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

Photosensitive resin composition, cured product, and image display device

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

[0002] An organic EL (Electro Luminescence) element is a self-luminous element that utilizes the principle that, when an electric field is applied, a fluorescent substance or the like emits light due to the recombination energy between holes injected from an anode and electrons injected from a cathode. In recent years, active research and development of organic EL elements has been conducted for applications such as lighting devices and display devices.

[0003] For example, organic EL display devices have advantages over conventional CRTs and LCDs in terms of visibility and viewing angle, as well as excellent features such as light weight, thin layering, 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. As a result, total reflection or interference of emitted light is likely to occur at the interface, resulting in a light extraction efficiency of less than 20%, with most of the light being lost.

[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 is laminated on the organic layer, on which a plurality of pixel electrodes constituting the back electrode and TFTs (thin film transistors) serving as switching elements for the pixel electrodes are formed in a matrix.

[0005] Light emitted from the organic layer is emitted directly or after being reflected by a back electrode made of aluminum or the like from the light-transmitting substrate. At this 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 may undergo total reflection, becoming guided light that travels inside the element while being totally reflected in the plane 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 electroluminescence (EL) display devices but also for liquid crystal display applications. For example, Patent Document 2 describes a photosensitive composition having a high refractive index and high adhesion, which uses oxide fine particles such as titanium oxide and a specific fluorene skeleton-containing compound. Patent Document 3 also describes a composition for optical materials, which uses a specific compound.

[0008] Japanese Patent Publication No. 2006-12826 Japanese Patent Publication No. 2014-91790 Japanese Patent Publication No. 2021-24842

[0009] TiO ２ and ZrO ２ While a cured product with a high refractive index can be obtained by incorporating high refractive index metal oxide particles, such as those described in Patent Document 1, into a photosensitive resin composition, the high dielectric constant derived from the metal oxide particles can cause problems such as signal delay and heat loss due to dielectric loss when a planarizing film or microlens formed from the cured product is disposed between a TFT and a pixel electrode for the purpose of improving light extraction efficiency. In recent years, it has been preferable to reduce or remove the amount of metal oxide particles. The inventors have conducted studies and found that a photosensitive composition containing a fluorene skeleton-containing compound described in Patent Document 2 has a low refractive index and insufficient hole resolution. Furthermore, it has been found that the compound described in Patent Document 3 has problems 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 that can form a cured product with 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 including the cured product of the present invention.

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

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

[0013]

[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 are each independently —O—, —S—, or —NR ２ -, -NR ２ -(C=O)- or -NR ２ represents —(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 ２represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) [3] The photosensitive resin composition of [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] The photosensitive resin composition of any of [1] to [3], wherein the content of the ethylenically unsaturated compound (A1) is 120 mass% or less based on 100 mass parts of the alkali-soluble resin (C). [5] The photosensitive resin composition of any of [1] to [4], 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):

[0015]

[0016] (In formula (i), R a 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 of any one of [1] to [5], wherein the refractive index of the cured film obtained by curing the photosensitive resin composition at a wavelength of 633 nm is 1.620 or more. [7] A cured product obtained by curing the photosensitive resin composition of any one of [1] to [6]. [8] An image display device comprising the cured product of [7].

[0017] According to the present invention, it is possible to provide a photosensitive resin composition that can form a cured product with a high refractive index and excellent hole resolution.

[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 exceeds the gist of the present invention. In the present invention, "(meth)acrylic" means "either acrylic or methacrylic, or both." "Total solids" means all components in a 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, "(co)polymer" means both a homopolymer and a copolymer, and "(acid) anhydride" and "(anhydrous)...acid" mean 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 refers to the acid value calculated as the 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 needed, 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 their composition 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 including (A) the ethylenically unsaturated compound, the curability of the coating film is improved. The photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound (A1) (hereinafter, sometimes simply referred to as ethylenically unsaturated compound (A1)) having 1 to 3 ethylenically unsaturated bonds and 1 to 3 sulfur-containing aromatic heterocycles in the molecule.

[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 atoms and aromatic rings are increased, thereby imparting a high refractive index to the cured product.

[0023] From the viewpoint of curability, 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 achieving a high refractive index and ensuring solubility, 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 achieving a high refractive index and ensuring solubility, it is more preferable that the ethylenically unsaturated compound (A1) have two ethylenically unsaturated bonds and two 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 both an oxygen atom and a nitrogen atom. The number of sulfur atoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1, from the viewpoint of avoiding coloration and ensuring solubility. 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 monocycle or a fused ring. A fused ring is preferred from the viewpoint of increasing the refractive index. The number of rings constituting the fused ring is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3 from the viewpoint of facilitating raw material availability 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 a high 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]

[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 ２Each of X independently represents an alkylene group having 1 to 6 carbon atoms. １ and X ２ are each independently —O—, —S—, or —NR ２ -, -NR ２ -(C=O)- or -NR ２ represents —(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 both an oxygen atom and a nitrogen atom. The number of sulfur atoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1, from the viewpoint of avoiding coloration. The number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1, from the viewpoint of avoiding coloration and ensuring solubility. The sulfur-containing aromatic heterocycle may be a monocycle or a fused ring. A fused ring is preferred from the viewpoint of achieving a high refractive index. The number of rings constituting the fused ring is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3, from the viewpoint of facilitating raw material availability 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 a high 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 independently represent 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 ２ may be the same or different. Q is preferred in terms of ease of obtaining raw materials and ease of controlling 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—, or —NR ２ -, -NR ２ -(C=O)- or -NR ２ represents —(C═O)—O—. ２represents 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 less likely to decrease, and the viscosity is more likely to decrease due to the small molecular weight, and processability is more 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 refractive index, n is preferably 2 to 3, and more preferably 2. It is particularly preferable that m and n each are 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 more likely the refractive index is to be high. It is particularly preferable that p and q are each 0.

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

[0036]

[0037]

[0038] From the viewpoint of refractive index, the ethylenically unsaturated compounds (A1) represented by formula (a3), (a4) or (a5) are 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, and 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 setting the amount at or above the lower limit, a high refractive index tends to be obtained. On the other hand, by setting the amount at or below the upper limit, a low colorability tends to be obtained. The upper and lower limits can be arbitrarily combined. For example, the amount 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 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 setting the double bond equivalent at or above the lower limit, a high refractive index tends to be obtained. By setting the double bond equivalent at or below the upper limit, curability tends to be improved, and a low dielectric constant and high volume resistivity tend to be obtained. The above upper and lower limits can be arbitrarily combined. For example, the double bond equivalent 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 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, sometimes simply referred to as "other ethylenically unsaturated compounds"). In the present invention, the ethylenically unsaturated compound refers to 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 resulting ability to increase the difference in developer solubility between exposed and unexposed areas. 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 two or more, more preferably three or more, and is preferably 15 or less, more preferably eight or less, and even more preferably six or less. The above upper and lower limits can be arbitrarily combined. For example, it is 2 to 15, preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6. By setting the number at or above the lower limit, developability tends to be better, while by setting the number at or below the upper limit, curability tends to be improved and the resulting composition tends to have a low dielectric constant and high volume resistivity.

[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 of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with 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 some or all of the acrylates of the above-mentioned exemplary compounds are replaced with methacrylates; itaconic acid esters in which some or all of the acrylates of the above-mentioned exemplary compounds are replaced with itaconates; crotonate esters in which some or all of the acrylates of the above-mentioned exemplary compounds are replaced with cronates; and maleic acid esters in which some 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 polyvalent 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 typical examples include a condensate of acrylic acid, phthalic acid, and ethylene glycol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, and a condensate 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 addition reaction products of a polyfunctional epoxy compound with a hydroxy (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 compound is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid or a urethane (meth)acrylate, 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, and particularly preferably 40% by mass or more, based on the total solid content. It is also preferably 80% 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, it 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. A content above the lower limit tends to result in a high refractive index, while a content below the upper limit tends to result in good hole resolution.

[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, and particularly preferably 40% by mass or more, based on the total solid content. It is also preferably 80% 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, it 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 setting the content at or above the lower limit, the refractive index tends to be improved, while by setting the content at or below the upper limit, the hole resolution tends to be improved.

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

[0052] The content 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 at least 10 parts by mass, more preferably at least 20 parts by mass, even more preferably at least 40 parts by mass, even more preferably at least 60 parts by mass, and particularly preferably at least 80 parts by mass, and is preferably at most 200 parts by mass, more preferably at most 150 parts by mass, and even more preferably at most 120 parts by mass. The above upper and lower limits can be arbitrarily combined. For example, the content 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 120 parts by mass, and particularly preferably 80 to 120 parts by mass. Setting the content at or above the lower limit tends to improve curability, while setting the content at or below the upper limit tends to improve hole resolution.

[0053] The content 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, and 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, even more preferably 60 to 120 parts by mass, and particularly preferably 80 to 120 parts by mass. By setting the content at or above the lower limit, the refractive index tends to be improved, and by setting the content at or below 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 a photopolymerization initiator (B). The photopolymerization initiator (B) is not particularly limited as long as it is a compound that polymerizes the ethylenically unsaturated compound (A) by actinic rays, for example, polymerizes the ethylenically unsaturated bond of the ethylenically unsaturated compound (A).

[0055] The photosensitive resin composition of the present invention can use, as the photopolymerization initiator (B), a photopolymerization initiator commonly 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, and α-aminoalkylphenone derivatives; and oxime ester compounds described in JP-A-2000-80068 and JP-A-2006-36750.

[0056] Specific examples of the metallocene compound 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-(pyrro-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. For example, when an alkali-soluble resin containing a phenolic hydroxyl group is used, the sensitivity is disadvantageous, so an oxime ester compound with such excellent sensitivity is particularly useful. Oxime ester compounds have a high quantum yield in the photoreaction and the radicals generated are highly active, so they are highly sensitive and stable against thermal reactions, and a highly sensitive photosensitive resin composition can be obtained with a small amount.

[0062] Examples of the oxime ester compound include compounds represented by the following general formula (IV).

[0063]

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

[0065] R 21aThe number of carbon atoms in the alkyl group in the formula (I) is not particularly limited, but from the viewpoints of solubility in solvents and sensitivity, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and even more 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 cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. Examples of substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy 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 preferably unsubstituted. Furthermore, from the viewpoints of sensitivity, solubility, and chemical resistance, a methyloxycarbonyl group and an ethyloxycarbonyl group are preferred.

[0066] R 21a Examples of the aromatic ring group in 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. Furthermore, 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, 5 to 30 is preferred, 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, a phenyl group and a naphthyl group are preferred, and a 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 are linked are preferred, and linked alkoxy groups are more preferred. From the viewpoint of sensitivity, solubility, and chemical resistance, R 21a is preferably an alkyl group which may have a substituent.

[0068] R21b As the group, preferred are 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. 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 the formula (I) is not particularly limited, but from the viewpoint of solubility in solvents 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 carboxy group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, it is preferable that the alkanoyl group be unsubstituted.

[0070] R 22a The number of carbon atoms in the aroyl group in is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is preferably 7 or more, and preferably 20 or less, more preferably 15 or less, and even more 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 viewpoint of sensitivity, R 22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

[0071] For example, Japanese Patent No. 4454067, WO 2002 / 100903, WO 2012 / 45736, WO 2015 / 36910, WO 2006 / 18973, WO 2008 / 78678, Japanese Patent No. 4818458, WO 2005 / 80338, WO 2008 / 75564, WO 2009 / 131189, WO 2009 / 131189, WO 2010 / 133077, WO 2010 / 102502, photopolymerization initiators described in WO 2012 / 68879, and the like 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 light source for image exposure may be blended with the photopolymerization initiator (B) in order to increase sensitivity.

[0073] Examples of sensitizing dyes 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, and compounds described in JP-A-47-2528, JP-A-54-155292, and compounds described in JP-A-54-155293. Examples of dyes having a dialkylaminobenzene skeleton include those described in JP-B No. 45-37377, JP-A No. 48-84183, JP-A No. 52-112681, JP-A No. 58-15503, JP-A No. 60-88005, JP-A No. 59-56403, JP-A No. 2-69, JP-A No. 57-168088, JP-A No. 5-107761, JP-A No. 5-210240, and JP-A No. 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. Examples thereof include 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, and 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole. More preferred are p-dialkylaminophenyl group-containing compounds such as (p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine, with 4,4'-dialkylaminobenzophenone being particularly preferred. One type of sensitizing dye may be used alone, or two or more types may be used in combination.

[0075] Examples of the polymerization accelerator that can be used include 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. One type of polymerization accelerator may be used alone, or two or more types may be used in combination.

[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, and even more preferably 2% by mass or more, based on the total solid content of the photosensitive resin composition. It is also 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. The above 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, 1 to 10% by mass is even more preferred, and 2 to 7% by mass is particularly preferred. By setting the content at or above the lower limit, sensitivity tends to be improved. By setting the content at or below the upper limit, hole resolution tends to be improved.

[0077] The blending ratio of the (B) photopolymerization initiator to the (A) ethylenically unsaturated compound 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, per 100 parts by mass of the (A) ethylenically unsaturated compound. It is also 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. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1 to 20 parts by mass, even more preferably 2 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass. By adjusting the blending ratio to be equal to or greater than the lower limit, sensitivity tends to be improved. By adjusting the blending ratio to be equal to or less than the upper limit, hole resolution tends to be improved.

[0078] A chain transfer agent may be used in combination with the (B) photopolymerization initiator. Examples of chain transfer agents include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use a mercapto group-containing compound because it has a high chain transfer effect and tends to improve sensitivity and surface curability. This is thought to be because the small S—H bond energy makes bond cleavage more likely to occur, facilitating hydrogen abstraction reactions and chain transfer reactions.

[0079] Examples of mercapto group-containing compounds 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 compounds 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 (C) alkali-soluble resins include various resins having a carboxy group or a hydroxy group, but from the viewpoint of excellent developability, those having a carboxy group are preferred. Furthermore, 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, sometimes abbreviated as epoxy(meth)acrylate resin (C1)). The presence of an aromatic ring in the main chain tends to result in a high refractive index. Furthermore, due to the good compatibility with the sulfur-containing aromatic heterocycle in the ethylenically unsaturated compound (A1), the alkali-soluble resin is easily distributed uniformly in the coating film of the photosensitive resin composition without phase separation. This facilitates penetration of the alkaline developer during development, which tends to result in good hole resolution.

[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, a resin obtained by ring-opening addition of a carboxy group of an unsaturated monocarboxylic acid to the epoxy group of the epoxy resin, thereby adding an ethylenically unsaturated bond to the epoxy compound via an ester bond (—COO—), and adding one carboxy group of a polybasic acid anhydride to the hydroxyl group generated in this process, may be used. Another example is a resin obtained by simultaneously adding a polyhydric alcohol when adding a polybasic acid anhydride.

[0083] Furthermore, a resin obtained by reacting a compound having a functional group capable of further reacting with the carboxy group of the resin obtained by the above reaction is also included in the above epoxy (meth)acrylate resin (C1). As described above, epoxy (meth)acrylate resins have substantially no epoxy groups in their chemical structure and are not limited to "(meth)acrylate", but are named as such according to convention because epoxy compounds (epoxy resins) are used as raw materials and "(meth)acrylate" is a typical example.

[0084] Here, the term "epoxy resin" refers to raw material compounds before they are thermoset to form a resin, and the epoxy resin can be appropriately selected from known epoxy resins. Furthermore, the epoxy resin can be a compound obtained by reacting a phenolic compound with an epihalohydrin. The phenolic compound is preferably a compound having a divalent or higher 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 ethers of 9,9-bis(4'-hydroxyphenyl)fluorene, and diglycidyl ethers of 1,1-bis(4'-hydroxyphenyl)adamantane, and thus those having an aromatic ring in the main chain can be suitably 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, and bisphenol A epoxy resin is particularly preferred. Examples of epoxy resins include bisphenol A type epoxy resins (e.g., "jER (registered trademark, the same applies hereinafter) 828," "jER1001," "jER1002," and "jER1004" manufactured by Mitsubishi Chemical Corporation, and "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resins (e.g., "jER807," "jER4004P," "jER4005P," and "jER1302" manufactured by Mitsubishi Chemical Corporation), and the like. 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 (for example, "jERYX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, "EPPN (registered trademark, the same applies hereinafter)-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 (for example, "EOCN (registered trademark, the same applies hereinafter)-102S," "EOCN-1020," and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resins (for example, "EPPN-501," "EPPN-502" manufactured by Nippon Kayaku Co., Ltd.), "," "EPPN-503"," alicyclic epoxy resins ("CELLOXIDE (registered trademark, the same applies hereinafter) 2021P" and "CELLOXIDE EHPE" manufactured by Daicel Corporation), 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]

[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]

[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]

[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]

[0093] In formulas (i-13-1) and (i-13-2), R 131 ~R 134 and R 135 ~R 137 each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. * represents a bond.

[0094]

[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, and 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 ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., 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 reaction products 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] The use of a polyhydric alcohol increases the molecular weight of the epoxy (meth)acrylate resin (C1), allows for the introduction of branches into the molecule, and tends to balance the molecular weight and viscosity. Furthermore, the introduction rate of acid groups into the molecule can be increased, which tends to make it easier to balance sensitivity, adhesion, and the like. Examples of polyhydric alcohols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol.

[0100] In addition to the above-mentioned epoxy (meth)acrylate resins (C1), resins described in Korean Patent Publication No. 10-2013-0022955 can be used.

[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, and particularly preferably 80 mgKOH / g or more. It is also 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 making the content equal to or greater than the lower limit, the developability tends to be improved, and by making the content 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 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000 or more, and is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, even more preferably 10,000 or less, and particularly preferably 8,000 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 1,000 to 30,000, preferably 2,000 to 20,000, more preferably 3,000 to 15,000, even more preferably 4,000 to 10,000, and particularly preferably 5,000 to 8,000. Setting it to a value equal to or greater than the lower limit tends to improve film strength, while setting it to a value equal to or less than the upper limit tends to reduce residue.

[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, 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, and particularly preferably 50% by mass or more, and is 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, the content is 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. Setting the content at or above the lower limit tends to improve linearity, while setting the content at or below the upper limit tends to form a cured product with narrow line widths and high resolution.

[0104] The epoxy (meth)acrylate resin (C1) can be synthesized by a conventionally known method. Specifically, a method can be used in which the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, an acid or ester compound having an ethylenically unsaturated bond is added to cause an addition reaction, and then a polybasic acid or an anhydride thereof is added to continue the reaction. For example, the methods described in Japanese Patent Nos. 3,938,375 and 5,169,422 can be mentioned.

[0105] Examples of organic solvents used in the reaction include methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. The organic solvents 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. Examples of thermal polymerization inhibitors used in the reaction include one or more of hydroquinone, hydroquinone monomethyl ether, and methylhydroquinone. The thermal polymerization inhibitors 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 is preferably 0.7 to 1.3 chemical equivalents, more preferably 0.9 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the epoxy group of the epoxy resin. The temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C. The amount of the polybasic acid (anhydride) used is preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the hydroxyl group generated in 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]

[0109] In formula (i), R a 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]

[0111] In formula (ii), R c R 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]

[0113] In formula (iii), R erepresents 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 an arbitrary 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]

[0116] In formula (i), R a represents a hydrogen atom or a methyl group, R 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.

[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 to one or more divalent aromatic ring groups.

[0118] Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. Among these, linear aliphatic groups are preferred from the viewpoint of development solubility. Cyclic aliphatic groups are preferred from the viewpoint of reducing penetration of a developer into exposed areas. 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 above upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 3 to 15, and more preferably 6 to 10. By setting the number at or above the lower limit, film strength tends to be improved, and by setting the number at or below the upper limit, hole resolution tends to be improved.

[0119] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene. From the viewpoints of refractive index, hole resolution, and production costs, a methylene group is preferred. Examples of divalent branched aliphatic groups include structures in which the aforementioned divalent linear aliphatic groups are bonded to a side chain, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group. The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, and more preferably 5 or less. The above upper and lower limits can be arbitrarily combined. For example, the number is 1 to 10, preferably 2 to 5. By setting the number equal to or greater than the lower limit, film strength tends to be improved, while by setting the number equal to or less than the upper limit, 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] Examples of the divalent aromatic ring group include 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 above 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 setting it to be equal to or greater than the lower limit, film strength tends to be improved, and by setting it to be equal to or less than the upper limit, 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 heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, 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, unsubstituted groups are preferred.

[0125] Examples of the group linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include groups linking one or more of the aforementioned divalent aliphatic groups with one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups in the group linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups is not particularly limited, but is preferably one or more, more preferably two or more, and is preferably 10 or less, more preferably five or less, and even more preferably three 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. Setting the number at or above the lower limit tends to improve developability, while setting it at or below the upper limit tends to improve film strength. The number of divalent aromatic ring groups in the group linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups is not particularly limited, but is preferably one or more, more preferably two or more, and is preferably 10 or less, more preferably five or less, and even more preferably three or less. The upper and lower limits can be arbitrarily combined, for example, 1 to 10, preferably 1 to 5, and more preferably 2 to 3. By setting the value to be equal to or greater than the lower limit, the film strength tends to be improved, and by setting the value to be 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 formulae (i-A) to (i-F). From the viewpoints of refractive index and hole resolution, the group represented by the following general formula (i-A) is preferred.

[0127]

[0128] The benzene ring in formula (i) may be further substituted with any substituent. Examples of the substituent that can be used on 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 substituents is not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably 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]

[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 monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Examples of polybasic acids 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 properties, 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 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, and 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 the number equal to or greater than the lower limit, developability tends to be improved, and by making the number 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, and 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 the number equal to or greater than the lower limit, developability tends to be improved, and by making the number 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 listed below.

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146] An 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]

[0148] In formula (ii), R c R 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 cyclic group and an aromatic cyclic group.

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

[0151] Examples of the aliphatic ring in the aliphatic cyclic 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, 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 the number equal to or greater than the lower limit, film strength tends to be improved, and by making the number equal to or less than the upper limit, 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, and particularly preferably 12 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 40, more preferably 8 to 30, even more preferably 10 to 20, and even more preferably 12 to 15. By setting it to be equal to or greater than the lower limit, film strength tends to be improved, and by setting it to be equal to or less than the upper limit, 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] Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. Among these, linear aliphatic groups are preferred from the viewpoint of improving developability. Cyclic aliphatic groups are 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 above upper and lower limits can be arbitrarily combined. For example, it is 1 to 25, preferably 3 to 20, and more preferably 6 to 15. By setting the number at or above the lower limit, film strength tends to be improved, and by setting the number at or below the upper limit, developability tends to be improved.

[0157] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene. From the viewpoints of refractive index and hole resolution, a methylene group is preferred. Examples of divalent branched aliphatic groups include structures in which the aforementioned divalent linear aliphatic groups are bonded to, as a side chain, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl groups.

[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 the number equal to or greater than the lower limit, film strength tends to be improved, and by making the number equal to or less than the upper limit, 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] Examples of the divalent aromatic ring group include 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 setting it to the lower limit or more, film strength tends to be improved, and by setting it to the upper limit or less, 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 heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, 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, unsubstituted groups are preferred.

[0165] Examples of the group linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include groups linking one or more of the aforementioned divalent aliphatic groups with one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups in the group linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups is not particularly limited, but is preferably one or more, more preferably two or more, and is preferably 10 or less, more preferably five or less, and even more preferably three 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. Setting the number at or above the lower limit tends to improve developability, while setting it at or below the upper limit tends to improve film strength. The number of divalent aromatic ring groups in the group linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups is not particularly limited, but is preferably one or more, more preferably two or more, and is preferably 10 or less, more preferably five or less, and even more preferably three or less. The upper and lower limits can be arbitrarily combined, for example, 1 to 10, preferably 1 to 5, and more preferably 2 to 3. By setting the value to be equal to or greater than the lower limit, the film strength tends to be improved, and by setting the value to be 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 formulae (i-A) to (i-F). From the viewpoints of film strength and a high refractive index, the group represented by formula (i-A) 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 aromatic ring group is substituted with the cyclic hydrocarbon group as a side chain, and a mode in which one carbon atom of an aliphatic group is included to form the cyclic hydrocarbon group as a side chain.

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

[0169]

[0170] In formula (ii-1), R chas 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 a monovalent cyclic hydrocarbon group which may have a substituent. Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

[0172] The number of rings in the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The above upper and lower limits can be combined in any combination. For example, it is 1 to 6, preferably 1 to 4, and more preferably 2 to 3. By setting the number at or above the lower limit, film strength tends to be improved, and by setting it at or below the upper limit, developability tends to be improved. The number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and 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 combined in any combination. For example, it is 4 to 40, preferably 4 to 30, more preferably 6 to 20, and even more preferably 8 to 15. By setting it at or above the lower limit, film strength tends to be improved, and by setting it at or below the upper limit, 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, even more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. The above upper and lower limits can be combined in any combination. For example, it is 1 to 10, preferably 2 to 10, and more preferably 3 to 5. By setting the number at or above the lower limit, film strength tends to be improved, and by setting it at or below the upper limit, developability tends to be improved. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The above upper and lower limits can be combined in any combination. For example, it is 4 to 30, preferably 5 to 20, and more preferably 6 to 15. By setting it at or above the lower limit, film strength tends to be improved, and by setting it at or below the upper limit, 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, unsubstituted groups are 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 n equal to or more than the lower limit, developability tends to be improved, and by making n 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, more preferably an adamantyl group.

[0179] The benzene ring in formula (ii-1) may be further substituted with any substituent. Examples of the substituent acceptable for the benzene ring in formula (ii-1) 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 substituents is not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.

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

[0181]

[0182]

[0183]

[0184]

[0185]

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

[0187]

[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 cyclic group and an aromatic cyclic group.

[0190] The number of rings in the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less. The above upper and lower limits can be combined in any combination. For example, it is 1 to 10, preferably 2 to 5. By setting the number equal to or greater than the lower limit, film strength tends to be improved, and by setting the number equal to or less than the upper limit, developability tends to be improved. The number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The above upper and lower limits can be combined in any combination. For example, it is 4 to 40, preferably 6 to 35, and more preferably 8 to 30. By setting the number equal to or greater than the lower limit, film strength tends to be improved, and by setting the number equal to or less than the upper limit, 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, even more preferably 3 or more, and is preferably 10 or less, more preferably 5 or less. The above upper and lower limits can be combined in any combination. For example, it is 1 to 10, preferably 2 to 10, and more preferably 3 to 5. By setting the number at or above the lower limit, film strength tends to be improved, and by setting the number at or below the upper limit, developability tends to be improved. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. 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 combined in any combination. For example, it is 4 to 40, preferably 6 to 30, more preferably 8 to 20, and even more preferably 10 to 15. By setting the content to be equal to or greater than the lower limit, the film strength tends to be improved, and by setting the content to be 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, a 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, unsubstituted groups are 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. β is 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 acceptable for the benzene ring in formula (ii-2) 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 substituents is not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.

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

[0197]

[0198]

[0199]

[0200]

[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]

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

[0204] The polybasic acid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Examples of polybasic acids 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 properties, 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 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 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 the number equal to or greater than the lower limit, film strength tends to be improved, and by making the number equal to or less than the upper limit, 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 above can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, and more preferably 3 to 10. By making the number equal to or greater than the lower limit, the film strength and refractive index tend to be improved, and by making the number 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 the number equal to or greater than the lower limit, the film strength and refractive index tend to be improved, and by making the number 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 above can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, and more preferably 3 to 10. By making the number equal to or greater than the lower limit, film strength tends to be improved, and by making the number equal to or less than the upper limit, 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]

[0212] In formula (iii), R erepresents 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 an arbitrary 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, a straight chain is preferable. From the viewpoint of development adhesion, a branched chain is preferable. 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 greater than the lower limit, film strength tends to be improved, and by making it equal to or less than the upper limit, 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 cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less. The above upper and lower limits can be combined in any combination. For example, it is 1 to 10, preferably 2 to 5. By setting the number equal to or greater than the lower limit, film strength tends to be improved, and by setting the number equal to or less than the upper limit, developability tends to be improved. The number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The above upper and lower limits can be combined in any combination. For example, it is 4 to 40, preferably 6 to 35, and more preferably 8 to 30. By setting the number equal to or greater than the lower limit, film strength tends to be improved, and by setting the number equal to or less than the upper limit, 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, even more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. The above upper and lower limits can be combined in any combination. For example, it is 1 to 10, preferably 2 to 10, and more preferably 3 to 5. By setting the number at or above the lower limit, film strength tends to be improved, and by setting it at or below the upper limit, developability tends to be improved. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. 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 combined in any combination. For example, it is 4 to 40, preferably 6 to 30, more preferably 8 to 20, and even more preferably 10 to 15. By setting it at or above the lower limit, film strength tends to be improved, and by setting it at or below the upper limit, 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, a 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, unsubstituted groups are 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 on the benzene ring in formula (iii) 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 substituents is not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferable that the benzene 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]

[0225] In formula (iii-1), R e and γ have the same meaning as 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 monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Examples of polybasic acids 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 properties, 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, more preferably 10 to 15. By making the number equal to or greater than the lower limit, hole resolution tends to be improved, and by making the number 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 above 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 the number equal to or greater than the lower limit, hole resolution tends to be improved, and by making the number 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 listed below.

[0230]

[0231]

[0232] [Alkali-soluble resin other than epoxy (meth)acrylate resin (C1)] The alkali-soluble resin (C) 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, this may be referred to as "other alkali-soluble resin"). Examples of other alkali-soluble resins include 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, and even more preferably 70 mgKOH / g or more. It is also preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. The above 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 setting the acid value at or above the lower limit, developability tends to be improved, while by setting the acid value at or below the upper limit, development adhesion tends to be improved. When the alkali-soluble resin (C) is a mixture of two or more types, the acid value refers to a weighted average value based on the content ratio of the resins.

[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, based on the total solid content of the photosensitive resin composition. It is also preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it is 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 setting the content at or above the lower limit, hole resolution tends to be improved, while by setting the content at or below the upper limit, the refractive index tends to be improved.

[0236] The sum of the content of the (A) ethylenically unsaturated compound and the content of the (C) alkali-soluble resin in the total solids 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, and particularly preferably 90% by mass or more, and is preferably 100% by mass or less, and more preferably 95% by mass or less. The above 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 setting the content at or above the lower limit, the adhesion of the cured product to the substrate tends to be improved, while by setting the content at or below the upper limit, the curability tends to be improved.

[0237] [1-2] Other Components of the Photosensitive Resin Composition In addition to the components described above, 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] Surfactant 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, and among these, silicone-based surfactants and fluorine-based surfactants are preferred. Silicone-based surfactants are preferred because they have the effect of removing residues of the photosensitive resin composition from unexposed areas during development and also have the function of exhibiting wettability, and polyether-modified silicone-based surfactants are more preferred.

[0239] The fluorine-based surfactant is preferably a compound having a fluoroalkyl or fluoroalkylene group at at least one site of the terminal, main chain, or side chain. Commercially available fluorine-based surfactants include "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 Ltd., and "DFX-18" manufactured by Neos Corporation.

[0240] Commercially available silicone surfactants include, for example, "DC3PA," "SH7PA," "DC11PA," "SH21PA," "SH28PA," "SH29PA," "8032 Additive," and "SH8400" manufactured by Dow Corning Toray Co., Ltd., and "BYK (registered trademark, the same applies hereinafter) 323" and "BYK330" manufactured by BYK-Chemie Co., Ltd. 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 types, for example, a combination of a silicone surfactant / a fluorine-based surfactant, a combination of a silicone surfactant / a special polymer surfactant, or a combination of a fluorine-based surfactant / a special polymer surfactant, and a combination of a silicone surfactant / a fluorine-based surfactant is preferred. Examples of silicone surfactant / fluorine surfactant combinations include: BYK-300 or BYK-330 manufactured by BYK / NEOS "DFX-18" combination; BYK-300 or BYK-330 manufactured by BYK / AGC Seimi Chemical Co., Ltd. "S-393" combination; BYK-300 or BYK-330 manufactured by BYK / DIC "F-554" or "F-559" combination; Shin-Etsu Silicone Co., Ltd. "KP340" / DIC "F-478" or "F-475" combination; Toray Dow Corning Co., Ltd. "SH7PA" / Daikin "DS-401" combination; and NUC "L-77" / 3M Japan Ltd. "FC4430" combination.

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

[0243] Examples of metal oxide particles include particles of 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, with titanium oxide particles and zirconium oxide particles being more preferred. [1-2-3] Colorant The photosensitive resin composition of the present invention may contain a colorant. As the colorant, known colorants such as pigments and dyes, and their derivatives, can be used. When a pigment is used, a known dispersant or dispersion aid may be used in combination so that the pigment does not aggregate and remains stable in the photosensitive resin composition. When the photosensitive resin composition of the present invention contains a colorant, from the viewpoint of curability, the content of the colorant is 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 solids 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 Agent The photosensitive resin composition of the present invention may contain a silane coupling agent to improve adhesion to the substrate. Examples of silane coupling agents 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, from the viewpoint of adhesion, the content thereof is preferably 1% by mass or more, and preferably 10% by mass or less, 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 10% by mass, more preferably 1 to 5% by mass.

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

[0247]

[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 phosphate-based ethylenic monomers may be used alone or in combination of two or more.

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

[0251] Examples of the ultraviolet absorber include compounds having an absorption maximum at wavelengths between 250 nm and 400 nm, from the viewpoint of inhibiting the light absorption of the (B) photopolymerization initiator. Examples of the ultraviolet absorber include benzotriazole-based compounds, triazine-based compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes. It is desirable for the ultraviolet absorber to contain either one or both of a benzotriazole-based compound and a triazine-based compound.

[0252] [1-2-7] Polymerization Inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor. The inclusion of a polymerization inhibitor inhibits radical polymerization, which 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. When producing the alkali-soluble resin (C), a polymerization inhibitor may be contained in the resin. In that case, the resin may be used as it is, or in addition to the polymerization inhibitor contained in the resin, a polymerization inhibitor identical to or different from the polymerization inhibitor may be further added during 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 containing a thermal polymerization initiator, the degree of crosslinking of the film tends to be increased. Examples of thermal polymerization initiators 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 Compound The photosensitive resin composition of the present invention may contain an amino compound to promote thermal curing. Examples of amino compounds include amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups formed by condensing the methylol group with an alcohol having 1 to 8 carbon atoms. Specific examples include melamine resins obtained by polycondensation of melamine and formaldehyde; benzoguanamine resins obtained by polycondensation of benzoguanamine and formaldehyde; glycoluril resins obtained by polycondensation of glycoluril and formaldehyde; urea resins obtained by polycondensation of urea and formaldehyde; resins obtained by copolycondensation of two or more of melamine, benzoguanamine, glycoluril, or urea with formaldehyde; and modified resins obtained by alcohol condensation-modifying the methylol groups of the above-mentioned resins. These may be used alone or in combination.

[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 dissolved or dispersed state in the solvent. The solvent is not particularly limited, and 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, 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 and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride;Ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran;

[0259] Commercially available solvents include, for example, mineral spirits, Balsol #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 depending on the method of use of the photosensitive resin composition of the present invention. From the viewpoint of coatability, solvents having a boiling point at atmospheric pressure of 60 to 280°C are preferred, and solvents having a boiling point of 70 to 260°C are more preferred. Examples of such solvents 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. The solvent is used so that the total solids 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 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 total solids 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 using a solvent at or above the lower limit, the occurrence of coating unevenness tends to be suppressed, and by using a solvent at or below the upper limit, the occurrence of foreign matter, repelling, etc. tends to 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 stirrer. When the photosensitive resin composition of the present invention contains a colorant, it is preferable to disperse the colorant in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. The colorant is microparticulated by the dispersion treatment, thereby improving the coating properties of the photosensitive resin composition.

[0263] The dispersion treatment is preferably carried out in a system containing a colorant, a solvent, a dispersant, and part or all of the alkali-soluble resin (C) in combination (hereinafter, the mixture subjected to the dispersion treatment and the composition obtained by the dispersion treatment may be referred to as a "pigment dispersion"). In particular, using a polymeric dispersant as a dispersant is preferred because it inhibits thickening over time of the resulting pigment dispersion and photosensitive resin composition, i.e., it provides excellent dispersion stability. When the photosensitive resin composition of the present invention contains a colorant, it is preferred to produce a pigment dispersion containing at least a colorant, a solvent, and a dispersant in the process for producing the photosensitive resin composition. The colorants, organic solvents, and dispersants that can be used in the pigment dispersion are preferably those described above as being usable in photosensitive resin compositions. Furthermore, the content ratios of each colorant in the pigment dispersion are preferably those described above as being usable in photosensitive resin compositions.

[0264] When dispersing a colorant using a sand grinder, glass beads or zirconia beads with a particle size of about 0.1 to 8 mm are preferably used. The dispersion treatment temperature is preferably 0°C to 100°C, more preferably 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 therefore adjusted appropriately. A 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 even more preferably 0.03 to 0.3 μm. The dispersed particle size is measured, for example, as the number-based median diameter by dynamic light scattering. 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 particles 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, for example, using a filter.

[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 that improves light extraction efficiency in organic electroluminescent devices. The method for forming a cured product using the photosensitive resin composition is not particularly limited, and conventionally known methods can be used. For example, there is a photolithography method including a coating step of applying the photosensitive resin composition to 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.

[0267] The substrate on which the cured product is formed is not particularly limited in material as long as it has an appropriate strength. It can be appropriately selected according to the type of organic electroluminescent device, etc., to be manufactured using the substrate on which the cured product is formed. Examples of substrate materials 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. Glass and heat-resistant resins are preferred from the viewpoint of heat resistance. Furthermore, 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. Furthermore, an organic film such as an insulating film may be formed on top of the substrate. In addition to the above-mentioned substrates, the cured product may also 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 onto 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 the solvent is removed by drying as necessary 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 that emits ultraviolet rays, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used. The exposure dose varies depending on the composition of the photosensitive resin composition, but is, for example, 10 to 400 mJ / cm. 2 The degree is preferable.

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

[0272] After development, a post-exposure step and a post-baking step may be carried out. 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 above 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 setting the film thickness at or above the lower limit, the refractive index of the cured product tends to be improved, and by setting the film thickness at or below the upper limit, the hole resolution tends to be improved. The film thickness of the cured product is measured using a step / surface roughness / microshape measuring device, a scanning white light interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, or an electron microscope.

[0274] The cured product prepared 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 higher, more preferably 1.630 or higher, and even more preferably 1.640 or higher. It is also preferably 1.680 or lower, more preferably 1.660 or lower. The upper and lower limits can be arbitrarily combined. For example, a refractive index of 1.620 to 1.680 is preferred, 1.630 to 1.680 is more preferred, and 1.640 to 1.660 is even more preferred. A refractive index above the lower limit tends to improve light extraction efficiency. The refractive index of the cured product can be measured, for example, using a prism coupler. Specifically, as described in the examples, a refractive index measurement substrate having a cured product formed on a glass substrate is prepared, and the value measured at a wavelength of 633 nm using a prism coupler at 20°C using a He—Ne laser as a light source can be used to measure the refractive index of the cured product.

[0275] [4] Image Display Device The image display device of the present invention includes 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 electroluminescent device.

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

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

[0278]

[0279] <Ethylenically unsaturated compound-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]

[0281] <Alkali-soluble resin-I> ZCR-1761 (weight average molecular weight Mw = 3,400, acid value = 60 mg KOH / g) manufactured by Nippon Kayaku Co., Ltd. An epoxy (meth)acrylate resin having the following partial structure, where * represents each bond. Alkali-soluble resin-I corresponds to epoxy (meth)acrylate resin (C1-1).

[0282]

[0283] <Alkali-soluble resin-II> ZCR-8024 (weight average molecular weight Mw = 3,400, acid value = 60 mg KOH / g) manufactured by Nippon Kayaku Co., Ltd. An epoxy (meth)acrylate resin having the following partial structure, where * represents each bond. Alkali-soluble resin-II corresponds to epoxy (meth)acrylate resin (C1-1).

[0284]

[0285] <Alkali-Soluble Resin-III> An alkali-soluble acrylic copolymer resin obtained by subjecting a copolymer resin having dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.10 / 0.60 / 0.30) as constituent monomers to an addition reaction of an equal amount of acrylic acid and glycidyl methacrylate, and further 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) measured by GPC in terms of polystyrene was 10,000, and the acid value of the solid content was 68.8 mgKOH / g.

[0286] <Alkali-Soluble Resin-IV> An alkali-soluble acrylic copolymer resin obtained by subjecting a copolymer resin having dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.02 / 0.05 / 0.93) as constituent monomers to an addition reaction of an equal amount of acrylic acid with glycidyl methacrylate, and further 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 was 8900, and the acid value of the solid content was 26.9 mgKOH / g.

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

[0288]

[0289] <Surfactant-I> DIC Megafac 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] <Measurement of refractive index> Using a spinner, the photosensitive resin composition was applied onto a glass substrate so that the thickness would be 2 μm after heat curing. The obtained substrate was vacuum dried for 1 minute and further dried by heating on a hot plate at 100°C for 100 seconds to obtain a coated substrate. Next, using a manual exposure machine (MA-1100) manufactured by Dai Nippon Kaken Co., Ltd., an exposure dose of 100 mJ / cm was applied using a high-pressure mercury lamp that cut off wavelengths of 330 nm or less. 2 The entire surface of the coated substrate was exposed to light with a light intensity of 45 mW / cm at a wavelength of 365 nm. 2 Finally, the substrate that had been exposed to light from the entire surface was cured by heating 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 substrate. Specifically, the measurement was performed under conditions of 20°C using a Metricon Prism Coupler Model 2010 with a He-Ne laser having a wavelength 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> Using a spinner, the photosensitive resin composition obtained in each Example and Comparative Example was applied onto a glass substrate so that the thickness after heat curing would be 2 μm. 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 carried out so that the illuminance was 500 mW / cm ２ The slit width was 1.6 mm. A photomask with a 10 μm × 10 μm covering area was used. Next, a development process was performed using a 2.38% TMAH aqueous solution in a shower at a pressure of 0.05 MPa for 40 seconds, followed by rinsing 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 substrate for hole resolution evaluation.

[0295] <Preparation of Glass Substrate with Organic Undercoat Film> An ethylenically unsaturated compound, alkali-soluble resin, photopolymerization initiator, additives, and solvent were mixed in the following composition, and the resulting 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, the ethylenically unsaturated compound, alkali-soluble resin, photopolymerization initiator, and additives were added so that the solid content ratios were as shown below. Solvent-I was then added as a solvent so that the total solid content was 30% by mass, followed by stirring and dissolution 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 parts by mass represent the amount of solids in each component excluding the solvent.

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

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

[0298] <Preparation of a substrate with an organic undercoat film for hole resolution evaluation> Using a spinner, a photosensitive resin composition obtained in each of the Examples and Comparative Examples described below was applied onto a glass substrate with an organic undercoat film so that the thickness after heat curing would be 2 μm. 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 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 so that the illuminance was 500 mW / cm ２ The slit width was 1.6 mm. A photomask with a 10 μm × 10 μm covering area 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, followed by rinsing 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 substrates> Of the hole resolution evaluation substrates and hole resolution evaluation substrates with organic underlayer films obtained above, the 10 μm × 10 μm unexposed area was evaluated as "A" if the substrate or organic underlayer film was exposed by sufficient development, and as "C" if the film was not sufficiently developed and remained.

[0300] [Examples 1-2 and Comparative Examples 1-3] Each component was added so that the solid content ratio of each component in the total solid content was the blending ratio shown in Table 1, and then solvent was added so that the total solid content was 20% by mass and that the ratio of solvent-I / solvent-II in the total solvent was 90 / 10 (mass ratio), followed by stirring and dissolution to prepare a photosensitive resin composition. Using each of the resulting photosensitive resin compositions, the refractive index and hole resolution were evaluated using the methods described above. The blending ratios of the ethylenically unsaturated compound, alkali-soluble resin, photopolymerization initiator, and surfactant in Table 1 are values ​​calculated as solid content.

[0301]

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

[0303] It can also be seen that Examples 1 and 2 are capable of achieving both a high refractive index and good hole resolution. This is thought to be because, when a coating film of the photosensitive resin composition is developed with an alkaline developer, the use of an ethylenically unsaturated compound-I having a sulfur-containing aromatic heterocycle can reduce the molecular volume while imparting a high refractive index, and because 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, the alkali-soluble resin can be uniformly distributed in the coating film of the photosensitive resin composition without phase separation, which in turn makes it easier for the alkaline developer to penetrate during development, resulting in good hole resolution.

[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 alkali-soluble resin-IV are acrylic acid ester copolymers having no aromatic group in the main chain, and therefore, it is understood 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 solid content ratio of each component in the total solid content was the blending ratio shown in Table 2, and then solvent was added so that the total solid content was 20% by mass and that the ratio of solvent-I to solvent-II in the total solvent was 90 / 10 (mass ratio), followed by stirring and dissolution to prepare a photosensitive resin composition. Each of the resulting photosensitive resin compositions was evaluated for refractive index and hole resolution using the methods described below. The blending ratios of the ethylenically unsaturated compound, alkali-soluble resin, photopolymerization initiator, and surfactant in Table 2 are values ​​calculated on a solids basis.

[0306]

[0307] <Measurement of refractive index> Using a spinner, the photosensitive resin composition was applied onto a glass substrate so that the thickness after heat curing would be 1.5 μm. The obtained substrate was vacuum dried for 1 minute and further heated and dried on a hot plate at 100°C for 100 seconds to obtain a coated substrate. Next, using a manual exposure machine (MA-1100) manufactured by Dai Nippon Kaken Co., Ltd., an exposure dose of 100 mJ / cm was applied using a high-pressure mercury lamp that cut off wavelengths of 330 nm or less. 2 The entire surface of the coated substrate was exposed to light with a light intensity of 45 mW / cm at a wavelength of 365 nm. 2 Finally, the substrate that had been exposed to light from the entire surface was cured by heating 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 substrate. Specifically, the measurement was performed under conditions of 20°C using a Metricon Prism Coupler Model 2010 with a He-Ne laser having a wavelength 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> Using a spinner, the photosensitive resin composition obtained in each Example and Comparative Example was applied onto a glass substrate having an indium tin oxide (ITO) film formed on its surface, so that the thickness after heat curing (baking) would be 1.5 μm. 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 exposure machine (MPA-600FA) manufactured by Canon Inc. was used, and the exposure dose was 60 mJ / cm. ２ The exposure was carried out so that the illuminance was 500 mW / cm ２ The slit width was 1.6 mm. A photomask with a 10 μm × 10 μm covering area was used. Next, a development process was performed using a 2.38% TMAH aqueous solution at 24°C and a shower pressure of 0.05 MPa for 40 seconds, followed by rinsing 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 substrate for hole resolution evaluation.

[0310] <Evaluation of hole resolution evaluation substrates> Of the hole resolution evaluation substrates obtained above, those in which the substrate on which the ITO film was formed was exposed by sufficient development in the 10 μm × 10 μm unexposed area were evaluated as "AA", those in which the substrate on which the ITO film was formed was exposed by sufficient development in the 30 μm × 30 μm unexposed area were evaluated as "A", and those in which the film remained without sufficient development were evaluated as "C".

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

[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 acid ester copolymer having no aromatic ring in the main chain, and therefore 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. [Case 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): [Case 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): [C3]

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