersed phase containing component (A1). Whether a portion of component (A1) is included in component (D) can be determined, for example, by separating the photosensitive resin composition into a dispersed phase and a dispersion medium by centrifugation or filtration, further separating component (D) from the dispersed phase, and measuring TG-DTA, pyrolysis GC / MS, ESCA, etc., to confirm the presence or absence of component (A1). As a method for separating component (D) and component (E) from the dispersed phase obtained from the photosensitive resin composition, for example, a known method described in the Journal of the Rubber Association of Japan 2000, 73(7), 379-384 can be used.

[0047] The reason why the above photosensitive resin composition reduces the reflectivity of the black resist on the glass surface, suppresses aggregated foreign matter, and improves adhesion to the glass substrate is not entirely clear, but it is thought to be as follows.

[0048] Regarding aggregated foreign matter, for example, if component (A1) is dissolved in component (F) and not contained in component (D), and the light-shielding component is dispersed by a dispersant other than component (A1), then in the liquid of the photosensitive resin composition, the dispersant contained in component (D) can be stabilized more by interacting with other dispersants contained in component (D) than by interacting with component (A1) dissolved in component (F). Therefore, aggregation of component (D) is more likely to occur.

[0049] On the other hand, in the photosensitive resin composition according to this embodiment, component (A1) is contained in a dissolved state in component (F), and a portion of component (A1) is contained in component (D). In this case, in the liquid of the photosensitive resin composition, component (A1) contained in component (D) and component (A1) dissolved in component (F) blend together easily, making it difficult for a driving force to occur that would cause components (D) to aggregate with each other. Therefore, aggregation of components (D) is suppressed, and aggregated foreign matter is more easily suppressed.

[0050] Next, regarding reflectivity, generally speaking, aliphatic resins have a lower refractive index than glass, and compounds containing many aromatic rings in their molecular structure tend to have a higher refractive index. Component (A1) has a structure containing many aromatic rings, so its refractive index is higher than that of aliphatic resins, and the refractive index difference with glass tends to be smaller. As a result, reflection between the black resist and the glass substrate is easily reduced.

[0051] Similarly, light-shielding components often have a higher refractive index than aliphatic resins. When component (A1) is included as a dispersant for the light-shielding component, the refractive index difference between the light-shielding component and its dispersant tends to decrease. This reduces the reflection that occurs between the light-shielding component and its dispersant in component (D).

[0052] Furthermore, as mentioned above, component (A1) is included in component (F) in a dissolved state, and a portion of component (A1) is included in component (D). This suppresses aggregation of components (D) and reduces scattering and other phenomena caused by component (D), thus making it easier to reduce reflectance.

[0053] Furthermore, regarding the adhesion to the glass substrate after patterning (hereinafter also referred to as "development adhesion"), component (A1) contains many aromatic rings, and generally, as can be understood from solubility parameters, aromatic compounds are considered to be more hydrophilic than aliphatic compounds. Therefore, component (A1) is relatively hydrophilic, and thus has a high affinity for glass substrates with hydrophilic surfaces. As a result, the adhesion between the black resist containing component (A1) and the glass substrate tends to improve.

[0054] Furthermore, when developing with an alkaline solution, as mentioned above, component (A1) contains many aromatic rings, so in the region where it is exposed and polymerization progresses, components (A1) tend to come into close proximity to each other, making it easier to form π-π interactions. This increases the cohesive force of the black resist in the exposed region, thus improving adhesion when patterning.

[0055] The components (A) through (F) will be explained below.

[0056] 1-1.(A) Unsaturated group-containing photosensitive resin Component (A) is a photosensitive resin containing unsaturated groups, and each molecule contains polymerizable unsaturated groups. Furthermore, from the viewpoint of improving patternability, it is preferable that component (A) has acidic groups to exhibit alkali solubility. Any resin described above can be used without particular limitations.

[0057] Examples of acidic groups that can exhibit alkali solubility in component (A) include carboxyl groups, phosphate groups, and sulfonic acid groups. From the viewpoint of improving developability, carboxyl groups are preferred.

[0058] Component (A) only needs to include component (A1), and may include other components (hereinafter also referred to as "component (A2)"), or may not include component (A2). Furthermore, two or more types of component (A2) may be used.

[0059] 1-1-1. (A1) Component Component (A1) is obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (1) with (meth)acrylic acid, and further reacting the result with a polybasic carboxylic acid or its anhydride. The polybasic carboxylic acid or its anhydride is (a) a dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dianhydride, in a range where the molar ratio of (a) / (b) is 0.01 or more and less than 2.0, resulting in an unsaturated group-containing photosensitive resin. Furthermore, a portion of component (A1) is included in component (F) in a dissolved state, and a portion of component (A1) is included in component (D).

[0060] [ka]

[0061] In general formula (1), R1, R2, R3, and R4 are each independently a hydrogen atom, a C1-C5 alkyl group, or a halogen atom, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group represented by general formula (2), or a single bond, and l is an integer from 0 to 10.

[0062] [ka]

[0063] In general formula (2), * indicates a bonding site with the structure represented by general formula (1).

[0064] X is preferably a fluorene-9,9-diyl group. With such a substituent, the refractive index of component (A1) tends to increase, thus reducing the refractive index difference with the light-shielding component and with the glass substrate. As a result, the reflectance tends to decrease. In addition, the structure containing many aromatic rings tends to reduce the alkali solubility of the exposed region, thus improving developability.

[0065] (A1) component is, (Step 1) A step to obtain a diol compound by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (1) with (meth)acrylic acid. (Step 2) A step in which the above reaction product is reacted with a polybasic carboxylic acid or its anhydride to obtain component (A1). It can be manufactured by [this method].

[0066] Of these steps, the epoxy compound may be prepared and steps (1) and (2) may be performed, or the diol compound may be prepared and only step (2) may be performed, or component (A1) may be prepared.

[0067] 1-1-1-1. (Step 1) A step to obtain a diol compound by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (1) with (meth)acrylic acid. Bisphenol-type epoxy compounds represented by general formula (1) are epoxy compounds having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. Since this reaction usually involves oligomerization of the diglycidyl ether compound, bisphenol-type epoxy compounds represented by general formula (1) include epoxy compounds containing two or more bisphenol skeletons.

[0068] Examples of 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) (Droxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl) Propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy(hydroxyphenyl) This includes fluorene (-3-chlorophenyl), 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-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, 4,4'-biphenol, 3,3'-biphenol, and others.Among these, bisphenols having a fluorene-9,9-diyl group are preferred.

[0069] The reaction between the epoxy compound and (meth)acrylic acid can be carried out using known methods. For example, a method for producing epoxy (meth)acrylate compounds by the reaction of an epoxy compound with (meth)acrylic acid can be referenced, such as the method described in Japanese Patent Application Publication No. 9-325494, in which a bisphenol fluorene-type epoxy resin and acrylic acid are reacted at 100°C using tetraethylammonium bromide or the like as a catalyst. The reaction temperature is preferably in the range of 40 to 120°C, and more preferably 60 to 110°C.

[0070] A catalyst may be used in this addition reaction, and ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine, and phosphines such as tris(2,6-dimethoxyphenyl)phosphine may be used.

[0071] This reaction is usually carried out in a solvent. Examples of solvents include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling-point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone solvents such as cyclohexanone and diisobutyl ketone. There are no particular restrictions on the reaction conditions such as the solvent and catalyst used, but it is preferable to use a solvent that does not have hydroxyl groups and has a boiling point higher than the reaction temperature as the reaction solvent.

[0072] 1-1-1-2. (Step 2) A step to obtain component (A1) by reacting the above diol compound with a polybasic carboxylic acid or its anhydride. Next, the diol compound obtained in step 1 is reacted with (a) a dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dianhydride, with a polybasic carboxylic acid or its anhydride such that the molar ratio of (a) / (b) is 0.01 or more and less than 2.0.

[0073] The examples of dicarboxylic acids or tricarboxylic acids or their acid anhydrides mentioned above (a) include chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or their acid anhydrides.

[0074] Examples of the above-mentioned chain-like hydrocarbon dicarboxylic acids or tricarboxylic acids include 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, diglycolic acid, etc., and dicarboxylic acids or tricarboxylic acids to which any substituent has been introduced.

[0075] Furthermore, examples of the above-mentioned alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and dicarboxylic acids or tricarboxylic acids to which any substituent has been introduced.

[0076] Furthermore, examples of the above aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and dicarboxylic acids or tricarboxylic acids to which any substituent has been introduced.

[0077] Furthermore, in the case of dicarboxylic acids or tricarboxylic acids, it is preferable to use their acid monoanhydrides. The acid monoanhydrides of dicarboxylic acids or tricarboxylic acids mentioned above may be used individually or in combination of two or more.

[0078] (a) Among dicarboxylic acids or tricarboxylic acids or their acid anhydrides, succinic acid, itaconic acid, 1,2,3,6-tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid or 2,3-naphthalenedicarboxylic acid or their acid anhydrides are preferred, and 1,2,3,6-tetrahydrophthalic acid, 1,8-naphthalenedicarboxylic acid or 2,3-naphthalenedicarboxylic acid or their acid anhydrides are more preferred.

[0079] Furthermore, (b) examples of tetracarboxylic acids or their dianhydrides include chain-type hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, or their dianhydrides.

[0080] Examples of the above-mentioned chain-type hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain-type hydrocarbon tetracarboxylic acids into which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups have been introduced.

[0081] Furthermore, examples of alicyclic hydrocarbon tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and alicyclic tetracarboxylic acids into which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups have been introduced.

[0082] Examples of aromatic hydrocarbon tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfonetetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0083] In addition, aryl bis-trimellitic anhydride esters can also be used. Arilly bis-trimellitic anhydride esters are a group of compounds produced, for example, by the method described in International Publication No. 2010 / 074065, and are structurally acidic dianhydrides in which two hydroxyl groups of an aromatic diol (such as naphthalenediol, biphenol, or terphenyldiol) react with the carboxyl groups of two molecules of trimellitic anhydride to form an ester bond. These compounds will be referred to below as bis-trimellitic anhydride esters of aromatic diols.

[0084] Furthermore, in the case of tetracarboxylic acids, it is preferable to use these acid dianhydrides. The acid dianhydrides of tetracarboxylic acids described above may be used individually or in combination of two or more.

[0085] (b) Among the tetracarboxylic acids or their dianhydrides, 3,3',4,4'-biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, diphenyl ethertetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid are preferred, and 3,3',4,4'-biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid are more preferred.

[0086] The reaction conditions for the above-mentioned diol compound with a polybasic carboxylic acid or its anhydride are not particularly limited, and known methods can be employed. For example, Japanese Patent Publication No. 9-325494 describes a method for reacting epoxy (meth)acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0087] The molar ratio (a) / (b) of (a) dicarboxylic acid or tricarboxylic acid monoanhydride and (b) tetracarboxylic acid dianhydride reacted with the above diol compound is 0.01 or more and less than 2.0, preferably 0.02 or more and less than 1.8, and more preferably 0.02 or more and less than 1.6. When the molar ratio (a) / (b) is 0.01 or more, the molecular weight of component (A1) does not become too large, so the alkali solubility of the unexposed areas becomes sufficiently high, making it easier to form patterns. When the molar ratio (a) / (b) is less than 2.0, the molecular weight of component (A1) does not become too small, so when patterning is performed, the alkali solubility of the exposed areas becomes sufficiently low, making it easier to improve development adhesion.

[0088] 1-1-1-3. Other properties of component (A1) The content of component (A1) is preferably 51% to 100% by mass relative to the total mass of component (A) contained in the black resist photosensitive resin composition, more preferably substantially free of component (A2), and even more preferably free of component (A2). The higher the content of component (A1), the easier it is to improve adhesion to the substrate after patterning. In this application, "substantially free of component (A2)" means that component (A2) is 1.0% by mass or less relative to the total mass of component (A).

[0089] The content of component (A1) is preferably 16% to 50% by mass, and more preferably 20% to 50% by mass, relative to the total mass of solids contained in the black resist photosensitive resin composition. If the content of component (A1) is 16% by mass or more, adhesion to the substrate after patterning tends to improve. If the content of component (A1) is 50% by mass or less, components (D) and (E) can be sufficiently included, making it easier to obtain a light-shielding film with high light-shielding degree and low reflectivity.

[0090] 1-1-2.(A2) Component Examples of component (A2) include unsaturated group-containing photosensitive resins which are acrylic copolymers, and unsaturated group-containing photosensitive resins obtained by reacting a reaction product of an epoxy compound having two or more epoxy groups (not included in general formula (1)) with (meth)acrylic acid, and further reacting this product with a polybasic acid carboxylic acid or its anhydride.

[0091] Examples of the unsaturated group-containing photosensitive resins that are acrylic copolymers include copolymers of (meth)acrylic acid, (meth)acrylic acid esters, etc., which have (meth)acryloyl groups and carboxyl groups. Examples of the above resins include unsaturated group-containing photosensitive resins obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, reacting the copolymer with (meth)acrylic acid, and finally reacting it with an anhydride of a dicarboxylic acid or tricarboxylic acid. Examples of the copolymers mentioned above include a copolymer described in Japanese Patent Publication No. 2014-111722, which consists of 20-90 mol% repeating units derived from diester glycerol with hydroxyl groups at both ends esterified with (meth)acrylic acid, and 10-80 mol% repeating units derived from one or more polymerizable unsaturated compounds copolymerizable thereto, with a number average molecular weight (Mn) of 2000-20000 and an acid value of 35-120 mgKOH / g, and a polymerized unsaturated group-containing alkali-soluble resin described in Japanese Patent Publication No. 2018-141968, which contains units derived from (meth)acrylic acid ester compounds and units having (meth)acryloyl groups and di or tricarboxylic acid residues, with a weight average molecular weight (Mw) of 3000-50000 and an acid value of 30-200 mg / KOH.

[0092] Examples of epoxy compounds having two or more epoxy groups that are not included in the above general formula (1) include: glycidyl ethers of polyhydric alcohols, glycidyl esters of polyhydric carboxylic acids, copolymers of monomers having a (meth)acryloyl group that include (meth)acrylate glycidyl as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, epoxy compounds having glycidyl groups such as hydrogenated bisphenol A diglycidyl ether (e.g., Licarezin HBE-100: manufactured by Shin Nippon Rika Co., Ltd., "Licarezin" is a registered trademark of the company), 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175: manufactured by Huntsman, "Araldite" is a registered trademark of the company), bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128 (manufactured by Dow Chemical), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celoxide 2021P: manufactured by Daicel Corporation, "Celoxide" is a registered trademark of the company), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolid GT401: manufactured by Daicel Corporation, "Epolid" is a registered trademark of the company), epoxy compounds having an epoxycyclohexyl group (e.g., HiREM-1: manufactured by Shikoku Chemicals Co., Ltd.) These include polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the company), and epoxy compounds having a silicone skeleton.

[0093] 1-1-3. Other properties of component (A) The content of component (A) is preferably 10% to 60% by mass, and more preferably 15% to 45% by mass, relative to the total mass of solids. When the above content of component (A) is 10% by mass or more, sufficient photosensitive resin is included, which tends to improve patterning properties. Furthermore, when the above content of component (A) is 60% by mass or less, sufficient other components can be included, making it easier to obtain a light-shielding film with excellent patterning properties and low reflectivity.

[0094] The weight-average molecular weight (Mw) of the unsaturated group-containing polymerizable resin, measured by gel permeation chromatography (GPC), is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 15,000. When the weight-average molecular weight (Mw) is 1,000 or higher, the alkali solubility of the exposed area becomes sufficiently low when patterning is performed, which improves development adhesion. Furthermore, when the weight-average molecular weight (Mw) is 40,000 or lower, the viscosity of the photosensitive resin composition can be easily adjusted to a range suitable for coating, making coating onto the surface of the support easier. Also, when the weight-average molecular weight (Mw) is 40,000 or lower, the alkali solubility of the unexposed area becomes sufficiently high, which facilitates pattern formation. The weight-average molecular weight (Mw) was measured using gel permulation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by Tosoh Corporation), temperature: 40℃, rate: 0.6 ml / min), and the value was determined as a conversion to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0095] The acid value of the polymerizable resin containing unsaturated groups is preferably 20 mg KOH / g to 200 mg KOH / g, and more preferably 25 mg KOH / g to 200 mg KOH / g. If the acid value is 20 mg KOH / g or higher, residue is less likely to remain during alkaline development. If the acid value is 200 mg KOH / g or lower, the penetration of the alkaline developer does not become too fast, which tends to improve development adhesion. The acid value is determined by titration with a 1 / 10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0096] 1-2. (B) Photopolymerizable compounds having at least two or more unsaturated bonds Component (B) forms an appropriate cross-linked structure during the curing of the photosensitive resin composition, thereby improving the developability of the light-shielding film. Component (B) is a compound not included in component (A), and may or may not have an acidic group to exhibit alkali solubility. Furthermore, component (B) may or may not have an aromatic ring.

[0097] Component (B) is not particularly limited as long as it is a photopolymerizable compound having at least two or more unsaturated bonds, but examples of component (B) include 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, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, penta Examples of (meth)acrylic acid esters include erythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and dendritic polymers having a (meth)acrylic group as compounds having an ethylenic double bond.

[0098] Examples of the above-mentioned dendritic polymers include dendrimer acrylates, which are spherical macromolecules formed by radially assembling branch molecules having acrylic groups; hyperbranched acrylic polymers; hyperbranched acrylic oligomers; and dendritic polymers obtained by adding a polyvalent mercapto compound to a portion of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specifically, this includes dendritic polymers obtained by reacting the (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the following general formula (B-1) with a polyvalent mercapto compound represented by the following general formula (B-2). It is also preferable to use such polyfunctional dendritic polymers from the viewpoint of facilitating photopolymerization reactions.

[0099] [ka]

[0100] In formula (B-1), R6 is a hydrogen atom or a methyl group, and R7 is R8(OH) k This is the remaining portion after r of the k hydroxyl groups have been donated to the ester bond in the formula. Preferred R8(OH) k This is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyhydric alcohol ether formed by linking multiple molecules of the polyhydric alcohol via ether bonds through dehydration condensation of the alcohol, or an ester of these polyhydric alcohols or polyhydric alcohol ethers with a hydroxy acid. k and r independently represent integers from 2 to 20, where k ≥ r.

[0101] [ka]

[0102] In formula (B-2), R9 is a single bond or a 2-6 valent hydrocarbon group having 1-6 carbon atoms, and s is 2 when R9 is a single bond, and the valency of R9 is the same as that of R9 when R9 is a 2-6 valent group.

[0103] Examples of polyfunctional (meth)acrylates represented by general formula (B-1) include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified pentaerythritol tri(meth)acrylate.

[0104] Examples of polyvalent mercapto compounds represented by general formula (B-2) include trimethylolpropanetri(mercaptoacetate), trimethylolpropanetri(mercaptopropionate), pentaerythritoltetra(mercaptoacetate), pentaerythritoltri(mercaptoacetate), pentaerythritoltetra(mercaptopropionate), dipentaerythritolhexa(mercaptoacetate), and dipentaerythritolhexa(mercaptopropionate).

[0105] Component (B) may be one of these photopolymerizable compounds used alone, or two or more may be used in combination. Component (B) can act as a bridge between the molecules of component (A), and to exhibit this function, it is preferable that it has three or more unsaturated bonds. Increasing the number of unsaturated bonds makes it easier to increase the degree of hardening of the light-shielding film and improve its adhesion to the developer.

[0106] Similarly, from the viewpoint of making it easier to increase the degree of hardening, component (B) is preferably such that the acrylic equivalent obtained by dividing the molecular weight by the number of (meth)acrylic groups in one molecule is 50 g / eq to 300 g / eq, and more preferably 80 g / eq to 200 g / eq.

[0107] The content of component (B) is preferably 10% to 60% by mass, and more preferably 10% to 50% by mass, relative to the total mass of component (A) and component (B). When the above content of component (B) is 10% by mass or more, not only does the resolution of the pattern tend to increase, but the degree of hardening of the resin film also tends to increase, making it easier to improve the adhesion to the developer. Furthermore, when the content of component (B) is 60% by mass or less, it is easier to suppress the generation of residue and to further control the shape of the pattern.

[0108] 1-3. (C) Photopolymerization initiator Component (C) is not particularly limited as long as it is a compound that can initiate polymerization of a polymerizable unsaturated bond and is capable of addition polymerization upon light stimulation.

[0109] Examples of component (C) include acetophenone-based photopolymerization initiators, triazine-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, imidazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators. In this specification, the term "photopolymerization initiator" is used to include sensitizers.

[0110] Component (C) preferably contains an oxime ester-based photopolymerization initiator. Oxime ester-based photopolymerization initiators have high sensitivity, which can help improve developability.

[0111] Examples of acetophenone-based photopolymerization initiators include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one. Examples of commercially available products include the Omnirad 127, Omnirad 369, Omnirad 1173, Omnirad 184, and Omnirad 651 (the Omnirad series is manufactured by IGM Resins BV).

[0112] Examples of triazine-based photopolymerization initiators include 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 Examples include 5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0113] Examples of benzoin-based photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin-tert-butyl ether.

[0114] Examples of benzophenone-based photopolymerization initiators include benzophenone, o-methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(N,N-diethylamino)benzophenone.

[0115] Examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxane, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0116] Examples of imidazole-based photopolymerization initiators include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,4,5-triarylimidazole dimer.

[0117] Examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Examples of commercially available products include Omnirad TPO H and Omnirad 819 (the Omnirad series is manufactured by IGM Resins BV).

[0118] Examples of oxime ester-based photopolymerization initiators include 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 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-onoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-onoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-onoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1- Onoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-onoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-onoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-onoxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl] [9-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-tricyclodecane carbosichlate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-adamantane carbosichlate, 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, Ethanone, 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-Acetyl Oxime), 1,2-Octanediene, 1-[4-(phenylthio)-,2-(O-Benzoyl Oxime)], Ethanone This includes non-, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), 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-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime, etc.

[0119] Examples of commercially available oxime ester-based photopolymerization initiators include 1,2-octanedione,1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)] (IRGACURE OXE-01, BASF), etanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (IRGACURE OXE-02, BASF), and [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazoyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (IRGACURE OXE-03 (manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (IRGACURE OXE-04, manufactured by BASF, and Lunar 6, manufactured by DKSH Japan), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (TR Examples include -PBG-326 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arcules NCI-831E (manufactured by ADEKA Corporation), Omnirad 1312 (manufactured by IGM Resins BV), and DFI-020 (manufactured by Daito Chemix Co., Ltd.).

[0120] Examples of oxime ester-based photopolymerization initiators include oxime ester compound-based photopolymerization initiators represented by general formula (C-1) or general formula (C-2).

[0121] [ka]

[0122] In formula (C-1), R 10 and R 11 are each independently an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms, and R 12 is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Further, the alkyl group may be any of a linear, branched, or cyclic alkyl group.

[0123]

Chemical Formula

[0124] In formula (C-2), R 13 and R 14 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group or an alkylcycloalkyl group, or a phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms. R 15 is independently a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and a part of the -CH2- groups in the alkyl group or alkenyl group may be substituted with an -O- group. Further, a part of the hydrogen atoms in these R 13 to R 15 groups may be substituted with halogen atoms.

[0125] The content of component (C) is preferably 3.0% to 30.0% and more preferably 5.0% to 20.0% relative to the total mass of components (A) and (B). When the amount of component (C) is 3.0% or more, the sensitivity of the photosensitive resin composition is good and the rate of photopolymerization can be sufficiently accelerated. When the amount of component (C) is 30.0% or less, the sensitivity of the photosensitive resin composition is kept within an appropriate range, and it is easy to obtain a cured film having the desired pattern line width and the desired pattern edge shape.

[0126] Furthermore, compounds that do not act as photoinitiators or sensitizers on their own but can increase the photoinitiator or sensitizer capabilities 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.

[0127] 1-4. (D) A pigment disperse containing at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments, and light-shielding materials. Component (D) is a pigment disperse containing a light-shielding component, which is a black pigment, a mixed organic pigment, or a light-shielding material, and component (A1), which can enhance the light-shielding properties of the black resist. Known black pigments, mixed pigments, and light-shielding materials can be used as the light-shielding component without particular limitations.

[0128] Furthermore, it is preferable that the light-shielding component is dispersed such that the average particle diameter (average particle diameter measured by a laser diffraction / scattering particle size distribution analyzer or a dynamic light scattering particle size distribution analyzer) is between 1 nm and 1000 nm or less.

[0129] Examples of the black pigments mentioned above include perylene black, cyanine black, aniline black, lactam black, carbon black, titanium black, and zirconium nitride.

[0130] Examples of the above-mentioned mixed pigments include mixed organic pigments, which are mixtures of at least two colors from among organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, surene pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments, as well as mixed inorganic pigments, which are mixtures of white pigments such as titanium dioxide and zinc oxide with the aforementioned black pigments.

[0131] Depending on the desired function of the photosensitive resin composition, the light-shielding component may be used alone or in combination of two or more types.

[0132] Examples of organic pigments that can be used as light-blocking components include, but are not limited to, those with the following color index numbers. Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue in 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

[0133] Among these, the light-shielding component is preferably a black pigment, and more preferably carbon black.

[0134] In this specification, the carbon black may or may not be surface-treated with a dye or the like, as described below. Carbon black with a surface coated with a dye (dye-coated carbon black) enhances the developability of the photosensitive resin composition, and makes it easier to improve the adhesion to the substrate, fine line reproduction, and light shielding properties of the resin film obtained by curing it, and makes it easier to increase the resistance value of the resin film.

[0135] The above dyes can be any dye that can be adsorbed onto the surface of carbon black, and basic dyes, acid dyes, direct dyes, reactive dyes, etc., can be used. In this case, if acidic functional groups are imparted to the surface of the carbon black (oxidation treatment) to improve its dispersibility, acid dyes that readily interact with the acidic functional groups (particularly acid dyes having sulfonic acid groups or carboxyl groups) are preferred. Also, from the viewpoint of suppressing the reaction with the acidic groups of component (A), acid dyes or nonionic dyes are preferred over dyes having amino groups, etc. Furthermore, from the viewpoint of making it easier to improve the light-shielding properties of the resin film, dark-colored dyes are preferred.

[0136] Specific examples of the above dyes include food coloring dyes such as Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1, Food Yellow No. 7, acid dyes of various colors such as Bernacid Red 2BMN, Basacid Black X34 (BASF X-34) (manufactured by BASF), Kayanol Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz), Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Basacid Black X34 (BASF X-34) (manufactured by BASF), Basacid Blue 750 (manufactured by BASF), Bernacid Red (manufactured by Bemcolors, Poughkeepsie, NY), BASF Basacid Black SE 0228 (manufactured by BASF), Pontamine Brilliant Bond Blue A and other Pontamine Brilliant Bond Blue A and other Pontamine® dyes (manufactured by Bayer Chemicals Corporation, Pittsburgh, PA), Cartasol Yellow GTF Presscake (manufactured by Sandoz, Inc.); Cartasol Yellow GTF Liquid Special 110 (manufactured by Sandoz, Inc.); Yellow Shade 16948 (manufactured by Tricon), Direct Brilliant Pink B (manufactured by Crompton & Knowles), Carta Black 2GT (manufactured by Sandoz, Inc.), Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (manufactured by Sandoz); Pergasol Yellow CGP (manufactured by Ciba-Geigy), Pyrazol Black BG (manufactured by JCI), Diazol Black RN Quad (manufactured by JCJ), Pontamine Brilliant Bond Blue; Berncolor AYDirect dyes of various colors such as 34, dyes such as Cibacron Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (Pylam Products, Inc., Tempe, AZ), Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA, and similar Levafix® dyes Dystar LP (Charlotte, NC), reactive dyes of various colors such as Procion Red H8B (Reactive Red 31) (JCI America), Neozapon Red 492 (BASF), Orasol Red G (Ciba-Geigy), Aizen Spilon Red C-BH (Hodogaya Chemical Company), Spirit Fast Yellow 3G, Aizen Spilon Yellow This includes oil-soluble dyes such as C-GNH (Hodogaya Chemical Company), Orasol Black RL (Ciba-Geigy), Orasol Black RLP (Ciba-Geigy), Savinyl Black RLS (Sandoz), Orasol Blue GN (Ciba-Geigy), Luxol Blue MBSN (Morton-Thiokol), Morfast Black Concentrate A (Morton-Thiokol), CI Direct BLACK 38, and Direct Deep BLACK. These may be used individually or in combination of two or more.

[0137] The amount of the above dye is preferably 0.5% to 10% by mass, and more preferably 1% to 7% by mass, relative to the total mass of the carbon black. The greater the amount of dye, the higher the resistance value of the resin film can be. By keeping the amount of dye below an excessive level, it is possible to suppress the thickening of the photosensitive resin composition due to excess dye and the occurrence of aggregation caused by excess dye inhibiting the dispersibility of other components.

[0138] Furthermore, the above dye may be laked with a metal or metal salt. By lakeing the dye, the dye can be fixed to the surface of the carbon black via the metal or metal salt, thereby suppressing the reduction of the above effect due to the detachment of the dye from the surface of the carbon black. Examples of the above metals include aluminum, magnesium, calcium, strontium, barium, and manganese. Examples of the above metal salts include hydrochlorides and sulfates of these metals. The content of the above metal or metal salt is preferably 0.3 times or more in molar amount relative to the dye, more preferably 0.5 times or more in molar amount, and even more preferably 0.6 times or more in molar amount.

[0139] Component (D) is a pigment disperse containing a light-shielding component, and preferably contains a dispersant for dispersing the light-shielding component, and more preferably the dispersant contains component (A1). As the dispersant for dispersing the light-shielding component, only component (A1) may be used, or a mixture of dispersants other than component (A1) may be used. As the dispersant other than component (A1), any known compound used for dispersing pigments (light-shielding components) (compounds commercially available under names such as dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation.

[0140] Examples of dispersants other than component (A1) of the light-shielding component include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative type dispersants (dispersion aids), etc. In particular, the above dispersant is preferably a cationic polymer dispersant having cationic functional groups such as imidazolyl groups, pyrrolyl groups, pyridyl groups, primary, secondary, or tertiary amino groups as adsorption sites to the colorant, with an amine value in the range of 1 mg KOH / g to 100 mg KOH / g and a number average molecular weight (Mn) in the range of 1,000 to 100,000.

[0141] The total amount of component (A1) and dispersants other than component (A1) relative to the light-shielding component is preferably 10% to 60% by mass, and more preferably 15% to 60% by mass, based on the total mass of the light-shielding component. By setting it within this range, the dispersibility of the light-shielding component is enhanced, and even when the photosensitive resin composition is stored over time, aggregation of the light-shielding component is suppressed, and the reflectance and aggregated foreign matter in the black resist are suppressed. Note that if the light-shielding component is dye-coated carbon black, the mass of the dye coating the carbon black is not included in the total amount of component (A1) and dispersants other than component (A1).

[0142] The content of component (A1) in component (D) relative to the total mass of the above dispersant is preferably 15% to 100% by mass, and more preferably 20% to 90% by mass. By setting it within this range, the dispersibility of the light-shielding component is enhanced, making it easier to suppress aggregation of the light-shielding component regardless of the storage time of the photosensitive resin composition, and thus making it easier to suppress reflectivity and aggregated foreign matter in the black resist.

[0143] The amount of light-shielding component is preferably 20% to 80% by mass, and more preferably 30% to 60% by mass, relative to the total mass of solids in the photosensitive resin composition. If the amount of light-shielding component is 20% by mass or more relative to the solids in the photosensitive resin composition, the light-shielding properties of the black resist can be sufficiently enhanced. If the amount of light-shielding component is 80% by mass or less relative to the solids in the photosensitive resin composition, the content of component (A), which is the original binder, can be sufficiently increased, making it easier to enhance the desired developing characteristics and film-forming ability.

[0144] 1-5. (E) Silica dispersed powder containing silica particles Component (E) is a silica dispersed powder containing silica particles, which can lower the refractive index of the cured film (light-shielding film). As a result, reflection caused by the difference in refractive index between the cured film (light-shielding film) and the transparent substrate, air, transparent protective film, etc., can be suppressed, thereby lowering the reflectivity of the cured film.

[0145] The type of silica particles is not particularly limited, nor are the manufacturing methods (gas-phase or liquid-phase reaction) or the shape (spherical or non-spherical) particularly limited. Furthermore, the silica particles may be solid or hollow. "Hollow silica particles" refer to silica particles that have a cavity inside.

[0146] The average particle diameter of the silica particles is more preferably 20 nm to 150 nm, and even more preferably 60 nm to 100 nm. Compared to silica particles with a small average particle diameter of a few nanometers, silica particles within the above size range are less likely to aggregate. Therefore, when the particle diameter of the silica particles is 20 nm or larger, the dispersion stability of the silica particles is improved, the movement in the thickness direction due to aggregation of silica particles is less restricted, and a sufficient amount of silica particles can be unevenly distributed on the glass surface side, thus allowing for a more significant reduction in the reflectance on the glass surface side. Furthermore, by setting the average particle diameter of the silica particles to 150 nm or less, it is possible to move the silica particles to a certain extent within the coating film, making it easier to unevenly distribute the silica particles on the glass surface side, and suppressing the decrease in linearity and surface smoothness of the cured film caused by scattering by silica particles.

[0147] The average particle size of silica particles is measured using the cumulant method with the "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.), a particle size distribution analyzer that employs dynamic light scattering.

[0148] The refractive index of the silica particles is preferably 1.10 to 1.47. While ordinary silica particles with a refractive index of 1.45 to 1.47 can be used, using hollow silica particles with a lower refractive index can also lower the refractive index of the light-shielding film compared to a light-shielding film containing only ordinary silica particles.

[0149] The refractive index of silica particles can be determined from a transparent mixture obtained by mixing the silica particles, which have been processed into a powder, with a standard refractive index solution of known refractive power. The refractive index of inorganic fine particles is a value measured using an Abbe refractometer, and the refractive index value in this application refers to the refractive index value for light with a wavelength of 550 nm. The method for measuring the refractive index of silica particles using an Abbe refractometer is as follows: The refractive index of a transparent mixture obtained by mixing the silica particles, which have been processed into a powder, with a standard refractive index solution of known refractive power is measured, and the refractive index of the silica particles is calculated based on the change in refractive index between the refractive index of the standard refractive index solution before mixing the silica particles and the refractive index of the mixture after mixing the silica particles, and the amount of silica particles added to the standard refractive index solution.

[0150] The silica particles may be perfectly spherical or elliptical in shape, but a perfectly spherical shape is preferable because it is easier to lower the refractive index and increase the strength of the light-shielding film. For example, inorganic fine particles are preferably sphericity 1.0 to 1.5. If the sphericity of the inorganic fine particles is within this range, the particle shape will be close to a perfect sphere. As a result, they can be uniformly filled into a thin light-shielding film, and a light-shielding film can be formed in which the inorganic fine particles are not exposed to the outside from the film surface while maintaining the smoothness of the film surface. Therefore, a light-shielding film with a low refractive index and sufficient strength can be obtained.

[0151] The sphericity of the silica particles is preferably 1.0 to 1.5. When the sphericity of the silica particles is within this range, the particle shape is close to a perfect sphere. As a result, the silica particles can be uniformly filled in the in-plane direction (the direction horizontal to the substrate surface) within a thin light-shielding film, and a light-shielding film can be formed in which the silica particles are not exposed to the outside from the surface of the cured film while maintaining the smoothness of the surface of the cured film. Therefore, a light-shielding film with a low refractive index and sufficient strength can be obtained.

[0152] The sphericity of silica particles can be determined from the ratio of the longest diameter to the shortest diameter of the particles (the average value of any 100 silica particles). Here, the longest and shortest diameters of the silica particles are determined by photographing the silica particles with a transmission electron microscope and measuring the longest and shortest diameters from the resulting microscope images.

[0153] Component (E) is a silica dispersed phase containing silica particles, and may or may not contain a dispersant for dispersing the silica particles, but it is preferable to include a dispersant. The silica particles may be silica particles that have been hydrophobized using a known hydrophobic agent such as a silane coupling agent. As the dispersant for silica particles, any known compound used for dispersing silica particles (compounds commercially available under names such as dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation.

[0154] Furthermore, it is preferable that a portion of component (A1) is included in component (E), and it is even more preferable that component (A1) is included as a dispersant for the silica particles. When a portion of component (A1) is included in component (E), the dispersibility of the silica particles is enhanced, and even when the photosensitive resin composition is stored over time, the aggregation of silica particles is more easily suppressed, and the reflectivity and aggregated foreign matter in the black resist are more easily suppressed. In addition, when forming a coating film of the photosensitive resin composition, the suppression of silica particle aggregation increases mobility, and the silica particles tend to segregate towards the glass substrate side, which has a high affinity for silica particles, thus reducing the reflectivity on the glass surface side. Furthermore, during development and exposure, component (A1) included as a dispersant for silica particles and component (A1) included as a binder form a cross-linked structure, so the degree of hardening in the exposed area is sufficiently increased, and the development adhesion is more easily enhanced.

[0155] Furthermore, "a portion of component (A1) is included in component (E)" means, similar to the "a portion of component (A1) is included in component (D)" configuration, that component (A1) and silica particles interact, causing component (A1) to adsorb onto the silica particles and form a dispersed phase containing component (A1), or, if component (E) contains a dispersant other than (A1), that component (A1) interacts with the dispersant other than (A1) or silica particles adsorbed onto the silica particles, causing component (A1) to exist in close proximity to the dispersant other than (A1) or silica particles, thereby forming a dispersed phase containing component (A1). The method for confirming whether a portion of component (A1) is included in component (E) and the method for separating component (D) and component (E) are the same as the methods for confirming whether a portion of component (A1) is included in component (D) and the separation methods described above.

[0156] Known dispersants can be used as dispersants for silica particles. Examples of dispersants include alkylammonium salts and alkylol ammonium salts of acidic polymers, alkylammonium salts and alkylol ammonium salts of polymer copolymers having acidic groups, neutralized salts of polymers having alkylamino groups, and phosphate ester salts of polymer copolymers. Of these, polymer compounds having an alkylammonium salt structure are preferred, and alkylammonium salts of acidic polymers and alkylammonium salts of polymer copolymers having acidic groups are more preferred. By using polymer compounds having an alkylammonium salt structure as a dispersant, the generation of aggregated foreign matter derived from silica particles can be suppressed more significantly.

[0157] The dispersant used for silica particles preferably has an acid value or an amine value, more preferably 10 mg KOH / g to 80 mg KOH / g, and even more preferably both the acid value and the amine value are between 10 mg KOH / g and 80 mg KOH / g. If the amine value is 10 mg KOH / g or higher, the dispersibility of silica particles can be improved. Also, if both the acid value and the amine value are 10 mg KOH / g or higher, residue at the pattern edges is more easily reduced, and linearity is more easily improved. However, if the amine value of the dispersant is 10 mg KOH / g or higher, and the acid value is also 10 mg KOH / g or higher, it becomes possible to form a high-resolution pattern while improving the dispersibility of silica particles. On the other hand, by setting either the acid value or the amine value to 80 mg KOH / g or lower, the solubility of component (E) in the developer does not become excessively high, and a decrease in the resolution of the formed pattern can be suppressed. From the above viewpoint, the dispersant may be configured such that one of its amine value and acid value is 30 mg KOH / g to 80 mg KOH / g, and it is also preferable that both of these be 30 mg KOH / g to 80 mg KOH / g.

[0158] The acid value of the dispersant refers to the number of mg of KOH required to neutralize 1 g of resin component (solids), and can be measured in accordance with JIS K 0070:1992. The amine value of the dispersant, which is component (F), refers to the number of mg of KOH equivalent to the amount of acid (acetic acid, etc.) required to neutralize 1 g of resin component (solids), and can be measured in accordance with JIS K 7237:1995.

[0159] Examples of commercially available silica particle dispersants include DISPERBYK-140, 142, 145, 2001, 2025, and 9076 (all manufactured by Bic Chemie Japan, "DISPERBYK" is a registered trademark of the company). Of the above commercially available products, DISPERBYK-140, 142, and 9076 are preferred, and DISPERBYK-140 and 9076 are more preferred.

[0160] The total amount of component (A1) and other dispersants relative to the silica particles is preferably 10% to 50% by mass, and more preferably 15% to 40% by mass, based on the total mass of the silica particles. By setting the amount within this range, the dispersibility of the silica particles is enhanced, making it easier to suppress the aggregation of silica particles even when the photosensitive resin composition is stored over time, and thus making it easier to suppress reflectivity and aggregated foreign matter in the black resist.

[0161] The content of component (A1) in component (E) relative to the total mass of the above dispersant is preferably 10% to 100% by mass, more preferably 15% to 90% by mass, and even more preferably 15% to 70% by mass. By setting it within this range, the dispersibility of silica particles is increased, making it easier to suppress the aggregation of silica particles regardless of the storage time of the photosensitive resin composition, and thus making it easier to suppress reflectivity and aggregated foreign matter in the black resist.

[0162] Furthermore, the ratio of the total mass of silica particles (mE1) to the total mass of light-shielding components (mD1) in the black resist photosensitive resin composition (mE1 / mD1) is preferably 0.01 to 0.20, and more preferably 0.06 to 0.12. When mE1 / mD1 is 0.01 or higher, there is a sufficient amount of silica particles, which reduces the reflectance regardless of the time elapsed in the photosensitive resin composition. In addition, the presence of a sufficient amount of dispersed silica particles reduces the collision frequency between pigment dispersed particles, thereby suppressing aggregation of light-shielding components and making it easier to suppress aggregated foreign matter when the photosensitive resin composition is aged. Furthermore, when mE1 / mD1 is 0.20 or lower, it is possible to form a film with low reflectance while maintaining high light-shielding properties, which makes it easier to improve development adhesion.

[0163] 1-6. (F) Solvent Component (F) dissolves or disperses each component contained in the photosensitive resin composition and adjusts the viscosity of the photosensitive resin composition.

[0164] Examples of component (F) include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, and 3-methoxy-3-methyl-1-butanol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene Examples include glycol ethers such as pyrene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, and 3-methoxy-3-methyl-1-butyl acetate; and esters such as ethyl 3-ethoxypropionate, γ-butyrolactone, and ethyl lactate.

[0165] Component (F) may be used alone or in combination of two or more types. Component (F) preferably contains propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA"), and more preferably contains PGMEA and a solvent having a dielectric constant of 10.0 to 30.0 at 23°C.

[0166] The inclusion of PGMEA facilitates the dissolution of components (A) to (C), thereby improving the coatability of the photosensitive resin composition and suppressing aggregated foreign matter. Furthermore, the inclusion of a solvent with a dielectric constant of 10.0 to 30.0 at 23°C stabilizes the silanol groups on the surface of the silica particles through solvation, suppressing the aggregation of component (E) in the photosensitive resin composition. This reduces reflectivity and further suppresses aggregated foreign matter. From this viewpoint, the dielectric constant of the solvent with a dielectric constant of 10.0 to 30.0 at 23°C is preferably 13.0 to 20.0, and more preferably 13.0 to 18.0.

[0167] Examples of solvents with a dielectric constant of 10.0 to 30.0 at 23°C include ethyl lactate (dielectric constant 13.7), 3-methoxy-3-methyl-1-butanol (dielectric constant 13.3), 1-methoxy-2-propanol (dielectric constant 12.5), and cyclohexanone (dielectric constant 16.4).

[0168] The amount of PGMEA is preferably 10% to 100% by mass, more preferably 20% to 100% by mass, even more preferably 30% to 100% by mass, and most preferably 45% to 85% by mass, relative to the total mass of component (F). By increasing the amount of PGMEA, the solubility of components (A) to (C) and the dispersibility of components (D) and (E) can be further improved.

[0169] The amount of solvent with a dielectric constant of 10.0 to 30.0 at 23°C is preferably 0% to 90% by mass, more preferably 0% to 80% by mass, even more preferably 0% to 70% by mass, and most preferably 15% to 55% by mass, relative to the total mass of component (F). By increasing the amount of solvent with a dielectric constant of 10.0 to 30.0 at 23°C, aggregation of component (E) can be suppressed and the reflectance can be reduced more efficiently. By setting the amount of solvent with a dielectric constant of 10.0 to 30.0 at 23°C to 90% by mass or less, the coatability of the photosensitive resin composition can be more easily improved.

[0170] The amount of component (F) is preferably 40% to 90% by mass, more preferably 60% to 90% by mass, and even more preferably 80% to 90% by mass, based on the total mass of the photosensitive resin composition.

[0171] 1-7. Other ingredients The photosensitive resin composition may optionally contain epoxy compounds and their curing agents and curing accelerators, coupling agents, surfactants, resins other than alkali-soluble resins, thermal polymerization inhibitors and antioxidants, plasticizers, fillers, leveling agents, defoamers, ultraviolet absorbers, and other components.

[0172] Examples of epoxy compounds 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 (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), epoxy compounds with aromatic structures such as tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, and glycidyl ethers of polyhydric carboxylic acids. Esters, copolymers of monomers having a (meth)acryloyl group containing (meth)acrylate glycidyl as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, epoxy compounds having a glycidyl group such as hydrogenated bisphenol A diglycidyl ether (e.g., Licarezin HBE-100: manufactured by Shin Nippon Rika Co., Ltd., "Licarezin" is a registered trademark of the company), 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175: manufactured by Huntsman, "Araldite" is a registered trademark of the company), bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128 (manufactured by Dow Chemical), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celoxide 2021P: manufactured by Daicel Corporation, "Celoxide" is a registered trademark of the company), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolid GT401: manufactured by Daicel Corporation, "Epolid" is a registered trademark of the company), epoxy compounds having epoxycyclohexyl groups (e.g., HiREM-1: manufactured by Shikoku Chemicals, Inc.), polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 2,Examples include alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the company), and epoxy compounds having a silicone skeleton. Of these, epoxy compounds having the above-mentioned aromatic structure are preferred from the viewpoint of improving the flatness and low gas emission of the coating film or cured film.

[0173] Examples of curing agents include amine compounds, polycarboxylic acid compounds or their anhydrides, thermally decomposable esters of polycarboxylic acids, phenolic resins, amino resins, dicyandiamides, Lewis acid complex compounds, etc., that contribute to the curing of epoxy resins. Among these, compounds selected from the group consisting of polycarboxylic acids and their anhydrides, and thermally decomposable esters of polycarboxylic acids are preferred.

[0174] Examples of curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene-7, and 1,5-diazabicyclo[4.3.0]nona-5-ene; phosphines such as triphenylphosphine, tricyclohexylphosphine, and triphenylphosphinetriphenylborane; and metal compounds such as tin octylate. Among these, 1,8-diazabicyclo[5.4.0]undeca-7-ene or 1,5-diazabicyclo[4.3.0]nona-5-ene or their salts are preferred.

[0175] Examples of coupling agents include silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane, as well as titanium-based coupling agents and aluminum-based coupling agents. Among these, 3-isocyanatetopropyltriethoxysilane is preferred.

[0176] Examples of surfactants include compounds containing hydrocarbon chains as side chains, silicone-containing compounds, and fluorinated compounds.

[0177] Examples of compounds containing hydrocarbon chains as side chains include polymers obtained by polymerizing alkyl (meth)acrylates. Examples of alkyl (meth)acrylates include ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isononyl (meth)acrylate.

[0178] Examples of silicone-containing compounds include reaction products of (meth)acrylic acid with hydroxyl group-containing silicone (e.g., α,ω-polydimethylsilicone diol) and reaction products of (meth)acrylic acid with epoxy group-containing silicone (e.g., polydimethylsilicone containing pendant epoxy groups).

[0179] Examples of fluorine-containing compounds include perfluoroalkyl sulfonic acids, perfluoroalkyl carboxylic acids, perfluoroalkyl alkylene oxide adducts, perfluoroalkyltrialkylammonium salts, oligomers containing a perfluoroalkyl group and a hydrophilic group, oligomers containing a perfluoroalkyl group and a lipophilic group, oligomers containing a perfluoroalkyl group, a hydrophilic group and a lipophilic group, urethanes containing a perfluoroalkyl group and a hydrophilic group, perfluoroalkyl esters, perfluoroalkyl phosphate esters, and fluorine-containing organic compounds such as compounds containing a fluorine atom in the side chain.

[0180] Furthermore, the surfactant may contain a crosslinking group. The crosslinking group is preferably an epoxy group or an ethylenically unsaturated group.

[0181] Examples of commercially available surfactants include DOWSIL SH 3775 M Fluid (manufactured by Dow-Toray Industries, Inc.), MEGAFACE EFS-131, MEGAFACE EFS-321, MEGAFACE EFS-521, MEGAFACE EFS-801 (manufactured by DIC Corporation), and others.

[0182] Of these, the surfactant is preferably a silicone-containing compound.

[0183] The surfactant content is preferably 0.01% to 10.00% by mass, more preferably 0.01% to 5.00% by mass, and even more preferably 0.01% to 1.00% by mass, relative to the total solid content of the photosensitive resin composition. Here, a surfactant content of 0.01% by mass or more tends to increase smoothness, while a surfactant content of 10.00% by mass or less makes it less likely for the surfactant to aggregate, thus also tending to increase smoothness.

[0184] Examples of resins other than alkali-soluble resins include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, and melamine resins.

[0185] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds.

[0186] Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fibers.

[0187] Examples of defoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic compounds.

[0188] Examples of UV absorbers include benzotriazole compounds, benzophenone compounds, and triazine compounds. The photosensitive resin composition may optionally contain additives other than component (A), such as epoxy resins, curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, leveling agents, defoamers, surfactants, and coupling agents.

[0189] 2. Method for producing a photosensitive resin composition for black resist The method of manufacture is not particularly limited, as long as the photosensitive resin composition is prepared by mixing components (A) to (F) and optionally other components such that a portion of component (A1) is contained in component (F) in a dissolved state, and a portion of component (A1) is contained in component (D).

[0190] Examples of methods for producing a photosensitive resin composition include: (Step A) A step of preparing a pigment dispersion containing component (D) which contains component (A1) and a solvent, (Step B)(E) A step of preparing a silica dispersion containing the components and a solvent, (Step C) A step in which component (A) containing component (A1), component (B), component (C), the pigment dispersion prepared in Step A, a silica dispersion containing silica particles and solvent, and a solvent are mixed. Preferably, the silica dispersion used in step B above is A silica dispersion containing component (E) containing component (A1) and a solvent, It is preferable that it be so.

[0191] In steps A and B described above, the steps for preparing the pigment dispersion and silica dispersion may involve using pre-prepared materials, or the pigment dispersion and silica dispersion may be prepared from scratch.

[0192] A known particle dispersion method can be used to prepare the above-mentioned pigment dispersion or silica dispersion. For example, by mixing a light-shielding component or silica particles, component (A1), and optionally a dispersant other than component (A1) in a solvent, and dispersing the particles in a bead mill, a pigment dispersion containing component (D) containing component (A1) and a solvent, or a silica dispersion containing component (E) containing component (A1) and a solvent, can be prepared.

[0193] At this time, the particle size can be adjusted by measuring the particle size of the light-shielding components and silica particles as needed, and stopping the dispersion when the desired particle size is reached.

[0194] 3. Light-shielding film The light-shielding film according to this embodiment includes a coating film forming step of applying the above-mentioned photosensitive resin composition to a substrate to form a coating film, and optionally includes an exposure step and / or a heat treatment step. When patterning the light-shielding film, in the exposure step, a photomask or the like is used to create areas that are exposed to light and areas that are not, so that only the areas exposed to light are cured and the other areas are dissolved with an alkaline solution to form a desired pattern shape.

[0195] 3-1. Paint film formation process The photosensitive resin composition can be applied to a substrate by known methods such as immersion in a solution, spraying, using a roller coater, land coater, slit coater, or spinner. After applying the composition to the desired thickness using these methods, the solvent is removed to form a coating film.

[0196] The solvent may be dried under reduced pressure, or at atmospheric pressure without reduced pressure. Furthermore, the solvent may be dried under reduced pressure followed by heat drying (pre-baking), or either one of these methods may be performed alone.

[0197] For example, when reducing pressure, it is acceptable to do so under conditions that the target pressure reaches 5 to 1000 Pa in 10 to 180 seconds. Alternatively, degassing may be performed all at once until the target pressure is reached, or the pressure may be reduced gradually to prevent membrane defects such as bumping. From the viewpoint of production cycle time, it is preferable to dry under conditions that the target pressure reaches 50 to 1000 Pa in 10 to 50 seconds.

[0198] Pre-baking is performed by heating in an oven, on a hot plate, vacuum drying, or a combination of these methods. The heating temperature and time during pre-baking can be appropriately selected depending on the solvent used, but it is preferable to heat at 80-120°C for 1-10 minutes, for example.

[0199] 3-2. Exposure Process Exposure can be performed by irradiating a portion of the aforementioned coating film with radiation through a photomask. This exposure photo-cures the portion of the coating film corresponding to the pattern.

[0200] The above-mentioned photomasks can be any known type. Examples of photomasks include multi-tone masks such as halftone masks and graytone masks. In a graytone mask, a light-shielding area and a diffraction grating are formed on a translucent substrate. The diffraction grating has light-transmitting areas such as slits, dots, and meshes spaced at intervals less than or equal to the resolution limit of the light used for exposure, and this configuration controls the light transmittance. In a halftone mask, a light-shielding area and a semi-transparent area are formed on a translucent substrate. The semi-transparent area controls the transmittance of the light used for exposure.

[0201] The exposure apparatus and exposure irradiation conditions used for exposure can be selected as appropriate. Examples of radiation to be irradiated include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among the above radiations, ultraviolet light is preferred. In addition, known exposure apparatuses (ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, far ultraviolet lamps, etc.) can be used as the radiation irradiation apparatus. Furthermore, the wavelength of the radiation to be irradiated is preferably 250 nm to 400 nm. The radiation exposure dose is 25 mJ / cm². 2 ~3000 mJ / cm 2 It is preferable that this be the case.

[0202] 3-3.Developing process After exposure, the irradiated coating is subjected to alkaline development to remove the coating from the unexposed areas.

[0203] Examples of development methods for coated films include shower development, spray development, dip development, and paddle development. These development processes can be carried out using commercially available developing machines or ultrasonic cleaners.

[0204] Examples of developers suitable for development include aqueous solutions of alkali metal or alkaline earth metal carbonates, and aqueous solutions of alkali metal hydroxides. Among these, it is preferable to use an alkaline aqueous solution containing 0.04 to 3% by mass of an organic alkaline substance such as hydroxides (sodium hydroxide, potassium hydroxide, etc.), carbonates (sodium carbonate, potassium carbonate, lithium carbonate, etc.), or tetramethylammonium hydroxide, at a temperature of 21 to 27°C. In the development process, commercially available developing machines or ultrasonic cleaning machines can be used.

[0205] 3-4. Heat treatment process The formed coating may be heat-treated. This promotes a thermal crosslinking reaction, which improves the adhesion between the light-shielding film and the substrate.

[0206] Heat treatment can be carried out by known methods (heating using an oven, hot air blower, hot plate, infrared heater, etc., vacuum drying, or a combination thereof).

[0207] The heat treatment conditions are not particularly limited as long as the temperature at which the coating film undergoes full curing (post-bake) is reached. Preferably, the heating temperature is 60 to 250°C for 20 to 60 minutes.

[0208] After heat curing, the cured film may be cleaned with short-wavelength radiation to remove organic contaminants from the surface of the coated film.

[0209] The above cleaning can be performed, for example, by irradiating with ultraviolet light of wavelengths of 185 nm and 254 nm using a low-pressure mercury lamp. The irradiation dose in this case can be 1000 mJ.

[0210] The reflectance of the light-shielding film on the glass surface side is preferably 5.6% or less, more preferably 5.3% or less, and even more preferably 5.0% or less. As a method for manufacturing the light-shielding film, for example, a photosensitive resin composition is applied to a glass substrate, the solvent is evaporated by reducing the pressure to 50 Pa for 45 seconds using a vacuum dryer at 23°C, and then the film is pre-baked at 90°C for 1 minute using a hot plate to produce a light-shielding film, and the i-line illuminance is 30 mW / cm². 2 50 mJ / cm² with an ultra-high pressure mercury lamp 2 The film used is manufactured by irradiating the substrate with ultraviolet light, then developing it at 25°C with a 0.04% potassium hydroxide solution for 20 seconds beyond the break time (BT) at which the pattern begins to appear, followed by washing with water and then post-bake curing at 230°C for 30 minutes using a hot air dryer. The reflectance mentioned above refers to the reflectance of the substrate (glass substrate) side measured at an incident angle of 2° using the ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.) on the substrate with the cured film obtained by the above method.

[0211] 4. Color Filters The color filter according to this embodiment has the above-mentioned light-shielding film. For example, the light-shielding film can be used as a black matrix, black column spacer, frame, etc. of the color filter.

[0212] A known method can be used to form the color filter. For example, a color filter can be formed by applying a color resist material, exposing it to light, developing it to form a pattern, transferring a photosensitive transfer material, exposing it to light, developing it to form a pattern, or by using an inkjet method.

[0213] For example, a color filter having the above-mentioned light-shielding film as a black matrix can be manufactured by forming a light-shielding film with a thickness of 1.0 to 2.0 μm on a transparent substrate, and then forming red, blue, and green pixels by photolithography after the light-shielding film is formed, or by impregnating the light-shielding film with red, blue, and green inks using an inkjet process.

[0214] Furthermore, when the above light-shielding film is used as a black column spacer, multiple portions with different film thicknesses may be fabricated using a single black resist, with one portion functioning as a spacer and the other functioning as a black matrix.

[0215] 5. Touch panel The touch panel according to this embodiment has the above-mentioned light-shielding film. For example, the light-shielding film can be used as a black matrix, black column spacer, frame, etc. of the touch panel.

[0216] The touch panel according to this embodiment can be any known touch panel. It may be any type of touch panel from among various types such as resistive, capacitive, surface acoustic wave, infrared, electromagnetic induction, image recognition, and optical sensor types. There are methods that detect a touch when there is contact with the touch panel, and methods that detect a touch when a finger or pen approaches the touch panel, and either method is acceptable.

[0217] 6.Display device The display device according to this embodiment has the above-mentioned light-shielding film.

[0218] The display device according to this embodiment can use a known display device. Examples of display devices include liquid crystal displays and organic EL displays.

[0219] The photosensitive resin composition according to this embodiment is particularly useful as an ink for color filters used in liquid crystal displays, and the light-shielding film formed therefrom is useful as a black matrix for color filters. In addition to being used as an ink for color filters in color liquid crystal displays, the photosensitive resin composition of the present invention can also be used as an ink material for color separation or light shielding in various multi-color displays such as organic EL displays represented by organic EL elements and color liquid crystal displays, as well as as an overcoat (OC) layer with appropriate light-shielding properties that can cut off ambient light reflected by organic EL panels.

[0220] The light source of the above-mentioned display device may be a known light source such as an organic electroluminescent (EL) light source or a laser light-emitting diode (LED) light source. Furthermore, the display device may have a configuration in which a wavelength conversion layer containing quantum dots or a phosphor compound is placed between the light source and the substrate with the cured film described above. The above-mentioned cured film has particularly good flexibility resistance even when it is a thick film of 2 μm or 3 μm or more, making it useful as a light-shielding film with such a thickness, positioned laterally to the LED light source in an LED display to suppress lateral light leakage.

[0221] In particular, since the above-mentioned light-shielding film can reduce reflectivity, when used in applications where the film surface, such as a liquid crystal display, is located inside the display device, it can suppress the loss of light due to reflection within the device from an internal light source. Furthermore, when used in applications where the film surface, such as an organic LED (OLED), is located outside the display device, it can improve contrast in bright light by reducing the reflection of external light, and improve luminous efficiency by improving the light extraction efficiency from the light-emitting side.

[0222] 7. Other uses The photosensitive resin composition according to this embodiment is useful as an ink for color filters used in image sensors. Furthermore, the light-shielding film according to this embodiment is also useful as a black matrix for liquid crystal projection. Additionally, the photosensitive resin composition according to this embodiment can be used as an ink material for color separation or light shielding in various multi-color displays such as image sensors. Suitable sensors include those used in components requiring precise light-receiving sensitivity, such as sensors for light (laser) detection and distance measurement (LiDAR) for autonomous vehicles, and encoder light-receiving elements. [Examples]

[0223] The embodiments of the present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these. In the present invention, when the first decimal place of the content of each component is 0, the decimal part may be omitted.

[0224] First, we will explain the synthesis examples of the unsaturated group-containing alkali-soluble resin, which is component (A). Unless otherwise noted, the evaluation of the resin in these synthesis examples was performed as follows.

[0225] [Solid content concentration] The weight of 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)] and weighed [W1 (g)]. After heating at 160°C for 2 hours, the weight [W2 (g)] was calculated using the following formula. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0226] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the result.

[0227] [Molecular weight] The molecular weight was measured using gel permulation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuperH-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuperH-5000 (1) (manufactured by Tosoh Corporation), temperature: 40℃, rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was determined as a value converted to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0228] [Average particle size] The average particle size of silica particles was determined using the cumulant method with a dynamic light scattering particle size analyzer, "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.).

[0229] The abbreviations used in the synthesis examples are as follows: BPFE: Bisphenol fluorene type epoxy compound (a reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. In the compound of general formula (1), X is a fluorene-9,9-diyl group, R1 to R4 are hydrogen atoms, and l is 0.) AA: Acrylic acid BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride THPA: Tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene AA: Acrylic acid THPA: Tetrahydrophthalic anhydride SA: Succinic anhydride AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone TEA: Triethylamine PGMEA: Propylene glycol monomethyl ether acetate

[0230] [Synthesis Example 1] BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) were charged into a 500 ml four-necked flask equipped with a reflux condenser, and the mixture was stirred at 100-105°C for 20 hours to allow it to react. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged into the flask, and the mixture was stirred at 120-125°C for 6 hours to obtain unsaturated group-containing photosensitive resin (A1)-1. The solid content concentration of the obtained resin solution was 56.0% by mass, the acid value (based on solid content) was 103 mg KOH / g, and the Mw value determined by GPC analysis was 3600.

[0231] [Synthesis Example 2] BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) were charged into a 500 ml four-necked flask equipped with a reflux condenser, and the mixture was stirred at 100-105°C for 20 hours to allow it to react. Next, BPDA (67.7 g, 0.23 mol) and THPA (1.5 g, 0.01 mol) were charged into the flask, and the mixture was stirred at 120-125°C for 6 hours to obtain unsaturated group-containing photosensitive resin (A1)-2. The solid content concentration of the obtained resin solution was 56.0% by mass, the acid value (based on solid content) was 97 mg KOH / g, and the Mw value determined by GPC analysis was 5500.

[0232] [Synthesis Example 3] 300.0 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser, and the flask system was purged with nitrogen before being heated to 120°C. A monomer mixture [a mixture of DCPMA (66.1 g, 0.3 mol), GMA (85.3 g, 0.6 mol), and St (10.4 g, 0.10 mol) in which AIBN (10 g) was dissolved] was added dropwise to this flask using a dropping funnel over 2 hours, and the mixture was stirred at 120°C for another 2 hours to obtain a copolymer solution. Next, after purging the flask system with air, 43.2 g of AA (0.6 mol), 0.8 g of TDMAMP (0.8 g), and 0.15 g of HQ (0.15 g) were added to the obtained copolymer solution, and the mixture was stirred at 120°C for 6 hours to obtain an unsaturated group-containing photosensitive resin solution. Furthermore, THPA (59.3 g, 0.39 mol) and TEA (0.5 g) were added to the obtained unsaturated group-containing photosensitive resin solution and reacted at 120°C for 4 hours to obtain polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (A2)-1. The solid content concentration of the resin solution was 48.0% by mass, the acid value (based on solid content) was 79 mg KOH / g, and the Mw value determined by GPC analysis was 8500.

[0233] [Preparation Example 1] 1000g of carbon black (TPX-1099: manufactured by Cabot) was mixed with water to prepare 10L of slurry, which was stirred at 95°C for 1 hour, allowed to cool, and then washed with water. This slurry was mixed again with water to prepare another 10L of slurry, and 42.9g of 70% nitric acid was added and stirred at 40°C for 4 hours. After allowing to cool and washing with water, another 10L of slurry was prepared by mixing with water, and 769.2g of 13% sodium hypochlorite aqueous solution was added and stirred at 40°C for 6 hours. After allowing to cool and washing with water, another 10L of slurry was prepared by mixing with water, and 38.1g of 38.4% purity dye (Direct Deep BLACK) was added and stirred at 40°C for 1 hour, and then 10.1g of aluminum sulfate was added and stirred at 40°C for 1 hour. After allowing to cool and washing with water, the mixture was filtered and dried to obtain dye-coated carbon black.

[0234] The photosensitive resin compositions of Examples 1 to 17 and Comparative Examples 1 to 5 were prepared with the compounding amounts (unit: parts by mass) shown in Tables 1 and 2. The compounding components used in Tables 1 and 2 are as follows. As the component (D) (pigment dispersion liquid) and the component (E) (silica dispersion liquid), dispersion liquids having the following compositions (D)-1 to (D)-6 and (E)-1 to (E)-5 were prepared and used, respectively. Among these, (D)-1 to (D)-4 are pigment dispersion liquids containing the component (A1) as a dispersant for the light-shielding component and a solvent, and (E)-2 to (E)-5 are silica dispersion liquids containing the component (A1) as a dispersant for silica particles and a solvent.

[0235] (Unsaturated group-containing photosensitive soluble resin) (A1)-1: Unsaturated group-containing photosensitive resin obtained in Synthesis Example 1 above (solid content concentration 56.0% by mass) (A1)-2: Unsaturated group-containing photosensitive resin obtained in Synthesis Example 2 above (solid content concentration 56.0% by mass) (A2)-1: Unsaturated group-containing photosensitive resin obtained in Synthesis Example 3 above (solid content concentration 48.0% by mass)

[0236] (Photopolymerizable compound) (B): Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by Toagosei Co., Ltd., "Aronix" is a registered trademark of the company)

[0237] (Photopolymerization initiator) (C)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetoxyoxime) (Irgacure OXE-02, manufactured by BASF Japan Ltd., "Irgacure" is a registered trademark of the company) (C)-2: Adeka Arcles NCI-831, manufactured by Adeka Corporation, "Adeka Arcles" is a registered trademark of the company)

[0238] (Pigment dispersion liquid) (D)-1: Pigment dispersion containing 25.0% by mass of carbon black and 10.0% by mass of dispersant (2.0% by mass of polymer dispersant, 8.0% by mass of (A1)-1) (solids content 35.0% by mass, PGMEA solvent) (D)-2: Pigment dispersion containing 25.0% by mass of carbon black and 10.0% by mass of dispersant (7.0% by mass of polymer dispersant, 3.0% by mass of (A1)-1) (solids content 35.0% by mass, PGMEA solvent) (D)-3: Pigment dispersion containing 25.0% by mass of carbon black and 10.0% by mass of dispersant (2.0% by mass of polymer dispersant, 8.0% by mass of (A1)-2) (solids content 35.0% by mass, PGMEA solvent) (D)-4: A pigment dispersion (solids content 35.0% by mass, PGMEA solvent) containing the dye-coated carbon black obtained in Preparation Example 1 with a concentration of 25.0% by mass (carbon black 24.0% by mass, dye 1.0% by mass) and a dispersant 10.0% by mass (polymer dispersant 2.0% by mass, (A1)-1 8.0% by mass). (D)-5: Pigment dispersion containing 25.0% by mass of carbon black and 10.0% by mass of a dispersant (10.0% by mass of a polymeric dispersant) (solids content 35.0% by mass, PGMEA solvent) (D)-6: Pigment dispersion containing 25.0% by mass of carbon black and 10.0% by mass of dispersant (2.0% by mass of polymer dispersant, 8.0% by mass of (A2)-1) (solids content 35.0% by mass, PGMEA solvent)

[0239] (Silica dispersion) (E)-1: PGMEA dispersion of silica particles "YA050C" (manufactured by Admatex Co., Ltd., solid content concentration 30% by mass, average particle diameter 50 nm) (E)-2: A silica dispersion containing 25.0% by mass of silica particles (average particle size 50 nm) and 5.0% by mass of a dispersant (3.0% polymer dispersant, 2.0% by mass of (A)-1) (solids content 30.0% by mass, PGMEA solvent). (E)-3: A silica dispersion containing 25.0% by mass of silica particles (average particle size 80 nm) and 5.0% by mass of a dispersant (3.0% polymer dispersant, 2.0% by mass of (A)-1) (solids content 30.0% by mass, PGMEA solvent). (E)-4: A silica dispersion containing 25.0% by mass of silica particles (average particle size 120 nm) and 5.0% by mass of a dispersant (3.0% polymer dispersant, 2.0% by mass of (A)-1) (solids content 30.0% by mass, PGMEA solvent). (E)-5: Silica dispersion containing 25.0% by mass of silica particles (average particle size 200 nm) and 5.0% by mass of dispersant (3.0% polymer dispersant, 2.0% by mass of (A)-1) (solids content 30.0% by mass, PGMEA solvent)

[0240] (solvent) (F)-1: Propylene glycol monomethyl ether acetate (PGMEA) (F)-2: Ethyl lactate (EL)

[0241] [Table 1] Note that the values ​​listed in columns (A1)-1, (A1)-2, and (A2)-1 of the above-mentioned ingredients indicate the amount of ingredient (A) contained in ingredient (F) when dissolved, and do not include the amount of ingredient (D) or ingredient (A) contained as a dispersant for ingredient (E).

[0242] [Table 2] Note that the values ​​listed in columns (A1)-1, (A1)-2, and (A2)-1 of the above-mentioned ingredients indicate the amount of ingredient (A) contained in ingredient (F) when dissolved, and do not include the amount of ingredient (D) or ingredient (A) contained as a dispersant for ingredient (E).

[0243] [evaluation] A light-shielding film was prepared by curing a photosensitive resin composition for black resist, for use in evaluation, as follows.

[0244] [Preparation of a light-shielding film for immediate evaluation after preparation] A 25mm x 125mm glass substrate "#1737" (manufactured by Corning) (hereinafter referred to as "glass substrate") was pre-heated with a low-pressure mercury lamp at a wavelength of 254nm and an illuminance of 1000mJ / cm². 2 The surface was cleaned by irradiating it with ultraviolet light. After preparing the photosensitive resin compositions of the examples and comparative examples shown in Tables 1 and 2 above, without storing them for a period of time, they were applied to a glass substrate using a spin coater so that the film thickness after heat curing was 1.2 μm. The solvent was evaporated by reducing the pressure to 50 Pa for 45 seconds using a vacuum dryer at 23°C, and then a light-shielding film was prepared by pre-baking at 90°C for 1 minute using a hot plate. Next, the exposure gap was adjusted to 100 μm, and a negative-type photomask with line / space = 5 μm / 5 μm to 20 μm / 20 μm was placed over the dried light-shielding film, with an i-line irradiance of 30 mW / cm². 2 50 mJ / cm² with an ultra-high pressure mercury lamp 2 The photosensitive portion was subjected to a photocuring reaction by irradiating it with ultraviolet light.

[0245] Next, the exposed light-shielding film was subjected to a 1 kgf / cm² treatment with a 0.04% potassium hydroxide solution at 25°C. 2 After performing a development process at a shower pressure of +20 seconds from the development time (break time = BT) when the pattern begins to appear, 5 kgf / cm² 2 The light-shielding film was spray-washed to remove the unexposed portion of the light-shielding film, forming a light-shielding film pattern on the glass substrate. The film was then cured (post-bake) at 230°C for 30 minutes using a hot air dryer to obtain the light-shielding films for evaluation according to the examples and comparative examples.

[0246] The light-shielding film prepared for evaluation was evaluated against the following items.

[0247] [Development adhesion] (Evaluation method) The mask patterns of 5 μm to 20 μm after final curing (post-bake) were observed using an optical microscope. A result of △ or higher was considered acceptable.

[0248] (Evaluation Criteria) ◎: The cured film (coating) retains a 5μm pattern. 〇: The cured film (coating film) has peeling occurring in a 5-μm pattern, and at least one of the 6-μm to 10-μm patterns remains. △: The cured film (coating film) has peeling occurring in all patterns from 5 μm to 10 μm, and at least one of the 11-μm to 20-μm patterns remains. ×: The cured film (coating film) has peeled in all patterns from 5 μm to 20 μm.

[0249] [Reflectance Evaluation (on the Glass Substrate Side)] (Evaluation Method) For the substrate with a light-shielding film prepared in the same manner as the above-mentioned light-shielding film for evaluation, the reflectance on the substrate (glass substrate) side was measured at an incident angle of 2° using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Technologies Corporation).

[0250] [Optical Density Evaluation] (Evaluation Method) Using a Macbeth transmission densitometer, the optical density (OD) of the prepared light-shielding film for evaluation was determined. Also, the film thickness of the light-shielding film formed on the substrate was measured, and the value obtained by dividing the value of the optical density (OD) by the film thickness was defined as OD[ / μm].

[0251] The optical density (OD) was calculated by the following formula (1). Optical density (OD)=-log 10 T Formula (1) (T indicates the transmittance)

[0252] [Agglomerated Foreign Matter Evaluation] (Evaluation Method) The light-shielding film for evaluation after this curing (post-baking) was observed using an optical microscope to confirm the presence or absence of agglomerated foreign matter. Note that △ or above was considered qualified.

[0253] (Evaluation Criteria) ◎: No agglomerated foreign matter was confirmed in the light-shielding film. 〇: Agglomerated foreign matter was confirmed in a part of the light-shielding film, and the number was 5 or less. △: Agglomerated foreign matter was confirmed in a part of the light-shielding film, and the number was 6 to 10. ×: Aggregated foreign matter was observed across the entire surface of the light-shielding film.

[0254] The evaluation results are shown in Tables 3 and 4.

[0255] [Preparation of a light-shielding film for evaluation of long-term storage (long-term stability)] For the evaluation of stability over time, after preparing the photosensitive resin composition, it was stored at 5°C for one month, and then a light-shielding film was prepared using the same procedure as above. Reflectance evaluation (glass substrate side), optical density evaluation, and aggregated foreign matter evaluation were then performed in the same manner as above.

[0256] [Table 3]

[0257] [Table 4]

[0258] As shown in Tables 3 and 4, the photosensitive resin composition of the example, which contains components (A) to (F), with component (A) containing component (A1), a portion of component (A1) being dissolved in component (F), and a portion of component (A1) being contained in component (D), can be used to make a light-shielding film that reduces the reflectivity on the glass substrate side, suppresses aggregated foreign matter, and improves adhesion to the substrate after patterning. [Industrial applicability]

[0259] The present invention provides a photosensitive resin composition for black resists that exhibits low reflectivity, suppresses aggregated foreign matter, and enhances development adhesion; a method for producing the photosensitive resin composition; a light-shielding film obtained by curing the same; a color filter and a touch panel having the light-shielding film; and a display device having the color filter or touch panel.

Claims

1. (A) Photosensitive resin containing unsaturated groups, (B) A photopolymerizable compound having at least two or more unsaturated bonds, (C) Photopolymerization initiator and (D) A pigment disperse comprising at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments, and light-shielding materials, (E) A silica dispersed powder containing silica particles, (F) Solvent and A photosensitive resin composition for black resist, comprising: The aforementioned component (A) is obtained by further reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (1) with (meth)acrylic acid and a polybasic carboxylic acid or its anhydride, and includes an unsaturated group-containing photosensitive resin obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dianhydride, in a range where the molar ratio of (a) / (b) is 0.01 or more and less than 2.

0. A portion of component (A1) is included in a dissolved state in component (F), A portion of the aforementioned component (A1) is included in the aforementioned component (D), A photosensitive resin composition for black resist. 【Chemistry 1】 (In general formula (1), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO ２ -, -C(CF ３ )([[]] ２ [[]]), -Si(CH ３ )([[]] ２ [[]]), -CH ２ -, -C(CH ３ )([[]] ２ [[]]), -O-, a fluorene-9,9-diyl group represented by general formula (2), or a single bond, and l is an integer from 0 to 10.)​​​​​​ 【Chemistry 2】 (In general formula (2), * indicates the bonding site with the structure represented by general formula (1).)

2. A portion of the aforementioned component (A1) is included in the aforementioned component (E), The photosensitive resin composition for black resist according to claim 1.

3. The total mass of component (A1) contained in the black resist photosensitive resin composition is 51% to 100% by mass relative to the total mass of component (A) contained in the black resist photosensitive resin composition. The photosensitive resin composition for black resist according to claim 1.

4. The aforementioned component (A) substantially contains no components other than the aforementioned component (A1). The photosensitive resin composition for black resist according to claim 3.

5. The ratio (mE1 / mD1) of the total mass of the silica particles to the total mass (mD1) of at least one light-shielding component selected from the group consisting of the black pigment, mixed color pigment, and light-shielding material contained in the black resist photosensitive resin composition is 0.01 to 0.

20. The photosensitive resin composition for black resist according to claim 1.

6. The above (mE1 / mD1) is between 0.06 and 0.

12. The photosensitive resin composition for black resist according to claim 5.

7. The average particle size of the silica particles contained in component (E) is 20 nm to 150 nm. The photosensitive resin composition for black resist according to claim 1.

8. The average particle size of the silica particles contained in component (E) is 60 nm to 100 nm. The photosensitive resin composition for black resist according to claim 7.

9. (A) Photosensitive resin containing unsaturated groups, (B) A photopolymerizable compound having at least two or more unsaturated bonds, (C) Photopolymerization initiator and (D) A pigment disperse comprising at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments, and light-shielding materials, (E) A silica dispersed powder containing silica particles, (F) containing a solvent, A method for producing a photosensitive resin composition for black resist, wherein the (A) component is obtained by reacting a reaction product of (A1) an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (1) with (meth)acrylic acid, and further reacting this product with a polybasic carboxylic acid or its anhydride, and the polybasic carboxylic acid or its anhydride is (a) a dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dianhydride, in a range where the molar ratio of (a) / (b) is 0.01 or more and less than 2.0, the method comprising: A step of preparing a pigment dispersion containing the component (D) containing the component (A1) and a solvent, A step of preparing a silica dispersion containing the above-mentioned component (E) and a solvent, A step of mixing component (A) containing component (A1), component (B), component (C), the pigment dispersion, the silica dispersion, and a solvent, A method for producing a photosensitive resin composition for black resist, including the following. 【Transformation 3】 (In general formula (1), R １ , R ２ , R ３ and R ４ Each of these is independently a hydrogen atom, a C1-C5 alkyl group, or a halogen atom, and X is -CO-, -SO ２ -, -C (CF ３ ) ２ -, -Si(CH ３ ) ２ -ien-CH ２ -, -C(CH ３ ) ２ -, -O-, is a fluorene-9,9-diyl group or single bond represented by general formula (2), where l is an integer from 0 to 10. 【Chemistry 4】 (In general formula (2), * indicates the bonding site with the structure represented by general formula (1).)

10. The step of preparing the silica dispersion is, The step is to prepare a silica dispersion containing component (E) which contains component (A1), and a solvent. A method for producing a photosensitive resin composition for black resist according to claim 9.

11. A light-shielding film obtained by curing a photosensitive resin composition for black resist according to any one of claims 1 to 8.

12. A color filter having the light-shielding film described in claim 11 as a black matrix.

13. A touch panel having the light-shielding film described in claim 11.

14. A display device having the color filter described in claim 12.

15. A display device having a touch panel as described in claim 13.

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