Polymerizable compound, active energy ray-curable resin composition, cured product, resist composition, and resist film

Abstract

Provided is a polymerizable compound which is excellent in wettability for a fine space, and which is also excellent in optical properties, etching resistance, curability, solvent solubility, and the like, and thus can be used for formation of a wiring pattern which has been ultra-fined. Specifically, it is a polymerizable compound represented by the following general formula (1).

Description

TECHNICAL FIELD

[0001] The present application relates to a polymerizable compound, an active energy ray-curable resin composition, a cured product, a resist composition, and a resist film. BACKGROUND

[0002] In recent years, with the high integration and high speed of LSIs, there is a demand for finer and finer patterning, and in photolithography using an ArF excimer laser (193 nm), the resolution limit inherent to the wavelength of the light source has been exceeded by the use of the optical properties of the process materials and improvements in the process equipment.

[0003] In the field of photoresists, various methods for forming finer wiring patterns have been developed, one of which is a multi-layer resist method. In the multi-layer resist method, after a layer or layers of a layer called an underlayer resist film, an antireflection film, or the like, are formed on a substrate, a resist pattern based on the usual photolithography is formed thereon, and then a wiring pattern is transferred to the substrate by dry etching. One of the important components in the technology of the multi-layer resist method is the aforementioned underlayer resist film, and the underlayer resist film is required to have high dry etching resistance, low light reflectivity, and the like. In addition, the underlayer resist film is formed in a solvent-diluted state, and therefore the resin material for the underlayer resist film needs to be soluble in general organic solvents.

[0004] In addition, in recent years, fine wiring patterns are formed mostly using a process in which multiple exposure and etching called double patterning, multiple patterning are repeated, and for the underlayer film, on the basis of filling the fine pattern made in the previous process, the underlayer film also plays an important role in forming a smooth surface for the next process. Therefore, the underlayer film material used in the base material is also required to have high wettability in fine spaces.

[0005] In addition, as a conventional underlayer resist film containing a phenolic hydroxyl group, a compound containing an anthracene skeleton is known (Patent Document 1).

[0006] PRIOR ART DOCUMENTS

[0007] PATENT DOCUMENTS

[0008] Patent Document 1: Japanese Patent Application Publication No. 2010-285403 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] The compound containing an anthracene skeleton described in the aforementioned Patent Document 1 has low light reflectivity in a cured coating film, and is excellent in the properties as an antireflection film, but has low wettability in fine spaces due to the molecular size and the π-π interaction caused by the wide aromatic electron cloud.

[0011] The present application provides a polymerizable compound which is excellent in wettability for a fine space and which is also excellent in optical properties, etching resistance, curability, solvent solubility, and the like, and which can be used for forming a wiring pattern which is ultra-finely processed.

[0012] In addition, the present application provides a reactive energy ray-curable resin composition which can be used for forming a wiring pattern which is ultra-finely processed.

[0013] In addition, the present application provides a resist composition which can form a wiring pattern which is ultra-finely processed.

[0014] Solution to the problem

[0015] The present application is a polymerizable compound represented by the following general formula (1).

[0016]

[0017] [In the above general formula (1), X represents a structural site having an aromatic ring structure and a polymerizable unsaturated group. In addition, the three Xs in the above general formula (1) are optionally the same structure or different structures, respectively.]

[0018] In addition, the present application is a polymerizable compound which uses, as reaction raw materials, a reaction product (A) of trihydroxybenzene and an epoxy halopropane, and an aromatic compound (B) containing a polymerizable unsaturated group.

[0019] In addition, the present application is a polymerizable compound which uses, as reaction raw materials, a reaction product (A) of trihydroxybenzene and an epoxy halopropane, a non-aromatic compound (C) containing a polymerizable unsaturated group, and an aromatic compound (D) which links the aforementioned reaction product (A) and the aforementioned non-aromatic compound (C) containing a polymerizable unsaturated group.

[0020] In addition, the present application is a reactive energy ray-curable resin composition which contains the aforementioned polymerizable compound, a photopolymerization initiator, and an organic solvent.

[0021] In addition, the present application is a resist composition which contains the aforementioned polymerizable compound.

[0022] Effects of the invention

[0023] According to the present application, it is possible to provide a polymerizable compound which is excellent in wettability for a fine space and which is also excellent in optical properties, etching resistance, curability, solvent solubility, and the like, and which can be used for forming a wiring pattern which is ultra-finely processed.

[0024] In addition, according to the present application, it is possible to provide a reactive energy ray-curable resin composition which can be used for forming a wiring pattern which is ultra-finely processed.

[0025] In addition, according to the present application, it is possible to provide a resist composition which can be used to form a wiring pattern which is ultra-fined. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 GPC chart of the polymerizable compound (1) obtained in Example 1

[0027] Figure 2 GPC chart of the polymerizable compound (1) obtained in Example 1 1 H-NMR chart of the polymerizable compound (1) obtained in Example 1

[0028] Figure 3 GPC chart of the polymerizable compound (1) obtained in Example 1 13 C-NMR chart of the polymerizable compound (1) obtained in Example 1

[0029] Figure 4 FD-MS chart of the polymerizable compound (1) obtained in Example 1

[0030] Figure 5 GPC chart of the polymerizable compound (2) obtained in Example 2

[0031] Figure 6 GPC chart of the polymerizable compound (3) obtained in Example 3

[0032] Figure 7 GPC chart of the polymerizable compound (4) obtained in Example 4

[0033] Figure 8 GPC chart of the polymerizable compound (4) obtained in Example 4 1 H-NMR chart of the polymerizable compound (4) obtained in Example 4

[0034] Figure 9 C-NMR chart of the polymerizable compound (4) obtained in Example 4 13 C-NMR chart of the polymerizable compound (4) obtained in Example 4

[0035] Figure 10 FD-MS chart of the polymerizable compound (4) obtained in Example 4

[0036] Figure 11 GPC chart of the polymerizable compound (5) obtained in Example 5

[0037] Figure 12 GPC chart of the polymerizable compound (6) obtained in Example 6

[0038] Figure 13 GPC chart of the polymerizable compound (7) obtained in Example 7

[0039] Figure 14GPC spectrum of the polymerizable compound (1) obtained in Comparative Example 1 1 H-NMR spectrum

[0040] Figure 15 GPC spectrum of the polymerizable compound (1) obtained in Comparative Example 1 13 C-NMR spectrum

[0041] Figure 16 FD-MS spectrum of the polymerizable compound (7) obtained in Example 7

[0042] Figure 17 GPC spectrum of the polymerizable compound (8) obtained in Example 8

[0043] Figure 18 GPC spectrum of the polymerizable compound (8) obtained in Example 9

[0044] Figure 19 GPC spectrum of the polymerizable compound (1) obtained in Comparative Example 1

[0045] Figure 20 GPC spectrum of the polymerizable compound (2) obtained in Comparative Example 2

[0046] Figure 21 GPC spectrum of the polymerizable compound (3) obtained in Comparative Example 3 DETAILED DESCRIPTION

[0047] In one embodiment of the present application, the polymerizable compound is represented by the following general formula (1).

[0048]

[0049] [In the above general formula (1), X represents a structural moiety having an aromatic ring structure and a polymerizable unsaturated group. In addition, the three X's in the above general formula (1) are optionally the same structure or different structures, respectively.]

[0050] The X in the above general formula (1) is not particularly limited in its specific structure as long as it is a structural moiety having an aromatic ring structure and a polymerizable unsaturated group, and can take a variety of structures. The polymerizable compound of the present embodiment represented by the above general formula (1) has a structure derived from trihydroxybenzene, and has an aromatic ring structure and a polymerizable unsaturated group at three molecular terminal ends, thereby becoming a compound which is excellent in infiltration into a fine space, and is also excellent in optical properties, etching resistance, curability, solvent solubility, and the like.

[0051] With respect to the X in the above general formula (1), from the viewpoints of solubility in an organic solvent and infiltration into a fine space, the following structural moieties represented by general formulas (2-1), (2-2), (2-3), or (2-4) are preferred.

[0052]

[0053] [In the above general formulae (2-1) to (2-4), Y is a direct bond, an ether bond, or an amide bond, Z is a structural moiety having a polymerizable unsaturated group, R 1 is an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom. In the above structural formulae, m is an integer of 1 to 5, n is an integer of 0 to 4, and m + n is 5 or less. p is an integer of 1 to 7, q is an integer of 0 to 6, and p + q is 7 or less. The plurality of R 1 and the (Y-Z) group are optionally the same or different. In the above general formulae (2-2) and (2-4), R 1 and the (Y-Z) group are optionally bonded to any carbon atom of the naphthalene ring.

[0054] In the above general formulae (2-1) to (2-4), Z is a structural moiety having a polymerizable unsaturated group. As the polymerizable unsaturated group, for example, an alkenyl group, an alkynyl group, an acryloyl group, a methacryloyl group, or the like can be given. Among them, from the viewpoints of solubility in an organic solvent and wettability to a fine space, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an acryloyl group, a methacryloyl group are preferable, and an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms are more preferable.

[0055] In the above general formulae (2-1) to (2-4), m is an integer of 1 to 5, and p is an integer of 1 to 7. Among them, from the aspect of becoming a compound excellent in balance of each performance such as wettability to a fine space, optical properties, etching resistance, curability, solvent solubility, the values of m and p are preferably 1 to 3, and particularly preferably 1. In the case where the value of m in the above general formula (2-1) is 1, the bonding position of the (Y-Z) group with respect to the oxygen atom to which X is bonded in the above general formula (1) is preferably the para position. In the case where the value of m in the above general formula (2-2) is 1, the bonding position of the (Y-Z) group with respect to the carbonyl group is preferably the para position. In the case where p is 1 in the above general formula (2-2), the bonding position of the (Y-Z) group and the bonding position of the oxygen atom to which X is bonded in the above general formula (1) are preferably located at the 1, 6-positions, the 2, 6-positions, the 2-7 positions of the naphthalene ring, and more preferably at the 2, 6-positions. In the case where p is 1 in the above general formula (2-4), the bonding position of the (Y-Z) group and the bonding position of the carbonyl group are preferably located at the 1, 6-positions, the 2, 6-positions, the 2-7 positions of the naphthalene ring, and more preferably at the 2, 6-positions.

[0056] In the above general formulae (2-1) to (2-4), R 1aliphatic hydrocarbon group, an alkoxy group, or a halogen atom. The aforementioned aliphatic hydrocarbon group can be linear or branched. In addition, it can have a ring structure. More specifically, there can be mentioned a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, and the like, each having 1 to 6 carbon atoms. As the aforementioned alkoxy group, there can be mentioned a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, a cyclohexyloxy group, and the like. As the aforementioned halogen atom, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Among them, from the viewpoints of solubility in an organic solvent and wettability in a fine space, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom are preferable, and the value of n or q is more preferably 0.

[0057] The aforementioned polymerizable compound can be produced by any method, and the production method thereof is not particularly limited. As examples of the production method of the aforementioned polymerizable compound, there can be mentioned the following two examples.

[0058] [Production Method Example 1]

[0059] A production method in which a reaction product (A) of trihydroxybenzene and an epoxy halopropane, and an aromatic compound (B) containing a polymerizable unsaturated group are used as raw materials.

[0060] [Production Method Example 2]

[0061] A production method in which a reaction product (A) of trihydroxybenzene and an epoxy halopropane, a non-aromatic compound (C) containing a polymerizable unsaturated group, and an aromatic compound (D) for linking the aforementioned reaction product (A) and the non-aromatic compound (C) containing a polymerizable unsaturated group are used as raw materials.

[0062] The aforementioned Production Method Example 1 will be described. The aforementioned Production Method Example 1 is specifically a production method of a polymerizable compound including the following steps: Step (1-1) of reacting trihydroxybenzene with an epoxy halopropane to obtain the aforementioned reaction product (A); and Step (1-2) of reacting the aforementioned reaction product (A) with an aromatic compound (B) containing a polymerizable unsaturated group to obtain the aforementioned polymerizable compound.

[0063] The aforementioned Step (1-1) is a step of reacting trihydroxybenzene with an epoxy halopropane to obtain the aforementioned reaction product (A).

[0064] From the viewpoint of the yield of the aforementioned target reaction product (A), the aforementioned Step (1-1) preferably includes the following steps: Step (1-1a) of reacting trihydroxybenzene with an epoxy halopropane in the presence of a quaternary onium salt and / or a basic compound; and Step (1-1b) of closing the ring of the reactant obtained in the aforementioned Step (1-1a) in the presence of a basic compound.

[0065] The trihydroxybenzene used as a raw material for the aforementioned polymerizable compound is not particularly limited, and one or more selected from the group consisting of 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene is preferred from the viewpoint of easiness in obtaining the raw material.

[0066] As the aforementioned epoxy halopropane, there is no particular limitation, and epoxy chloropropane, epoxy bromopropane, β-methyl epoxy chloropropane, β-methyl epoxy bromopropane, and the like can be given. These epoxy halopropanes can be used alone or in combination of two or more.

[0067] As the aforementioned quaternary onium salt, for example, quaternary ammonium salts, quaternary phosphonium salts, and the like can be given. These quaternary onium salts can be used alone or in combination of two or more.

[0068] As the aforementioned quaternary ammonium salt, for example, chloride salts of tetramethylammonium cation, methyltriethylammonium cation, tetraethylammonium cation, tributylmethylammonium cation, tetrabutylammonium cation, phenyltrimethylammonium cation, benzyltrimethylammonium cation, phenyltriethylammonium cation, benzyltriethylammonium cation, bromide salts of tetramethylammonium cation, trimethylpropylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, and the like can be given.

[0069] As the aforementioned quaternary phosphonium salt, for example, bromide salts of tetraethylphosphonium cation, tetrabutylphosphonium cation, methyltriphenylphosphonium cation, tetraphenylphosphonium cation, ethyltriphenylphosphonium cation, butyltriphenylphosphonium cation, benzyltriphenylphosphonium cation, and the like can be given.

[0070] Among these quaternary onium salts, chloride salts of tetramethylammonium cation, benzyltrimethylammonium cation, benzyltriethylammonium cation, and bromide salts of tetrabutylammonium cation are preferred.

[0071] In addition, as the amount of the aforementioned quaternary onium salt, from the viewpoint of good progress of the reaction and reduction of the residue in the product, 0.15 to 5 parts by mass, more preferably 0.18 to 3 parts by mass, relative to 100 parts by mass of the total mass of the aforementioned trihydroxybenzene and epoxy halopropane is preferred.

[0072] As the aforementioned basic compound, for example, potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, and the like can be given. These basic compounds can be used alone or in combination of two or more. Among them, potassium hydroxide and sodium hydroxide are preferred.

[0073] In addition, the amount of the aforementioned basic compound to be added is preferably in the range of 0.01 to 0.3 mol, and more preferably in the range of 0.02 to 0.2 mol, relative to 1 mol of the hydroxyl group of the aforementioned trihydroxybenzene, from the viewpoint of the reaction proceeding favorably and the amount of the residual product being reduced.

[0074] The aforementioned quaternary onium salt and the aforementioned basic compound can be used individually or in combination with two or more kinds.

[0075] The reaction of the aforementioned step (1-1a) is a reaction in which the epoxy halopropane is added to the hydroxyl group of the aforementioned trihydroxybenzene. The reaction temperature of the aforementioned step (1-1a) is preferably in the range of 20 to 80°C, and more preferably in the range of 40 to 75°C. The reaction time of the aforementioned step (1-1a) is preferably 0.5 hours or more, and more preferably in the range of 1 to 50 hours.

[0076] In addition, the reaction of the aforementioned step (1-1a) can be performed in an organic solvent as needed. As the aforementioned organic solvent, for example, there can be mentioned ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, and methyl amyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, ethanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; and methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, ethyl lactate, and γ-butyrolactone. These organic solvents can be used individually or in combination with two or more kinds.

[0077] In the case where the aforementioned organic solvent is used, the amount thereof is preferably in the range of 5 to 150 parts by mass, and more preferably in the range of 7.5 to 100 parts by mass, and further preferably in the range of 10 to 50 parts by mass, relative to 100 parts by mass of the total of the aforementioned trihydroxybenzene and the epoxy halopropane.

[0078] The aforementioned step (1-1b) is a step in which the reactant obtained in the aforementioned step (1-1a) is subjected to ring closure in the presence of a basic compound, and the aforementioned step (1-1b) can be performed directly using the reactant obtained in the aforementioned step (1-1a), or the aforementioned step (1-1b) can be performed after removing a part or all of the unreacted epoxy halopropane and the reaction solvent present in the system.

[0079] As the basic compound used in the aforementioned step (1-1b), the same substances as the aforementioned basic compound can be used, and the aforementioned basic compound can be used alone or in combination with two or more kinds.

[0080] The amount of the aforementioned basic compound is not particularly limited, and is preferably in the range of 0.8 to 1.5 moles, and more preferably in the range of 0.9 to 1.3 moles, relative to 1 mole of the hydroxyl group possessed by the aforementioned trihydroxybenzene. If the amount of the aforementioned basic compound is 0.8 moles or more, the ring-closing reaction of the aforementioned step (1-1b) can be suitably performed, and thus is preferred. On the other hand, if the amount of the aforementioned basic compound is 1.5 moles or less, side reactions can be prevented or suppressed, and thus is preferred. Note that, in the case where a basic compound is used in step (1-1a), the amount used in the aforementioned step (1-1a) is preferably included in the aforementioned amount.

[0081] The reaction temperature of the aforementioned step (1-1b) is preferably in the range of 20 to 120°C, and more preferably in the range of 25 to 80°C. The reaction time is preferably in the range of 0.5 to 8 hours, and more preferably in the range of 1 to 5 hours.

[0082] From the viewpoint of obtaining the aforementioned polymerizable compound having excellent wettability and curability to a fine space, the epoxy equivalent of the reaction product (A) of the aforementioned trihydroxybenzene and the epoxy halopropane is preferably in the range of 98 to 196, and more preferably in the range of 105 to 140. Note that, in the present specification, the epoxy equivalent is measured according to the method described in JIS K 7236.

[0083] After the aforementioned step (1-1b) is performed, purification or the like of the obtained reaction product can be performed as needed.

[0084] The aforementioned step (1-2) is a step of obtaining the aforementioned polymerizable compound by reacting the aforementioned reaction product (A) with the aforementioned polymerizable-unsaturated-group-containing aromatic compound (B).

[0085] The aforementioned polymerizable-unsaturated-group-containing aromatic compound (B) is an aromatic compound having a polymerizable unsaturated group, and is not particularly limited as long as it has a group that reacts with the epoxy group possessed by the aforementioned reaction product (A). From the viewpoints of reactivity, ease of manufacture, and the like, the group that reacts with the epoxy group possessed by the aforementioned reaction product (A) is preferably a carboxyl group or a hydroxyl group. That is, the aforementioned polymerizable-unsaturated-group-containing aromatic compound (B) is preferably a polymerizable-unsaturated-group-containing phenolic compound (B1) or a polymerizable-unsaturated-group-containing aromatic carboxylic compound (B2).

[0086] The aforementioned phenolic compound (B1) containing a polymerizable unsaturated group can be exemplified by a compound represented by the following general formula (3-1) or (3-2), or the like.

[0087]

[0088] [In the aforementioned general formula (3-1), (3-2), Y is a direct bond, an ether bond, or an amide bond, Z is a structural moiety having a polymerizable unsaturated group, R 1 is an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom. In the aforementioned structural formula, m is an integer of 1 to 5, n is an integer of 0 to 4, and m + n is 5 or less. p is an integer of 1 to 7, q is an integer of 0 to 6, and p + q is 7 or less. The plurality of R 1 and the (Y-Z) group are optionally the same or different. In the aforementioned general formula (3-2), R 1 and the (Y-Z) group are optionally bonded to any carbon atom of the naphthalene ring.

[0089] The respective symbols in the aforementioned general formula (3-1), (3-2) have the same meanings as the respective symbols in the aforementioned general formula (2-1), (2-2), and R 1 the specific examples, the preferred examples, m, n, p, q, and the like are the same as in the aforementioned general formula (2-1), (2-2).

[0090] In the case where the value of m in the aforementioned general formula (3-1) is 1, the bonding position of the (Y-Z) group is preferably the para position with respect to the hydroxyl group. In the case where the value of p in the aforementioned general formula (3-2) is 1, the bonding position of the (Y-Z) group and the bonding position of the hydroxyl group are preferably the 1, 6-positions, the 2, 6-positions, the 2-7 positions, and more preferably the 2, 6-positions of the naphthalene ring.

[0091] As the aforementioned phenolic compound (B1) containing a polymerizable unsaturated group, from the viewpoint of the balance of each performance such as the wettability to a fine space, the optical properties, the etching resistance, the curability, the solvent solubility, and the like, one or more selected from the group consisting of 2-vinylphenol, 3-vinylphenol, 4-vinylphenol, 2-isopropenylphenol, 3-isopropenylphenol, 4-isopropenylphenol, 2-allylphenol, 3-allylphenol, 4-allylphenol, 4-(hydroxymethyl)acrylanilide, N-(3-hydroxyphenyl)acrylamide, 4-hydroxyphenyl methacrylate, 4-vinyl-1-naphthol, 6-vinyl-1-naphthol, 6-vinyl-2-naphthol, 7-vinyl-2-naphthol is preferable, and one or more selected from the group consisting of 4-vinylphenol, 4-isopropenylphenol, 4-allylphenol, 4-(hydroxymethyl)acrylanilide is more preferable.

[0092] The aforementioned aromatic carboxylic acid compound (B2) containing a polymerizable unsaturated group can be exemplified by a compound represented by the following general formula (4-1) or (4-2), or the like.

[0093]

[0094] [In the aforementioned general formula (4-1), (4-2), Y is a direct bond, an ether bond, or an amide bond, Z is a structural moiety having a polymerizable unsaturated group, R 1 is an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom. In the aforementioned structural formula, m is an integer of 1 to 5, n is an integer of 0 to 4, and m + n is 5 or less. p is an integer of 1 to 7, q is an integer of 0 to 6, and p + q is 7 or less. The plurality of R 1 and the (Y-Z) group are optionally the same or different. In the aforementioned general formula (4-2), R 1 and the (Y-Z) group are optionally bonded to any carbon atom of the naphthalene ring.

[0095] The respective symbols in the aforementioned general formula (4-1), (4-2) have the same meanings as the respective symbols in the aforementioned general formula (2-3), (2-4), and R 1 the specific examples, the preferred examples, m, n, p, q, and the like are the same as in the aforementioned general formula (2-3), (2-4).

[0096] In the case where the value of m in the aforementioned general formula (4-1) is 1, the bonding position of the (Y-Z) group with respect to the carboxyl group is preferably the para position. In the case where the value of p in the aforementioned general formula (4-2) is 1, the bonding position of the (Y-Z) group and the bonding position of the carboxyl group are preferably the 1, 6-positions, the 2, 6-positions, the 2-7 positions, and more preferably the 2, 6-positions of the naphthalene ring.

[0097] As the aforementioned aromatic carboxylic acid compound (B2) containing a polymerizable unsaturated group, from the viewpoint of the balance of each performance such as the wettability to a fine space, optical properties, etching resistance, curability, solvent solubility, and the like, one or more selected from the group consisting of 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2-isopropenylbenzoic acid, 3-isopropenylbenzoic acid, 4-isopropenylbenzoic acid, 2-allylbenzoic acid, 3-allylbenzoic acid, 4-allylbenzoic acid, and 2-vinyl-6-carboxylic acid is preferable, and one or more selected from the group consisting of 4-vinylbenzoic acid, 4-isopropenylbenzoic acid, and 4-allylbenzoic acid is more preferable.

[0098] In the aforementioned process (1-2), from the viewpoint of the yield of the aforementioned target polymerizable compound, it is preferable to cause the aforementioned reaction product (A) and the aforementioned polymerizable unsaturated group-containing aromatic compound (B) to react in the presence of a catalyst. The aforementioned catalyst that can be used in the aforementioned process (1-2) is not particularly limited, and from the viewpoint of the yield of the aforementioned target polymerizable compound, a quaternary phosphonium salt is preferable. In the aforementioned process (1-2), as the quaternary phosphonium salt that can be used as a catalyst, the same as the quaternary phosphonium salt that can be used in the aforementioned process (1-1a) can be cited. The quaternary phosphonium salt can be used alone, or two or more kinds thereof can be used in combination. As the amount of the aforementioned quaternary phosphonium salt to be used, from the viewpoint of the fact that the reaction proceeds well and the fact that the residual amount in the product can be reduced, 0.01 to 0.15 moles, more preferably 0.02 to 0.10 moles, relative to 1 mole of the epoxy group in the aforementioned reaction product (A) is preferable.

[0099] In addition, the reaction of the aforementioned process (1-2) can be performed in an organic solvent as necessary. As the organic solvent that can be used in the aforementioned process (1-2), the same as the organic solvent that can be used in the aforementioned process (1-1a) can be cited. The aforementioned organic solvent can be used alone, or two or more kinds thereof can be used in combination. In addition, from the aspect that the reaction efficiency becomes good, the amount of the aforementioned organic solvent to be used is preferably in the range of about 0.1 to 5 times the total mass of the raw materials for the reaction.

[0100] As the reaction temperature of the aforementioned process (1-2), the range of 20 to 80°C is preferable. As the reaction time of the aforementioned process (1-2), the range of 0.5 hours or more, more preferably 1 to 50 hours, is preferable.

[0101] The aforementioned Production Method Example 2 is explained. The aforementioned Production Method Example 2 is a production method in which a reaction product (A) of trihydroxybenzene and an epoxy halopropane, a polymerizable unsaturated group-containing non-aromatic compound (C), and an aromatic compound (D) that links the aforementioned reaction product (A) and the polymerizable unsaturated group-containing non-aromatic compound (C) are used as raw materials for the reaction. As to the aforementioned reaction product (A), the aforementioned polymerizable unsaturated group-containing non-aromatic compound (C), and the aforementioned aromatic compound (D), it is possible to cause the three components to react simultaneously, or it is possible to perform the reaction in two stages in order. In particular, from the aspect that the aforementioned polymerizable compound can be produced at a high yield and with high efficiency, a method in which the reaction is performed in two stages in order is preferable. Specifically, a production method of a polymerizable compound that includes a process (2-1) in which trihydroxybenzene and an epoxy halopropane are caused to react to obtain the aforementioned reaction product (A), a process (2-2) in which the aforementioned reaction product (A) and the aforementioned aromatic compound (D) are caused to react, and a process (2-3) in which a reaction product obtained in the aforementioned process (2-2) and the aforementioned polymerizable unsaturated group-containing non-aromatic compound (C) are caused to react to obtain the aforementioned polymerizable compound is preferable.

[0102] The aforementioned process (2-1) is the same as the aforementioned process (1-1).

[0103] The aforementioned process (2-2) is a process of reacting the aforementioned reaction product (A) with the aforementioned aromatic compound (D).

[0104] The aforementioned aromatic compound (D) is not particularly limited as long as it is an aromatic compound having a group that reacts with the epoxy group possessed by the aforementioned reaction product (A), and a group that reacts with the aforementioned non-aromatic compound containing a polymerizable unsaturated group (C). As an example of the combination of the aforementioned non-aromatic compound containing a polymerizable unsaturated group (C) and the aforementioned aromatic compound (D), from the viewpoints of reactivity, ease of obtaining raw materials, and the like, it is preferable that the aforementioned aromatic compound (D) be a phenolic compound having a carboxyl group (D1), and the aforementioned non-aromatic compound containing a polymerizable unsaturated group (C) be an aliphatic halide containing a polymerizable unsaturated group (C1).

[0105] In the aforementioned aromatic compound (D), the aforementioned phenolic compound having a carboxyl group (D1) can be exemplified by, for example, a compound represented by the following general formula (5-1) or (5-2), or the like.

[0106]

[0107] [In the aforementioned general formula (5-1), (5-2), R 1 is an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom. In the aforementioned structural formula, m is an integer of 1 to 5, and n is an integer of 0 to 4, with m + n being 5 or less. p is an integer of 1 to 7, and q is an integer of 0 to 6, with p + q being 7 or less. The plurality of R 1 are optionally the same or different. In the aforementioned general formula (5-2), R 1 is optionally bonded to any carbon atom of the naphthalene ring.

[0108] The symbols in the aforementioned general formula (5-1), (5-2) have the same meanings as the symbols in the aforementioned general formula (2-3), (2-4), and R 1 the specific examples, preferable examples, m, n, p, q, and the like are the same as in the aforementioned general formula (2-3), (2-4).

[0109] In the case where the value of m in the aforementioned general formula (5-1) is 1, the bonding position of the hydroxyl group with respect to the carboxyl group is preferably the para position. In the case where the value of p in the aforementioned general formula (5-2) is 1, the bonding position of the hydroxyl group and the bonding position of the carboxyl group are preferably the 1, 6-positions, the 2, 6-positions, the 2-7 positions, and more preferably the 2, 6-positions of the naphthalene ring.

[0110] As specific examples of the aforementioned phenolic compound having a carboxyl group (D1), one or more selected from the group consisting of 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 1,3-dihydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid can be given. Among them, from the viewpoint of balance of each performance such as wettability to a fine space, optical properties, etching resistance, curability, solvent solubility, and the like, one or more selected from the group consisting of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid is more preferable.

[0111] In the aforementioned process (2-2), from the viewpoint of yield of the target compound, it is preferable to allow the aforementioned reaction product (A) to react with the aforementioned aromatic compound (D) in the presence of a catalyst. The aforementioned catalyst which can be used in the aforementioned process (2-2) also differs depending on the kind of the aforementioned aromatic compound (D), and in the case of using the aforementioned phenolic compound having a carboxyl group (D1), from the viewpoint of yield of the target compound, a quaternary ammonium salt is preferable. In the aforementioned process (2-2), as the quaternary ammonium salt which can be used as a catalyst, the same as the quaternary ammonium salt which can be used in the aforementioned process (1-1a) can be given. The quaternary ammonium salt can be used alone, or two or more can be used in combination. As the amount of the aforementioned quaternary phosphonium salt, from the viewpoint of allowing the reaction to proceed favorably and reducing the residue in the product, relative to 1 mole of the epoxy group in the aforementioned reaction product (A), a range of 0.01 to 0.15 moles, and more preferably a range of 0.02 to 0.10 moles is preferable.

[0112] In addition, the reaction of the aforementioned process (2-2) can be performed in an organic solvent as necessary. As the organic solvent which can be used in the aforementioned process (2-2), the same as the organic solvent which can be used in the aforementioned process (1-1a) can be given. The aforementioned organic solvent can be used alone, or two or more can be used in combination. In addition, from the aspect that the reaction efficiency becomes favorable, the amount of the aforementioned organic solvent is preferably used in a range of about 0.1 to 5 times the total mass of the raw materials for the reaction.

[0113] As the reaction temperature of the aforementioned process (2-2), a range of 20 to 120°C, and more preferably a range of 80 to 110°C is preferable. As the reaction time of the aforementioned process (2-2), a range of 0.5 hours or more, and more preferably a range of 1 to 50 hours is preferable.

[0114] The aforementioned procedure (2-3) is a procedure of obtaining the aforementioned polymerizable compound by reacting the reactant obtained in the aforementioned procedure (2-2) with the aforementioned non-aromatic compound containing a polymerizable unsaturated group (C). The aforementioned procedure (2-3) can be continuously performed by adding the aforementioned aromatic compound (C) to the reaction mixture of the aforementioned procedure (2-2), or can be performed separately after the reactant obtained in the aforementioned procedure (2-2) is once isolated and purified.

[0115] As the aforementioned non-aromatic compound containing a polymerizable unsaturated group (C), from the viewpoints of reactivity, ease of obtaining the starting material, and the like, an aliphatic halide containing a polymerizable unsaturated group (C1) is preferable. As the polymerizable unsaturated group possessed by the aforementioned aliphatic halide containing a polymerizable unsaturated group (C1), for example, an alkenyl group, an alkynyl group, an acryloyl group, a methacryloyl group, and the like can be given. Among them, from the viewpoints of solubility in an organic solvent, and wettability of a fine space, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an acryloyl group, a methacryloyl group are preferable, and an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms are more preferable.

[0116] As a specific example of the aforementioned aliphatic halide containing a polymerizable unsaturated group (C1), one or more selected from the group consisting of a halogenated vinyl group, a halogenated allyl group, a propargyl halide, a halogenated acryloyl group, and a halogenated methacryloyl group can be given.

[0117] In the aforementioned procedure (2-3), from the viewpoint of the yield of the target polymerizable compound, it is preferable to react the reactant obtained in the aforementioned procedure (2-2) with the aforementioned non-aromatic compound containing a polymerizable unsaturated group (C) in the presence of a catalyst. The aforementioned catalyst that can be used in the aforementioned procedure (2-3) differs depending on the kind of the aforementioned aromatic compound (D), the aforementioned non-aromatic compound containing a polymerizable unsaturated group (C), and in the case where the aforementioned phenolic compound having a carboxyl group (D1) and the aforementioned aliphatic halide containing a polymerizable unsaturated group (C1) are used, from the viewpoint of the yield of the target polymerizable compound, an alkaline compound is preferable. As the alkaline compound that can be used as a catalyst in the aforementioned procedure (2-3), the same as the alkaline compound that can be used in the aforementioned procedure (1-1a) can be given. The alkaline compound can be used alone, or two or more can be used in combination.

[0118] In the aforementioned step (2-3), from the viewpoint of being able to produce the target polymerizable compound at a high yield and with high efficiency, it is preferable to use potassium carbonate, sodium carbonate as the aforementioned basic compound. In addition, from the viewpoint of the reaction proceeding well and the amount of residue in the product being able to be reduced, the amount of the aforementioned basic compound added is preferably in the range of 0.5 to 2.0 moles, more preferably in the range of 0.8 to 1.5 moles, relative to the polyunsaturated group-containing aliphatic halide (C1).

[0119] In addition, the reaction of the aforementioned step (2-3) can be performed in an organic solvent as necessary. As the organic solvent that can be used in the aforementioned step (2-3), the same as the organic solvent that can be used in the aforementioned step (1-1a) can be cited. The aforementioned organic solvent can be used alone, or two or more can be used in combination. In addition, in the case of continuously performing the aforementioned step (2-2) and step (2-3), the organic solvent used in the aforementioned step (2-2) can be used directly. The amount of the aforementioned organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, from the viewpoint of the reaction efficiency becoming good.

[0120] The reaction temperature of the aforementioned step (2-3) is preferably in the range of 20 to 80°C, more preferably in the range of 40 to 75°C. The reaction time of the aforementioned step (2-3) is preferably in the range of 0.5 hours or more, more preferably in the range of 1 to 50 hours.

[0121] The number average molecular weight (Mn) of the aforementioned polymerizable compound is preferably in the range of 660 to 2500, more preferably in the range of 800 to 1500, from the viewpoints of solubility in an organic solvent, wettability of a fine space, etching resistance, and curability. Note that in this specification, the number average molecular weight of the polymerizable compound is measured by the method described in the examples.

[0122] The weight average molecular weight (Mw) of the aforementioned polymerizable compound is preferably in the range of 660 to 3000, more preferably in the range of 800 to 2000, from the viewpoints of solubility in an organic solvent, wettability of a fine space, etching resistance, and curability. Note that in this specification, the weight average molecular weight of the polymerizable compound is measured by the method described in the examples.

[0123] The polydispersity (Mw / Mn) of the aforementioned polymerizable compound is preferably in the range of 1.00 to 2.00, more preferably in the range of 1.00 to 1.50, from the viewpoints of solubility in an organic solvent, wettability of a fine space, etching resistance, and curability. Note that in this specification, the polydispersity (Mw / Mn) of the polymerizable compound is calculated from the number average molecular weight (Mn) and the weight average molecular weight (Mw) measured by the method described in the examples.

[0124] The aforementioned polymerizable compound has a polymerizable unsaturated group in the molecular structure, and thus, for example, by adding a photopolymerization initiator, it can be used as a active energy ray-curable resin composition.

[0125] The active energy ray-curable resin composition of the present embodiment contains the aforementioned polymerizable compound, a photopolymerization initiator, and an organic solvent.

[0126] The addition amount of the aforementioned polymerizable compound in the aforementioned active energy ray-curable resin composition is, for example, preferably in the range of 1 to 99% by mass, more preferably in the range of 5 to 95% by mass, with respect to the total of the components other than the organic solvent of the active energy ray-curable resin composition

[0127] The aforementioned photopolymerization initiator can be used as appropriate according to the kind of the active energy ray to be irradiated, and the like. In addition, it can be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, a nitrile compound, and the like. As specific examples of the photopolymerization initiator, for example, there can be mentioned 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-〔4-(2-hydroxyethoxy)phenyl〕-2-hydroxy-2-methyl-1-propane-1-one, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 1-〔4-(2-hydroxyethoxy)phenyl〕-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, and the like alkylphenone-based photopolymerization initiators; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and the like acylophosphine oxide-based photopolymerization initiators; thioxanthone and thioxanthone derivatives; intramolecular hydrogen-abstraction type photopolymerization initiators such as benzophenone compounds, and the like. They can be used individually, or two or more of them can be used in combination.

[0128] As commercially available products of the aforementioned photopolymerization initiator, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM Inc.), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA", "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "BYCURE-10", "BYCURE-55" (manufactured by STAUFFER CHEMICAL COMPANY), "Trigonal P1" (manufactured by akzon), "Sandoray 1000" (manufactured by Sandoz), "Deep" (manufactured by Upjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by WordBrenkinsop), "Runtecure-1104" (manufactured by Runtec), and the like can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more.

[0129] The addition amount of the aforementioned photopolymerization initiator is, for example, preferably in the range of 0.05 to 15% by mass, more preferably in the range of 0.1 to 10% by mass, with respect to the total of the components of the active energy ray-curable resin composition excluding the organic solvent.

[0130] The aforementioned organic solvent can be used without particular limitation as a variety of organic solvents. As specific examples, there can be mentioned alkyl monohydric alcohol solvents such as methanol, ethanol, propanol, and the like; alkyl polyhydric alcohol solvents such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerol, and the like; alkylene glycol monoalkyl ether solvents such as 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, and the like; dialkylene glycol dialkyl ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and the like; alkylene glycol alkyl ether acetate solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like; cyclic ether solvents such as 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, cyclopentyl methyl ether, and the like; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, and the like; ester solvents such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxoacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, and the like; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and the like; and the like.

[0131] The amount of addition of the aforementioned organic solvent is preferably an amount in which the concentration of solid components in the aforementioned active energy ray-curable resin composition becomes in the range of preferably 5% by mass or more to preferably 95% by mass or less from the viewpoints of the flowability of the composition and the obtaining of a uniform coating film by a coating method such as a spin coating method.

[0132] The aforementioned active energy ray-curable resin composition can also contain, within a range not impairing the effects of the present application, a resin component other than the aforementioned polymerizable compound, a surfactant such as a leveling agent, a filler, a pigment, an adhesion improver, a dissolution promoter, and the like. As the resin component other than the aforementioned polymerizable compound, there can be mentioned various (meth)acrylate monomers, and the like.

[0133] The aforementioned active energy ray-curable resin composition can also contain a surfactant from the viewpoint of planarization of film thickness, wettability to fine spaces. As the surfactant, known and commonly used silicone-based surfactants, fluorine-based surfactants and the like used in semiconductor resist applications can be used. As the surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and the like polyoxyethylene alkyl ether compounds, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like polyoxyethylene alkyl allyl ether compounds, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and the like sorbitan fatty acid ester compounds, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate and the like polyoxyethylene sorbitan fatty acid ester compounds, nonionic surfactants; fluorine-based surfactants having a fluorine atom in the molecular structure such as a copolymer of a polymerizable monomer having a fluorine aliphatic group and [poly(oxyalkylene)] (meth)acrylate; silicone-based surfactants having a silicone structural site in the molecular structure and the like can be used. They can be used individually or two or more of them can be used in combination.

[0134] The addition amount of the aforementioned surfactant is preferably in the range of 0.001 to 2 parts by mass per 100 parts by mass of the resin solid content in the aforementioned active energy ray-curable resin composition.

[0135] As the aforementioned various (meth)acrylate monomers, there is no particular limitation as long as having a (meth)acryloyl group, and examples thereof include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate; aromatic mono(meth)acrylate compounds such as benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds obtained by introducing a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain into the molecular structure of the aforementioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the aforementioned various mono(meth)acrylate compounds; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornanedimethanol di(meth)acrylate, and dicyclopentyl di(meth)acrylate; aromatic di(meth)acrylate compounds such as diphenol di(meth)acrylate and bisphenol di(meth)acrylate; (poly)oxyalkylene-modified di(meth)acrylate compounds obtained by introducing a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain into the molecular structure of the aforementioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the aforementioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerol tri(meth)acrylate;(poly)alkylene oxide chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, a (poly)oxytetramethylene chain, and the like; a lactone-modified tri(meth)acrylate compound obtained by introducing a (poly)lactone structure into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compound; a pentaerythritol tetra(meth)acrylate, a di(trihydroxymethyl)propane tetra(meth)acrylate, a dipentaerythritol hexa(meth)acrylate, and the like aliphatic poly(meth)acrylate compound having a functionality of 4 or more; a (poly)alkylene oxide-modified poly(meth)acrylate compound having a functionality of 4 or more obtained by introducing a (poly)alkylene oxide chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, a (poly)oxytetramethylene chain, and the like into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compound; a lactone-modified poly(meth)acrylate compound having a functionality of 4 or more obtained by introducing a (poly)lactone structure into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compound; a (meth)acrylate compound containing a hydroxyl group such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di(trihydroxymethyl)propane (meth)acrylate, di(trihydroxymethyl)propane di(meth)acrylate, di(trihydroxymethyl)propane tri(meth)acrylate, and the like; a (poly)alkylene oxide-modified product obtained by introducing a (poly)alkylene oxide chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, a (poly)oxytetramethylene chain, and the like into the molecular structure of the aforementioned (meth)acrylate compound containing a hydroxyl group; a lactone-modified product obtained by introducing a (poly)lactone structure into the molecular structure of the aforementioned (meth)acrylate compound containing a hydroxyl group; a (meth)acrylate compound containing an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, and the like; a (meth)acrylate monomer containing a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate, and the like; a (meth)acrylate compound containing an epoxy group such as a mono(meth)acrylate of a diglycidyl ether compound of a dihydroxybenzene diglycidyl ether, a dihydroxynaphthalene diglycidyl ether, a diphenol diglycidyl ether, and the like. The aforementioned various (meth)acrylate monomers can be used alone or in combination with two or more kinds.

[0136] The aforementioned various (meth)acrylate monomers are preferably used in an amount that does not hinder the effects exerted by the present application. Specifically, the amount of the aforementioned various (meth)acrylate monomers is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 10 parts by mass or less, relative to 100 parts by mass of the polymerizable compound of the present application.

[0137] The aforementioned polymerizable compound, the aforementioned photopolymerization initiator, and the aforementioned organic solvent, and various additives that are further added as needed are stirred and mixed in a usual manner to form a uniform liquid, whereby the aforementioned active energy ray-curable resin composition can be produced.

[0138] The cured product of the present embodiment is obtained by curing the aforementioned active energy ray-curable resin composition. The cured product can be used, for example, as an antireflection underlayer film. As a substrate (processed substrate) on which the antireflection underlayer film is formed, for example, a silicon wafer, a wafer covered with aluminum, and the like can be mentioned. The aforementioned antireflection underlayer film can be formed, for example, by applying the aforementioned active energy ray-curable resin composition to the surface of the aforementioned processed substrate, another underlayer film described later, or the like, removing the organic solvent to form a coating film, and performing irradiation with an active energy ray and a heating treatment on the coating film to cure it. As a method of applying the aforementioned active energy ray-curable resin composition, for example, spin coating, roll coating, dipping, and the like can be mentioned. As a heating temperature, a range of 50 to 450°C, and preferably a range of 150 to 300°C is generally used. As a heating time, a range of 5 to 600 seconds is generally used.

[0139] As the aforementioned active energy ray, for example, ultraviolet rays, electron beams, α rays, β rays, γ rays, and the like ionizing radiation can be mentioned. In the case where ultraviolet rays are used as the aforementioned active energy ray, irradiation can be performed in a non-active gas atmosphere such as nitrogen, or irradiation can be performed in an air atmosphere, on the basis of efficient performance of a curing reaction based on ultraviolet rays.

[0140] As the ultraviolet rays, g rays (wavelength: 436 nm), h rays (wavelength: 405 nm), i rays (wavelength: 365 nm) of a high-pressure mercury lamp, a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an F2 excimer laser (wavelength: 157 nm), an EUV laser (wavelength: 13.5 nm), and the like can be mentioned.

[0141] The cumulative light amount of the aforementioned active energy ray is not particularly limited, and is preferably in a range of 10 to 5000 mJ / cm 2 , and more preferably in a range of 50 to 1000 mJ / cm 2The cumulative light amount is preferably in the above range, and the occurrence of uncured portions can be prevented or suppressed.

[0142] Note that the irradiation of the active energy ray can be performed in one stage or in two or more stages.

[0143] The film thickness of the aforementioned resist underlayer film is usually in the range of 10 to 1000 nm, and preferably in the range of 10 nm to 500 nm.

[0144] The resist composition of the present embodiment contains the aforementioned polymerizable compound. By curing the resist composition, a resist film can be used.

[0145] Examples

[0146] The present application will be specifically described below by citing examples, but the present application is not limited to these.

[0147] < Gel Permeation Chromatography (GPC) Measurement Conditions >

[0148] Measurement device: "HLC-8220 GPC" manufactured by Tosoh Corporation

[0149] Column: Guard column "HXL-L" manufactured by Tosoh Corporation

[0150] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0151] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0152] + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

[0153] + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

[0154] Detector: RI (differential refractometer)

[0155] Data processing: "GPC-8020 moldel II version 4.10" manufactured by Tosoh Corporation

[0156] Measurement conditions: Column temperature 40°C

[0157] Eluent solvent tetrahydrofuran

[0158] Flow rate 1.0 ml / minute

[0159] Standard: According to the measurement manual of the aforementioned "GPC-8020 moldel II version 4.10", the following monodisperse polystyrene having a known molecular weight was used.

[0160] (Used Polystyrene)

[0161] "A-500" manufactured by DOW CORNING

[0162] "A-1000" manufactured by DOW CORNING

[0163] "A-2500" manufactured by DOW CORNING

[0164] "A-5000" manufactured by DOW CORNING

[0165] "F-1" manufactured by DOW CORNING

[0166] "F-2" manufactured by DOW CORNING

[0167] "F-4" manufactured by DOW CORNING

[0168] "F-10" manufactured by DOW CORNING

[0169] "F-20" manufactured by DOW CORNING

[0170] "F-40" manufactured by DOW CORNING

[0171] "F-80" manufactured by DOW CORNING

[0172] "F-128" manufactured by DOW CORNING

[0173] Sample: Obtained by filtering a tetrahydrofuran solution of 1.0 mass% of the resin solid content with a microfilter (50 μl).

[0174] In this example, 1 H-NMR was measured under the following conditions.

[0175] < Measurement Conditions of H-NMR 1 H-NMR was measured under the following conditions.

[0176] Apparatus: JNM-ECA500 manufactured by JEOL Ltd.

[0177] Measurement mode: SGNNE (NOE eliminated 1 H complete decoupling method)

[0178] Solvent: Deuterated dimethyl sulfoxide

[0179] Pulse angle: 45° pulse

[0180] Sample concentration: 30 wt%

[0181] Cumulative number: 10,000 times

[0182] In this example, 13 C-NMR was measured under the following conditions.

[0183] < 13 Measurement conditions of C-NMR

[0184] Apparatus: JNM-ECA500 manufactured by JEOL Ltd.

[0185] Measurement mode: inverse-gated decoupling

[0186] Solvent: deuterated dimethyl sulfoxide

[0187] Pulse angle: 30° pulse

[0188] Sample concentration: 30 wt%

[0189] Number of accumulations: 4000

[0190] Chemical shift reference: peak of dimethyl sulfoxide: 39.5 ppm

[0191] Measurement of FD-MS

[0192] FD-MS was measured using a double focusing mass spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

[0193] Example Synthesis of Epoxide (A-1)

[0194] In a flask equipped with a thermometer, a dropping funnel, a condenser, a nitrogen inlet tube, and a stirrer, 1,2,3-trihydroxybenzene 126 g (1.50 mol) and epichlorohydrin 1388 g (15 mol) were added, and the temperature was raised to 50°C. Then, trimethylbenzylammonium chloride 11.2 g (0.06 mol) was added, and stirring was performed at 50°C for 15 hours. Distilled water 1000 mL was added to the obtained reaction solution, and stirring was performed, and the upper layer was removed after standing. To the remaining lower layer, 48% sodium hydroxide aqueous solution 318 g was added dropwise over 2.5 hours, and after stirring for 1 hour, distilled water 400 mL was added, and the solution was allowed to stand. The lower layer (aqueous layer) containing the salt generated in the reaction was removed, and distillation recovery of epichlorohydrin was performed at 120°C. Then, methyl isobutyl ketone (hereinafter, abbreviated as "MIBK") 500 g and water 167 g were added in this order, and water washing was performed at 80°C. The lower layer (aqueous layer) was removed, dehydration and filtration were performed, and MIBK was desolvated at 150°C, thereby obtaining epoxide (A-1). The obtained epoxide (A-1) was a liquid, and the epoxide equivalent weight was 128 g / eq, and the weight average molecular weight (Mw) was 370.

[0195] Synthesis of Epoxide (A-2)

[0196] In a flask equipped with a thermometer, a dropping funnel, a condenser, a nitrogen inlet tube, and a stirrer, a mixture of 1,2,3-trihydroxybenzene 63 g (0.75 mol) and 1,2,4-trihydroxybenzene 63 g (0.75 mol) and epichlorohydrin 1388 g (15 mol) was added, and the temperature was raised to 50°C. Then, trimethylbenzylammonium chloride 11.2 g (0.06 mol) was added, and stirring was performed at 50°C for 15 hours. Distilled water 1000 mL was added to the resulting reaction solution, and stirring was performed, and the upper layer was removed after standing. To the remaining lower layer, 48% sodium hydroxide aqueous solution 318 g was added dropwise over 2.5 hours, and stirring was performed for 1 hour, and then distilled water 400 mL was added and allowed to stand. The lower layer (aqueous layer) containing the salt generated in the reaction was removed, and distillation recovery of the epichlorohydrin was performed at 120°C. Then, MIBK 500 g and water 167 g were added in this order, and water washing was performed at 80°C. The lower layer (aqueous layer) was removed, and dehydration and filtration were performed, and MIBK was desolvated at 150°C, thereby obtaining the epoxide (A-2). The obtained epoxide (A-2) was a liquid, and the epoxy equivalent weight was 121 g / eq, and the weight average molecular weight (Mw) was 382.

[0197] Synthesis of Epoxide (A-3)

[0198] In a flask equipped with a thermometer, a dropping funnel, a condenser, a nitrogen inlet tube, and a stirrer, 1,2,4-trihydroxybenzene 126 g (1.50 mol) and epichlorohydrin 1388 g (15 mol) were added, and the temperature was raised to 50°C. Then, trimethylbenzylammonium chloride 11.2 g (0.06 mol) was added, and stirring was performed at 50°C for 15 hours. Distilled water 1000 mL was added to the resulting reaction solution, and stirring was performed, and the upper layer was removed after standing. To the remaining lower layer, 48% sodium hydroxide aqueous solution 318 g was added dropwise over 2.5 hours, and stirring was performed for 1 hour, and then distilled water 400 mL was added and allowed to stand. The lower layer (aqueous layer) containing the salt generated in the reaction was removed, and distillation recovery of the epichlorohydrin was performed at 120°C. Then, MIBK 500 g and water 167 g were added in this order, and water washing was performed at 80°C. The lower layer (aqueous layer) was removed, and dehydration and filtration were performed, and MIBK was desolvated at 150°C, thereby obtaining the epoxide (A-3). The obtained epoxide (A-3) was a liquid, and the epoxy equivalent weight was 114 g / eq, and the weight average molecular weight (Mw) was 406.

[0199] Synthesis of Polymerizable Compound (1)

[0200] In a flask equipped with a thermometer, a dropping funnel, a condenser, a nitrogen inlet tube, and a stirrer, was placed 128 g (1.00 mol of an epoxy group) of the epoxide (A-1) of Example 1, 134 g (1.00 mol) of 4-isopropenylphenol, 18.6 g (0.05 mol) of ethyltriphenylphosphonium bromide (manufactured by Kanto Chemical Co., Inc.), 0.6 g (0.005 mol) of hydroquinone, and 656 g of methoxypropanol. The mixture was stirred at 70°C for 10 hours. After that, the solvent was replaced with propylene glycol methyl ether acetate under reduced pressure, to obtain the target polymerizable compound (1). The number average molecular weight (Mn) of the obtained polymerizable compound (1) was 1043, the weight average molecular weight (Mw) was 1143, and the polydispersity (Mw / Mn) was 1.10. The GPC spectrum of the polymerizable compound (1) is shown in FIG. 1. Figure 1 、 1 The H-NMR spectrum is shown in FIG. 2. Figure 2 、 13 The C-NMR spectrum is shown in FIG. 3. Figure 3 The FD-MS spectrum is shown in FIG. 4. Figure 4 From the peak at 696.3 in the FD-MS spectrum, and 1 H-NMR, 13 C-NMR, the generation of the following compound was confirmed.

[0201]

[0202] Example 2 Synthesis of Polymerizable Compound (2)

[0203] The epoxide (A-1) of Example 2 was changed to epoxide (A-2) 121 g (1.00 mol of an epoxy group), and otherwise, the polymerizable compound (2) was obtained in the same manner as in Example 1. The number average molecular weight (Mn) of the obtained polymerizable compound (2) was 1125, the weight average molecular weight (Mw) was 1246, and the polydispersity (Mw / Mn) was 1.11. The GPC spectrum of the polymerizable compound (2) is shown in FIG. 5. Figure 5 .

[0204] Example 3 Synthesis of Polymerizable Compound (3)

[0205] The epoxide (A-1) of Example 1 was changed to epoxide (A-3) 114 g (1.00 mol of an epoxy group), and otherwise, the polymerizable compound (3) was obtained in the same manner as in Example 1. The number average molecular weight (Mn) of the obtained polymerizable compound (3) was 1244, the weight average molecular weight (Mw) was 1409, and the polydispersity (Mw / Mn) was 1.13. The GPC spectrum of the polymerizable compound (3) is shown in FIG. 6. Figure 6 .

[0206] Synthesis of the polymerizable compound (4)

[0207] In a flask equipped with a thermometer, a dropping funnel, a condenser, a nitrogen inlet tube, and a stirrer, 128 g (1.00 mol of an epoxy group) of the epoxide (A-1), 177 g (1.00 mol) of 4- (hydroxy) methyl methacrylanilide (manufactured by Osaka Organic Chemical Industry Ltd.), 18.6 g (0.05 mol) of ethyltriphenylphosphonium bromide (manufactured by Hokoku Corporation), 0.6 g (0.005 mol) of hydroquinone, and 656 g of methoxypropanol were added, and the mixture was stirred at 70°C for 24 hours. Thereafter, the solvent was replaced with propylene glycol methyl ether acetate under reduced pressure, to obtain the target polymerizable compound (4). The number average molecular weight (Mn) of the obtained polymerizable compound (4) was 1053, the weight average molecular weight (Mw) was 1157, and the polydispersity (Mw / Mn) was 1.10. The GPC spectrum of the polymerizable compound (4) is shown in FIG. 1, respectively. Figure 7 、 1 The1H-NMR spectrum is shown in FIG. 2. Figure 8 、 13 The13C-NMR spectrum is shown in FIG. 3. Figure 9 The FD-MS spectrum is shown in FIG. 4. Figure 10 The generation of the following compound was confirmed from the peak at 825.3 in the FD-MS spectrum, and 1 the1H-NMR, 13 the13C-NMR.

[0208]

[0209] Synthesis of the polymerizable compound (5)

[0210] The epoxide (A-1) of Example 4 was changed to 121 g (1.00 mol of an epoxy group) of the epoxide (A-2), and otherwise, the polymerizable compound (5) was obtained in the same manner as in Example 4. The number average molecular weight (Mn) of the obtained polymerizable compound (B-2) was 1136, the weight average molecular weight (Mw) was 1258, and the polydispersity (Mw / Mn) was 1.11. The GPC spectrum of the polymerizable compound (5) is shown in FIG. 5. Figure 11 .

[0211] Synthesis of the polymerizable compound (6)

[0212] The epoxy compound (A-1) of 128 g (1.00 mol of epoxy group) of Example 4 was changed to the epoxy compound (A-3) of 114 g (1.00 mol of epoxy group), and otherwise, the resin (6) was obtained in the same manner as in Example 4. The number average molecular weight (Mn) of the obtained resin (6) was 1256, the weight average molecular weight (Mw) was 1423, and the polydispersity (Mw / Mn) was 1.13. The GPC spectrum of the polymerizable compound (6) is shown in Figure 12 .

[0213] Example 7 Synthesis of polymerizable compound (7)

[0214] In a flask equipped with a thermometer, a dropping funnel, a condenser, a nitrogen inlet tube, and a stirrer, the epoxy compound (A-1) of 128 g (1.00 mol of epoxy group) of Example 4, 6-hydroxy-2-naphthoic acid of 188 g (1.00 mol), trimethylbenzylammonium chloride of 11.4 g (0.05 mol), and dimethylformamide of 512 g were added, and stirred at 100°C for 6 hours. After natural cooling, potassium carbonate of 166 g and propargyl bromide of 131 g were added, and stirred at 60°C for 20 hours. Then, MIBK of 500 g and water of 200 g were added in this order, and subjected to water washing at 60°C. After removing the lower layer (water layer), the solvent was replaced with propylene glycol methyl ether acetate under reduced pressure, to obtain the target polymerizable compound (7). The number average molecular weight (Mn) of the obtained polymerizable compound (7) was 1166, the weight average molecular weight (Mw) was 1259, and the polydispersity (Mw / Mn) was 1.08. The GPC spectrum of the polymerizable compound (7) is shown in Figure 13 、 1 The H-NMR spectrum is shown in Figure 14 、 13 The C-NMR spectrum is shown in Figure 15 The FD-MS spectrum is shown in Figure 16 From the peak of 97.3 in the FD-MS spectrum, and 1 H-NMR, 13 C-NMR, the generation of the following compound was confirmed.

[0215]

[0216] Example 8 Synthesis of polymerizable compound (8)

[0217] The epoxy compound (A-1) of 128 g (1.00 mol of epoxy group) of Example 4 was changed to the epoxy compound (A-2) of 121 g (1.00 mol of epoxy group) of Example 7, and otherwise, the polymerizable compound (8) was obtained in the same manner as in Example 7. The number average molecular weight (Mn) of the obtained polymerizable compound (8) was 1136, the weight average molecular weight (Mw) was 1258, and the polydispersity (Mw / Mn) was 1.11. The GPC spectrum of the polymerizable compound (8) is shown inFigure 17 .

[0218] Synthesis of polymerizable compound (9)

[0219] The epoxy compound (A-1) of Example 7 was changed to the epoxy compound (A-3) 114 g (corresponding to 1.00 mol of epoxy group), and otherwise, polymerizable compound (9) was obtained in the same manner as in Example 7. The number average molecular weight (Mn) of the obtained polymerizable compound (9) was 1339, the weight average molecular weight (Mw) was 1552, and the polydispersity (Mw / Mn) was 1.11. The GPC spectrum of polymerizable compound (9) is shown in Fig. 9. Figure 18 .

[0220] Synthesis of polymerizable compound (1')

[0221] The epoxy compound (A-1) of Example 1 was changed to the epoxy compound of tert-butyl pyrocatechol (epoxy equivalent 209 g / equivalent) 209 g, and otherwise, polymerizable compound (1') was obtained in the same manner as in Example 1. The number average molecular weight (Mn) of the obtained polymerizable compound (1') was 1000, the weight average molecular weight (Mw) was 1050, and the polydispersity (Mw / Mn) was 1.05. The GPC spectrum of polymerizable compound (1') is shown in Fig. 4. Figure 19 .

[0222] Synthesis of polymerizable compound (2')

[0223] The epoxy compound (A-1) of Example 4 was changed to the epoxy compound of tert-butyl pyrocatechol (epoxy equivalent 209 g / equivalent) 209 g, and otherwise, polymerizable compound (2') was obtained in the same manner as in Example 4. The number average molecular weight (Mn) of the obtained polymerizable compound (2') was 956, the weight average molecular weight (Mw) was 999, and the polydispersity (Mw / Mn) was 1.04. The GPC spectrum of polymerizable compound (2') is shown in Fig. 8. Figure 20 .

[0224] Synthesis of polymerizable compound (3')

[0225] The epoxy compound (A-1) of Example 7 was changed to the epoxy compound of tert-butyl pyrocatechol (epoxy equivalent 209 g / equivalent) 209 g, and otherwise, polymerizable compound (3') was obtained in the same manner as in Example 7. The number average molecular weight (Mn) of the obtained polymerizable compound (3') was 1044, the weight average molecular weight (Mw) was 1100, and the polydispersity (Mw / Mn) was 1.05. The GPC spectrum of polymerizable compound (3') is shown in Fig. 10. Figure 21 .

[0226] Evaluation of optical properties

[0227] A solution of 5 mass% of the nonvolatile component was prepared by dissolving the polymerizable compound obtained in each of the examples and comparative examples in propylene glycol monomethyl ether acetate. Using the obtained polymerizable compound solution, a silicon wafer was coated using a spin coater at 1500 rpm for 30 seconds. The coated wafer was heated on a hot plate at 100°C for 60 seconds and dried to obtain a coating film having a thickness of 0.1 μm. The n value (refractive index) and k value (extinction coefficient) at a wavelength of 193 nm and 248 nm were measured for the obtained coating film using a spectroscopic ellipsometer (J. A. Woollam's "VUV-VASE GEN-1").

[0228] Preparation of the composition for the evaluation of etching resistance and the evaluation of the wettability to fine spaces

[0229] A solution was prepared by adding and mixing, dissolving 5 mass% of the polymerizable compound obtained in each of the examples and comparative examples in 95 mass% of propylene glycol monomethyl ether acetate. To the solution, 0.5 mass% of a photoinitiator ("Omnirad-184" manufactured by IGM Inc.) and 3 mass% of a propylene glycol monomethyl ether acetate solution of 5 mass% of a fluorine-based surfactant ("Megaface R-2011" manufactured by DIC Corporation) were added, and after mixing and dissolving, filtration was performed using a 0.2 μm filter to obtain a composition for the resist underlayer film.

[0230] Evaluation of etching resistance

[0231] After the obtained composition for the resist underlayer film was coated on a silicon wafer having a diameter of 5 inches using a spin coater, the wafer was heated at 180°C for 60 seconds in a hot plate having an oxygen concentration of 20 vol%. Further, the wafer was heated at 350°C for 120 seconds to obtain a silicon wafer having a resist underlayer film having a thickness of 0.3 μm. Etching treatment was performed on the formed resist underlayer film using an etching device ("EXAM" manufactured by Shinkuu Seiki Co., Ltd.) under the conditions of CF4 / Ar / O2 (CF4: 40 mL / minute, Ar: 20 mL / minute, O2: 5 mL / minute, pressure: 20 Pa, RF power: 200 W, treatment time: 40 seconds, temperature: 15°C). The film thickness before and after the etching treatment was measured, and the etching rate was calculated to evaluate the etching resistance. The evaluation criteria are as follows. A: the case where the etching rate was 150 nm / minute or less B: the case where the etching rate exceeded 150 nm / minute

[0232] Evaluation of the wettability to fine spaces

[0233] A silicon wafer having a resist underlayer film was prepared using the composition for the resist underlayer film obtained in each of the examples and comparative examples. A silicon wafer of 5 inches in diameter having a hole pattern of 300 nm in depth was obtained in the same manner as described above with the exception that the hole pattern was 300 nm in depth. The silicon wafer was cut on the hole pattern line, and cross-sectional observation was performed using a scanning electron microscope (Hitachi High-Tech Corporation "SU-3500") to evaluate the wettability of the fine spaces. The evaluation criteria are described below. A: the case where the cured product filled to the bottom of the hole B: the case where the cured product did not fill to the bottom of the hole or a portion thereof had a cavity

[0234] [evaluation of sensitivity]

[0235] In 50 parts by mass of PGMEA, 50 parts by mass of the polymerizable compound obtained in each of the examples and comparative examples was added and mixed and dissolved. Further, 3 parts by mass of a 5 mass% PGMEA solution of a photopolymerization initiator (Omnirad-184" manufactured by IGM) and a fluorine-based surfactant ("Megaface R-2011" manufactured by DIC) was added and mixed and dissolved. The resulting solution was filtered using a 0.2 μm cartridge filter to obtain a photosensitive composition. Using an applicator, the photosensitive composition was applied to a glass substrate so as to have a film thickness of 50 μm, and dried at 80°C for 30 minutes. Then, using a high-pressure mercury lamp, ultraviolet rays were irradiated to obtain a cured coating film. The surface of the obtained cured coating film was touched with a finger, and the minimum value of the cumulative light amount at which tackiness disappeared was evaluated. The evaluation criteria are described below.

[0236] A: the case where the cumulative light amount was 50 mJ / cm 2 The following was cured.

[0237] B: the case where the cumulative light amount exceeded 50 mJ / cm 2 and was 100 mJ / cm 2 The following was cured.

[0238] C: the case where the cumulative light amount exceeded 100 mJ / cm 2 and was not cured.

[0239] The results of each evaluation are shown in Table 1.

[0240] [Table 1]

[0241] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Polymerizable compound 1 2 3 4 5 6 n value (193 nm) 1.51 1.80 1.16 1.57 1.80 1.16 k value (193 nm) 0.54 0.73 0.34 0.53 0.73 0.27 n value (248 nm) 1.80 1.73 1.81 1.88 1.73 1.79 k value (248 nm) 0.31 0.11 0.49 0.33 0.11 0.52 Etch resistance A A A A A A Infiltration into fine spaces A A A A A A Sensitivity A A A A A A Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polymerizable compound 7 8 9 1’ 2’ 3′ n value (193 nm) 1.74 1.80 1.46 1.59 1.52 1.48 k value (193 nm) 0.25 0.19 0,28 0.48 0,44 0.47 n value (248 nm) 1,88 1.74 1.80 1.92 1，79 1.82 k value (248 nm) 0.32 0.10 0.50 0.40 0.32 0.43 Etch resistance A A A A A A Infiltration into fine spaces A A A B B B Sensitivity A A A C C C

[0242] From the results of Table 1, it was determined that the composition containing the polymerizable compound represented by the aforementioned general formula (1) was excellent in wettability of fine spaces, and was also excellent in optical properties, etching resistance, curability, solvent solubility, and the like. On the other hand, it was determined that the resins of Comparative Examples 1 to 3 could not solve the problems of the present application.

Claims

1. A polymeric compound represented by the following general formula (1), In the general formula (1), X is the structural part shown in the following general formulas (2-1), (2-2), (2-3) or (2-4), and the three X's in the general formula (1) can be optionally the same structure or different structures. In the general formulas (2-1) to (2-4), Y represents a direct bond, an ether bond, or an amide bond; Z represents a structural site with a polymerizable unsaturated group; and R... 1 It is an aliphatic hydrocarbon group, alkoxy group, or halogen atom; in the structural formula, m is an integer from 1 to 5, n is an integer from 0 to 4, and m+n is less than 5; p is an integer from 1 to 7, q is an integer from 0 to 6, and p+q is less than 7; the multiple R groups present in the general formulas (2-1) to (2-4) 1 The (YZ) bases may be chosen to be the same or different; in the general formulas (2-2) and (2-4), R 1 The (YZ) group is optionally bonded to any carbon atom of the naphthalene ring.

2. The polymerizable compound according to claim 1, wherein the reaction product (A) of trihydroxybenzene and epoxy halopropane and the aromatic compound (B) containing polymerizable unsaturated groups are used as reaction raw materials.

3. The polymerizable compound according to claim 2, wherein, The aromatic compound (B) containing polymerizable unsaturated groups is either a phenolic compound (B1) containing polymerizable unsaturated groups or an aromatic carboxylic acid compound (B2) containing polymerizable unsaturated groups.

4. The polymerizable compound according to claim 1, wherein the reaction product (A) of trihydroxybenzene and epoxy halopropane, the non-aromatic compound (C) containing polymerizable unsaturated groups, and the aromatic compound (D) connecting the reaction product (A) and the non-aromatic compound (C) containing polymerizable unsaturated groups are used as reaction raw materials.

5. The polymerizable compound according to claim 4, wherein, The non-aromatic compound (C) containing polymerizable unsaturated groups is an aliphatic halide (C1) containing polymerizable unsaturated groups, and the aromatic compound (D) is a phenolic compound (D1) having a carboxyl group.

6. An active energy ray-curable resin composition, comprising: The polymeric compound according to any one of claims 1 to 5 Photopolymerization initiators, and Organic solvents.

7. A cured product, which is a cured product of the active energy ray curable resin composition of claim 6.

8. A composition for use as a corrosion resist, comprising the polymeric compound according to any one of claims 1 to 5.

9. A resist film obtained by curing the resist of claim 8 with a composition.

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