Photosensitive resin composition, cured product, and image display device

Abstract

To provide a photosensitive resin composition capable of forming a high refractive index cured product, and exhibiting excellent hole resolution.SOLUTION: This photosensitive resin composition contains (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.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product, and an image display device. This application claims priority based on Japanese Patent Application No. 2022-048750 filed on March 24, 2022, and incorporates its content herein by reference.

Background Art

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

[0003] For example, an organic EL display device has advantages in terms of visibility and viewing angle compared to conventional CRTs and LCDs, and also has excellent characteristics such as weight reduction, thinning, and flexibility. However, generally, the refractive index of the organic layer including the light-emitting layer is higher than that of air, ranging from 1.6 to 2.1. Therefore, total reflection or interference at the interface of the emitted light easily occurs, and the light extraction efficiency is 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 transparent electrode, at least one organic layer including a light-emitting layer, and a back electrode are sequentially laminated on a transparent substrate. In an active matrix type organic EL device, for example, a TFT substrate on which a plurality of pixel electrodes forming the back electrode and a TFT (thin film transistor) serving as its switching element are formed in a matrix is laminated on the above organic layer.

[0005] The light emitted from the organic layer is reflected directly or by a back electrode formed of aluminum or the like, and exits from the translucent substrate. At this time, it is preferable that the generated light is efficiently extracted to the side of the translucent substrate. However, depending on the angle of incidence on the interface of adjacent layers with different refractive indices, the light undergoes total internal reflection, becomes guided light that travels while undergoing total internal reflection in the plane direction inside the element, and is absorbed and attenuated inside, resulting in the problem that it cannot be extracted to the outside.

[0006] As a method for improving the light extraction efficiency, for example, Patent Document 1 describes an organic electroluminescent element in which the light extraction efficiency is improved by combining a high refractive index layer and a nanoporous layer.

[0007] As the photosensitive composition having a high refractive index, studies have been conducted not only for organic 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 using oxide fine particles such as titanium oxide and a specific fluorene skeleton-containing compound. Patent Document 3 also describes a composition for optical materials using a specific compound.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

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

[0010] Therefore, an object of the present invention is to provide a photosensitive resin composition capable of forming a cured product with a high refractive index and excellent in 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.

Means for Solving the Problems

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

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

[0013] [Chemical formula]

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

[0015] [Chemical formula]

[0016] (In the formula (i), R arepresents 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. * each represents a bond.) [6] The photosensitive resin composition according to 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 according to any one of [1] to [6]. [8] An image display device including the cured product of [7]. [Effect of the Invention]

[0017] According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a cured product having a high refractive index and excellent in hole resolution. [Mode for Carrying Out the Invention]

[0018] Hereinafter, the present invention will be described in detail. Note that the following description is an example of an embodiment of the present invention, and the present invention is not limited to these as long as the gist thereof is not exceeded. In the present invention, “(meth)acryl” means “either one or both of acrylic and methacrylic”. “Total solid content” means all components other than the solvent in the photosensitive resin composition. Even if the component other than the solvent is liquid at normal temperature, the component is not included in the solvent but is included in the total solid content. In the present invention, the numerical range represented by “~” means a range including the numerical values described before and after “~” as the lower limit value and the upper limit value. In the present invention, “(co)polymer” means including both a single polymer (homopolymer) and a copolymer (copolymer), and “(acid)anhydride”, “(anhydrous)... acid” means including both an acid and its anhydride. In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography). In the present invention, the acid value, unless otherwise specified, represents the acid value in terms of effective solid content and is calculated by neutralization titration.

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

[0020] [1-1] Components and composition of the photosensitive resin composition The components constituting the photosensitive resin composition of the present invention and its 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) an ethylenically unsaturated compound, the curability of the coating film is improved. In the photosensitive resin composition of the present invention, the (A) ethylenically unsaturated compound contains an ethylenically unsaturated compound (A1) having 1 to 3 ethylenically unsaturated bonds and 1 to 3 sulfur-containing aromatic heterocycles in the molecule (hereinafter, may be simply referred to as ethylenically unsaturated compound (A1)).

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

[0023] The number of ethylenically unsaturated bonds contained in the ethylenically unsaturated compound (A1) is preferably 2 to 3 from the viewpoint of curability. The number of sulfur-containing aromatic heterocycles contained in the ethylenically unsaturated compound (A1) is preferably 2 from the viewpoints of increasing the refractive index and ensuring solubility. From the viewpoints of curability, increasing the refractive index, and ensuring solubility, it is more preferable that the ethylenically unsaturated compound (A1) has 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 as a heteroatom, it 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 coloring. The number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, from the viewpoints of avoiding coloring and ensuring solubility. The sulfur-containing aromatic heterocycle may be a monocyclic ring or a condensed ring. A condensed ring is preferable in terms of increasing the refractive index. The number of rings constituting the condensed ring is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3 in terms of easy availability of raw materials and ease of synthesis. Examples of the sulfur-containing aromatic heterocycle 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; 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 thienooxazole ring, a thienothiadiazole ring, and a thiazolothiadiazole ring. As the sulfur-containing aromatic heterocyclic ring, a benzothiazole ring, a dibenzothiophene ring, or a benzothiophene ring is preferable from the viewpoints of increasing the refractive index, low coloring property, and solubility, and a benzothiazole ring is more preferable.

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

[0026]

Chemical formula

[0027] In formula (A1-1), R 1 represents a hydrogen atom or a methyl group. Cy represents a sulfur-containing aromatic heterocyclic ring. Q 1 and Q 2 each independently represent an alkylene group having 1 to 6 carbon atoms. X 1 and X 2 each independently represent -O-, -S-, -NR 2 -, -NR 2 -(C=O)-, or -NR 2 -(C=O)-O-. Z 1 and Z 2 each independently represent a divalent hydrocarbon group which may have a substituent. m and n each independently represent an integer of 1 to 3. p and q each independently represent 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 heterocyclic ring which may have a substituent. The sulfur-containing aromatic heterocyclic ring contributes to a high refractive index. The sulfur-containing aromatic heterocyclic ring has at least one sulfur atom as a hetero atom constituting the aromatic heterocyclic ring. In addition to the sulfur atom as a hetero atom, it may have an oxygen atom, a nitrogen atom, or both an oxygen atom and a nitrogen atom. From the viewpoint of avoiding coloring, the number of sulfur atoms constituting the sulfur-containing aromatic heterocyclic ring is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. From the viewpoints of avoiding coloring and ensuring solubility, the number of heteroatoms constituting the sulfur-containing aromatic heterocyclic ring is preferably 1 to 3, and more preferably 1 to 2. The sulfur-containing aromatic heterocyclic ring may be a monocyclic ring or a condensed ring. A condensed ring is preferred in terms of increasing the refractive index. The number of rings constituting the condensed ring is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3 in terms of facilitating the availability of raw materials and synthesis.

[0029] Examples of the sulfur-containing aromatic heterocyclic ring include aromatic heterocyclic rings containing 1 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 heterocyclic rings containing 2 or more sulfur atoms such as a thianthrene ring; aromatic heterocyclic rings containing 2 or more heteroatoms such as a thiazole ring, an isothiazole ring, a benzothiazole ring, a naphthothiazole ring, a phenothiazine ring, a thiazolimidazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a dioxazolopyrazine ring, a thiazolopyrazine ring, a thiazolooxazole ring, a dibenzobenzothiophene ring, a thienooxazole ring, a thienothiadiazole ring, and a thiazolothiadiazole ring. From the viewpoints of increasing the refractive index, low coloring property, and solubility, a benzothiazole ring, a dibenzothiophene ring, and a benzothiophene ring are preferred as the sulfur-containing aromatic heterocyclic ring, and a benzothiazole ring is more preferred.

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

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

[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 of the hydrocarbon group (excluding the number of carbon atoms of the substituent) is preferably 1 to 8. When the number of carbon atoms is 8 or less, it is difficult for the refractive index to decrease, the viscosity is easily decreased due to the small molecular weight, and the processability is easily improved. Specific examples include, for example, 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, more preferably 2. From the viewpoint of refractive index, n is preferably 2 to 3, more preferably 2. It is particularly preferred that m and n are each 2.

[0034] In formula (A1-1), p and q each independently represent an integer from 0 to 3. The smaller p and q are, the more likely it is to have a high refractive index. It is particularly preferred that p and q are each 0.

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

[0036]

Chemical formula

[0037]

Chemical formula

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

[0039] The sulfur atomic weight contained in one molecule of the ethylenically unsaturated compound (A1) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. Also, it is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less. By setting it to the above lower limit or more, there is a tendency to have a high refractive index. Also, by setting it to the above upper limit or less, there is a tendency to have low colorability. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, still 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, still more preferably 500 g / mol or less, and particularly preferably 300 g / mol or less. By setting it to be not less than the lower limit value, there is a tendency to obtain a high refractive index. Also, by setting it to be not more than the upper limit value, the curability is improved, and there is a tendency to obtain a low dielectric constant and a high volume resistivity. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 200 to 900 g / mol, more preferably 200 to 700 g / mol, still more preferably 250 to 500 g / mol, and particularly preferably 250 to 300 g / mol.

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

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

[0043] Examples of other ethylenically unsaturated compounds include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by an esterification reaction of polyvalent 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 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 esters obtained by replacing part or all of the acrylates of the above-exemplified compounds with methacrylates; itaconic esters obtained by replacing part or all of the acrylates of the above-exemplified compounds with itaconates; crotonic esters obtained by replacing part or all of the acrylates of the above-exemplified compounds with crotonates; and maleic esters obtained by replacing part or all of the acrylates of the above-exemplified compounds with maleates.

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

[0046] Esters obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single substances, but representative specific examples include condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerol.

[0047] Other polyfunctional ethylenically unsaturated monomers include, for example, urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylate or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound with hydroxy (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; 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, other ethylenically unsaturated compounds are preferably esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth)acrylates, and more preferably dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate. These may be used alone or in combination of two or more.

[0049] The content ratio of the (A) ethylenically unsaturated compound 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, still more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more in the total solid content, and is preferably 80% by mass or less, more preferably 70% by mass or less, still 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, still more preferably 30 to 60% by mass, and particularly preferably 40 to 60% by mass in the total solid content. By setting it to be not less than the lower limit value, there is a tendency to have a high refractive index, and by setting it to be not more than the upper limit value, there is a tendency to have good hole resolution.

[0050] The content ratio 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, still more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more in the total solid content, and is preferably 80% by mass or less, more preferably 70% by mass or less, still 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, still more preferably 30 to 60% by mass, particularly preferably 40 to 60% by mass in the total solid content. By setting it to be not less than the lower limit value, the refractive index tends to improve, and by setting it to be not more than the upper limit value, the hole resolution tends to be good.

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

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

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

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

[0055] In the photosensitive resin composition of the present invention, as the (B) photoinitiator, a photoinitiator commonly used in this field can be used. Examples of such photoinitiators include metallocene compounds containing 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, N-aryl-α-amino acid esters and other radical activators, α-aminoalkylphenone derivatives described in JP-A-10-39503; oxime ester compounds described in JP-A-2000-80068, JP-A-2006-36750, etc.

[0056] Specifically, for example, as the metallocene compound, there are dichlorocyclopentadienyltitanium 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), dicyclopentadienyltitanium [2,6-difluoro-3-(pyrrol-1-yl)phenyl].

[0057] Examples of the benzimidazole 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 the 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 the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0060] Examples of the 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] (B) As a photoinitiator, 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, it is disadvantageous in terms of sensitivity. Therefore, an oxime ester compound having such excellent sensitivity is particularly useful. The oxime ester compound has a high quantum yield of photoreaction and high activity of the generated radicals, so it has high sensitivity and is stable against thermal reactions, and it is possible to obtain a highly sensitive photosensitive resin composition with a small amount.

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

[0063]

Chemical formula

[0064] In formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 21b represents any substituent containing an aromatic ring. R 22a represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent. n represents an integer of 0 or 1.

[0065] R 21a The carbon number of the alkyl group in is not particularly limited, but from the viewpoints of solubility in a solvent and sensitivity, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and 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 the substituent 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. Further, from the viewpoints of sensitivity, solubility, and chemical resistance, a methyloxycarbonyl group and an ethyloxycarbonyl group are preferable.

[0066] R 21a Examples of the aromatic ring group in R 21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but it is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, 5 to 30 is preferable, 5 to 20 is more preferable, and 5 to 12 is even more preferable.

[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 preferable, and a phenyl group is more preferable. Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group formed by linking these substituents. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group formed by linking these are preferable, and a linked alkoxy group is more preferable. From the viewpoints of sensitivity, solubility, and chemical resistance, R 21a is preferably an alkyl group which may have a substituent.

[0068] R 21bExamples include a carbazolyl group which may be preferably substituted, a thioxanthonyl group which may be preferably substituted, a diphenyl sulfide group which may be preferably substituted, a fluorenyl group which may be preferably substituted, and an indolyl group which may be preferably substituted. From the viewpoint of hole resolution, a diphenyl sulfide group which may be preferably substituted is preferred.

[0069] R 22a The number of carbon atoms of the alkanoyl group in R is not particularly limited, but from the viewpoints of solubility in a solvent and sensitivity, it is preferably 2 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and even more preferably 5 or less. Examples of the alkanoyl group include an acetyl group, an ethyroyl group, a propanoyl group, and a butanoyl group. Examples of the substituent which 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 preferably unsubstituted.

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

[0071] For example, photoinitiators and the like described in Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, International Publication No. 2008 / 78678, Japanese Patent No. 4818458, International Publication No. 2005 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, and International Publication No. 2012 / 68879 can be used.

[0072] (B) The photoinitiator may be used alone or in combination of two or more. (B) For the photoinitiator, a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source may be blended, if necessary, for the purpose of enhancing the sensitivity.

[0073] Examples of the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Laid-Open No. 4-219756, coumarin dyes having a heterocyclic ring described in Japanese Patent Application Laid-Open No. 3-239703 and Japanese Patent Application Laid-Open No. 5-289335, 3-ketocoumarin compounds described in Japanese Patent Application Laid-Open No. 3-239703 and Japanese Patent Application Laid-Open No. 5-289335, pyromethene dyes described in Japanese Patent Application Laid-Open No. 6-19240, dyes having a dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818.

[0074] As the sensitizing dye, an amino group-containing sensitizing dye is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable. For example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine and other p-dialkylaminophenyl group-containing compounds are more preferable, and 4,4'-dialkylaminobenzophenone is particularly preferable. The sensitizing dye may be used alone or in combination of two or more.

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

[0076] Although the content ratio of the (B) photoinitiator in the photosensitive resin composition of the present invention is not particularly limited, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and even more preferably 2% by mass or more in the total solid content of the photosensitive resin composition. Also, it is preferably 15% by mass or less, more preferably 10% by mass or less, still 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 preferable, 0.01 to 10% by mass is more preferable, 1 to 10% by mass is still more preferable, 1 to 10% by mass is even more preferable, and 2 to 7% by mass is particularly preferable. By setting it to be not less than the lower limit value, the sensitivity tends to improve. By setting it to be not more than the upper limit value, the hole resolution tends to improve.

[0077] As the blending ratio of the (B) photoinitiator to the (A) ethylenically unsaturated compound in the photosensitive resin composition of the present invention, based on 100 parts by mass of the (A) ethylenically unsaturated compound, 1 part by mass or more is preferable, 3 parts by mass or more is more preferable, 5 parts by mass or more is still more preferable. Also, 100 parts by mass or less is preferable, 50 parts by mass or less is more preferable, 20 parts by mass or less is still more preferable, and 10 parts by mass or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 to 100 parts by mass is preferable, 1 to 50 parts by mass is more preferable, 1 to 20 parts by mass is still more preferable, 2 to 20 parts by mass is even more preferable, and 2 to 10 parts by mass is particularly preferable. By setting it to be not less than the lower limit value, the sensitivity tends to improve. By setting it to be not more than the upper limit value, the hole resolution tends to improve.

[0078] (B) A chain transfer agent may be used in combination with the photoinitiator. Examples of the chain transfer agent include mercapto group-containing compounds and carbon tetrachloride. Since the chain transfer effect is high and the sensitivity and surface curability tend to improve, it is more preferable to use a mercapto group-containing compound. This is considered to be because the S-H bond energy is small, so bond cleavage easily occurs, and hydrogen abstraction reactions and chain transfer reactions easily occur.

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

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

[0081] The photosensitive resin composition of the present invention contains, as the (C) alkali-soluble resin, an epoxy(meth)acrylate resin (C1) having an aromatic ring in the main chain (hereinafter, may be abbreviated as epoxy(meth)acrylate resin (C1)). Since it has an aromatic ring in the main chain, the refractive index tends to be high. Further, since the compatibility with the sulfur-containing aromatic heterocyclic ring in the ethylenically unsaturated compound (A1) is good, the alkali-soluble resin is likely to be uniformly distributed in the coating film of the photosensitive resin composition without phase separation. Along with this, the alkali developer at the time of development easily penetrates, so that the hole resolution tends to be good.

[0082] [Epoxy (meth)acrylate resin (C1)] The epoxy (meth)acrylate resin (C1) having an aromatic ring in the main chain is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or an 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, when the carboxy group of an unsaturated monocarboxylic acid undergoes ring-opening addition to the epoxy group of an epoxy resin, an ethylenically unsaturated bond is added to the epoxy compound via an ester bond (-COO-), and at the same time, one carboxy group of a polybasic acid anhydride is added to the hydroxyl group generated at that time. Also included are those obtained by simultaneously adding a polyhydric alcohol when adding the polybasic acid anhydride.

[0083] Also included in the epoxy (meth)acrylate resin (C1) is 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. Thus, the epoxy (meth)acrylate resin does not substantially have an epoxy group in its chemical structure and is not limited to "(meth)acrylate", but is named in this way according to convention because an epoxy compound (epoxy resin) is the raw material and "(meth)acrylate" is a representative example.

[0084] Here, the epoxy resin refers to including the raw material compound before forming the resin by thermosetting, and as the epoxy resin, it can be appropriately selected and used from known epoxy resins. Also, as the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. As the phenolic compound, a compound having a divalent or higher divalent phenolic hydroxyl group is preferred, and it may be a monomer or a polymer. Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, tris-phenol epoxy resin, polymerization epoxy resin of phenol and dicyclopentadiene, dihydroxyl fluorene type epoxy resin, dihydroxyl alkyleneoxyl fluorene type epoxy resin, diglycidyl etherified product of 9,9-bis(4'-hydroxyphenyl)fluorene, diglycidyl etherified product of 1,1-bis(4'-hydroxyphenyl)adamantane can be mentioned, and those having an aromatic ring in the main chain can be preferably used in this way.

[0085] From the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerization epoxy resin of phenol and dicyclopentadiene, diglycidyl etherified product of 9,9-bis(4'-hydroxyphenyl)fluorene are preferable, and bisphenol A epoxy resin is particularly preferable. Examples of the epoxy resin include bisphenol A type epoxy resins (e.g., "jER (registered trademark, the same applies hereinafter) 828", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Corporation, "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd., etc.), bisphenol F type resins (e.g., "jER807", "jER4004P", "jER4005P", "jER4007P" manufactured by Mitsubishi Chemical Corporation, "NER-7406" (epoxy equivalent 350, softening point 66°C) manufactured by Nippon Kayaku Co., Ltd., etc.), bisphenol S type epoxy resins, biphenyl glycidyl ether (e.g., "jERYX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins (e.g., "EPPN (registered trademark, the same applies hereinafter)-201" manufactured by Nippon Kayaku Co., Ltd., "jER152", "jER154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Company), (o,m,p-) cresol novolac type epoxy resins (e.g., "EOCN (registered trademark, the same applies hereinafter)-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (e.g., "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenol methane type epoxy resins (e.g., "EPPN-501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resins ("Celoxide (registered trademark, the same applies hereinafter) 2021P", "Celoxide EHPE" manufactured by Daicel Corporation), epoxy resins obtained by glycidylating a phenol resin resulting from the reaction of dicyclopentadiene and phenol (e.g., "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins represented by the following general formulas (i-11) to (i-14). Examples of the epoxy resin represented by the following general formula (i-11) include "XD-1000" manufactured by Nippon Kayaku Co., Ltd. Examples of the epoxy resin represented by the following general formula (i-12) include "NC-3000" manufactured by Nippon Kayaku Co., Ltd. Examples of the epoxy resin represented by the following general formula (i-14) include "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

[0086] [Chemical formula]

[0087] In formula (i-11), n is an average value and represents a number from 0 to 10. R 111 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Note that a plurality of R 111 present in one molecule may be the same or different from each other.

[0088]

Chemical formula

[0089] In formula (i-12), n is an average value and represents a number from 0 to 10. R 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Note that a plurality of R 121 present in one molecule may be the same or different from each other.

[0090]

Chemical formula

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

[0092]

Chemical formula

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

[0094] [Chemical formula]

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

[0096] As the epoxy resin, an epoxy resin represented by any of formulas (i-11) to (i-14) is preferable.

[0097] Examples of the ethylenically unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., and 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 a reaction product of (meth)acrylic acid and ε-caprolactone. From the viewpoint of sensitivity, (meth)acrylic acid is preferable.

[0098] Examples of the polybasic acid (anhydride) 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 their anhydrides. From the perspective of outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred.

[0099] By using a polyhydric alcohol, the molecular weight of the epoxy (meth)acrylate resin (C1) can be increased, branches can be introduced into the molecule, and there is a tendency to balance the molecular weight and viscosity. In addition, the introduction rate of acid groups into the molecule can be increased, and the balance of sensitivity, adhesion, etc. is likely to be achieved. Examples of the polyhydric alcohol include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol.

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

[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, still more preferably 50 mgKOH / g or more, even more preferably 70 mgKOH / g or more, particularly preferably 80 mgKOH / g or more. Also, it is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, still more preferably 150 mgKOH / g or less, even more preferably 120 mgKOH / g or less, 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, still more preferably 70 to 120 mgKOH / g, even more preferably 80 to 110 mgKOH / g. By setting it to be not less than the lower limit value, the developability tends to improve, and by setting it to be not more than the upper limit value, the film strength tends to improve.

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

[0103] (C) The content ratio of the epoxy (meth) acrylate resin (C1) contained in the alkali-soluble resin is not particularly limited, but it is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, even more preferably 35% by mass or more, yet even more preferably 40% by mass or more, and particularly preferably 50% by mass or more in the (C) alkali-soluble resin. Also, it is preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 60% 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 90% by mass, more preferably 30 to 70% by mass, still more preferably 35 to 70% by mass, even more preferably 40 to 60% by mass, and particularly preferably 50 to 60% by mass. By setting it to be not less than the lower limit value, the linearity tends to improve, and by setting it to be not more than the upper limit value, there is a tendency to form a high-definition cured product with a narrow line width.

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

[0105] Examples of the organic solvent used in the reaction include methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. The organic solvent used in the reaction may be used alone or in combination of two or more. Examples of the catalyst 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 catalyst used in the reaction may be used alone or in combination of two or more kinds. Examples of the thermal polymerization inhibitor used in the reaction include one or more of hydroquinone, hydroquinone monomethyl ether, and methylhydroquinone. The thermal polymerization inhibitor used in the reaction may be used alone or in combination of two or more kinds.

[0106] The amount of the acid or ester compound having an ethylenically unsaturated bond used can be 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 can be preferably 60 to 150 °C, more preferably 80 to 120 °C. The amount of the polybasic acid (anhydride) used can be 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 viewpoints of film strength and linearity, it is preferable to contain one or more of the epoxy (meth)acrylate resins having a partial structure represented by the following general formula (i), the epoxy (meth)acrylate resins having a partial structure represented by the following general formula (ii), and the epoxy (meth)acrylate resins having a partial structure represented by the following general formula (iii).

[0108]

Chemical formula

[0109] 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. * each represents a bond.

[0110]

Chemical formula

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

[0112]

Chemical formula

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

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

[0115]

Chemical formula

[0116] In formula (i), R a represents a hydrogen atom or a methyl group, and R brepresents a divalent hydrocarbon group which may have a substituent. k represents 1 or 2. The benzene ring in formula (i) may be further substituted by 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 formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups.

[0118] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. Among these, from the viewpoint of development solubility, a linear aliphatic group is preferred. From the viewpoint of reducing the penetration of the developer into the exposed area, a cyclic aliphatic group is preferred. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, still 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, more preferably 6 to 10. By setting it to be not less than the lower limit value, the film strength tends to be improved, and by setting it to be not more than the upper limit value, the hole resolution tends to be improved.

[0119] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. From the viewpoints of refractive index, hole resolution, and manufacturing cost, a methylene group is preferred. Examples of the divalent branched aliphatic group include a structure in which, as a side chain, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group is bonded to the aforementioned divalent linear aliphatic group. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, and 5 or less is preferable. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 5. By setting it to be not less than the lower limit value, the film strength tends to be improved, and by setting it to be not more than the upper limit value, the developability tends to be improved. Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, dicyclopentane ring, norbornane ring, isobornane ring, and adamantane ring. From the viewpoints of film strength and developability, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

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

[0121] Examples of the divalent aromatic ring group include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, still 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, more preferably 6 to 10. By setting it to be not less than the lower limit value, the film strength tends to be improved, and by setting it to be not more than the upper limit value, the developability tends to be improved.

[0122] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring having two free valences.

[0123] As for the aromatic heterocyclic ring in the divalent aromatic heterocyclic group, it may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, 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 benzoisoxazole ring, a benzoisothiazole 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 having two free valences. From the perspective of manufacturing cost, a benzene ring and a naphthalene ring having two free valences are 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 perspective of curability, unsubstituted is preferred.

[0125] Examples of the group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include a group formed by linking one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups in the group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups is not particularly limited, but one or more is preferred, two or more is preferred, and ten or less is preferred, five or less is more preferred, and three or less is even more preferred. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3. By setting it to be equal to or greater than the lower limit value, the developability tends to improve, and by setting it to be equal to or less than the upper limit value, the film strength tends to improve. In the group connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups, the number of divalent aromatic ring groups is not particularly limited, but one or more is preferable, two or more is more preferable, and 10 or less is preferable, 5 or less is more preferable, and 3 or less is even more preferable. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3. By setting it to be not less than the lower limit value, the film strength tends to be improved, and by setting it to be not more than the upper limit value, the developability tends to be improved.

[0126] Examples of the group connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the following general formulas (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 preferable.

[0127]

Chemical formula

[0128] The benzene ring in formula (i) may be further substituted with any substituent. Examples of the substituent allowed for the benzene ring in formula (i) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, and it 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 viewpoints of developability and curability, k is preferably 2.

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

[0131]

Chemical formula

[0132] In formula (i-1), R a and R b are synonymous with formula (i). R 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 means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic 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 one kind or two or more kinds.

[0135] The number of the partial structures represented by formula (i) contained in one molecule of the epoxy (meth)acrylate resin (C1-1) is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 3 or more is further preferred, and 10 or less is preferred, 8 or less is further preferred. The above 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 setting the value to be not less than the lower limit value, the developability tends to be improved, and by setting the value to be not more than the upper limit value, the film strength tends to be improved.

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

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

[0138] [Chemical formula]

[0139] [Chemical formula]

[0140] [Chemical formula]

[0141] [Chemical formula]

[0142] [Chemical formula]

[0143] [Chemical formula]

[0144] [Chemical formula]

[0145] [Chemical formula]

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

[0147] [Chemical formula]

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

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

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

[0153] Examples of the aromatic cyclic group include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic cyclic group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, even more preferably 10 or more, and particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or less, still 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, still more preferably 10 to 20, and even more preferably 12 to 15. By setting it to be not less than the lower limit value, the film strength tends to be improved, and by setting it to be not more than the upper limit value, the developability tends to be improved.

[0154] Examples of the aromatic ring in the aromatic group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring. From the viewpoint of patterning properties, the fluorene ring is preferred.

[0155] In the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, the divalent hydrocarbon group is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic groups are linked.

[0156] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. Among these, from the viewpoint of improving developability, a linear aliphatic group is preferred. From the viewpoint of film strength, a cyclic aliphatic group is preferred. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, still 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, more preferably 6 to 15. By setting the value to be equal to or greater than the lower limit value, the film strength tends to be improved, and by setting the value to be equal to or less than the upper limit value, the developability tends to be improved.

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

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

[0159] Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, dicyclopentane ring, norbornane ring, isobornane ring, and adamantane ring. From the viewpoint of film strength, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

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

[0161] Examples of the divalent aromatic ring group include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms thereof 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, even more preferably 15 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 4 to 30, preferably 5 to 20, more preferably 6 to 15. By setting it to be not less than the lower limit value, the film strength tends to improve, and by setting it to be not more than the upper limit value, the developability tends to improve.

[0162] As the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon group, it may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring having two free valences.

[0163] As the aromatic heterocyclic ring in the divalent aromatic heterocyclic group, it may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrrolopyrimidine ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzoisoxazole ring, a benzoisothiazole 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 having two free valences. From the viewpoint of production cost, a benzene ring and a naphthalene ring having two free valences are preferable, and a benzene ring having two free valences is more preferable.

[0164] Examples of the substituent that the divalent aromatic 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 is preferable.

[0165] Examples of the group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic groups include a group formed by linking one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic groups. In a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, the number of divalent aliphatic groups is not particularly limited, but one or more are preferred, two or more are more preferred, 10 or less is preferred, 5 or less is more preferred, and 3 or less is even more preferred. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3. By setting it to be not less than the lower limit value, the developability tends to improve, and by setting it to be not more than the upper limit value, the film strength tends to improve. In a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, the number of divalent aromatic ring groups is not particularly limited, but one or more are preferred, two or more are more preferred, 10 or less is preferred, 5 or less is more preferred, and 3 or less is even more preferred. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3. By setting it to be not less than the lower limit value, the film strength tends to improve, and by setting it to be not more than the upper limit value, the developability tends to improve.

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

[0167] Regarding these divalent hydrocarbon groups, the bonding mode of the cyclic hydrocarbon group as a side chain is not particularly limited. For example, there are modes in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group as a side chain, and modes in which a cyclic hydrocarbon group as a side chain is formed including one carbon atom of an aliphatic group.

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

[0169]

Chemical formula

[0170] In formula (ii-1), R c is synonymous with formula (ii). R 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 ring group and an aromatic ring group.

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

[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 preferable.

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

[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 preferable.

[0176] Examples of the substituent that the cyclic hydrocarbon group may have include an alkyl group 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; an alkoxy group 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 is preferable.

[0177] n represents an integer of 1 or more, but 2 or more is preferable, and 3 or less is preferable. For example, it is 1 to 3, preferably 2 to 3. By setting it to be not less than the lower limit value, the developability tends to improve, and by setting it to be not more than the upper limit value, the film strength tends to improve.

[0178] From the viewpoints 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 optionally substituted with any substituent. Examples of the substituent allowed 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 above formula (ii-1) are given below.

[0181]

Chemical formula

[0182]

Chemical formula

[0183]

Chemical formula

[0184]

Chemical formula

[0185]

Chemical formula

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

[0187]

Chemical formula

[0188] In formula (ii-2), R c is synonymous with formula (ii). R 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 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, and 5 or less is more preferable. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 5. By setting it to be not less than the lower limit value, the film strength tends to be improved, and by setting it to be not more than the upper limit value, the 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, still more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 6 to 35, more preferably 8 to 30. By setting it to be not less than the lower limit value, the film strength tends to be improved, and by setting it to be not more than the upper limit value, the developability tends to be improved. 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 preferable.

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

[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 an alkyl group 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; an alkoxy group 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 simplicity of synthesis, unsubstituted is preferred.

[0194] From the viewpoints of film strength and developability, R β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. From the viewpoints of film strength and developability, R βIt 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 allowed 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 given.

[0197]

Chemical formula

[0198]

Chemical formula

[0199]

Chemical formula

[0200]

Chemical formula

[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]

Chemical formula

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

[0204] The polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic 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 the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (C1-2) may be one kind or two or more kinds.

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

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

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

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

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

[0211]

Chemical formula

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

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

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

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

[0216] Examples of the substituent which the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and 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 preferably unsubstituted.

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

[0218] The number of rings in the aliphatic cyclic group is not particularly limited, but 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, and 5 or less is more preferable. The above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 5. By setting it to be not less than the lower limit value, the film strength tends to be improved, and by setting it to be not more than the upper limit value, the developability tends to be improved. The carbon number of the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, and preferably 40 or less, more preferably 35 or less, further preferably 30 or less. The above upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 6 to 35, more preferably 8 to 30. By setting it to be not less than the lower limit value, the film strength tends to be improved, and by setting it to be not more than the upper limit value, the developability tends to be improved. 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 preferable.

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

[0220] Examples of the substituent that the cyclic hydrocarbon group may have include an alkyl group 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; an alkoxy group 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 simplicity of synthesis, unsubstituted is preferred.

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

[0222] The benzene ring in formula (iii) may be further substituted by an arbitrary substituent. Examples of the substituent allowed for 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 it may be one or two or more. From the viewpoint of curability, being unsubstituted is preferred.

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

[0224] [Chemical formula]

[0225] In formula (iii-1), R e and γ have the same meaning as in the above formula (iii). R 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 means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic 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 1 or more is preferred, 5 or more is more preferred, 10 or more is further preferred, and 18 or less is preferred, and 15 or less is further preferred. The above 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 setting the value to be equal to or greater than the lower limit value, the hole resolution tends to improve, and by setting the value to be equal to or less than the upper limit value, the developability tends to improve.

[0228] The number of repeating unit structures represented by the 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, still more preferably 5 or more, and preferably 18 or less, and still 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, and more preferably 5 to 15. By setting it to be equal to or higher than the lower limit value, the hole resolution tends to improve, and by setting it to be equal to or lower than the upper limit value, the developability tends to improve.

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

[0230] [Chemical formula]

[0231] [Chemical formula]

[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, may be referred to as "other alkali-soluble resin"). Examples of the other alkali-soluble resin include acrylic copolymer resins, epoxy resins, urethane resins, novolak resins, polyimide resins, and polyvinylphenol resins.

[0233] For example, the resins described in Japanese Patent Application Laid-Open No. 8-297366, Japanese Patent Application Laid-Open No. 2001-89533, and International Publication No. 2019 / 146685 can be mentioned. These may be used alone or in combination of two or more.

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

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

[0236] The total proportion of (A) ethylenically unsaturated compound and (C) alkali-soluble resin in the total solid content of the photosensitive resin composition is not particularly limited, but is preferably 30% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and is preferably 100% or less, more preferably 95% by mass or less. The 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, still 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 it to be not less than the lower limit value, the adhesion of the cured product to the substrate tends to improve, and by setting it to be not more than the upper limit value, the curability tends to improve.

[0237] [1-2] Other compounding components of the photosensitive resin composition In addition to the above-mentioned components, the photosensitive resin composition of the present invention can be appropriately blended with a surfactant, metal oxide particles, a colorant, a silane coupling agent, an adhesion improver, a phosphoric acid compound, an ultraviolet absorber, a polymerization inhibitor, a thermal polymerization initiator, an amino compound, a solvent, etc.

[0238] [1-2-1] Surfactant In the photosensitive resin composition of the present invention, a surfactant may be contained. The surfactant can be used for the purpose of improving the coatability of the photosensitive resin composition as a coating solution and the developability of the coating film. Among them, silicone-based surfactants and fluorine-based surfactants are preferred. During development, it has the effect of removing the residue of the photosensitive resin composition from the unexposed part and has the function of expressing wettability. Therefore, silicone-based surfactants are preferred, and polyether-modified silicone-based surfactants are more preferred.

[0239] As the fluorine-based surfactant, a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain, and side chain sites is suitable. Examples of commercially available fluorosurfactants include "BM-1000" and "BM-1100" manufactured by BM Chemie, "Megafac F142D", "Megafac F172", "Megafac F173", "Megafac F183", "Megafac F470", "Megafac F475", "Megafac F554", "Megafac F559" manufactured by DIC, "FC430" manufactured by 3M Japan, and "DFX-18" manufactured by NEOSTEC.

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

[0241] Two or more types of surfactants may be used in combination. Examples include combinations of silicone surfactants / fluorosurfactants, silicone surfactants / special polymer surfactants, and fluorosurfactants / special polymer surfactants. A combination of silicone surfactants / fluorosurfactants is preferred. In the case of a combination of a silicone surfactant and a fluorine surfactant, for example, combinations such as "BYK-300" or "BYK-330" manufactured by BYK Chemie / "DFX-18" manufactured by Neos, "BYK-300" or "BYK-330" manufactured by BYK Chemie / "S-393" manufactured by AGC Seimi Chemical Co., Ltd., "BYK-300" or "BYK-330" manufactured by BYK Chemie / "F-554" or "F-559" manufactured by DIC Corporation, "KP340" manufactured by Shin-Etsu Silicone Co., Ltd. / "F-478" or "F-475" manufactured by DIC Corporation, "SH7PA" manufactured by Toray Dow Corning Co., Ltd. / "DS-401" manufactured by Daikin Industries, Ltd., "L-77" manufactured by NUC / "FC4430" manufactured by 3M Japan Co., Ltd. can be mentioned.

[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 increase.

[0243] Examples of the 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 preferable, and titanium oxide particles and zirconium oxide particles are more preferable. [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 using a pigment, known dispersants or dispersion aids may be used in combination so that the pigment can stably exist in the photosensitive resin composition without aggregation. 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, still more preferably 5% by mass or less in the total solid content of the photosensitive resin composition. For example, it is preferably 1 to 30% by mass, more preferably 1 to 10% by mass, still 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 the adhesion to the substrate. Examples of the silane coupling agent include epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are preferred. When the photosensitive resin composition of the present invention contains a silane coupling agent, its content is preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less in the total solid content of the photosensitive resin composition from the viewpoint of adhesion. For example, it is preferably 1 to 10% by mass, more preferably 1 to 5% by mass.

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

[0247]

Chemical formula

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

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

[0250] [1-2-6] Ultraviolet absorber The photosensitive resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of the light source used for exposure with the ultraviolet absorber. By adding the ultraviolet absorber, an effect of increasing the taper angle can be obtained.

[0251] Examples of the ultraviolet absorber include compounds having an absorption maximum between 250 nm and 400 nm from the viewpoint of inhibiting the light absorption of the (B) photoinitiator. 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 that the ultraviolet absorber contains either or both of benzotriazole-based compounds and triazine-based compounds.

[0252] [1-2-7] Polymerization inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing the polymerization inhibitor, since it inhibits radical polymerization, there is a tendency 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 controlling the taper angle, 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. (C) When producing the alkali-soluble resin, a polymerization inhibitor may be contained in the resin. In that case, it may be used as it is, or in addition to the polymerization inhibitor contained in the resin, the same or different polymerization inhibitor may be further added during the production of the photosensitive resin composition.

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

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

[0257] [1-2-10] Solvent The photosensitive resin composition of the present invention may contain a solvent. If a solvent is contained, each of the above-described components can be used in a state of being dissolved or dispersed 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, and 1,6 - hexanediol 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, 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, methoxymethyl pentanol, glycerin, benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene, 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, γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride, amyl chloride; Ether ketones such as methoxymethyl pentanone; Nitriles such as acetonitrile, benzonitrile; Tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran.

[0259] Examples of commercially available solvents include mineral spirit, Varsol #2, Apco #18 solvent, Apco thinner, Solvesso 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 are trade names).

[0260] The solvent only needs to be able to dissolve or disperse each component in the photosensitive resin composition, and is selected according to the usage method of the photosensitive resin composition of the present invention. From the viewpoint of coatability, a solvent having a boiling point of 60 to 280°C under atmospheric pressure is preferable, and a solvent having a boiling point of 70 to 260°C is more preferable. For example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate can be mentioned.

[0261] The solvent may be used alone or in combination of two or more. The solvent is preferably used such that the content ratio of the total solid content in the photosensitive resin composition solution is preferably 10% by mass or more, more preferably 15% by mass or more, still 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, still more preferably 40% by mass or less, particularly preferably 35% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it is used so as to be 10 to 90% by mass, preferably 15 to 50% by mass, more preferably 20 to 40% by mass, still more preferably 25 to 35% by mass. By setting the value to be not less than the lower limit value, the occurrence of coating unevenness can be suppressed, and by setting the value to be not more than the upper limit value, the occurrence of foreign matters, peeling, etc. can be suppressed.

[0262] [2] Method for preparing the photosensitive resin composition The photosensitive resin composition of the present invention can be prepared by mixing the above components with a stirrer. When the photosensitive resin composition of the present invention contains a colorant, it is preferably subjected to dispersion treatment in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the colorant is micronized by the dispersion treatment, the coating properties of the photosensitive resin composition are improved.

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

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

[0265] The dispersion particle size of the colorant dispersed in the pigment dispersion is preferably from 0.01 to 1 μm, more preferably from 0.02 to 0.5 μm, and still more preferably from 0.03 to 0.3 μm. The dispersion particle size is measured, for example, as the number-based median diameter by the dynamic light scattering method. The pigment dispersion obtained by the dispersion treatment and the other above-mentioned components contained in the photosensitive resin composition are mixed to form a uniform solution or dispersion. In the manufacturing process of the photosensitive resin composition, since fine dust may be mixed in the liquid, it is desirable to filter the obtained photosensitive resin composition, for example, by 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 in an organic electroluminescent element, it can be suitably used as an insulating film or a functional film for improving the light extraction efficiency. The method for forming a cured product using the photosensitive resin composition is not particularly limited, and a conventionally known method can be employed. For example, a photolithography method including a coating step of coating the photosensitive resin composition on a substrate to form a photosensitive resin composition layer, an exposure step of exposing the photosensitive resin composition layer, and a development step can be mentioned.

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

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

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

[0270] In the exposure step, using a negative mask, the photosensitive resin composition layer is irradiated with actinic energy rays such as ultraviolet rays or excimer laser light and exposed. 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 amount varies depending on the composition of the photosensitive resin composition, but for example, about 10 to 400 mJ / cm 2 is preferable.

[0271] In the development step, the exposed photosensitive resin composition layer is developed with a developer to form a cured product. The developing method is not particularly limited, and an immersion method, a spray method, etc. can be used. Examples of the developer include organic developers such as tetramethylammonium hydroxide (TMAH), dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as 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 process and a post-bake (firing) process may be performed. The post-bake temperature is preferably 150 to 250°C. The post-bake 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, still more preferably 0.8 μm or more, and preferably 10 μm or less, more preferably 5.0 μm or less, still 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, more preferably 0.8 to 3.0 μm. By setting it to be not less than the lower limit value, the refractive index of the cured product tends to improve, and by setting it to be not more than the upper limit value, the hole resolution tends to improve. The film thickness of the cured product is measured by a step, surface roughness, and fine shape measuring device, a scanning white light interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, or an electron microscope.

[0274] The cured product produced from the photosensitive composition of the present invention has a high refractive index. The refractive index of the cured product is preferably 1.620 or more, more preferably 1.630 or more, still more preferably 1.640 or more. Also, it is preferably 1.680 or less, more preferably 1.660 or less. The above upper and lower limits can be arbitrarily combined. For example, 1.620 to 1.680 is preferable, 1.630 to 1.680 is more preferable, and 1.640 to 1.660 is still more preferable. By being not less than the lower limit value, the light extraction efficiency tends to improve. As a method for measuring the refractive index of a cured product, for example, a method of measuring using a prism coupler can be mentioned. Specifically, as described in the examples, a substrate for refractive index measurement having a cured product formed on a glass substrate is prepared, and under the condition of 20 °C, using a He-Ne laser as a light source, the value at a wavelength of 633 nm measured using a prism coupler can be taken as 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, for example, a liquid crystal display device and an image display device including an organic electroluminescence element.

Examples

[0276] Hereinafter, the photosensitive resin composition of the present invention will be described with specific examples, but the present invention is not limited to the following examples as long as it does not exceed the gist thereof. The constituent components of the photosensitive resin compositions 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 Japanese Patent Application Laid - Open No. 2021 - 024842. Ethylenically unsaturated compound - I corresponds to the ethylenically unsaturated compound (A1).

[0278]

Chemical formula

[0279] <Ethylenically unsaturated compound - II> Ogsoal EA - 0200 manufactured by Osaka Gas Chemical Co., Ltd. A compound having the following structure. Ethylenically unsaturated compound - II does not correspond to the ethylenically unsaturated compound (A1).

[0280]

Chemical formula

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

[0282]

Chemical formula

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

[0284]

Chemical formula

[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 acrylic acid in an amount equal to that of glycidyl methacrylate, and further adding tetrahydrophthalic anhydride in an amount of 0.40 mol per 1 mol of the total number of moles of the above constituent monomers of the copolymer resin. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is 10000, and the solid content acid value is 68.8 mgKOH / g.

[0286] <Alkali-soluble resin-IV> An alkali-soluble acrylic copolymer resin was prepared 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 acrylic acid in an amount equal to that of glycidyl methacrylate, and further adding tetrahydrophthalic anhydride in an amount of 0.10 mol per 1 mol of the total number of moles of the constituent monomers of the copolymer resin. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 8900, and the solid content acid value was 26.9 mgKOH / g.

[0287] <Photoinitiator-I> It is a compound having the following chemical structure and can be produced by the synthesis method described in International Publication No. 2019 / 131189.

[0288]

Chemical formula

[0289] <Surfactant-I> Megafac F-559 manufactured by DIC Corporation

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

[0291] The method for performance evaluation will be described below.

[0292] <Measurement of refractive index> Using a spinner on a glass substrate, a photosensitive resin composition was applied so as to have a thickness of 2 μm after heat curing. The obtained substrate was dried in vacuo for 1 minute, and further dried by heating on a hot plate at 100 °C for 100 seconds to obtain a coated film substrate. Next, using a manual exposure machine (MA-1100) manufactured by Dainippon Kagaku Kenkyusho Co., Ltd. and a high-pressure mercury lamp with a wavelength cut off at 330 nm or less, the coated film substrate was exposed over the entire surface with an exposure amount of 100 mJ / cm 2 At this time, the light intensity at a wavelength of 365 nm was 45 mW / cm2 It was. Finally, the substrate exposed entirely was heated and cured at 230°C for 30 minutes in an oven to obtain a substrate for refractive index measurement.

[0293] Using the substrate for refractive index measurement, the refractive index of the cured product was measured. Specifically, under the condition of 20°C, using a prism coupler Model 2010 manufactured by Metricon Corporation, a He-Ne laser with a wavelength of 633 nm was used as the incident light for measurement. If the refractive index was 1.630 or more, it was evaluated as "A"; if it was 1.600 or more and less than 1.630, it was evaluated as "B"; and if it was less than 1.600, it was evaluated as "C".

[0294] <Fabrication of Hall Resolution Evaluation Substrate> On a glass substrate, using a spinner, the photosensitive resin composition obtained in each example and comparative example was coated so as to have a thickness of 2 μm after heat curing. The obtained substrate was dried in vacuo for 1 minute, and further dried by heating on a hot plate at 100°C for 100 seconds. The obtained coating film was exposed using a photomask. Using a mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc., exposure was performed so that the exposure amount became 40 mJ / cm 2 The illuminance was 500 mW / cm 2 , and the slit width was 1.6 mm. As the photomask, a mask having a coating portion of 10 μm × 10 μm was used. Next, using a 2.38% aqueous TMAH solution, development treatment was performed with a shower at a pressure of 0.05 MPa for a development time of 40 seconds, and then washed with pure water for 30 seconds. Finally, it was heated and cured at 230°C for 30 minutes in an oven to fabricate a Hall resolution evaluation substrate.

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

[0296] [Composition of Photosensitive Resin Composition for Forming Organic Underlayer 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 underlayer film. · Ethylenically unsaturated compound: Dipentaerythritol hexaacrylate manufactured by Toagosei Co., Ltd., 49.2 parts by mass · Alkali-soluble resin: Alkali-soluble resin-IV, 49.2 parts by mass · Photopolymerization initiator: Photopolymerization initiator-I, 3 parts by mass · Additive: BYK-330 manufactured by BYK, 0.1 part by mass, PM-21 manufactured by Nippon Kayaku Co., Ltd., 0.5 part by mass

[0297] Next, the photosensitive resin composition for forming an organic underlayer film was applied onto a glass substrate using a spinner so as to have a thickness of 1.5 μm after heat curing. The obtained substrate was vacuum dried for 1 minute, and further heat dried on a hot plate at 90 °C for 90 seconds. Next, the obtained coated film substrate was exposed to light over the entire surface using a high-pressure mercury lamp with a wavelength of 330 nm or less cut off, and an exposure amount of 40 mJ / cm 2 At this time, the light intensity at a wavelength of 365 nm was 45 mW / cm 2 Finally, the substrate was heat cured in an oven at 230 °C for 30 minutes, and then dry cleaning was performed with the lamp lighting time of the UV dryer processor VUM-3073-F02-00 manufactured by Okuno Seisakusho set to 1 minute to obtain a glass substrate with an organic underlayer film.

[0298] <Fabrication of Hole Resolution Evaluation Substrate with Organic Underlayer Film> On a glass substrate with an organic underlayer film, using a spinner, the photosensitive resin compositions obtained in the following Examples and Comparative Examples were applied so as to have a thickness of 2 μm after heat curing. The obtained substrate was vacuum dried for 1 minute, and further heat dried on a hot plate at 100 °C for 100 seconds. The obtained coating film was exposed using a photomask. Using a mirror projection type exposure machine (MPA-600FA) manufactured by Canon, exposure was performed for 10 seconds so that the exposure amount became 40 mJ / cm 2 The illuminance was 500 mW / cm 2 and the slit width was 1.6 mm. As the photomask, a mask having a coated portion of 10 μm × 10 μm was used. Next, using a 2.38% aqueous TMAH solution, development treatment was performed with a shower at a pressure of 0.05 MPa for a development time of 40 seconds, and then washed with pure water for 30 seconds. Finally, it was heat cured in an oven at 230 °C for 30 minutes to fabricate a hole resolution evaluation substrate with an organic underlayer film.

[0299] <Evaluation of Hole Resolution Evaluation Substrate> Among the hole resolution evaluation substrates and the hole resolution evaluation substrates with organic underlayer films obtained above, in the unexposed portion of 10 μm × 10 μm, when the substrate or the organic underlayer film was exposed by sufficient development, it was evaluated as "A", and when the film remained without sufficient development, it was evaluated as "C".

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

[0301]

Table 1

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

[0303] Also, it can be seen that Examples 1 to 2 can achieve not only a high refractive index but also good hole resolution. This is because when developing the coating film of the photosensitive resin composition with an alkali developer, by using the ethylenically unsaturated compound-I having a sulfur-containing aromatic heterocyclic ring, it is possible to reduce the molecular volume while giving a high refractive index. Moreover, since 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 heterocyclic ring, the alkali-soluble resin can be uniformly distributed in the coating film of the photosensitive resin composition without phase separation. Along with this, the alkali developer during development can easily penetrate, so it is considered that the hole resolution was good.

[0304] In Comparative Example 1, the ethylenically unsaturated compound-II is not a compound having a sulfur-containing aromatic heterocyclic ring, and in Comparative Examples 2 to 3, the alkali-soluble resins-III and -IV are acrylic ester copolymers having no aromatic group in the main chain. Therefore, it can be seen that they are inferior in refractive index and hole resolution.

[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 became the blending ratio shown in Table 2. Further, the content ratio of the total solid content was 20% by mass, and the solvent was added so that Solvent-I / Solvent-II = 90 / 10 (mass ratio) in the total solvent, followed by stirring and dissolution to prepare a photosensitive resin composition. Using each of the obtained photosensitive resin compositions, the refractive index and hole resolution were evaluated by the method described below. Note that the blending ratios of the ethylenically unsaturated compound, alkali-soluble resin, photopolymerization initiator, and surfactant in Table 2 are values in terms of solid content.

[0306]

Table 2

[0307] <Measurement of Refractive Index> Using a spinner on a glass substrate, the photosensitive resin composition was applied so as to have a thickness of 1.5 μm after heat curing. The obtained substrate was vacuum dried for 1 minute, and further heat dried on a hot plate at 100 °C for 100 seconds to obtain a coated film substrate. Next, using a manual exposure machine (MA-1100) manufactured by Dainippon Scientific Co., Ltd. and a high-pressure mercury lamp with a wavelength cut off at 330 nm or less, the coated film substrate was exposed to light with an exposure amount of 100 mJ / cm 2 over the entire surface. The light intensity at a wavelength of 365 nm at this time was 45 mW / cm 2 . Finally, the substrate exposed over the entire surface was heat cured in an oven at 230 °C for 30 minutes to obtain a substrate for refractive index measurement.

[0308] The refractive index of the cured product was measured using a substrate for refractive index measurement. Specifically, under the condition of 20 °C, using a prism coupler Model 2010 manufactured by Metricon, a He-Ne laser with a wavelength of 633 nm was used as the incident light for measurement. If the refractive index was 1.640 or more, it was rated as "AA"; if it was 1.630 or more, it was rated as "A"; if it was 1.600 or more and less than 1.630, it was rated as "B"; and if it was less than 1.600, it was rated as "C".

[0309] <Fabrication of Hall Resolution Evaluation Substrate> On a substrate with an indium tin oxide (ITO) film formed on the surface of a glass substrate, using a spinner, the photosensitive resin composition obtained in each example and comparative example was coated so as to have a thickness of 1.5 μm after heat curing (firing). The obtained substrate was vacuum dried for 1 minute, and further dried by heating on a hot plate at 100 °C for 100 seconds. The obtained coating film was exposed using a photomask. Using a mirror projection type exposure machine (MPA-600FA) manufactured by Canon, exposure was performed so that the exposure amount was 60 mJ / cm 2 The exposure was carried out so that the illuminance was 500 mW / cm 2 and the slit width was 1.6 mm. As the photomask, a mask having a coated portion of 10 μm × 10 μm was used. Next, using a 2.38% aqueous TMAH solution, development treatment was performed with a shower at a temperature of 24 °C and a pressure of 0.05 MPa for a development time of 40 seconds, and then washed with pure water for 30 seconds. Finally, it was heat cured at 230 °C in an oven for 30 minutes to fabricate a Hall resolution evaluation substrate.

[0310] <Evaluation of Hall Resolution Evaluation Substrate> Among the Hall resolution evaluation substrates obtained above, when the substrate on which the ITO film was formed was exposed by sufficient development in the unexposed portion of 10 μm × 10 μm, it was rated as "AA"; when the substrate on which the ITO film was formed was exposed by sufficient development in the unexposed portion of 30 μm × 30 μm, it was rated as "A"; and when the film remained without sufficient development, it was rated as "C".

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

[0312] In Comparative Example 4, the ethylenically unsaturated compound-II is not a compound containing a sulfur-containing aromatic heterocyclic ring, and in Comparative Example 5, the alkali-soluble resin-IV is an acrylate copolymer having no aromatic ring in the main chain. Therefore, it can be seen that the refractive index and hole resolution are inferior.

Claims

1. A photosensitive resin composition comprising (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, the (A) ethylenically unsaturated compound contains an ethylenically unsaturated compound (A1) having 1 to 3 ethylenically unsaturated bonds and 1 to 3 sulfur-containing aromatic heterocycles in the molecule, The ethylenically unsaturated compound (A1) is a compound represented by the following general formula (A1-1): the alkali-soluble resin (C) contains an epoxy (meth)acrylate resin (C1) having an aromatic ring in its main chain, The photosensitive resin composition is characterized in that the epoxy (meth)acrylate resin (C1) having an aromatic ring in the main chain has a partial structure represented by the following general formula (i): 【Chemistry 1】 (In formula (A1-1), R 1 represents a hydrogen atom or a methyl group. Cy represents a benzothiazole ring. Q 1 and Q 2 each independently represent an alkylene group having 1 to 6 carbon atoms. X 1 and X 2 each independently represent —O—, —S—, —NR 2 —, —NR 2 —(C═O)—, or —NR 2 —(C═O)—O—. Z 1 and Z 2 each independently represent a divalent hydrocarbon group which may have a substituent. m and n each independently represent an integer of 1 to 3. p and q each represent 0. R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 【Chemistry 2】 (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 an optional substituent. * represents a bond.)

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

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

5. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 4.

6. An image display device comprising the cured product according to claim 5 .

Images