Photosensitive resin composition for black resistant, method for manufacturing resin composition, light-sensitive film, optical filter, touch panel,

Abstract

The present invention addresses the problem of providing a photosensitive resin composition for a black resist, which can reduce the reflectivity of the black resist on the glass substrate side, suppress the aggregation of foreign matters, and improve the adhesion to the substrate after patterning, and also providing a method for producing the photosensitive resin composition, a light-shielding film, an optical filter, a touch panel, and a display device. The photosensitive resin composition for a black resist contains (A) a photosensitive resin containing an unsaturated group; (B) a photopolymerizable compound having at least two unsaturated bonds; (C) a photopolymerization initiator; (D) a pigment dispersoid containing at least one light-blocking component selected from the group consisting of a black pigment, a mixed color pigment, and a light-blocking material; (E) a silica dispersoid containing silica particles; and (F) a solvent. The component (A) contains a component (A1) having a specific structure, a part of the component (A1) is contained in a state of being dissolved in the component (F), and a part of the component (A1) is contained in the component (D).

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition for black resist, a method for manufacturing the photosensitive resin composition, a light-shielding film formed by curing the photosensitive resin composition, a filter and a touch panel having the light-shielding film, and a display device having the filter or the touch panel. Background Technology

[0002] In recent years, the development of portable terminals has led to an increase in display devices with touch panels or LCD panels used 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 periphery of the LCD panel on the back, and a light-shielding film (black matrix) is provided to suppress the leakage of black light from the screen and to suppress the mixing of adjacent color photoresists.

[0003] Black matrices require high light-blocking properties and low reflectivity. For example, in Patent Document 1, both high light-blocking properties and low reflectivity of black matrices can be achieved by using hydrophobic silica microparticles dispersed with a specific ethyl carbamate dispersant.

[0004] [Existing technical documents] [Patent Literature] Patent document 1: Japanese Patent Application Publication No. 2015-161815. Summary of the Invention

[0005] [The problem that the invention aims to solve] However, according to the discoveries of the inventors, if a photosensitive resin composition as described in Patent Document 1 is used and a black resist is formed on a glass substrate, there are problems such as high reflectivity on the glass side, generation of aggregated foreign matter, and deterioration of the adhesion between the patterned surface and the substrate.

[0006] The present invention was developed in view of this point, 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 the aggregation of foreign matter, improve the adhesion to the substrate after patterning, and provide a method for manufacturing the photosensitive resin composition, a light-shielding film formed by curing the photosensitive resin composition, a filter and a touch panel having the light-shielding film, and a display device having the filter or the touch panel.

[0007] [Methods used to solve problems] In order to solve the above-mentioned problems, one aspect of the present invention relates to the photosensitive resin composition for black resist as described below [1] to [8].

[0008] [1] A photosensitive resin composition for use as a black resist, comprising: (A) Photosensitive resin containing unsaturated groups; (B) Photopolymerizable compounds having at least two or more unsaturated bonds; (C) Photopolymerization initiator; (D) A pigment dispersion containing at least one light-blocking component selected from the group consisting of black pigment, mixed pigment and light-blocking material; (E) A silica dispersion containing silica particles; and (F) Solvent; The aforementioned component (A) contains an epoxy compound derived from bisphenols having two glycidyl ether groups, as shown in the following general formula (1), and a reactant of (meth)acrylic acid, which is further reacted with a polycarboxylic acid or its anhydride. The resulting photosensitive resin containing unsaturated groups is obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or its anhydride, which is the aforementioned polycarboxylic acid or its anhydride, and (b) a tetracarboxylic acid or its dianhydride, in a (a) / (b) molar ratio of 0.01 or more and less than 2.0. A portion of the aforementioned component (A1) is contained in a state dissolved in the aforementioned component (F). A portion of the aforementioned component (A1) is contained in the aforementioned component (D).

[0009] (1) In general formula (1), R1, R2, R3 and R4 are hydrogen atoms, alkyl or halogen atoms with 1 to 5 carbon atoms, respectively, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-dimethyl or single bond as shown in general formula (2), and l is an integer from 0 to 10.

[0010] (2) In general formula (2), * represents the bonding site with the structure shown in general formula (1).

[0011] [2] The photosensitive resin composition for black resist as described in [1], wherein a portion of the aforementioned (A1) component is contained in the aforementioned (E) component.

[0012] [3] The photosensitive resin composition for black resist as described in [1] or [2], wherein the total mass of the aforementioned (A1) component contained in the aforementioned photosensitive resin composition for black resist is 51% to 100% by mass relative to the total mass of the aforementioned (A) component contained in the aforementioned photosensitive resin composition for black resist.

[0013] [4] The photosensitive resin composition for black resist as described in any one of [1] to [3], wherein the aforementioned component (A) does not substantially contain any component other than the aforementioned component (A1).

[0014] [5] The photosensitive resin composition for black resist as described in any one of [1] to [4], wherein the ratio (mE1 / mD1) of the total mass (mE1) of the aforementioned silica particles contained in the aforementioned photosensitive resin composition for black resist to the total mass (mD1) of at least one light-blocking component selected from the group consisting of black pigment, mixed pigment and light-blocking material is 0.01 to 0.20.

[0015] [6] The photosensitive resin composition for black resist as described in [5], wherein the aforementioned (mE1 / mD1) is 0.06 to 0.12.

[0016] [7] The photosensitive resin composition for black resist as described in any one of [1] to [6], wherein the average particle size of the silica particles contained in the aforementioned (E) component is 20 nm to 150 nm.

[0017] [8] The photosensitive resin composition for black resist as described in [7], wherein the average particle size of the silica particles contained in the aforementioned component (E) is 60 nm to 100 nm.

[0018] One aspect of the present invention for solving the above-mentioned problems is a method for manufacturing a photosensitive resin composition for a black resist as described in [9] or

[10] .

[0019] [9] A method for manufacturing a photosensitive resin composition for black resist, wherein the aforementioned photosensitive resin composition for black resist comprises: (A) Photosensitive resin containing unsaturated groups; (B) Photopolymerizable compounds having at least two or more unsaturated bonds; (C) Photopolymerization initiator; (D) A pigment dispersion containing at least one light-blocking component selected from the group consisting of black pigment, mixed pigment and light-blocking material; (E) A silica dispersion containing silica particles; and (F) Solvent; The aforementioned component (A) contains an epoxy compound derived from bisphenols having two glycidyl ether groups, as shown in the following general formula (1), and a reactant of (meth)acrylic acid, which is further reacted with a polycarboxylic acid or its anhydride. The resulting photosensitive resin containing unsaturated groups is obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or its anhydride, which is the aforementioned polycarboxylic acid or its anhydride, and (b) a tetracarboxylic acid or its dianhydride, in a (a) / (b) molar ratio of 0.01 or more and less than 2.0. The method for manufacturing the aforementioned photosensitive resin composition for black resist includes: The steps for preparing a pigment dispersion containing the aforementioned component (D) and a solvent, which includes the aforementioned component (A1); The steps for preparing a silica dispersion containing the aforementioned component (E) and solvent; and The step of mixing the aforementioned component (A), component (B), component (C), pigment dispersion, silica dispersion, and solvent containing the aforementioned component (A1).

[0020] (1) In general formula (1), R1, R2, R3 and R4 are hydrogen atoms, alkyl or halogen atoms with 1 to 5 carbon atoms, respectively, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-dimethyl or single bond as shown in general formula (2), and l is an integer from 0 to 10.

[0021] (2) In general formula (2), * represents the bonding site with the structure shown in general formula (1).

[0022]

[10] The method for manufacturing a photosensitive resin composition for black resist as described in [9], wherein the aforementioned step of preparing a silica dispersion is a step of preparing a silica dispersion comprising the aforementioned component (E) containing the aforementioned component (A1) and a solvent.

[0023] One aspect of the present invention for solving the above-mentioned problems is a light-shielding film as described below

[11] .

[0024]

[11] A light-shielding film is formed by curing a black resist with a photosensitive resin composition as described in any one of [1] to [8].

[0025] In order to solve the above-mentioned problems, one aspect of the present invention relates to the filter described below

[12] .

[0026]

[12] A filter having a light-shielding film as described in

[11] as a black matrix.

[0027] One aspect of the present invention for solving the above-mentioned problems is a touch panel as described below

[13] .

[0028]

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

[11] .

[0029] One aspect of the present invention for solving the above-mentioned problems is a display device as described in

[14] or

[15] .

[0030]

[14] A display device having a filter as described in

[12] .

[0031]

[15] A display device having a touch panel as described in

[13] .

[0032] [Effects of the invention] According to the present invention, a photosensitive resin composition for black resist can be provided, which can reduce the reflectivity of the glass substrate side of the black resist, suppress the aggregation of foreign matter, and improve the adhesion to the substrate after patterning. The present invention also provides a method for manufacturing the photosensitive resin composition, a light-shielding film formed by curing the photosensitive resin composition, a filter and a touch panel having the light-shielding film, and a display device having the filter or the touch panel. Detailed Implementation

[0033] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. Furthermore, in this specification, the content of each component is omitted when the first decimal place is 0. Additionally, unless otherwise specified, the compounds, functional groups, or structures illustrated below may use only one of the illustrated types, or multiple types may be used in combination.

[0034] In addition, in this specification, "(meth)acrylic acid" refers to the general term for acrylic acid and methacrylic acid, and "(meth)acryloyl" refers to the general term for acryloyl and methacryloyl, which are one or both of these.

[0035] 1. Photosensitive resin composition for black resist The photosensitive resin composition for black resist in this embodiment (hereinafter referred to as "photosensitive resin composition") contains: (A) Photosensitive resin containing unsaturated groups (hereinafter referred to as "component A"); (B) Photopolymerizable compounds having at least two unsaturated bonds (hereinafter referred to as "(B) component"); (C) Photopolymerization initiator (hereinafter referred to as "component C"); (D) A pigment dispersion containing at least one light-blocking component selected from the group consisting of black pigment, mixed pigment and light-blocking material (hereinafter referred to as "(D) component"); (E) Silica dispersion containing silica particles (hereinafter referred to as "(E) component"); (F) Solvent (hereinafter referred to as "(F) component"); The aforementioned component (A) contains the following component (A1). A portion of the aforementioned component (A1) is contained in a state dissolved in the aforementioned component (F). A portion of the aforementioned component (A1) is contained in the aforementioned component (D).

[0036] Here, component (A1) is a photosensitive resin containing unsaturated groups obtained by further reacting a bisphenol-derived epoxy compound having two glycidyl ether groups, as shown in the following general formula (1), with a reactant of (meth)acrylic acid and a polycarboxylic acid or its anhydride, and by reacting (a) dicarboxylic acid or tricarboxylic acid or its anhydride and (b) tetracarboxylic acid or its dianhydride, which are the aforementioned polycarboxylic acid or its anhydride, in a (a) / (b) molar ratio of 0.01 or more and not exceeding 2.0.

[0037] (1) In general formula (1), R1, R2, R3 and R4 are hydrogen atoms, alkyl or halogen atoms with 1 to 5 carbon atoms, respectively, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-dimethyl or single bond as shown in general formula (2), and l is an integer from 0 to 10.

[0038] (2) In general formula (2), * represents the bonding site with the structure shown in general formula (1).

[0039] In addition, "(A1) component is contained in the state of being dissolved in (F) component" means that (F) component and (A1) component are mixed and form a homogeneous phase.

[0040] Furthermore, in this application, the "dispersed phase" forms a phase different from component (F) (dispersion medium) and contains at least light-shielding components or silica particles. When these contain dispersants, it refers to a dispersed phase containing dispersants. Next, "a portion of component (A1) is contained in the aforementioned component (D)" means that component (A1) interacts with the light-shielding component, and component (A1) is adsorbed onto the light-shielding component to form a dispersed phase containing component (A1). Alternatively, when component (D) contains dispersants other than (A1), it means that component (A1) interacts with dispersants other than (A1) or light-shielding components adsorbed onto the light-shielding component, and component (A1) is close to and present with dispersants other than (A1), thereby forming a dispersed phase containing component (A1). To determine whether a portion of component (A1) is present in the aforementioned component (D), the dispersed phase can be separated from the dispersion medium by centrifugation or filtration of the photosensitive resin composition. Component (D) can then be further separated from the dispersed phase, and TG-DTA, thermal decomposition GC / MS, ESCA, etc., can be measured to confirm the presence or absence of component (A1). For example, a well-known method described in the Japan Rubber Industry Association Journal 2000, 73(7), 379-384 can be used to separate components (D) and (E) from the dispersed phase obtained from the photosensitive resin composition.

[0041] The above-mentioned photosensitive resin composition can reduce the reflectivity of the glass side of the black resist, suppress the aggregation of foreign matter, and improve the adhesion with the glass substrate. The reason for this is still unclear, but it is speculated as follows.

[0042] Regarding the aggregation of foreign matter, for example, when component (A1) is dissolved in component (F) but not contained in component (D), and the light-shielding component is dispersed in a dispersant other than component (A1), in the liquid of the photosensitive resin composition, the dispersants contained in component (D) interact with each other more effectively than the dispersants in component (D) interacting with component (A1) dissolved in component (F). Therefore, aggregation of component (D) is easier to achieve.

[0043] On the other hand, in the photosensitive resin composition of this embodiment, component (A1) is contained in a state where it is dissolved in component (F), and a portion of component (A1) is contained in component (D). In this way, in the liquid form of the photosensitive resin composition, the component (A1) contained in component (D) is readily compatible with the component (A1) dissolved in component (F), thus reducing the likelihood of aggregation driving forces between components (D). Therefore, the aggregation of components (D) is suppressed, and the aggregation of foreign matter is easily suppressed.

[0044] Next, regarding reflectivity, generally speaking, aliphatic resins have a lower refractive index than glass. Furthermore, compounds with a large number of aromatic rings in their molecular structure tend to have a higher refractive index. (A1) has a structure containing a large number of aromatic rings, therefore its refractive index is higher than that of aliphatic resins, and the refractive index difference with glass tends to be smaller. This results in a reduction of reflections generated between the black resist and the glass substrate.

[0045] Similarly, the refractive index of the light-blocking component is generally higher than that of the aliphatic resin. If component (A1) is included as a dispersant for the light-blocking component, the difference in refractive index between the light-blocking component and its dispersant tends to decrease. In this way, it is easier to reduce the reflection generated between the light-blocking component (D) and its dispersant.

[0046] Furthermore, as mentioned above, component (A1) is contained in a state dissolved in component (F), and a portion of component (A1) is contained in component (D). This makes it easier to suppress the aggregation of components (D) and reduce the scattering produced by components (D), thus making it easier to reduce reflectivity.

[0047] Furthermore, regarding the adhesion between the patterned material and the glass substrate (hereinafter referred to as "development adhesion"), the (A1) component contains a large number of aromatic rings. Generally speaking, as understood from solubility parameters, aromatic compounds are more hydrophilic than aliphatic compounds. Therefore, the (A1) component has high hydrophilicity, resulting in higher affinity with glass substrates having hydrophilic surfaces. This makes it easier to improve the adhesion between the black resist containing the (A1) component and the glass substrate.

[0048] Furthermore, when developing with alkaline solution, as mentioned above, the (A1) component contains a large number of aromatic rings, so the (A1) components are easy to approach each other in the exposed and polymerized areas, thus easily forming π-π interactions, which easily increases the cohesion of the black resist in the exposed areas, thus easily improving the adhesion during patterning.

[0049] The following describes components (A) to (F).

[0050] 1-1.(A) Photosensitive resin containing unsaturated groups Component (A) is a photosensitive resin containing unsaturated groups, and each molecule contains a polymerizable unsaturated group. Furthermore, from the viewpoint of easily improving patternability, component (A) is preferably an acidic group that exhibits alkali solubility. The above-mentioned resin can be used without particular limitation.

[0051] (A) The component may have acidic groups that exhibit alkali solubility, such as carboxyl groups, phosphate groups, and sulfonic acid groups. From the viewpoint of easily improving developability, carboxyl groups are preferred.

[0052] (A) Components must contain at least component (A1), and may contain other components besides component (A1) (hereinafter referred to as component (A2)), or may not contain component (A2). In addition, more than two types of component (A2) may be used.

[0053] 1-1-1.(A1)Ingredients Component (A1) is a photosensitive resin containing unsaturated groups obtained by further reacting a bisphenol-derived epoxy compound having two glycidyl ether groups, as shown in general formula (1), with a reactant of (meth)acrylic acid and a polycarboxylic acid or its anhydride, wherein the (a) dicarboxylic acid or tricarboxylic acid or its anhydride and (b) tetracarboxylic acid or its dianhydride, which are the aforementioned polycarboxylic acid or its anhydride, are reacted in a molar ratio of (a) / (b) of 0.01 or more and not exceeding 2.0. Additionally, a portion of component (A1) is contained in component (F) in a dissolved state, and a portion of component (A1) is contained in the aforementioned component (D).

[0054] (1) In general formula (1), R1, R2, R3 and R4 are hydrogen atoms, alkyl or halogen atoms with 1 to 5 carbon atoms, respectively, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-dimethyl or single bond as shown in general formula (2), and l is an integer from 0 to 10.

[0055] (2) In general formula (2), * represents the bonding site with the structure shown in general formula (1).

[0056] X is preferably fluorene-9,9-diyl. With this substituent, the refractive index of the (Al) component is easily increased, thus easily reducing the refractive index difference with the light-shielding component or with the glass substrate. This results in a reduction in reflectivity. Furthermore, the structure contains a large number of aromatic rings, which easily reduces the alkali solubility of the exposed area, thus easily improving the adhesion during development.

[0057] (A1) ingredient can be manufactured through the following steps.

[0058] (Step 1) React the bisphenol-derived epoxy compound having two glycidyl ether groups, as shown in general formula (1), with (meth)acrylic acid to obtain a diol compound.

[0059] (Step 2) React the above reactants with polycarboxylic acids or their anhydrides to obtain component (A1).

[0060] In these steps, the above-mentioned epoxy compound can be prepared and (step 1) and (step 2) can be performed, or the above-mentioned diol compound can be prepared and (step 2) can be performed only, or component (A1) can be prepared.

[0061] 1-1-1-1. (Step 1) The step of reacting an epoxy compound with two glycidyl ether groups derived from bisphenols, as shown in general formula (1), with (meth)acrylic acid to obtain a diol compound. The bisphenol-type epoxy compounds shown in general formula (1) are epoxy compounds with two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. This reaction is usually accompanied by oligomerization of diglycidyl ether compounds, so the bisphenol-type epoxy compounds shown in general formula (1) include epoxy compounds containing more than two bisphenol skeletons.

[0062] Examples of bisphenols used in this reaction include bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, etc. 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-hydroxy-3-methylphenyl)fluorene, 9,9-bis Fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-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, etc. Among these, bisphenols containing fluorene-9,9-diyl groups are preferred.

[0063] The reaction of the aforementioned epoxy compound with (meth)acrylic acid can be carried out using well-known methods. For example, a method for producing epoxy-based (meth)acrylate compounds can be referred to, as described in Japanese Patent Application Publication No. 9-325494, which involves reacting a bisphenol fluorene-type epoxy resin with acrylic acid, using tetraethylammonium bromide or the like as a catalyst, at 100°C. The reaction temperature is preferably in the range of 40 to 120°C, and more preferably 60 to 110°C.

[0064] Catalysts can be used in this addition reaction, such as ammonium salts like tetraethylammonium bromide and triethylbenzylammonium chloride, as well as phosphines like triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0065] This reaction is typically carried out in a solvent. Examples of such solvents include celestrexate solvents such as ethyl celestrexate and butyl celestrexate; high-boiling-point ether or ester solvents such as dimethyl ether diglyceride, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone solvents such as cyclohexanone and diisobutyl ketone. Furthermore, there are no particular restrictions on the solvents, catalysts, or other reaction conditions used; however, it is preferable to use a solvent without hydroxyl groups and with a boiling point higher than the reaction temperature.

[0066] 1-1-1-2. (Step 2) The step of reacting the above diol compound with a polycarboxylic acid or its anhydride to obtain component (A1). The diol compound obtained in step 1 is then reacted with (a) a dicarboxylic acid or tricarboxylic acid or its anhydride and (b) a tetracarboxylic acid or its dianhydride in a (a) / (b) molar ratio of 0.01 or more but less than 2.0 with a polycarboxylic acid or its anhydride.

[0067] Examples of the dicarboxylic acids or tricarboxylic acids or their anhydrides mentioned above (a) include, for example, chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or their monoanhydrides.

[0068] Examples of the aforementioned chain-type dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citrate, malonic acid, glutaric acid, citric acid, tartaric acid, ketoglutaric acid, pimelic acid, sebacic acid, octanoic acid, diethylene glycol, etc., as well as dicarboxylic acids or tricarboxylic acids introduced with any substituent.

[0069] In addition, examples of the above-mentioned alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, northoalkyl dicarboxylic acid, and dicarboxylic acids or tricarboxylic acids with any substituent introduced.

[0070] In addition, examples of the aforementioned 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 introduced with any substituent.

[0071] Furthermore, among dicarboxylic or tricarboxylic acids, the monohydric anhydrides of these acids are preferred. The monohydric anhydrides of the aforementioned dicarboxylic or tricarboxylic acids may be used alone or in combination with two or more.

[0072] (a) Among dicarboxylic acids or tricarboxylic acids or their anhydrides, succinic acid, itconic acid, 1,2,3,6-tetrahydrophthalic acid, hexahydrotriphenyl phthalic acid, phthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid or 2,3-naphthalenedicarboxylic acid, or their anhydrides are more preferred, and 1,2,3,6-tetrahydrophthalic acid, 1,8-naphthalenedicarboxylic acid or 2,3-naphthalenedicarboxylic acid, or their anhydrides are more preferred.

[0073] In addition, (b) examples of tetracarboxylic acids or their dianhydrides include chain-type tetracarboxylic acids, alicyclic tetracarboxylic acids, aromatic tetracarboxylic acids, or their dianhydrides.

[0074] Examples of the aforementioned chain tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain tetracarboxylic acids that have been substituted with alicyclic hydrocarbon groups, unsaturated hydrocarbon groups, or other substituents.

[0075] In addition, examples of the aforementioned alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, northoalkyl tetracarboxylic acid, and alicyclic tetracarboxylic acids introduced with substituents such as chain hydrocarbon groups or unsaturated hydrocarbon groups.

[0076] In addition, examples of aromatic hydrocarbon tetracarboxylic acids include pyrocalcite, diphenyl ketone tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0077] Alternatively, aryl bis(p-p-phenylene trioxide) esters can be used. Examples of aryl bis(p-p-phenylene trioxide) esters are compounds manufactured using the method described in International Publication No. 2010 / 074065, and are acid dianhydrides in the form of ester bonds formed by the reaction of two hydroxyl groups of an aromatic diol (naphthalene glycol, biphenol, terphenyl ethylene glycol, etc.) with the carboxyl groups of two molecules of trimellitic anhydride. These compounds will be referred to below as bis(p-p-phenylene trioxide) esters of aromatic diols.

[0078] Furthermore, the dianhydrides used in the tetracarboxylic acids are preferred. The dianhydrides of the aforementioned tetracarboxylic acids may be used alone or in combination with two or more.

[0079] (b) Among tetracarboxylic acids or their dianhydrides, 3,3',4,4'-biphenyltetracarboxylic acid, diphenyl ketone tetracarboxylic acid, diphenyl ether tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid are more preferred, and 3,3',4,4'-biphenyltetracarboxylic acid, diphenyl ketone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid are even more preferred.

[0080] The reaction conditions for the aforementioned diol compounds, polycarboxylic acids, or their anhydrides are not particularly limited, and well-known methods can be used. For example, Japanese Patent Application Publication No. 9-325494 describes a method for reacting epoxy (meth)acrylates with tetracarboxylic acid dianhydrides at a reaction temperature of 90 to 140°C.

[0081] The molar ratio (a) / (b) of the monoanhydride of (a) dicarboxylic acid or tricarboxylic acid reacting with the above-mentioned diol compound to the dianhydride of (b) tetracarboxylic acid 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. If the molar ratio (a) / (b) is 0.01 or more, the molecular weight of the (A1) component will not be too large, thus sufficiently increasing the alkali solubility of the unexposed area, making it easy to form patterns. If the molar ratio (a) / (b) is less than 2.0, the molecular weight of the (A1) component will not be too small, thus sufficiently reducing the alkali solubility of the exposed area during patterning, thus easily improving the adhesion of the developed area.

[0082] 1-1-1-3. (A1) Other properties of the component The content of component (A1) is preferably 51% to 100% by mass relative to the total mass of component (A) in the photosensitive resin composition for black resist, 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 the adhesion to the substrate after patterning. In addition, in this application, "substantially free of component (A2)" means that the content of component (A2) is 1.0% by mass or less relative to the total mass of component (A).

[0083] The content of component (A1) is preferably 16% to 50% by mass, more preferably 20% to 50% by mass, relative to the total mass of solids contained in the photosensitive resin composition for black resist. If the content of component (A1) is 16% by mass or more, the adhesion to the substrate after patterning is easily improved. If the content of component (A1) is 50% by mass or less, component (D) or component (E) can be present in sufficient amounts, and a light-shielding film with high light-shielding properties and low reflectivity can be easily obtained.

[0084] 1-1-2. (A2) Components (A2) Examples of components include photosensitive resins containing unsaturated groups, such as acrylic copolymers, or photosensitive resins containing unsaturated groups obtained by further reacting an epoxy compound having two or more epoxy groups with a reactant of (meth)acrylic acid with a polycarboxylic acid or its anhydride, which are not included in general formula (1).

[0085] Examples of photosensitive resins containing unsaturated groups from the aforementioned acrylic copolymers include copolymers of (meth)acrylic acid, (meth)acrylates, etc., and resins having (meth)acryloyl and carboxyl groups. For example, such resins can be obtained by copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent, reacting the resulting copolymer with (meth)acrylic acid, and finally reacting it with an anhydride of dicarboxylic acid or tricarboxylic acid to obtain a photosensitive resin containing unsaturated groups. Examples of the aforementioned copolymers include: the copolymer disclosed in Japanese Patent Application Publication No. 2014-111722, which is composed of 20 to 90 mol% repeating units derived from diglyceride esters with hydroxyl groups at both ends esterified by (meth)acrylate, and 10 to 80 mol% repeating units derived from one or more polymerizable unsaturated compounds that can be copolymerized therewith, having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mg KOH / g; and the alkali-soluble resin containing polymerizable unsaturated groups disclosed in Japanese Patent Application Publication No. 2018-141968, which contains units derived from (meth)acrylate compounds, units having (meth)acryloyl groups and di or tricarboxylic acid residues, and a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200 mg / KOH.

[0086] Examples of epoxy compounds having two or more epoxy groups not included in the above general formula (1) include epoxy propylene ethers of polyols, epoxy propylene esters of polycarboxylic acids, copolymers of monomers having (meth)acryloyl groups, represented by copolymers of methacrylic acid and epoxy propylene methacrylate as units, epoxy compounds having epoxy groups such as hydrogenated bisphenol A diepoxy propylene ether (e.g., RIKARESIN HBE-100: manufactured by Shin Nippon Rikka Co., Ltd., "RIKARESIN" is a registered trademark of the same company), 1,4-cyclohexanediethanol-bis3,4-epoxycyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dialkyl (e.g., Araldite CY175: manufactured by Huntsman, "Araldite" is a registered trademark of the same company), bis(3,4-epoxycyclohexylmethyl) adipate (e.g., CYRACURE) UVR-6128: manufactured by Dow Chemical Company), 3,4-epoxycyclohexanecarboxylic acid 3',4'-epoxycyclohexylmethyl ester (e.g., celloxide 2021P: manufactured by Daicel Inc., "celloxide" is a registered trademark of the same company), tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., EPOLEAD) GT401: manufactured by Daicel Co., Ltd., "EPOLEAD" is a registered trademark of the same company), epoxy compounds with epoxy cyclohexyl groups (e.g., HiREM-1: manufactured by Shikoku Chemical Industry Co., Ltd.), polyfunctional epoxy compounds with a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Co., Ltd.), 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Co., Ltd.), etc., alicyclic epoxy compounds, epoxidized polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the same company), epoxy compounds with a polysiloxane skeleton, etc.

[0087] 1-1-3. (A) Other properties of the component The content of component (A) relative to the total mass of the solids is preferably 10% to 60% by mass, more preferably 15% to 45% by mass. If the content of component (A) is 10% by mass or more, the patterning characteristics are easily improved because it contains sufficient photosensitive resin. In addition, if the content of component (A) is 60% by mass or less, other components can be contained sufficiently, and a light-shielding film with excellent patterning properties and low reflectivity is easily obtained.

[0088] The weight-average molecular weight (Mw) of polystyrene, determined by colloidal permeation chromatography (GPC) of the polymeric resin containing unsaturated groups, is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 15,000. If the weight-average molecular weight (Mw) is 1,000 or higher, the alkali solubility of the exposed areas can be sufficiently reduced during patterning, thus easily improving the adhesion during development. Furthermore, if the weight-average molecular weight (Mw) is 40,000 or lower, the viscosity of the photosensitive resin composition can be easily adjusted to a suitable coating range, making it easier to coat onto the surface of the support. Additionally, if the weight-average molecular weight (Mw) is 40,000 or lower, the alkali solubility of the unexposed areas is sufficiently increased, thus facilitating patterning. In addition, the weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using "HLC-8220GPC" (manufactured by TOSOH Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by TOSOH Corporation), temperature: 40℃, speed: 0.6 ml / min) and converted as a standard polystyrene (PS-Oligomer Kit manufactured by TOSOH Corporation).

[0089] The preferred acid value of the polymeric resin containing unsaturated groups is 20 mg KOH / g to 200 mg KOH / g, 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 below 200 mg KOH / g, the penetration of the alkaline developer is not too rapid, thus easily improving the adhesion of the developed solution. Furthermore, the acid value is determined by titration with a 1 / 10 N-KOH aqueous solution using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0090] 1-2. (B) Photopolymerizable compounds having at least two or more unsaturated bonds Component (B) forms a moderately cross-linked structure during the curing of the photosensitive resin composition, which easily improves the developability of the light-shielding film. Furthermore, component (B) is a compound not included in component (A), and component (B) may or may not have an acidic group to exhibit alkali solubility. Additionally, component (B) may or may not have an aromatic ring.

[0091] (B) Components are not particularly limited as long as they are photopolymerizable compounds having at least two unsaturated bonds. Examples of components (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, and pentaerythritol tri(meth)acrylate. Acrylates, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphono-nitrogen olefin-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. (meth)acrylates, and dendritic polymers with (meth)acryloyl groups as compounds having vinyl double bonds, etc.

[0092] Examples of the aforementioned dendritic polymers include dendritic acrylates, which are spherical giant molecules with acryloyl groups arranged radially; hyperbranched acrylic polymers; hyperbranched acrylic oligomers; and dendritic polymers obtained by adding a polyvalent thiol compound to a portion of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specifically, dendritic polymers obtained by reacting the (meth)acryloyl group of a polyfunctional (meth)acrylate shown in general formula (B-1) with a polyvalent thiol compound shown in general formula (B-2) are examples. From the viewpoint of easily promoting photopolymerization, the use of such a multifunctional dendritic polymer is preferred.

[0093] (B-1) In formula (B-1), R6 is a hydrogen atom or a methyl group, and R7 is R8(OH). k Of the k hydroxyl groups, r hydroxyl groups provide for the remaining portion after the ester bond in the formula. A preferred option is R8(OH). k Polyols are non-aromatic straight-chain or branched hydrocarbon skeletons with 2 to 8 carbon atoms, or polyol ethers formed by the dehydration condensation of multiple molecules of such polyols through ether bonds, or esters of these polyols or polyol ethers with hydroxy acids. k and r independently represent integers from 2 to 20, where k ≥ r.

[0094] (B-2) In formula (B-2), R9 is a single bond or a hydrocarbon group with 1 to 6 carbon atoms in the 2 to 6 valences, and s is 2 when R9 is a single bond, and has the same valence as R9 when R9 is a 2 to 6 valence group.

[0095] Examples of polyfunctional (meth)acrylates represented by general formula (B-1) include 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, caprolactone modified pentaerythritol tri(meth)acrylate, and other (meth)acrylates.

[0096] Examples of polyvalent thiol compounds represented by general formula (B-2) include trimethylolpropane tris (thioglycolate), trimethylolpropane tris (thioglycolate), pentaerythritol tetras (thioglycolate), pentaerythritol tris (thioglycolate), pentaerythritol tetras (thioglycolate), dipentaerythritol hexas (thioglycolate), dipentaerythritol hexas (thioglycolate), etc.

[0097] Component (B) may be used alone or in combination with two or more of these photopolymerizable compounds. Component (B) may be a component that crosslinks the molecules of component (A) with each other. To perform this function, it is more preferably to have three or more unsaturated bonds. By increasing the number of unsaturated bonds, the curing degree of the light-shielding film can be easily improved, and the adhesion during development can be easily improved.

[0098] Similarly, from the viewpoint of easily improving the curing degree, the acrylic equivalent of component (B) divided by the number of (meth)acryloyl groups in one molecule is preferably 50 g / eq to 300 g / eq, more preferably 80 g / eq to 200 g / eq.

[0099] The content of component (B) relative to the total mass of components (A) and (B) is preferably 10% to 60% by mass, more preferably 10% to 50% by mass. If the content of component (B) is 10% by mass or more, it is easier to improve the pattern resolution and the curing degree of the resin film, thus easily improving the development adhesion. Furthermore, if the content of component (B) is 60% by mass or less, it is easier to suppress residue formation and further facilitates the control of the pattern shape.

[0100] 1-3. (C) Photopolymerization initiator (C) The component is not particularly limited as long as it is a compound that can be polymerized by light stimulation, having polymerizable unsaturated bonds and capable of addition polymerization.

[0101] Examples of components (C) include acetophenone-based photopolymerization initiators, triterpenoid-based photopolymerization initiators, benzoin-based photopolymerization initiators, diphenyl ketone-based photopolymerization initiators, thioxanone-based photopolymerization initiators, imidazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators. Additionally, in this specification, photopolymerization initiators include sensitizers.

[0102] (C) The preferred component is an oxime ester-based photopolymerization initiator. Oxime ester-based photopolymerization initiators have high sensitivity, thus easily improving developability.

[0103] Examples of acetophenone-based photopolymerization initiators include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diphenylethylenedione dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-N-holylinyl-1-(4-methylthiophenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-N-holylinylphenyl)butane-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one. Examples of products sold on the market include Omnirad 127, Omnirad 369, Omnirad 1173, Omnirad 184, and Omnirad 651 (the Omnirad series is manufactured by IGM Resins BV).

[0104] Examples of trichlorophenyl photopolymerization initiators include 2,4,6-tris(trichloromethyl)-1,3,5-trichlorophenyl, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-trichlorophenyl, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-trichlorophenyl, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-trichlorophenyl, and 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-trichlorophenyl. -Tris(trichloromethyl)-4,6-bis(trichloromethyl)-1,3,5-tris(trichloromethyl)-4,6-bis(trichloromethyl)-1,3,5-tris(trichloromethyl)-1,3,5-tris(trichloromethyl)-4,6-bis(trichloromethyl)-1,3,5-tris(trichloromethyl)-1,3,5-tris(trichloromethyl)-4,6-bis(trichloromethyl)-1,3,5-tris(trichloromethyl)-1,3,5-tris(trichloromethyl)-4,6-bis(trichloromethyl)-1,3,5-tris(trichloromethyl)-1,3,5-tris(trichloromethyl)-1,3,5-tris(trichloromethyl)-1,6 ...

[0105] 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.

[0106] Examples of diphenyl ketone-based photopolymerization initiators include diphenyl ketone, methyl phthalobenzoate, 4-phenyl diphenyl ketone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butyl carbonyl peroxide) diphenyl ketone, 2,4,6-trimethyl diphenyl ketone, and 4,4'-bis(N,N-diethylamino) diphenyl ketone.

[0107] Examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0108] Examples of imidazole-based photopolymerization initiators include 2-(o-chlorophenyl)-4,5-phenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2,4,5-triarylimidazolium dimer.

[0109] Examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Commercially available examples include Omnirad TPOH and Omnirad 819 (the Omnirad series is manufactured by IGM Resins BV).

[0110] Examples of oxime ester-based photopolymerization initiators include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-bicyclohepty-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-benzoate, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-benzoate. Hydrofuranylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-ketooxime-O-acetate, 1-[9-ethyl [9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] -Ethane-1-ketooxime-O-bicycloheptane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-adamantane carboxylate, 1-[4-(phenylaminebenzenesulfonyl)phenyl]octane-1,2-dione=2-o-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl] ethyl ketone-o-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethyl ketone, 1-[7-(2-methylbenzoyl)-9 ,9-Dipropyl-9H-fluoren-2-yl]-1-(O-acetyl oxime), acetone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o-acetyl oxime, acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), 1,2-octanediene,1 -[4-(phenylthio)-,2-(O-benzoyl oxime)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), 1-(4-phenylaminebenzenesulfonylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane-1,2-Diketone-2-oxime-O-acetate, 1-(4-methylthiophenyl)butane-1-ketooxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazolo-3-yl-O-acetyloxime, etc.

[0111] Commercially available oxime ester-based photopolymerization initiators include, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)] (IRGACURE OXE-01, manufactured by BASF), acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) (IRGACURE OXE-02, manufactured by BASF), and [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]hydrazinoyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl ketone-(O-acetyl oxime) (IRGACURE). OXE-03 (BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyl oxime) (IRGACURE OXE-04 (BASF), and Lunar6 (DKSH) (manufactured by JAPAN Corporation), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyl oxime) (TR-PBG-326, manufactured by Changzhou Qiangli 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-benzoyl oxime) (TR-PBG-391, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ADEKA ARKLS NCI-831E (manufactured by ADEKA Corporation), Omnirad 1312 (manufactured by IGM Resins BV Corporation), DFI-020 (manufactured by DaitoChemix Corporation).

[0112] Examples of oxime ester-based photopolymerization initiators include oxime ester compounds represented by general formula (C-1) or general formula (C-2) as photopolymerization initiators.

[0113] (C-1) In equation (C-1), R 10 R 11Each of the following groups is 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, R 12 It 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 and aryl groups can be substituted with alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkanoyl groups having 1 to 10 carbon atoms, or halogens. The alkylene moiety can contain unsaturated bonds, ether bonds, thioether bonds, or ester bonds. Furthermore, the alkyl group can be any straight-chain, branched, or cyclic alkyl group.

[0114] (C-2) In equation (C-2), R 13 and R 14 Each is independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group, or an alkylcycloalkyl group, or a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms. R 15 Independently, it is a straight-chain or branched alkyl or alkenyl group having 2 to 10 carbon atoms, wherein a portion of the -CH2- group in the alkyl or alkenyl group may be substituted with an -O- group. Further, these R... 13 ~R 15 Some of the hydrogen atoms in the radical can be replaced by halogen atoms.

[0115] The content of component (C) relative to the total mass of components (A) and (B) is preferably 3.0% to 30.0%, more preferably 5.0% to 20.0%. If the amount of component (C) is 3.0% or more, the photosensitive resin composition has good sensitivity and can sufficiently accelerate the photopolymerization rate. If the amount of component (C) is 30.0% or less, the sensitivity of the photosensitive resin composition can be within a suitable range, and a hardened film with the desired pattern line width and desired pattern edge shape can be easily obtained.

[0116] Additionally, compounds that do not act as photopolymerization initiators or sensitizers on their own but whose ability to act as photopolymerization initiators or sensitizers can be increased by combining them with the aforementioned compounds. Examples of such compounds include amine compounds that are effective when used in combination with diphenyl ketones. Examples of such amine compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(ethylmethylamino)diphenyl ketone, etc.

[0117] 1-4.(D) A pigment dispersion containing at least one light-blocking component selected from the group consisting of black pigment, mixed pigment, and light-blocking material. Component (D) is a light-blocking component containing black pigment, mixed organic pigments, or light-blocking materials, and component (A1) is a pigment dispersion, which can improve the light-blocking properties of the black resist. The light-blocking component can be well-known black pigments, mixed pigments, or light-blocking materials, without particular restrictions.

[0118] In addition, the light-shielding component is preferably a component that is dispersed in such a way that the average particle size (the average particle size measured by a particle size distribution meter by laser diffraction scattering or dynamic light scattering scattering) is less than 1 nm to 1000 nm.

[0119] Examples of the aforementioned black pigments include perylene black, indigo black, aniline black, lactam black, carbon black, titanium black, zirconium nitride, etc.

[0120] Examples of the aforementioned mixed pigments include mixed organic pigments containing at least two colors of organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacrine pigments, isoindoline ketone pigments, isoindoline pigments, bis(2-3-3) pigments, indanthrene-based pigments, perylene pigments, violet ketone pigments, quinoline yellow pigments, diketopyrrolopyrrole pigments, and sulfur indigo pigments; or mixed inorganic pigments containing white pigments such as titanium dioxide and zinc oxide mixed with the aforementioned black pigments.

[0121] The light-blocking component may be used alone or in combination with two or more types, depending on the function of the intended photosensitive resin composition.

[0122] In addition, organic pigments that can be used as light-blocking components include, for example, pigments with the following numbers as pigment index names, but are not limited thereto.

[0123] 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 ratios of 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, and 80, etc. Pigment purple 19, 23, 37, etc.

[0124] Among these, the light-blocking component is preferably a black pigment, and more preferably carbon black.

[0125] Furthermore, the carbon black in this specification can be surface-treated with dyes or the like, as described later, or it can be surface-treated without dyes or the like. Carbon black with a dye-coated surface (dye-coated carbon black) can improve the developability of the photosensitive resin composition, and easily improve the adhesion of the resin film formed by curing it to the substrate, the fine line reproduction, and the light-shielding properties, and easily improve the resistivity of the resin film.

[0126] The aforementioned dyes can be any dyes that can be adsorbed onto the surface of carbon black, and can be basic dyes, acid dyes, direct dyes, reactive dyes, etc. Furthermore, when acidic functional groups are imparted to the surface of carbon black (oxidation treatment) to improve its dispersibility, acidic dyes (especially acidic dyes with sulfonic acid groups or carboxyl groups) that readily interact with these acidic functional groups are preferred. Additionally, from the viewpoint of suppressing reactions with the acidic groups present in component (A), acidic dyes or nonionic dyes are preferred over dyes with amine groups, etc. Furthermore, from the viewpoint of more easily improving the light-shielding properties of the resin film, dark-colored dyes are preferred.

[0127] Specific examples of the aforementioned dyes include food colorings such as Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1, and Food Yellow No. 7; food colorings such as Bernac Red 2BMN, Basacid Black X34 (BASFX-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 SE0228, Basacid Black X34 (BASFX-34) (manufactured by BASF), Basacid Blue 750 (manufactured by BASF), Bernac Red (manufactured by Bemcolors, Poughkeepsie, NY), and BASF Basacid Black SE 0228 (manufactured by BASF); and various acid dyes such as Pontamine Brilliant Bond Blue A and other Pontamine Brilliant Bond... BlueA and other Pontamine (registered trademark) 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); CartaBlack 2GT (manufactured by Sandoz, Inc.); Sirius Supra Yellow GD167; 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 in 34 grades; Cibacron Brilliant Red 3B-A (Reactive Red 4) (manufactured by Aldrich Chemical, Milwaukee, WI); Drimarene Brilliant Red X-2B (Reactive Red 56) (manufactured by Pylam Products, Inc., Tempe, AZ); Levafix Brilliant Red E-4B; Levafix Brilliant Red F-6BA; and similar dyes such as Levafix (registered trademark) dyes Dystar LP (manufactured by Charlotte, NC); Procion Red H8B (Reactive Red 31) (manufactured by JCI America); reactive dyes such as Neozapon Red 492 (manufactured by BASF); Orasol Red G (manufactured by Ciba-Geigy); Aizen Spilon Red C-BH (manufactured by Hodogaya Chemical Company); Spirit Fast Yellow 3G; Aizen Spilon Yellow C-GNH (manufactured by Hodogaya Chemical Company). Oil-soluble dyes such as 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 DirectBLACK 38, and Direct Deep BLACK can be used individually or in combination of two or more.

[0128] The content of the dye relative to the total mass of carbon black is preferably 0.5% to 10% by mass, more preferably 1% to 7% by mass. The more dye, the higher the resistivity of the resin film. By ensuring that the amount of dye is not excessive, the thickening of the photosensitive resin composition caused by excess dye and the agglomeration caused by excess dye hindering the dispersibility of other components can be suppressed.

[0129] Furthermore, the aforementioned dyes can be laked using metals or metal salts. Laked dyes, whereby the dye can be fixed to the surface of carbon black using the aforementioned metals or metal salts, can suppress the reduction of the aforementioned effect due to dye detachment from the carbon black surface. Examples of the aforementioned metals include aluminum, magnesium, calcium, strontium, barium, and manganese. Examples of the aforementioned metal salts include hydrochlorides and sulfates of these metals. The content of the aforementioned metals or metal salts relative to the dye is preferably 0.3 times or more in molar amounts, more preferably 0.5 times or more in molar amounts, and even more preferably 0.6 times or more in molar amounts.

[0130] (D) is a pigment dispersion containing a light-blocking component, preferably a dispersant containing a light-blocking component, and more preferably a dispersant containing component (A1). The dispersant containing the light-blocking component may use only component (A1) or may be mixed with other dispersants besides component (A1). The dispersant besides component (A1) may be a well-known compound used for dispersing pigments (light-blocking components) (compounds sold commercially under names such as dispersant, wetting agent, dispersion accelerator, etc.), without particular limitation.

[0131] Examples of dispersants other than the (A1) component of the light-blocking component include cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, and pigment derivative-type dispersants (dispersing aids). In particular, the above-mentioned dispersants are preferably cationic polymeric dispersants having cationic functional groups such as imidazole groups, pyrrole groups, pyridyl groups, primary, secondary, or tertiary amine groups as adsorption sites for colorants, and having 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 1000 to 100000.

[0132] The total amount of component (A1) and dispersants other than component (A1) relative to the total mass of the light-blocking component is preferably 10% to 60% by mass, more preferably 15% to 60% by mass. This range improves the dispersibility of the light-blocking component, effectively suppressing aggregation of the light-blocking component even after prolonged storage of the photosensitive resin composition, and easily suppressing the reflectivity of the black resist and the aggregation of foreign matter. Furthermore, when the light-blocking component is dye-coated carbon black, the total amount of component (A1) and dispersants other than component (A1) does not include the mass of the dye coating the carbon black.

[0133] The content of component (A1) in component (D) is preferably 15% to 100% by mass relative to the total mass of the above dispersant, more preferably 20% to 90% by mass. By falling within this range, the dispersibility of the light-shielding component can be improved, and the aggregation of the light-shielding component can be easily suppressed regardless of the storage time of the photosensitive resin composition, and the reflectivity of the black resist and the aggregation of foreign matter can be easily suppressed.

[0134] The content of the light-blocking component relative to the total solids in the photosensitive resin composition is preferably 20% to 80% by mass, more preferably 30% to 60% by mass. If the amount of the light-blocking component is 20% by mass or more relative to the solids in the photosensitive resin composition, the light-blocking properties of the black resist can be sufficiently improved. If the amount of the light-blocking component is 80% by mass or less relative to the solids in the photosensitive resin composition, the content of component (A), which is originally a binder, is sufficiently high, and the desired development characteristics and film-forming ability can be easily improved.

[0135] 1-5.(E) Silica dispersions containing silica particles (E) The component is a silica dispersion containing silica particles, which can reduce the refractive index of the hardened film (light-shielding film). As a result, reflections caused by the difference in refractive index between the transparent substrate or air, transparent protective film, etc. and the hardened film (light-shielding film) can be suppressed, and the reflectivity of the hardened film can be reduced.

[0136] There are no particular limitations on the type of silica particles, nor on the manufacturing methods (gas-phase reaction or liquid-phase reaction) or shape (spherical or non-spherical). Furthermore, both solid and hollow silica particles can be used. "Hollow silica particles" refers to silica particles with internal cavities.

[0137] The average particle size of silica particles is more preferably 20 nm to 150 nm, and even more preferably 60 nm to 100 nm. Compared to small-sized silica particles with an average particle size of several nm, silica particles with a size within the above range are less prone to aggregation. Therefore, if the particle size of silica particles is 20 nm or more, the dispersion stability of silica particles can be improved, and the movement in the thickness direction caused by the aggregation of silica particles is less restricted. Since a sufficient amount of silica particles can be biased towards the glass surface, the reflectivity of the glass surface can be sufficiently reduced. In addition, if the average particle size of silica particles is 150 nm or less, the silica particles can be moved appropriately to a certain extent in the coating film, making it easier for the silica particles to be biased towards the glass surface, and suppressing the reduction in the linearity or surface smoothness of the hardened film caused by the scattering of silica particles.

[0138] The average particle size of the silica particles was determined by the cumulative method using a particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) with a dynamic light scattering method.

[0139] The refractive index of the silica particles is preferably 1.10 to 1.47. Silica particles with a refractive index of 1.45 to 1.47 can be used. Furthermore, compared to the refractive index of a light-shielding film containing only ordinary silica particles, the refractive index of the light-shielding film can be lowered by using hollow silica particles with a low refractive index.

[0140] The refractive index of silica particles can be determined by mixing silica particles processed into powder with a standard refractive liquid with a known refractive index to obtain a transparent mixture. Furthermore, the refractive index of inorganic microparticles is a value measured using an Abbe refractometer; in this application, the refractive index value is the refractive index relative to a wavelength of 550 nm. The method for measuring the refractive index of silica particles using an Abbe refractometer is as follows: Silica particles processed into powder are mixed with a standard refractive liquid with a known refractive index; the refractive index of the resulting transparent mixture is measured; and the refractive index of the silica particles is calculated based on the change in refractive index between the standard refractive liquid before and after mixing, and the amount of silica particles added to the standard refractive liquid.

[0141] Silica particles can be spherical or elliptical, but spherical shapes are preferred because they easily reduce the refractive index and increase the strength of the light-shielding film. For example, the sphericity of inorganic microparticles is preferably 1.0 to 1.5. If the sphericity of inorganic microparticles is within this range, the particle shape is close to that of a sphere. Therefore, they can be homogeneously filled into a thin light-shielding film, forming a light-shielding film that maintains the smoothness of the film surface and prevents the inorganic microparticles from protruding from the film surface. Thus, a light-shielding film with a low refractive index and sufficient strength can be obtained.

[0142] 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 approximates a true sphere. Therefore, in a light-shielding film of varying thickness, the particles can be homogeneously filled in the in-plane direction (horizontal direction of the substrate surface), forming a light-shielding film that maintains the surface smoothness of the hardened film and prevents the silica particles from protruding from the surface of the hardened film. Thus, a light-shielding film with a low refractive index and sufficient strength can be obtained.

[0143] The true sphericity of silica particles can be determined by the ratio of the longest diameter to the shortest diameter of the particles (the average of any 100 silica particles). Here, the longest and shortest diameters of the silica particles are obtained by measuring the longest and shortest diameters of the silica particles from the microscopic images obtained using a transmission electron microscope.

[0144] (E) The component is a silica dispersion containing silica particles, which may or may not contain a dispersant for dispersing the silica particles, but is preferably containing a dispersant. The silica particles may be silica particles that have been hydrophobized using a well-known hydrophobicating agent such as a silane coupling agent. The dispersant for the silica particles may be a well-known compound used for dispersing silica particles (compounds commercially available under names such as dispersant, wetting agent, dispersion accelerator, etc.), and there are no particular restrictions.

[0145] Furthermore, a portion of component (A1) is preferably contained in component (E), and the dispersant for the aforementioned silica particles is more preferably containing component (A1). The presence of a portion of component (A1) in component (E) improves the dispersibility of the silica particles, effectively suppressing the aggregation of silica particles even after prolonged storage of the photosensitive resin composition, and easily suppressing the reflectivity of the black resist and the aggregation of foreign matter. Additionally, when forming a coating of the photosensitive resin composition, the aggregation of silica particles is suppressed, thereby improving mobility and allowing segregation on the glass substrate side, which has a high affinity for silica particles, thus easily reducing the reflectivity of the glass surface side. Furthermore, during development and exposure, since the component (A1) contained as a dispersant for silica particles and the component (A1) contained as a binder form a cross-linked structure, the hardening degree of the exposed area is sufficiently improved, thus easily improving the adhesion during development.

[0146] Furthermore, the states of "a portion of component (A1) being contained in the aforementioned component (E)" and "a portion of component (A1) being contained in the aforementioned component (D)" similarly refer to the state where component (A1) interacts with silica particles, adsorbs onto silica particles, and forms a dispersion containing component (A1); or when component (E) contains a dispersant other than (A1), it refers to the state where component (A1) interacts with a dispersant other than (A1) or silica particles adsorbed onto silica particles, and is present near the dispersant other than (A1) or silica particles, thereby forming a dispersion containing component (A1). The method for confirming whether a portion of component (A1) is contained in the aforementioned component (E), or the method for separating component (D) and component (E), uses the same method as the method for confirming or separating "a portion of component (A1) being contained in the aforementioned component (D)".

[0147] The dispersant used for silica particles can be a well-known dispersant, such as alkylammonium salts and alkanolammonium salts of acidic polymers, alkylammonium salts and alkanolammonium salts of polymers with acid groups, neutralizing salts of polymers with alkylamine groups, and phosphate ester salts of polymers. Among these, polymers with alkylammonium salt structures are preferred, and alkylammonium salts of acidic polymers and alkylammonium salts of polymers with acid groups are more preferred. Using polymers with alkylammonium salt structures as dispersants can significantly suppress the formation of aggregates originating from silica particles.

[0148] The dispersant used for silica particles is preferably an acid value or an amine value, more preferably an acid value or amine value of 10 mg KOH / g to 80 mg KOH / g, and even more preferably both an acid value and an amine value of 10 mg KOH / g to 80 mg KOH / g. If the amine value is 10 mg KOH / g or higher, the dispersibility of the silica particles can be improved. Furthermore, if both the acid value and the amine value are 10 mg KOH / g or higher, it is easier to reduce residue at the edges of the pattern and improve straightness. On the other hand, if either the acid value or the amine value is 80 mg KOH / g or lower, the solubility of component (E) in the developer will not be excessively increased, and the reduction in the fineness of the formed pattern can be suppressed. From the above perspective, a dispersant having either an amine value or an acid value of 30 mg KOH / g to 80 mg KOH / g is preferable, and both being 30 mg KOH / g to 80 mg KOH / g is more preferred.

[0149] In addition, the acid value of the dispersant refers to the number of mg of KOH required to neutralize 1 g of the resin component (solids), which can be determined according to JIS K 0070:1992. The amine value of the dispersant for component (F) refers to the number of mg of KOH required to neutralize 1 g of the resin component (solids) in an equivalent amount of acid (acetic acid, etc.), which can be determined according to JIS K 7237:1995.

[0150] Commercially available dispersants for silica particles include, for example, DISPERBYK-140, 142, 145, 2001, 2025, and 9076 (all manufactured by BYKCHEMI JAPAN, "DISPERBYK" is a registered trademark of the same company). Among these commercially available products, DISPERBYK-140, 142, and 9076 are preferred, and DISPERBYK-140 and 9076 are even more preferred.

[0151] The total amount of the (A1) component and the dispersant other than the (A1) component in the silica particles is preferably 10% to 50% by mass, more preferably 15% to 40% by mass, relative to the total mass of the silica particles. By falling within this range, the dispersibility of the silica particles can be improved, and even when the photosensitive resin composition is stored for a long time, the aggregation of silica particles can be easily suppressed, and the reflectivity of the black resist and the aggregation of foreign matter can be easily suppressed.

[0152] The content of component (A1) in component (E) is preferably 10% to 100% by mass relative to the total mass of the above-mentioned dispersant, more preferably 15% to 90% by mass, and even more preferably 15% to 70% by mass. By achieving this range, the dispersibility of silica particles can be improved, and regardless of the storage time of the photosensitive resin composition, the aggregation of silica particles can be easily suppressed, and the reflectivity of the black resist and the aggregation of foreign matter can be easily suppressed.

[0153] Furthermore, the ratio (mE1 / mD1) of the total mass of silica particles (mE1) to the total mass of the light-blocking component (mD1) in the photosensitive resin composition for black resist is preferably 0.01 to 0.20, more preferably 0.06 to 0.12. When mE1 / mD1 is 0.01 or higher, the presence of sufficient silica particles reduces reflectivity regardless of the time elapsed in the photosensitive resin composition. Additionally, the presence of sufficient silica particles in the dispersion reduces the frequency of collisions between pigment dispersions, thus suppressing the aggregation of the light-blocking component and easily inhibiting the aggregation of foreign matter in the photosensitive resin composition over time. Furthermore, when mE1 / mD1 is 0.20 or lower, a film with high light-blocking properties and low reflectivity can be formed, easily improving development adhesion.

[0154] 1-6. (F) Solvent (F) component can dissolve or disperse the components contained in the photosensitive resin composition and adjust the viscosity of the photosensitive resin composition.

[0155] (F) Examples of components 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; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, and N-methyl-2-pyrrolidone (Methyl Ketones such as pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cerroxene, ethyl cerroxene, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; acetates such as ethyl acetate, cerroxene acetate, ethyl cerroxene acetate, butyl cerroxene 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.

[0156] (F) Component may be used alone or in combination with two or more types. Component (F) is more preferably containing propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), and more preferably further containing PGMEA and a solvent with a relative permittivity of 10.0 to 30.0 at 23°C.

[0157] PGMEA readily dissolves components (A) to (C), thus the presence of PGMEA easily improves the coatability of the photosensitive resin composition and effectively suppresses the aggregation of foreign matter. Furthermore, the presence of a solvent with a relative permittivity of 10.0 to 30.0 at 23°C allows for the solvation and stabilization of the silanol groups on the surface of the silica particles, suppressing the aggregation of component (E) in the photosensitive resin composition. This effectively reduces reflectivity and suppresses the aggregation of foreign matter. Based on the above considerations, the relative permittivity of the solvent with a relative permittivity of 10.0 to 30.0 at 23°C is preferably 13.0 to 20.0, and more preferably 13.0 to 18.0.

[0158] Solvents with a relative permittivity of 10.0 to 30.0 at 23°C include, for example, ethyl lactate (relative permittivity 13.7), 3-methoxy-3-methyl-1-butanol (relative permittivity 13.3), 1-methoxy-2-propanol (relative permittivity 12.5), and cyclohexanone (relative permittivity 16.4).

[0159] The amount of PGMEA incorporated relative to the total mass of component (F) 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. This increases the amount of PGMEA incorporated, thereby further improving the solubility of components (A) to (C) and the dispersibility of components (D) and (E).

[0160] The amount of solvent with a relative permittivity 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). A higher amount of solvent with a relative permittivity of 10.0 to 30.0 at 23°C suppresses the aggregation of component (E) and reduces reflectivity more efficiently. A solvent with a relative permittivity of 10.0 to 30.0 at 23°C of 90% by mass or less makes it easier to improve the coatability of the photosensitive resin composition.

[0161] The amount of component (F) relative to the total mass of the photosensitive resin composition is preferably 40% to 90% by mass, more preferably 60% to 90% by mass, and even more preferably 80% to 90% by mass.

[0162] 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.

[0163] Examples of epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthyl fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenolic varnish type epoxy compounds, cresol phenolic varnish type epoxy compounds, phenol aralkyl type epoxy compounds, phenolic varnish compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthyl aralkyl type epoxy compounds, triphenol methane type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetraphenol ethane type epoxy compounds, and other epoxy compounds with aromatic structures; glycidyl ethers of polyols; glycidyl esters of polycarboxylic acids; copolymers of monomers containing (meth)acryloyl groups, represented by copolymers of methacrylic acid and glycidyl methacrylate, with (meth)acryloyl ester as the unit; and hydrogenated bisphenol A diglycidyl ethers (e.g., RIKARESIN). HBE-100 (manufactured by Rika Senka Co., Ltd., "RIKARESIN" is a registered trademark of the same company) and other epoxy compounds containing glycidyl groups, 1,4-cyclohexanedimethyl-bis(3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dicarboxylate (e.g., Araldite CY175: manufactured by Huntsman Corporation, "Araldite" is a registered trademark of the same company), bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128: manufactured by Dow Chemical Company), 3,4-epoxycyclohexanecarboxylate 3',4'-epoxycyclohexylmethyl ester (e.g., celloxide 2021P: manufactured by Daicel Corporation, "celloxide" is a registered trademark of the same company), tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone of butanetetracarboxylate (e.g., EPOLEAD) GT401: manufactured by Daicel Co., Ltd., "EPOLEAD" is a registered trademark of the same company; epoxy compounds containing cyclohexyl epoxide (e.g., HiREM-1: manufactured by Shikoku Chemical Industry Co., Ltd.); polyfunctional epoxy compounds with a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Co., Ltd.); 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Co., Ltd.); epoxidized polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the same company); and epoxy compounds with a polysiloxane skeleton, etc. Among these, from the viewpoint of improving the flatness and low gas release of the coating or hardened film, the above-mentioned epoxy compounds with aromatic structures are preferred.

[0164] Examples of curing agents include amine compounds, polyvalent carboxylic acid compounds or their anhydrides, thermally decomposable esters of polycarboxylic acids, phenolic resins, amino resins, dicyandiamine, Lewis acid complexes, etc., which cure epoxy resins. Among these, compounds composed of polycarboxylic acids and their anhydrides, as well as thermally decomposable esters of polycarboxylic acids, are preferred.

[0165] Examples of hardening 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]non-5-ene; phosphines such as triphenylphosphine, tricyclohexylphosphine, and triphenylphosphine triphenylborane; and metal compounds such as tin octoate. Among these, 1,8-diazabicyclo[5.4.0]undecene-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene or their salts are preferred.

[0166] Examples of coupling agents include silane coupling agents such as 3-epoxypropoxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-ureopropyltriethoxysilane, as well as titanium-based coupling agents and aluminum-based coupling agents. Among these, 3-isocyanatepropyltriethoxysilane is preferred.

[0167] Examples of surfactants include compounds with hydrocarbon chains in their side chains, compounds containing polysiloxane, fluorinated compounds, etc.

[0168] Compounds containing hydrocarbon chains in their side chains include, for example, polymers obtained by polymerizing alkyl (meth)acrylates. Examples of alkyl (meth)acrylates include, for example, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isononyl (meth)acrylate.

[0169] Examples of polysiloxane-containing compounds include the reaction products of (meth)acrylic acid with hydroxyl-containing polysiloxane (e.g., α,ω-polydimethylpolysiloxane diol), or the reaction products of (meth)acrylic acid with epoxy-containing polysiloxane (e.g., polydimethylpolysiloxane containing pendant epoxy groups).

[0170] Examples of fluorinated compounds include perfluoroalkyl sulfonic acids, perfluoroalkyl carboxylic acids, perfluoroalkyl olefin adducts, perfluoroalkyl trialkylammonium salts, oligomers containing perfluoroalkyl and hydrophilic groups, oligomers containing perfluoroalkyl and lipophilic groups, oligomers containing perfluoroalkyl, hydrophilic and lipophilic groups, ethyl carbamate containing perfluoroalkyl and hydrophilic groups, perfluoroalkyl esters, perfluorophosphate alkyl esters, and compounds with fluorine atoms in their side chains, etc.

[0171] In addition, surfactants may also contain crosslinking groups. Preferably, these crosslinking groups are epoxy groups or vinyl unsaturated groups.

[0172] Commercially available surfactants include DOWSIL SH 3775 M Fluid (manufactured by Dow Toray Corporation), MEGAFACE EFS-131, MEGAFACE EFS-321, MEGAFACE EFS-521, and MEGAFACE EFS-801 (manufactured by DIC Corporation).

[0173] Among these, surfactants are preferably polysiloxane-containing compounds.

[0174] The content of the surfactant relative to the total solids content of the photosensitive resin composition 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. Here, when the content of the surfactant is 0.01% by mass or more, the smoothness is easily improved, and when it is 10.00% by mass or less, the surfactant is less likely to aggregate, which also easily improves the smoothness.

[0175] Examples of resins other than alkali-soluble resins include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, and melamine resins.

[0176] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenthiazoline, hindered phenolic compounds, etc.

[0177] Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber.

[0178] Examples of defoamers or leveling agents include polysiloxane-based, fluorine-based, and acrylic compounds.

[0179] Examples of ultraviolet absorbers include benzotriazole compounds, diphenyl ketone compounds, triterpenoid compounds, etc. The photosensitive resin composition may optionally contain resins other than component (A), such as epoxy resin, curing agents, curing accelerators, thermal polymerization inhibitors, antioxidants, plasticizers, leveling agents, defoamers, surfactants, coupling agents, and other additives.

[0180] 2. Method for manufacturing a photosensitive resin composition for black resist. Regarding the photosensitive resin composition, the manufacturing method is not particularly limited to mixing the above-mentioned components (A) to (F) and any other components in such a way that a portion of component (A1) is dissolved in component (F) and a portion of component (A1) is contained in component (D).

[0181] A preferred example of a method for manufacturing a photosensitive resin composition includes the following steps: (Step A) The step of preparing a pigment dispersion containing component (D) and solvent, which includes component (A1); (Step B) The step of preparing a silica dispersion containing component (E) and solvent; (Step C) The step of mixing components (A), (B), (C), the pigment dispersion prepared in step A, the silica dispersion containing silica particles and solvent, and the solvent, containing component (A1). Furthermore, it is more preferable that the silica dispersion used in the above (step B) is a silica dispersion containing the aforementioned (E) component containing (A1) and a solvent.

[0182] In step A or step B above, the step of preparing the pigment dispersion or silica dispersion can be prepared by preparing a pre-mixed pigment dispersion or silica dispersion, or by preparing the above-mentioned pigment dispersion or silica dispersion.

[0183] The preparation method of the above-mentioned pigment dispersion or silica dispersion can use well-known particle dispersion methods. For example, a light-shielding component or silica particles, component (A1), and any dispersant other than component (A1) are mixed in a solvent, and the particles are dispersed in a bead mill, thereby preparing a pigment dispersion containing component (D) containing component (A1) and a solvent, or a silica dispersion containing the aforementioned component (E) containing component (A1) and a solvent.

[0184] At this point, the particle size of the light-shielding component or silica particles can be measured appropriately, and dispersion can be stopped when the desired particle size is achieved, thereby adjusting the particle size accordingly.

[0185] 3.Light-shielding film The light-shielding film of this embodiment includes a coating formation step of applying the above-mentioned photosensitive resin composition to a substrate and forming a coating film, and may include an exposure step and / or a heat treatment step, depending on the situation. When patterning the light-shielding film, in the exposure step, a photomask or the like is used to set up light-exposed and unexposed areas, and only the light-exposed areas are hardened, while the other areas are dissolved with an alkaline solution, thereby forming the desired pattern shape.

[0186] 3-1. Coating Formation Steps The photosensitive resin composition can be applied to a substrate using well-known methods such as solution immersion, spraying, using a roller coater, blade coater, slot coater, or rotary coater. After achieving the desired thickness using these methods, the solvent is removed, thereby forming a coating film.

[0187] Solvent drying can be carried out under reduced pressure or at atmospheric pressure without reducing pressure. Alternatively, solvent drying can be followed by heat drying (pre-baking) after reduced pressure drying, or either of these methods can be used alone.

[0188] For example, when reducing pressure, it can be carried out under conditions of reaching a pressure of 5 to 1000 Pa over 10 to 180 seconds. Alternatively, degassing can be performed all at once until the target pressure is reached, or the pressure can be reduced in stages to prevent defects such as sudden boiling. From the viewpoint of production cycle time, drying under conditions of reaching a pressure of 50 to 1000 Pa over 10 to 50 seconds is preferred.

[0189] Pre-baking can be carried out by heating in an oven, heating plate, vacuum drying, or a combination thereof. The heating temperature and time for pre-baking can be appropriately selected according to the solvent used, for example, it is more preferably carried out at 80~120°C for 1~10 minutes.

[0190] 3-2. Exposure Steps Exposure can be performed by irradiating a portion of the coating film with radiation through a photomask. This exposure allows the portion corresponding to the pattern of the coating film to be photocured.

[0191] The aforementioned photomask can be a well-known one. Examples of photomasks include halftone masks, grayscale masks, and other multi-tone masks. A grayscale mask has a light-blocking portion and a diffraction grating formed on a light-transmitting substrate. The diffraction grating uses intervals between light-passing areas such as slits, dots, and grids that are below the resolution limit of the light used for exposure, thereby controlling the light transmittance. A halftone mask has a light-blocking portion and a half-passing portion formed on a light-transmitting substrate. The light transmittance used for exposure is controlled by the half-passing portion.

[0192] The exposure apparatus and exposure conditions used for the exposure can be appropriately selected. Examples of radiation include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Ultraviolet light is preferred among these. Furthermore, well-known exposure apparatuses (ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, far ultraviolet lamps, etc.) can be used for irradiation. The wavelength of the irradiated radiation is preferably between 250 nm and 400 nm. The exposure dose of the radiation is preferably 25 mJ / cm². 2 ~3000mJ / cm 2 .

[0193] 3-3. Developing Steps After exposure, the coating film irradiated with radiation is developed with alkali to remove the coating film from the unexposed areas.

[0194] Examples of developing methods for coated films include rinsing development, spray development, immersion development, and paddle (liquid) development. Furthermore, the above-mentioned developing processes can be performed using commercially available developing machines or ultrasonic cleaners.

[0195] Examples of suitable developing solutions include aqueous solutions of alkali metal or alkaline earth metal carbonates, and aqueous solutions of alkali metal hydroxides. Among these, a 0.04–3% by mass alkaline aqueous solution containing hydroxides such as sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate, potassium carbonate, or lithium carbonate, or organic bases such as tetramethylammonium hydroxide is preferred, and the development process is carried out at a temperature of 21–27°C. Furthermore, commercially available developing machines or ultrasonic washing machines can be used in the developing step.

[0196] 3-4. Heat treatment steps The resulting coating can be heat-treated. This allows for a thermal cross-linking reaction, which easily improves the adhesion between the light-shielding film and the substrate.

[0197] Heat treatment can be carried out by well-known methods (heating by ovens, hot air blowers, heating plates, infrared heaters, etc., vacuum drying, or a combination thereof).

[0198] There are no particular restrictions on the heat treatment conditions, as long as the temperature at which the coating can actually harden (post-baking) is met. The preferred heating temperature is 60~250℃ for 20~60 minutes.

[0199] After heat curing, the hardened film can be washed with short-wavelength radiation to remove organic pollutants from the surface of the coated film.

[0200] The aforementioned washing can be performed, for example, by irradiating a low-pressure mercury lamp with ultraviolet light at wavelengths of 185 nm and 254 nm. The irradiation dose can be 1000 mJ.

[0201] The reflectivity of the glass side of the light-shielding film 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 coated onto a glass substrate, the pressure is reduced to 50 Pa in a vacuum dryer at 23°C for 45 seconds to evaporate the solvent, and then the film is pre-baked at 90°C for 1 minute using a heating plate to produce the light-shielding film. The light-shielding film is then subjected to an i-ray illuminance of 30 mW / cm². 2 Irradiation with an ultra-high pressure mercury lamp at 50 mJ / cm 2 After exposure to ultraviolet light, the film is developed at 25°C with a 0.04% potassium hydroxide solution for 20 seconds from the time when the pattern begins to appear (film breaking time = BT). It is then washed with water and cured (post-baked) at 230°C using a hot air dryer for 30 minutes. The resulting film is then used. The reflectance described above is the reflectance of the substrate (glass substrate) side, measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi Hightech Science Co., Ltd.) at an incident angle of 2° relative to the substrate with the cured film obtained by the above method.

[0202] 4. Filter The filter of this embodiment has the light-shielding film described above. For example, the light-shielding film can be a black matrix, black column spacers, frame, etc., which are used as the filter.

[0203] The filter can be formed using well-known methods. For example, it can be formed by applying a colored photoresist material and exposing and developing it to form a pattern, or by transferring a photosensitive transfer material and exposing and developing it to form a pattern, or by inkjet printing, etc.

[0204] For example, a filter with the aforementioned light-shielding film as a black matrix is ​​made by forming a light-shielding film with a thickness of 1.0~2.0μm on a transparent substrate. After the light-shielding film is formed, red, blue and green pixels are formed by photolithography, or red, blue and green inks are printed into the light-shielding film by inkjet printing process, etc.

[0205] In addition, when the above-mentioned light-shielding film is formed into a black column spacer, a single black resist can be used to make multiple parts with different film thicknesses, so that one part functions as a spacer and the other part functions as a black matrix.

[0206] 5. Touch panel The touch panel of this embodiment has the aforementioned light-shielding film. For example, the light-shielding film can be a black matrix, black pillar spacers, frame, etc., used as the touch panel.

[0207] The touch panel in this embodiment can be a well-known touch panel. It can be any of the various types of touch panels, such as resistive film, capacitive, surface acoustic wave, infrared, electromagnetic induction, image recognition, and light sensor. It can be any type of touch panel that detects a touch by contact with the touch panel, or by the proximity of a finger or stylus to the touch panel.

[0208] 6. Display device The display device of this embodiment has the above-described light-shielding film.

[0209] The display device in this embodiment can be a well-known display device. Examples of display devices include liquid crystal displays (LCDs) and organic EL displays.

[0210] The photosensitive resin composition of this embodiment, particularly the ink for a filter in a liquid crystal display device, and the light-shielding film formed therefrom, can utilize the black matrix of a filter, etc. Furthermore, in addition to the ink for a filter in a color liquid crystal display, the photosensitive resin composition of the present invention can also use ink materials for color differentiation or light-shielding in various multicolor displays such as organic EL display devices (represented by organic EL elements) and color liquid crystal display devices, or it can use a protective layer (OC) layer with moderate light-shielding properties that can block external light reflected from the organic EL panel.

[0211] The light source of the aforementioned display device can be any well-known light source such as an organic electroluminescent (EL) light source or a laser light-emitting diode (LED) light source. Furthermore, the display device can be configured such that a wavelength conversion layer containing quantum dots or phosphor compounds is disposed between the light source and the substrate with the hardened film. The hardened film, especially when formed into a thick film of 2 μm or 3 μm or more, exhibits good flexibility and toughness; therefore, light-shielding films of this thickness can be used to suppress lateral light leakage when disposed on the side of the LED light source in an LED display.

[0212] In particular, the aforementioned light-shielding film can reduce reflectivity, so when used in applications such as liquid crystal displays where the film surface is disposed on the inside of a display device, it can suppress the loss caused by the reflection of light from the internal light source inside the device. Furthermore, when used in applications such as organic LED (OLED) displays where the film surface is disposed on the outside of a display device, it can improve the contrast of bright areas by reducing the reflection of external light, or improve the light extraction efficiency from the light-emitting side and increase luminous efficiency.

[0213] 7. Other uses The photosensitive resin composition of this embodiment can be used as a printing ink for a filter used in imaging elements. Additionally, the light-shielding film of this embodiment can be used as a black matrix for liquid crystal projection, etc. Furthermore, the photosensitive resin composition of this embodiment can also be used as a printing ink material for color differentiation or light-shielding in various multicolor displays such as image sensors. The sensor is preferably a sensor used in components requiring precise light sensitivity, such as a light (laser) detection and ranging (LiDAR) sensor for autonomous vehicles, or an encoder light-receiving element.

[0214] [Example] The embodiments of the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these. Furthermore, in the present invention, when the content of each component is 0 in the first decimal place, the decimal part is omitted.

[0215] First, let's describe the synthesis examples of alkali-soluble resins containing unsaturated groups in component (A). The evaluation of these resins is carried out in the following manner unless otherwise specified.

[0216] [Solids concentration] 1g of the resin solution obtained in the synthesis example was immersed in a glass filter [weight: W0(g)] and weighed [W1(g)]. The weight [W2(g)] after heating at 160°C for 2 hours was obtained by the following formula.

[0217] Solid fraction concentration (wt%) = 100 × (W2 - W0) / (W1 - W0) [Acid Value] The resin solution was dissolved in dimethyl methacrylate and titrated with a 1 / 10 N-KOH aqueous solution using a potentiometric titration apparatus “COM-1600” (manufactured by Hiranuma Sangyo Co., Ltd.).

[0218] [Molecular weight] The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using "HLC-8220GPC" (manufactured by TOSOH Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by TOSOH Corporation), temperature: 40℃, speed: 0.6 ml / min). The Mw was calculated by converting the Mw values ​​to the standard polystyrene (PS-Oligomer Kit manufactured by TOSOH Corporation).

[0219] [Average Particle Size] The average particle size of the silica particles was determined by the cumulative method using a particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method.

[0220] The abbreviations used in the synthesis examples are as follows.

[0221] BPFE: Bisphenol fluorene-type epoxy compound (the reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyl ethylene oxide. It is a compound of general formula (1) in which X is fluorene-9,9-diyl, R1~R4 are hydrogen atoms, and l is 0). AA: Acrylic acid BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide DCPMA: Dicyclopentyl methacrylate GMA: Glycidyl methacrylate St: Styrene AA: Acrylic acid THPA: Tetrahydrophthalic anhydride SA: Succinic anhydride AIBN: Azobisisobutyronitrile TDMAMP: Tris(dimethylaminomethyl)phenol HQ: Hydroquinone TEA: Triethylamine PGMEA: Propylene glycol monomethyl ether acetate [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 added to 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 the reaction to proceed. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were added to the flask, and the mixture was stirred at 120–125 °C for 6 hours to obtain a photosensitive resin (A1)-1 containing unsaturated groups. The resulting resin solution had a solids content of 56.0% by mass, an acid value (converted from solids content) of 103 mg KOH / g, and a Mw of 3600 according to GPC analysis.

[0222] [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 added to 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 the reaction to proceed. Then, BPDA (67.7 g, 0.23 mol) and THPA (1.5 g, 0.01 mol) were added to the flask, and the mixture was stirred at 120–125 °C for 6 hours to obtain a photosensitive resin (A1)-2 containing unsaturated groups. The resulting resin solution had a solids content of 56.0% by mass, an acid value (converted from solids content) of 97 mg KOH / g, and a Mw of 5500 according to GPC analysis.

[0223] [Synthesis example 3] PGMEA (300.0 g) was added to a 1 L four-necked flask equipped with a reflux condenser to replace nitrogen in the flask system, and the temperature was raised 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) dissolved in AIBN (10 g)] was added dropwise to the flask over 2 hours using a dropping funnel, and the mixture was further stirred at 120 °C for 2 hours to obtain a copolymer solution. Then, the flask system was replaced with air, and AA (43.2 g, 0.6 mol), TDMAMP (0.8 g), and HQ (0.15 g) were added to the resulting copolymer solution. The mixture was stirred at 120 °C for 6 hours to obtain a photosensitive resin solution containing unsaturated groups. Further, THPA (59.3 g, 0.39 mol) and TEA (0.5 g) were added to the obtained photosensitive resin solution containing unsaturated groups, and the mixture was reacted at 120 °C for 4 hours to obtain a base-soluble copolymer resin solution (A2)-1 containing polymerizable unsaturated groups. The solids concentration of the resin solution was 48.0% by mass, the acid value (converted from solids) was 79 mg KOH / g, and the Mw from GPC analysis was 8500.

[0224] [Modulation Example 1] 1000g of carbon black (TPX-1099: manufactured by Cabot) was mixed with water to prepare 10L of slurry. The mixture was stirred at 95°C for 1 hour, cooled, and washed with water. This mixture was then mixed with water again to prepare 10L of slurry. 42.9g of 70% nitric acid was added, and the mixture was stirred at 40°C for 4 hours. This mixture was cooled, washed with water, and mixed with water again to prepare 10L of slurry. 769.2g of 13% sodium hypochlorite aqueous solution was added, and the mixture was stirred at 40°C for 6 hours. This mixture was cooled, washed with water, and mixed with water again to prepare 10L of slurry. 38.1g of 38.4% purity dye (Direct Deep BLACK) was added, and the mixture was stirred at 40°C for 1 hour. Then, 10.1g of aluminum sulfate was added, and the mixture was stirred at 40°C for 1 hour. This mixture was cooled, washed with water, filtered, and dried to obtain dye-coated carbon black.

[0225] The photosensitive resin compositions of Examples 1-17 and Comparative Examples 1-5 were prepared using the mixing amounts (in parts by mass) listed in Tables 1 and 2. The mixing components used in Tables 1 and 2 are as follows. In addition, dispersions with the following configurations were prepared for components (D)-1 to (D)-6 and (E)-1 to (E)-5, respectively, for component (D) (pigment dispersion) and component (E) (silica dispersion). Among these, (D)-1 to (D)-4 are pigment dispersions containing component (D) as a dispersant containing component (A1) as a light-shielding component and a solvent, and (E)-2 to (E)-5 are silica dispersions containing component (E) as a dispersant containing component (A1) as silica particles and a solvent.

[0226] (Photosensitive soluble resin containing unsaturated groups) (A1)-1: The photosensitive resin containing unsaturated groups obtained in the above synthesis example 1 (solids concentration 56.0% by mass). (A1)-2: The photosensitive resin containing unsaturated groups obtained in the above synthesis example 2 (solids concentration 56.0% by mass). (A2)-1: The photosensitive resin containing unsaturated groups obtained in the above synthesis example 3 (solids concentration 48.0% by mass). (Photopolymerizable compounds) (B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (aronix M-405, manufactured by Dong-A Synthetic Co., Ltd., "aronix" is a registered trademark of the same company) (Photopolymerization initiator) (C)-1: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(0-acetyl oxime) (Irgacure OXE-02, manufactured by BASF JAPAN, "Irgacure" is a registered trademark of the same company) (C)-2: ADEKA ARKLS NCI-831, manufactured by ADEKA Corporation. "ADEKA ARKLS" is a registered trademark of the same company. (pigment dispersion) (D)-1: A pigment dispersion containing 25.0% by mass carbon black and 10.0% by mass dispersant (2.0% by mass polymeric dispersant and 18.0% by mass (A1)-1) (35.0% by mass solids, PGMEA solvent). (D)-2: A pigment dispersion containing 25.0% by mass carbon black and 10.0% by mass dispersant (7.0% by mass polymeric dispersant and 13.0% by mass (A1)-13.0% by mass) (35.0% by mass solids, PGMEA solvent). (D)-3: A pigment dispersion containing 25.0% by mass carbon black and 10.0% by mass dispersant (2.0% by mass polymeric dispersant and 28.0% by mass (A1)-) (35.0% by mass solids, PGMEA solvent). (D)-4: A pigment dispersion containing 25.0% by mass of carbon black (24.0% by mass of carbon black, 1.0% by mass of dye) and 10.0% by mass of dispersant (2.0% by mass of polymeric dispersant, 18.0% by mass of (A1)-) obtained from Modification Example 1 (35.0% by mass of solids, PGMEA solvent). (D)-5: A pigment dispersion containing 25.0% by mass carbon black and 10.0% by mass dispersant (10.0% by mass polymeric dispersant) (35.0% by mass solids, PGMEA solvent). (D)-6: A pigment dispersion containing 25.0% by mass carbon black and 10.0% by mass dispersant (2.0% by mass polymeric dispersant, (A2)-18.0% by mass) (35.0% by mass solids, PGMEA solvent). (Silica dispersion) (E)-1: PGMEA dispersion of silica particles "YA050C" (manufactured by Admatechs Inc., solids concentration 30% by mass, average particle size 50 nm). (E)-2: A silica dispersion containing 25.0% by mass of silica particles (average particle size 50 nm), 5.0% by mass of dispersant (3.0% polymeric dispersant, (A)-12.0% by mass) (30.0% by mass of solids, PGMEA solvent). (E)-3: A silica dispersion containing 25.0% by mass of silica particles (average particle size 80 nm), 5.0% by mass of dispersant (3.0% polymeric dispersant, (A)-12.0% by mass) (30.0% by mass of solids, PGMEA solvent). (E)-4: A silica dispersion containing 25.0% by mass of silica particles (average particle size 120 nm), 5.0% by mass of dispersant (3.0% polymeric dispersant, (A)-12.0% by mass) (30.0% by mass of solids, PGMEA solvent). (E)-5: A silica dispersion containing 25.0% by mass of silica particles (average particle size 200 nm), 5.0% by mass of dispersant (3.0% polymeric dispersant, (A)-12.0% by mass) (30.0% by mass of solids, PGMEA solvent). (solvent) (F)-1: Propylene glycol monomethyl ether acetate (PGMEA) (F)-2: Ethyl lactate (EL) [Table 1]

[0227] In addition, the values ​​recorded for (A1)-1, (A1)-2, and (A2)-1 in the above-mentioned formulations represent the amount of component (A) contained in the state of being dissolved in component (F), and are values ​​excluding the amount of component (A) contained in the dispersant as component (D) or component (E).

[0228] [Table 2]

[0229] In addition, the values ​​recorded for (A1)-1, (A1)-2, and (A2)-1 in the above-mentioned formulations represent the amount of component (A) contained in the state of being dissolved in component (F), and are values ​​excluding the amount of component (A) contained in the dispersant as component (D) or component (E).

[0230] [evaluate] The light-shielding film used for evaluation, which is made by curing a black resist with a photosensitive resin composition, is manufactured in the following manner.

[0231] [Prepare a light-shielding film for immediate evaluation after preparation] A 25mm × 125mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") was irradiated with a low-pressure mercury lamp at a wavelength of 254nm and an illuminance of 1000mJ / cm². 2The ultraviolet light was applied and the surface was washed. After preparing the photosensitive resin compositions of the examples and comparative examples shown in Tables 1 and 2 above, the compositions were applied to a glass substrate using a spin coater with a film thickness of 1.2 μm after heat curing treatment, without storage. The film was then dried in a vacuum dryer at 23°C for 45 seconds at reduced pressure to 50 Pa to evaporate the solvent, followed by pre-baking at 90°C for 1 minute using a hot plate to create a light-shielding film. Next, the exposure gap was adjusted to 100 μm, and a negative photomask with a linewidth / spacing of 5 μm / 5 μm to 20 μm / 20 μm was applied to the dried light-shielding film, with an i-ray illuminance of 30 mW / cm². 2 Irradiation with an ultra-high pressure mercury lamp at 50 mJ / cm 2 The ultraviolet light causes the photosensitive part to undergo a photocuring reaction.

[0232] The exposed light-shielding film was then passed through a 0.04% potassium hydroxide solution at 25°C at a flow rate of 1 kgf / cm². 2 After a rinsing and developing process of 20 seconds from the time when the pattern begins to appear (film breakage time = BT), the film is subjected to a 5 kgf / cm² development process. 2 The unexposed portions of the light-shielding film are removed by spraying water to form a light-shielding film pattern on a glass substrate. The film is then cured (post-baked) at 230°C for 30 minutes using a hot air dryer to obtain the light-shielding film for evaluation of the examples and comparative examples.

[0233] The following items are evaluated on the light-blocking film used for the above evaluation.

[0234] [Developable Adhesion] (Evaluation Method) The mask pattern, measuring 5μm to 20μm after actual hardening (post-baking), was observed using an optical microscope. Additionally, a value of △ or higher is considered acceptable.

[0235] (Evaluation Criteria) ◎: A 5μm pattern remains in the hardened film (coating). 〇: In the hardened film (coating), a 5μm pattern undergoes peeling, and at least one of the 6μm~10μm patterns remains. △: In the hardened film (coating), all patterns in the 5μm~10μm range delamination occurred, but at least one pattern in the 11μm~20μm range remained. ×: In the hardened film (coating), patterns ranging from 5μm to 20μm are all peeled off. [Reflectivity Evaluation (Glass Substrate Side)] (Evaluation Method) Compared to a substrate with a light-shielding film manufactured in the same manner as the light-shielding film used in the evaluation above, the reflectance of the substrate (glass substrate) side was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi-Hightech Co., Ltd.) at an incident angle of 2°.

[0236] [Optical Concentration Evaluation] (Evaluation Method) The optical density (OD) of the fabricated evaluation light-shielding film was determined using a MACBETH concentration meter. Additionally, the film thickness of the light-shielding film formed on the substrate was measured, and the OD value was calculated by dividing the optical density (OD) value by the film thickness [ / μm].

[0237] Optical density (OD) is calculated using the following formula (1).

[0238] Optical density (OD) = -log 10 T-form (1) (T represents the pass rate) [Evaluation of Aggregated Foreign Matter] (Evaluation Method) The evaluation film after actual hardening (post-baking) was observed using an optical microscope to confirm the absence of any aggregated foreign matter. Additionally, a value of △ or higher is considered acceptable.

[0239] (Evaluation Criteria) ◎: No foreign matter was found to have accumulated on the light-blocking film. 〇: A portion of the light-shielding film was found to contain aggregated foreign matter, with the number being 5 or fewer. △: Aggregated foreign matter was confirmed in a portion of the light-shielding film, numbering 6 to 10. ×: The light-shielding film has been fully confirmed to contain condensed foreign matter. The evaluation results are shown in Tables 3 and 4.

[0240] [Preparation of a light-shielding film for evaluating stability over time] The stability evaluation over time was conducted by storing the photosensitive resin composition at 5°C for one month after preparation, followed by the fabrication of a light-shielding film in the same order as described above, and then performing the same reflectivity evaluation (glass substrate side), optical concentration evaluation, and foreign matter aggregation evaluation as described above.

[0241] [Table 3]

[0242] [Table 4]

[0243] As shown in Tables 3 and 4, the photosensitive resin composition of the embodiment contains components (A) to (F), component (A) contains component (A1), a portion of component (A1) is contained in a state dissolved in component (F), and a portion of component (A1) is contained in component (D). The light-shielding film using the photosensitive resin composition of the embodiment can reduce the reflectivity of the glass substrate side, suppress the agglomeration of foreign matter, and improve the adhesion to the substrate after patterning.

[0244] [Industrial applicability] The photosensitive resin composition according to the present invention provides a photosensitive resin composition for black resist, which has low reflectivity and inhibits the aggregation of foreign matter and can improve the adhesion of development; and provides a method for manufacturing the photosensitive resin composition, a light-shielding film formed by curing the photosensitive resin composition, a filter and a touch panel having the light-shielding film, and a display device having the filter or the touch panel.

Claims

1. A photosensitive resin composition for use as a black resist, comprising: (A) Photosensitive resin containing unsaturated groups; (B) Photopolymerizable compounds having at least two or more unsaturated bonds; (C) Photopolymerization initiator; (D) A pigment dispersion containing at least one light-blocking component selected from the group consisting of black pigment, mixed pigment and light-blocking material; (E) A silica dispersion containing silica particles; and (F) Solvent; The aforementioned component (A) contains an epoxy compound derived from bisphenols and having two glycidyl ether groups, as shown in the following general formula (1), and a reactant of (meth)acrylic acid, which is further reacted with a polycarboxylic acid or its anhydride. The resulting photosensitive resin containing unsaturated groups is obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or its anhydride, which is the aforementioned polycarboxylic acid or its anhydride, and (b) a tetracarboxylic acid or its dianhydride, in a (a) / (b) molar ratio of 0.01 or more and not exceeding 2.

0. A portion of the aforementioned component (A1) is contained in a state dissolved in the aforementioned component (F). A portion of the aforementioned component (A1) is contained in the aforementioned component (D). (1) In general formula (1), R1, R2, R3, and R4 are independently hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, or halogen atoms, respectively; X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-dimethyl or single bond as shown in general formula (2); and l is an integer from 0 to 10. (2) In general formula (2), * represents the bonding site with the structure shown in general formula (1).

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

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

4. The photosensitive resin composition for black resist according to claim 3, wherein the aforementioned component (A) substantially does not contain any component other than the aforementioned component (A1).

5. The photosensitive resin composition for black resist according to claim 1, wherein the total mass (mE1) of the aforementioned silica particles contained in the aforementioned photosensitive resin composition for black resist is in the ratio (mE1 / mD1) of 0.01 to 0.20 relative to the total mass (mD1) of at least one light-blocking component selected from the group consisting of black pigment, mixed pigment and light-blocking material.

6. The photosensitive resin composition for black resist according to claim 5, wherein the aforementioned (mE1 / mD1) is 0.06~0.

12.

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

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

9. A method for manufacturing a photosensitive resin composition for black resist, wherein the aforementioned photosensitive resin composition for black resist contains... (A) Photosensitive resin containing unsaturated groups; (B) Photopolymerizable compounds having at least two or more unsaturated bonds; (C) Photopolymerization initiator; (D) A pigment dispersion containing at least one light-blocking component selected from the group consisting of black pigment, mixed pigment and light-blocking material; (E) A silica dispersion containing silica particles; and (F) Solvent; The aforementioned component (A) contains an epoxy compound derived from bisphenols having two glycidyl ether groups, as shown in the following general formula (1), and a reactant of (meth)acrylic acid, which is further reacted with a polycarboxylic acid or its anhydride. The resulting photosensitive resin containing unsaturated groups is obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or its anhydride, which is the aforementioned polycarboxylic acid or its anhydride, and (b) a tetracarboxylic acid or its dianhydride, in a (a) / (b) molar ratio of 0.01 or more and less than 2.

0. The method for manufacturing the aforementioned photosensitive resin composition for black resist includes the following steps: Prepare a pigment dispersion containing the aforementioned component (D) containing component (A1) and a solvent; Prepare a silica dispersion containing the aforementioned component (E) and solvent; and Mix the aforementioned components (A), (B), (C), pigment dispersion, silica dispersion, and solvent containing the aforementioned component (A1); (1) In general formula (1), R1, R2, R3, and R4 are independently hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, or halogen atoms, respectively; X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-dimethyl or single bond as shown in general formula (2); and l is an integer from 0 to 10. (2) In general formula (2), * represents the bonding site with the structure shown in general formula (1).

10. The method for manufacturing a photosensitive resin composition for black resist according to claim 9, wherein the aforementioned step of preparing the silica dispersion is a step of preparing a silica dispersion comprising the aforementioned component (E) containing the aforementioned component (A1) and a solvent.

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

12. A filter having a light-shielding film as a black matrix according to claim 11.

13. A touch panel having a light-shielding film according to claim 11.

14. A display device having a filter according to claim 12.

15. A display device having a touch panel according to claim 13.

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