Photosensitive resin composition, cured product, and image display device

Abstract

Provided is a photosensitive resin composition capable of forming a high refractive index cured product, and having excellent hole resolution. This photosensitive resin composition is characterized by containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali soluble resin, the (A) ethylenically unsaturated compound containing an ethylenically unsaturated compound (A1) having, in each molecule, one to three ethylenically unsaturated bonds and one to three sulfur-containing aromatic heterocycles, and the (C) alkali soluble resin containing an epoxy (meth)acrylate resin (C1) having an aromatic ring in the main chain.

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a cured product, and an image display device. This application claims priority based on Japanese Patent Application No. 2022-048750, filed on March 24, 2022, the contents of which are incorporated herein by reference. [Background technology]

[0002] Organic EL (Electro Luminescence) elements are self-luminous elements that utilize the principle that fluorescent materials emit light due to the recombination energy between holes injected from the anode and electrons injected from the cathode when an electric field is applied. Organic EL elements have been actively researched and developed in recent years for use in lighting devices and display devices.

[0003] For example, organic EL display devices have advantages in terms of visibility and viewing angle compared to conventional CRTs and LCDs, and also have excellent features such as light weight, thin layer and flexibility. However, the refractive index of the organic layer including the light-emitting layer is generally 1.6 to 2.1, which is higher than that of air. Therefore, total reflection or interference of the emitted light is likely to occur at the interface, and the light extraction efficiency is less than 20%, resulting in a loss of most of the light.

[0004] The basic structure of an organic EL device is a structure in which a light-transmitting electrode, at least one organic layer including a light-emitting layer, and a back electrode are sequentially laminated on a light-transmitting substrate. In an active-matrix organic EL device, for example, a TFT substrate on which a plurality of pixel electrodes constituting the back electrode and TFTs (thin film transistors) serving as switching elements thereof are formed in a matrix is ​​laminated on the organic layer.

[0005] The light emitted from the organic layer is reflected directly or by a back electrode made of aluminum or the like, and is emitted from the light-transmitting substrate. At that time, it is preferable that the generated light is efficiently extracted to the light-transmitting substrate side. However, depending on the angle of incidence at the interface of adjacent layers with different refractive indices, the light is totally reflected, and becomes guided light that travels inside the element while being totally reflected in the surface direction, and is absorbed and attenuated inside, making it impossible to extract to the outside.

[0006] As a method for improving the light extraction efficiency, for example, Patent Document 1 describes an organic electroluminescent device in which a high refractive index layer and a nanoporous layer are combined to improve the light extraction efficiency.

[0007] Photosensitive compositions having a high refractive index have been studied not only for organic EL display devices, but also for liquid crystal display applications. For example, Patent Document 2 describes a photosensitive composition with high refractive index and high adhesion, which uses oxide particles such as titanium oxide and a specific fluorene skeleton-containing compound. Patent Document 3 describes a composition for optical materials, which uses a specific compound. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2006-12826 [Patent Document 2] Japanese Patent Application Publication No. 2014-91790 [Patent Document 3] Japanese Patent Application Publication No. 2021-24842 Summary of the Invention [Problem to be solved by the invention]

[0009] By incorporating high refractive index metal oxide particles, such as TiO2 or ZrO2, into a photosensitive resin composition, a cured product with a high refractive index can be obtained. However, due to the high dielectric constant derived from the metal oxide particles, when a planarizing film or microlens formed from the cured product is disposed between the TFT and pixel electrode for the purpose of improving light extraction efficiency, problems such as signal delay and heat loss due to dielectric loss may occur. In recent years, it has become preferable to reduce or eliminate the amount of metal oxide particles. As a result of the present inventors' investigations, it was found that the photosensitive composition containing the fluorene skeleton-containing compound described in Patent Document 2 has a low refractive index and insufficient hole resolution. In addition, it was found that the compound described in Patent Document 3 has a problem with the refractive index and insufficient hole resolution when combined with a specific alkali-soluble resin.

[0010] Therefore, an object of the present invention is to provide a photosensitive resin composition which can form a cured product having a high refractive index and excellent hole resolution. Another object of the present invention is to provide a cured product obtained by curing the photosensitive resin composition of the present invention, and an image display device comprising the cured product of the present invention. [Means for solving the problem]

[0011] As a result of extensive investigations, the present inventors have found that the above problems can be solved by using a specific ethylenically unsaturated compound and an alkali-soluble resin, and have thus completed the present invention. That is, the gist of the present invention is as follows.

[0012] [1] A photosensitive resin composition comprising (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, the (A) ethylenically unsaturated compound contains an ethylenically unsaturated compound (A1) having 1 to 3 ethylenically unsaturated bonds and 1 to 3 sulfur-containing aromatic heterocycles in the molecule, 1. A photosensitive resin composition, wherein the alkali-soluble resin (C) contains an epoxy (meth)acrylate resin (C1) having an aromatic ring in its main chain. [2] The photosensitive resin composition according to [2], wherein the ethylenically unsaturated compound (A1) is a compound represented by the following general formula (A1-1):

[0013] [ka]

[0014] (In formula (A1-1), R 1 represents a hydrogen atom or a methyl group. Cy represents a sulfur-containing aromatic heterocycle. Q 1 and Q 2 Each of X independently represents an alkylene group having 1 to 6 carbon atoms. 1 and X 2 each independently represents -O-, -S-, or -NR 2 -, -NR 2 -(C=O)- or -NR 2 -(C=O)-O-. Z 1 and Z 2 Each of m and n independently represents an integer of 1 to 3. Each of p and q independently represents an integer of 0 to 3. R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. [3] The photosensitive resin composition according to [1] or [2], wherein the content of the ethylenically unsaturated compound (A1) is 20 mass % or more based on the total solid content of the photosensitive resin composition. [4] (C) The photosensitive resin composition according to any one of [1] to [3], wherein the content ratio of the ethylenically unsaturated compound (A1) per 100 parts by mass of the alkali-soluble resin is 120 parts by mass or less. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the epoxy (meth)acrylate resin (C1) having an aromatic ring in the main chain has a partial structure represented by the following general formula (i):

[0015] [ka]

[0016] (In formula (i), R aR represents a hydrogen atom or a methyl group. b represents a divalent hydrocarbon group which may have a substituent. k represents 1 or 2. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the photosensitive resin composition is cured to produce a cured film having a refractive index of 1.620 or more at a wavelength of 633 nm. [7] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [6]. [8] An image display device comprising the cured product according to [7]. Effect of the Invention

[0017] According to the present invention, it is possible to provide a photosensitive resin composition which can form a cured product having a high refractive index and excellent hole resolution. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be described in detail below. Note that the following description is an example of an embodiment of the present invention, and the present invention is not limited to these unless it goes beyond the gist of the present invention. In the present invention, "(meth)acrylic" means "either one or both of acrylic and methacrylic". The term "total solids" refers to all components in the photosensitive resin composition other than the solvent. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solids. In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​before and after "to" as the lower and upper limits. In the present invention, the term "(co)polymer" refers to both a homopolymer and a copolymer, and the terms "(acid) anhydride" and "(anhydride)...acid" refer to both an acid and its anhydride. In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography). In the present invention, the acid value means an acid value calculated based on an effective solid content unless otherwise specified, and is calculated by neutralization titration.

[0019] [1] Photosensitive resin composition The photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, and may further contain other components as necessary, such as metal oxides, colorants, and solvents.

[0020] [1-1] Components and composition of photosensitive resin composition The components constituting the photosensitive resin composition of the present invention and the composition thereof will be described in order.

[0021] [1-1-1] Component (A): Ethylenically unsaturated compound The photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound. By containing (A) an ethylenically unsaturated compound, the curability of the coating film is improved. The photosensitive resin composition of the present invention contains an ethylenically unsaturated compound (A) having 1 to 3 ethylenically unsaturated bonds and 1 to 3 sulfur-containing aromatic heterocycles in the molecule (A1) (hereinafter, may be simply referred to as ethylenically unsaturated compound (A1)).

[0022] <Ethylenically unsaturated compound (A1)> The ethylenically unsaturated compound (A1) has 1 to 3 ethylenically unsaturated bonds and 1 to 3 sulfur-containing aromatic heterocycles in the molecule. By containing the ethylenically unsaturated compound (A1), the electron density and polarizability derived from the sulfur atom and aromatic ring are increased, and thus a high refractive index can be imparted to the cured product.

[0023] The number of 1 to 3 ethylenically unsaturated bonds in the molecule of the ethylenically unsaturated compound (A1) is preferably 2 to 3 from the viewpoint of curability. The number of 1 to 3 sulfur-containing aromatic heterocycles in the molecule of the ethylenically unsaturated compound (A1) is preferably 2 from the viewpoint of increasing the refractive index and ensuring solubility. From the viewpoint of curability, increasing the refractive index and ensuring solubility, it is more preferable that the ethylenically unsaturated compound (A1) has 2 ethylenically unsaturated bonds and 2 sulfur-containing aromatic heterocycles.

[0024] The sulfur-containing aromatic heterocycle has at least one sulfur atom as a heteroatom constituting the aromatic heterocycle. In addition to the sulfur atom, the heteroatom may have an oxygen atom, a nitrogen atom, or an oxygen atom and a nitrogen atom. The number of sulfur atoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3 from the viewpoint of avoiding coloration, more preferably 1 to 2, and further preferably 1. The number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of avoiding coloration and ensuring solubility. The sulfur-containing aromatic heterocycle may be a single ring or a condensed ring. A condensed ring is preferred from the viewpoint of increasing the refractive index. The number of rings constituting the condensed ring is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3 from the viewpoint of facilitating the availability of raw materials and synthesis. Examples of sulfur-containing aromatic heterocycles include aromatic heterocycles containing one sulfur atom, such as a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a thiopyran ring, a naphthothiophene ring, a dinaphthothiophene ring, and a dibenzothiopyran ring; aromatic heterocycles containing two or more sulfur atoms, such as a thianthrene ring; and aromatic heterocycles containing two or more heteroatoms, such as a thiazole ring, an isothiazole ring, a benzothiazole ring, a naphthothiazole ring, a phenothiazine ring, a thiazoloimidazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a dioxazolopyrazine ring, a thiazolopyrazine ring, a thiazolooxazole ring, a dibenzobenzothiophene ring, a thienoxazole ring, a thienothiadiazole ring, and a thiazolothiadiazole ring. As the sulfur-containing aromatic heterocycle, from the viewpoints of increasing the refractive index, low coloring property and solubility, a benzothiazole ring, a dibenzothiophene ring and a benzothiophene ring are preferred, and a benzothiazole ring is more preferred.

[0025] The ethylenically unsaturated compound (A1) is preferably a compound represented by the following general formula (A1-1).

[0026] [ka]

[0027] In formula (A1-1), R 1 represents a hydrogen atom or a methyl group. Cy represents a sulfur-containing aromatic heterocycle. Q 1 and Q 2 Each of X independently represents an alkylene group having 1 to 6 carbon atoms. 1 and X 2 each independently represents -O-, -S-, or -NR 2 -, -NR 2 -(C=O)- or -NR 2 -(C=O)-O-. Z 1 and Z 2 Each of m and n independently represents an integer of 1 to 3. Each of p and q independently represents an integer of 0 to 3. R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0028] In formula (A1-1), Cy represents a sulfur-containing aromatic heterocycle which may have a substituent. The sulfur-containing aromatic heterocycle contributes to a high refractive index. The sulfur-containing aromatic heterocycle has at least one sulfur atom as a heteroatom constituting the aromatic heterocycle. In addition to the sulfur atom, the heteroatom may have an oxygen atom, a nitrogen atom, or an oxygen atom and a nitrogen atom. The number of sulfur atoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3 from the viewpoint of avoiding coloration, more preferably 1 to 2, and further preferably 1. The number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of avoiding coloration and ensuring solubility. The sulfur-containing aromatic heterocycle may be a single ring or a condensed ring. A condensed ring is preferred from the viewpoint of increasing the refractive index. The number of rings constituting the condensed ring is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3 from the viewpoint of facilitating the availability of raw materials and synthesis.

[0029] Examples of sulfur-containing aromatic heterocycles include aromatic heterocycles containing one sulfur atom, such as a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a thiopyran ring, a naphthothiophene ring, a dinaphthothiophene ring, and a dibenzothiopyran ring; aromatic heterocycles containing two or more sulfur atoms, such as a thianthrene ring; and aromatic heterocycles containing two or more heteroatoms, such as a thiazole ring, an isothiazole ring, a benzothiazole ring, a naphthothiazole ring, a phenothiazine ring, a thiazoloimidazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a dioxazolopyrazine ring, a thiazolopyrazine ring, a thiazolooxazole ring, a dibenzobenzothiophene ring, a thienoxazole ring, a thienothiadiazole ring, and a thiazolothiadiazole ring. As the sulfur-containing aromatic heterocycle, from the viewpoints of increasing the refractive index, low coloring property and solubility, a benzothiazole ring, a dibenzothiophene ring and a benzothiophene ring are preferred, and a benzothiazole ring is more preferred.

[0030] In formula (A1-1), Q 1 and Q 2 each independently represents an alkylene group having 1 to 6 carbon atoms. The alkylene group having 1 to 6 carbon atoms may be linear or branched. The alkylene group preferably has 1 to 4 carbon atoms. Specifically, a methylene group, an ethylene group, a methylmethylene group, or an ethylmethylene group is more preferred, a methylene group or an ethylene group is even more preferred, and a methylene group is particularly preferred. Q in one molecule 1 , Q 2may be the same or different. Q is preferred because it is easy to obtain raw materials and it is easy to control the stereoisomers of the product. 1 , Q 2 are preferably the same as each other.

[0031] In formula (A1-1), X 1 and X 2 are independently -O-, -S-, -NR 2 -, -NR 2 -(C=O)- or -NR 2 -(C=O)-O-. R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. X 1 , X 2 In terms of facilitating synthesis and reducing viscosity, -O- or -S- is preferred. In terms of availability of raw materials, -O- is more preferred, and in terms of refractive index, -S- is more preferred.

[0032] In formula (A1-1), Z 1 and Z 2 each independently represents a hydrocarbon group which may have a substituent. The number of carbon atoms in the hydrocarbon group (not including the number of carbon atoms in the substituent) is preferably 1 to 8. When the number of carbon atoms is 8 or less, the refractive index is unlikely to decrease, the viscosity is likely to decrease due to the small molecular weight, and processability is likely to improve. Specific examples include a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, and a butylene group. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a fluoroalkyl group.

[0033] In formula (A1-1), m and n each independently represent an integer of 1 to 3. From the viewpoint of curability, m is preferably 2 to 3, and more preferably 2. From the viewpoint of the refractive index, n is preferably 2 to 3, and more preferably 2. It is particularly preferred that m and n are each 2.

[0034] In formula (A1-1), p and q each independently represent an integer of 0 to 3. The smaller p and q are, the higher the refractive index tends to be. It is particularly preferred that p and q are each 0.

[0035] Specific examples of the ethylenically unsaturated compound (A1) are shown below.

[0036] [ka]

[0037] [ka]

[0038] From the viewpoint of refractive index, the ethylenically unsaturated compound (A1) represented by formula (a3), (a4) or (a5) is preferred, and the ethylenically unsaturated compound (A1) represented by formula (a3) ​​is more preferred.

[0039] The amount of sulfur atoms contained in one molecule of the ethylenically unsaturated compound (A1) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. By making it equal to or more than the lower limit, a high refractive index tends to be obtained. Also, by making it equal to or less than the upper limit, a low colorability tends to be obtained. The upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 30% by mass, and particularly preferably 20 to 25% by mass.

[0040] The double bond equivalent of the ethylenically unsaturated compound (A1) is preferably 200 g / mol or more, more preferably 250 g / mol or more, and also preferably 900 g / mol or less, more preferably 700 g / mol or less, even more preferably 500 g / mol or less, and particularly preferably 300 g / mol or less. By making it equal to or more than the lower limit, a high refractive index tends to be obtained. Also, by making it equal to or less than the upper limit, curability is improved, and a low dielectric constant and a high volume resistance tend to be obtained. The upper and lower limits can be arbitrarily combined. For example, it is preferably 200 to 900 g / mol, more preferably 200 to 700 g / mol, even more preferably 250 to 500 g / mol, and particularly preferably 250 to 300 g / mol.

[0041] <(A) Ethylenically unsaturated compound other than the ethylenically unsaturated compound (A1)> The photosensitive resin composition of the present invention may contain, as the (A) ethylenically unsaturated compound, an ethylenically unsaturated compound other than the ethylenically unsaturated compound (A1) (hereinafter, may be simply referred to as other ethylenically unsaturated compounds). In the present invention, the ethylenically unsaturated compound means a compound having one or more ethylenically unsaturated bonds in the molecule. As the other ethylenically unsaturated compound, a compound having two or more ethylenically unsaturated bonds in the molecule is preferred from the viewpoints of polymerizability, crosslinkability, and the associated difference in developer solubility between exposed and unexposed parts. The ethylenically unsaturated bond is preferably derived from a (meth)acryloyloxy group. In other words, as the other ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0042] In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule as the other ethylenically unsaturated compound. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and is preferably 15 or less, more preferably 8 or less, and even more preferably 6 or less. The above upper and lower limits can be arbitrarily combined. For example, 2 to 15, preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6. By setting it to be equal to or more than the lower limit, the developability tends to be better, and by setting it to be equal to or less than the upper limit, the curability tends to be improved, and the dielectric constant and volume resistance tend to be low.

[0043] Other ethylenically unsaturated compounds include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification reactions between polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds and unsaturated carboxylic acids and polybasic carboxylic acids.

[0044] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters 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; methacrylic acid esters in which part or all of the acrylates of the above-mentioned exemplary compounds are replaced with methacrylates; itaconic acid esters in which part or all of the acrylates of the above-mentioned exemplary compounds are replaced with itaconates; crotonic acid esters in which part or all of the acrylates of the above-mentioned exemplary compounds are replaced with cronates; and maleic acid esters in which part or all of the acrylates of the above-mentioned exemplary compounds are replaced with maleates.

[0045] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0046] The ester obtained by the esterification reaction of a polyhydric hydroxy compound, such as an aliphatic polyhydroxy compound or an aromatic polyhydroxy compound, with an unsaturated carboxylic acid and a polybasic carboxylic acid is not necessarily a single compound, but representative specific examples include a condensation product of acrylic acid, phthalic acid, and ethylene glycol, a condensation product of acrylic acid, maleic acid, and diethylene glycol, a condensation product of methacrylic acid, terephthalic acid, and pentaerythritol, and a condensation product of acrylic acid, adipic acid, butanediol, and glycerin.

[0047] Other examples of polyfunctional ethylenic monomers include urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester; epoxy acrylates such as the addition reaction product of a polyfunctional epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.

[0048] From the viewpoints of curability, low dielectric constant, and high volume resistivity, the other ethylenically unsaturated compounds are preferably esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth)acrylates, and more preferably dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, or trimethylolpropane tri(meth)acrylate. These may be used alone or in combination of two or more.

[0049] The content of the ethylenically unsaturated compound (A) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on the total solid content. The upper and lower limits can be arbitrarily combined. For example, the content is 1 to 80% by mass, preferably 10 to 70% by mass, more preferably 20 to 60% by mass, even more preferably 30 to 60% by mass, and particularly preferably 40 to 60% by mass, based on the total solid content. By making the content equal to or more than the lower limit, a high refractive index tends to be obtained, and by making the content equal to or less than the upper limit, hole resolution tends to be good.

[0050] The content of the ethylenically unsaturated compound (A1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on the total solid content. The upper and lower limits can be arbitrarily combined. For example, the content is 1 to 80% by mass, preferably 10 to 70% by mass, more preferably 20 to 60% by mass, even more preferably 30 to 60% by mass, and especially preferably 40 to 60% by mass, based on the total solid content. By making the content equal to or more than the lower limit, the refractive index tends to be improved, and by making the content equal to or less than the upper limit, the hole resolution tends to be good.

[0051] The content ratio of the ethylenically unsaturated compound (A1) relative to the total content of the ethylenically unsaturated compound (A) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 1 mass% or more, more preferably 50 mass% or more, even more preferably 70 mass% or more, particularly preferably 90 mass% or more, and also preferably 100 mass% or less, relative to the total content of the ethylenically unsaturated compound (A). For example, it is 1 to 100 mass%, preferably 70 to 100 mass%, more preferably 90 to 100 mass%. By making it equal to or more than the lower limit, the refractive index tends to be improved.

[0052] The content ratio of the ethylenically unsaturated compound (A) relative to 100 parts by mass of the alkali-soluble resin (C) is not particularly limited, but is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 40 parts by mass or more, even more preferably 60 parts by mass or more, particularly preferably 80 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 120 parts by mass or less. The upper and lower limits can be arbitrarily combined. For example, 10 to 200 parts by mass, preferably 20 to 150 parts by mass, more preferably 40 to 150 parts by mass, even more preferably 60 to 150 parts by mass, even more preferably 60 to 120 parts by mass, and particularly preferably 80 to 120 parts by mass. By making it equal to or more than the lower limit, the curability tends to be improved, and by making it equal to or less than the upper limit, the hole resolution tends to be improved.

[0053] The content ratio of the ethylenically unsaturated compound (A1) relative to 100 parts by mass of the alkali-soluble resin (C) is not particularly limited, but is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 40 parts by mass or more, even more preferably 60 parts by mass or more, particularly preferably 80 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, even more preferably 130 parts by mass or less, and even more preferably 120 parts by mass or less. For example, it is 10 to 200 parts by mass, preferably 20 to 150 parts by mass, more preferably 40 to 150 parts by mass, even more preferably 60 to 150 parts by mass, even more preferably 60 to 130 parts by mass, especially more preferably 60 to 120 parts by mass, and particularly preferably 80 to 120 parts by mass. By making it equal to or more than the lower limit, the refractive index tends to be improved, and by making it equal to or less than the upper limit, the hole resolution tends to be improved.

[0054] [1-1-2] Component (B): Photopolymerization initiator The photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. The (B) photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the (A) ethylenically unsaturated compound by the action of actinic rays, for example, polymerizes the ethylenically unsaturated bond contained in the (A) ethylenically unsaturated compound.

[0055] The photosensitive resin composition of the present invention can use photopolymerization initiator (B) that is generally used in this field. Examples of such photopolymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; and oxime ester compounds described in JP-A-2000-80068 and JP-A-2006-36750.

[0056] Specifically, for example, the metallocene compound may include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl), dicyclopentadienyltitanium di(2,6-difluorophenyl), dicyclopentadienyltitanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), and dicyclopentadienyltitanium [2,6-difluoro-3-(pyro-1-yl)phenyl].

[0057] Examples of biimidazole 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.

[0058] Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

[0059] Examples of 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.

[0060] Examples of α-aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 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.

[0061] As the (B) photopolymerization initiator, an oxime ester compound is particularly effective in terms of sensitivity and plate making properties, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, for example, it is disadvantageous in terms of sensitivity, so an oxime ester compound with such excellent sensitivity is particularly useful. Oxime ester compounds have a high quantum yield of photoreaction and the activity of the radicals generated is high, so they are highly sensitive and stable against thermal reactions, and it is possible to obtain a highly sensitive photosensitive resin composition with a small amount.

[0062] An example of the oxime ester compound is a compound represented by the following general formula (IV).

[0063] [ka]

[0064] 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. R 21b represents an optional substituent containing an aromatic ring. R 22a represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent. n represents an integer of 0 or 1.

[0065] R 21a In the formula, the number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoints of solubility in a solvent and sensitivity, it 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. 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 cyclopentyl methyl group, a cyclopentyl ethyl group, a cyclohexyl methyl group, and a cyclohexyl ethyl group. Examples of the substituent that the alkyl group may have include 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, an N-acetyl-N-acetoxyamino group, a methyloxycarbonyl group, and an ethyloxycarbonyl group. From the viewpoint of ease of synthesis, it is preferable that the alkyl group is unsubstituted. Moreover, from the viewpoint of sensitivity, solubility, and chemical resistance, a methyloxycarbonyl group and an ethyloxycarbonyl group are preferable.

[0066] R 21a In the above, examples of the aromatic ring group 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. Also, from the viewpoint of developability, the number of carbon atoms is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, the number is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.

[0067] Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. From the viewpoint of developability, the phenyl group and the naphthyl group are preferred, and the phenyl group is more preferred. Examples of the substituent that the aromatic ring 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 in which these substituents are linked. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group in which these substituents are linked are preferred, and a linked alkoxy group is more preferred. From the viewpoints of sensitivity, solubility, and chemical resistance, R 21a is preferably an alkyl group which may have a substituent.

[0068] R 21bAs the alkyl group, preferably, an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group, and an optionally substituted indolyl group are included. From the viewpoint of hole resolution, an optionally substituted diphenyl sulfide group is preferred.

[0069] R 22a The number of carbon atoms in the alkanoyl group in is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is preferably 2 or more and preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and still more preferably 5 or less. Examples of the alkanoyl group include an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group. Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the alkanoyl group is preferably unsubstituted.

[0070] R 22a The number of carbon atoms in the aroyl group is not particularly limited, but from the viewpoints of solubility in a solvent and sensitivity, it is preferably 7 or more and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. Examples of the aroyl group include a benzoyl group and a naphthoyl group. Examples of the substituent that the aroyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferable that the aroyl group is unsubstituted. From the perspective of sensitivity, R 22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and further preferably an acetyl group.

[0071] 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.

[0072] The photopolymerization initiator (B) may be used alone or in combination of two or more. If necessary, a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source may be blended with the photopolymerization initiator (B) for the purpose of increasing sensitivity.

[0073] Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocycle described in JP-A-3-239703 and JP-A-5-289335, 3-ketocoumarin compounds described in JP-A-3-239703 and JP-A-5-289335, pyrromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292, and JP-A-54-2702. Examples of dyes having a dialkylaminobenzene skeleton include those described in JP-B-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818.

[0074] The sensitizing dye is preferably an amino group-containing sensitizing dye, and more preferably a compound having an amino group and a phenyl group in the same molecule. 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; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, and ... p-Dialkylaminophenyl group-containing compounds such as (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine are more preferred, and 4,4'-dialkylaminobenzophenone is particularly preferred. The sensitizing dyes may be used alone or in combination of two or more kinds.

[0075] As the polymerization accelerator, for example, aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate can be used. The polymerization accelerator may be used alone or in combination of two or more kinds.

[0076] The content of the (B) photopolymerization initiator in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, and even more preferably 5% by mass or less, based on the total solid content of the photosensitive resin composition. The upper and lower limits can be arbitrarily combined. For example, 0.01 to 15% by mass is preferred, 0.01 to 10% by mass is more preferred, 1 to 10% by mass is even more preferred, and 2 to 7% by mass is particularly preferred. By making it equal to or more than the lower limit, the sensitivity tends to be improved. By making it equal to or less than the upper limit, the hole resolution tends to be improved.

[0077] The compounding ratio of the photopolymerization initiator (B) to the ethylenically unsaturated compound (A) in the photosensitive resin composition of the present invention is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, and is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less, relative to 100 parts by mass of the ethylenically unsaturated compound (A). The upper and lower limits can be arbitrarily combined. For example, 1 to 100 parts by mass is preferred, 1 to 50 parts by mass is more preferred, 1 to 20 parts by mass is more preferred, 2 to 20 parts by mass is even more preferred, and 2 to 10 parts by mass is particularly preferred. By making the amount equal to or more than the lower limit, the sensitivity tends to be improved. By making the amount equal to or less than the upper limit, the hole resolution tends to be improved.

[0078] A chain transfer agent may be used in combination with the photopolymerization initiator (B). Examples of the chain transfer agent include mercapto group-containing compounds and carbon tetrachloride, and it is more preferable to use mercapto group-containing compounds because they have a high chain transfer effect and tend to improve sensitivity and surface curing properties. This is thought to be because the SH bond energy is small, which makes bond cleavage easy to occur, and hydrogen abstraction reactions and chain transfer reactions easy to occur.

[0079] Examples of the mercapto group-containing compound include mercapto group-containing compounds having an aromatic ring, such as 2-mercaptobenzothiazole and 2-mercaptobenzimidazole; and aliphatic polyfunctional mercapto group-containing compounds, such as trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. These may be used alone or in combination of two or more.

[0080] [1-1-3] Component (C): Alkali-soluble resin The photosensitive resin composition of the present invention contains (C) an alkali-soluble resin. Examples of the alkali-soluble resin (C) include various resins having a carboxy group or a hydroxyl group, and from the viewpoint of excellent developability, those having a carboxy group are preferred, and from the viewpoints of sensitivity and curability, alkali-soluble resins having an ethylenically unsaturated group are preferred.

[0081] The photosensitive resin composition of the present invention contains, as the alkali-soluble resin (C), an epoxy (meth)acrylate resin (C1) having an aromatic ring in the main chain (hereinafter, may be abbreviated to epoxy (meth)acrylate resin (C1)). Since the aromatic ring is present in the main chain, the refractive index tends to be high. In addition, since the compatibility with the sulfur-containing aromatic heterocycle in the ethylenically unsaturated compound (A1) is good, the alkali-soluble resin is easily distributed uniformly in the coating film of the photosensitive resin composition without phase separation. Accordingly, the alkali developer is easily permeated during development, and the hole resolution tends to be good.

[0082] [Epoxy (meth)acrylate resin (C1)] The epoxy (meth)acrylate resin (C1) having an aromatic ring in the main chain is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin having an aromatic ring in the main chain, optionally reacting with an isocyanate group-containing compound, and then further reacting with a polybasic acid or its anhydride. For example, the carboxy group of an unsaturated monocarboxylic acid is ring-opened and added to the epoxy group of the epoxy resin, thereby adding an ethylenically unsaturated bond to the epoxy compound via an ester bond (-COO-), and one of the carboxy groups of a polybasic acid anhydride is added to the hydroxyl group generated at that time. In addition, when adding a polybasic acid anhydride, a polyhydric alcohol is added at the same time.

[0083] Furthermore, a resin obtained by reacting the carboxy group of the resin obtained by the above reaction with a compound having a functional group that can further react is also included in the above epoxy (meth)acrylate resin (C1). Thus, epoxy (meth)acrylate resins have substantially no epoxy groups in their chemical structure, and are not limited to "(meth)acrylate", but are named in this manner according to convention because epoxy compounds (epoxy resins) are the raw material and "(meth)acrylate" is a representative example.

[0084] Here, the epoxy resin includes the raw material compound before the resin is formed by thermal curing, and the epoxy resin can be appropriately selected from known epoxy resins. Also, the epoxy resin can be a compound obtained by reacting a phenolic compound with epihalohydrin. The phenolic compound is preferably a compound having a divalent or more than divalent phenolic hydroxyl group, and may be a monomer or a polymer. Specific examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, dihydroxylfluorene type epoxy resin, dihydroxylalkyleneoxylfluorene type epoxy resin, diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene, and diglycidyl ether of 1,1-bis(4'-hydroxyphenyl)adamantane. Thus, those having an aromatic ring in the main chain can be preferably used.

[0085] From the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, and diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene are preferred, with bisphenol A epoxy resin being particularly preferred. Examples of epoxy resins include bisphenol A type epoxy resins (e.g., Mitsubishi Chemical Corporation's "jER (registered trademark, the same applies below) 828," "jER1001," "jER1002," and "jER1004," and Nippon Kayaku's "NER-1302" (epoxy equivalent: 323, softening point: 76°C), etc.), bisphenol F type resins (e.g., Mitsubishi Chemical Corporation's "jER807," "jER4004P," "jER4005P," and "jER1004"). ER4007P" manufactured by Nippon Kayaku Co., Ltd., "NER-7406" (epoxy equivalent 350, softening point 66°C), etc.), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g., "jERYX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (e.g., "EPPN (registered trademark, the same applies below)-201" manufactured by Nippon Kayaku Co., Ltd., "jER152" and "jER154" manufactured by Mitsubishi Chemical Corporation, Dow Chemical Co., Ltd. "DEN-438" manufactured by Nippon Kayaku Co., Ltd.), (o,m,p-)cresol novolac type epoxy resins (e.g., "EOCN (registered trademark, the same applies below)-102S", "EOCN-1020", and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (e.g., "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resins (e.g., "EPPN-501", "EPPN-502" manufactured by Nippon Kayaku Co., Ltd.), ", "EPPN-503"), alicyclic epoxy resins (Daicel's "Celloxide (registered trademark, the same applies below) 2021P" and "Celloxide EHPE"), epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene with phenol (for example, "EXA-7200" manufactured by DIC Corporation and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins represented by the following general formulas (i-11) to (i-14). An example of the epoxy resin represented by the following general formula (i-11) is "XD-1000" manufactured by Nippon Kayaku Co., Ltd. An example of the epoxy resin represented by the following general formula (i-12) is "NC-3000" manufactured by Nippon Kayaku Co., Ltd. An example of the epoxy resin represented by the following general formula (i-14) is "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

[0086] [ka]

[0087] In formula (i-11), n ​​is an average value and represents a number from 0 to 10. 111 Each of R 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. 111 may be the same or different.

[0088] [ka]

[0089] In formula (i-12), n is an average value and represents a number from 0 to 10. 121 Each of R 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. 121 may be the same or different.

[0090] [ka]

[0091] In formula (i-13), X represents a linking group represented by the following general formula (i-13-1) or (i-13-2), provided that the molecular structure contains one or more adamantane structures. c represents 2 or 3.

[0092] [ka]

[0093] In formulas (i-13-1) and (i-13-2), R 131 ~R 134 and R 135 ~R 137each 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. * represents a bond.

[0094] [ka]

[0095] In formula (i-14), p and q each independently represent an integer of 0 to 4; 141 and R 142 R each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom. 143 and R 144 each independently represents an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or greater.

[0096] The epoxy resin is preferably an epoxy resin represented by any one of formulas (i-11) to (i-14).

[0097] Examples of the ethylenically unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, as well as pentaerythritol tri(meth)acrylate succinic anhydride adduct, pentaerythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, and the reaction product of (meth)acrylic acid and ε-caprolactone. From the viewpoint of sensitivity, (meth)acrylic acid is preferred.

[0098] Examples of polybasic acids (anhydrides) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. From the viewpoint of outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred.

[0099] By using polyhydric alcohol, it is possible to increase the molecular weight of the epoxy (meth)acrylate resin (C1), introduce branches into the molecule, and tend to balance the molecular weight and viscosity. In addition, it is possible to increase the introduction rate of acid groups into the molecule, and tend to balance the sensitivity, adhesion, etc. Examples of polyhydric alcohols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol.

[0100] In addition to the above, examples of the epoxy (meth)acrylate resin (C1) include the resins described in Korean Patent Publication No. 10-2013-0022955.

[0101] The acid value of the epoxy (meth)acrylate resin (C1) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, even more preferably 50 mgKOH / g or more, even more preferably 70 mgKOH / g or more, particularly preferably 80 mgKOH / g or more, and is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, even more preferably 150 mgKOH / g or less, even more preferably 120 mgKOH / g or less, and particularly preferably 110 mgKOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, it is 10 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, more preferably 50 to 150 mgKOH / g, even more preferably 70 to 120 mgKOH / g, and even more preferably 80 to 110 mgKOH / g. By setting the content to be equal to or more than the lower limit, the developability tends to be improved, and by setting the content to be equal to or less than the upper limit, the film strength tends to be improved.

[0102] The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (C1) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, particularly preferably 5000 or more, and is preferably 30000 or less, more preferably 20000 or less, even more preferably 15000 or less, even more preferably 10000 or less, and particularly preferably 8000 or less. The above upper and lower limits can be arbitrarily combined. For example, 1000 to 30000, preferably 2000 to 20000, more preferably 3000 to 15000, even more preferably 4000 to 10000, and particularly preferably 5000 to 8000. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the residue tends to be reduced.

[0103] The content of the epoxy (meth)acrylate resin (C1) in the alkali-soluble resin (C) is not particularly limited, but is preferably 10% by mass or more in the alkali-soluble resin (C), more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 35% by mass or more, even more preferably 40% by mass or more, particularly preferably 50% by mass or more, and also preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 10 to 90% by mass, preferably 20 to 90% by mass, more preferably 30 to 70% by mass, even more preferably 35 to 70% by mass, even more preferably 40 to 60% by mass, and particularly preferably 50 to 60% by mass. By making it equal to or more than the lower limit, linearity tends to be improved, and by making it equal to or less than the upper limit, a high-definition cured product with a narrow line width tends to be formed.

[0104] The epoxy (meth)acrylate resin (C1) can be synthesized by a conventional method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having an ethylenically unsaturated bond is added to cause an addition reaction, and then a polybasic acid or anhydride thereof is added to continue the reaction. For example, the methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422 can be used.

[0105] Examples of the organic solvent used in the reaction include methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. The organic solvent used in the reaction may be used alone or in combination of two or more. Examples of catalysts used in the reaction include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and stibines such as triphenylstibine. The catalysts used in the reaction may be used alone or in combination of two or more. The thermal polymerization inhibitor used in the reaction may be, for example, one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, etc. The thermal polymerization inhibitor used in the reaction may be used alone or in combination of two or more.

[0106] The amount of the acid or ester compound having an ethylenically unsaturated bond used may be preferably 0.7 to 1.3 chemical equivalents, more preferably 0.9 to 1.1 chemical equivalents, per chemical equivalent of the epoxy group of the epoxy resin. The temperature during the addition reaction may be preferably 60 to 150°C, more preferably 80 to 120°C. The amount of polybasic acid (anhydride) used may be preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, per chemical equivalent of the hydroxyl group generated by the addition reaction.

[0107] Among the epoxy (meth)acrylate resins (C1), from the viewpoint of film strength and linearity, it is preferable to include one or more of an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (i), an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii), and an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii):

[0108] [ka]

[0109] In formula (i), R a R represents a hydrogen atom or a methyl group. b represents a divalent hydrocarbon group which may have a substituent. k represents 1 or 2. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.

[0110] [ka]

[0111] In formula (ii), R c Each independently represents a hydrogen atom or a methyl group. d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.

[0112] [ka]

[0113] In formula (iii), R e represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.

[0114] Hereinafter, the epoxy (meth)acrylate resin having a partial structure represented by formula (i) (hereinafter, may be referred to as "epoxy (meth)acrylate resin (C1-1)") will be described in detail.

[0115] [ka]

[0116] In formula (i), R a represents a hydrogen atom or a methyl group, R brepresents a divalent hydrocarbon group which may have a substituent. k represents 1 or 2. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.

[0117] (R b ) In formula (i), R b represents a divalent hydrocarbon group which may have a substituent. 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 are linked with one or more divalent aromatic ring groups.

[0118] The divalent aliphatic group may be a linear, branched, or cyclic aliphatic group. Among these, a linear aliphatic group is preferred from the viewpoint of development solubility. A cyclic aliphatic group is preferred from the viewpoint of reducing the penetration of the developer into the exposed area. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be arbitrarily combined. For example, 1 to 20, preferably 3 to 15, and more preferably 6 to 10. By making the number equal to or more than the lower limit, the film strength tends to be improved, and by making the number equal to or less than the upper limit, the hole resolution tends to be improved.

[0119] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. From the viewpoints of refractive index, hole resolution, and production costs, a methylene group is preferred. Examples of the divalent branched aliphatic group include a structure in which 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 is bonded as a side chain to the above-mentioned divalent linear aliphatic group. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 5. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, or an adamantane ring. From the viewpoints of film strength and developability, groups in which two hydrogen atoms have been removed from an adamantane ring are preferred.

[0120] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group, a hydroxyl group, a nitro group, a cyano group, and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.

[0121] The divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be arbitrarily combined. For example, it is 4 to 20, preferably 5 to 15, and more preferably 6 to 10. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0122] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single 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 benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each of which has two free valences.

[0123] The aromatic heterocycle in the divalent aromatic heterocycle group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocycle group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has two free valences. From the viewpoint of production costs, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0124] Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of curability, it is preferably unsubstituted.

[0125] Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups. The number of divalent aliphatic groups in the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, and more preferably 2 to 3. By making it equal to or more than the lower limit, developability tends to be improved, and by making it equal to or less than the upper limit, film strength tends to be improved. The number of divalent aromatic ring groups in the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, and more preferably 2 to 3. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0126] Examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include groups represented by the following general formulas (iA) to (iF). From the viewpoints of refractive index and hole resolution, the group represented by the following general formula (iA) is preferred.

[0127] [ka]

[0128] The benzene ring in formula (i) may be further substituted with any substituent. Examples of the substituent permitted for the benzene ring in formula (i) include a hydroxy 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 1 or 2 or more. From the viewpoint of curability, it is preferable that the substituents are unsubstituted.

[0129] (k) k represents 1 or 2. From the viewpoint of refractive index, k is preferably 1. From the viewpoint of developability and curability, k is preferably 2.

[0130] From the viewpoint of development solubility, the partial structure represented by formula (i) is preferably a partial structure represented by the following formula (i-1).

[0131] [ka]

[0132] In formula (i-1), R a and R b has the same meaning as in formula (i). Y represents a hydrogen atom or a polybasic acid residue. k represents 1 or 2. * represents a bond. The benzene ring in formula (i-1) may be further substituted with any substituent.

[0133] The polybasic acid residue refers to a mono- or divalent group obtained by removing one or two OH groups from a polybasic acid. 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, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0134] The repeating unit structure represented by formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (C1-1) may be of one type or of two or more types.

[0135] The number of partial structures represented by formula (i) contained in one molecule of the epoxy (meth)acrylate resin (C1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is preferably 10 or less, even more preferably 8 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, more preferably 3 to 8. By making it equal to or more than the lower limit, developability tends to be improved, and by making it equal to or less than the upper limit, film strength tends to be improved.

[0136] The number of partial structures represented by formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (C1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is preferably 10 or less, even more preferably 8 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, more preferably 3 to 8. By making it equal to or more than the lower limit, developability tends to be improved, and by making it equal to or less than the upper limit, film strength tends to be improved.

[0137] Specific examples of the epoxy (meth)acrylate resin (C1-1) are shown below.

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] The epoxy (meth)acrylate resin having a partial structure represented by formula (ii) (hereinafter, may be referred to as "epoxy (meth)acrylate resin (C1-2)") will be described in detail.

[0147] [ka]

[0148] In formula (ii), R c Each independently represents a hydrogen atom or a methyl group. d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.

[0149] (R d ) In formula (ii), R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0150] The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, and more preferably 2 to 3. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more, and is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 4 to 30, more preferably 6 to 20, and even more preferably 8 to 15. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0151] Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoints of film strength and developability, an adamantane ring is preferred.

[0152] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 5, and more preferably 3 to 4. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0153] Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, particularly preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, 4 to 40, preferably 6 to 40, more preferably 8 to 30, even more preferably 10 to 20, and even more preferably 12 to 15. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0154] 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 benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. From the viewpoint of patterning properties, a fluorene ring is preferred.

[0155] 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 are linked to one or more divalent aromatic ring groups.

[0156] The divalent aliphatic group may be a linear, branched, or cyclic aliphatic group. Among these, a linear aliphatic group is preferred from the viewpoint of improving developability. A cyclic aliphatic group is preferred from the viewpoint of film strength. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more, and is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, 1 to 25, preferably 3 to 20, and more preferably 6 to 15. By making the number equal to or more than the lower limit, the film strength tends to be improved, and by making the number equal to or less than the upper limit, the developability tends to be improved.

[0157] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. From the viewpoints of refractive index and hole resolution, a methylene group is preferred. Examples of the divalent branched aliphatic group include a structure in which 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 is bonded as a side chain to the above-mentioned divalent linear aliphatic group.

[0158] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, and more preferably 2 to 3. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0159] Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, or an adamantane ring. From the viewpoint of film strength, groups in which two hydrogen atoms have been removed from an adamantane ring are preferred.

[0160] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group, a hydroxyl group, a nitro group, a cyano group, and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.

[0161] The divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, it is 4 to 30, preferably 5 to 20, and more preferably 6 to 15. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0162] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single 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 benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each of which has two free valences.

[0163] The aromatic heterocycle in the divalent aromatic heterocycle group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocycle group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has two free valences. From the viewpoint of production costs, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0164] Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of curability, it is preferably unsubstituted.

[0165] Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups. The number of divalent aliphatic groups in the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, and more preferably 2 to 3. By making it equal to or more than the lower limit, developability tends to be improved, and by making it equal to or less than the upper limit, film strength tends to be improved. The number of divalent aromatic ring groups in the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, and more preferably 2 to 3. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0166] Examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include the groups represented by the above formulas (iA) to (iF). From the viewpoints of film strength and high refractive index, the group represented by formula (iA) is preferred.

[0167] The bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but examples include a mode in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group as a side chain, and a mode in which a cyclic hydrocarbon group as a side chain is formed by including one carbon atom of an aliphatic group.

[0168] From the viewpoint of improving the refractive index, the partial structure represented by formula (ii) is preferably a partial structure represented by the following general formula (ii-1).

[0169] [ka]

[0170] In formula (ii-1), R c has the same meaning as in formula (ii). α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. * represents a bond. The benzene ring in formula (ii-1) may be further substituted with any substituent.

[0171] (R α ) In formula (ii-1), R α represents an optionally substituted monovalent cyclic hydrocarbon group. Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0172] The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The upper and lower limits can be arbitrarily combined. For example, 1 to 6, preferably 1 to 4, and more preferably 2 to 3. By making the number equal to or more than the lower limit, the film strength tends to be improved, and by making the number equal to or less than the upper limit, the developability tends to be improved. The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more, and is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 4 to 30, more preferably 6 to 20, and even more preferably 8 to 15. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0173] Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoints of film strength and developability, an adamantane ring is preferred.

[0174] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, and more preferably 3 to 5. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, it is 4 to 30, preferably 5 to 20, and more preferably 6 to 15. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0175] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoints of film strength and developability, a fluorene ring is preferred.

[0176] Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as a hydroxy group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, and an isoamyl group; alkoxy groups having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, non-substitution is preferred.

[0177] n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less, for example, 1 to 3, and preferably 2 to 3. By making it equal to or more than the lower limit, developability tends to be improved, and by making it equal to or less than the upper limit, film strength tends to be improved.

[0178] From the viewpoint of film strength and developability, R α is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.

[0179] The benzene ring in formula (ii-1) may be further substituted with any substituent. Examples of the substituent that can be used for the benzene ring in formula (ii-1) 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 more than one. From the viewpoint of curability, it is preferable that the substituent is unsubstituted.

[0180] Specific examples of the partial structure represented by the formula (ii-1) are given below.

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] [ka]

[0186] From the viewpoint of development adhesion, the partial structure represented by formula (ii) is preferably a partial structure represented by the following formula (ii-2).

[0187] [ka]

[0188] In formula (ii-2), R c has the same meaning as in formula (ii). β represents a divalent cyclic hydrocarbon group which may have a substituent. * represents a bond. The benzene ring in formula (ii-2) may be further substituted with any substituent.

[0189] (R β ) In formula (ii-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent. Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0190] The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 5. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more, and is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 6 to 35, and more preferably 8 to 30. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoints of film strength and developability, an adamantane ring is preferred.

[0191] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, and more preferably 3 to 5. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and particularly preferably 10 or more, and is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 6 to 30, more preferably 8 to 20, and even more preferably 10 to 15. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0192] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoints of film strength and developability, the fluorene ring is preferred.

[0193] Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as a hydroxy group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, and an isoamyl group; alkoxy groups having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, non-substitution is preferred.

[0194] From the viewpoint of film strength and developability, R β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. βis preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

[0195] The benzene ring in formula (ii-2) may be further substituted with any substituent. Examples of the substituent that can be used for the benzene ring in formula (ii-2) 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 more than one. From the viewpoint of curability, it is preferable that the substituent is unsubstituted.

[0196] Specific examples of the partial structure represented by formula (ii-2) are given below.

[0197] [ka]

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] From the viewpoint of developability, the partial structure represented by formula (ii) is preferably a partial structure represented by the following general formula (ii-3).

[0202] [ka]

[0203] In formula (ii-3), R c and R d has the same meaning as in formula (ii). Zrepresents a hydrogen atom or a polybasic acid residue.

[0204] The polybasic acid residue refers to a mono- or divalent group obtained by removing one or two OH groups from a polybasic acid. 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, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0205] The partial structure represented by formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (C1-2) may be of one type or of two or more types.

[0206] The number of partial structures represented by formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (C1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, and more preferably 3 to 10. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the hole resolution tends to be improved.

[0207] The number of partial structures represented by formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (C1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, and more preferably 3 to 10. By making it equal to or more than the lower limit, the film strength and refractive index tend to be improved, and by making it equal to or less than the upper limit, the hole resolution tends to be improved.

[0208] The number of partial structures represented by formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (C1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, and more preferably 3 to 10. By making it equal to or more than the lower limit, the film strength and refractive index tend to be improved, and by making it equal to or less than the upper limit, the hole resolution tends to be improved.

[0209] The number of partial structures represented by formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (C1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, and more preferably 3 to 10. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the hole resolution tends to be improved.

[0210] An epoxy (meth)acrylate resin having a partial structure represented by formula (iii) (hereinafter, may be referred to as "epoxy (meth)acrylate resin (C1-3)") will be described in detail.

[0211] [ka]

[0212] In formula (iii), R e represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.

[0213] (γ) In formula (iii), γ represents a single bond, —CO—, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.

[0214] The alkylene group may be a straight chain or a branched chain. From the viewpoint of development solubility, it is preferably a straight chain. From the viewpoint of development adhesion, it is preferably a branched chain. The number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more preferably 4 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 6, preferably 2 to 4. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved.

[0215] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and a heptylene group. From the viewpoints of film strength and developability, an ethylene group and a propylene group are preferred, and a propylene group is more preferred.

[0216] Examples of the substituent that the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group, a hydroxyl group, a nitro group, a cyano group, and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the alkylene group is unsubstituted.

[0217] Examples of the divalent cyclic hydrocarbon group include a divalent aliphatic ring group and a divalent aromatic ring group.

[0218] The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 5. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more, and is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 6 to 35, and more preferably 8 to 30. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoints of film strength and developability, an adamantane ring is preferred.

[0219] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, and more preferably 3 to 5. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and particularly preferably 10 or more, and is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 6 to 30, more preferably 8 to 20, and even more preferably 10 to 15. By making it equal to or more than the lower limit, the film strength tends to be improved, and by making it equal to or less than the upper limit, the developability tends to be improved. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, the fluorene ring is preferred from the viewpoints of film strength and developability.

[0220] Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as a hydroxy group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, and an isoamyl group; alkoxy groups having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, non-substitution is preferred.

[0221] From the viewpoint of developability, γ is preferably an alkylene group which may have a substituent, and more preferably a dimethylmethylene group.

[0222] The benzene ring in formula (iii) may be further substituted with any substituent. Examples of the substituent that can be used for the benzene ring in formula (iii) 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 more than one. From the viewpoint of curability, it is preferable that the ring is unsubstituted.

[0223] From the viewpoint of development solubility, the partial structure represented by formula (iii) is preferably a partial structure represented by the following general formula (iii-1).

[0224] [ka]

[0225] In formula (iii-1), R e and γ are the same as those in formula (iii). W represents a hydrogen atom or a polybasic acid residue. * represents a bond. The benzene ring in formula (iii-1) may be further substituted with any substituent.

[0226] The polybasic acid residue refers to a mono- or divalent group obtained by removing one or two OH groups from a polybasic acid. 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, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0227] The number of repeating unit structures represented by formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (C1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and is preferably 18 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 18, preferably 5 to 18, and more preferably 10 to 15. By making it equal to or more than the lower limit, hole resolution tends to be improved, and by making it equal to or less than the upper limit, developability tends to be improved.

[0228] The number of repeating unit structures represented by formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (C1-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and is preferably 18 or less, even more preferably 15 or less. The upper and lower limits can be arbitrarily combined. For example, it is 1 to 18, preferably 3 to 18, more preferably 5 to 15. By making it equal to or more than the lower limit, hole resolution tends to be improved, and by making it equal to or less than the upper limit, developability tends to be improved.

[0229] Specific examples of the epoxy (meth)acrylate resin (C1-3) are shown below.

[0230] [ka]

[0231] [ka]

[0232] [Alkali-soluble resins other than epoxy (meth)acrylate resins (C1)] The (C) alkali-soluble resin contained in the photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the epoxy (meth)acrylate resin (C1) (hereinafter, may be referred to as "other alkali-soluble resin"). Other alkali-soluble resins include, for example, acrylic copolymer resins, epoxy resins, urethane resins, novolac resins, polyimide resins, and polyvinylphenol resins.

[0233] For example, resins described in JP-A-8-297366, JP-A-2001-89533, and WO 2019 / 146685 can be mentioned. These may be used alone or in combination of two or more.

[0234] The acid value of the alkali-soluble resin (C) is not particularly limited, but is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, even more preferably 70 mgKOH / g or more, and is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. The upper and lower limits can be arbitrarily combined. For example, it is 30 to 200 mgKOH / g, preferably 50 to 150 mgKOH / g, and more preferably 70 to 100 mgKOH / g. By making it equal to or more than the lower limit, the developability tends to be improved, and by making it equal to or less than the upper limit, the development adhesion tends to be improved. (C) When the alkali-soluble resin is a mixture of two or more kinds, the acid value means a weighted average value according to the content ratio of the mixture.

[0235] The content of the alkali-soluble resin (C) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on the total solid content of the photosensitive resin composition. The upper and lower limits can be arbitrarily combined. For example, 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 70% by mass. By making it equal to or more than the lower limit, hole resolution tends to be improved, and by making it equal to or less than the upper limit, the refractive index tends to be improved.

[0236] The sum of the content of the ethylenically unsaturated compound (A) and the content of the alkali-soluble resin (C) in the total solid content of the photosensitive resin composition is not particularly limited, but is preferably 30% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and is preferably 100% or less, more preferably 95% by mass or less. The upper and lower limits can be arbitrarily combined. For example, it is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 90 to 95% by mass. By making it equal to or more than the lower limit, the adhesion of the cured product to the substrate tends to be improved, and by making it equal to or less than the upper limit, the curability tends to be improved.

[0237] [1-2] Other ingredients of the photosensitive resin composition In addition to the above-mentioned components, the photosensitive resin composition of the present invention may appropriately contain surfactants, metal oxide particles, colorants, silane coupling agents, adhesion improvers, phosphoric acid compounds, ultraviolet absorbers, polymerization inhibitors, thermal polymerization initiators, amino compounds, solvents, and the like.

[0238] [1-2-1] Surfactants The photosensitive resin composition of the present invention may contain a surfactant. The surfactant can be used for the purpose of improving the coatability of the photosensitive resin composition as a coating liquid and the developability of the coating film, etc., and among them, silicone-based surfactants and fluorine-based surfactants are preferred. Silicone-based surfactants are preferred, and polyether-modified silicone-based surfactants are more preferred, since they have the effect of removing residues of the photosensitive resin composition from unexposed areas during development and also have the function of expressing wettability.

[0239] As the fluorine-based surfactant, a compound having a fluoroalkyl or fluoroalkylene group at least at any one of the terminal, main chain, and side chain is preferable. Commercially available fluorine-based surfactants include, for example, "BM-1000" and "BM-1100" manufactured by BM Chemie; "Megafac F142D," "Megafac F172," "Megafac F173," "Megafac F183," "Megafac F470," "Megafac F475," "Megafac F554," and "Megafac F559" manufactured by DIC Corporation; "FC430" manufactured by 3M Japan; and "DFX-18" manufactured by Neos.

[0240] Examples of commercially available silicone surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", and "SH8400" manufactured by Dow Corning Toray Co., Ltd., and "BYK (registered trademark, the same applies below) 323" and "BYK330" manufactured by BYK-Chemie. The surfactant may include surfactants other than fluorine-based surfactants and silicone-based surfactants, and other surfactants include, for example, nonionic, anionic, cationic and amphoteric surfactants.

[0241] The surfactants may be used in combination of two or more kinds, for example, a combination of a silicone surfactant / a fluorosurfactant, a combination of a silicone surfactant / a special polymer surfactant, or a combination of a fluorosurfactant / a special polymer surfactant may be mentioned, with a combination of a silicone surfactant / a fluorosurfactant being preferred. Examples of combinations of silicone surfactants / fluorine surfactants include the combination of BYK-300 or BYK-330 manufactured by BYK / DFX-18 manufactured by NEOS, the combination of BYK-300 or BYK-330 manufactured by BYK / S-393 manufactured by AGC Seimi Chemical, the combination of BYK-300 or BYK-330 manufactured by BYK / F-554 or F-559 manufactured by DIC, the combination of Shin-Etsu Silicone's KP340 / F-478 or F-475 manufactured by DIC, the combination of Toray Dow Corning's SH7PA / Daikin's DS-401, and the combination of NUC's L-77 / 3M Japan's FC4430.

[0242] [1-2-2] Metal oxide particles The photosensitive resin composition of the present invention may contain metal oxide particles. By including metal oxide particles, the refractive index tends to be high.

[0243] Examples of metal oxide particles include titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, iron oxide, copper oxide, zinc oxide, yttrium oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, tantalum oxide, tungsten oxide, lead oxide, bismuth oxide, cerium oxide, antimony oxide, and germanium oxide. Composite oxide particles composed of two or more metal elements, such as barium titanate, can also be used.

[0244] From the viewpoints of dispersibility and high refractive index, titanium oxide particles, zirconium oxide particles, and hafnium oxide particles are preferred, and titanium oxide particles and zirconium oxide particles are more preferred. [1-2-3] Colorants The photosensitive resin composition of the present invention may contain a colorant. As the colorant, known colorants such as pigments and dyes, and derivatives thereof can be used. When using a pigment, a known dispersant or dispersing aid may be used in combination so that the pigment does not aggregate and is present stably in the photosensitive resin composition. When the photosensitive resin composition of the present invention contains a colorant, the content of the colorant is, from the viewpoint of curability, preferably 1% by mass or more, and preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on the total solid content of the photosensitive resin composition. For example, it is preferably 1 to 30% by mass, more preferably 1 to 10% by mass, and even more preferably 1 to 5% by mass.

[0245] [1-2-4] Silane coupling agents The photosensitive resin composition of the present invention may contain a silane coupling agent in order to improve adhesion to a substrate. Examples of the silane coupling agent include epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are preferred. When the photosensitive resin composition of the present invention contains a silane coupling agent, the content thereof is preferably 1 mass % or more, and preferably 10 mass % or less, more preferably 5 mass % or less, based on the total solid content of the photosensitive resin composition from the viewpoint of adhesion. For example, it is preferably 1 to 10 mass %, more preferably 1 to 5 mass %.

[0246] [1-2-5] Phosphate compounds The photosensitive resin composition of the present invention may contain a phosphoric acid compound for the purpose of imparting adhesion to a substrate. The phosphoric acid compounds include ethylenic phosphoric acid monomers. As the phosphoric acid-based ethylenic monomer, (meth)acryloyloxy group-containing phosphates are preferred, and phosphoric acid-based ethylenic monomers represented by the following general formulas (g1), (g2) and (g3) are preferred.

[0247] [ka]

[0248] In formulas (g1), (g2), and (g3), R 51 represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2, or 3.

[0249] The phosphoric acid-based ethylenic monomer may be used alone or in combination of two or more kinds.

[0250] [1-2-6] UV absorbers The photosensitive resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorbing agent is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of the light source used for exposure. The addition of an ultraviolet absorbing agent has the effect of increasing the taper angle.

[0251] As the ultraviolet absorbing agent, from the viewpoint of inhibiting light absorption by the (B) photopolymerization initiator, for example, a compound having an absorption maximum in the wavelength range of 250 nm to 400 nm can be mentioned. Examples of the ultraviolet absorbing agent include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes. The ultraviolet absorbing agent preferably contains either one or both of a benzotriazole compound and a triazine compound.

[0252] [1-2-7] Polymerization inhibitors The photosensitive resin composition of the present invention may contain a polymerization inhibitor. The inclusion of a polymerization inhibitor inhibits radical polymerization, and therefore tends to increase the taper angle of the resulting cured product.

[0253] Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of taper angle control, hydroquinone or methoxyphenol is preferred, and methylhydroquinone is more preferred.

[0254] The polymerization inhibitor may be used alone or in combination of two or more kinds. (C) When the alkali-soluble resin is produced, a polymerization inhibitor may be contained in the resin. In that case, the resin may be used as it is, or a polymerization inhibitor the same as or different from the polymerization inhibitor contained in the resin may be further added during the production of the photosensitive resin composition.

[0255] [1-2-8] Thermal polymerization initiator The photosensitive resin composition of the present invention may contain a thermal polymerization initiator. By including a thermal polymerization initiator, the degree of crosslinking of the film tends to be increased. Examples of the thermal polymerization initiator include azo compounds, organic peroxides, and hydrogen peroxide. These may be used alone or in combination of two or more.

[0256] [1-2-9] Amino compounds The photosensitive resin composition of the present invention may contain an amino compound to promote thermal curing. Examples of the amino compound include an amino compound having a methylol group as a functional group and at least two alkoxymethyl groups obtained by condensing the methylol group with an alcohol having 1 to 8 carbon atoms.Specific examples include a melamine resin obtained by polycondensing melamine with formaldehyde, a benzoguanamine resin obtained by polycondensing benzoguanamine with formaldehyde, a glycoluril resin obtained by polycondensing glycoluril with formaldehyde, a urea resin obtained by polycondensing urea with formaldehyde, a resin obtained by copolycondensing two or more of melamine, benzoguanamine, glycoluril, or urea with formaldehyde, and a modified resin obtained by condensing the methylol group of the above-mentioned resin with alcohol. These may be used alone or in combination of two or more.

[0257] [1-2-10] Solvent The photosensitive resin composition of the present invention may contain a solvent. When a solvent is contained, the above-mentioned components can be used in a state of being dissolved or dispersed in the solvent. The solvent is not particularly limited, but examples thereof include the following organic solvents:

[0258] glycol monoalkyl ethers such as 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-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as 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, 3-methoxy-1-butyl 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, and 3-methyl-3-methoxybutyl acetate; Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl 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 pentanone; monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride, amyl chloride; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile, benzonitrile; Tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.

[0259] Commercially available solvents include, for example, mineral spirits, Valsol #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, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all trade names).

[0260] The solvent may be any solvent capable of dissolving or dispersing each component in the photosensitive resin composition, and is selected according to the method of using the photosensitive resin composition of the present invention. From the viewpoint of coating properties, a solvent having a boiling point of 60 to 280° C. under atmospheric pressure is preferred, and a solvent having a boiling point of 70 to 260° C. is more preferred. Examples of the solvent include propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate.

[0261] The solvent may be used alone or in combination of two or more kinds. The solvent is used so that the content of the total solid content in the photosensitive resin composition solution is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, and also preferably 90% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, the solvent is used so that the content is 10 to 90% by mass, preferably 15 to 50% by mass, more preferably 20 to 40% by mass, and even more preferably 25 to 35% by mass. By setting the content to be equal to or more than the lower limit, there is a tendency that the occurrence of coating unevenness can be suppressed, and by setting the content to be equal to or less than the upper limit, there is a tendency that the occurrence of foreign matter, repelling, etc. can be suppressed.

[0262] [2] Method for preparing photosensitive resin composition The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components with a mixer. When the photosensitive resin composition of the present invention contains a colorant, it is preferable to previously carry out a dispersion treatment using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc. The colorant is microparticulated by the dispersion treatment, and thus the coating properties of the photosensitive resin composition are improved.

[0263] The dispersion treatment is preferably carried out in a system in which a colorant, a solvent, and a dispersant, as well as part or all of the (C) alkali-soluble resin are used in combination (hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the dispersion treatment may be referred to as a "pigment dispersion liquid.") In particular, when a polymer dispersant is used as a dispersant, thickening over time of the obtained pigment dispersion liquid and photosensitive resin composition is suppressed, that is, the dispersion stability is excellent, and therefore it is preferable. When the photosensitive resin composition of the present invention contains a colorant, it is preferable to produce a pigment dispersion containing at least the colorant, a solvent, and a dispersant in the step of producing the photosensitive resin composition as described above. As the colorant, organic solvent, and dispersant that can be used in the pigment dispersion, those described as those that can be used in the photosensitive resin composition can be preferably used. Also, as the content ratio of each colorant in the pigment dispersion, those described as the content ratio in the photosensitive resin composition can be preferably used.

[0264] When dispersing the colorant with a sand grinder, glass beads or zirconia beads with a particle size of about 0.1 to 8 mm are preferably used. The dispersion temperature is preferably 0°C to 100°C, more preferably in the range of room temperature to 80°C. The dispersion time varies depending on the composition of the liquid and the size of the dispersion treatment device, and is adjusted appropriately. The guideline for dispersion is to control the gloss so that the 20 degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.

[0265] The dispersed particle size of the colorant dispersed in the pigment dispersion is preferably 0.01 to 1 μm, more preferably 0.02 to 0.5 μm, and further preferably 0.03 to 0.3 μm. The dispersed particle size is measured as the number-based median size by, for example, a dynamic light scattering method. The pigment dispersion obtained by the dispersion treatment and the other components contained in the photosensitive resin composition are mixed to form a uniform solution or dispersion. Since fine dust may be mixed into the liquid during the production process of the photosensitive resin composition, it is desirable to filter the obtained photosensitive resin composition using a filter, for example.

[0266] [3] Cured product The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. The use of the cured product is not particularly limited, but it can be suitably used as an insulating film or a functional film for improving light extraction efficiency in an organic electroluminescent device. The method for forming a cured product using the photosensitive resin composition is not particularly limited, and a conventionally known method can be adopted. For example, a photolithography method including a coating step of coating a photosensitive resin composition on a substrate to form a photosensitive resin composition layer, an exposure step of exposing the photosensitive resin composition layer to light, and a development step can be mentioned.

[0267] The material of the substrate for forming the cured product is not particularly limited as long as it has an appropriate strength, and can be appropriately selected according to the type of organic electroluminescent device or the like to be manufactured using the substrate on which the cured product is formed. Examples of the material for the substrate include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, thermoplastic resin sheets such as polymethyl methacrylate and polysulfone, epoxy resins, unsaturated polyester resins, thermosetting resin sheets such as poly(meth)acrylic resins, and various glasses. From the viewpoint of heat resistance, glass and heat-resistant resins are preferred. In addition, a transparent electrode such as ITO or IZO, or a metal electrode such as silver, gold, platinum, aluminum, or magnesium may be formed on the surface of the substrate, and an organic film such as an insulating film may be further formed thereon. In addition to the above-mentioned substrates, the cured product may be formed on a TFT array.

[0268] In the photolithography method, a photosensitive resin composition is applied to substantially the entire surface of a substrate to form a photosensitive resin composition layer. The formed photosensitive resin composition layer is exposed to light according to a predetermined pattern, and then the exposed photosensitive resin composition layer is developed to form a cured product on the substrate.

[0269] In the photolithography method, in the coating step of coating a substrate with a photosensitive resin composition, the photosensitive resin composition is coated on the substrate using a contact transfer type coating device such as a roll coater, reverse coater, or bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.

[0270] In the exposure step, the photosensitive resin composition layer is exposed to active energy rays such as ultraviolet rays and excimer laser light using a negative mask. For exposure, a light source emitting ultraviolet rays such as a high pressure mercury lamp, an extra high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The exposure dose varies depending on the composition of the photosensitive resin composition, but is, for example, 10 to 400 mJ / cm 2 degree is preferred.

[0271] In the development step, the exposed photosensitive resin composition layer is developed with a developer to form a cured product. The developing method is not particularly limited, and may be a dipping method, a spray method, or the like. Examples of the developing solution include organic developing solutions such as tetramethylammonium hydroxide (TMAH), dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. The developing solution may contain an antifoaming agent or a surfactant.

[0272] After the development, a post-exposure step and a post-baking (firing) step may be performed. The post-baking temperature is preferably 150 to 250° C. The post-baking time is preferably 15 to 60 minutes.

[0273] The film thickness of the cured product is preferably 0.1 μm or more, more preferably 0.5 μm or more, even more preferably 0.8 μm or more, and preferably 10 μm or less, more preferably 5.0 μm or less, and even more preferably 3.0 μm or less. The upper and lower limits can be arbitrarily combined. For example, it is 0.1 μm to 10 μm, preferably 0.5 to 5 μm, and more preferably 0.8 to 3.0 μm. By making it equal to or more than the lower limit, the refractive index of the cured product tends to be improved, and by making it equal to or less than the upper limit, the hole resolution tends to be improved. The thickness of the cured film is measured using a step / surface roughness / microshape measuring device, a scanning white light interference microscope, an ellipsometer, a reflectance spectroscopic film thickness meter, and an electron microscope.

[0274] The cured product produced from the photosensitive composition of the present invention has a high refractive index. The refractive index of the cured product is preferably 1.620 or more, more preferably 1.630 or more, and even more preferably 1.640 or more. Also, it is preferably 1.680 or less, and more preferably 1.660 or less. The upper and lower limits can be arbitrarily combined. For example, it is preferably 1.620 to 1.680, more preferably 1.630 to 1.680, and even more preferably 1.640 to 1.660. By being equal to or greater than the lower limit, the light extraction efficiency tends to be improved. The refractive index of the cured product can be measured, for example, by using a prism coupler.Specifically, as described in the examples, a refractive index measurement substrate is prepared by forming a cured product on a glass substrate, and a value at a wavelength of 633 nm measured by using a prism coupler under the condition of 20° C. using a He-Ne laser as a light source can be used as the refractive index of the cured product.

[0275] [4] Image display device The image display device of the present invention comprises the cured product of the present invention. Examples of the image display device include a liquid crystal display device and an image display device including an organic electroluminescence device. EXAMPLES

[0276] The photosensitive resin composition of the present invention will be described below with reference to specific examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention. The components of the photosensitive resin composition used in the following Examples and Comparative Examples are as follows.

[0277] <Ethylenically unsaturated compounds-I> A compound having the following structure. The ethylenically unsaturated compound-I can be produced, for example, by the method described in JP 2021-024842 A. The ethylenically unsaturated compound-I corresponds to the ethylenically unsaturated compound (A1).

[0278] [ka]

[0279] <Ethylenically unsaturated compounds-II> OGSOL EA-0200 manufactured by Osaka Gas Chemicals Co., Ltd. A compound having the following structure: Ethylenically unsaturated compound-II does not fall under the category of ethylenically unsaturated compound (A1).

[0280] [ka]

[0281] <Alkali-soluble resin-I> Nippon Kayaku ZCR-1761 (weight average molecular weight Mw = 3400, acid value = 60 mgKOH / g). An epoxy (meth)acrylate resin with the following partial structure, where * indicates each bond. Alkali-soluble resin-I corresponds to epoxy (meth)acrylate resin (C1-1).

[0282] [ka]

[0283] <Alkali-soluble resin-II> Nippon Kayaku ZCR-8024 (weight average molecular weight Mw = 3400, acid value = 60 mgKOH / g). An epoxy (meth)acrylate resin with the following partial structure, where * indicates each bond. Alkali-soluble resin-II corresponds to epoxy (meth)acrylate resin (C1-1).

[0284] [ka]

[0285] <Alkali-soluble resin-III> An alkali-soluble acrylic copolymer resin, which is made by subjecting a copolymer resin consisting of dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.10 / 0.60 / 0.30) as constituent monomers to an equal amount of addition reaction with acrylic acid and glycidyl methacrylate, and then adding 0.40 moles of tetrahydrophthalic anhydride per mole of the total number of moles of the constituent monomers of the copolymer resin. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is 10,000, and the acid value of the solid content is 68.8 mgKOH / g.

[0286] <Alkali-soluble resin-IV> An alkali-soluble acrylic copolymer resin, which is made by subjecting a copolymer resin consisting of dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.02 / 0.05 / 0.93) as constituent monomers to an equal amount of addition reaction with acrylic acid and glycidyl methacrylate, and then adding 0.10 moles of tetrahydrophthalic anhydride per mole of the total number of moles of the constituent monomers of the copolymer resin. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene is 8900, and the acid value of the solid content is 26.9 mgKOH / g.

[0287] <Photopolymerization initiator-I> It is a compound having the following chemical structure and can be produced by the synthesis method described in WO 2019 / 131189.

[0288] [ka]

[0289] <Surfactant-I> DIC Megafack F-559

[0290] <Solvent-I> PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II> MB: 3-methoxy-1-butanol

[0291] The performance evaluation method is explained below.

[0292] <Refractive index measurement> The photosensitive resin composition was applied onto a glass substrate using a spinner so that the thickness would be 2 μm after heat curing. The obtained substrate was vacuum dried for 1 minute, and then heated and dried on a hot plate at 100° C. for 100 seconds to obtain a coated substrate. Next, a manual exposure machine (MA-1100) manufactured by Dainihon Kaken Co., Ltd. was used to expose the substrate to light at a dose of 100 mJ / cm using a high-pressure mercury lamp that cuts off wavelengths of 330 nm or less. 2 The entire surface of the coated substrate was exposed to light with a wavelength of 365 nm at a light intensity of 45 mW / cm.2 Finally, the entire exposed substrate was heated and cured in an oven at 230° C. for 30 minutes to obtain a substrate for refractive index measurement.

[0293] The refractive index of the cured product was measured using a refractive index measurement plate. Specifically, the measurement was performed at 20°C using a Metricon Prism Coupler Model 2010 with a He-Ne laser of 633 nm as incident light. If the refractive index was 1.630 or more, it was rated as "A", if it was 1.600 or more but less than 1.630, it was rated as "B", and if it was less than 1.600, it was rated as "C".

[0294] <Preparation of hole resolution evaluation substrate> The photosensitive resin composition obtained in each Example and Comparative Example was applied onto a glass substrate using a spinner so that the thickness would be 2 μm after heat curing. The obtained substrate was vacuum dried for 1 minute, and then heated and dried on a hot plate at 100° C. for 100 seconds. The obtained coating film was exposed using a photomask. A mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used, and the exposure dose was 40 mJ / cm. 2 The exposure was performed so that the illuminance was 500 mW / cm 2 The slit width was 1.6 mm. A photomask with a covering area of ​​10 μm × 10 μm was used. Next, a development process was performed using a 2.38% TMAH aqueous solution with a shower at a pressure of 0.05 MPa for 40 seconds, and then the substrate was washed with pure water for 30 seconds. Finally, the substrate was heated and cured in an oven at 230°C for 30 minutes to prepare a hole resolution evaluation substrate.

[0295] <Preparation of glass substrate with organic undercoat> The ethylenically unsaturated compound, alkali-soluble resin, photopolymerization initiator, additive, and solvent were mixed in the following composition, and the obtained photosensitive resin composition for forming an organic undercoat film was used to prepare an organic undercoat film on a glass substrate by the following method. First, each component was added so that the solid content ratio of the ethylenically unsaturated compound, alkali-soluble resin, photopolymerization initiator, and additive was the following mixing ratio, and further, solvent-I was added as a solvent so that the total solid content ratio was 30 mass%, and the mixture was stirred and dissolved to prepare a photosensitive resin composition for forming an organic undercoat film. The composition of the photosensitive resin composition for forming an organic undercoat film is as follows, and the parts by mass represent the amount of solid content excluding the solvent in each component.

[0296] [Composition of photosensitive resin composition for organic base film formation] The following compounds were mixed, diluted with PGMEA to 30% by mass, and stirred and dissolved to prepare a photosensitive resin composition for forming an organic undercoat film. Ethylenically unsaturated compound: Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.) 49.2 parts by mass Alkali-soluble resin: Alkali-soluble resin-IV 49.2 parts by weight Photopolymerization initiator: Photopolymerization initiator-I 3 parts by weight Additives: BYK-330 (0.1 parts by weight), Nippon Kayaku PM-21 (0.5 parts by weight)

[0297] Next, the photosensitive resin composition for forming an organic undercoat film was applied onto a glass substrate using a spinner so that the thickness would be 1.5 μm after heat curing. The obtained substrate was vacuum dried for 1 minute, and then heated and dried on a hot plate at 90° C. for 90 seconds. Next, the obtained coated substrate was irradiated with a high-pressure mercury lamp to cut off wavelengths of 330 nm or less, and exposed to an exposure dose of 40 mJ / cm. 2 The light intensity at a wavelength of 365 nm was 45 mW / cm 2 Finally, the substrate was cured by heating in an oven at 230°C for 30 minutes, and then dry-cleaned using an ORC Manufacturing UV Dry Processor VUM-3073-F02-00 with the lamp on for 1 minute to obtain a glass substrate with an organic undercoat film.

[0298] <Preparation of hole resolution evaluation substrate with organic underlayer> The photosensitive resin composition obtained in each of the Examples and Comparative Examples described below was applied to a glass substrate with an organic undercoat film using a spinner so that the thickness would be 2 μm after heat curing. The resulting substrate was vacuum dried for 1 minute, and then heated and dried on a hot plate at 100° C. for 100 seconds. The resulting coating film was exposed using a photomask. A mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used, and the exposure dose was 40 mJ / cm. 2 The exposure time was 10 seconds. The illuminance was 500 mW / cm 2 The slit width was 1.6 mm. A photomask with a covering area of ​​10 μm × 10 μm was used. Next, a development process was performed using a 2.38% TMAH aqueous solution with a shower at a pressure of 0.05 MPa for 40 seconds, and then the substrate was washed with pure water for 30 seconds. Finally, the substrate was heated and cured in an oven at 230°C for 30 minutes to produce a hole resolution evaluation substrate with an organic undercoat film.

[0299] <Evaluation of hole resolution evaluation substrate> Of the hole resolution evaluation substrates and hole resolution evaluation substrates with organic undercoat film obtained above, the substrates in the 10 μm × 10 μm unexposed area were rated as "A" if they were sufficiently developed to expose the substrate or organic undercoat film, and as "C" if they were not sufficiently developed and the film remained.

[0300] [Examples 1-2 and Comparative Examples 1-3] Each component was added so that the ratio of the solid content of each component in the total solid content was the blending ratio in Table 1, and solvent was added so that the content of the total solid content was 20 mass% and the total solvent had a ratio of Solvent-I / Solvent-II = 90 / 10 (mass ratio), and the mixture was stirred and dissolved to prepare a photosensitive resin composition. Using each of the obtained photosensitive resin compositions, the refractive index and hole resolution were evaluated by the above-mentioned method. The blending ratios of the ethylenically unsaturated compound, the alkali-soluble resin, the photopolymerization initiator, and the surfactant in Table 1 are calculated on a solid content basis.

[0301] [Table 1]

[0302] From Examples 1 and 2, it can be seen that when the ethylenically unsaturated compound-I is used in combination with the alkali-soluble resin-I or II, the resulting cured product has a high refractive index. This is because the ethylenically unsaturated compound-I has a sulfur-containing aromatic heterocycle, and the alkali-soluble resin-I and II are epoxy (meth)acrylate resins having an aromatic ring in the main chain. In order to increase the refractive index, it is necessary to reduce the speed of light when passing through the molecule relative to the speed of light in a vacuum. That is, it is effective to locally increase the electron density in the molecule and introduce a structure with a large polarizability. From this, it is considered that by combining the ethylenically unsaturated compound-I having a sulfur-containing aromatic heterocycle with the epoxy (meth)acrylate resin resin-I or II having an aromatic ring in the main chain, the electron density and polarizability are increased due to sulfur or π electrons, and at the same time, the molecular volume is reduced by promoting the packing of the polymer chain due to the aromatic ring in the main chain, so that the resulting cured product has a high refractive index.

[0303] It is also found that Examples 1 and 2 can achieve not only a high refractive index but also good hole resolution. This is because, when developing the coating film of the photosensitive resin composition with an alkaline developer, the ethylenically unsaturated compound-I having a sulfur-containing aromatic heterocycle can be used to reduce the molecular volume while providing a high refractive index, and the alkali-soluble resins-I and II are epoxy (meth)acrylate resins having an aromatic ring in the main chain, and have good compatibility with the ethylenically unsaturated compound-I having a sulfur-containing aromatic heterocycle, so that the alkali-soluble resin can be uniformly distributed in the coating film of the photosensitive resin composition without phase separation, which makes it easier for the alkali developer to penetrate during development, and therefore the hole resolution is good.

[0304] In Comparative Example 1, the ethylenically unsaturated compound-II is not a compound having a sulfur-containing aromatic heterocycle, and in Comparative Examples 2 and 3, the alkali-soluble resin-III and the alkali-soluble resin-IV are acrylic ester copolymers having no aromatic group in the main chain, so that the refractive index and hole resolution are inferior.

[0305] [Examples 3 to 7 and Comparative Examples 4 and 5] Each component was added so that the ratio of the solid content of each component in the total solid content was the blending ratio in Table 2, and solvent was added so that the content of the total solid content was 20 mass% and the total solvent had a ratio of Solvent-I / Solvent-II = 90 / 10 (mass ratio), and the mixture was stirred and dissolved to prepare a photosensitive resin composition. Using each of the obtained photosensitive resin compositions, the refractive index and hole resolution were evaluated by the methods described below. The blending ratios of the ethylenically unsaturated compound, the alkali-soluble resin, the photopolymerization initiator, and the surfactant in Table 2 are calculated based on the solid content.

[0306] [Table 2]

[0307] <Refractive index measurement> The photosensitive resin composition was applied onto a glass substrate using a spinner so that the thickness would be 1.5 μm after heat curing. The obtained substrate was vacuum dried for 1 minute, and then heated and dried on a hot plate at 100° C. for 100 seconds to obtain a coated substrate. Next, a manual exposure machine (MA-1100) manufactured by Dainihon Kaken Co., Ltd. was used to expose the substrate to light at a dose of 100 mJ / cm using a high-pressure mercury lamp that cuts off wavelengths of 330 nm or less. 2 The entire surface of the coated substrate was exposed to light with a wavelength of 365 nm at a light intensity of 45 mW / cm. 2 Finally, the entire exposed substrate was heated and cured in an oven at 230° C. for 30 minutes to obtain a substrate for refractive index measurement.

[0308] The refractive index of the cured product was measured using a refractive index measurement plate. Specifically, the measurement was performed at 20°C using a Metricon Prism Coupler Model 2010 with a He-Ne laser of 633 nm as incident light. If the refractive index was 1.640 or higher, it was rated as "AA", if it was 1.630 or higher, it was rated as "A", if it was 1.600 or higher but less than 1.630, it was rated as "B", and if it was less than 1.600, it was rated as "C".

[0309] <Preparation of hole resolution evaluation substrate> The photosensitive resin composition obtained in each Example and Comparative Example was applied using a spinner onto a glass substrate having an indium tin oxide (ITO) film formed on the surface thereof, so that the thickness would be 1.5 μm after heat curing (baking). The obtained substrate was vacuum dried for 1 minute, and then heated and dried on a hot plate at 100°C for 100 seconds. The obtained coating film was exposed using a photomask. A Canon mirror projection type exposure machine (MPA-600FA) was used, and the exposure dose was 60 mJ / cm. 2 The exposure was performed so that the illuminance was 500 mW / cm 2 The slit width was 1.6 mm. A photomask with a covering area of ​​10 μm × 10 μm was used. Next, a development process was carried out using a 2.38% TMAH aqueous solution at a temperature of 24°C and a shower pressure of 0.05 MPa for 40 seconds, and then the substrate was washed with pure water for 30 seconds. Finally, the substrate was heated and cured in an oven at 230°C for 30 minutes to prepare a hole resolution evaluation substrate.

[0310] <Evaluation of hole resolution evaluation substrate> Of the hole resolution evaluation substrates obtained above, those in which the 10 μm x 10 μm unexposed area was sufficiently developed to expose the substrate on which the ITO film was formed were rated as "AA," those in which the 30 μm x 30 μm unexposed area was sufficiently developed to expose the substrate on which the ITO film was formed were rated as "A," and those in which the area was not sufficiently developed and the film remained were rated as "C."

[0311] From Examples 3 to 7, it can be seen that when the ethylenically unsaturated compound-I is used in combination with the alkali-soluble resin-I, the resulting cured product has a high refractive index. This is due to the fact that the ethylenically unsaturated compound-I has a sulfur-containing aromatic heterocycle, and the alkali-soluble resin-I is an epoxy (meth)acrylate resin having an aromatic ring in the main chain. In order to increase the refractive index, it is necessary to reduce the speed of light when passing through the molecule relative to the speed of light in a vacuum. That is, it is effective to locally increase the electron density in the molecule and introduce a structure with a large polarizability. From this, it is considered that by combining the ethylenically unsaturated compound-I having a sulfur-containing aromatic heterocycle with the resin-I, which is an epoxy (meth)acrylate resin having an aromatic ring in the main chain, the electron density and polarizability are increased due to sulfur or π electrons, and at the same time, the aromatic ring in the main chain promotes packing of the polymer chain, thereby reducing the molecular volume, and the resulting cured product has a high refractive index. From Examples 3 to 7, it is found that by setting the content ratio of the ethylenically unsaturated compound-I to 100 parts by mass of the alkali-soluble resin-I to 67 parts by mass to 200 parts by mass, the obtained cured product has a high refractive index exceeding 1.630. In particular, it is found that by setting the content ratio of the ethylenically unsaturated compound-I to 100 parts by mass of the alkali-soluble resin-I to 100 parts by mass to 200 parts by mass, the obtained cured product has an extremely high refractive index exceeding 1.640. In addition, by setting the content ratio of the ethylenically unsaturated compound-I to 100 parts by mass of the alkali-soluble resin-I to 67 parts by mass to 125 parts by mass, the hole resolution becomes good. In particular, it is found that by setting the content ratio of the ethylenically unsaturated compound-I to 100 parts by mass of the alkali-soluble resin-I to 67 parts by mass to 100 parts by mass, the hole resolution becomes extremely good.

[0312] In Comparative Example 4, the ethylenically unsaturated compound-II is not a compound containing a sulfur-containing aromatic heterocycle, and in Comparative Example 5, the alkali-soluble resin-IV is an acrylic ester copolymer not having an aromatic ring in the main chain, so that the refractive index and hole resolution are inferior.

Claims

1. A photosensitive resin composition comprising (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, The (A) ethylenically unsaturated compound contains an ethylenically unsaturated compound (A1) having two ethylenically unsaturated bonds and two benzothiazole rings in the molecule, The ethylenically unsaturated compound (A1) is a compound represented by the following general formula (A1-1):

1. A photosensitive resin composition, wherein the alkali-soluble resin (C) contains an epoxy (meth)acrylate resin (C1) having an aromatic ring in its main chain. 【Chemistry 1】 (In formula (A1-1), R １ represents a hydrogen atom or a methyl group. Cy represents a benzothiazole ring. Q １ and Q. ２ Each of X independently represents an alkylene group having 1 to 6 carbon atoms. １ and X ２ each independently represents -O-, -S-, or -NR ２ --, --NR ２ -(C=O)- or -NR ２ represents -(C=O)-O-. １ and Z ２ Each of m and n independently represents a divalent hydrocarbon group which may have a substituent. Each of p and q represents 0. ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

2. The photosensitive resin composition according to claim 1, wherein the content of the ethylenically unsaturated compound (A1) is 20 mass % or more based on the total solid content of the photosensitive resin composition.

3. 2. The photosensitive resin composition according to claim 1, wherein a content ratio of the ethylenically unsaturated compound (A1) per 100 parts by mass of the alkali-soluble resin (C) is 120 parts by mass or less.

4. A photosensitive resin composition as described in claim 1, wherein the epoxy (meth)acrylate resin (C1) having an aromatic ring in its main chain has a partial structure represented by the following general formula (i): 【Chemistry 2】 (In formula (i), R a represents a hydrogen atom or a methyl group. b represents a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, each of which may have a substituent. k represents 1 or 2. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.

5. The R b The photosensitive resin composition according to claim 4, wherein the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups is a group represented by the following general formula (i-A): 【Chemistry 3】

6. 6. The photosensitive resin composition according to claim 1, wherein a cured film obtained by curing the photosensitive resin composition has a refractive index of 1.620 or more at a wavelength of 633 nm.

7. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5.

8. An image display device comprising the cured product according to claim 7.

Images