Black photosensitive resin composition, method for producing patterned cured product, patterned cured product, and black matrix

Abstract

The present invention provides a black photosensitive resin composition that can form a light-shielding cured product with high solvent resistance even at a low baking temperature, a method for producing a patterned cured product using the black photosensitive resin composition, a patterned cured product composed of the cured product of the black photosensitive resin composition, and a black matrix composed of the cured product of the black photosensitive resin composition. The present invention uses a black photosensitive resin composition comprising an alkali-soluble resin (A), a specific photopolymerizable monomer (B), a photopolymerization initiator (C), and a specific light-shielding agent (D).

Description

Technical Field

[0001] The present invention relates to a black photosensitive resin composition, a method for producing a patterned cured product, the patterned cured product and a black matrix. Background Art

[0002] In a panel for a display device such as a liquid crystal display device, a patterned light-shielding film such as a black matrix or a black columnar spacer is generally formed. Various photosensitive compositions containing a light-shielding black pigment and a photopolymerization initiator have been proposed for forming a light-shielding film for such an application.

[0003] As such a photosensitive composition, for example, a black photosensitive resin composition containing a perylene-based black pigment as an organic pigment, carbon black, a photopolymerization initiator, a resin, and an ethylenically unsaturated compound has been proposed (see Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2012-068613 Summary of the invention

[0007] Technical problem to be solved by the invention

[0008] However, a light-shielding cured film such as a black matrix is ​​sometimes formed in an image display device using a material with low heat resistance such as an organic EL display. Therefore, it is desired that a light-shielding cured product can be formed by baking a black photosensitive resin composition at a lower temperature.

[0009] On the other hand, a light-shielding cured film such as a black matrix formed using a black photosensitive resin composition is sometimes used in a layer formation process for forming other functional layers connected to the cured film after the cured film is formed. In such a layer formation process, a composition obtained by dissolving components such as a resin in a solvent is typically used. Therefore, if the black matrix formed using a black photosensitive resin composition does not have resistance to the solvent, then in the layer formation process, for a light-shielding cured film such as a black matrix, there is a situation where the film thickness is reduced or swelling, deformation, or light-shielding properties are reduced. Based on the above actual situation, it is expected that a light-shielding cured product with higher solvent resistance can be formed for a black photosensitive resin composition.

[0010] However, conventional black photosensitive resin compositions such as the black photosensitive resin composition described in Patent Document 1 have a problem that it is difficult to form a cured product having high solvent resistance when the baking temperature is low.

[0011] The present invention is completed in view of the above-mentioned technical problems, and its purpose is to provide a black photosensitive resin composition that can form a light-shielding cured product with high solvent resistance even at a low baking temperature, a method for producing a patterned cured product using the black photosensitive resin composition, a patterned cured product composed of the cured product of the above-mentioned black photosensitive resin composition, and a black matrix composed of the cured product of the above-mentioned black photosensitive resin composition.

[0012] Solutions for solving the above technical problems

[0013] The present inventors have found that the above-mentioned technical problems can be solved by using a black photosensitive resin composition containing an alkali-soluble resin (A), a specific photopolymerizable monomer (B), a photopolymerization initiator (C), and a specific light-shielding agent (D), thereby completing the present invention. Specifically, the present invention provides the following.

[0014] A first embodiment of the present invention is a black photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D).

[0015] The photopolymerizable monomer (B) includes a polyfunctional (meth)acrylate represented by the following formula (b1),

[0016]

Chemistry 1

[0017]

[0018] (In formula (b1), R b1 is a hydrogen atom or a (meth)acryloyl group, R b2 are each independently a hydrogen atom or a methyl group.)

[0019] The light-shielding agent (D) contains at least one selected from a lactam-based pigment (D1) and a titanium-based pigment (D2) composed of at least one of titanium oxynitride and titanium nitride.

[0020] A second aspect of the present invention is a method for producing a patterned cured product, comprising: applying the black photosensitive resin composition of the first aspect to form a coating film;

[0021] A step of selectively exposing the coating film to light;

[0022] A step of developing the exposed coating film;

[0023] A step of heating the developed coating film.

[0024] A third aspect of the present invention is a patterned cured product, which is composed of a cured product of the black photosensitive resin composition of the first aspect.

[0025] A fourth aspect of the present invention is a black matrix composed of a cured product of the black photosensitive resin composition of the first aspect.

[0026] Effects of the Invention

[0027] According to the present invention, there can be provided a black photosensitive resin composition capable of forming a light-shielding cured product having high solvent resistance even at a low baking temperature, a method for producing a patterned cured product using the black photosensitive resin composition, a patterned cured product composed of the cured product of the above-mentioned black photosensitive resin composition, and a black matrix composed of the cured product of the above-mentioned black photosensitive resin composition. DETAILED DESCRIPTION

[0028] Hereinafter, the present invention will be described based on preferred embodiments. In addition, in this specification, the range expressed using "to" is defined as a range of numerical values ​​or ratios including both ends.

[0029] 《Black photosensitive resin composition》

[0030] The black photosensitive resin composition comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light shielding agent (D). The photopolymerizable monomer (B) comprises a multifunctional (meth)acrylate represented by the following formula (b1). In addition, the light shielding agent (D) comprises at least one selected from a lactam pigment (D1) and a titanium pigment (D2) composed of at least one of titanium oxynitride and titanium nitride.

[0031]

Chemistry 2

[0032]

[0033] (In formula (b1), R b1 is a hydrogen atom or a (meth)acryloyl group, R b2 are each independently a hydrogen atom or a methyl group.)

[0034] For example, in the

[0035] A step of coating to form a coating film,

[0036] A step of selectively exposing the coating film to light.

[0037] The process of developing the exposed coating film, and

[0038] In the method of heating the developed coating film, by using such a black photosensitive resin composition as a material for coating film formation, as shown in the examples described below, even when the heating temperature in the step of heating (baking) the developed coating film is low, that is, even when the baking temperature is low, a patterned cured product with high solvent resistance can be formed. For example, even if the baking temperature is 120°C or less, further 100°C or less, or 95°C or less, a patterned cured product with high solvent resistance and light-shielding properties can be formed.

[0039] On the other hand, when the black photosensitive resin composition does not contain a multifunctional (meth)acrylate represented by formula (b1) as the photopolymerizable monomer (B) but only contains a multifunctional (meth)acrylate such as trimethylolpropane triacrylate and dipentaerythritol hexaacrylate that does not belong to the structure of formula (b1), it is difficult to form a cured product with excellent solvent resistance when the baking temperature is low.

[0040] Furthermore, when the black photosensitive composition contains only a pigment other than the lactam pigment (D1) and the titanium pigment (D2) such as carbon black as the light shielding agent (D), it is difficult to form a cured product having excellent solvent resistance even when the baking temperature is low.

[0041] In addition, the black photosensitive resin composition provides a light-shielding patterned cured product through a predetermined process. For example, the OD value (optical density) of the cured product of the black photosensitive resin composition per 1 μm thickness is 0.6 or more, preferably 1.0 or more, more preferably 1.4 or more, and even more preferably 1.9 or more.

[0042] Furthermore, by using the black photosensitive resin composition, a patterned cured product having excellent linearity can be formed.

[0043] Hereinafter, essential or optional components of the black photosensitive resin composition will be described.

[0044] <Alkali-soluble resin (A)>

[0045] The black photosensitive resin composition contains an alkali-soluble resin (A) (hereinafter also referred to as component (A)). By blending the alkali-soluble resin (A) into the black photosensitive resin composition, alkali developability can be imparted to the black photosensitive resin composition.

[0046] Here, in the present specification, the alkali-soluble resin refers to a resin having a functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) in the molecule that makes the resin alkali-soluble.

[0047] The alkali-soluble resin (A) preferably contains a resin having a photopolymerizable group such as an ethylenically unsaturated double bond in the molecule. In this case, when a cured product (cured film) is formed using the black photosensitive resin composition, crosslinking occurs between the alkali-soluble resin (A) and the photopolymerizable monomer (B). Therefore, even if the baking temperature when forming the cured film is a relatively low temperature such as 120°C or less, further 100°C or less, or 95°C or less, it is easy to form a cured film having high solvent resistance.

[0048] Typical examples of the photopolymerizable group include functional groups having an unsaturated double bond, such as a vinyl group, an allyl group, and a (meth)acryloyl group.

[0049] The alkali-soluble resin (A) preferably contains a resin (a-1) having a cardo structure in the molecule. The cardo structure will be described in detail below.

[0050] When a resin having a cardo structure in a molecule is used, a black photosensitive resin composition having excellent resolution is easily obtained, and a cured film which does not easily flow excessively due to heating is easily formed using the black photosensitive resin composition.

[0051] [Resin having cardo structure (a-1)]

[0052] As the resin (a-1) having a cardo structure (hereinafter also referred to as cardo resin (a-1)), a predetermined alkali-soluble resin having a cardo structure in the molecule can be used. The cardo structure refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting the first ring structure. In addition, the second ring structure and the third ring structure may be the same structure or different structures.

[0053] A representative example of the cardo structure is a skeleton in which two aromatic rings (for example, benzene rings) are bonded to the carbon atom at the 9-position of the fluorene ring.

[0054] There is no particular limitation on the cardo resin (a-1), and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferred. The resin represented by the following formula (a-1) has a (meth)acryloyl group in the molecule as shown in the following formula (a-2). Therefore, the resin represented by the following formula (a-1) belongs to a resin containing a photopolymerizable group in the molecule.

[0055]

Chemistry 3

[0056]

[0057] In formula (a-1), X a represents a group represented by the following formula (a-2). m1 represents an integer of 0 or more and 20 or less.

[0058]

Chemistry 4

[0059]

[0060] In the above formula (a-2), R a1 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R a2 Each independently represents a hydrogen atom or a methyl group, R a3 Each independently represents a linear or branched alkylene group, m2 represents 0 or 1, W a It represents a group represented by the following formula (a-3).

[0061]

Chemistry 5

[0062]

[0063] In formula (a-2), R a3 , preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 6 carbon atoms, most preferably ethane-1,2-diyl, propane-1,2-diyl and propane-1,3-diyl.

[0064] Ring A in formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.

[0065] The aliphatic ring may, for example, be a monocycloalkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane.

[0066] Specifically, monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, or adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane may be mentioned.

[0067] The aromatic ring that may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferred.

[0068] Preferred examples of the divalent group represented by the formula (a-3) include the following groups.

[0069]

Chemistry 6

[0070]

[0071] The divalent group X in formula (a-1) a By providing residue Z aThe tetracarboxylic dianhydride reacts with a diol compound represented by the following formula (a-2a) to be introduced into the cardo resin (a-1).

[0072]

Chemistry 7

[0073]

[0074] In formula (a-2a), R a1 , R a2 , R a3 and m2 is the same as described for formula (a-2). Ring A in formula (a-2a) is the same as described for formula (a-3).

[0075] The diol compound represented by the formula (a-2a) can be produced, for example, by the following method.

[0076] First, if necessary, the hydrogen atoms in the phenolic hydroxyl groups of the diol compound represented by the following formula (a-2b) are substituted with -R a3 The group represented by -OH is then glycidylated using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2c).

[0077] Next, the epoxy compound represented by the formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by the formula (a-2a).

[0078] In formula (a-2b) and formula (a-2c), R a1 , R a3 The ring A in formula (a-2b) and formula (a-2c) is the same as the description of formula (a-3).

[0079] In addition, the method for producing the diol compound represented by the formula (a-2a) is not limited to the above method.

[0080]

Chemistry 8

[0081]

[0082] Preferred examples of the diol compound represented by the formula (a-2b) include the following diol compounds.

[0083]

Chemistry 9

[0084]

[0085] In the above formula (a-1), R a0 A hydrogen atom or -CO-Y a -COOH represents a group. Here, Y aIt represents the residue after removing the anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

[0086] In the above formula (a-1), Z a It represents a residue after removing two anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

[0087] In the above formula (a-1), m1 represents an integer of 0 or more and 20 or less.

[0088]

Chemistry 10

[0089]

[0090] (In formula (a-4), R a4 , R a5 and R a6 Each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and m3 represents an integer of 0 to 12.)

[0091] R in formula (a-4) may be selected a4 The alkyl group is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms in the alkyl group to this range, the heat resistance of the obtained carboxylic acid ester can be further improved. a4 In the case of an alkyl group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, particularly preferably 1 to 3, from the viewpoint of easily obtaining a cardol resin having excellent heat resistance.

[0092] In R a4 In the case of an alkyl group, the alkyl group may be linear or branched.

[0093] From the viewpoint of easily obtaining a cardo resin having excellent heat resistance, R in the formula (a-4) a4 , and more preferably each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. a4 More preferably, it is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably, it is a hydrogen atom or a methyl group.

[0094] From the viewpoint of facilitating the preparation of high-purity tetracarboxylic dianhydride, the plurality of R in formula (a-4) a4 The same groups are preferred.

[0095] m3 in the formula (a-4) represents an integer of 0 to 12. When the value of m3 is 12 or less, purification of tetracarboxylic dianhydride can be facilitated.

[0096] The upper limit of m3 is preferably 5, more preferably 3, from the viewpoint of easy purification of tetracarboxylic dianhydride.

[0097] The lower limit of m3 is preferably 1, more preferably 2, from the viewpoint of the chemical stability of tetracarboxylic dianhydride.

[0098] In the formula (a-4), m3 is particularly preferably 2 or 3.

[0099] R in formula (a-4) may be selected a5 and R a6 The alkyl group having 1 to 10 carbon atoms and optionally R a4 The alkyl groups have 1 to 10 carbon atoms.

[0100] From the viewpoint that the purification of tetracarboxylic dianhydride is relatively easy, R a5 and R a6 It is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, particularly preferably 1 to 3), and particularly preferably a hydrogen atom or a methyl group.

[0101] Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5", 6,6"-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5", 6,6"-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-(methylnorbornane)-5,5", 6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-norbornane-5,5", 6,6"-tetracarboxylic dianhydride (also known as "norbornane-2-spiro- 2'-cyclohexanone-6'-spiro-2"-norbornane-5,5", 6,6"-tetracarboxylic dianhydride"), methyl norbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-(methyl norbornane)-5,5", 6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α'-spiro-2"-norbornane-5,5", 6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2"-norbornane-5,5", 6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2"-norbornane-5,5", 6,6"-tetracarboxylic dianhydride, norbornane- 2-spiro-α-cyclooctanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride Spiro-α-cyclotridecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclopentanone)-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, and the like.

[0102] The mass average molecular weight of the cardol resin (a-1) is preferably 1000 to 40000, more preferably 1500 to 30000, and even more preferably 2000 to 10000. By setting it as the above range, good developability can be obtained, and sufficient heat resistance and mechanical strength for the cured film can be obtained.

[0103] In this specification, the mass average molecular weight Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC).

[0104] The content of the resin (a-1) having a cardo structure in the alkali-soluble resin (A) is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0105] The alkali-soluble resin (A) may contain an alkali-soluble resin other than the resin (a-1) having a cardo structure.

[0106] The content of the alkali-soluble resin (A) in the total solid content of the black photosensitive resin composition is, for example, 5% by mass to 65% by mass, preferably 5% by mass to 55% by mass, and more preferably 10% by mass to 45% by mass. By setting it in the above range, a black photosensitive resin composition with excellent developability can be easily obtained.

[0107] In addition, in this specification, solid content means the mass of the black photosensitive resin composition after removing the organic solvent.

[0108] <Photopolymerizable Monomer (B)>

[0109] The black photosensitive resin composition contains a photopolymerizable monomer (B). The photopolymerizable monomer (B) contains a polyfunctional (meth)acrylate represented by the above formula (b1) as an essential component.

[0110] In the present specification, “(meth)acrylate” refers to both “acrylate” and “methacrylate”, “(meth)acrylic acid” refers to both “acrylic acid” and “methacrylic acid”, and “(meth)acryloyloxy” refers to both “acryloyloxy” and “methacryloyloxy”.

[0111] As described above, by using a black photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerization initiator (C), a specific light-shielding agent (D) described in detail below, and further comprising a polyfunctional (meth)acrylate represented by the above formula (b1), a patterned cured product having high solvent resistance and light-shielding properties can be formed even when the heating temperature in the step of heating the developed coating film is low, that is, even when the baking temperature is low. The reason why a patterned cured product having high solvent resistance and light-shielding properties can be formed even when the baking temperature is low is not clear in detail, but one reason is presumed to be that the distance between crosslinking points in the cured product is short due to the structure of the polyfunctional (meth)acrylate represented by the formula (b1).

[0112] The content of the polyfunctional (meth)acrylate represented by the formula (b1) in the photopolymerizable monomer (B) is not particularly limited, but is preferably 50% by mass or more, and more preferably 70% by mass or more.

[0113] The photopolymerizable monomer (B) may contain a photopolymerizable monomer other than the polyfunctional (meth)acrylate represented by the formula (b1). The mass ratio of the polyfunctional (meth)acrylate represented by the formula (b1) to the photopolymerizable monomer other than the polyfunctional (meth)acrylate represented by the formula (b1) is, for example, 30:70 to 95:5, preferably 50:50 to 80:20, and more preferably 55:45 to 70:30.

[0114] As the photopolymerizable monomer other than the polyfunctional (meth)acrylate represented by formula (b1), a compound other than the polyfunctional (meth)acrylate represented by formula (b1) having an ethylenically unsaturated group is preferred. Such a compound having an ethylenically unsaturated group includes a monofunctional compound and a polyfunctional compound.

[0115] Examples of the monofunctional compound include (meth)acrylamide, hydroxymethyl (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like. The monofunctional compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and semi-(meth)acrylate of phthalic acid derivatives. These monofunctional compounds can be used alone or in combination of two or more.

[0116] On the other hand, examples of the polyfunctional compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, The present invention also includes polyfunctional compounds such as (methyl)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ether di(meth)acrylate, glycerol polyglycidyl ether poly(meth)acrylate, (meth)acrylic acid urethane (i.e., a reaction product of toluene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, a condensate of a polyol and N-methylol (meth)acrylamide, and triacrylate formal. These polyfunctional compounds can be used alone or in combination of two or more.

[0117] The content of the photopolymerizable monomer (B) in the total solid content of the black photosensitive resin composition is, for example, 1% by mass to 30% by mass, preferably 5% by mass to 20% by mass. By setting it to 5% by mass to 20% by mass, it is easy to obtain a patterned cured product with higher solvent resistance and excellent straightness.

[0118] <Photopolymerization Initiator (C)>

[0119] The photopolymerization initiator (C) is not particularly limited, and a conventionally known photopolymerization initiator can be used.

[0120] As the photopolymerization initiator (C), an oxime ester compound may be mentioned.

[0121] As the oxime ester compound, a compound having a partial structure represented by the following formula (c1) is preferred.

[0122]

Chemistry 11

[0123]

[0124] (In formula (c1),

[0125] n1 is 0 or 1,

[0126] R c2 is a monovalent organic group,

[0127] R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent,

[0128] * is a key. )

[0129] The compound having a partial structure represented by the formula (c1) preferably has a carbazole skeleton, a fluorene skeleton, a diphenyl ether skeleton, or a phenylene sulfide skeleton.

[0130] The compound having a partial structure represented by the formula (c1) preferably has one or two partial structures represented by the formula (c1).

[0131] Examples of the compound having a partial structure represented by the formula (c1) include compounds represented by the following formula (c2).

[0132]

Chemistry 12

[0133]

[0134] (In formula (c2), R c1 is a group represented by the following formula (c3), (c4) or (c5),

[0135] n1 is 0 or 1,

[0136] R c2 is a monovalent organic group,

[0137] R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

[0138]

Chemistry 13

[0139]

[0140] (In formula (c3), R c4 and R c5 are each independently a monovalent organic group,

[0141] n2 is an integer from 0 to 3,

[0142] When n2 is 2 or 3, multiple R c5 Can be the same or different, multiple R c5 They may be bonded to each other to form a ring.

[0143] * is a key. )

[0144]

Chemistry 14

[0145]

[0146] (In formula (c4), R c6 and R c7 are each independently a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom,

[0147] R c6 and R c7 They may also be bonded to each other to form a ring,

[0148] R c7 The benzene rings in the fluorene skeleton can be bonded to each other to form a ring.

[0149] R c8 is a nitro group or a monovalent organic group,

[0150] n3 is an integer from 0 to 4,

[0151] * is a key. )

[0152]

Chemistry 15

[0153]

[0154] (In formula (c5), R c9 is a monovalent organic group, a halogen atom, a nitro group or a cyano group,

[0155] A is S or O,

[0156] n4 is an integer from 0 to 4,

[0157] * is a key. )

[0158] In formula (c3), R c4 is a monovalent organic group. c4 It can be selected from various organic groups within the range that does not hinder the purpose of the present invention. As the organic group, a carbon atom-containing group is preferred, and a group consisting of 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and halogen atoms is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, but is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.

[0159] As R c4Preferred examples of include an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, a saturated aliphatic acyl group having 2 to 20 carbon atoms which may have a substituent, an alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a heterocycliccarbonyl group which may have a substituent.

[0160] In R c4 Among them, an alkyl group having 1 to 20 carbon atoms is preferred. The alkyl group may be linear or branched. From the viewpoint of good solubility of the compound represented by formula (c3) in the photosensitive resin composition, R c4 The number of carbon atoms of the alkyl group is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. In addition, from the viewpoint of good compatibility between the compound represented by formula (c3) in the photosensitive resin composition and other components, R c4 The number of carbon atoms in the alkyl group is preferably 15 or less, more preferably 10 or less.

[0161] In R c4 When there is a substituent, preferred examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, an aliphatic acyloxy group having 2 to 20 carbon atoms, a phenoxy group, a benzoyl group, a benzoyloxy group, a group represented by -PO(OR)2 (R is an alkyl group having 1 to 6 carbon atoms), a halogen atom, a cyano group, a heterocyclic group, and the like.

[0162] R c4 When it is a heterocyclic group, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. c4In the case of a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing one or more N, S, or O, or a heterocyclic group formed by condensing the monocyclic rings, or a heterocyclic group formed by condensing the monocyclic rings with a benzene ring. In the case of a condensed ring, the number of rings is 3 or less. As the heterocyclic ring constituting the heterocyclic group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran and tetrahydrofuran can be cited.

[0163] R c4 In the case of a heterocyclic group, examples of the substituent which the heterocyclic group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group and the like.

[0164] As described above, R c4 Preferred specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, pentane-3-yl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl.

[0165] Furthermore, from the viewpoint of good solubility of the compound represented by the formula (c3) in the photosensitive resin composition, an n-octyl group and a 2-ethylhexyl group are preferred, and a 2-ethylhexyl group is more preferred.

[0166] In formula (c3), R c5 is a monovalent organic group. c5 It can be selected from various organic groups within the range that does not hinder the purpose of the present invention. As the organic group, a carbon atom-containing group is preferred, and a group consisting of 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and halogen atoms is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, but is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.

[0167] As R c5Examples of preferred monovalent organic groups include alkyl, alkoxy, cycloalkyl, cycloalkyloxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenyl which may have a substituent, phenoxy which may have a substituent, benzoyl which may have a substituent, phenoxycarbonyl which may have a substituent, benzoyloxy which may have a substituent, phenylalkyl which may have a substituent, naphthyloxy which may have a substituent, naphthyloxy which may have a substituent, naphthyloxy which may have a substituent, naphthyloxycarbonyl which may have a substituent, naphthyloxy which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino substituted with one or two organic groups, morpholin-1-yl, piperazin-1-yl, halogen, nitro, cyano, and substituents containing a group represented by HX2C- or H2XC- (wherein X is each independently a halogen atom).

[0168] In R c5 In the case of an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 6. c5 When it is an alkyl group, it may be a straight chain or a branched chain. c5 Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl and isodecyl. c5 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

[0169] In R c5 In the case of an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 6. c5 In the case of an alkoxy group, it may be a straight chain or a branched chain. c5 Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy and isodecyloxy. c5In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, and methoxypropoxy.

[0170] In R c5 In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. c5 Specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. c5 Specific examples of the cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy and cyclooctyloxy.

[0171] In R c5 In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. c5 Specific examples of saturated aliphatic acyl groups include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2,2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. c5 Specific examples of the saturated aliphatic acyloxy group include an acetyloxy group, a propionyloxy group, an n-butyryloxy group, a 2-methylpropionyloxy group, an n-pentanoyloxy group, a 2,2-dimethylpropionyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group and an n-hexadecanoyloxy group.

[0172] In R c5 In the case of an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 20, and more preferably 2 to 7. c5Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl and isodecyloxycarbonyl.

[0173] In R c5 In the case of a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. c5 In the case of a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 to 20, and more preferably 11 to 14. c5 Specific examples of the group R in the case of a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. c5 Specific examples of the naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl and 2-(β-naphthyl)ethyl. c5 When it is phenylalkyl or naphthylalkyl, R c5 The phenyl group or the naphthyl group may further have a substituent.

[0174] In R c5 When it is a heterocyclic group, the heterocyclic group and R in formula (c3) c4 The same is true for the case of a heterocyclic group, which may further have a substituent.

[0175] In R c5 In the case of a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R c5 The same applies to the case of a heterocyclic group.

[0176] In R c5 In the case of an amino group substituted with one or two organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group which may have a substituent and has 11 to 20 carbon atoms, and a heterocyclic group. Specific examples of these preferred organic groups are as follows: c5Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentanoylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α-naphthoylamino, and β-naphthoylamino.

[0177] As R c5 In the case where the phenyl, naphthyl and heterocyclic group contained in further has a substituent, the substituent may include a substituent including a group represented by HX2C- or H2XC- (for example, a haloalkoxy group including a group represented by HX2C- or H2XC-, a haloalkyl group including a group represented by HX2C- or H2XC-), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a benzoyl group, a halogen group, a nitro group and a cyano group. In R c5 When the phenyl group, naphthyl group and heterocyclic group contained in further have a substituent, the number of the substituent is not limited within the range not hindering the purpose of the present invention, and is preferably 1 or more and 4 or less. c5 When the phenyl group, naphthyl group and heterocyclic group included in have a plurality of substituents, the plurality of substituents may be the same or different.

[0178] As in R c5 When the benzoyl group contained in further has a substituent, the substituent may, for example, be an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, 2-thiophenecarbonyl (thiophen-2-ylcarbonyl), furan-3-ylcarbonyl, or phenyl.

[0179] The halogen atom represented by X may, for example, be a fluorine atom, a chlorine atom or a bromine atom, and is preferably a fluorine atom.

[0180] As the substituent containing a group represented by HX2C- or H2XC-, a haloalkoxy group containing a group represented by HX2C- or H2XC-, a group having a haloalkoxy group containing a group represented by HX2C- or H2XC-, a haloalkyl group containing a group represented by HX2C- or H2XC-, a group having a haloalkyl group containing a group represented by HX2C- or H2XC-, and the like can be mentioned, and a haloalkoxy group containing a group represented by HX2C- or H2XC- or a group having a haloalkoxy group containing a group represented by HX2C- or H2XC- is more preferable.

[0181] As the group having a haloalkyl group containing a group represented by HX2C- or H2XC-, there can be mentioned an aromatic group substituted with a haloalkyl group containing a group represented by HX2C- or H2XC- (for example, phenyl, naphthyl, etc.), a cycloalkyl group substituted with a haloalkyl group containing a group represented by HX2C- or H2XC- (for example, cyclopentyl, cyclohexyl, etc.), etc., preferably an aromatic group substituted with a haloalkyl group containing a group represented by HX2C- or H2XC-.

[0182] As the group having a haloalkoxy group containing a group represented by HX2C- or H2XC-, there can be mentioned an aromatic group substituted with a haloalkoxy group containing a group represented by HX2C- or H2XC- (for example, phenyl, naphthyl, etc.), an alkyl group substituted with a haloalkoxy group containing a group represented by HX2C- or H2XC- (for example, methyl, ethyl, n-propyl, isopropyl, etc.), a cycloalkyl group substituted with a haloalkoxy group containing a group represented by HX2C- or H2XC- (for example, cyclopentyl, cyclohexyl, etc.), etc., and preferably an aromatic group substituted with a haloalkoxy group containing a group represented by HX2C- or H2XC-.

[0183] In addition, as R c5 , cycloalkylalkyl, phenoxyalkyl which may have a substituent on the aromatic ring, and phenylthioalkyl which may have a substituent on the aromatic ring are also preferred. The substituents that phenoxyalkyl and phenylthioalkyl may have are the same as R c5 The substituents that the contained phenyl groups may have are the same.

[0184] In a monovalent organic group, as R c5, preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring. As the alkyl group, an alkyl group having a carbon number of 1 to 20 is preferred, an alkyl group having a carbon number of 1 to 8 is more preferred, an alkyl group having a carbon number of 1 to 4 is particularly preferred, and a methyl group is most preferred. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The carbon number of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The carbon number of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The carbon number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferred.

[0185] In the group represented by formula (c3), when there are multiple R c5 , multiple R c5 When the two or more R atoms are bonded to each other to form a ring, the formed ring may be a hydrocarbon ring or a heterocyclic ring. Examples of heteroatoms contained in the heterocyclic ring include N, O, and S. c5 The ring formed by bonding to each other is particularly preferably an aromatic ring. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. As the aromatic ring, an aromatic hydrocarbon ring is preferred. In formula (c3), a plurality of R c5 Specific examples of the case where they are bonded to each other to form a benzene ring are shown below.

[0186]

Chemistry 16

[0187]

[0188] In the group represented by formula (c4), R c8 is a nitro group or a monovalent organic group. c8 On the condensed ring in formula (c4) and with -(CO) n1 - is bonded to a six-membered aromatic ring different from the aromatic ring to which the group represented by - is bonded. c8 The bonding position of is not particularly limited. In the group represented by formula (c4), there are one or more R c8 In the case of the compound represented by formula (c4), it is preferred that one or more R c8 One of them is bonded to the 7-position of the fluorene skeleton. That is, in the group represented by formula (c4), one or more R c8In the case of R, the group represented by formula (c4) is preferably represented by the following formula (c6). c8 In the case of multiple R c8 Can be the same or different.

[0189]

Chemistry 17

[0190]

[0191] (In formula (c6), R c6 , R c7 , R c8 , n3 are respectively the same as R in formula (c4) c6 , R c7 , R c8 , n3 are the same.)

[0192] In R c8 When R is a monovalent organic group, c8 There is no particular limitation within the scope of not hindering the purpose of the present invention. As an organic group, a carbon-containing group is preferably a group, and more preferably a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and halogen atoms. The number of carbon atoms in the carbon-containing group is not particularly limited, and is preferably 1 to 50, and more preferably 1 to 20.

[0193] As R c8 In the case of a monovalent organic group, preferred examples include the following: c5 Preferred examples of the monovalent organic group are the same as those of .

[0194] In formula (c4), R c6 and R c7 R is a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. c6 and R c7 can be bonded to each other to form a ring. Among these groups, c6 and R c7 , preferably a chain alkyl group which may have a substituent. c6 and R c7 In the case of a chain alkyl group which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

[0195] In R c6 and R c7 In the case of an unsubstituted linear alkyl group, the number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6.c6 and R c7 Specific examples of the chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl and isodecyl. c6 and R c7 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

[0196] In R c6 and R c7 In the case of a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably straight-chain.

[0197] The substituents that the alkyl group may have are not particularly limited within the scope that does not hinder the purpose of the present invention. Preferred examples of substituents include alkoxy groups, cyano groups, halogen atoms, halogenated alkyl groups, cyclic organic groups, and alkoxycarbonyl groups. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these atoms, fluorine atoms, chlorine atoms, and bromine atoms are preferred. Cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclic groups. Specific examples of cycloalkyl groups include R c8 The preferred examples of the case where R is a cycloalkyl group are the same. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. Specific examples of heterocyclic groups include R c8 The preferred examples in the case of a heterocyclic group are the same. c8 In the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, and more preferably 1 to 6.

[0198] In the case where the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group. The typical number of substituents is 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

[0199] In R c6 and R c7In the case of an unsubstituted chain alkoxy group, the number of carbon atoms in the chain alkoxy group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. c6 and R c7 Specific examples of the chain alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, sec-octoxy, tert-octoxy, n-nonyloxy, isononyloxy, n-decyloxy and isodecyloxy. c6 and R c7 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, and methoxypropoxy.

[0200] In R c6 and R c7 In the case of a chain alkoxy group having a substituent, the substituent that the alkoxy group may have is the same as R c6 and R c7 The same applies to the case of a chain alkyl group.

[0201] In R c6 and R c7 In the case of a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. c6 and R c7 In the case of a cyclic organic group, the cyclic organic group may have a substituent having the same c6 and R c7 The same applies to the case of a chain alkyl group.

[0202] In R c6 and R c7 In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond, or a group formed by condensing a plurality of benzene rings. In the case where the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Specific preferred examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl.

[0203] In R c6 and R c7In the case of an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.

[0204] In R c6 and R c7 In the case of a heterocyclic group, the following examples include the following as R in formula (c3): c5 The same group as the heterocyclic group.

[0205] R c6 and R c7 They can be bonded to each other to form a ring. c6 and R c7 The group formed by the ring is preferably a cycloalkylene group. c6 and R c7 When the groups are bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

[0206] In R c7 When forming a ring with the benzene ring of the fluorene skeleton, the ring may be an aromatic ring or an aliphatic ring.

[0207] In R c6 and R c7 When the group formed by bonding is a cycloalkylene group, the cycloalkylene group may also be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring.

[0208] As described above, R c6 and R c7 Preferred examples of the group include groups represented by the formula -A1-A2, wherein A1 is a linear alkylene group, and A2 is an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group or an alkoxycarbonyl group.

[0209] The number of carbon atoms of the straight-chain alkylene group of A1 is preferably 1 to 10, more preferably 1 to 6. When A2 is an alkoxy group, the alkoxy group may be straight-chain or branched, preferably straight-chain. The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. When A2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. When A2 is a haloalkyl group, the halogen atom contained in the haloalkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group may be straight-chain or branched, preferably straight-chain. When A2 is a cyclic organic group, examples of cyclic organic groups are the same as R c6 and R c7 The cyclic organic group having as a substituent is the same as that of R. c6 and R c7 The alkoxycarbonyl group which may be a substituent is the same.

[0210] As R c6 and R c7Preferred specific examples include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl and n-octyl; alkoxyalkyl groups such as 2-methoxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl and 8-ethoxy-n-octyl; 2-cyanoethyl, 3 ... cyanoalkyl such as cyanopropyl, 4-cyanobutyl, 5-cyanopentyl, 6-cyanohexyl, 7-cyanoheptyl and 8-cyanooctyl; phenylalkyl such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl and 8-phenyl-n-octyl; 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, cycloalkylalkyl such as ethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-propyl, Alkoxycarbonylalkyl such as n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl and 8-ethoxycarbonyl-n-octyl; halogenated alkyl such as 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

[0211] As R c6 and R c7 Among the above, preferred groups are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

[0212] In formula (c5), A is particularly preferably S from the viewpoint of easily obtaining a photopolymerization initiator having excellent sensitivity.

[0213] In formula (c5), R c9It is a monovalent organic group, a halogen atom, a nitro group or a cyano group.

[0214] In formula (c5), R c9 In the case of a monovalent organic group, it can be selected from various organic groups within the scope of not hindering the purpose of the present invention. As the organic group, it is preferably a group containing carbon atoms, and more preferably a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and halogen atoms. The number of carbon atoms in the group containing carbon atoms is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.

[0215] As R in formula (c5) c9 In the case of being an organic group, preferred examples include the following as R in formula (c3): c5 The same group as the monovalent organic group.

[0216] In R c9 Among them, preferred are: benzoyl; naphthoyl; benzoyl substituted by a group selected from the group consisting of alkyl having 1 to 6 carbon atoms, morpholine-1-yl, piperazine-1-yl and phenyl; nitro; benzofuranylcarbonyl which may have a substituent, and more preferred are: benzoyl; naphthoyl; 2-methylphenylcarbonyl; 4-(piperazine-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

[0217] In formula (c5), n4 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n4 is 1, R c9 The bonding position is preferably relative to R c9 The bond between the phenyl group and the oxygen atom or sulfur atom is at the para position.

[0218] In formula (c1) and (c2), R c2 The monovalent organic group is not particularly limited within the range that does not hinder the purpose of the present invention. As the organic group, a carbon atom-containing group is preferred, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si and halogen atoms is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20.

[0219] As R c2 Preferred examples of the monovalent organic group include the following: c5 Specific examples of these groups are the same as those for R in formula (c3). c5 The groups described are the same.

[0220] In addition, as R c2 , cycloalkylalkyl, phenoxyalkyl which may have a substituent on the aromatic ring, and phenylthioalkyl which may have a substituent on the aromatic ring are also preferred. The substituents that phenoxyalkyl and phenylthioalkyl may have are the same as those in R in formula (c3). c5 When the phenyl group, naphthyl group and heterocyclic group further have a substituent, the substituent is the same as that of the group included.

[0221] In organic groups, as R c2 , preferably, the substituents of the above-mentioned groups represented by HX2C- or H2XC-, alkyl, cycloalkyl, phenyl which may have a substituent, or cycloalkylalkyl, phenylthioalkyl which may have a substituent on the aromatic ring. The carbon number of the alkyl, phenyl which may have a substituent, cycloalkylalkyl, alkylene contained in the cycloalkylalkyl, cycloalkylalkyl, phenylthioalkyl which may have a substituent on the aromatic ring, or phenylthioalkyl which may have a substituent on the aromatic ring and R of formula (c3) c5 same.

[0222] In addition, as R c2 , and a group represented by -A3-CO-O-A4 is also preferred. A3 is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A4 is a monovalent organic group, preferably a monovalent hydrocarbon group.

[0223] When A3 is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A3 is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0224] Preferred examples of A4 include alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. Preferred specific examples of A4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl.

[0225] Preferred specific examples of the group represented by -A3-CO-O-A4 include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonylethyl, 2-n-butyloxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propyloxycarbonyl-n-propyl, 3-n-butyloxycarbonyl-n-propyl, 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl and 3-phenoxycarbonyl-n-propyl.

[0226] In addition, as R c2 , and is also preferably a group represented by the following formula (c7) or (c8).

[0227]

Chemistry 18

[0228]

[0229] (In formula (c7) and (c8), R c10 and R c11 are each independently a monovalent organic group,

[0230] n5 is an integer from 0 to 4,

[0231] In R c10 and R c11 When present at adjacent positions on the benzene ring, R c10 With R c11 can bond to each other to form a ring,

[0232] R c12 is a monovalent organic group,

[0233] n6 is an integer from 1 to 8,

[0234] n7 is an integer from 1 to 5,

[0235] n8 is an integer greater than or equal to 0 and less than or equal to (n7+3).

[0236] In formula (c7), R c10 and R c11 The organic group and R in formula (c4) c8 Same as R c10 , preferably a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a halogenated alkyl group containing a group represented by HX2C- or H2XC-, an alkyl group or a phenyl group. c10 With R c11When they are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. c10 With R c11 Preferred examples of the group forming a ring include naphthalen-1-yl and 1,2,3,4-tetrahydronaphthalen-5-yl.

[0237] In the above formula (c7), n7 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

[0238] In the above formula (c8), R c12 As the organic group, there can be mentioned the organic group which is the same as R in formula (c4) c8 The same group as the organic group described above. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. c12 , preferably exemplified are methyl, ethyl, propyl, isopropyl, butyl and the like, and among these, methyl is more preferred.

[0239] In the above formula (c8), n7 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the above formula (c8), n8 is 0 to (n7+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0.

[0240] In the above formula (c8), n8 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

[0241] In formula (c2), R c3 R is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. c3 In the case of an aliphatic hydrocarbon group, the substituent that the aliphatic hydrocarbon group may have is preferably exemplified by a phenyl group, a naphthyl group, and the like.

[0242] In formula (c1) and formula (c2), R c3 , preferably, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, a cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like can be exemplified, and among these groups, a methyl group or a phenyl group is more preferable.

[0243] As a group represented by formula (c2) and having a group represented by formula (c3) as R c1 Preferred specific examples of the compound include the following compounds.

[0244]

Chemistry 19

[0245]

[0246]

Chemical Formula 20

[0247]

[0248]

Chemical Formula 21

[0249]

[0250]

Chemical Formula 22

[0251]

[0252] As a compound represented by formula (c2) and having a group represented by formula (c4) as R c1 Preferred specific examples of the compound are the following compounds.

[0253]

Chemical Formula 23

[0254]

[0255]

Chemical Formula 24

[0256]

[0257]

Chemical Formula 25

[0258]

[0259]

Chemical Formula 26

[0260]

[0261]

Chemical Formula 27

[0262]

[0263] As a compound represented by formula (c2) and having a group represented by formula (c5) as R c1 Preferred specific examples of the compound are the following compounds.

[0264]

Chemical Formula 28

[0265]

[0266] Examples of the photopolymerization initiator (C) other than the oxime ester compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)butane-1-one, 2-(4-methylbenzyl)-2-diethylamino-1-(4-morpholinophenyl)butane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one α-amino ketone compounds such as 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl) ... -propyl) ketone, 1-hydroxycyclohexyl phenyl ketone and other α-hydroxy ketone photopolymerization initiators; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl methyl ketal and other benzoin photopolymerization initiators; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl, 4'-methyldiphenyl sulfide, 4,4'-bis(diethylamino)benzophenone and other diphenyl Ketone photopolymerization initiators; thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, etc.; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4.Triazine-based photoinitiators such as 6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-[4-(4-methoxystyryl)phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine; carbazole-based photoinitiators; benzimidazole-based photoinitiators represented by the following formula, etc.

[0267]

Chemical 29

[0268]

[0269] The photoinitiator can be used alone or in combination of two or more. By using two or more in combination, it is easy to effectively utilize light rays of a wide range of wavelengths contained in the exposure light. In addition, it is easy to adjust the sensitivity of the black photosensitive resin composition to an appropriate range.

[0270] The content of the photoinitiator (C) in the total solid content of the black photosensitive resin composition is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less.

[0271] When other photoinitiators other than the oxime ester compound are used in combination, the ratio of the mass of the oxime ester compound to the mass of the photoinitiator (C) is preferably 50% by mass or more, more preferably 50% by mass or more and 99% by mass or less, particularly preferably 70% by mass or more and 97% by mass or less, and most preferably 80% by mass or more and 95% by mass or less.

[0272] When the oxime ester compound is contained in the photopolymerization initiator (C) in an amount within the above range, it is particularly difficult to form a patterned cured film having a width wider than a desired width.

[0273] <Sunscreen (D)>

[0274] The black photosensitive resin composition contains a light shielding agent (D). The light shielding agent (D) contains at least one selected from a lactam pigment (D1) and a titanium pigment (D2), and the titanium pigment (D2) is composed of at least one of titanium oxynitride and titanium nitride.

[0275] 〔Lactam pigments (D1)〕

[0276] The lactam pigment (D1) is not particularly limited as long as it is a pigment that is a compound recognized as a lactam by those skilled in the art. Examples of the lactam pigment (D1) include compounds represented by the following formula (d-1).

[0277]

Chemistry 30

[0278]

[0279] In formula (d-1), X d represents a double bond, and the geometric isomers are independently E or Z, R d1 R each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, a chlorine atom, a fluorine atom, a carboxyl group or a sulfone group. d2 R each independently represents a hydrogen atom, a methyl group or a phenyl group. d3 Each independently represents a hydrogen atom, a methyl group or a chlorine atom.

[0280] The compound represented by the formula (d-1) can be used alone or in combination of two or more.

[0281] From the viewpoint of easy production of the compound represented by formula (d-1), R d1 Preferably, it is bonded to the 6-position of the indolinone ring, R d3 Preferably, it is bonded to the 4-position of the indolinone ring. d1 , R d2 and R d3 Preferred is a hydrogen atom.

[0282] The compound represented by the formula (d-1) has EE isomers, ZZ isomers, and EZ isomers as geometric isomers, but may be a single compound of any of these geometric isomers or a mixture of these geometric isomers.

[0283] The compound represented by the formula (d-1) can be produced by the methods described in, for example, International Publication Nos. 2000 / 24736 and 2010 / 081624.

[0284] In order to disperse the lactam pigment well in the black photosensitive resin composition, the average particle size of the lactam pigment is preferably 10 nm to 1000 nm.

[0285] When the sunscreen (D) contains a lactam pigment (D1), the content of the lactam pigment (D1) in the sunscreen (D) is preferably, for example, 50% by mass or more, and more preferably 70% by mass or more, from the viewpoint of improving solvent resistance. The upper limit of the content of the lactam pigment (D1) in the sunscreen (D) is not particularly limited and may be 100% by mass.

[0286] 〔Titanium pigments (D2)〕

[0287] The titanium pigment (D2) is composed of at least one of titanium oxynitride and titanium nitride. In the present specification, titanium oxynitride also includes titanium oxide.

[0288] When the sunscreen (D) contains a titanium pigment (D2), the content of the titanium pigment (D2) in the sunscreen (D) is preferably, for example, 50% by mass or more, and more preferably 70% by mass or more, from the viewpoint of improving solvent resistance. The upper limit of the content of the titanium pigment (D2) in the sunscreen (D) is not particularly limited and may be 100% by mass.

[0289] 〔Carbon black (D3)〕

[0290] The sunscreen agent (D) may also contain carbon black (D3).

[0291] As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, and channel black having excellent light-shielding properties is preferably used.

[0292] The carbon black (D3) may be subjected to a surface treatment selected from a coating treatment with an organic substance and a treatment for introducing an acidic group.

[0293] When the light-shielding agent (D) contains at least one selected from the lactam pigment (D1) and the titanium pigment (D2) and carbon black (D3), the ratio of the contents of the two is not particularly limited within the range that does not hinder the purpose of the present invention. When the light-shielding agent (D) contains at least one selected from the lactam pigment (D1) and the titanium pigment (D2) and carbon black (D3), from the viewpoint of improving solvent resistance, the ratio of the total mass of the lactam pigment (D1) and the titanium pigment (D2) to the total mass of the lactam pigment (D1) and the titanium pigment (D2) and the mass of the carbon black (D3) is preferably 50% by mass or more, and more preferably 70% by mass or more.

[0294] 〔Other sunscreens〕

[0295] The sunscreen (D) may contain other sunscreens besides the lactam pigment (D1), the titanium pigment (D2) and the carbon black (D3). The other sunscreen may be a black pigment or a color pigment.

[0296] Examples of black pigments include perylene pigments, fine particles containing silver-tin (AgSn) alloy as a main component, metal oxides, composite oxides, metal sulfides, metal sulfates or metal carbonates of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and the like, and various pigments whether organic or inorganic.

[0297] As the color pigment, various pigments can be used regardless of whether they are organic or inorganic. Examples of the color pigment include blue pigments, violet pigments, yellow pigments, orange pigments, and green pigments.

[0298] Specific examples of the blue pigment include CI Pigment Blue 1 (hereinafter, “CI Pigment Blue” is referred to as such and only the number is described), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64 and 66.

[0299] Specific examples of the violet pigment include CI Pigment Violet 1 (hereinafter referred to as “CI Pigment Violet” and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40 and 50.

[0300] Specific examples of yellow pigments include CI Pigment Yellow 1 (hereinafter referred to as “CI Pigment Yellow” and only the numbers are described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 and 185.

[0301] Specific examples of the orange pigment include CI Pigment Orange 1 (hereinafter referred to as “CI Pigment Orange” and only the numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71 and 73.

[0302] Specific examples of the green pigment include green pigments such as CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37 and CI Pigment Green 58.

[0303] In the black photosensitive resin composition, the light shielding agent (D) may contain a dye within a range not hindering the purpose of the present invention. The dye may be appropriately selected from known materials.

[0304] Examples of dyes that can be used in the black photosensitive resin composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.

[0305] These dyes can be dispersed in an organic solvent or the like by laking (salification) and used as a light-shielding agent (D).

[0306] In addition to these dyes, dyes described in, for example, JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, JP-A-2014-197206, etc. can also be preferably used.

[0307] The form of the light shielding agent (D) such as the lactam pigment (D1), titanium pigment (D2), carbon black (D3) used in the preparation of the black photosensitive resin composition is not particularly limited. The light shielding agent (D) can be used as a powder or as a dispersion. The light shielding agent (D) is preferably used as a dispersion for the preparation of the black photosensitive resin composition.

[0308] As the dispersion liquid, a dispersion liquid containing two or more types of sunscreen agents (D) may be used. Furthermore, two or more dispersion liquids each containing a different type of sunscreen agent may be used.

[0309] As the dispersion medium, for example, an organic solvent such as propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate 3-ethoxyethyl propionate, and propylene glycol monomethyl ether propionate can be used.

[0310] A dispersant may be used in order to stabilize the dispersion of the light-shielding agent (D) in the dispersion liquid and improve the dispersibility of the light-shielding agent (D) in the black photosensitive resin composition.

[0311] As the dispersant, it is preferable to use a polyethyleneimine-based, polyurethane resin-based, or acrylic resin-based polymer dispersant.

[0312] Among these, polyurethane resin-based dispersants are preferred from the viewpoint of good solubility in a developer and less likely to cause residue to adhere to a substrate, a developing device, a pipe, etc. after development.

[0313] When using a dispersant, content of the dispersant in the black photosensitive resin composition is, for example, 5 mass % to 50 mass %, preferably 10 mass % to 40 mass %, relative to content of the light-shielding agent (D).

[0314] In addition, corrosive gas may be generated from the cured film due to the dispersant. Therefore, dispersing the light shielding agent (D) without using a dispersant is also an example of a preferred embodiment.

[0315] The viscosity of the dispersion of the light-shielding agent (D) is not particularly limited. The viscosity of the dispersion is preferably 3 mPa·s or more and 200 mPa·s or less as a value measured at 25° C. using a cone-plate viscometer.

[0316] The particle size of the light shielding agent (D) in the dispersion is preferably 80 nm or more and 300 nm or less as a dispersed average particle size. The dispersed average particle size can be measured using a laser diffraction particle size distribution system.

[0317] The content of the light shielding agent (D) in the total solid content of the black photosensitive resin composition is preferably 10% to 60% by mass, more preferably 20% to 50% by mass. By setting the content in the above range, a patterned cured product having high light shielding properties and excellent straightness can be easily obtained.

[0318] <Thermosetting compound (E)>

[0319] The black photosensitive resin composition may also contain a thermosetting compound (E). By making the black photosensitive resin composition contain the above-mentioned alkali-soluble resin (A), a specific photopolymerizable monomer (B), a photopolymerization initiator (C), a specific light-shielding agent (D), and a thermosetting compound (E), the black photosensitive resin composition is easy to cure well at low temperature.

[0320] As the thermosetting compound (E), various thermosetting compounds that have been mixed in the black photosensitive resin composition in the past can be used. In addition, a thermosetting compound (E) and a curing agent corresponding to the type of the thermosetting compound (E) may also be included as needed. In the case of using a curing agent, from the viewpoint of the long-term stability of the black photosensitive resin composition, it is preferred to use a potential curing agent that acts as a curing agent by baking. In addition, the thermosetting compound (E) is a compound having a molecular weight (Mw) of 2000 or less, preferably a compound having a molecular weight (Mw) of 1500 or less. The thermosetting compound is preferably not a polymer or an oligomer, but a monomer compound or a compound having no more than two repeating units.

[0321] Typical examples of the thermosetting compound (E) include isocyanate compounds, melamine compounds, oxetane compounds, epoxy compounds, etc. Among them, epoxy compounds and oxetane compounds are preferred, and epoxy compounds are more preferred, because of good curability.

[0322] As the epoxy compound, a multifunctional epoxy compound (E1) is preferred because it can form a close crosslink in the cured product of the black photosensitive resin composition. Here, the multifunctional epoxy compound (E1) is an epoxy compound having two or more epoxy groups in one molecule. When the black photosensitive resin composition contains a multifunctional epoxy compound (E1) as the thermosetting compound (E), it is easy to form a cured film with better solvent resistance.

[0323] Examples of general-purpose epoxy compounds include bifunctional epoxy compounds such as bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, bisphenol AD ​​epoxy compounds, naphthalene epoxy compounds, and biphenyl epoxy compounds; 9,9-bis[4-(glycidyloxy)phenyl]-9H-fluorene, 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fluorene, 9 , 9-bis[4-[2-(glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene and 9,9-bis(6-glycidyloxynaphthalen-2-yl)-9H-fluorene and other epoxy group-containing fluorene compounds; tetraglycidylaminodiphenylmethane, Glycidylamine epoxy compounds such as triglycidyl-p-aminophenol, tetraglycidyl-m-phenylenediamine and tetraglycidyl-bis-aminomethylcyclohexane; fluoroglycerol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane and trifunctional epoxy compounds such as 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; and tetrafunctional epoxy compounds such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether and tetraglycidyloxybiphenyl.

[0324] As other preferred examples of epoxy compounds, polyfunctional alicyclic epoxy compounds having alicyclic epoxy groups can be cited. As specific examples of the above-mentioned alicyclic epoxy compounds, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-methyl-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane Carboxylates, trimethyl caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylates, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylates, methylenebis(3,4-epoxycyclohexane), di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate) and tricyclodecenyloxy polyfunctional epoxy compounds, compounds represented by the following formulas (E1-1) to (E1-5).

[0325] These alicyclic epoxy compounds can be used alone or in combination of two or more thereof.

[0326]

Chemical formula 31

[0327]

[0328] (In formula (E1-1), Z represents a single bond or a linking group (a divalent group having one or more atoms). R E1 ~R E18 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

[0329] Examples of the linking group Z include a divalent group selected from the group consisting of a divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO-, -SO2-, -CBr2-, -C(CBr3)2-, -C(CF3)2-, and -R E19 -O-CO-, and a group formed by bonding multiple of these groups.

[0330] Examples of the divalent hydrocarbon group as the linking group Z include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, etc. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene group, etc. Examples of the divalent alicyclic hydrocarbon group include cycloalkylene groups such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, cyclohexylene (including cycloalkylidene groups), etc.

[0331] R E19 is an alkylene group having 1 to 8 carbon atoms, preferably a methylene group or an ethylene group.

[0332]

Chemical formula 32

[0333]

[0334] (In formula (E1-2), R E1 ~R E12 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

[0335]

Chemical formula 33

[0336]

[0337] (In formula (E1-3), R E1 ~RE10 is a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R E2 and R E8 may be bonded to each other.)

[0338]

Chemical formula 34

[0339]

[0340] (In formula (E1-4), R E1 ~R E12 is a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R E2 and R E10 may be bonded to each other.)

[0341]

Chemical formula 35

[0342]

[0343] (In formula (E1-5), R E1 ~R E12 is a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

[0344] In formulas (E1-1) to (E1-5), when R E1 ~R E18 is an organic group, the organic group is not particularly limited as long as it does not hinder the object of the present invention, and may be a hydrocarbon group, a group composed of a carbon atom and a halogen atom, or a group containing a carbon atom, a hydrogen atom, and also containing a heteroatom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, etc.

[0345] As the organic group, a hydrocarbon group, a group composed of a carbon atom, a hydrogen atom, and an oxygen atom, a halogenated hydrocarbon group, a group composed of a carbon atom, an oxygen atom, and a halogen atom, and a group composed of a carbon atom, a hydrogen atom, an oxygen atom, and a halogen atom are preferred. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 5 or less.

[0346] Specific examples of the hydrocarbon group include chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl; vinyl, 1-propenyl, 2-propenyl (olefins); chain alkenyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; aryl groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, α-naphthyl, β-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, anthracenyl and phenanthryl; aralkyl groups such as benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, α-naphthylethyl and β-naphthyl.

[0347] Specific examples of the halogenated hydrocarbon group include halogenated chain alkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl and perfluorodecyl; halogenated cycloalkyl groups such as 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl and 4-bromocyclohexyl; 2-chloro phenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl and the like; and halogenated aralkyl groups such as 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl and the like.

[0348] Specific examples of the group consisting of carbon atoms, hydrogen atoms and oxygen atoms include: hydroxy chain alkyl groups such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl and 4-hydroxy-n-butyl; halogenated cycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl and 4-hydroxycyclohexyl; hydroxyaryl groups such as 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3-dihydroxyphenyl, 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 3,4-dihydroxyphenyl and 3,5-dihydroxyphenyl; hydroxyaralkyl groups such as 2-hydroxyphenylmethyl, 3-hydroxyphenylmethyl and 4-hydroxyphenylmethyl; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, chain alkoxy groups such as oxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy and n-eicosyloxy; chain alkenyloxy groups such as vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy and 3-n-butenyloxy; aryloxy groups such as phenoxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, α-naphthyloxy, β-naphthyloxy, biphenyl-4-yloxy, biphenyl-3-yloxy, biphenyl-2-yloxy, anthracenyloxy and phenanthryloxy; benzyloxy, phenylethoxy, α-naphthylmethoxy, β-naphthylmethoxy, α-naphthylethoxy and β-naphthylethoxy, aralkyloxy such as methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, 4-methoxy-n-butyl, 4-ethoxy-n-butyl and 4-n-propoxy-n-butyl, methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, 2-methoxy-ethoxy, 2-ethoxy-ethoxy, 3-methoxy-n-propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy-n-propoxy, 4-methoxy-n-butyl alkoxyalkoxy groups such as oxy, 4-ethoxy-n-butoxy and 4-n-propoxy-n-butoxy; alkoxyaryl groups such as 2-methoxyphenyl, 3-methoxyphenyl and 4-methoxyphenyl; alkoxyaryloxy groups such as 2-methoxyphenoxy, 3-methoxyphenoxy and 4-methoxyphenoxy; aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, valeryl, hexanoyl, heptanoyl, octanoyl, nonanoyl and decanoyl; aromatic acyl groups such as benzoyl, α-naphthoyl and β-naphthoyl; chain alkyloxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentyloxycarbonyl, n-hexylcarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl and n-decyloxycarbonyl;Aryloxycarbonyl groups such as phenoxycarbonyl, α-naphthyloxycarbonyl, and β-naphthyloxycarbonyl; aliphatic acyloxy groups such as formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, caproyloxy, heptyryloxy, octyryloxy, nonyryloxy, and decyryloxy; aromatic acyloxy groups such as benzoyloxy, α-naphthoyloxy, and β-naphthoyloxy.

[0349] R E1 ~R E18 Preferably, they are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. In particular, from the perspective of easily forming a cured film with excellent mechanical properties, it is more preferable that R E1 ~R E18 are all hydrogen atoms.

[0350] In formulas (E1-2) to (E1-5), R E1 ~R E12 are the same as R E1 ~R E12 in formula (E1-1). In formulas (E1-2) and (E1-4), as the divalent group formed when R E2 and R E10 are bonded to each other, examples include -CH2- and -C(CH3)2-. In formula (E1-3), as the divalent group formed when R E2 and R E8 are bonded to each other, examples include -CH2- and -C(CH3)2-.

[0351] In the alicyclic epoxy compound represented by formula (E1-1), specific examples of preferred compounds include alicyclic epoxy compounds represented by the following formulas (E1-1a), (E1-1b), and (E1-1c), 2,2-bis(3,4-epoxycyclohexan-1-yl)propane [=2,2-bis(3,4-epoxycyclohexyl)propane], etc.

[0352]

Chemical formula 36

[0353]

[0354] In the alicyclic epoxy compound represented by formula (E1-2), specific examples of preferred compounds include dicyclononadiene diepoxide or dicyclononadiene diepoxide represented by the following formula (E1-2a), etc.

[0355]

Chemical formula 37

[0356]

[0357] Among the alicyclic epoxy compounds represented by the formula (E1-3), specific examples of preferred compounds include S-spiro[3-oxatricyclo[3.2.1.0 2，4 octane-6,2'-epoxyethane] and the like.

[0358] Among the alicyclic epoxy compounds represented by the formula (E1-4), specific examples of preferred compounds include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, 1-methyl-4-(3-methyloxirane-2-yl)-7-oxabicyclo[4.1.0]heptane and the like.

[0359] Among the alicyclic epoxy compounds represented by the formula (E1-5), specific examples of preferred compounds include 1,2,5,6-diepoxycyclooctane and the like.

[0360] Furthermore, a compound represented by the following formula (E-1) can be preferably used as the epoxy compound.

[0361]

Chemical formula 38

[0362]

[0363] (In the formula (E-1), X e1 , X e2 and X e3 are each independently a hydrogen atom or an organic group that may contain an epoxy group, and the total number of epoxy groups in X e1 , X e2 and X e3 is 2 or more.)

[0364] As the compound represented by the above formula (E-1), a compound represented by the following formula (E1-6) is preferred.

[0365]

Chemical formula 39

[0366]

[0367] (In the formula (E1-6), R e20 ~R e22 are groups composed of linear, branched or cyclic alkylene, arylene, -O-, -C(=O)-, -NH- and combinations thereof, and may be the same or different from each other. E 1 ~E 3 are at least one substituent selected from the group consisting of an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, a thiol group, a carboxyl group, a hydroxyl group and a succinic anhydride group or a hydrogen atom. Among them, E 1 ~E 3At least two of them are groups having epoxy groups. )

[0368] In formula (E1-6), R e20 With E 1 , R e21 With E 2 and R e22 With E 3 The groups shown are preferably at least two groups represented by the following formula (E1-6a), and more preferably all groups represented by the following formula (E1-6a). The multiple groups represented by the formula (E1-6a) bonded to one compound are preferably the same group.

[0369] -LC a (E1-6a)

[0370] (In formula (E1-6a), L is a linear, branched or cyclic alkylene group, arylene group, -O-, -C(=O)-, -NH- or a group consisting of a combination thereof, C a In formula (E1-6a), L and C a Can bond to form a ring structure.)

[0371] In formula (E1-6a), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is preferably an arylene group having 5 to 10 carbon atoms. In formula (E1-6a), L is preferably a group consisting of a linear alkylene group having 1 to 3 carbon atoms, a phenylene group, -O-, -C(=O)-, -NH-, and a combination thereof, and preferably a group consisting of at least one of a linear alkylene group having 1 to 3 carbon atoms such as a methylene group and a phenylene group, or a group consisting of a combination of these and at least one of -O-, -C(=O)-, and NH-.

[0372] In formula (E1-6a), between L and C a In the case of bonding to form a cyclic structure, for example, when a branched alkylene group and an epoxy group bond to form a cyclic structure (a structure of an epoxy group having an alicyclic structure), an organic group represented by the following formula (E1-6b) or (E1-6c) may be mentioned.

[0373]

Chemistry 40

[0374]

[0375] (In formula (E1-6b), R e23 is a hydrogen atom or a methyl group.)

[0376] Hereinafter, as examples of the compound represented by the formula (E1-6), examples of epoxy compounds having an ethylene oxide group or an alicyclic epoxy group are shown, but the present invention is not limited to these.

[0377]

Chemistry 41

[0378]

[0379] Furthermore, examples of compounds that can be preferably used as epoxy compounds include siloxane compounds having two or more epoxy groups in the molecule (hereinafter also simply referred to as “siloxane compounds”).

[0380] Siloxane compounds are compounds having a siloxane skeleton composed of a siloxane bond (Si-O-Si) and two or more glycidyl groups or alicyclic epoxy groups in the molecule. In addition, an alicyclic epoxy group refers to an aliphatic cyclic group in which two adjacent carbon atoms as ring-constituting atoms in an aliphatic cyclic group are bonded via an oxygen atom. That is, an alicyclic epoxy group has an epoxy group containing a three-membered ring composed of two carbon atoms and one oxygen atom on an aliphatic ring.

[0381] Examples of the siloxane skeleton in the siloxane compound include a cyclic siloxane skeleton and a cage-type or ladder-type polysilsesquioxane skeleton.

[0382] Among them, the siloxane compound is preferably a compound having a cyclic siloxane skeleton represented by the following formula (E1-7) (hereinafter sometimes referred to as “cyclic siloxane”).

[0383]

Chemistry 42

[0384]

[0385] In formula (E1-7), R e24 and R e25 represents a monovalent group containing an epoxy group or an alkyl group. e24 and x1 R e25 In the formula (E1-7), at least two of them are monovalent groups containing an epoxy group. In addition, x1 in the formula (E1-7) represents an integer greater than 3. In addition, R in the compound represented by the formula (E1-7) e24 , R e25 They can be the same or different. e24 Can be the same or different. e25 It can be the same or different.

[0386] As the above-mentioned monovalent group containing an epoxy group, preferably -DOR e26 The glycidyl ether group represented by [D represents an alkylene group, R e26represents a glycidyl group]. Examples of the D (alkylene group) include linear or branched alkylene groups having 1 to 18 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, dimethylene, and trimethylene.

[0387] In addition, it is also preferred to use -DR e27 The group containing an alicyclic epoxy group represented by R e27 is an epoxycycloalkyl group. D is an alkylene group as described above. Preferred examples of the alkylene group as D are also described above. e27 The epoxycycloalkyl group is preferably 2,3-epoxycyclopentyl, 3,4-epoxycyclohexyl and 2,3-epoxycyclohexyl. e27 The group represented by is preferably 2-(3,4-epoxycyclohexyl)ethyl.

[0388] As R e24 and R e25 Preferred examples of the alkyl group include linear or branched alkyl groups having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), such as methyl, ethyl, propyl, isopropyl, etc.

[0389] In the formula (E1-7), x1 represents an integer of 3 or more, and is preferably an integer of 3 or more and 6 or less from the viewpoint of excellent crosslinking reactivity when forming a cured film.

[0390] The number of epoxy groups in the siloxane compound in the molecule is 2 or more, preferably 2 or more and 6 or less, particularly preferably 2 or more and 4 or less, from the viewpoint of excellent crosslinking reactivity when forming a cured film.

[0391] In addition to the siloxane compound represented by formula (E1-7), the black photosensitive resin composition may also contain a compound having a siloxane skeleton, such as a cyclic siloxane containing an alicyclic epoxy group, a silicone resin containing an alicyclic epoxy group described in Japanese Patent Publication No. 2008-248169, and an organic polysilsesquioxane resin having at least two epoxy functional groups in one molecule described in Japanese Patent Publication No. 2008-19422.

[0392] As the siloxane compound, more specifically, cyclic siloxanes represented by the following formula having two or more epoxy groups in the molecule can be exemplified. In addition, as the siloxane compound, for example, commercial products such as trade names "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738", "X-40-2740" (all manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

[0393]

Chemistry 43

[0394]

[0395]

Chemistry 44

[0396]

[0397] The content of the thermosetting compound (E) in the black photosensitive resin composition is preferably 1% by mass to 15% by mass, more preferably 1.5% by mass to 12% by mass, and particularly preferably 2% by mass to 10% by mass, based on the total solid content of the black photosensitive resin composition.

[0398] <(S) Organic Solvent>

[0399] The black photosensitive resin composition preferably contains (S) an organic solvent for dilution. Examples of the (S) organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, (Poly) alkylene glycol monoalkyl ethers such as propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; methyl ethyl ketone , cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionic acid methyl ester, 2-hydroxypropionic acid ethyl ester and other lactic acid alkyl esters; 2-hydroxy-2-methylpropionic acid ethyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethoxyethyl ester, hydroxyethyl ester, 2-hydroxy-3-methylbutyric acid methyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionic acid Esters, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0400] Among them, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, alkyl lactates, the above-mentioned other esters are preferred, and alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, the above-mentioned other esters are more preferred. These solvents can be used alone or in combination of two or more.

[0401] The content of the organic solvent (S) is preferably an amount such that the solid content concentration of the black photosensitive resin composition is 1 mass % to 50 mass %, and more preferably 5 mass % to 40 mass %.

[0402] <Other ingredients>

[0403] The black photosensitive resin composition may contain various additives as required, such as sensitizers, curing accelerators, fillers, dispersants, adhesion promoters such as silane coupling agents, antioxidants, anti-aggregating agents, thermal polymerization inhibitors, defoaming agents, surfactants, etc.

[0404] <Method for preparing black photosensitive resin composition>

[0405] The black photosensitive resin composition is prepared by mixing the above-mentioned components with a stirrer. In order to make the prepared black photosensitive resin composition more uniform, the composition may be filtered using a filter membrane through which the light shielding agent (D) can pass.

[0406] 《Method for producing patterned cured product, patterned cured product, and black matrix》

[0407] By using the black photosensitive resin composition described above, a patterned cured product can be produced.

[0408] The patterned cured article is typically produced by a method comprising the following steps:

[0409] A step of coating the black photosensitive resin composition to form a coating film;

[0410] A step of selectively exposing the coating film to light;

[0411] A step of developing the exposed coating film;

[0412] A step of heating the developed coating film.

[0413] Each step is described below. The step of applying a black photosensitive resin composition to form a coating film is referred to as a "coating film forming step". The step of selectively exposing the coating film position is referred to as an "exposure step". The step of developing the exposed coating film is referred to as a "development step". The step of heating the developed coating film is referred to as a "heating step".

[0414] <Coating film forming step>

[0415] In the coating film forming step, a black photosensitive resin composition is applied onto a substrate on which a pattern is to be formed using a contact transfer coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact coating device such as a spin coater (rotary coating device) or a curtain flow coater.

[0416] There is no particular limitation on the type of substrate, and various substrates used in optical devices such as liquid crystal display devices, organic EL display devices, and organic TFT arrays can be appropriately used. As the substrate, for example, quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, and Fe, SOG (Spin On Glass: Spin-on Glass), polyester film, polycarbonate film, polyimide film, etc., TFT array substrate, PDP electrode plate, glass or transparent plastic substrate, ITO or metal and other conductive substrates, insulating substrates, semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, etc. Furthermore, for example, in the case of forming a stacked structure on a substrate, some layers that have been formed on the substrate to form a lower structure are also included in the concept of a substrate to which a black photosensitive resin composition is applied. In addition, the shape of the substrate is not particularly limited, and it can be a plate or a roll. The substrate can have concave and convex surfaces, for example, through various patterns. In addition, as the above-mentioned substrate, a translucent or non-translucent substrate can be selected.

[0417] After the photosensitive resin composition is applied, the solvent is removed by drying as necessary to form a coating film.

[0418] Drying is preferably performed at a low temperature such as 100° C. or lower, preferably 80° C. or lower, so that thermal curing of the photosensitive resin composition does not proceed excessively. Drying may be performed in a reduced pressure atmosphere as necessary.

[0419] The thickness of the coating film is not particularly limited. As the thickness of the coating film, it is preferably 0.05 μm or more, and more preferably 1 μm or more. The upper limit of the thickness of the coating film is not particularly limited, for example, it can be 50 μm or less, and it can also be 20 μm or less. The thickness of the coating film is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 2 μm or less.

[0420] <Exposure Process>

[0421] In the exposure step, the coating film formed in the coating film forming step is selectively exposed. In the exposure step, the coating film is exposed by irradiating active energy rays such as i-rays (365nm) and excimer lasers according to the shape of the desired pattern. The position-selective exposure is performed, for example, through a mask having a shape corresponding to the pattern shape of the cured product.

[0422] For exposure, a light source emitting ultraviolet rays such as a high pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The exposure dose varies depending on the composition of the black photosensitive resin composition, but is preferably 10 mJ / cm 2 Above 600mJ / cm 2 Below left and right.

[0423] <Development Process>

[0424] In the development step, the unexposed portion of the coating film exposed in the exposure step is developed with a developer such as an alkaline developer.

[0425] The developing method is not particularly limited, and can be an immersion method, a spray method, etc. Specific examples of the developer include organic developers such as monoethanolamine, diethanolamine, triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salts, and the like.

[0426] <Heating process>

[0427] In the heating step, the developed coating film is heated (baked), whereby the developed coating film is heated and cured, thereby forming a patterned cured product.

[0428] The baking temperature can be, for example, 120°C or less, 100°C or less, or 95°C or less. The lower limit of the baking temperature is not particularly limited as long as the curing of the coating film is well advanced, but is preferably 80°C or more. The baking time is not particularly limited, and the baking is performed until the curing of the coating film is sufficiently advanced. Typically, the baking time is preferably 15 to 60 minutes.

[0429] Thus, even at a low baking temperature, a patterned cured product having a light-shielding property with high solvent resistance can be formed. Therefore, the patterned cured product formed using the black photosensitive resin composition can be preferably used as a light-shielding material such as a black matrix in a device using a material with particularly low heat resistance, such as an image display device such as an organic EL display.

[0430] [Example]

[0431] The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is not limited to these Examples.

[0432] [Examples 1 to 12 and Comparative Examples 1 to 3]

[0433] In the examples and comparative examples, an alkali-soluble cardol resin, that is, resin A1 was used as the alkali-soluble resin (A) (component (A)). Resin A1 was obtained in the following Preparation Example 1.

[0434] (Preparation Example 1)

[0435] First, in a 500ml four-necked flask, add 235g of bisphenol fluorene epoxy resin (epoxy equivalent 235), 110mg of tetramethylammonium chloride, 100mg of 2,6-di-tert-butyl-4-methylphenol and 72.0g of acrylic acid, and heat and dissolve at 90-100°C while passing air at a rate of 25ml / min. Then, the solution is slowly heated in an emulsified state and heated to 120°C to completely dissolve it. At this time, the solution gradually becomes transparent and viscous, and stirring is continued in this state. During this period, the acid value is measured, and heating and stirring are continued until it is less than 1.0mgKOH / g. It takes 12 hours for the acid value to reach the target value. Then cool to room temperature to obtain a colorless, transparent solid bisphenol fluorene epoxy acrylate represented by the following formula.

[0436]

Chemistry 45

[0437]

[0438] Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene epoxy acrylate thus obtained and dissolved, and then 80.5 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised and reacted at 110-115° C. for 4 hours. After confirming that the anhydride group disappeared, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was added and reacted at 90° C. for 6 hours to obtain resin A1. The disappearance of the anhydride group was confirmed by infrared spectroscopy.

[0439] In the examples and comparative examples, the following B1 to B4 were used as the photopolymerizable monomer (B) (component (B)). In addition, B1 and B2 are high-purity glyceryl diacrylate and glyceryl triacrylate.

[0440] B1: Glyceryl triacrylate (R b1 is acryloyl, R b2 A polyfunctional (meth)acrylate represented by the formula (b1) in which a hydrogen atom is present, manufactured by Toagosei Co., Ltd., trade name: ARONIX M930)

[0441] B2: Glyceryl diacrylate (R b1 and R b2 A polyfunctional (meth)acrylate represented by the formula (b1) in which a hydrogen atom is present, manufactured by Toagosei Co., Ltd., trade name: ARONIX M920)

[0442] B3: Dipentaerythritol hexaacrylate (DPHA)

[0443] B4: Trimethylolpropane triacrylate (TMPTA)

[0444] In Examples and Comparative Examples, compound C1 represented by the following formula was used as a photopolymerization initiator (C) (component (C)).

[0445]

Chemistry 46

[0446]

[0447] In the Examples and Comparative Examples, the following D1 to D3 were used as the light-shielding agent (D) (component (D)).

[0448] D1: Lactam pigments with the following structure

[0449]

Chemistry 47

[0450]

[0451] D2: Titanium Nitride

[0452] D3: Carbon black (volume average particle size below 150nm)

[0453] In Examples and Comparative Examples, compound E1 represented by the following formula was used as the thermosetting compound (E) (component (E)).

[0454]

Chemistry 48

[0455]

[0456] Black photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 3 were prepared as follows.

[0457] Separately, a black dispersion using the component (D) of the type described in Table 1 and a polyurethane-based resin dispersant at 30% by mass relative to the component (D) was prepared, and the black dispersion, the components (A), (B), (C), and (E) of the types described in Table 1, were used to uniformly dissolve and disperse the black photosensitive resin compositions obtained by uniformly dissolving and dispersing the black photosensitive resin compositions such that the solid content concentration including the polyurethane-based resin dispersant was 15% by mass. The mass parts of each component in the black photosensitive resin compositions of each example prepared are shown in Table 1, and the mass parts in Table 1 are mass parts when the total solid content of each black photosensitive resin composition is 100 parts by mass.

[0458] The obtained black photosensitive resin compositions of the respective Examples and Comparative Examples were used to evaluate the OD value, solvent resistance, and linearity of the pattern according to the following methods.

[0459] 〔Evaluation of OD value〕

[0460] The black photosensitive composition was applied on a 10 cm 2 After being placed on a glass substrate (manufactured by Dow Corning, EAGLE XG, the same below), the coating film was dried at 80°C for 120 seconds to form a coating film. 2 The i-line (365 nm) was irradiated with an exposure amount of 1000 nm. Then, baking was performed on a hot plate at 90°C for 30 minutes. The film thickness of the formed film (cured product) was 0.8 μm, 1.0 μm, and 1.2 μm. For the film (cured product), the OD value at each film thickness was measured using D200-II (manufactured by Macbeth), and the OD value per 1 μm was calculated based on the slope of the linear approximation.

[0461] [Evaluation of solvent resistance]

[0462] The black photosensitive composition of the example and the comparative example was applied on a 10 cm 2 The coating film was formed by pre-baking at 80°C for 120 seconds on a glass substrate. Next, a proximity exposure device (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) was used, and the exposure gap was set to 50 μm. The coating film was irradiated with i-ray (365 nm) through a negative mask having a wiring spacing pattern with a line width of 20 μm and a spacing width of 20 μm. The exposure amount was set to 100 mJ / cm 2The exposed coating film was developed in a 0.04 mass % KOH aqueous solution at 26° C. for 50 seconds and then heated (baked) at 90° C. for 30 minutes to form a wiring pitch pattern (patterned cured product) having a film thickness of 1.5 μm.

[0463] The thickness of the formed patterned solidified product was set as T1, and the thickness of the patterned solidified product after being immersed in propylene glycol monomethyl ether acetate (PGMEA) for 100 seconds was set as T2. The value of T2 / T1 was evaluated as ◎ when it was 0.95 or more and 1 or less, ○ when it was 0.90 or more and less than 0.95, △ when it was 0.85 or more and less than 0.90, and × when it was less than 0.85, and the solvent resistance was evaluated. The results are recorded in Table 1.

[0464] [Evaluation of the linearity of patterns]

[0465] The patterned cured product formed in the same manner as in [Evaluation of Solvent Resistance] was observed using an optical microscope to evaluate the straightness of the pattern. In the evaluation of the straightness of the pattern, a case where the edge of the line was not shaken was evaluated as ○, a case where there was a gap in a part (30% or less in the observed area) was evaluated as △, and a case where the entire wiring pitch pattern in the observed area was shaken was evaluated as ×.

[0466]

Table 1

[0467]

[0468]

Table 2

[0469]

[0470] According to Examples 1 to 12, the black photosensitive resin composition comprising the alkali-soluble resin (A), the specific photopolymerizable monomer (B), the photopolymerization initiator (C), and the specific light shielding agent (D) can provide a light shielding cured product having high solvent resistance even at a relatively low baking temperature (90°C). b1 In Example 2, a multifunctional (meth)acrylate represented by the formula (b1) was used in which R b1Example 1, which is a (meth)acryloyl group and a multifunctional (meth)acrylate represented by formula (b1), provides a cured product with higher solvent resistance. In addition, Example 7, which has a higher content of the light-shielding agent (D), and Example 10, which contains a thermosetting compound (E), provide a cured product with higher solvent resistance. In addition, in Examples 1 to 12, the straightness of the pattern is also excellent. Compared with Examples 1 to 10 that satisfy the requirements that the content of the light-shielding agent (D) in the total solid content of the black photosensitive resin composition is 20% by mass or more and 50% by mass or less and the content of the photopolymerizable monomer (B) in the total solid content of the black photosensitive resin composition is 5% by mass or more and 20% by mass or less, Examples 11 and 12 that do not meet this range provide cured products with poor solvent resistance or pattern straightness.

[0471] On the other hand, according to Comparative Examples 1 to 3, it can be seen that if a black photosensitive composition that does not contain a multifunctional (meth)acrylate represented by formula (b1) as a photopolymerizable monomer (B) or a black photosensitive composition that does not contain a lactam pigment (D1) or a titanium pigment (D2) is used, it is difficult to form a cured product with excellent solvent resistance.

Claims

1. A black photosensitive resin composition, comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C) and a light shielding agent (D), and excluding a thermosetting compound (E), characterized in that: The photopolymerizable monomer (B) includes a multifunctional (meth)acrylate represented by the following formula (b1), In formula (b1), R b1 is a hydrogen atom or a (meth)acryloyl group, R b2 are each independently a hydrogen atom or a methyl group, The light-shielding agent (D) comprises at least one selected from a lactam pigment (D1) and a titanium pigment (D2) composed of titanium nitride, The lactam pigment (D1) is a compound represented by the following formula (d-1): In formula (d-1), X d represents a double bond, and the geometric isomers are independently E or Z, R d1 each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, a chlorine atom, a fluorine atom, a carboxyl group or a sulfone group, and R d2 Each independently represents a hydrogen atom, a methyl group or a phenyl group, and R d3 Each independently represents a hydrogen atom, a methyl group or a chlorine atom.

2. The black photosensitive resin composition according to claim 1, wherein The content of the light-shielding agent (D) in the total solid content of the black photosensitive resin composition is 20% by mass or more and 50% by mass or less.

3. The black photosensitive resin composition according to claim 1, wherein The content of the photopolymerizable monomer (B) in the total solid content of the black photosensitive resin composition is 5% by mass or more and 20% by mass or less.

4. The black photosensitive resin composition according to any one of claims 1 to 3, wherein The R b1 It is a (meth)acryloyl group.

5. The black photosensitive resin composition according to claim 1, wherein The photopolymerization initiator (C) includes a photopolymerization initiator represented by the following formula (c2): In formula (c2), R c1 is a group represented by the following formula (c3), n1 is 0 or 1, R c2 is a monovalent organic group, R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, In formula (c3), R c4 and R c5 are each independently a monovalent organic group, n2 is an integer from 0 to 3, When n2 is 2 or 3, multiple R c5 Can be the same or different, multiple R c5 can bond to each other to form a ring, * is a key.

6. The black photosensitive resin composition according to claim 1, wherein The sunscreen agent (D) contains carbon black (D3).

7. A method for producing a patterned solidified product, characterized in that: include: A step of applying the black photosensitive resin composition according to any one of claims 1 to 6 to form a coating film; A step of selectively exposing the coating film to light; A step of developing the exposed coating film; A step of heating the developed coating film.

8. The method for producing a patterned cured product according to claim 7, wherein: The heating step is performed at a temperature of 100° C. or lower.

9. A patterned cured product, characterized in that: The invention comprises a cured product of the black photosensitive resin composition according to any one of claims 1 to 6.

10. A black matrix, characterized in that: The invention comprises a cured product of the black photosensitive resin composition according to any one of claims 1 to 6.

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