Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, and image display device

Abstract

The present invention relates to a photosensitive resin composition containing (A) a photopolymerization initiator, (B) a compound having an ethylenically unsaturated group and a Cardo structure, and (E) a colorant, in which the photopolymerization initiator (A) contains a compound (A1) represented by general formula (1). (In formula (1), X represents an aryl group having 6-10 carbon atoms. R1 represents an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 10 carbon atoms. And R2 represents an alkanoyl group having 2 to 6 carbon atoms or an aroyl group having 7 to 13 carbon atoms. And R3 represents an optionally substituted alkyl group having 1-10 carbon atoms. And R4 represents an optionally substituted alkyl group having 1-6 carbon atoms. Z represents-(C = O)-O-or-O-(C = O)-. And n represents an integer of 1 or 2. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product, a partition wall, an organic electroluminescent element and an image display device. Background Art

[0002] Liquid crystal displays (LCDs) utilize the property that the arrangement of liquid crystal molecules can be switched by turning on / off voltage applied to liquid crystals. On the other hand, the various components constituting a cell of an LCD are often formed by a method using a photosensitive composition, such as photolithography.

[0003] The photosensitive composition can be easily formed into a fine structure and can be easily processed into a substrate for a large screen. For these reasons, the scope of its application is further expanding.

[0004] Image display devices including organic electroluminescent elements (also called organic electroluminescence, organic EL) have attracted much attention as the next generation of flat panel displays (FPDs) because of their excellent visual recognition and responsiveness such as contrast and viewing angle, and their ability to achieve low power consumption, thinness and lightness, and flexibility of the display body.

[0005] The organic electroluminescent element has a structure in which a light-emitting layer or an organic layer including various functional layers is sandwiched between a pair of electrodes at least one of which has light-transmitting properties.

[0006] An image display device is a device that displays images by driving a panel in which an organic electroluminescent element is arranged for each pixel.

[0007] Conventionally, such an organic electroluminescent element is manufactured by forming partition walls (dams) on a substrate and then laminating a light-emitting layer or various functional layers in the region surrounded by the partition walls.

[0008] In order to form a light-emitting layer or the like in a region surrounded by the partition walls, a vapor deposition method is mainly used in which a material is sublimated in a vacuum state and adhered to a substrate to form a film.

[0009] In recent years, methods of forming films by wet processes such as casting, spin coating, and inkjet printing have attracted attention. In particular, inkjet printing is suitable as a film forming method for organic layers in large panels because it can reduce uneven film thickness when forming a large area and can achieve high-definition displays, reduce the amount of materials used, and improve the yield rate based on the split coating during coating.

[0010] As a method for easily forming partition walls, a method of forming by photolithography using a photosensitive composition is known. In addition, as a method of imparting light-shielding properties to the partition walls to suppress light leakage between pixels, a method of adding a colorant to a photosensitive composition is known.

[0011] Patent Document 1 describes a photosensitive resin composition having high light-shielding properties and a low dielectric constant by using a specific organic black pigment and a dispersant.

[0012] Patent Document 2 describes a photosensitive resin composition for use in partition walls of an organic electroluminescent element, which effectively suppresses outgassing by using a specific organic black pigment and an alkali-soluble resin.

[0013] Patent Document 3 describes a composition that achieves both high brightness and high sensitivity as a pixel of a color filter by using a specific photopolymerization initiator and the photopolymerization initiator.

[0014] Prior art literature

[0015] Patent Literature

[0016] Patent Document 1: International Publication No. 2015 / 46178

[0017] Patent Document 2: International Publication No. 2018 / 101314

[0018] Patent Document 3: International Publication No. 2021 / 175855 Summary of the invention

[0019] Problems to be solved by the invention

[0020] In organic electroluminescent element, when a certain voltage is applied, the higher the current value flowing through the element, the higher the brightness, the better. However, in the developing process and the firing process during the manufacture of the partition wall, the decomposed products, by-products, uncured materials in the composition, etc. sometimes remain or are attached to the anode again. In this case, the hole injection from the anode is sometimes hindered, and the desired current value cannot be obtained even if a certain voltage is applied. In addition, when the cathode as the common electrode is set, the taper angle of the partition wall is smaller, and the disconnection etc. are less likely to occur, and the productivity of the element is good, but sometimes a good taper angle cannot be obtained during the manufacture of the partition wall.

[0021] As a result of conducting studies, the present inventors have found that the photosensitive resin compositions described in Patent Documents 1 and 2 have insufficient current values ​​when emitting light.

[0022] In addition, in the composition described in Patent Document 3, sufficient light-shielding properties cannot be obtained, and the partition wall shape is insufficient.

[0023] The present invention provides a photosensitive resin composition capable of forming partition walls having a high current value when light is emitted when the partition walls are formed and having a small taper angle.

[0024] Another object of the present invention is to provide an organic electroluminescent element and an image display device having high brightness using the photosensitive resin composition.

[0025] Solutions to the problem

[0026] The present inventors have found that the above-mentioned problems can be solved by using a specific photopolymerization initiator and a compound having an ethylenically unsaturated group and a cardo structure, thereby completing the present invention.

[0027] That is, the gist of the present invention is as follows.

[0028] [1] A photosensitive resin composition comprising (A) a photopolymerization initiator and (B) a compound having an ethylenically unsaturated group and a cardo structure, wherein:

[0029] The photopolymerization initiator (A) comprises a compound (A1) represented by the following general formula (1):

[0030] The weight average molecular weight of the compound (B) having an ethylenically unsaturated group and a cardo structure is 1,000 to 20,000.

[0031] [Chemical formula 1]

[0032]

[0033] In formula (1), X represents an aryl group having 6 to 10 carbon atoms,

[0034] R 1 represents an alkyl group having 1 to 8 carbon atoms which may have a substituent or an aryl group having 6 to 10 carbon atoms which may have a substituent,

[0035] R 2 represents an alkanoyl group having 2 to 6 carbon atoms or an aroyl group having 7 to 13 carbon atoms,

[0036] R 3 represents an alkyl group having 1 to 10 carbon atoms which may have a substituent,

[0037] R 4 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent,

[0038] Z represents -(C=O)-O- or -O-(C=O)-,

[0039] n represents an integer of 1 or 2.

[0040] [2] The photosensitive resin composition according to [1], wherein

[0041] The compound (B) having an ethylenically unsaturated group and a cardo structure is a compound (B1) further containing a carboxyl group.

[0042] [3] The photosensitive colored resin composition according to [2], wherein

[0043] The acid value of the compound (B1) is 20 to 150 mgKOH / g.

[0044] [4] The photosensitive resin composition according to any one of [1] to [3], further comprising (C) an alkali-soluble resin.

[0045] [5] The photosensitive resin composition according to [4], wherein

[0046] The compound (B1) is contained in an amount of 50% by mass or more based on the total mass of the compound (B1) and the (C) alkali-soluble resin.

[0047] [6] The photosensitive resin composition according to any one of [2] to [5], wherein

[0048] When content of the said compound (B1) is 100 parts by mass, 3.0 parts by mass or more of the said compound (A1) is contained.

[0049] [7] The photosensitive resin composition according to any one of [2] to [6], wherein

[0050] The compound (B1) has a partial structure represented by the following general formula (B1-1):

[0051] [Chemical formula 2]

[0052]

[0053] The benzene ring in formula (B1-1) may be further substituted by any substituent.

[0054] X b Indicates O, S, CO or direct bonding,

[0055] * indicates the bonding position.

[0056] [8] The photosensitive resin composition according to [7], wherein

[0057] The compound (B1) has a partial structure represented by the following general formula (B1-2):

[0058] [Chemical formula 3]

[0059]

[0060] The benzene ring in formula (B1-2) may be further substituted by any substituent.

[0061] R1b each independently represents a hydrogen atom or a methyl group,

[0062] X b Each independently represents O, S, CO or a direct bond,

[0063] nb represents an integer from 0 to 4,

[0064] * indicates the bonding position.

[0065] [9] The photosensitive resin composition according to any one of [1] to [8], further comprising (D) an ethylenically unsaturated compound, wherein the (D) ethylenically unsaturated compound is different from the (B) compound having an ethylenically unsaturated group and a cardo structure.

[0066]

[10] The photosensitive resin composition according to any one of [1] to [9], further comprising (E) a coloring agent.

[0067]

[11] The photosensitive resin composition according to

[10] , wherein

[0068] The colorant (E) contains a benzodifuranone-based black pigment.

[0069]

[12] The photosensitive resin composition according to

[11] , wherein

[0070] The benzodifuranone-based black pigment is contained in an amount of 5% by mass or more and 25% by mass or less based on the total solid content of the photosensitive resin composition.

[0071]

[13] The photosensitive resin composition according to any one of [1] to

[12] , wherein

[0072] The optical density of the cured coating film per 1 μm of film thickness is 0.5 or more.

[0073]

[14] The photosensitive resin composition according to any one of [1] to

[13] , which is a photosensitive resin composition for partition formation.

[0074]

[15] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to

[14] .

[0075]

[16] A partition wall formed from the cured product described in

[15] .

[0076]

[17] An organic electroluminescent element comprising the partition wall according to

[16] .

[0077]

[18] A color filter including luminescent nanocrystals, comprising the partition wall described in

[16] .

[0078]

[19] An image display device comprising the partition wall described in

[16] .

[0079] Effects of the Invention

[0080] According to the present invention, it is possible to provide a photosensitive resin capable of forming partition walls having a high current value when light is emitted and a small taper angle when the partition walls are formed.

[0081] Furthermore, according to the present invention, an organic electroluminescent element and an image display device having high brightness can be provided by using the photosensitive resin composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0082] Figure 1 It is a cross-sectional schematic diagram showing an example of the partition wall of the present invention.

[0083] Explanation of symbols

[0084] 10: Support body

[0085] 20: Next door

[0086] 30: Cone Angle DETAILED DESCRIPTION

[0087] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof.

[0088] In the present invention, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid." The same applies to "(meth)acrylate" and "(meth)acryloyl."

[0089] In the present invention, the "acrylic resin" refers to a (co)polymer containing (meth)acrylic acid or a (co)polymer containing a (meth)acrylate having a carboxyl group.

[0090] In the present invention, the “total solid content” refers to all components other than the solvent in the photosensitive resin composition. Even if a component other than the solvent is liquid at room temperature, the component is not included in the solvent but is included in the total solid content.

[0091] The meaning of "(co)polymer" includes both homopolymers (homopolymers) and copolymers (copolymers). The meaning of "acid (anhydride)" and "···acid (anhydride)" includes both acids and their anhydrides.

[0092] In the present invention, the term "monomer" is used in contrast to a so-called high molecular substance (polymer), and has the meaning of including dimers, trimers, and oligomers in addition to monomers in a narrow sense.

[0093] In the present invention, the “weight average molecular weight” refers to a polystyrene-equivalent weight average molecular weight (Mw) based on GPC (gel permeation chromatography).

[0094] In the present invention, the “amine value” refers to the amine value converted to effective solid content unless otherwise specified, and is a value expressed by the mass of KOH equivalent to the amount of alkali per 1 g of the solid content of the dispersant.

[0095] The method for measuring the amine value will be described later.

[0096] Unless otherwise specified, the “acid value” means an acid value converted into an effective solid content, and is calculated by neutralization titration.

[0097] With respect to pigments, "CI" refers to Pigment Index.

[0098] In this specification, percentages and parts expressed by "mass" have the same meaning as percentages and parts expressed by "weight".

[0099] In addition, in the following, when it is stated that "the benzene ring is optionally further substituted by any substituent" in the general formula, the substituent is not particularly limited, and examples thereof include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is also not particularly limited, and may be one or more than two.

[0100] [Photosensitive resin composition]

[0101] The photosensitive resin composition of the present invention contains as essential components:

[0102] (A) a photopolymerization initiator, and

[0103] (B) A compound having an ethylenically unsaturated group and a cardo structure.

[0104] The photosensitive resin composition of the present invention may further contain (C) an alkali-soluble resin, (D) an ethylenically unsaturated compound other than (B), (E) a colorant, (F) a dispersant, a surfactant, a solvent, and the like as optional components.

[0105] <(A) Photopolymerization initiator>

[0106] (A) The photopolymerization initiator is a component having the function of directly absorbing light to cause a decomposition reaction or a hydrogen abstraction reaction to generate polymerization active radicals.

[0107] (A) The photopolymerization initiator in the photosensitive resin composition of the present invention contains a compound (A1) represented by the following general formula (1).

[0108] [Chemical formula 4]

[0109]

[0110] In formula (1), X represents an aryl group having 6 to 10 carbon atoms.

[0111] R 1 It represents an alkyl group having 1 to 8 carbon atoms which may have a substituent or an aryl group having 6 to 10 carbon atoms which may have a substituent.

[0112] R 2 It represents an alkanoyl group having 2 to 6 carbon atoms or an aroyl group having 7 to 13 carbon atoms.

[0113] R 3 It represents an alkyl group having 1 to 10 carbon atoms which may have a substituent.

[0114] R 4 It represents an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0115] Z represents -(C=O)-O- or -O-(C=O)-.

[0116] n represents an integer of 1 or 2.

[0117] The compound (A1) contained in the present invention has a high curing property due to the presence of a carbazole ring. In addition, since a carbonyl group is present between the oxime group and the carbazole ring, a free radical derived from the carbonyl group is also generated after exposure, and it can be inferred that it is not easy to dissociate from the coating film due to bonding with the compound (B1) described later, (C) an alkali-soluble resin, (D) a compound containing an ethylenically unsaturated group, etc., and is not easy to remain in the anode in the subsequent development process and firing process.

[0118] In addition, compound (A1) has an alkyl group R in the side chain of the aryl group X via an ester bond Z. 4 The residue of the compound (A1) after exposure has a high affinity with the compound (B1) and the alkali-soluble resin (C), and therefore it can be inferred that it is unlikely to remain on the anode in the subsequent development step and baking step.

[0119] As a result, it is estimated that when a device is formed using the partition wall and a voltage is applied, a high current value can be obtained.

[0120] (X)

[0121] X represents an aryl group having 6 to 10 carbon atoms. Examples of X include a phenyl group and a naphthyl group. From the viewpoint of the current value during light emission, X is more preferably a phenyl group.

[0122] (R 1 )

[0123] R 1It represents an alkyl group having 1 to 8 carbon atoms which may have a substituent or an aryl group having 6 to 10 carbon atoms which may have a substituent.

[0124] From the perspective of the current value during light emission, R 1 The number of carbon atoms of the alkyl group in is preferably 1 or more, more preferably 3 or more, and is preferably 8 or less, more preferably 6 or less, and further preferably 5 or less.

[0125] The alkyl group may be a linear chain or a branched chain.

[0126] As R 1 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cyclopentylethyl group, and a cyclohexylethyl group.

[0127] As R 1 The substituent that the alkyl group may have includes, for example, an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, and an N-acetyl-N-acetoxyamino group. 1 The alkyl group is preferably unsubstituted.

[0128] As R 1 The aryl group in R includes, for example, phenyl and naphthyl. 1 More preferred is phenyl.

[0129] As R 1 Examples of the substituent which the aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group to which these substituents are linked.

[0130] From the perspective of the current value during light emission, R 1 An alkyl group is preferred, a butyl group, a pentyl group, or a hexyl group is more preferred, and a pentyl group is further preferred.

[0131] (R 2 )

[0132] R 2 It represents an alkanoyl group having 2 to 6 carbon atoms or an aroyl group having 6 to 13 carbon atoms.

[0133] From the perspective of the current value during light emission, R 2 The number of carbon atoms of the alkanoyl group in is preferably 3 or less, more preferably 2 or less. 2 Examples of the alkanoyl group include acetyl, propionyl and butyryl, and acetyl is more preferred.

[0134] R 2The number of carbon atoms of the aromatic acyl group in is preferably 7 or less. 2 Examples of the aromatic acyl group include a benzoyl group and a naphthoyl group, and a benzoyl group is more preferable.

[0135] From the perspective of the current value during light emission, R 2 More preferred is acetyl.

[0136] (R 3 )

[0137] R 3 It represents an alkyl group having 1 to 10 carbon atoms which may have a substituent.

[0138] From the viewpoint of solubility in solvent, R 3 The number of carbon atoms of the alkyl group in is preferably 2 or more, more preferably 6 or more, and preferably 8 or less.

[0139] The alkyl group may be a linear chain or a branched chain.

[0140] As R 3 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an ethylpentyl group, an octyl group, and an ethylhexyl group.

[0141] As R 3 The substituent which the alkyl group may have includes, for example, an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, and an amino group. 3 The alkyl group is preferably unsubstituted.

[0142] From the viewpoint of solubility in solvents and ease of synthesis, R 3 More preferred is ethyl, ethylpentyl, and ethylhexyl, and even more preferred is ethylhexyl.

[0143] (R 4 )

[0144] R 4 It represents an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0145] From the perspective of the current value during light emission, R 4 The number of carbon atoms of the alkyl group in the group is preferably 4 or less, more preferably 2 or less.

[0146] The alkyl group may be a linear chain or a branched chain.

[0147] As R 4 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0148] As R 4The substituent which the alkyl group may have includes, for example, an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, and an amino group. 4 The alkyl group is preferably unsubstituted.

[0149] From the perspective of the current value during light emission, R 4 More preferred is an unsubstituted methyl group.

[0150] (Z)

[0151] Z represents -(C=O)-O- or -O-(C=O)-. Among them, -(C=O)-O- is preferred from the viewpoint of the current value during light emission.

[0152] (n)

[0153] n represents an integer of 1 or 2. Among them, n=1 is preferred from the viewpoint of developability.

[0154] Specific examples of the compound (A1) include the following compounds.

[0155] [Chemical formula 5]

[0156]

[0157] Among them, from the viewpoint of the current value during light emission, preferred are compounds represented by formula (A1-6), formula (A1-7), and formula (A1-8), and more preferred is a compound represented by formula (A1-7).

[0158] The photosensitive resin composition of the present invention may contain only one type of compound (A1), or may contain two or more types of compound (A1).

[0159] The photosensitive resin composition of the present invention may contain a photopolymerization initiator other than the compound (A1). Furthermore, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used as necessary.

[0160] Examples of the photopolymerization initiator other than the compound (A1) include oxime ester compounds, metallocene compounds including titanocene compounds, hexaarylbiimidazole derivatives, halomethylated Oxadiazole derivatives, halomethyl-s-triazine derivatives, α-aminoalkylphenone derivatives.

[0161] Among them, oxime ester compounds other than compound (A1) are particularly effective from the viewpoint of sensitivity and platemaking properties.

[0162] Examples of oxime ester compounds other than compound (A1) include compounds represented by the following general formula (IV).

[0163] [Chemical formula 6]

[0164]

[0165] In formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0166] R 21b represents any substituent containing an aromatic ring.

[0167] R 22a It represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.

[0168] nx represents an integer of 0 or 1.

[0169] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less from the viewpoint of solubility in a solvent and sensitivity. 21a Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.

[0170] As R 21a The substituent that the alkyl group may have includes, for example, an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, and an N-acetyl-N-acetoxyamino group. 21a The alkyl group is preferably unsubstituted.

[0171] As R 21a The aromatic ring group in the photosensitive resin composition may include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. In addition, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less. The number of carbon atoms in the aromatic ring group is, for example, preferably 5 to 30, more preferably 5 to 20, and further preferably 5 to 12.

[0172] As R 21a The aromatic ring group includes, for example, phenyl, naphthyl, pyridyl, and furyl. From the viewpoint of developability, R 21a It is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0173] As R 21aThe substituents optionally possessed by the aromatic ring group include, for example, hydroxyl, carboxyl, halogen, amino, amide, alkyl, alkoxy, and groups connected with these substituents. From the viewpoint of developability, alkyl, alkoxy, and groups connected with these substituents are preferred, and connected alkoxy is more preferred.

[0174] From the perspective of developability, R 21a An aromatic ring group which may have a substituent is preferred, and an aromatic ring group which has an alkoxy group linked to the substituent is more preferred.

[0175] As R 21b The arbitrary substituent containing an aromatic ring may include an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group or an optionally substituted indolyl group. From the viewpoint of sensitivity, an optionally substituted carbazolyl group is preferred. From the viewpoint of electrical reliability, an optionally substituted diphenyl sulfide group is preferred.

[0176] R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but is preferably 2 or more, and preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and particularly preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity. 22a Examples of the alkanoyl group include acetyl, propionyl and butyryl.

[0177] As R 22a The substituent that the alkanoyl group may have includes, for example, an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. 22a The alkyl group is preferably unsubstituted.

[0178] R 22a The number of carbon atoms in the aromatic acyl group is not particularly limited, but is preferably 7 or more, more preferably 8 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less from the viewpoint of solubility in a solvent and sensitivity. 22a The aromatic acyl group includes benzoyl and naphthoyl.

[0179] As R 22a The substituent that the aromatic acyl group may have includes, for example, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. 22a The aroyl group is preferably unsubstituted.

[0180] From the perspective of sensitivity, R 22aAn alkanoyl group which may have a substituent is preferred, an unsubstituted alkanoyl group is more preferred, and an acetyl group is further preferred.

[0181] As oxime ester compounds other than compound (A1), for example, photopolymerization initiators described in Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, International Publication No. 2008 / 78678, Japanese Patent No. 4818458, International Publication No. 2005 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, and International Publication No. 2012 / 68879 can be used.

[0182] The initiators described in JP-A-2016-133574 can also be preferably used.

[0183] Examples of the metallocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorobenzene-1-yl)titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorobenzene-1-yl)titanium, dicyclopentadienyl bis(2,4,6-trifluorobenzene-1-yl)titanium, dicyclopentadienyl bis(2,6-difluorobenzene-1-yl)titanium, dicyclopentadienyl bis(2,4-difluorobenzene-1-yl)titanium, di(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorobenzene-1-yl)titanium, di(methylcyclopentadienyl)bis(2,6-difluorobenzene-1-yl)titanium, and dicyclopentadienyl[2,6-difluoro-3-(pyrrol-1-yl)-benzene-1-yl]titanium.

[0184] Examples of the hexaarylbiimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0185] As halomethylation Examples of oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4- Oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- Oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuranyl)vinyl)]-1,3,4- Oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4- Oxadiazole.

[0186] Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0187] Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.

[0188] (A) The photopolymerization initiator other than the compound (A1) may be used alone or in combination of two or more.

[0189] In order to improve the sensing sensitivity, a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source may be mixed with the photopolymerization initiator as needed.

[0190] Examples of the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open Nos. 4-221958 and 4-219756, coumarin dyes containing heterocyclic rings described in Japanese Patent Application Laid-Open Nos. 3-239703 and 5-289335, 3-ketocoumarin compounds described in Japanese Patent Application Laid-Open Nos. 3-239703 and 5-289335, methylenepyrrole dyes described in Japanese Patent Application Laid-Open No. 6-19240, and pyrrole dyes described in Japanese Patent Application Laid-Open Nos. 47-2528 and 54-155292. The dyes having a dialkylaminobenzene skeleton described in Japanese Patent Publication No. 45-37377, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818.

[0191] As the sensitizing dye, a sensitizing dye containing an amino group is preferred, and a compound containing an amino group and a phenyl group in the same molecule is more preferred.

[0192] As such sensitizing dyes, for example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone are preferred, as are 2-(p-dimethylaminophenyl)benzophenone and benzophenone. oxazole, 2-(p-diethylaminophenyl)benzo oxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzo oxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzo oxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4- Preferably, the compound contains p-dialkylaminophenyl group, such as oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, and the like, and 4,4'-dialkylaminobenzophenone is particularly preferred.

[0193] The sensitizing dye may be used alone or in combination of two or more.

[0194] As the polymerization accelerator, for example, aromatic amines such as 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylaminoethyl ester, 4-dimethylaminoacetophenone, 4-dimethylaminopropiophenone, etc.; aliphatic amines such as n-butylamine and N-methyldiethanolamine; and mercapto compounds described later as other compounding components can be used.

[0195] The polymerization accelerator may be used alone or in combination of two or more.

[0196] <(B) Compounds Having an Ethylenically Unsaturated Group and a Cardo Structure>

[0197] The photosensitive resin composition of the present invention contains (B) a compound having an ethylenically unsaturated group and a Cardo structure. (Hereinafter, the compound (B) having an ethylenically unsaturated group and a Cardo structure may be referred to as "compound (B)".)

[0198] In the present invention, the Cardo structure refers to a structure in which a main chain and a bulky side chain are connected by one atom.

[0199] For example, compound (B) has a cyclic structure such as a fluorene ring which has high heat resistance and is rigid as a bulky side chain.

[0200] The compound (B) can strongly crosslink the ethylenically unsaturated groups by exposure, and has a rigid skeleton, so that the dissolution of the exposed part during development can be suppressed, and it is not easy to shrink during firing, which has the effect of increasing the residual film rate. On the other hand, the compound (B) has a low thermal softening point, so it will melt flow during firing, which has the effect of reducing the cone angle.

[0201] Examples of the compound (B) include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-BPEF-2) and fluorene-based acrylate monomers (manufactured by Osaka Gas Chemical Co., Ltd., trade names: OGSOL, EA-0200, OGSOLEA-0300, OGSOLGA-5060P, OGSOLGA-2800, OGSOLEA-F5710).

[0202] From the viewpoint of residual film rate and cone angle shape, the compound (B) having an ethylenically unsaturated group and a cardo structure is preferably a compound (B1) further having a carboxyl group. (Hereinafter, a compound having an ethylenically unsaturated group and a cardo structure and further having a carboxyl group may be referred to as "compound (B1)".)

[0203] [Compound (B1)]

[0204] The compound (B1) is not particularly limited as long as it has an ethylenically unsaturated group and a cardo structure and further has a carboxyl group. From the viewpoint of the residual film rate and the taper angle shape, the compound (B1) preferably has a partial structure represented by the following general formula (B1-1).

[0205] [Chemical formula 7]

[0206]

[0207] The benzene ring in the formula (B1-1) may be further substituted by any substituent.

[0208] X b Indicates O, S, CO or direct bonding.

[0209] * indicates the bonding position.

[0210] The compound (B1) further preferably has a partial structure represented by the following general formula (B1-2).

[0211] [Chemical formula 8]

[0212]

[0213] The benzene ring in the formula (B1-2) may be further substituted by any substituent.

[0214] R 1b Each independently represents a hydrogen atom or a methyl group.

[0215] X b Each independently represents O, S, CO or a direct bond.

[0216] nb represents an integer of 0-4.

[0217] * indicates the bonding position.

[0218] In the above general formula (B1-2), nb is preferably 3 or less, more preferably 2 or less, and even more preferably 0, from the viewpoint of the taper angle.

[0219] R 1b Preferred is a hydrogen atom.

[0220] In the above general formulas (B1-1) and (B1-2), from the viewpoint of the taper angle, X b Direct bonding is preferred.

[0221] Moreover, from the viewpoint of developability, the partial structure represented by the above formula (B1-2) is preferably a partial structure represented by the following formula (B1-3).

[0222] [Chemical formula 9]

[0223]

[0224] The benzene ring in the formula (B1-3) may be further substituted by any substituent.

[0225] R 1b , X b and nb have the same meanings as in formula (B1-2).

[0226] R X1b , R X2b , R X3b Each independently represents a hydrogen atom or a polyacid residue.

[0227] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid.

[0228] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridgeic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0229] Among them, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred, and tetrahydrophthalic acid is further preferred.

[0230] The acid value of compound (B1) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, it is preferably 150 mgKOH / g or less, more preferably 140 mgKOH / g or less, further preferably 130 mgKOH / g or less, and further preferably 120 mgKOH / g or less.

[0231] When the acid value of the compound (B1) is at least the above lower limit, developability tends to be improved. When the acid value of the compound (B1) is at most the above upper limit, resolution tends to be improved.

[0232] The weight average molecular weight (Mw) of compound (B) such as compound (B1) is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. In addition, it is usually 20000 or less, preferably 15000 or less, more preferably 10000 or less, further preferably 8000 or less, and particularly preferably 6000 or less.

[0233] When the weight average molecular weight (Mw) of compound (B) such as compound (B1) is set to be above the above lower limit, there is a tendency for the developing adhesion to be improved. When the weight average molecular weight (Mw) of compound (B) such as compound (B1) is set to be below the above upper limit, there is a tendency for the developing property to be improved.

[0234] The photosensitive resin composition of the present invention may contain only one kind of compound (B) such as the compound (B1), or may contain two or more kinds of the compound (B).

[0235] <(C) Alkali-soluble resin>

[0236] The photosensitive resin composition of the present invention may contain (C) an alkali-soluble resin.

[0237] (C) The alkali-soluble resin is a component other than the (B) compound having an ethylenically unsaturated group and a Cardo structure, and the (B) compound having an ethylenically unsaturated group and a Cardo structure is not included in the (C) alkali-soluble resin.

[0238] (C) The alkali-soluble resin is not particularly limited as long as it is a resin that is alkali-soluble, and examples thereof include resins containing carboxyl groups or hydroxyl groups. More specifically, examples thereof include epoxy (meth)acrylate resins, acrylic resins, carboxyl-containing epoxy resins, carboxyl-containing urethane resins, novolac resins, polyvinylphenol resins, polyimide resins, polybenzoic acid resins, and the like. Azole resins.

[0239] From the viewpoint of excellent platemaking properties, it is particularly preferable to use the following as the (C) alkali-soluble resin:

[0240] (C1) Epoxy (meth)acrylate resin

[0241] (C2) Acrylic copolymer resin.

[0242] These (C) alkali-soluble resins may be used alone or in combination of two or more.

[0243] <(C1) Epoxy (meth)acrylate resin>

[0244] (C1) Epoxy (meth)acrylate resin is a resin obtained by further reacting a hydroxyl group generated by the reaction of an epoxy compound (epoxy resin) with an α,β-unsaturated monocarboxylic acid and / or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion (referred to as "reaction (1)") with a compound having two or more substituents capable of reacting with a hydroxyl group, such as a polyacid and / or its anhydride (referred to as a "hydroxyl-reactive compound").

[0245] The (C1) epoxy (meth)acrylate resin includes a resin obtained by reacting a compound having two or more substituents capable of reacting with a hydroxyl group, such as a polyisocyanate compound, with the hydroxyl-reactive compound before reacting the hydroxyl group generated in the above reaction (1) with the hydroxyl-reactive compound, and then reacting the compound with the hydroxyl-reactive compound.

[0246] A resin obtained by reacting a compound having a functional group capable of reacting with a carboxyl group with the carboxyl group of the resin obtained in the above reaction is also included in the (C1) epoxy (meth)acrylate resin.

[0247] Epoxy (meth)acrylate resins do not substantially have epoxy groups in their chemical structures and are not limited to "(meth)acrylates". However, since epoxy compounds (epoxy resins) are raw materials and "(meth)acrylates" are representative examples, they are named as such by convention.

[0248] As the (C1) epoxy (meth)acrylate resin used in the present invention, from the viewpoint of developability and reliability, it is preferred to use the following epoxy (meth)acrylate resin (C1-1) and / or epoxy (meth)acrylate resin (C1-2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth)acrylate resin").

[0249] As the epoxy (meth)acrylate resin (C1), an epoxy (meth)acrylate resin having an aromatic ring in its main chain can be more preferably used from the viewpoint of outgassing.

[0250] Epoxy (meth) acrylate resin (C1-1):

[0251] An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and further reacting a polybasic acid and / or an anhydride thereof.

[0252] Epoxy (meth) acrylate resin (C1-2):

[0253] An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polyol with a polybasic acid and / or an anhydride thereof.

[0254] Here, epoxy resin also includes the raw material compound before forming resin by heat curing. As this epoxy resin, it is possible to appropriately select to use from known epoxy resin. In addition, epoxy resin can use the compound obtained by reacting phenolic compound and epihalohydrin. As phenolic compound, it is preferably a compound with a divalent or more divalent phenolic hydroxyl group, which can be a monomer or a polymer.

[0255] As the kind of epoxy resin becoming raw material, for example, cresol novolac epoxy resin, phenol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, trisphenol methane epoxy resin, biphenyl novolac epoxy resin, naphthol novolac epoxy resin, dicyclopentadiene and phenol or cresol addition reaction product and epihalohydrin reaction product, i.e. epoxy resin, epoxy resin containing adamantyl group can be preferably used.Wherein, epoxy resin having aromatic ring in main chain can be more preferably used.

[0256] As the epoxy resin, specifically, the following epoxy resins can be preferably used.

[0257] Bisphenol A type epoxy resin (for example, "jER (registered trademark, hereinafter the same) 828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Corporation)

[0258] Epoxy resin obtained by reaction of alcoholic hydroxyl groups of bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76° C.))

[0259] Bisphenol F type resin (for example, "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation)

[0260] Epoxy resin obtained by reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resin with epichlorohydrin (e.g., "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66° C.))

[0261] Bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation)

[0262] Phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152" and "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by The Dow Chemical Company)

[0263] (o-, m-, p-)cresol novolac type epoxy resin (e.g., "EOCN (registered trademark, hereinafter the same)-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.)

[0264] Triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.)

[0265] Trisphenol methane type epoxy resin (for example, "EPPN (registered trademark, hereinafter the same)-501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.)

[0266] Alicyclic epoxy resin ("Celloxide (registered trademark, hereinafter the same) 2021P", "Celloxide EHPE" manufactured by Daicel Corporation)

[0267] An epoxy resin obtained by glycidylating a phenolic resin obtained by reacting dicyclopentadiene with phenol (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.)

[0268] Epoxy resins represented by the following general formulas (C1) to (C3)

[0269] Specifically, for example, as an epoxy resin represented by the following general formula (C1), there can be mentioned "XD-1000" manufactured by Nippon Kayaku Co., Ltd., as an epoxy resin represented by the following general formula (C2), there can be mentioned "NC-3000" and "NC-3500" manufactured by Nippon Kayaku Co., Ltd., and as an epoxy resin represented by the following general formula (C3), there can be mentioned "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0270] [Chemical formula 10]

[0271]

[0272] In the formula (C1), na is an average value and represents a number from 0 to 10.

[0273] R 111 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group.

[0274] It should be noted that the presence of multiple R 111 They can be the same or different.

[0275] [Chemical formula 11]

[0276]

[0277] In the formula (C2), nb1 and nb2 are each independently an average value and represent a number from 0 to 10.

[0278] R 121 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group.

[0279] It should be noted that the presence of multiple R 121 They can be the same or different.

[0280] [Chemical formula 12]

[0281]

[0282] In formula (C3), Q represents a linking group represented by the following general formula (C3-1) or (C3-2): wherein the molecular structure contains one or more adamantane structures.

[0283] nc means 2 or 3.

[0284] [Chemical formula 13]

[0285]

[0286] In formula (C3-1) and (C3-2), R 131 ~R 134 and R 135 ~R 137 Each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent.

[0287] * indicates the bonding position.

[0288] As the epoxy resin, an epoxy resin represented by any one of the above formulae (C1) to (C3) is preferably used.

[0289] Examples of the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include: (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth)acrylic acid having an α-halogenated alkyl, alkoxy, halogen, nitro or cyano group-substituted monocarboxylic acid; 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylsuccinic acid, 2-(meth)acryloyloxypropyladipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxyethyl Acryloxypropylphthalic acid, 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxybutylsuccinic acid, 2-(meth)acryloxybutyladipic acid, 2-(meth)acryloxybutylhydrophthalic acid, 2-(meth)acryloxybutylphthalic acid, 2-(meth)acryloxybutylmaleic acid, a monomer obtained by adding (meth)acrylic acid to lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone; or a monomer obtained by adding hydroxyalkyl (meth)acrylate or pentaerythritol tri(meth)acrylate to an acid (anhydride) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride); (meth)acrylic acid dimer. From the viewpoint of sensitivity, (meth)acrylic acid is preferred.

[0290] As a method for adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group and an epoxy resin can be reacted at a temperature of 50 to 150° C. in the presence of an esterification catalyst.

[0291] As the esterification catalyst used here, for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine, etc., and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, etc. can be used.

[0292] Each component of the epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be selected and used alone or in combination of two or more.

[0293] The amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group used is preferably 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin.

[0294] By setting the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to be above the above lower limit, the insufficient amount of the unsaturated group introduced can be suppressed, and there is a tendency that the subsequent reaction with the polyacid and / or its anhydride is also easily carried out. By setting the amount to be below the above upper limit, the remaining unreacted product of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed, and it can be confirmed that the curing characteristics are easily improved.

[0295] Examples of the polybasic acid and / or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridgeic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

[0296] Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid or anhydrides thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride or biphenyltetracarboxylic dianhydride.

[0297] The addition reaction of the polybasic acid and / or its anhydride can be carried out by a known method. For example, the target substance can be obtained by continuing the reaction under the same conditions as the addition reaction of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin.

[0298] The amount of polyacid and / or its anhydride component added is preferably such that the acid value of the generated carboxyl-containing epoxy (meth)acrylate resin is 10 to 150 mgKOH / g, and more preferably 20 to 140 mgKOH / g. By setting the acid value to be above the lower limit, there is a tendency for alkali developability to be improved. By setting the acid value to be below the upper limit, there is a tendency for curing performance to be improved.

[0299] Trimethylolpropane, di(trimethylol)propane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol and other polyfunctional alcohols (polyols) can be added during the addition reaction of polyacids and / or their anhydrides to introduce a multi-branched structure. In this case, the mixing order of polyacids and / or their anhydrides and polyfunctional alcohols is not particularly limited. By heating, any hydroxyl group present in the mixture of the reaction product of epoxy resin and α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group and polyfunctional alcohols is subjected to addition reaction with polyacids and / or their anhydrides.

[0300] By using a polyol, the molecular weight of the epoxy (meth)acrylate resin (C1) can be increased, branches can be introduced into the molecule, and there is a tendency to achieve a balance between the molecular weight and the viscosity. In addition, there is a tendency to increase the introduction rate of the acid group into the molecule, and it is easy to achieve a balance between sensitivity and adhesion.

[0301] Examples of the carboxyl group-containing epoxy (meth)acrylate resin include, in addition to the above, carboxyl group-containing epoxy (meth)acrylate resins described in Korean Patent Publication No. 10-2013-0022955.

[0302] The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin containing a carboxyl group measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, further preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. In addition, it is preferably 30000 or less, more preferably 20000 or less, and further preferably 15000 or less. The above upper and lower limits can be combined arbitrarily. For example, the weight average molecular weight (Mw) of the epoxy (meth) acrylate resin containing a carboxyl group is preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 1500 to 15000, and further preferably 2000 to 15000. By setting the weight average molecular weight (Mw) of the epoxy (meth) acrylate resin containing a carboxyl group to be above the above lower limit, there is a tendency that the solubility in the developer can be suppressed from becoming too high. When the weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin is set to be the above upper limit or less, the solubility in a developer tends to be easily improved.

[0303] The acid value of the epoxy (meth) acrylate resin containing a carboxyl group is not particularly limited, and is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, the acid value of the epoxy (meth) acrylate resin containing a carboxyl group is preferably 20 to 200 mgKOH / g, more preferably 60 to 150 mgKOH / g, further preferably 80 to 130 mgKOH / g, and further preferably 100 to 130 mgKOH / g. When the acid value of the epoxy (meth) acrylate resin containing a carboxyl group is set to be equal to or greater than the above lower limit, the developing solubility is improved and the resolution tends to be improved. When the acid value of the epoxy (meth) acrylate resin containing a carboxyl group is set to be equal to or less than the above upper limit, the residual film rate of the photosensitive resin composition tends to be improved.

[0304] The chemical structure of the epoxy (meth)acrylate resin is not particularly limited. From the viewpoint of developability and reliability, it is preferred to contain an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (C1-I) (hereinafter, sometimes referred to as "(C1-I) epoxy (meth)acrylate resin") and / or an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (C1-II) (hereinafter, sometimes referred to as "(C1-II) epoxy (meth)acrylate resin").

[0305] [Chemical formula 14]

[0306]

[0307] In formula (C1-I), R 11 represents a hydrogen atom or a methyl group. 12 represents a divalent hydrocarbon group which may have a substituent. k represents 1 or 2. * represents a bonding position.

[0308] The benzene ring in formula (C1-I) may be further substituted by any substituent.

[0309] [Chemical formula 15]

[0310]

[0311] In formula (C1-II), R 13 Each independently represents a hydrogen atom or a methyl group. 14represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent. p and q each independently represent an integer of 0 to 2. * represents a bonding position.

[0312] <(C1-I) Epoxy (meth)acrylate resin>

[0313] [Chemical formula 16]

[0314]

[0315] In formula (C1-I), R 11 represents a hydrogen atom or a methyl group. 12 represents a divalent hydrocarbon group which may have a substituent. k represents 1 or 2. * represents a bonding position.

[0316] The benzene ring in formula (C1-I) may be further substituted by any substituent.

[0317] (R 12 )

[0318] In the above formula (C1-I), R 12 It represents a divalent hydrocarbon group which may have a substituent.

[0319] Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

[0320] The divalent aliphatic group may be a straight-chain, branched, or cyclic aliphatic group. From the viewpoint of development solubility, a straight-chain aliphatic group is preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, a cyclic aliphatic group is preferred. The number of carbon atoms in the aliphatic group is preferably 1 or more, more preferably 3 or more, and further preferably 6 or more. In addition, it is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 10. By setting the number of carbon atoms to be above the above lower limit, a firm film is easily obtained, surface roughness generated during development is less likely to occur, and there is a tendency for the adhesion to the substrate to become good. By setting the number of carbon atoms to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0321] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of rigidity of the skeleton, a methylene group is preferred.

[0322] Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group as a side chain.

[0323] The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 12 or less, more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of rings is preferably 1 to 12, more preferably 1 to 10, and further preferably 2 to 10. By setting the number of rings to be above the above lower limit, a strong film is obtained, and there is a tendency that the substrate adhesion becomes good. By setting the number of rings to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency that the resolution is improved.

[0324] Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring of a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a dicyclopentadiene ring, a dicyclopentane ring, etc. From the viewpoint of the rigidity of the skeleton, groups obtained by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring are preferred.

[0325] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, the divalent aliphatic group is preferably unsubstituted.

[0326] As the divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group can be cited. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and further preferably 6 or more. In addition, it is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 20, and the number of carbon atoms is more preferably 5 to 15, and further preferably 6 to 10. By setting the number of carbon atoms to be above the above lower limit, it is easy to obtain a firm film, and it is not easy to have surface roughness generated during development, and there is a tendency for the adhesion with the substrate to become good. By setting the number of carbon atoms to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0327] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring.

[0328] The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzisocyanate ring azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, Pyridine ring, quinazoline ring, quinazolinone ring, azulene ring.

[0329] From the viewpoint of patterning properties, the divalent aromatic ring group is preferably a benzene ring or a naphthalene ring having two free valences, and more preferably a benzene ring having two free valences.

[0330] Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of developing solubility, the divalent aromatic ring group is preferably unsubstituted.

[0331] Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked to each other include groups in which one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic ring groups are linked to each other.

[0332] In this case, the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of divalent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of divalent aliphatic groups to be above the above lower limit, a strong film is easily obtained, surface roughness generated during development is less likely to occur, and there is a tendency for the adhesion with the substrate to become good. By setting the number of divalent aliphatic groups to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0333] The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of divalent aromatic ring groups is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of divalent aromatic ring groups to be above the above lower limit, it is easy to obtain a firm film, and surface roughness generated during development is less likely to occur, and there is a tendency for the adhesion with the substrate to become good. By setting the number of divalent aromatic ring groups to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0334] As a group formed by linking one or more divalent aliphatic groups to one or more divalent aromatic ring groups, for example, groups represented by the following formulas (C1-IA) to (C1-IF) can be cited. From the viewpoint of the rigidity of the skeleton and the hydrophobization of the membrane, a group represented by the following formula (C1-IA) is preferred. Hereinafter, * represents a bonding position.

[0335] [Chemical formula 17]

[0336]

[0337] In formula (C1-I), k represents 1 or 2. From the viewpoint of adhesion and patterning properties, k is preferably 1. From the viewpoint of sensitivity, electrical reliability and dispersibility, k is preferably 2. In addition, (C1-I) epoxy (meth)acrylate may contain both a partial structure in which k is 1 and a partial structure in which k is 2.

[0338] The benzene ring in formula (C1-I) may be further substituted by any substituent.

[0339] Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of the substituents is not particularly limited, and may be one or two or more.

[0340] From the viewpoint of patterning properties, the benzene ring in formula (C1-I) is preferably unsubstituted.

[0341] From the viewpoint of ease of synthesis, the partial structure represented by formula (C1-I) is preferably a partial structure represented by the following general formula (C1-I-1).

[0342] [Chemical formula 18]

[0343]

[0344] In formula (C1-I-1), R 11 , R 12and k have the same meanings as in formula (C1-I). X represents a hydrogen atom or a polyacid residue. * represents a bonding position.

[0345] The benzene ring in the formula (C1-I-1) may be further substituted by any substituent.

[0346] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid.

[0347] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridgeic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0348] From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

[0349] The benzene ring in formula (C1-I-1) may be further substituted by any substituent. As the substituent, preferably, the substituents exemplified for the benzene ring in formula (C1-I) can be used.

[0350] The partial structure represented by formula (C1-I-1) contained in one molecule of epoxy (meth)acrylate resin may be one or more, for example, R X is the structure of hydrogen atom and R X It is the structure of a polyacid residue.

[0351] The number of partial structures represented by formula (C1-I) contained in one molecule of (C1-I) epoxy (meth) acrylate resin is not particularly limited, and is preferably 1 or more, and more preferably 3 or more. In addition, it is preferably 20 or less, and further preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of partial structures represented by formula (C1-I) contained in one molecule of (C1-I) epoxy (meth) acrylate resin is preferably 1 to 20, more preferably 1 to 15, and further preferably 3 to 15. By setting the number of partial structures to be above the above lower limit, it is easy to obtain a firm film, and there is a tendency that surface roughness that occurs during development is not easily generated. By setting the number of partial structures to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0352] The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (C1-I) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, further preferably 3000 or more, particularly preferably 4000 or more, and most preferably 5000 or more. In addition, it is preferably 30000 or less, more preferably 20000 or less, and further preferably 15000 or less. The above upper and lower limits can be combined arbitrarily. For example, the weight average molecular weight of the epoxy (meth) acrylate resin (C1-I) is preferably 1000 to 30000, more preferably 1500 to 2000, further preferably 1500 to 15000, and further preferably 2000 to 1500. By setting the weight average molecular weight of the epoxy (meth) acrylate resin (C1-I) to be above the above lower limit, there is a tendency that the residual film rate of the photosensitive resin composition becomes good. When the weight average molecular weight of the epoxy (meth)acrylate resin (C1-I) is equal to or less than the above upper limit, solubility in a developer tends to be good.

[0353] The acid value of the epoxy (meth) acrylate resin (C1-I) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, the acid value of the epoxy (meth) acrylate resin (C1-I) is preferably 20 to 200 mgKOH / g, more preferably 60 to 150 mgKOH / g, further preferably 80 to 130 mgKOH / g, and further preferably 100 to 130 mgKOH / g. When the acid value of the epoxy (meth)acrylate resin (C1-I) is set to be equal to or greater than the above lower limit, the developing solubility is improved and the resolution tends to be good. When the acid value of the epoxy (meth)acrylate resin (C1-I) is set to be equal to or less than the above upper limit, the residual film rate of the photosensitive resin composition tends to be good.

[0354] Specific examples of the epoxy (meth)acrylate resin (C1-I) are given below. In addition, * in the examples represents a bonding position.

[0355] [Chemical formula 19]

[0356]

[0357] [Chemical formula 20]

[0358]

[0359] <(C1-II) Epoxy (meth)acrylate resin>

[0360] [Chemical formula 21]

[0361]

[0362] In formula (C1-II), R 13 Each independently represents a hydrogen atom or a methyl group. 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent. p and q each independently represent an integer of 0 to 2. * represents a bonding position.

[0363] (R 14 )

[0364] In formula (C1-II), R 14 It represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

[0365] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0366] The number of rings possessed by the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of rings possessed by the aliphatic cyclic group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of rings possessed by the aliphatic cyclic group to be above the above lower limit, a strong film is easily obtained, and there is a tendency that surface roughness that occurs during development is not easily generated. By setting the number of rings possessed by the aliphatic cyclic group to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency to improve the resolution.

[0367] The number of carbon atoms in the aliphatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and further preferably 8 or more. In addition, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aliphatic ring group is preferably 4 to 40, more preferably 4 to 30, further preferably 6 to 20, and particularly preferably 8 to 15. By setting the number of carbon atoms in the aliphatic ring group to be above the above lower limit, a strong film is easily obtained, and there is a tendency that surface roughness that occurs during development is not easily generated. By setting the number of carbon atoms in the aliphatic ring group to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency to improve the resolution.

[0368] Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of the residual film rate and resolution of the photosensitive resin composition, an adamantane ring is preferred.

[0369] The number of rings possessed by the aromatic ring group is not particularly limited, and is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 4 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of rings possessed by the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 4, further preferably 2 to 4, and particularly preferably 3 to 4. By setting the number of rings possessed by the aromatic ring group to be above the above lower limit, it is easy to obtain a strong film, and there is a tendency that the surface roughness generated during development is not easy to occur. By setting the number of rings possessed by the aromatic ring group to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency to improve the resolution.

[0370] Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

[0371] The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, 8 or more, further preferably 10 or more, and particularly preferably 12 or more. In addition, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic ring group is preferably 4 to 40, more preferably 6 to 40, further preferably 8 to 30, further preferably 10 to 20, and particularly preferably 12 to 15. By setting the number of carbon atoms in the aromatic ring group to be above the above lower limit, a strong film is easily obtained, and there is a tendency that surface roughness that occurs during development is not easily generated. By setting the number of carbon atoms in the aromatic ring group to be below the above upper limit, there is a tendency that patterning characteristics become good.

[0372] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring.

[0373] R 14 The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

[0374] The divalent aliphatic group may be a linear, branched, or cyclic aliphatic group. From the viewpoint of development solubility, a linear aliphatic group is preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, a cyclic aliphatic group is preferred. The number of carbon atoms in the divalent aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 6 or more. In addition, it is preferably 25 or less, more preferably 20 or less, and further preferably 15 or less. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the divalent aliphatic group is preferably 1 to 25, more preferably 3 to 20, and further preferably 6 to 15. By setting the number of carbon atoms in the divalent aliphatic group to be above the above lower limit, a firm film is easily obtained, surface roughness generated during development is less likely to occur, and there is a tendency for the adhesion to the substrate to become good. By setting the number of carbon atoms in the divalent aliphatic group to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0375] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of rigidity of the skeleton, a methylene group is preferred.

[0376] Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group as a side chain.

[0377] The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, and is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of rings possessed by the divalent cyclic aliphatic group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of rings possessed by the divalent cyclic aliphatic group to be above the above lower limit, a strong film is obtained, and there is a tendency that the substrate adhesion becomes good. In addition, by setting the number of rings possessed by the divalent cyclic aliphatic group to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency that the resolution is improved.

[0378] Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from an adamantane ring is preferred.

[0379] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, the divalent aliphatic group is preferably unsubstituted.

[0380] As the divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group can be cited. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and further preferably 6 or more. In addition, it is preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the divalent aromatic ring group is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15. By setting the number of carbon atoms of the divalent aromatic ring group to be above the above lower limit, it is easy to obtain a firm film, it is not easy to have surface roughness generated during development, and there is a tendency for the adhesion with the substrate to become good. By setting the number of carbon atoms of the divalent aromatic ring group to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0381] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring.

[0382] The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzisocyanate ring azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, Pyridine ring, quinazoline ring, quinazolinone ring, azulene ring.

[0383] From the viewpoint of patterning properties, the divalent aromatic ring group is preferably a benzene ring or a naphthalene ring having two free valences, and more preferably a benzene ring having two free valences.

[0384] Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of developing solubility, the divalent aromatic ring group is preferably unsubstituted.

[0385] Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked to each other include groups in which one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic ring groups are linked to each other.

[0386] In this case, the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of divalent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of divalent aliphatic groups to be above the above lower limit, a strong film is easily obtained, surface roughness generated during development is less likely to occur, and there is a tendency for the adhesion with the substrate to become good. By setting the number of divalent aliphatic groups to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0387] The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of divalent aromatic ring groups is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of divalent aromatic ring groups to be above the above lower limit, it is easy to obtain a firm film, and surface roughness generated during development is less likely to occur, and there is a tendency for the adhesion with the substrate to become good. By setting the number of divalent aromatic ring groups to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0388] As a group formed by linking one or more divalent aliphatic groups to one or more divalent aromatic ring groups, for example, groups represented by the above-mentioned formulae (C1-IA) to (C1-IF) can be cited. From the viewpoint of the rigidity of the skeleton and the hydrophobization of the membrane, a group represented by formula (C1-IC) is preferred.

[0389] For these divalent hydrocarbon groups, the bonding method of the cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include: a method in which a hydrogen atom on an aliphatic group or an aromatic ring group is substituted by a cyclic hydrocarbon group as a side chain, and a method in which a cyclic hydrocarbon group as a side chain is constituted by including a carbon atom on an aliphatic group.

[0390] (R 15 , R 16 )

[0391] In formula (C1-II), R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent.

[0392] The divalent aliphatic group may be a linear, branched, or cyclic aliphatic group. From the viewpoint of development solubility, a linear aliphatic group is preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, a cyclic aliphatic group is preferred. The number of carbon atoms in the divalent aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 6 or more. In addition, it is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the divalent aliphatic group is preferably 1 to 20, more preferably 3 to 15, and further preferably 6 to 10. By setting the number of carbon atoms in the divalent aliphatic group to be above the above lower limit, a strong film is easily obtained, surface roughness generated during development is less likely to occur, and there is a tendency for the adhesion to the substrate to become good. By setting the number of carbon atoms in the divalent aliphatic group to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency for the resolution to be improved.

[0393] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of rigidity of the skeleton, a methylene group is preferred.

[0394] Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group as a side chain.

[0395] The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, and is preferably 1 or more, and more preferably 2 or more. In addition, it is preferably 12 or less, and more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of rings possessed by the divalent cyclic aliphatic group is preferably 1 to 12, and more preferably 2 to 10. By setting the number of rings possessed by the divalent cyclic aliphatic group to be above the above lower limit, a strong film is obtained, and there is a tendency that the substrate adhesion becomes good. By setting the number of rings possessed by the divalent cyclic aliphatic group to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film during development, and there is a tendency that the resolution is improved.

[0396] Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a dicyclopentadiene ring. From the viewpoint of the rigidity of the skeleton, groups obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring are preferred.

[0397] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, the divalent aliphatic group is preferably unsubstituted.

[0398] (p, q)

[0399] In formula (C1-II), p and q each independently represent an integer of 0 to 2. By setting it to be above the above lower limit, there is a tendency that patterning suitability becomes good and surface roughness that occurs during development is not easily generated. In addition, by setting it to be below the above upper limit, there is a tendency that developability becomes good. From the viewpoint of developability, p and q are preferably 0. From the viewpoint of patterning suitability and suppression of surface roughness that occurs during development, p and q are preferably 1 or more.

[0400] From the viewpoint of adhesion to the substrate, the partial structure represented by formula (C1-II) is preferably a partial structure represented by the following general formula (C1-II-1).

[0401] [Chemical formula 22]

[0402]

[0403] In formula (C1-II-1), R 13 , R 15 , R 16 , p and q have the same meanings as in formula (C1-II).

[0404] R α represents a monovalent cyclic hydrocarbon group which may have a substituent. r represents an integer of 1 or more. * represents a bonding position.

[0405] The benzene ring in the formula (C1-II-1) may be further substituted by any substituent.

[0406] (R α )

[0407] In formula (C1-II-1), R α It represents a monovalent cyclic hydrocarbon group which may have a substituent.

[0408] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0409] The number of rings possessed by the aliphatic cyclic group is not particularly limited, and is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of rings possessed by the aliphatic cyclic group is preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of rings possessed by the aliphatic cyclic group to be above the above lower limit, a strong film is easily obtained, and there is a tendency that surface roughness that occurs during development is not easily generated. By setting the number of rings possessed by the aliphatic cyclic group to be below the above upper limit, there is a tendency that patterning characteristics become good.

[0410] The number of carbon atoms in the aliphatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and further preferably 8 or more. In addition, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aliphatic ring group is preferably 4 to 40, more preferably 4 to 30, further preferably 6 to 20, and particularly preferably 8 to 15. By setting the number of carbon atoms in the aliphatic ring group to be above the above lower limit, a strong film is easily obtained, and there is a tendency that surface roughness that occurs during development is not easily generated. By setting the number of carbon atoms in the aliphatic ring group to be below the above upper limit, there is a tendency that patterning characteristics become good.

[0411] Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of strong film properties, an adamantane ring is preferred.

[0412] The number of rings possessed by the aromatic ring group is not particularly limited, and is preferably 1 or more, preferably 2 or more, and more preferably 3 or more. In addition, it is preferably 10 or less, and more preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of rings possessed by the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5. By setting the number of rings possessed by the aromatic ring group to be above the above lower limit, it is easy to obtain a strong film, and there is a tendency that the surface roughness that occurs during development is not easily generated. By setting the number of rings possessed by the aromatic ring group to be below the above upper limit, there is a tendency that the patterning characteristics become good.

[0413] Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

[0414] The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and further preferably 6 or more. In addition, it is preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic ring group is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15. By setting the number of carbon atoms in the aromatic ring group to be above the above lower limit, a strong film is easily obtained, and there is a tendency that surface roughness that occurs during development is not easily generated. By setting the number of carbon atoms in the aromatic ring group to be below the above upper limit, there is a tendency that patterning characteristics become good.

[0415] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.

[0416] Examples of the substituent that the cyclic hydrocarbon group may have include: alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxyl. From the viewpoint of ease of synthesis, the cyclic hydrocarbon group is preferably unsubstituted.

[0417] r represents an integer greater than 1, preferably greater than 2. In addition, it is preferably less than 3. For example, r is preferably 1 to 3, more preferably 2 to 3. By setting r to be greater than the above lower limit, there is a tendency that the film curing degree and the residual film rate become good. By setting r to be less than the above upper limit, there is a tendency that the developability becomes good.

[0418] From the perspective of firm film curing, R α It is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

[0419] The benzene ring in formula (C1-II-1) may be further substituted by any substituent. Examples of the substituent include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited and may be one or more than two.

[0420] From the viewpoint of patterning properties, the benzene ring is preferably unsubstituted.

[0421] Specific examples of the partial structure represented by formula (C1-II-1) are listed below. Hereinafter, * represents a bonding position.

[0422] [Chemical formula 23]

[0423]

[0424] From the viewpoint of the coating film residual rate and patterning characteristics, the partial structure represented by formula (C1-II) is preferably a partial structure represented by the following general formula (C1-II-3).

[0425] [Chemical formula 24]

[0426]

[0427] In formula (C1-II-3), R 13 , R 14 , R 15 , R 16 , p and q have the same meanings as in formula (C1-II). Z Each independently represents a hydrogen atom or a polyacid residue.

[0428] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid. It should be noted that one OH group may be further removed and the residue may be combined with R in another molecule represented by formula (C1-II-3). Z That is, it can also be shared through R Z A plurality of formulas (C1-II-3) are linked together.

[0429] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridgeic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0430] From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

[0431] The structure represented by formula (C1-II-3) contained in one molecule of the epoxy (meth)acrylate resin (C1-II) may be one or more. For example, R Z is the structure of hydrogen atom and R Z It is the structure of a polyacid residue.

[0432] The number of partial structures represented by formula (C1-II) contained in one molecule of the epoxy (meth)acrylate resin (C1-II) is not particularly limited, and is preferably 1 or more, more preferably 3 or more. In addition, it is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of the partial structures is preferably 1 to 20, more preferably 1 to 15, and further preferably 3 to 10. By setting the number of the partial structures to be above the above lower limit, it is easy to obtain a firm film, and there is a tendency that surface roughness that occurs during development is not easily generated. By setting the number of the partial structures to be below the above upper limit, it is easy to suppress the deterioration of sensitivity and the reduction of the film, and there is a tendency for the resolution to be improved.

[0433] The weight average molecular weight (Mw) of the (C1-II) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, further preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. In addition, it is preferably 10000 or less, more preferably 8000 or less, and further preferably 7000 or less. The above upper and lower limits can be arbitrarily combined. For example, the weight average molecular weight of the (C1-II) epoxy (meth) acrylate resin is preferably 1000 to 10000, more preferably 1500 to 10000, further preferably 1500 to 8000, further preferably 2000 to 8000, and particularly preferably 2000 to 7000. When the weight average molecular weight of the epoxy (meth)acrylate resin (C1-II) is set to be greater than the above lower limit, the residual film rate of the photosensitive resin composition tends to be good. When the weight average molecular weight of the epoxy (meth)acrylate resin (C1-II) is set to be less than the above upper limit, the solubility in the developer tends to be good.

[0434] The acid value of (C1-II) epoxy (meth) acrylate resin is not particularly limited, and is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, the acid value of (C1-II) epoxy (meth) acrylate resin is preferably 20 to 200 mgKOH / g, more preferably 60 to 150 mgKOH / g, further preferably 80 to 130 mgKOH / g, and further preferably 100 to 130 mgKOH / g. By setting the acid value of the epoxy (meth)acrylate resin (C1-II) to be above the lower limit, the developing solubility is improved and the resolution tends to be good. By setting the acid value of the epoxy (meth)acrylate resin (C1-II) to be below the upper limit, the residual film rate of the photosensitive resin composition tends to be good.

[0435] The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or in combination of two or more.

[0436] In addition, a part of the above-mentioned epoxy (meth) acrylate resin containing a carboxyl group may be replaced with other binder resins. That is, the epoxy (meth) acrylate resin containing a carboxyl group may be used in combination with other binder resins. In this case, the proportion of the epoxy (meth) acrylate resin containing a carboxyl group in the (C) alkali-soluble resin is preferably set to 50% by mass or more, more preferably to 60% by mass or more, further preferably to 70% by mass or more, and particularly preferably to 80% by mass or more. This proportion may be 100% by mass or less.

[0437] As the (C) alkali-soluble resin, from the viewpoint of compatibility with a pigment, a dispersant, etc., it is preferable to use an acrylic copolymer resin (C2), and the alkali-soluble resin described in JP-A-2014-137466 can be preferably used.

[0438] Examples of the (C2) acrylic copolymer resin include copolymers of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (c2-1)”) and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as “unsaturated monomer (c2-2)”).

[0439] Examples of the unsaturated monomer (c2-1) include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; mono[(meth)acryloxyalkyl] esters of polycarboxylic acids of divalent or higher valence such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate; mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends such as ω-carboxy polycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid.

[0440] These unsaturated monomers (c2-1) may be used alone or in combination of two or more.

[0441] As unsaturated monomer (c2-2), the following unsaturated monomers are mentioned, for example.

[0442] N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

[0443] Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;

[0444] Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate 2,6 ] decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane and the like (meth)acrylates;

[0445] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2.1.0 2,6 ] vinyl ethers such as decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane;

[0446] A macromonomer having a mono(meth)acryloyl group at the end of a polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

[0447] These unsaturated monomers (c2-2) may be used alone or in combination of two or more.

[0448] In the copolymer of the unsaturated monomer (c2-1) and the unsaturated monomer (c2-2), the copolymerization ratio of the unsaturated monomer (c2-1) is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (c2-1) in such a range, there is a tendency to obtain a photosensitive resin composition having excellent alkali developability and storage stability.

[0449] Examples of the copolymer of the unsaturated monomer (c2-1) and the unsaturated monomer (c2-2) include copolymers disclosed in JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, and JP-A-2004-101728.

[0450] The copolymer of the unsaturated monomer (c2-1) and the unsaturated monomer (c2-2) can be produced by a known method. For example, the structure, Mw, and Mw / Mn (Mn is the number average molecular weight) can be controlled by the method disclosed in Japanese Patent Application Publication No. 2003-222717, Japanese Patent Application Publication No. 2006-259680, and International Publication No. 2007 / 029871.

[0451] As the copolymer of the unsaturated monomer (c2-1) and the unsaturated monomer (c2-2), resins described in International Publication No. 2016 / 194619 and International Publication No. 2017 / 154439 can be used.

[0452] As the (C) alkali-soluble resin other than the (C1) epoxy (meth)acrylate resin and the (C2) acrylic copolymer resin, for example, the polyimide resin and polybenzoic acid resin described in International Publication No. 2018 / 181311 can be used. Azole resins.

[0453] <(D) Ethylenically unsaturated compound>

[0454] The photosensitive resin composition of the present invention may contain (D) an ethylenically unsaturated compound.

[0455] The (D) ethylenically unsaturated compound is a compound different from the (B) compound having an ethylenically unsaturated group and a cardo structure.

[0456] By containing the (D) ethylenically unsaturated compound, the sensitivity is improved and the current value during light emission tends to be high.

[0457] (D) The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule.

[0458] Specific examples thereof include (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond, and monoesters of polyhydric or monohydric alcohols.

[0459] In the present invention, it is particularly preferred to use a multifunctional olefinic monomer having two or more olefinic unsaturated groups in one molecule. The number of olefinic unsaturated groups possessed by the multifunctional olefinic monomer is not particularly limited, and is preferably 2 or more, more preferably 4 or more, and further preferably 5 or more, and preferably 8 or less, and more preferably 7 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of olefinic unsaturated groups of the multifunctional olefinic monomer is preferably 2 to 8, more preferably 2 to 7, further preferably 4 to 7, and particularly preferably 5 to 7. By setting the number of olefinic unsaturated groups of the multifunctional olefinic monomer to above the above lower limit, there is a tendency to become highly sensitive. By setting the number of olefinic unsaturated groups of the multifunctional olefinic monomer to below the above upper limit, there is a tendency to improve solubility in a solvent.

[0460] Examples of the polyfunctional ethylenic monomer include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

[0461] Examples of esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids include acrylates of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylates obtained by replacing these acrylates with methacrylates; itaconates obtained by replacing these acrylates with itaconates; crotonates obtained by replacing these acrylates with crotonates; and maleates obtained by replacing these acrylates with maleates.

[0462] Examples of the esters of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include acrylates and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and 1,2,3-pyrogallol triacrylate.

[0463] The esters obtained by the esterification reaction of polycarboxylic acids and unsaturated carboxylic acids with polyhydroxy compounds are not necessarily single substances, and examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol and glycerol.

[0464] In addition, examples of the polyfunctional olefinic monomer used in the present invention include: urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylate, or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl-containing compounds such as divinyl phthalate.

[0465] Examples of urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, and UX-5005 (manufactured by Nippon Kayaku Co., Ltd.); U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.); UA-306H, UA-510H, and UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.); and UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).

[0466] From the viewpoint of curability, as the (D) ethylenically unsaturated compound, it is preferred to use an alkyl (meth)acrylate; and urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylate, or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylate. It is more preferred to use urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylate.

[0467] These (D) ethylenically unsaturated compounds may be used alone or in combination of two or more.

[0468] <(E) Coloring agent>

[0469] The photosensitive resin composition of the present invention may contain (E) a colorant. By containing the (E) colorant, appropriate light absorption can be obtained, and in particular, when used for forming a light shielding member such as a partition wall, appropriate light shielding property can be obtained.

[0470] The colorant (E) that can be used in the photosensitive resin composition of the present invention is not particularly limited, and a pigment or a dye may be used. From the viewpoint of durability, a pigment is preferably used.

[0471] (E) The pigment contained in the colorant may be a single type or two or more types. From the viewpoint of achieving both uniform light shielding in the visible region and optical density (OD) per unit film thickness, it is preferred to use two or more types.

[0472] The pigment that can be used as the colorant (E) is not particularly limited, and examples thereof include organic coloring pigments and organic black pigments. Here, the organic coloring pigment refers to an organic pigment that exhibits a color other than black, and examples thereof include red pigments, orange pigments, blue pigments, violet pigments, green pigments, and yellow pigments.

[0473] Among pigments, organic pigments are preferred from the viewpoints of high dielectric constant and low dielectric constant. Organic coloring pigments are preferred from the viewpoints of suppressing the absorption of ultraviolet rays, having high curability, and being easy to control the shape of the cured product. Organic black pigments are preferred from the viewpoint of light-shielding properties.

[0474] The organic coloring pigment may be used alone or in combination of two or more. In particular, it is more preferred to use organic coloring pigments of different colors in combination, and it is further preferred to use a combination of organic coloring pigments that exhibit a color close to black.

[0475] The chemical structure of these organic coloring pigments is not particularly limited, and examples thereof include azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, isoindolinone pigments, diisocyanate pigments, and the like. Oxazine, indanthrene, perylene. Specific examples of pigments that can be used are shown below by pigment number.

[0476] "CI" in "CI Pigment Red 2" and the like mentioned below refers to a pigment index number.

[0477] Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, and 53:3. , 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 148 9, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 , 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276.

[0478] From the viewpoint of light-shielding property and dispersibility, CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, and 254 are preferably used, and CI Pigment Red 177, 209, 224, and 254 are more preferably used.

[0479] From the viewpoint of dispersibility and light-shielding property, CI Pigment Red 177, 254, and 272 are preferably used.

[0480] When the photosensitive resin composition is cured by ultraviolet rays, it is preferable to use a pigment having a low ultraviolet absorption rate as the red pigment, and from the above viewpoint, it is more preferable to use CI Pigment Red 254 or 272.

[0481] Examples of the orange pigment include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79.

[0482] From the viewpoint of dispersibility and light-shielding property, CI Pigment Orange 13, 43, 64, and 72 are preferably used.

[0483] When the photosensitive resin composition is cured by ultraviolet rays, it is preferable to use a pigment having a low ultraviolet absorption rate as the orange pigment, and from the above viewpoint, it is more preferable to use CI Pigment Orange 64 or 72.

[0484] Examples of the blue pigment include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0485] From the viewpoint of light-shielding properties, preferably, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are used, and more preferably, CI Pigment Blue 15:6 is used.

[0486] From the viewpoint of dispersibility and light-shielding property, CI Pigment Blue 15:6, 16, and 60 are preferably used.

[0487] When the photosensitive resin composition is cured by ultraviolet rays, it is preferable to use a pigment having a low ultraviolet absorption rate as the blue pigment, and from the above viewpoint, it is more preferable to use CI Pigment Blue 60.

[0488] Examples of the violet pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0489] From the viewpoint of light-shielding properties, CI Pigment Violet 19, 23, and 29 are preferably used, and CI Pigment Violet 23 is more preferably used.

[0490] From the viewpoint of dispersibility and light-shielding property, CI Pigment Violet 23 and 29 are preferably used.

[0491] When the photosensitive resin composition is cured by ultraviolet rays, it is preferable to use a pigment having a low ultraviolet absorption rate as the violet pigment, and from the above viewpoint, it is more preferable to use CI Pigment Violet 29.

[0492] Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and 59. Preferably, CI Pigment Green 7 and 36 are used.

[0493] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134 4, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Preferably, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are used, and more preferably, CI Pigment Yellow 83, 138, 139, 150, and 180 are used.

[0494] From the viewpoint of light-shielding property and shape control of the cured product, it is preferred to use at least one selected from a red pigment, an orange pigment, a blue pigment, and a violet pigment.

[0495] From the viewpoint of light-shielding property and shape control of the cured product, it is preferred that at least one of the following pigments be contained.

[0496] Red pigment: CI Pigment Red 177, 254, 272

[0497] Orange pigment: CI Pigment Orange 43, 64, 72

[0498] Blue pigment: CI Pigment Blue 15:6, 60

[0499] Violet Pigment: CI Pigment Violet 23, 29

[0500] When two or more organic coloring pigments are used in combination, the combination of the organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding properties, it is preferred that at least one selected from red pigments and orange pigments and at least one selected from blue pigments and violet pigments be contained.

[0501] The combination of more specific colors is not particularly limited, but from the viewpoint of light-shielding properties, examples thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment, and a violet pigment.

[0502] Examples of the organic black pigment include perylene-based black pigments, aniline-based black pigments, and benzodifuranone-based black pigments.

[0503] Examples of the perylene black pigment include Lumogen Black (registered trademark) FK4281, K0087, and Paliogen Black (registered trademark) EH0788 (all manufactured by BASF).

[0504] Examples of the aniline black pigment include Paliotol Black (registered trademark) L0080, D0080, and K0080 (all manufactured by BASF).

[0505] From the viewpoint of dispersibility, developability, and current density during light emission, benzodifuranone-based black pigments are preferred.

[0506] Among benzodifuranone black pigments, from the viewpoint of light-shielding properties and easy suppression of ultraviolet absorption to control the cone angle shape, it is preferred to use an organic black pigment comprising at least one selected from a compound represented by the following general formula (E1) (hereinafter, sometimes referred to as “compound (E1)”), a geometric isomer of the compound (E1), a salt of the compound (E1), and a salt of a geometric isomer of the compound (E1) (hereinafter, sometimes referred to as “organic black pigment represented by general formula (E1)”).

[0507] [Chemical formula 25]

[0508]

[0509] In formula (E1), R 611 and R 616Each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom.

[0510] R 612 , R 613 , R 614 , R 615 , R 617 , R 618 , R 619 and R 620 Each independently represents a hydrogen atom, a halogen atom, R 621 、COOH、COOR 621 、COO - ,CONH2,CONHR 621 ,CONR 621 R 622 、CN、OH、OR 621 、COCR 621 、OOCNH2、OOCNHR 621 、OOCNR 621 R 622 、NO2、NH2、NHR 621 NR 621 R 622 、NHCOR 622 NR 621 COR 622 、N=CH2、N=CHR 621 、N=CR 621 R 622 , SH, SR 621 、SOR 621 、SO2R 621 、SO3R 621 、SO3H、SO3 - 、SO2NH2、SO2NHR 621 or SO2NR 621 R 622 .

[0511] Selected from R 612 With R 613 , R 613 With R 614 , R 614 With R 615 , R 617 With R 618 , R 618 With R 619 , and R 619 With R 620 At least one of the combinations may be directly bonded to each other, or may be bonded via an oxygen atom, a sulfur atom, NH or NR 621 Bridged and bonded to each other.

[0512] R 621 and R 622 Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

[0513] Compound (E1) and the geometrical isomers of compound (E1) have the following core structure (wherein the substituents in the structural formula are omitted), and the trans-trans isomer is likely to be the most stable.

[0514] [Chemical formula 26]

[0515]

[0516] When compound (E1) is anionic, it is preferably a salt whose charge is compensated by any known appropriate cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or an organic metal complex. In addition, when the geometrical isomers of compound (1) are anionic, they are preferably the same salts.

[0517] The substituents in formula (E1) and their definitions are preferably the following from the viewpoint of the tendency to increase the shielding rate. This is presumably because the following substituents have no absorption and do not affect the hue of the pigment.

[0518] R 612 , R 614 , R 615 , R 617 , R 619 and R 620 Each independently is preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom.

[0519] R 613 and R 618 Each is independently preferably a hydrogen atom, NO2, OCH3, OC2H5, a bromine atom, a chlorine atom, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, SO3H or SO3 - , further preferably a hydrogen atom or SO3H, particularly preferably a hydrogen atom.

[0520] R 611 and R 616 Each independently is preferably a hydrogen atom, CH3 or CF3, and more preferably a hydrogen atom.

[0521] Preferably selected from R 611 With R616 , R 612 With R 617 , R 613 With R 618 , R 614 With R 619 , and R 615 With R 620 At least one combination is the same, preferably R 611 With R 616 Same, R 612 With R 617 Same, R 613 With R 618 Same, R 614 With R 619 The same, and R 615 With R 620 same.

[0522] R 621 and R 622 The alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.

[0523] R 621 and R 622 The cycloalkyl group having 3 to 12 carbon atoms is exemplified by cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thujyl, norbornyl, bornyl, norcaryl, caryl, alkyl, norpinyl, pinanyl, adamantane-1-yl or adamantane-2-yl.

[0524] R 621 and R 622 The alkenyl group having 2 to 12 carbon atoms is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

[0525] R 621 and R 622The cycloalkenyl group having 3 to 12 carbon atoms is exemplified by 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-cyclohexadien-1-yl, The present invention can be substituted with any of the following: 1,4-dimethyl-2,4-dicarbazyl, 2,5-dimethyl- ...2,4-dicarbazyl, 2,5-dimethyl-2,4-dicarbazyl, 2,5-dimethyl-2,4-dicarbazyl, 2,5-dimethyl-

[0526] R 621 and R 622 The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

[0527] The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0528] The organic black pigment represented by formula (E1) is preferably an organic black pigment comprising at least one selected from a compound represented by the following structural formula (E2) (hereinafter also referred to as “compound (E2)”) and geometric isomers of compound (E2).

[0529] [Chemical formula 27]

[0530]

[0531] Examples of the organic black pigment of the compound (E2) include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).

[0532] The organic black pigment is preferably used after being dispersed using a dispersant, a solvent, or a method described below.

[0533] When a sulfonic acid derivative of the compound (E1), particularly a sulfonic acid derivative of the compound (E2), is present during dispersion, dispersibility and storage stability may be improved. Therefore, the organic black pigment preferably contains these sulfonic acid derivatives.

[0534] On the other hand, from the viewpoint of higher light-shielding properties, it is preferable to use an inorganic black pigment as the coloring agent (E).

[0535] Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.

[0536] From the viewpoint of light-shielding property and image characteristics, carbon black can be preferably used. Examples of carbon black include the following.

[0537] Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, # 10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, # 960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #31 50, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

[0538] Made by Degussa: Printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, PrintexV, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, ColorBlack S170

[0539] Made by Cabot Corporation: Monarch (registered trademark, the same below) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, the same below) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 550R, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark, the same below) XC72R, ELFTEX (registered trademark) -8

[0540] Made by Birla: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN10 00, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

[0541] Carbon black can be obtained by coating with resin. If carbon black obtained by coating with resin is used, it has the effect of improving the adhesion to the glass substrate and the volume resistance value. As carbon black obtained by coating with resin, for example, carbon black described in Japanese Patent Publication No. 09-71733 can be preferably used. From the perspective of volume resistance and dielectric constant, it is preferred to use carbon black coated with resin.

[0542] These pigments are preferably dispersed and used so that the average particle size is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.25 μm or less. Here, the basis of the average particle size is the number of pigment particles.

[0543] In the photosensitive resin composition of the present invention, the average particle size of the pigment is a value obtained based on the pigment particle size measured by dynamic light scattering (DLS). The particle size measurement is performed on the photosensitive resin composition after being fully diluted (usually diluted to adjust the pigment concentration to about 0.005 to 0.2 mass %. However, depending on the measuring instrument, if there is a recommended concentration, it is based on the recommended concentration) and measured at 25°C.

[0544] In addition to the above-mentioned organic coloring pigments and black pigments, dyes can also be used.

[0545] Examples of dyes that can be used as the colorant (E) include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0546] Regarding the dye, only one type may be used, or two or more types may be used in combination.

[0547] Examples of the azo dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0548] Examples of the anthraquinone dye include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0549] As a phthalocyanine dye, CI vat blue 5 is mentioned, for example.

[0550] As a quinoneimine dye, CI Basic Blue 3 and CI Basic Blue 9 are mentioned, for example.

[0551] As a quinoline dye, CI solvent yellow 33, CI acid yellow 3, CI disperse yellow 64 are mentioned, for example.

[0552] Examples of the nitro dye include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0553] <(F) Dispersant>

[0554] The photosensitive resin composition of the present invention may contain a dispersant (F) in order to finely disperse the colorant (E) and stabilize the dispersion state thereof for the purpose of ensuring the stability of quality.

[0555] The (F) dispersant is preferably a polymer dispersant having a functional group. In addition, from the viewpoint of dispersion stability, for example, a polymer dispersant having functional groups such as a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary amino group; a quaternary ammonium salt group; a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine or pyrazine is more preferred. From the viewpoint of being able to disperse the pigment with a small amount of the dispersant, a polymer dispersant having a primary, secondary or tertiary amino group; a quaternary ammonium salt group; a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine or pyrazine is further preferred.

[0556] Examples of the polymer dispersant include carbamate dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants formed from monomers having an amino group and macromonomers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like.

[0557] Examples of such dispersants include: trade names EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.).

[0558] The polymer dispersants may be used alone or in combination of two or more.

[0559] From the viewpoint of the dispersibility of the pigment, the dispersant (F) preferably contains either or both of a urethane polymer dispersant and an acrylic polymer dispersant having a functional group, and particularly preferably contains an acrylic polymer dispersant.

[0560] From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having either or both of a polyester bond and a polyether bond is preferred.

[0561] Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, and BYK-LPN21116 (all acrylic-based) (all manufactured by BYK-Chemie).

[0562] The amine value of the polymer dispersant having a basic functional group is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. In addition, it is preferably 140 mgKOH / g or less, more preferably 120 mgKOH / g or less, further preferably 100 mgKOH / g or less, further preferably 90 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, the amine value of the polymer dispersant is preferably 1 to 140 mgKOH / g, more preferably 10 to 120 mgKOH / g, further preferably 20 to 100 mgKOH / g, further preferably 40 to 90 mgKOH / g, and particularly preferably 50 to 80 mgKOH / g. By setting the amine value of the polymer dispersant to be above the above lower limit, there is a tendency to suppress the surface roughness of the electrode. When the amine value of the polymer dispersant is equal to or less than the above upper limit, compatibility with the (C) alkali-soluble resin tends to be improved.

[0563] From the viewpoint of dispersibility, the acrylic dispersant is preferably an AB or BAB block copolymer composed of an A block having the above-mentioned functional group and a B block not having the above-mentioned functional group. In this case, in the A block, in addition to the partial structure derived from the unsaturated group-containing monomer containing the above-mentioned functional group, a partial structure derived from the unsaturated group-containing monomer not containing the above-mentioned functional group may also be contained, and they may be contained in the A block in any manner of random copolymerization or block copolymerization. The content ratio of the partial structure not containing a functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, further preferably 10% by mass or less, and particularly preferably 0% by mass.

[0564] From the viewpoint of dispersibility, the B block is preferably composed only of a partial structure derived from an unsaturated group-containing monomer that does not contain the above-mentioned functional group. One B block may contain partial structures derived from two or more monomers, which may be contained in the B block in any form of random copolymerization or block copolymerization.

[0565] The AB or BAB block copolymer can be prepared, for example, by the living polymerization method shown below.

[0566] Living polymerization methods include anionic living polymerization, cationic living polymerization, and radical living polymerization. Among them, in the anionic living polymerization method, the polymerization active species is an anion, as shown in the following figure, for example.

[0567] [Chemical formula 28]

[0568] (Anionic Living Polymerization)

[0569]

[0570] In the figure above, Ar 1 It is a monovalent organic group. 2 For Ar 1 different monovalent organic groups. M is a metal atom. s and t are each an integer greater than 1.

[0571] The polymerization active species in the free radical living polymerization method is a free radical, as shown in the following figure, for example.

[0572] [Chemical formula 29]

[0573] (Free radical living polymerization method) (Nitroxyl method)

[0574]

[0575] (ATRP method)

[0576]

[0577] In the figure above, Ar 1 It is a monovalent organic group. 2 For Ar 1 different monovalent organic groups. j and k are each an integer greater than 1. a is a hydrogen atom or a monovalent organic group. b For R a Different hydrogen atoms or monovalent organic groups.

[0578] When synthesizing the acrylic dispersant, the acrylic dispersant may be prepared by using methods described in Japanese Patent Application Laid-Open No. 9-62002, P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al. al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Yuhei Koichi, Hata Koichi, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collected Papers on Polymers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987), etc.

[0579] The acrylic dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer. The A block / B block ratio constituting the copolymer is also not particularly limited, and is preferably 1 / 99 to 80 / 20 (mass ratio), and more preferably 5 / 95 to 60 / 40 (mass ratio). By setting it within the above range, there is a tendency to easily ensure a balance between dispersibility and storage stability.

[0580] The amount of the quaternary ammonium salt group in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By setting the amount within the above range, good dispersibility tends to be easily ensured.

[0581] Such acrylic dispersants may contain amino groups. The amine value of the acrylic dispersant is preferably 1 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. In addition, it is preferably 140 mgKOH / g or less, more preferably 120 mgKOH / g or less, further preferably 100 mgKOH / g or less, further preferably 90 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, the amine value of the acrylic dispersant is preferably 1 to 140 mgKOH / g, more preferably 10 to 120 mgKOH / g, further preferably 20 to 100 mgKOH / g, further preferably 40 to 90 mgKOH / g, and particularly preferably 50 to 80 mgKOH / g. By setting the amine value of the acrylic dispersant to be above the above lower limit, there is a tendency for the dispersibility to become good. When the amine value of the acrylic dispersant is equal to or less than the above upper limit, compatibility with the (B) alkali-soluble resin tends to be improved.

[0582] Here, the amine value of the acrylic dispersant is represented by the mass of KOH corresponding to the amount of alkali per 1 g of the solid content excluding the solvent in the dispersant sample, and is measured by the following method.

[0583] Accurately weigh 0.5-1.5g of the dispersant sample in a 100mL beaker and dissolve it in 50mL of acetic acid. Use an automatic titrator equipped with a pH electrode to neutralize and titrate the solution with 0.1mol / L HClO4 acetic acid solution. Take the inflection point of the titration pH curve as the titration endpoint and calculate the amine value according to the following formula.

[0584] Amine value [mgKOH / g] = (561×V) / (W×S)

[0585] [W represents the amount of the dispersant sample weighed [g], V represents the titration amount at the titration endpoint [mL], and S represents the solid content concentration of the dispersant sample [mass %].]

[0586] The weight average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. In addition, it is preferably 50000 or less, more preferably 20000 or less, and further preferably 15000 or less. The above upper and lower limits can be combined arbitrarily. For example, the weight average molecular weight of the acrylic dispersant is preferably 1000 to 50000, more preferably 3000 to 50000, further preferably 4000 to 20000, and particularly preferably 5000 to 15000. By setting the weight average molecular weight of the acrylic dispersant to above the above lower limit, there is a tendency for the dispersibility to become good. In addition, by setting the weight average molecular weight of the acrylic dispersant to below the above upper limit, there is a tendency that the viscosity change is not easy to occur.

[0587] When the acrylic dispersant has a quaternary ammonium salt group as a functional group, the chemical structure of the repeating unit containing the quaternary ammonium salt group is not particularly limited. From the viewpoint of dispersibility, the acrylic dispersant preferably has a repeating unit represented by the following general formula (V) (hereinafter sometimes referred to as "repeating unit (V)").

[0588] [Chemical formula 30]

[0589]

[0590] In formula (V), R 31 ~R 33 Each is independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent. 31 ~R 33 Two or more of R may be bonded to each other to form a ring structure. 34 X is a hydrogen atom or a methyl group. 31 is a divalent linking group, Y - as counter anion.

[0591] R of formula (V) 31 ~R 33 The alkyl group optionally having a substituent may be any of a straight chain or a branched chain. In addition, a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group may be included. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, and is preferably 10 or less, more preferably 6 or less, further preferably 4 or less, and particularly preferably 2 or less. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 to 2.

[0592] Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups, preferably methyl, ethyl, propyl, butyl, pentyl and hexyl groups, more preferably methyl, ethyl, propyl and butyl groups, and further preferably methyl and ethyl groups.

[0593] R of formula (V) 31 ~R 33 The number of carbon atoms of the aryl group optionally having a substituent is not particularly limited, but is preferably 6 or more, and preferably 16 or less, and more preferably 12 or less. The above upper and lower limits may be combined arbitrarily. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms of the aryl group is preferably 6 to 16, and more preferably 6 to 12.

[0594] Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl and anthracenyl. Phenyl, methylphenyl, ethylphenyl, dimethylphenyl and diethylphenyl are preferred, and phenyl, methylphenyl and ethylphenyl are more preferred.

[0595] R of formula (V) 31 ~R 33 The number of carbon atoms of the aralkyl group which may have a substituent is not particularly limited, but is preferably 7 or more, and is preferably 16 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms of the aralkyl group is preferably 7 to 16, more preferably 7 to 12, further preferably 7 to 10, and particularly preferably 7 to 8.

[0596] Examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. A phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group are preferred, and a phenylmethyl group and a phenylethyl group are more preferred.

[0597] From the perspective of dispersibility, R 31 ~R 33 Preferably, each is independently an alkyl group or an aralkyl group, and more preferably, each is independently a methyl group or a phenylmethyl group.

[0598] As Y in formula (V) - For example, Cl - Br - ,I - 、ClO4 - 、BF4 - 、CH3COO - PF -In addition, aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions, and aromatic carboxylic acid anions described in International Publication No. 2018 / 079659; and alkyl sulfate anions and alkyl sulfonic acid anions described in International Publication No. 2019 / 107020 are also preferably used.

[0599] As Y - From the perspective of the development method, Cl - From the viewpoint of suppressing surface roughness, an alkylsulfonic acid anion is preferred.

[0600] When the polymer dispersant has a tertiary amine as a functional group, it preferably has a repeating unit represented by the following general formula (VI) (hereinafter sometimes referred to as "repeating unit (VI)") from the viewpoint of dispersibility and suppression of surface roughness.

[0601] [Chemical formula 31]

[0602]

[0603] In formula (VI), R 35 and R 36 are each independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, and R 35 and R 36 Optionally, they are bonded to each other to form a ring structure. 37 is a hydrogen atom or a methyl group. 31 It is a divalent linking group.

[0604] As R of formula (VI) 35 and R 36 The alkyl group optionally having a substituent in the formula (V) may preferably be 31 ~R 33 The alkyl groups exemplified are:

[0605] As R of formula (VI) 35 and R 36 The aryl group optionally having a substituent may preferably be R 31 ~R 33 The aryl group exemplified is.

[0606] As R of formula (VI) 35 and R 36 The aralkyl group optionally having a substituent may preferably be R 31 ~R 33 The aralkyl groups exemplified are:

[0607] From the perspective of dispersibility and suppression of surface roughness, R35 and R 36 Each independently is preferably an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

[0608] As R of formula (V) 31 ~R 33 and R of formula (VI) 35 and R 36 Examples of the substituent that the alkyl group, aralkyl group or aryl group in the formula (I) include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.

[0609] As X in formula (V) 31 and Z in formula (VI) 31 , respectively, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 43 -base, -COOR 44 -base (where R 43 and R 44 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms, preferably -COO-R 44 - group, more preferably -COO-C2H4- group.

[0610] The content ratio of the repeating unit (V) in the acrylic dispersant is not particularly limited. From the viewpoint of dispersibility and suppression of surface roughness, the total content ratio of the repeating unit (V) and the repeating unit (VI) is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, and particularly preferably 35 mol% or less. In addition, it is preferably 5 mol% or more, more preferably 8 mol% or more, further preferably 10 mol% or more, and particularly preferably 12 mol% or more. The above upper and lower limits can be combined arbitrarily. For example, the ratio is preferably 5 to 60 mol%, more preferably 8 to 50 mol%, further preferably 10 to 40 mol%, and particularly preferably 12 to 35 mol%.

[0611] The proportion of the repeating unit (V) of the acrylic dispersant in the total repeating units is not particularly limited. From the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 3 mol% or more, further preferably 5 mol% or more, and particularly preferably 8 mol% or more. In addition, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 15 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, the proportion is preferably 1 to 50 mol%, more preferably 3 to 30 mol%, further preferably 5 to 20 mol%, and particularly preferably 8 to 15 mol%.

[0612] The content ratio of the repeating unit (VI) in the acrylic dispersant is not particularly limited. From the viewpoint of dispersibility and suppression of surface roughness, the total content ratio of the repeating unit (V) and the repeating unit (VI) is preferably 100 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, and particularly preferably 85 mol% or less. In addition, it is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, and particularly preferably 60 mol% or more. The above upper and lower limits can be combined arbitrarily. For example, the ratio is preferably 10 to 100 mol%, more preferably 30 to 95 mol%, further preferably 50 to 90 mol%, and particularly preferably 60 to 85 mol%.

[0613] The proportion of the repeating unit (VI) of the acrylic dispersant in the total repeating units is not particularly limited. From the viewpoint of dispersibility and suppression of surface roughness, it is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, and particularly preferably 20 mol% or more. In addition, it is preferably 60 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 25 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, the ratio is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, further preferably 15 to 30 mol%, and particularly preferably 20 to 25 mol%.

[0614] From the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability, the acrylic dispersant preferably has a repeating unit represented by the following general formula (VII) (hereinafter sometimes referred to as "repeating unit (VII)").

[0615] [Chemical formula 32]

[0616]

[0617] In formula (VII), R 40 R is ethylene or propylene. 41 is an alkyl group which may have a substituent. 42 is a hydrogen atom or a methyl group. c is an integer of 1 to 20.

[0618] R of formula (VII) 41The alkyl group optionally having a substituent may be any of a straight chain or a branched chain. In addition, a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group may be included. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. Examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, preferably methyl, ethyl, propyl, butyl, pentyl, and hexyl, and more preferably methyl, ethyl, propyl, and butyl.

[0619] From the viewpoint of compatibility and dispersibility with binder components such as solvents, c in formula (VII) is preferably 1 or more, more preferably 2 or more. In addition, it is preferably 10 or less, more preferably 5 or less. The above upper and lower limits may be combined arbitrarily. For example, c is preferably 1 to 10, more preferably 2 to 5.

[0620] The proportion of the repeating unit (VII) of the acrylic dispersant in the total repeating units is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 4 mol% or more. In addition, it is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, the proportion is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and further preferably 4 to 10 mol%. When the proportion is within the above range, it is easy to take into account the compatibility and dispersion stability of adhesive components such as solvents.

[0621] From the viewpoint of improving the compatibility of the dispersant with the binder component such as the solvent and improving dispersion stability, the acrylic dispersant preferably has a repeating unit represented by the following general formula (VIII) (hereinafter sometimes referred to as "repeating unit (VIII)").

[0622] [Chemical formula 33]

[0623]

[0624] In formula (VIII), R 38 R is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. 39 A hydrogen atom or a methyl group.

[0625] R of formula (VIII) 38The alkyl group optionally having a substituent may be any of a straight chain or a branched chain. In addition, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more. In addition, it is preferably 10 or less, and more preferably 8 or less. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 10, preferably 2 to 8, and more preferably 4 to 8.

[0626] Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and 2-ethylhexyl. Preferably, the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl and 2-ethylhexyl. More preferably, the alkyl group is methyl, ethyl, propyl, butyl and 2-ethylhexyl.

[0627] R of formula (VIII) 38 The number of carbon atoms of the aryl group optionally having a substituent is not particularly limited, but is preferably 6 or more. In addition, it is preferably 16 or less, more preferably 12 or less, and further preferably 8 or less. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms of the aryl group is preferably 6 to 16, more preferably 6 to 12, and further preferably 6 to 8.

[0628] Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Preferred are phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl. More preferred are phenyl, methylphenyl, and ethylphenyl.

[0629] R of formula (VIII) 38 The number of carbon atoms of the aralkyl group which may have a substituent is not particularly limited, but is preferably 7 or more, and preferably 16 or less, more preferably 12 or less, and further preferably 10 or less. For example, the number of carbon atoms of the aralkyl group is preferably 7 to 16, more preferably 7 to 12, and further preferably 7 to 10.

[0630] Examples of the aralkyl group include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl. Preferred is phenylmethyl, phenylethyl, phenylpropyl, or phenylbutyl. More preferred is phenylmethyl or phenylethyl.

[0631] From the viewpoint of solvent compatibility and dispersion stability, R 38 It is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group or a phenylmethyl group.

[0632] As R 38The substituents that the alkyl group in the above may optionally have include, for example, a halogen atom and an alkoxy group. The substituents that the aryl group or the aralkyl group may optionally have include, for example, a chain alkyl group, a halogen atom and an alkoxy group. The chain alkyl group may include any of a straight chain and a branched chain.

[0633] From the viewpoint of dispersibility, the content ratio of the repeating unit (VIII) of the acrylic dispersant in the total repeating units is preferably 30 mol% or more, more preferably 40 mol% or more, and further preferably 50 mol% or more. In addition, it is preferably 80 mol% or less, and more preferably 70 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, the ratio is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and further preferably 50 to 70 mol%.

[0634] The acrylic dispersant may also have repeating units other than the repeating unit (V), the repeating unit (VI), the repeating unit (VII) and the repeating unit (VIII). Examples of such repeating units include repeating units derived from the following monomers: styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; and monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether and N-methacryloylmorpholine.

[0635] From the viewpoint of further improving dispersibility, the acrylic dispersant is preferably a block copolymer having an A block and a B block, wherein the A block has a repeating unit (V) and a repeating unit (VI), and the B block does not have a repeating unit (V) and a repeating unit (VI). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing not only a quaternary ammonium salt group but also a tertiary amino group into the A block, there is a tendency that the dispersing ability of the dispersant is significantly improved. In addition, the B block in the acrylic dispersant preferably has a repeating unit (VII), and more preferably further has a repeating unit (VIII).

[0636] In the A block, the repeating unit (V) and the repeating unit (VI) may be contained in any form of random copolymerization or block copolymerization. In addition, two or more repeating units (V) and repeating units (VI) may be contained in one A block, respectively. In this case, each repeating unit may be contained in the A block in any form of random copolymerization or block copolymerization.

[0637] The A block may contain repeating units other than the repeating units (V) and (VI), and examples of such repeating units include repeating units derived from the above-mentioned (meth)acrylate monomers. The content of repeating units other than the repeating units (V) and (VI) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and it is particularly preferred that the A block does not contain the above-mentioned repeating units.

[0638] The B block may contain repeating units other than the repeating units (VII) and (VIII). Examples of such repeating units include repeating units derived from the following monomers: styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as N-methylolacrylamide; and monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, and N-methylacryloylmorpholine. The content of repeating units other than the repeating units (VII) and (VIII) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and it is particularly preferred that the B block does not contain the above repeating units.

[0639] These acrylic dispersants may be used alone or in combination of two or more.

[0640] <Other ingredients of the photosensitive resin composition>

[0641] In addition to the above-mentioned components, the photosensitive resin composition of the present invention may contain additives such as adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors as appropriate.

[0642] (1) Adhesion enhancer

[0643] The photosensitive resin composition of the present invention may contain an adhesion improver in order to improve adhesion to a substrate. As the adhesion improver, a silane coupling agent or a phosphoric acid group-containing compound is preferred.

[0644] As the silane coupling agent, for example, various silane coupling agents such as epoxy-based, (meth)acrylic-based, and amino-based silane coupling agents may be used alone or in combination of two or more.

[0645] Examples of the silane coupling agent include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane; epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; and isocyanatesilanes such as 3-isocyanatepropyltriethoxysilane. Among them, epoxysilane-based silane coupling agents are particularly preferred.

[0646] The phosphoric acid group-containing compound is preferably a phosphoric acid ester containing a (meth)acryloyl group, and is preferably a phosphoric acid group-containing compound represented by the following general formula (g1), (g2) or (g3).

[0647] [Chemical formula 34]

[0648]

[0649] In formula (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group. e and e' are each independently an integer of 1 to 10. f is 1, 2 or 3.

[0650] These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

[0651] (2) Surfactants

[0652] The photosensitive resin composition of the present invention may contain a surfactant in order to improve coating properties.

[0653] As the surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. From the perspective of low possibility of adverse effects on various properties, nonionic surfactants are preferably used, and from the perspective of coating properties, fluorine-based and silicone-based surfactants are more preferred.

[0654] Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-3000114, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu Silicone Co., Ltd.), MEGAFAC F-470, F-475, F-478, F-554, F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Dow Corning Toray Co., Ltd.), DS-401 (manufactured by Daikin Co., Ltd.), L-77 (manufactured by Nippon Unicar Co., Ltd.), and FC4430 (manufactured by 3M Co., Ltd.).

[0655] The surfactant may be used alone or in combination of two or more.

[0656] (3) Pigment derivatives

[0657] The photosensitive resin composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.

[0658] Examples of the pigment derivatives include azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, quinophthalone pigments, isoindolinone pigments, diisocyanate pigments, and the like. Oxadiazoles, anthraquinones, indanthrenes, perylenes, perinones, diketopyrrolopyrroles, The derivatives of oxazine are preferably phthalocyanines and quinophthalones.

[0659] Examples of substituents of the pigment derivative include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimide methyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups bonded to the pigment skeleton directly or via, for example, alkyl groups, aryl groups, and heterocyclic groups, preferably sulfonic acid groups. Multiple substituents may be substituted in one pigment skeleton, or multiple substituents may be substituted.

[0660] Examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and dioxadiazole. Sulfonic acid derivatives of oxazine.

[0661] These may be used alone or in combination of two or more.

[0662] (4) Thiol compounds

[0663] Furthermore, in order to improve the adhesion to the substrate, a mercapto compound may be added as a polymerization accelerator.

[0664] Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, azole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioacetate, ethylene glycol dithioacetate, trimethylolpropane trimerioacetate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trimerioacetate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioacetate, trihydroxyethyl trithiopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1,4-di (3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and the like, and aliphatic polyfunctional mercapto compounds having a heterocyclic ring.

[0665] These various mercapto compounds may be used alone or in combination of two or more.

[0666] (5) Inhibitor

[0667] From the viewpoint of controlling the shape of the cured product, the photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, it will inhibit the free radical polymerization of the lower layer of the coating film, so it is considered that the taper angle (the angle between the support and the cured product in the cross section of the cured product) can be controlled.

[0668] Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol (BHT). From the viewpoint of shape control, 2,6-di-tert-butyl-4-methylphenol is preferred. From the viewpoint of particularly excellent safety to the human body, hydroquinone monomethyl ether and methyl hydroquinone are preferred.

[0669] The polymerization inhibitor may be used alone or in combination of two or more.

[0670] When producing (C) the alkali-soluble resin or the compound (B), a polymerization inhibitor may be contained in the resin, which may be used as the polymerization inhibitor. When producing the photosensitive resin composition, a polymerization inhibitor which is the same as or different from the polymerization inhibitor in the resin may be added.

[0671] In the case where the photosensitive resin composition includes a polymerization inhibitor, the content ratio is not particularly limited, and is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, and further preferably 0.01% by mass or more, relative to the total solid content of the photosensitive resin composition. In addition, it is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and further preferably 0.1% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the polymerization inhibitor is preferably 0.0005-0.3% by mass, more preferably 0.001-0.2% by mass, and further preferably 0.01-0.1% by mass. By setting the content ratio of the polymerization inhibitor to above the above lower limit, there is a tendency to control the shape of the cured product. By setting the content ratio of the polymerization inhibitor to below the above upper limit, there is a tendency to maintain the necessary sensitivity.

[0672] <Solvent>

[0673] The photosensitive resin composition of the present invention preferably contains a solvent. By containing a solvent, the (E) colorant can be dispersed or dissolved in the solvent, and coating becomes easy.

[0674] The photosensitive resin composition of the present invention can be used in a state where (E) a colorant, (B) a compound having an ethylenically unsaturated group and a cardo structure, (C) an alkali-soluble resin, (A) a photopolymerization initiator, (D) an ethylenically unsaturated compound, (F) a dispersant, and other various materials used as needed are dissolved or dispersed in a solvent. As the solvent, an organic solvent is preferably used from the viewpoint of dispersibility and coating properties.

[0675] From the viewpoint of coating properties, it is preferred to select an organic solvent having a boiling point of 100 to 300° C., more preferably 120 to 280° C. The boiling point here means the boiling point at a pressure of 1013.25 hPa, and the same shall apply to the boiling point hereinafter.

[0676] Examples of such an organic solvent include the following.

[0677] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether and other ethylene glycol monoalkyl ethers;

[0678] Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether;

[0679] Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate and other ethylene glycol alkyl ether acetates;

[0680] Ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate and other ethylene glycol diacetates;

[0681] Alkyl acetates such as cyclohexanol acetate;

[0682] Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

[0683] Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone and methoxymethyl amyl ketone;

[0684] Monovalent or polyvalent alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0685] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0686] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

[0687] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0688] Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone and other chain or cyclic esters;

[0689] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0690] Halogenated hydrocarbons such as butyl chloride and amyl chloride;

[0691] Ether ketones such as methoxymethylpentyl ketone;

[0692] Nitriles such as acetonitrile and benzonitrile;

[0693] As commercially available organic solvents, for example, Mineral Spirit, Varsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cellosolve" is a registered trademark, the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and Diglyme (all trade names) can be used.

[0694] These organic solvents may be used alone or in combination of two or more.

[0695] When forming the partition wall by photolithography, as the organic solvent, an organic solvent having a boiling point of 100 to 240°C is preferably selected, an organic solvent having a boiling point of 120 to 200°C is more preferably selected, and an organic solvent having a boiling point of 120 to 170°C is further preferably selected.

[0696] As the organic solvent, ethylene glycol alkyl ether acetates are preferred because they have a good balance between coating properties and surface tension and because the solubility of the constituent components in the photosensitive resin composition is high.

[0697] The ethylene glycol alkyl ether acetates may be used alone or in combination of two or more.

[0698] Ethylene glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, ethylene glycol monoalkyl ethers are preferred. Propylene glycol monomethyl ether is preferred in view of the solubility of the components in the composition.

[0699] Ethylene glycol monoalkyl ethers have high polarity. If added in excessive amounts, the pigment is easily aggregated, and there is a tendency for storage stability to decrease, such as an increase in the viscosity of the photosensitive resin composition over time. Therefore, the proportion of ethylene glycol monoalkyl ethers in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.

[0700] By using an organic solvent having a boiling point of 150°C or more (hereinafter, sometimes referred to as a "high boiling point solvent") in combination, the photosensitive resin composition is not easy to dry, and on the other hand, it has the effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed due to rapid drying. Therefore, for example, by using a high boiling point solvent, it is possible to prevent the occurrence of foreign matter defects due to the precipitation / solidification of the colorant at the front end of the slit nozzle. From the perspective of such a high effect, a high boiling point solvent can be used in combination. As a high boiling point solvent used in combination, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are preferred.

[0701] When a high boiling point solvent is used in combination, the content of the high boiling point solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. By setting the ratio to above the lower limit, there is a tendency to suppress, for example, the precipitation / solidification of colorants at the front end of the slit nozzle to cause foreign matter defects. By setting the ratio to below the upper limit, the drying time of the composition can be suppressed from becoming longer, and there is a tendency to suppress problems such as poor production rhythm of the reduced pressure drying process and pre-baked hole marks.

[0702] The high boiling point solvent may be ethylene glycol alkyl ether acetates or ethylene glycol alkyl ethers. In this case, the high boiling point solvent may not be contained separately.

[0703] Preferred high boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and glycerol triacetate.

[0704] <Content ratio of each component in the photosensitive resin composition>

[0705] The content ratio of the (A) photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and further preferably 2% by mass or more, relative to the total solid content of the photosensitive resin composition of the present invention. In addition, it is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and particularly preferably 6% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the (A) photopolymerization initiator is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass, further preferably 1 to 10% by mass, further preferably 2 to 8% by mass, and particularly preferably 2 to 6% by mass. By setting the content ratio of the (A) photopolymerization initiator to the above lower limit value or more, there is a tendency to suppress the decrease in sensitivity. By setting the content ratio of the (A) photopolymerization initiator to the above upper limit value or less, there is a tendency to suppress the decrease in solubility of the unexposed portion in the developer and suppress poor development.

[0706] The content of compound (A1) is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and further preferably 2% by mass or more, relative to the total solid content of the photosensitive resin composition of the present invention. In addition, it is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and particularly preferably 6% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content of compound (A1) is preferably 0.1-15% by mass, more preferably 0.5-15% by mass, further preferably 1-10% by mass, further preferably 2-8% by mass, and particularly preferably 2-6% by mass. By setting the content of compound (A1) to above the above lower limit, there is a tendency that the current value during light emission is high. By setting the content of compound (A1) to below the above upper limit, there is a tendency that the solubility of the unexposed portion in the developer can be suppressed and poor development can be suppressed.

[0707] The content of the compound (A1) in the photopolymerization initiator (A) is not particularly limited, but is preferably 30% by mass or more, more preferably 60% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass. By setting the content of the compound (A1) to be below the upper limit, there is a tendency for the current value during light emission to be high.

[0708] When a polymerization accelerator is used together with the photopolymerization initiator (A), the content of the polymerization accelerator is not particularly limited, and is preferably 0.05% by mass or more relative to the total solid content of the photosensitive resin composition of the present invention. In addition, it is preferably 10% by mass or less, and more preferably 5% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content of the polymerization accelerator is preferably 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass. In addition, relative to 100 parts by mass of the photopolymerization initiator (A), the polymerization accelerator is preferably used in a ratio of 0.1 to 50 parts by mass, and more preferably 0.1 to 20 parts by mass. By setting the content of the polymerization accelerator to above the above lower limit, there is a tendency to suppress the decrease in sensitivity to exposure light. By setting the content of the polymerization accelerator to below the above upper limit, there is a tendency to suppress the decrease in solubility of the unexposed portion in the developer and suppress poor development.

[0709] When a sensitizing dye is used together with the (A) photopolymerization initiator, the content of the sensitizing dye is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total solid content in the photosensitive resin composition from the viewpoint of sensitivity.

[0710] (B) The content ratio of the compound having an ethylenically unsaturated group and a Cardo structure is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, relative to the total solid content of the photosensitive resin composition of the present invention. In addition, it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, (B) The content ratio of the compound having an ethylenically unsaturated group and a Cardo structure is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, further preferably 20 to 60% by mass, further preferably 30 to 60% by mass, and particularly preferably 40 to 50% by mass. By setting the content ratio of the compound having an ethylenically unsaturated group and a Cardo structure (B) to be above the above lower limit, there is a tendency to reduce the taper angle and increase the residual film rate. When the content ratio of the compound (B) having an ethylenically unsaturated group and a Cardo structure is set to be less than the above upper limit, dispersibility becomes good and there is a tendency that the generation of outgassing can be suppressed.

[0711] When the photosensitive resin composition of the present invention contains compound (B1), the content of compound (B1) is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more relative to the total solid content of the photosensitive resin composition of the present invention. In addition, it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content of compound (B1) is preferably 5-70% by mass, more preferably 10-60% by mass, further preferably 20-60% by mass, further preferably 30-60% by mass, and particularly preferably 40-50% by mass. By setting the content of compound (B1) to above the above lower limit, there is a tendency to reduce the cone angle and increase the residual film rate. By setting the content of compound (B1) to below the above upper limit, there is a tendency to improve dispersibility and suppress the generation of outgassing.

[0712] When the photosensitive resin composition of the present invention contains compound (B1), the content ratio of compound (A1) relative to 100 parts by mass of compound (B1) is not particularly limited, and is preferably 1.0 parts by mass or more, more preferably 3.0 parts by mass or more, and further preferably 5.0 parts by mass or more. In addition, it is preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less, further preferably 10.0 parts by mass or less, and particularly preferably 8.0 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio is preferably 1.0 to 20.0 parts by mass, more preferably 3.0 to 15.0 parts by mass, further preferably 3.0 to 10.0 parts by mass, and further preferably 5.0 to 8.0 parts by mass. By setting the content ratio to be above the above lower limit, there is a tendency to increase the current value during light emission. By setting the content ratio to be below the above upper limit, there is a tendency to suppress the reduction of the solubility of the unexposed portion in the developer and suppress poor development.

[0713] When the photosensitive resin composition of the present invention contains (C) an alkali-soluble resin, the content ratio of the (C) alkali-soluble resin is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, relative to the total solid content of the photosensitive resin composition of the present invention. In addition, it is preferably 85% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 55% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the (C) alkali-soluble resin is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, further preferably 30 to 60% by mass, further preferably 30 to 55% by mass, and particularly preferably 40 to 55% by mass. By setting the content of the alkali-soluble resin (C) to be above the lower limit, there is a tendency that the solubility of the unexposed portion in the developer can be suppressed and poor development can be suppressed. By setting the content of the alkali-soluble resin (C) to be below the upper limit, there is a tendency that appropriate sensitivity can be maintained, dissolution of the exposed portion by the developer can be suppressed, and the clarity and adhesion of the pattern can be suppressed from being reduced.

[0714] When the photosensitive resin composition of the present invention contains compound (B1) and (C) alkali-soluble resin, the content ratio of compound (B1) relative to the total mass of compound (B1) and the above-mentioned (C) alkali-soluble resin is not particularly limited, and is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more. In addition, it is preferably 100% by mass or less, and more preferably 90% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, further preferably 50 to 100% by mass, further preferably 60 to 100% by mass, further preferably 70 to 100% by mass, and particularly preferably 70 to 90% by mass. By setting the content ratio to the above lower limit value or more, there is a tendency to reduce the taper angle and increase the residual film rate. In addition, by setting the content ratio to the above upper limit value or less, there is a tendency that the dispersibility becomes good and the generation of outgassing can be suppressed.

[0715] In the case where the photosensitive resin composition of the present invention contains (D) ethylenically unsaturated compounds, the content ratio of (D) ethylenically unsaturated compounds is not particularly limited, and is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more relative to the total solid content of the photosensitive resin composition of the present invention. In addition, it is preferably 30% by mass or less, more preferably 25% by mass or less, and more preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of (D) ethylenically unsaturated compounds is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and more preferably 10 to 20% by mass. By setting the content ratio of (D) ethylenically unsaturated compounds to above the above lower limit, there is a tendency to maintain appropriate sensitivity, suppress dissolution of the exposed portion caused by the developer, and suppress the clarity and adhesion of the pattern. By setting the content ratio of (D) ethylenically unsaturated compounds to below the above upper limit, there is a tendency to suppress the permeability of the developer to the exposed portion and easily obtain a good image.

[0716] In the case where the photosensitive resin composition of the present invention contains compound (B1) and (D) an ethylenically unsaturated compound, the content ratio of compound (B1) relative to 100 parts by mass of the (D) ethylenically unsaturated compound is not particularly limited, and is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more. In addition, it is preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 20 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio is preferably 5 to 60 parts by mass, more preferably 5 to 40 parts by mass, further preferably 10 to 40 parts by mass, further preferably 10 to 30 parts by mass, and particularly preferably 15 to 30 parts by mass. By setting the content ratio to above the above lower limit, there is a tendency that the current value during light emission is high and the cone angle can be reduced. By setting the content ratio to below the above upper limit, there is a tendency that the solubility of the unexposed portion in the developer can be suppressed and poor development can be suppressed.

[0717] The content ratio of the (E) colorant in the photosensitive resin composition of the present invention is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably 20% by mass or more relative to the total solid content of the photosensitive resin composition. In addition, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the (E) colorant is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, further preferably 15 to 40% by mass, further preferably 15 to 30% by mass, and particularly preferably 20 to 25% by mass. By setting the content ratio of the (E) colorant to the above lower limit value or more, there is a tendency to ensure light-shielding properties. By setting the content ratio of the (E) colorant to the above upper limit value or less, there is a tendency that the current value during light emission increases and residues can be suppressed.

[0718] In the case where the photosensitive resin composition of the present invention contains an organic coloring pigment, the content ratio is not particularly limited. In the total solid content of the photosensitive resin composition, it is preferably 5% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more. In addition, it is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the organic coloring pigment is preferably 5-70% by mass, more preferably 20-70% by mass, further preferably 20-60% by mass, and particularly preferably 20-50% by mass. By setting the content ratio of the organic coloring pigment to above the above lower limit, there is a tendency that the loss of ultraviolet light required for curing can be suppressed and the light-shielding property increases. By setting the content ratio of the organic coloring pigment to below the above upper limit, there is a tendency that the current value during light emission increases and the residue can be suppressed.

[0719] When the (E) colorant contains a red pigment and / or an orange pigment, the total content ratio of the red pigment and the orange pigment is not particularly limited. In the (E) colorant, it is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more. In addition, it is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio is preferably 5-40% by mass, more preferably 8-40% by mass, further preferably 10-30% by mass, and particularly preferably 12-20% by mass. By setting the content ratio to be above the above lower limit, there is a tendency to present a hue close to black. By setting the content ratio to be below the above upper limit, there is a tendency to become highly sensitive,

[0720] In the case where the (E) colorant contains a blue pigment and / or a purple pigment, the total content of the blue pigment and the purple pigment is not particularly limited. In the (E) colorant, it is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. In addition, it is preferably 95% by mass or less, more preferably 92% by mass or less, and particularly preferably 90% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio is preferably 30 to 95% by mass, more preferably 50 to 95% by mass, further preferably 70 to 92% by mass, and particularly preferably 80 to 90% by mass. By setting the content ratio to above the above lower limit, there is a tendency for the light-shielding property to increase. By setting the content ratio to below the above upper limit, there is a tendency for the current value to increase during light emission and for the residue to be suppressed.

[0721] In the case where the photosensitive resin composition of the present invention contains a black pigment, the content ratio thereof is not particularly limited, and is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% by mass or more in the total solid content of the photosensitive resin composition. In addition, it is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the black pigment is preferably 2 to 60% by mass, more preferably 5 to 60% by mass, further preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass. By setting the content ratio of the black pigment to above the above lower limit, there is a tendency for the light-shielding property to increase. By setting the content ratio of the black pigment to below the above upper limit, there is a tendency for the current value to increase during light emission and for the residue to be suppressed.

[0722] In the case where the photosensitive resin composition of the present invention contains an organic black pigment, the content ratio is not particularly limited. In the total solid content of the photosensitive resin composition, it is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% by mass or more. In addition, it is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the organic black pigment is preferably 2 to 60% by mass, more preferably 5 to 60% by mass, further preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass. By setting the content ratio of the organic black pigment to above the above lower limit, there is a tendency for the light-shielding property to increase. By setting the content ratio of the organic black pigment to below the above upper limit, there is a tendency for the current value to increase during light emission and for the residue to be suppressed.

[0723] When the (E) colorant contains an organic black pigment, the content ratio is not particularly limited. In the (E) colorant, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more. In addition, it is preferably 100% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the organic black pigment in the (E) colorant is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, further preferably 15 to 80% by mass, and particularly preferably 20 to 70% by mass. By setting the content ratio of the organic black pigment to above the above lower limit, there is a tendency for the light-shielding property to increase. By setting the content ratio of the organic black pigment to below the above upper limit, there is a tendency for the current value to increase during light emission and for the residue to be suppressed.

[0724] In the case where (E) the colorant contains benzodifuranone black pigment fluorine, the content ratio of the above-mentioned benzodifuranone black pigment is not limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 15% by mass or more relative to the total solid content of the photosensitive resin composition. In addition, it is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the ratio is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and more preferably 15 to 30% by mass. By setting the content ratio of the benzodifuranone black pigment to above the above lower limit, there is a tendency for the light-shielding property to increase. By setting the content ratio of the benzodifuranone black pigment to below the above upper limit, there is a tendency for the current value to increase during light emission and for the residue to be suppressed.

[0725] When the (E) colorant contains carbon black as an inorganic black pigment, the content ratio is not particularly limited. In the (E) colorant, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. In addition, it is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of carbon black is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass. By setting the content ratio of carbon black to above the above lower limit, there is a tendency for the light-shielding property to increase. By setting the content ratio of carbon black to below the above upper limit, there is a tendency for the current value to increase during light emission and for the residue to be suppressed.

[0726] When the (E) colorant contains an organic coloring pigment and a black pigment, the total content ratio is not particularly limited. In the (E) colorant, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. In addition, it is preferably 100% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio is preferably 5 to 100% by mass, more preferably 10 to 70% by mass, and further preferably 15 to 50% by mass. By setting the content ratio to above the above lower limit, there is a tendency for the light-shielding property to increase. By setting the content ratio to below the above upper limit, there is a tendency for the current value to increase during light emission and for the residue to be suppressed.

[0727] When the photosensitive resin composition of the present invention contains a dispersant (F), the content of the dispersant (F) is not particularly limited, and is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more, relative to the total solid content of the photosensitive resin composition. In addition, it is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content of the dispersant (F) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, more preferably 3 to 10% by mass, and particularly preferably 3 to 7% by mass. By setting the content of the dispersant (F) to above the above lower limit, there is a tendency to easily obtain sufficient dispersibility. By setting the content of the dispersant (F) to below the above upper limit, there is a tendency that the current value during light emission increases and the residue can be suppressed.

[0728] When the photosensitive resin composition of the present invention contains a dispersant (F), the content ratio of the dispersant (F) relative to 100 parts by mass of the colorant (E) is not particularly limited, and is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more. In addition, it is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 15 to 30 parts by mass. By setting the content ratio to be above the above lower limit, there is a tendency to easily obtain sufficient dispersibility. By setting the content ratio to be below the above upper limit, there is a tendency that the current value during light emission increases and the residue can be suppressed.

[0729] In the case where the photosensitive resin composition of the present invention contains (D) an ethylenically unsaturated compound and (C) an alkali-soluble resin, the content ratio of the (C) alkali-soluble resin relative to 100 parts by mass of the (D) ethylenically unsaturated compound is not particularly limited, and is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, further preferably 250 parts by mass or more, further preferably 300 parts by mass or more, and particularly preferably 350 parts by mass or more. In addition, it is preferably 700 parts by mass or less, more preferably 500 parts by mass or less, further preferably 450 parts by mass or less, and particularly preferably 400 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio is preferably 100 to 700 parts by mass, more preferably 200 to 700 parts by mass, further preferably 250 to 500 parts by mass, further preferably 250 to 450 parts by mass, and particularly preferably 250 to 400 parts by mass. By setting the content ratio to be above the above lower limit, there is a tendency to become an appropriate dissolved development state without peeling, etc. When the content ratio is equal to or less than the above upper limit, there is a tendency that an appropriate dissolution time in a developer can be obtained.

[0730] When a close-fitting agent is used, its content is not particularly limited, but is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and further preferably 0.4 to 2% by mass relative to the total solid content of the photosensitive resin composition. By setting the content of the close-fitting agent to be above the lower limit, there is a tendency to be able to fully obtain the effect of improving close-fitting properties. By setting the content of the close-fitting agent to be below the upper limit, there is a tendency to be able to suppress the decrease in sensitivity or the tendency to cause defects due to residual residues after development.

[0731] When a surfactant is used, its content is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.005 to 1% by mass, further preferably 0.01 to 0.5% by mass, and particularly preferably 0.03 to 0.3% by mass relative to the total solid content of the photosensitive resin composition. By setting the content of the surfactant to be above the above lower limit, there is a tendency that the smoothness and uniformity of the coating film are easily displayed. By setting the content of the surfactant to be below the above upper limit, there is a tendency that the smoothness and uniformity of the coating film are easily displayed, and the deterioration of other characteristics can also be suppressed.

[0732] For the photosensitive resin composition of the present invention, by using a solvent, the content ratio of the total solid content can be adjusted to preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, for the photosensitive resin composition of the present invention, the content ratio of the total solid content can be adjusted to preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass.

[0733] <Physical properties of photosensitive resin composition>

[0734] For the photosensitive resin composition of the present invention, the optical density (OD) of the cured coating film formed using the photosensitive resin composition per 1 μm film thickness is not particularly limited, and is preferably 0.2 or more, more preferably 0.5 or more, further preferably 0.7 or more, and further preferably 0.9 or more. In addition, it is preferably 4.0 or less, more preferably 3.0 or less, further preferably 2.0 or less, and particularly preferably 1.5 or less. The above upper and lower limits can be combined arbitrarily. For example, the OD is preferably 0.2 to 4.0, more preferably 0.5 to 4.0, further preferably 0.5 to 3.0, further preferably 0.5 to 2.0, further preferably 0.7 to 2.0, and particularly preferably 0.9 to 1.5. By setting the OD to above the above lower limit, there is a tendency to obtain sufficient light-shielding properties. By setting the OD to below the above upper limit, there is a tendency to suppress the surface roughness of the electrode.

[0735] The optical density (OD) per 1 μm film thickness of the coating film can be measured using a coating film obtained by curing the photosensitive resin composition of the present invention, and can be measured using a coating film having a film thickness of about 0.5 to 1.5 μm after heat curing at 230° C. for 20 minutes.

[0736] Optical density refers to the transmitted light density expressed by the spectral sensitivity characteristics of the light receiving part in the ISO visual density in the ISO 5-3 standard. Usually, as a light source, an A light source specified by CIE (International Commission on Illumination) can be used. As a measuring instrument that can be used to measure the transmitted light density, for example, X-Rite 361T (V) of Sakata Inx Engineering Company can be cited.

[0737] <Method for producing photosensitive resin composition>

[0738] The photosensitive resin composition of the present invention can be produced by a conventional method.

[0739] The (E) colorant is preferably dispersed in advance using a paint conditioner, sand mill, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. The (E) colorant is finely divided by the dispersion treatment, and thus the coating properties of the photosensitive resin composition are improved.

[0740] The dispersion treatment is preferably carried out in a system using a combination of (E) a colorant, (F) a dispersant, and a solvent, and part or all of (C) an alkali-soluble resin (hereinafter, the composition obtained by the dispersion treatment may be referred to as a "pigment dispersion"). In particular, when a polymer dispersant is used as the (F) dispersant, the obtained pigment dispersion and photosensitive resin composition can be suppressed from increasing in viscosity over time, that is, the dispersion stability is excellent, which is preferred.

[0741] As the (E) colorant, (F) dispersant, solvent and (C) alkali-soluble resin that can be used in the pigment dispersion, the components described as the (E) colorant, (F) dispersant, solvent and (C) alkali-soluble resin that can be used in the photosensitive resin composition can be preferably used. As the content ratio of each colorant in the (E) colorant in the pigment dispersion, the ratio described as the content ratio in the photosensitive resin composition can be preferably used.

[0742] When a liquid containing all the components to be blended into the photosensitive resin composition is dispersed, the highly reactive components may be modified due to the heat generated during the dispersion treatment. Therefore, it is preferred to disperse in a system containing a polymer dispersant.

[0743] When the colorant (E) is dispersed by a sand mill, it is preferred to use glass beads or zirconium oxide beads with a particle size of about 0.1 to 8 mm. The temperature of the dispersion treatment condition is preferably 0°C to 100°C, more preferably room temperature to 80°C. As for the dispersion time, since the appropriate time is different depending on the composition of the liquid and the size of the dispersion treatment device, it can be adjusted appropriately. The dispersion index is to control the gloss of the pigment dispersion liquid in such a way that the 20-degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300. When the gloss of the photosensitive resin composition is low, the dispersion treatment is insufficient, and there are many cases where rough pigment (colorant) particles remain, and the developability, adhesion, resolution, etc. may become insufficient. If the dispersion treatment is performed until the gloss value exceeds the above range, the pigment will be broken and a large amount of ultrafine particles will be produced, so there is a tendency for the dispersion stability to be impaired.

[0744] The dispersed particle size of the pigment dispersed in the pigment dispersion is preferably 0.03 to 0.3 μm, and can be measured by a dynamic light scattering method.

[0745] Next, the pigment dispersion obtained by the above dispersion treatment is mixed with the above other components contained in the photosensitive resin composition to prepare a uniform solution or dispersion. In the manufacturing process of the photosensitive resin composition, sometimes fine dirt is mixed in the liquid, so it is desirable to filter the obtained photosensitive resin composition through a filter or the like.

[0746] [cured material]

[0747] The cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention. The cured product obtained by curing the photosensitive resin composition of the present invention can be suitably used as a partition wall.

[0748] [Next door]

[0749] The photosensitive resin composition of the present invention can be suitably used to form partition walls, in particular, partition walls for partitioning the organic layer of an organic electroluminescent element. That is, the photosensitive resin composition of the present invention itself becomes a partition wall material. As an organic layer for an organic electroluminescent element, for example, an organic layer used for a hole injection layer, a hole transport layer, or a hole transport layer on a hole injection layer as described in Japanese Patent Application Laid-Open No. 2016-165396 can be cited.

[0750] Next, the partition wall using the photosensitive resin composition of the present invention will be described according to the production method thereof.

[0751] (1) Support

[0752] As a support for forming the partition wall, its material is not particularly limited as long as it has appropriate strength. The substrate is mainly used. As the material of the substrate, for example, there can be mentioned: polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, polysulfone, etc.; thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, poly (meth) acrylic resins; various glasses. From the viewpoint of heat resistance, glass and heat-resistant resins are preferred. In addition, sometimes a transparent electrode such as ITO, IZO, or a metal electrode such as silver, gold, platinum, aluminum, and magnesium is formed on the surface of the substrate. In addition to the above-mentioned substrates, it can also be formed on a TFT array.

[0753] In order to improve surface properties such as adhesiveness, the support may be subjected to, if necessary, a corona discharge treatment, an ozone treatment, or a treatment for forming a thin film of various resins such as a silane coupling agent or a urethane resin.

[0754] The thickness of the substrate is preferably 0.05 to 10 mm, more preferably 0.1 to 7 mm. When thin film formation of various resins is performed, the film thickness is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[0755] (2) Partition wall

[0756] The photosensitive resin composition of the present invention can be used for the same purpose as the known photosensitive resin composition for color filters. When used as partition walls, a specific example of a method for forming partition walls using the photosensitive resin composition of the present invention will be described below.

[0757] The photosensitive resin composition is supplied to the substrate on which the partition wall is formed in a film or pattern by a coating method or the like, and the solvent is dried. Then, the pattern is formed by a method such as a photolithography method for exposure-development. Then, additional exposure and thermal curing treatment are performed as needed to form the partition wall on the substrate.

[0758] [1] Supply method to substrate

[0759] The photosensitive resin composition of the present invention is preferably supplied to the substrate in a state of being dissolved or dispersed in a solvent. As a supply method, it can be carried out by a conventionally known method, such as a spin coating method, a wire rod method, a flow coating method, a die coating method, a roller coating method, and a spray coating method. In addition, for example, it can be supplied in a pattern by an inkjet method or a printing method. According to the die coating method, the amount of coating liquid can be greatly reduced, and there is no influence of mist attached when using the spin coating method, etc., and the generation of foreign matter can be suppressed, etc., which is preferred from such a comprehensive point of view.

[0760] The coating amount varies depending on the application. For example, in the case of the partition wall, the coating is preferably performed in a manner of 0.5 to 10 μm in dry film thickness, more preferably 1 to 9 μm, and particularly preferably 1 to 7 μm. It is important that the dry film thickness or the height of the partition wall finally formed is uniform over the entire area of ​​the substrate. By reducing the deviation, the light-emitting layer can be uniformly produced, and poor display during light emission can be suppressed.

[0761] When partitions having different heights are formed at once by photolithography using the photosensitive resin composition of the present invention, the heights of the partitions finally formed become different.

[0762] As the substrate, a known substrate such as a glass substrate or an array substrate can be used. The substrate surface is preferably a flat surface.

[0763] [2] Drying method

[0764] After the photosensitive resin composition is supplied onto the substrate, it is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. A reduced pressure drying method in which the composition is dried in a reduced pressure chamber without increasing the temperature may also be used in combination.

[0765] The drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, etc. The drying temperature and drying time are preferably selected within the range of 40 to 130° C. and 15 seconds to 5 minutes, and more preferably within the range of 50 to 110° C. and 30 seconds to 3 minutes, depending on the type of solvent component, the performance of the dryer used, etc.

[0766] [3] Exposure method

[0767] For exposure, a negative mask pattern is superimposed on the coating film of the photosensitive resin composition, and a light source of ultraviolet light or visible light is irradiated through the mask pattern. When exposure is performed using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive resin composition or a method of placing the exposure mask at a position away from the coating film of the photosensitive resin composition and projecting the exposure light through the exposure mask can be used. A scanning exposure method using a laser without using a mask pattern can also be used. If necessary, in order to prevent the sensitivity of the photosensitive resin layer from being reduced due to oxygen, exposure can be performed in a deoxygenated atmosphere, or after an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photosensitive resin layer.

[0768] As a preferred embodiment of the present invention, when forming partition walls of different heights simultaneously by photolithography, for example, an exposure mask having a light shielding portion (transmittance 0%) and a plurality of openings having a lower average transmittance (intermediate transmission openings) than an opening having the highest average transmittance (complete transmission openings) is used. By this method, a difference in residual film rate can be generated by the difference in average transmittance between the intermediate transmission openings and the complete transmission openings, that is, the difference in exposure amount.

[0769] For the intermediate transmission opening, there is a known method of producing it by a matrix-shaped light shielding pattern having minute polygonal light shielding units, or a known method of producing it by controlling the light transmittance by using a film of chromium, molybdenum, tungsten, or silicon as an absorber.

[0770] The light source used for exposure is not particularly limited. Examples of the light source include: lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. When used by irradiating light of a specific wavelength, a filter may also be used.

[0771] The filter may be of a type that can control the transmittance at the exposure wavelength by a thin film, and the material in this case may include, for example, Cr compounds (Cr oxides, nitrides, oxynitrides, fluorides, etc.), MoSi, Si, W, and Al.

[0772] The exposure dose is not particularly limited, but is preferably 1 mJ / cm 2 More preferably, 5 mJ / cm 2 More preferably, 10 mJ / cm 2 In addition, it is preferably 300mJ / cm 2 Less than, more preferably 200mJ / cm 2 Below, more preferably 150mJ / cm 2 the following.

[0773] In the case of the proximity exposure method, the distance between the exposure object and the mask pattern is not particularly limited, but is preferably 10 μm or more, more preferably 50 μm or more, and further preferably 75 μm or more. Also, it is preferably 500 μm or less, more preferably 400 μm or less, and further preferably 300 μm or less.

[0774] [4] Development method

[0775] After the exposure, an image pattern may be formed on the substrate by development using an aqueous solution of a basic compound or an organic solvent. The aqueous solution of the basic compound may further contain a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.

[0776] As the alkaline compound, for example, inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic alkaline compounds such as mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline can be mentioned. These alkaline compounds can be used alone or in combination of two or more.

[0777] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates; and amphoteric surfactants such as alkyl betaines and amino acids.

[0778] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more. In addition, the organic solvent may be used in combination with water or an aqueous solution of an alkaline compound.

[0779] The conditions for the development treatment are not particularly limited, but the development temperature is preferably 10 to 50° C., more preferably 15 to 45° C., and further preferably 20 to 40° C. The development method may include, for example, immersion development, spray development, brush development, and ultrasonic development.

[0780] [5] Additional exposure and thermal curing treatment

[0781] If necessary, the developed substrate can be exposed again by the same method as the above exposure method. After development or additional exposure, a thermal curing treatment (also called firing) can be performed. The thermal curing treatment conditions are preferably 100 to 280°C, more preferably 150 to 250°C, and the time is 5 to 60 minutes.

[0782] When the cured product of the photosensitive resin composition of the present invention is used as a partition wall, its size and shape can be appropriately adjusted according to the specifications of the organic electroluminescent element to which the cured product is applied. The height of the partition wall formed by the photosensitive resin composition of the present invention is preferably about 0.5 to 10 μm.

[0783] From the viewpoint of light-shielding properties, the optical density (OD) per 1 μm of the partition wall of the present invention is preferably 0.7 or more, more preferably 1.2 or more, further preferably 1.5 or more, and particularly preferably 1.8 or more. In addition, it is preferably 4.0 or less, and more preferably 3.0 or less. The above upper and lower limits can be combined arbitrarily. For example, the OD is preferably 0.7 to 4.0, more preferably 1.2 to 4.0, further preferably 1.5 to 3.0, and particularly preferably 1.8 to 3.0. Here, the optical density (OD) is a value measured by the method described later.

[0784] The shape of the partition wall preferably has a small taper angle. Figure 1 Thus, in the partition wall cross section, the angle formed by the support body 10 surface and the partition wall 20 is .

[0785] As described later, the organic electroluminescent element is provided with a hole transport layer, a light-emitting layer, an electron transport layer, and a metal or transparent cathode on an anode substrate provided with a partition wall. However, if the cone angle is too large, disconnection or increased resistance may occur when the metal or transparent cathode is provided, resulting in poor display.

[0786] The taper angle is preferably 10 degrees or more, and is preferably 70 degrees or less, more preferably 60 degrees or less, further preferably 50 degrees or less, and particularly preferably 45 degrees or less.

[0787] In the manufacture of the partition wall, the ratio of the film thickness after firing to the film thickness after coating / drying (film thickness after firing / film thickness after coating and drying) is preferably high. If the ratio is high, it is not easily affected by development and firing, so it has the advantage of being easy to manufacture a partition wall of a certain film thickness. The ratio of the film thickness after firing to the film thickness after coating and drying is preferably 0.80 or more, more preferably 0.85 or more. That is, the residual film rate described later is preferably 80% or more, more preferably 85% or more.

[0788] [Organic electroluminescent element]

[0789] The organic electroluminescent element of the present invention comprises a cured product, for example, a partition wall, formed from the photosensitive resin composition of the present invention.

[0790] For example, various organic electroluminescent elements can be manufactured using a substrate having a partition wall pattern manufactured by the above method. The method for forming the organic electroluminescent element is not particularly limited, and it is preferred that after forming a partition wall pattern on a substrate by the above method, an organic layer such as a pixel is formed by a wet process such as a vapor deposition method, a casting method, a spin coating method, or an inkjet printing method, thereby manufacturing the organic electroluminescent element. The above vapor deposition method is a method of sublimating a functional material in a vacuum state and attaching it to a region surrounded by a partition wall on a substrate to form a film.

[0791] Examples of the types of organic electroluminescent elements include a bottom emission type and a top emission type.

[0792] In the bottom emission type, for example, partition walls are formed on a glass substrate laminated with a transparent electrode, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition walls.

[0793] In the top emission type, for example, partition walls are formed on a glass substrate having a metal electrode layer stacked as a reflective layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in the opening surrounded by the partition walls.

[0794] Examples of the light-emitting layer include organic electroluminescent layers described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. In addition, quantum dots described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

[0795] The layer structure is not limited thereto. For example, from the viewpoint of luminous efficiency, each of the hole transport layer and the electron transport layer may be a stacked structure including two or more layers. The thickness of each layer is not particularly limited, but is preferably 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

[0796] The organic electroluminescent element can form RGB colors for each opening, or can stack two or more colors in one opening. From the perspective of improving reliability, the organic electroluminescent element can have a sealing layer. The sealing layer has the function of preventing moisture in the air from being adsorbed on the organic electroluminescent element and reducing the luminous efficiency. From the perspective of improving light extraction efficiency, the organic electroluminescent element can have a low-reflection film at the interface with the air. By configuring the low-reflection film at the interface between the air and the element, it can be expected to reduce the difference in refractive index and suppress reflection at the interface. Such a low-reflection film can be applied to the technology of moth-eye structure and super multilayer film, for example.

[0797] When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light from a light-emitting layer of a certain pixel from leaking to other pixels. In addition, when an electrode or the like is made of metal, it is necessary to prevent degradation of image quality due to reflection of external light. Therefore, it is preferred to impart light-shielding properties to the partition wall constituting the organic electroluminescent element.

[0798] In an organic electroluminescent element, it is necessary to provide electrodes on the upper and lower surfaces of the partition wall, so from the viewpoint of insulation, the partition wall is preferably high-resistance and low-dielectric constant. Therefore, when (E) a colorant is used in order to provide light-shielding properties to the partition wall, it is preferred to use the above-mentioned organic pigment with high resistance and low dielectric constant.

[0799] [Color Filters]

[0800] The color filter of the present invention comprises a cured product, such as partition walls, formed from the photosensitive resin composition of the present invention. The color filter of the present invention includes, for example, a color filter containing light-emitting nanocrystals.

[0801] The luminescent nanocrystals are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and are crystals having a maximum particle size of 100 nm or less as measured by, for example, a transmission electron microscope or a scanning electron microscope.

[0802] Luminescent nanocrystals can emit light of a different wavelength from the absorbed wavelength by absorbing light of a given wavelength (fluorescence or phosphorescence). For example, red luminescent nanocrystals emit light (red light) with a peak luminescence wavelength in the range of 605 to 665 nm. In addition, for example, green luminescent nanocrystals emit light (green light) with a peak luminescence wavelength in the range of 500 to 560 nm. Examples of luminescent nanocrystals include quantum dots and the like.

[0803] The method for manufacturing the color filter containing luminescent nanocrystal particles is not particularly limited, and the following method can be cited: preparing a substrate having the partition wall of the present invention, and forming a layer containing luminescent nanocrystal particles in the area divided by the partition wall. The method for forming the layer containing luminescent nanocrystal particles is not particularly limited, and for example, the method can be manufactured by the following method: selectively attaching an ink composition containing luminescent nanocrystal particles by inkjet method, and curing the ink composition by irradiation or heating with active energy rays.

[0804] [Image display device]

[0805] Examples of the image display device of the present invention include an organic EL display device having partition walls made of the cured product of the present invention and an organic electroluminescent element.

[0806] As long as the organic EL display device includes the above-mentioned organic electroluminescent element, there is no particular limitation on the style and structure of the image display device. For example, an organic electroluminescent element of active drive type can be used to assemble according to a conventional method. For example, it can be formed by the method described in "Organic EL Display" (OHM Co., Ltd., published on August 20, 2001, written by Shizuo Tokito, Chiba Ya Andachi, and Hideyuki Murata). For example, an organic electroluminescent element emitting white light can be combined with a color filter to display an image, or an organic electroluminescent element with different luminescent colors such as RGB can be combined to display an image.

[0807] Example

[0808] The present invention will be described in more detail below with reference to Examples and Comparative Examples. The present invention is not limited to the following Examples unless it exceeds the gist of the present invention.

[0809] The constituent components of the photosensitive resin compositions used in the following Examples and Comparative Examples and their evaluation methods are as follows.

[0810] <Compound I>

[0811] KISCO KBR-201

[0812] Resin with fluorene bisphenol skeleton

[0813] Weight average molecular weight: 3500

[0814] Acid value: 100mgKOH / g

[0815] Compound-I corresponds to compound (B1).

[0816] <Alkali-soluble resin-I>

[0817] 300 parts by mass of "XD1000" (polyglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent 252) manufactured by Nippon Kayaku Co., Ltd., 87 parts by mass of acrylic acid, 0.2 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine, and 255 parts by mass of propylene glycol monomethyl ether acetate were added to a reaction vessel, and stirred at 100° C. until the acid value reached 3.0 mg-KOH / g. Subsequently, 145 parts by mass of tetrahydrophthalic anhydride was further added, and the mixture was reacted at 120° C. for 4 hours to obtain an alkali-soluble resin-I having a solid content of 50% by mass, an acid value of 106 mg-KOH / g, and a polystyrene-equivalent weight average molecular weight (Mw) of 2600 as measured by GPC.

[0818] <Pigment-I>

[0819] Irgaphor (registered trademark) Black S 0100 CF manufactured by BASF (having a chemical structure represented by the following formula (E2))

[0820] [Chemical formula 35]

[0821]

[0822] <Dispersant-I>

[0823] BYK-LPN-21116 manufactured by BYK-Chemie

[0824] <Solvent-I>

[0825] PGMEA: Propylene glycol monomethyl ether acetate

[0826] <Solvent-II>

[0827] MB: 3-methoxy-1-butanol

[0828] <Photopolymerization Initiator-I>

[0829] The oxime ester photopolymerization initiator has the following chemical structure: Photopolymerization initiator-I corresponds to compound (A1).

[0830] [Chemical formula 36]

[0831]

[0832] <Photopolymerization Initiator-II>

[0833] Oxime ester photopolymerization initiator having the following chemical structure

[0834] [Chemical formula 37]

[0835]

[0836] <Photopolymerization Initiator-III>

[0837] Oxime ester photopolymerization initiator having the following chemical structure

[0838] [Chemical formula 38]

[0839]

[0840] <Photopolymerization Initiator-IV>

[0841] Oxime ester photopolymerization initiator having the following chemical structure

[0842] [Chemical formula 39]

[0843]

[0844] <Photopolymerization Initiator-V>

[0845] Oxime ester photopolymerization initiator having the following chemical structure

[0846] [Chemical formula 40]

[0847]

[0848] <Ethylenically unsaturated compounds-I>

[0849] DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

[0850] <Surfactant-I>

[0851] DIC Corporation MEGAFAC F-559

[0852] <Measurement of optical density per unit film thickness (unit OD value)>

[0853] The optical density per unit film thickness is measured by the following procedure.

[0854] First, the prepared photosensitive resin composition was applied to a glass substrate by a spin coater so that the film thickness after heat curing (firing) reached 1.5 μm, and then dried under reduced pressure for 1 minute. Then, it was dried at 100° C. for 100 seconds on a hot plate to obtain a coating film. The obtained coating film was exposed without using an exposure mask. As the irradiation light source, a mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used to make the exposure amount 80 mJ / cm 2 The exposure was performed for 20 seconds. The illumination was 500mW / cm 2 The slit width was 1.6 mm. Then, the resist-coated substrate 1 was obtained by heat curing at 230° C. for 30 minutes in an oven.

[0855] The optical density (OD value) of the obtained resist-coated substrate 1 was measured using a 361T(V) transmission densitometer manufactured by X-Rite (color temperature of the illumination light source: about 2850K (equivalent to CIE standard light source A), spectral sensitivity characteristics of the light receiving part: ISO visual density in the ISO 5-3 standard). In addition, the film thickness was measured using the non-contact surface / layer cross-sectional shape measurement system VertScan(R)2.0 manufactured by Ryoka Systems Co., Ltd.

[0856] The optical density (unit OD value) per unit film thickness (1 μm) was calculated from the measured values ​​of the optical density (OD value) and the film thickness.

[0857] The OD value is a numerical value indicating light-shielding ability, and a larger value indicates higher light-shielding ability.

[0858] <Preparation of substrate for evaluation of residual film ratio and taper angle>

[0859] First, the prepared photosensitive resin composition was applied to a substrate having an ITO electrode by a spin coater so that the film thickness after heat curing (firing) reached about 1.5 μm, and after 1 minute of reduced pressure drying, it was dried at 100°C for 100 seconds on a hot plate. The film thickness T1 after drying was measured. Next, the obtained coated substrate was exposed using a photomask. A mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used to achieve an exposure amount of 80 mJ / cm 2 The exposure was performed for 20 seconds. The illumination was 500mW / cm 2 The slit width was 1.6 mm. A mask having a grid-like opening (having a 50 μm square-shaped cover portion, and a plurality of such cover portions sandwiching a 50 μm wide exposure portion) was used as the photomask.

[0860] Next, a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution was used as a developer, and spray bath development was performed at a developer pressure of 0.05 MPa at 25° C. for 60 to 120 seconds, and then the developer was rinsed with pure water to stop the development. Then, the film was washed with a water spray for 60 seconds. The spray bath development time was set to 1.6 times the time it took for the unexposed part of the coating film to be dissolved and removed.

[0861] Through these operations, the opening portion was developed and removed, and an electrode substrate with a partition wall patterned was obtained. The substrate with the pattern was heated (fired) at 230°C for 30 minutes in an oven to cure the pattern and obtain an evaluation substrate. The film thickness T2 (μm) after heating and curing (firing) was measured.

[0862] <Calculation of residual film rate>

[0863] The film thickness T1 after hot plate drying and the film thickness T2 of the partition walls of the evaluation substrate were measured, and the residual film ratio was calculated by the following calculation formula.

[0864] Residual film rate (%) = T2 / T1×100

[0865] The higher the residual film rate, the more preferred it is.

[0866] <Measurement of cone angle>

[0867] The cross-sectional shape of the partition wall of the evaluation substrate was observed at 10,000 times magnification using a scanning electron microscope (SEM), and the angle between the substrate and the partition wall was measured as the taper angle. The smaller the taper angle, the more preferable.

[0868] A: Cone angle less than 50 degrees

[0869] B: The cone angle exceeds 50 degrees.

[0870] <Preparation of electrode substrate for evaluation of light-emitting characteristics>

[0871] The substrate was used by depositing an indium tin oxide (ITO) transparent conductive film on glass to a thickness of 70 nm, and forming an anode by conventional photolithography and hydrochloric acid etching. Each photosensitive resin composition was applied to the anode of the substrate by a spin coater so that the film thickness after firing was 1.5 μm, and after drying under reduced pressure for 1 minute, it was dried at 100° C. for 100 seconds on a hot plate to obtain a coating film.

[0872] Next, the obtained coating film was exposed using a photomask. A mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used to expose the film at an exposure dose of 80 mJ / cm 2 The exposure was performed for 20 seconds. The illumination was 500 mW / cm 2 The slit width was 1.6 mm. A mask having a lattice-shaped opening (having a rectangular cover portion of 40 μm in length and 80 μm in width, with a plurality of such cover portions sandwiching 20 μm wide exposure portions in the major and minor axis directions) was used.

[0873] Next, a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution was used as a developer, and spray development was performed at 25° C. for 60 to 120 seconds at a developer water pressure of 0.05 MPa, and then the developer was rinsed with pure water to stop the development, and then washed with a water washing spray for 60 seconds. The spray development time was set to 1.2 times the time it takes for the unexposed portion of the coating film to be dissolved and removed.

[0874] The openings were developed and removed by these operations, and the resulting substrate was heated (baked) in an oven at 230° C. for 30 minutes to cure the pattern, thereby producing an electrode substrate having patterned partition walls.

[0875] <Fabrication of equipment for evaluating organic electroluminescent elements>

[0876] On the entire surface of the electrode substrate formed by patterning the partition walls, a 10nm thick molybdenum oxide as a hole injection layer, a 60nm thick N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-9H-fluorene-2-amine as a hole transport layer, a 60nm thick tri(8-hydroxyquinoline)aluminum as a light-emitting layer, a 1nm thick 8-hydroxyquinoline lithium as an electron injection layer, and a 80nm thick aluminum as a cathode were sequentially stacked by vacuum evaporation to produce an organic electroluminescent element.

[0877] Next, a desiccant was attached to the concave portion of the sealing glass having a concave portion at the center, and a UV curing resin was applied to the frame portion around the concave portion. The sealing glass was arranged so that the concave portion of the sealing glass covered the entire organic electroluminescent element on the electrode substrate, and the sealing glass was attached to the electrode substrate. The UV curing resin was irradiated with UV to cure it, and the hollow structure was sealed, thereby manufacturing an organic electroluminescent element evaluation device.

[0878] <Evaluation of light-emitting properties of organic electroluminescent elements>

[0879] A direct current was passed through the produced device for evaluating the organic electroluminescent element, and the current density was measured when the driving voltage was 4 V. The higher the current density, the more preferable it is.

[0880] A: Current density 0.018mA / cm 2 above

[0881] B: Current density 0.010mA / cm 2 Above and less than 0.018mA / cm 2

[0882] C: Current density is less than 0.010mA / cm 2

[0883] <Preparation of Pigment Dispersion Liquid-1>

[0884] The pigment, dispersant, alkali-soluble resin and solvent described in Table 1 were mixed in a mass ratio as described in Table 1. The mixed solution was dispersed for 3 hours at 25 to 45° C. using a paint shaker. Zirconia beads of 0.5 mm φ were used as beads, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads were separated from the dispersion by a filter to prepare a pigment dispersion-1.

[0885] In addition, the amount of the solvent in Table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.

[0886] [Table 1]

[0887]

[0888]

[0889] [Example 1, Comparative Examples 1 to 4]

[0890] Each component was added so that the solid content of each component in the total solid content had the value shown in Table 2, and a solvent was further added so that PGMEA / MB=80 / 20 and the content of the total solid content was 17% by mass, and the mixture was stirred and dissolved to prepare photosensitive resin compositions of Example 1 and Comparative Examples 1 to 4, respectively.

[0891] The optical density per unit film thickness, the residual film ratio, the taper angle, and the light emission characteristics (current density) were evaluated using each photosensitive resin composition.

[0892] [Table 2]

[0893]

[0894]

[0895] Example 1 has a tendency to have a high current density during light emission. It can be inferred that this is because the photopolymerization initiator-I as compound (A1) has an ester bond in addition to the oxime moiety, and has a strong affinity with compound (B) (compound-I), so side reaction products, etc. are not easily released from the film during development or firing. In addition, Example 1 has a tendency to have a small cone angle. It can be inferred that this is because it contains compound (B), so melt flow is likely to occur during firing, thereby reducing the cone angle. In addition, Example 1 has a tendency to have a high residual film rate, which can be inferred that this is due to the small thermal shrinkage of compound (B).

[0896] On the other hand, the current density tends to be low in Comparative Examples 1 to 4. This is presumably because photopolymerization initiators II to V have no ester bond other than the oxime moiety and have low affinity for compound (B), and are therefore released outside the film during development and baking and remain on the anode.

[0897] Although the present invention has been described in detail using specific embodiments, it will be apparent to one skilled in the art that various modifications can be made therein without departing from the spirit and scope of the present invention.

[0898] This application is based on Japanese patent application 2022-093916 filed on June 9, 2022, the entire contents of which are incorporated by reference.

Claims

1. A photosensitive resin composition comprising (A) a photopolymerization initiator, and (B) a compound having an ethylenically unsaturated group and a cardo structure, wherein: The (A) photopolymerization initiator comprises a compound (A1) represented by the following general formula (1): The weight average molecular weight of the compound (B) having an ethylenically unsaturated group and a cardo structure is 1,000 to 20,000, In formula (1), X represents an aryl group having 6 to 10 carbon atoms, R 1 represents an alkyl group having 1 to 8 carbon atoms which may have a substituent or an aryl group having 6 to 10 carbon atoms which may have a substituent, R 2 represents an alkanoyl group having 2 to 6 carbon atoms or an aroyl group having 7 to 13 carbon atoms, R 3 represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, R 4 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, Z represents -(C=O)-O- or -O-(C=O)-, n represents an integer of 1 or 2.

2. The photosensitive resin composition according to claim 1, wherein The compound (B) having an ethylenically unsaturated group and a cardo structure is a compound (B1) further containing a carboxyl group.

3. The photosensitive colored resin composition according to claim 2, wherein The acid value of the compound (B1) is 20 to 150 mgKOH / g. The photosensitive resin composition according to claim 1 , further comprising (C) an alkali-soluble resin.

5. The photosensitive resin composition according to claim 4, wherein The compound (B1) is contained in an amount of 50% by mass or more based on the total mass of the compound (B1) and the (C) alkali-soluble resin.

6. The photosensitive resin composition according to claim 2, wherein When the content of the compound (B1) is 100 parts by mass, 3.0 parts by mass or more of the compound (A1) is contained.

7. The photosensitive resin composition according to claim 2, wherein The compound (B1) has a partial structure represented by the following general formula (B1-1), The benzene ring in formula (B1-1) may be further substituted by any substituent. X b Indicates O, S, CO or direct bonding, * indicates the bonding position.

8. The photosensitive resin composition according to claim 7, wherein The compound (B1) has a partial structure represented by the following general formula (B1-2), The benzene ring in formula (B1-2) may be further substituted by any substituent. R 1b each independently represents a hydrogen atom or a methyl group, X b Each independently represents O, S, CO or a direct bond, nb represents an integer from 0 to 4, * indicates the bonding position. 9 . The photosensitive resin composition according to claim 1 , further comprising (D) an ethylenically unsaturated compound, wherein the (D) ethylenically unsaturated compound is different from the (B) compound having an ethylenically unsaturated group and a Cardo structure. 10 . The photosensitive resin composition according to claim 1 , further comprising (E) a coloring agent.

11. The photosensitive resin composition according to claim 10, wherein The (E) colorant contains a benzodifuranone-based black pigment.

12. The photosensitive resin composition according to claim 11, wherein The benzodifuranone-based black pigment is contained in an amount of 5% by mass or more and 25% by mass or less based on the total solid content of the photosensitive resin composition.

13. The photosensitive resin composition according to claim 1, wherein The optical density of the cured coating film per 1 μm of film thickness is 0.5 or more. 14 . The photosensitive resin composition according to claim 1 , which is a photosensitive resin composition for partition formation. 15 . A cured product obtained by curing the photosensitive resin composition according to claim 1 . 16 . A partition wall formed of the cured product according to claim 15 .

17. An organic electroluminescent element comprising the partition wall according to claim 16. 18 . A color filter including luminescent nanocrystals, comprising the partition wall according to claim 16 . 19 . An image display device comprising the partition wall according to claim 16 .

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