WO2022130921A1 - 重合性化合物、活性エネルギー線硬化性樹脂組成物、硬化物、レジスト用組成物、及びレジスト膜 - Google Patents

重合性化合物、活性エネルギー線硬化性樹脂組成物、硬化物、レジスト用組成物、及びレジスト膜 Download PDF

Info

Publication number
WO2022130921A1
WO2022130921A1 PCT/JP2021/043093 JP2021043093W WO2022130921A1 WO 2022130921 A1 WO2022130921 A1 WO 2022130921A1 JP 2021043093 W JP2021043093 W JP 2021043093W WO 2022130921 A1 WO2022130921 A1 WO 2022130921A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
group
polymerizable
polymerizable compound
unsaturated group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/043093
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
知之 今田
教夫 長江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2022569817A priority Critical patent/JP7288233B2/ja
Priority to KR1020237009036A priority patent/KR102906921B1/ko
Priority to CN202180084130.6A priority patent/CN116670184B/zh
Publication of WO2022130921A1 publication Critical patent/WO2022130921A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/025—Non-macromolecular photopolymerisable compounds having carbon-to-carbon triple bonds, e.g. acetylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

Definitions

  • the present invention relates to a polymerizable compound, an active energy ray-curable resin composition, a cured product, a resist composition, and a resist film.
  • the multilayer resist method In the field of photoresists, various methods for forming finer wiring patterns have been developed, one of which is the multilayer resist method.
  • the multilayer resist method one or more layers called a resist underlayer film or an antireflection film are formed on a substrate, a resist pattern is formed on the layer by ordinary photolithography, and then the substrate is dry-etched. Process and transfer the wiring pattern.
  • One of the important members in the technique of the multilayer resist method is the resist underlayer film, and the underlayer film is required to have high dry etching resistance and low light reflectivity. Further, since the resist underlayer film is formed in a solvent-diluted state, the resin material for the resist underlayer film needs to be soluble in a general-purpose organic solvent.
  • ultra-fine wiring pattern formation often uses a process called double patterning or multi-patterning in which multiple exposures and etchings are repeated, and a fine pattern produced in the previous process is applied to the underlayer film. It also plays an important role in forming a smooth next-process fabrication surface after filling the holes. Therefore, the resist underlayer film material used as the base material is also required to have high infiltration into a fine space.
  • an anthracene skeleton-containing compound is known as a conventional phenol hydroxyl group-containing compound for a resist underlayer film (Patent Document 1).
  • the anthracene skeleton-containing compound described in Patent Document 1 has low light reflectance in a cured coating film and has excellent properties as an antireflection film, but has a fine space due to ⁇ - ⁇ interaction due to a molecular size and a wide aromatic electron cloud. Low infiltration into.
  • the present invention is a polymerizable compound that can be used for forming an ultrafine wiring pattern by being excellent in infiltration into a fine space and also in optical properties, etching resistance, curability, solvent solubility and the like. The challenge is to provide.
  • Another object of the present invention is to provide an active energy ray-curable resin composition that can be used for forming an ultrafine wiring pattern.
  • Another object of the present invention is to provide a resist composition capable of forming an ultrafine wiring pattern.
  • the present invention is a polymerizable compound represented by the following general formula (1).
  • X indicates an aromatic ring structure and a structural moiety having a polymerizable unsaturated group. Further, the three Xs in the general formula (1) may have the same structure or may be different from each other. ]
  • the present invention is a polymerizable compound using a reaction product (A) of trihydroxybenzene and epihalohydrin and a polymerizable unsaturated group-containing aromatic compound (B) as reaction raw materials.
  • the present invention comprises a reaction product (A) of trihydroxybenzene and epihalohydrin, a non-aromatic compound containing a polymerizable unsaturated group (C), and the reaction product (A) and the polymerizable unsaturated group. It is a polymerizable compound using the aromatic compound (D) that nods the non-aromatic compound (C) contained as a reaction raw material.
  • the present invention is an active energy ray-curable resin composition containing the polymerizable compound, a photopolymerization initiator, and an organic solvent.
  • the present invention is a resist composition containing the polymerizable compound.
  • the polymerization can be used for forming an ultrafine wiring pattern by being excellent in infiltration into a fine space and also in optical properties, etching resistance, curability, solvent solubility and the like. Sex compounds can be provided.
  • an active energy ray-curable resin composition that can be used for forming an ultrafine wiring pattern.
  • the polymerizable compound is represented by the following general formula (1).
  • X indicates an aromatic ring structure and a structural moiety having a polymerizable unsaturated group. Further, the three Xs in the general formula (1) may have the same structure or may be different from each other. ]
  • the specific structure of X in the general formula (1) is not particularly limited as long as it has an aromatic ring structure and a polymerizable unsaturated group, and can take a wide variety of structures.
  • the polymerizable compound of the present embodiment represented by the general formula (1) has a trihydroxybenzene-derived structure, and has an aromatic ring structure and a polymerizable unsaturated group at three molecular terminals. It is a compound that has excellent infiltration into fine spaces and also has excellent optical properties, etching resistance, curability, solvent solubility, and the like.
  • X in the general formula (1) is preferably the following general formulas (2-1), (2-2), (2-3) from the viewpoint of solubility in an organic solvent and infiltration into a fine space. ) Or (2-4).
  • Y is a direct bond, an ether bond, or an amide bond
  • Z is a structural site having a polymerizable unsaturated group
  • R 1 is an aliphatic group. It is a hydrocarbon group, an alkoxy group, or a halogen atom.
  • m is an integer of 1 to 5
  • n is an integer of 0 to 4
  • m + n is 5 or less.
  • R1 and (YZ) groups existing in the above general formulas (2-1) to (2-4) may be the same or different.
  • the R1 and (YZ) groups may be bonded to any carbon atom of the naphthalene ring.
  • Z is a structural site having a polymerizable unsaturated group.
  • the polymerizable unsaturated group include an alkenyl group, an alkynyl group, an acryloyl group, a methacryloyl group and the like.
  • an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an acryloyl group, and a methacryloyl group are preferable from the viewpoint of solubility in an organic solvent and infiltration into a fine space. More preferably, it is an alkenyl group having 2 to 6 carbon atoms and an alkynyl group having 2 to 6 carbon atoms.
  • m is an integer of 1 to 5 and p is an integer of 1 to 7.
  • the values of m and p are 1 to 3 because the compound has an excellent balance of various performances such as infiltration into a fine space, optical properties, etching resistance, curability, and solvent solubility. It is preferably 1, and particularly preferably 1.
  • the bond position of the (YZ) group is in the para position with respect to the oxygen atom to which X is bonded in the general formula (1). It is preferable to have.
  • the bond position of the (YZ) group is preferably the para position with respect to the carbonyl group.
  • the bond position of the (YZ) group and the bond position of the oxygen atom to which X is bonded in the general formula (1) are the naphthalene rings. It is preferably in the 1,6-position, 2,6-position, and 2-7-position, and more preferably in the 2,6-position.
  • the bond position of the (YZ) group and the bond position of the carbonyl group are the 1,6-position, 2,6-position and 2 of the naphthalene ring. It is preferably in the -7th position, more preferably in the 2nd and 6th positions.
  • R 1 is an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom.
  • the aliphatic hydrocarbon group may be a linear type or may have a branched structure. Further, it may have a cyclo ring structure. More specifically, examples thereof include aliphatic hydrocarbon groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group and a cyclohexyl group.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group and the like.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • 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 n or q.
  • the value of is more preferably 0.
  • the polymerizable compound may be produced by any method, and the production method is not particularly limited. The following two examples are given as examples of producing the polymerizable compound.
  • [Manufacturing method example 1] A production method using a reaction product (A) of trihydroxybenzene and epihalohydrin and a polymerizable unsaturated group-containing aromatic compound (B) as reaction raw materials.
  • [Manufacturing method example 2] The reaction product (A) of trihydroxybenzene and epihalohydrin, the polymerizable unsaturated group-containing non-aromatic compound (C), and the reaction product (A) and the polymerizable unsaturated group-containing non-aromatic compound (C). ) Is a production method using the aromatic compound (D) as a reaction raw material.
  • the manufacturing method example 1 will be described. Specifically, in the above-mentioned production method Example 1, the step (1-1) of reacting trihydroxybenzene with epihalohydrin to obtain the reaction product (A), and the step of reacting the reaction product (A) with a polymerizable unsaturated group.
  • This is a method for producing a polymerizable compound, which comprises a step (1-2) of reacting with the contained aromatic compound (B) to obtain the polymerizable compound.
  • the step (1-1) is a step of reacting trihydroxybenzene with epihalohydrin to obtain the reaction product (A).
  • the step (1-1) is a step of reacting trihydroxybenzene and epihalohydrin in the presence of a quaternary onium salt and / or a basic compound from the viewpoint of the yield of the desired reaction product (A). It is preferable to have (1-1a) and a step (1-1b) of closing the ring of the reaction product obtained in the above step (1-1a) in the presence of a basic compound.
  • the trihydroxybenzene used as the reaction raw material of the polymerizable compound is not particularly limited, but from the viewpoint of easy availability of the raw materials, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, and One or more selected from the group consisting of 1,3,5-trihydroxybenzene is preferable.
  • the epichlorohydrin is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, ⁇ -methylepichlorohydrin, and ⁇ -methylepibromohydrin. These epihalohydrins may be used alone or in combination of two or more.
  • quaternary onium salt examples include a quaternary ammonium salt and a quaternary phosphonium salt. These quaternary onium salts can be used alone or in combination of two or more.
  • Examples of the quaternary ammonium salt include tetramethylammonium cation, methyltriethylammonium cation, tetraethylammonium cation, tributylmethylammonium cation, tetrabutylammonium cation, phenyltrimethylammonium cation, benzyltrimethylammonium cation, and phenyltriethylammonium cation.
  • Examples thereof include benzyltriethylammonium cations, chloride salts of benzyltributylammonium cations, tetramethylammonium cations, trimethylpropylammonium cations, tetraethylammonium cations, and bromide salts of tetrabutylammonium cations.
  • Examples of the quaternary phosphonium salt include bromine of a tetraethylphosphonium cation, a tetrabutylphosphonium cation, a methyltriphenylphosphonium cation, a tetraphenylphosphonium cation, an ethyltriphenylphosphonium cation, a butyltriphenylphosphonium cation, and a benzyltriphenylphosphonium cation.
  • Examples include compound salts.
  • tetramethylammonium cations benzyltrimethylammonium cations, chloride salts of benzyltriethylammonium cations, and bromide salts of tetrabutylammonium cations are preferable.
  • the amount of the quaternary onium salt used is 100 parts by mass based on the total mass of the trihydroxybenzene and epihalohydrin from the viewpoint that the reaction proceeds well and the residue in the product can be reduced.
  • the range is preferably in the range of 0.15 to 5 parts by mass, and more preferably in the range of 0.18 to 3 parts by mass.
  • Examples of the basic compound include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate and the like. These basic compounds may be used alone or in combination of two or more. Among these, potassium hydroxide and sodium hydroxide are preferable.
  • the amount of the basic compound added is 0.01 to 0. With respect to 1 mol of the hydroxyl group of the trihydroxybenzene, from the viewpoint that the reaction proceeds well and the residue in the product can be reduced.
  • the range is preferably in the range of 3 mol, more preferably in the range of 0.02 to 0.2 mol.
  • the quaternary onium and the basic compound may be used alone or in combination of two or more.
  • the reaction in the step (1-1a) is mainly a reaction in which epihalohydrin is added to the hydroxyl group of the trihydroxybenzene.
  • the reaction temperature in the step (1-1a) 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 step (1-1a) is preferably 0.5 hours or more, and more preferably 1 to 50 hours.
  • the reaction of the step (1-1a) may be carried out in an organic solvent, if necessary.
  • organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone and methyl amyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolan; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; toluene.
  • Aromatic solvents such as xylene, solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, ethanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ethers, Glycol ether solvents such as dialkylene glycol monoalkyl ether and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dimethyl sulfone; dimethyl sulfoxide, ethyl lactate, gamma Butyrolactone and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.
  • the amount used is preferably in the range of 5 to 150 parts by mass, preferably in the range of 7.5 to 100 parts by mass with respect to 100 parts by mass of the total of the trihydroxybenzene and epihalohydrin. It is more preferably in the range of 10 to 50 parts by mass.
  • the step (1-1b) is a step of closing the ring of the reactant obtained in the step (1-1a) in the presence of a basic compound, and the reactant obtained in the step (1-1a) is used as it is.
  • the step (1-1b) may be performed after removing a part or all of the unreacted epihalohydrin and the reaction solvent present in the system.
  • the same basic compound as described above can be used, and the basic compound may be used alone or in combination of two or more. ..
  • the amount of the basic compound used is not particularly limited, but is preferably in the range of 0.8 to 1.5 mol, preferably 0.9 to 1.3 mol, with respect to 1 mol of the hydroxyl group of the trihydroxybenzene. More preferably, it is in the molar range.
  • the amount of the basic compound added is 0.8 mol or more, the ring closure reaction of the step (1-1b) can proceed suitably, which is preferable.
  • the addition amount of the basic compound is 1.5 mol or less, side reactions can be prevented or suppressed, which is preferable.
  • the basic compound is used in the step (1-1a), it is preferable to use the above-mentioned amount including the amount used in the step (1-1a).
  • the reaction temperature in the step (1-1b) is preferably in the range of 20 to 120 ° C, more preferably in the range of 25 to 80 ° C.
  • the reaction time is preferably in the range of 0.5 to 8 hours, more preferably in the range of 1 to 5 hours.
  • the epoxy equivalent of the reaction product (A) of the trihydroxybenzene and epihalohydrin is preferably in the range of 98 to 196 from the viewpoint of obtaining the polymerizable compound having excellent infiltration into a fine space and curability. , 105-140, more preferably.
  • the epoxy equivalent is measured by the method described in JIS K7236.
  • reaction product obtained After performing the above step (1-1b), the reaction product obtained can be purified as needed.
  • the step (1-2) is a step of reacting the reaction product (A) with the polymerizable unsaturated group-containing aromatic compound (B) to obtain the polymerizable compound.
  • the polymerizable unsaturated group-containing aromatic compound (B) is an aromatic compound having a polymerizable unsaturated group, and is particularly capable of having a group that reacts with the epoxy group of the reaction product (A). Not limited.
  • the group that reacts with the epoxy group of the reaction product (A) is preferably a carboxy group or a hydroxyl group from the viewpoint of reactivity and ease of production. That is, the 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 acid compound (B2).
  • Examples of the polymerizable unsaturated group-containing phenolic compound (B1) include compounds represented by the following general formula (3-1) or (3-2).
  • Y is a direct bond, an ether bond, or an amide bond
  • Z is a structural site having a polymerizable unsaturated group
  • R 1 is an aliphatic group. It is a hydrocarbon group, an alkoxy group, or a halogen atom.
  • m is an integer of 1 to 5
  • n is an integer of 0 to 4
  • m + n is 5 or less
  • p is an integer of 1 to 7
  • q is an integer of 0 to 6
  • p + q is 7 or less.
  • a plurality of R1 and (YZ) groups existing in the above general formulas (3-1) and (3-2) may be the same or different.
  • the R1 and (YZ) groups may be bonded to any carbon atom of the naphthalene ring.
  • Each symbol in the general formulas (3-1) and (3-2) has the same meaning as that in the general formulas (2-1) and (2-2), and specific examples and preferable ones of R1 .
  • Preferred values of m, n, p, q and the like are the same as those in the general formulas (2-1) and (2-2).
  • the bond position of the (YZ) group is preferably the para position with respect to the hydroxyl group.
  • the bonding position of the (YZ) group and the bonding position of the hydroxyl group are the 1,6-position, 2,6-position and 2 of the naphthalene ring. It is preferably in the -7th position, more preferably in the 2nd and 6th positions.
  • the polymerizable unsaturated group-containing phenolic compound (B1) is preferably 2 from the viewpoint of infiltration into fine spaces and a balance of various performances such as optical properties, etching resistance, curability, and solvent solubility.
  • Examples of the polymerizable unsaturated group-containing aromatic carboxylic acid compound (B2) include compounds represented by the following general formula (4-1) or (4-2).
  • Y is a direct bond, an ether bond, or an amide bond
  • Z is a structural site having a polymerizable unsaturated group
  • R 1 is an aliphatic group. It is a hydrocarbon group, an alkoxy group, or a halogen atom.
  • m is an integer of 1 to 5
  • n is an integer of 0 to 4
  • m + n is 5 or less
  • p is an integer of 1 to 7
  • q is an integer of 0 to 6
  • p + q is 7 or less.
  • a plurality of R1 and (YZ) groups existing in the above general formulas (4-1) and (4-2) may be the same or different.
  • the R1 and (YZ) groups may be bonded to any carbon atom of the naphthalene ring.
  • the bond position of the (YZ) group is preferably the para position with respect to the carboxy group.
  • the bonding position of the (YZ) group and the bonding position of the carboxy group are the 1,6-position and the 2,6-position of the naphthalene ring. It is preferably in the 2-7 position, more preferably in the 2,6-position.
  • the polymerizable unsaturated group-containing aromatic carboxylic acid compound (B2) is preferably from the viewpoint of the balance of various performances such as infiltration into a fine space, optical properties, etching resistance, curability, and solvent solubility.
  • the reaction product (A) and the polymerizable unsaturated group-containing aromatic compound (B) are mixed in the presence of a catalyst from the viewpoint of the yield of the target polymerizable compound. It is preferable to react.
  • the catalyst that can be used in the step (1-2) is not particularly limited, but a quaternary phosphonium salt is preferable from the viewpoint of the yield of the target polymerizable compound.
  • Examples of the quaternary phosphonium salt that can be used as a catalyst in the step (1-2) include the same as the quaternary phosphonium salt that can be used in the step (1-1a).
  • the quaternary phosphonium salt can be used alone or in combination of two or more.
  • the amount of the quaternary phosphonium salt used is 0. 1 mol of the epoxy group in the reaction product (A) from the viewpoint that the reaction proceeds well and the residue in the product can be reduced.
  • the range is preferably in the range of 01 to 0.15 mol, more preferably in the range of 0.02 to 0.10 mol.
  • the reaction of the step (1-2) may be carried out in an organic solvent if necessary.
  • the organic solvent that can be used in the step (1-2) include the same organic solvents that can be used in the step (1-1a).
  • the organic solvent may be used alone or in combination of two or more.
  • the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.
  • the reaction temperature in the step (1-2) is preferably in the range of 20 to 80 ° C.
  • the reaction time of the step (1-2) is preferably 0.5 hours or more, and more preferably 1 to 50 hours.
  • the manufacturing method example 2 will be described.
  • the production method Example 2 contains a reaction product (A) of trihydroxybenzene and epihalohydrin, a polymerizable unsaturated group-containing non-aromatic compound (C), and the reaction product (A) and a polymerizable unsaturated group.
  • This is a production method using an aromatic compound (D) that nods a non-aromatic compound (C) as a reaction raw material.
  • the reaction product (A), the polymerizable unsaturated group-containing non-aromatic compound (C), and the aromatic compound (D) may be reacted with three components at once, or in two steps in order. It may be reacted.
  • a method of reacting the polymerizable compound in two steps in order is preferable. Specifically, a step (2-1) of reacting trihydroxybenzene with epihalohydrin to obtain the reaction product (A), and a step of reacting the reaction product (A) with the aromatic compound (D). (2-2) and the step (2-3) of reacting the reactant obtained in the step (2-2) with the polymerizable unsaturated group-containing non-aromatic compound (C) to obtain the polymerizable compound.
  • the method for producing a polymerizable compound having the above is preferable.
  • the step (2-1) is the same as the step (1-1).
  • the step (2-2) is a step of reacting the reaction product (A) with the aromatic compound (D).
  • the aromatic compound (D) is an aromatic compound having a group that reacts with the epoxy group of the reaction product (A) and a group that reacts with the polymerizable unsaturated group-containing non-aromatic compound (C). If there is, it is not particularly limited.
  • the aromatic compound (D) is carboxy from the viewpoint of reactivity and availability of raw materials. It is preferable that the phenolic compound (D1) has a group and the polymerizable unsaturated group-containing non-aromatic compound (C) is a polymerizable unsaturated group-containing aliphatic halide (C1).
  • the phenolic compound (D1) having a carboxy group includes, for example, a compound represented by the following general formula (5-1) or (5-2).
  • R 1 is an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom.
  • m is an integer of 1 to 5
  • n is an integer of 0 to 4
  • 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.
  • a plurality of R 1s existing in the above general formulas (4-1) and (4-2) may be the same or different.
  • R 1 may be bonded to any carbon atom of the naphthalene ring.
  • the bond position of the hydroxyl group is preferably the para position with respect to the carboxy group.
  • the bonding position of the hydroxyl group and the bonding position of the carboxy group are at the 1,6-position, the 2,6-position and the 2-7-position of the naphthalene ring. It is preferably present, and more preferably in the 2,6-position.
  • phenolic compound (D1) having a carboxy group examples include 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, and 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- From the group consisting of naphthoic acid, 1,3-dihydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7-d
  • One or more selected species can be mentioned.
  • 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are more preferable from the viewpoint of the balance of various performances such as infiltration into fine spaces, optical properties, etching resistance, curability, and solvent solubility.
  • the reaction product (A) it is preferable to react the reaction product (A) with the aromatic compound (D) in the presence of a catalyst from the viewpoint of the yield of the target compound.
  • the catalyst that can be used in the step (2-2) varies depending on the type of the aromatic compound (D), but when the phenolic compound (D1) having a carboxy group is used, the target compound can be used. From the viewpoint of yield, a quaternary ammonium salt is preferable.
  • Examples of the quaternary ammonium salt that can be used as a catalyst in the step (2-2) include the same quaternary ammonium salts that can be used in the step (1-1a).
  • the quaternary ammonium salt can be used alone or in combination of two or more.
  • the amount of the quaternary phosphonium salt used is 0. 1 mol of the epoxy group in the reaction product (A) from the viewpoint that the reaction proceeds well and the residue in the product can be reduced.
  • the range is preferably in the range of 01 to 0.15 mol, more preferably in the range of 0.02 to 0.10 mol.
  • the reaction of the above step (2-2) may be carried out in an organic solvent if necessary.
  • the organic solvent that can be used in the step (2-2) include the same organic solvents that can be used in the step (1-1a).
  • the organic solvent may be used alone or in combination of two or more.
  • the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.
  • the reaction temperature in the step (2-2) is preferably in the range of 20 to 120 ° C, more preferably in the range of 80 to 110 ° C.
  • the reaction time of the step (2-2) is preferably 0.5 hours or more, and more preferably 1 to 50 hours.
  • the step (2-3) is a step of reacting the reactant obtained in the step (2-2) with the polymerizable unsaturated group-containing non-aromatic compound (C) to obtain the polymerizable compound.
  • the step (2-3) may be continuously carried out by adding the aromatic compound (C) to the reaction mixture of the step (2-2), or may be obtained in the step (2-2).
  • the reaction product may be isolated and purified once, and then separately performed.
  • the polymerizable unsaturated group-containing non-aromatic compound (C) may be a polymerizable unsaturated group-containing aliphatic halide (C1) from the viewpoint of reactivity, availability of raw materials, and the like. preferable.
  • the polymerizable unsaturated group contained in the polymerizable unsaturated group-containing aliphatic halide (C1) include an alkenyl group, an alkynyl group, an acryloyl group, and a methacryloyl group.
  • an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an acryloyl group, and a methacryloyl group are preferable from the viewpoint of solubility in an organic solvent and infiltration into a fine space. More preferably, it is an alkenyl group having 2 to 6 carbon atoms and an alkynyl group having 2 to 6 carbon atoms.
  • polymerizable unsaturated group-containing aliphatic halide (C1) include one or more selected from the group consisting of vinyl halide, allyl halide, propargyl halide, acryloyl halide, and methacryloyl halide. ..
  • the reactant obtained in the step (2-2) and the polymerizable unsaturated group-containing non-aromatic compound (C) Is preferably reacted in the presence of a catalyst.
  • the catalyst that can be used in the step (2-3) varies depending on the type of the aromatic compound (D) and the polymerizable unsaturated group-containing non-aromatic compound (C), but is a phenolic compound having the carboxy group.
  • a basic compound is preferable from the viewpoint of the yield of the target polymerizable compound.
  • Examples of the basic compound that can be used as a catalyst in the step (2-3) include the same basic compounds as those that can be used in the step (1-1a).
  • the basic compound may be used alone or in combination of two or more.
  • potassium carbonate or sodium carbonate is preferably used as the basic compound because the target polymerizable compound can be produced in high yield and high efficiency.
  • the amount of the basic compound added was 0, with respect to the polymerizable unsaturated group-containing aliphatic halide (C1), from the viewpoint that the reaction proceeds well and the residue in the product can be reduced. It is preferably in the range of 5 to 2.0 mol, more preferably in the range of 0.8 to 1.5 mol.
  • the reaction of the above step (2-3) may be carried out in an organic solvent if necessary.
  • the organic solvent that can be used in the step (2-3) include the same organic solvents that can be used in the step (1-1a).
  • the organic solvent may be used alone or in combination of two or more.
  • the organic solvent used in the step (2-2) may be used as it is.
  • the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.
  • the reaction temperature in the 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 step (2-3) is preferably 0.5 hours or more, and more preferably 1 to 50 hours.
  • the number average molecular weight (Mn) of the polymerizable compound is preferably in the range of 660 to 2,500, preferably 800 to 2,500, from the viewpoint of solubility in an organic solvent, infiltration into a fine space, etching resistance, and curability. A range of 1,500 is more preferred. In this specification, the number average molecular weight of the polymerizable compound is measured by the method described in Examples.
  • the weight average molecular weight (Mw) of the polymerizable compound is preferably in the range of 660 to 3,000, preferably 800 to 3,000, from the viewpoint of solubility in an organic solvent, infiltration into a fine space, etching resistance, and curability. A range of 2,000 is more preferred. In this specification, the weight average molecular weight of the polymerizable compound is measured by the method described in Examples.
  • the polydispersity (Mw / Mn) of the polymerizable compound ranges from 1.00 to 2.00 from the viewpoint of solubility in an organic solvent, infiltration into a fine space, etching resistance, and curability.
  • the range of 1.00 to 1.50 is preferable, and the range of 1.00 to 1.50 is more preferable.
  • 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 Examples.
  • the polymerizable compound Since the polymerizable compound has a polymerizable unsaturated group in its molecular structure, it can be used as an active energy ray-curable resin composition by adding, for example, a photopolymerization initiator.
  • the active energy ray-curable resin composition of the present embodiment contains the polymerizable compound, a photopolymerization initiator, and an organic solvent.
  • the amount of the polymerizable compound added to the active energy ray-curable resin composition may be, for example, in the range of 1 to 99% by mass with respect to the total of the components other than the organic solvent of the active energy ray-curable resin composition. It is preferably in the range of 5 to 95% by mass, more preferably.
  • the photopolymerization initiator may be selected and used as appropriate depending on the type of active energy ray to be irradiated. Further, it may 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, and a nitrile compound. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl.
  • Examples of commercially available products of the photopolymerization initiator include “Omnirad-1173”, “Omnirad-184", “Omnirad-127”, “Omnirad-2959”, “Omnirad-369”, “Omnirad-379”, and “Omnirad-379".
  • the amount of the photopolymerization initiator added is, for example, preferably in the range of 0.05 to 15% by mass, preferably 0.1 to 10% by mass, based on the total of the components of the active energy ray-curable resin composition other than the organic solvent. It is more preferably in the range of% by mass.
  • the organic solvent can be used in a wide variety without particular limitation.
  • alkyl monoalcohol solvents such as methanol, ethanol and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, Alkyl polyol solvents such as 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin; 2-ethoxyethanol, ethylene glycol monomethyl Alkylene glycol mono such as ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl
  • Alkyl ether solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene glycol such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate.
  • Alkyl ether acetate solvent such as 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, cyclopentylmethyl ether; Ketone solvent such as acetone, methylethylketone, methylisobutylketone, cyclohexanone, methylamylketone; 2-hydroxypropion Methyl acid, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3 -Ether solvents such as methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate: aromatic hydrocarbon solvents such as benz
  • the amount of the organic solvent added is preferably 5 mass by mass in the active energy ray-curable resin composition from the viewpoint of obtaining a uniform coating film by a coating method such as a spin coating method for the fluidity of the composition.
  • the amount is preferably in the range of% or more and preferably 95% by mass or less.
  • the active energy ray-curable resin composition is a resin component other than the polymerizable compound, a surfactant such as a leveling agent, a filler, a pigment, an adhesion improver, and a dissolution accelerator as long as the effect of the present invention is not impaired. Etc. may be contained.
  • the resin component other than the polymerizable compound include various (meth) acrylate monomers.
  • the active energy ray-curable resin composition may contain a surfactant from the viewpoint of flattening the film thickness and infiltrating into a fine space.
  • a surfactant all known and public silicone-based surfactants, fluorine-based surfactants and the like used for semiconductor resists can be used.
  • the surfactant include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene.
  • Polyoxyethylene alkylallyl ether compounds such as nonylphenol ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurates, sorbitan monopalmitates, sorbitan monostearates, sorbitan monooleates, sorbitan trioleates, sorbitan tristearates.
  • Solbitan fatty acid ester compounds such as, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene such as polyoxyethylene sorbitan tristearate.
  • Nonionic surfactants such as sorbitan fatty acid ester compounds; Fluorine having a fluorine atom in its molecular structure such as a copolymer of a polymerizable monomer having a fluoroaliphatic group and [poly (oxyalkylene)] (meth) acrylate.
  • System-based surfactants examples thereof include silicone-based surfactants having a silicone structure site in the molecular structure. These may be used alone or in combination of two or more.
  • the amount of the surfactant added is preferably in the range of 0.001 to 2 parts by mass with respect to 100 parts by mass of the resin solid content in the active energy ray-curable resin composition.
  • the various (meth) acrylate monomers are not particularly limited as long as they have a (meth) acryloyl group, and are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth).
  • Acrylate mono (meth) acrylate compounds such as acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate.
  • Alicyclic mono (meth) acrylate compounds such as adamantyl mono (meth) acrylate; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth).
  • aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylates and bisphenol di (meth) acrylates; (poly) oxyethylene chains, (poly) oxyethylene chains in the molecular structure of the various di (meth) acrylate compounds.
  • Polyoxyalkylene-modified di (meth) acrylate compounds introduced with (poly) oxyalkylene chains such as oxypropylene chains and (poly) oxytetramethylene chains; (poly) in the molecular structure of the various di (meth) acrylate compounds.
  • a tetrafunctional or higher functional aliphatic poly (meth) acrylate compound such as erismitol hexa (meth) acrylate; (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxypropylene chain, (poly) oxypropylene chain, (poly) oxypropylene chain, (poly) oxypropylene chain, (poly) oxypropylene chain, (poly) oxypropylene chain, (poly) oxypropylene chain, (poly) oxypropylene chain, A tetrafunctional or higher functional (poly) oxyalkylene-modified poly (meth) acrylate compound introduced with a (poly) oxyalkylene chain such as a poly) oxytetramethylene chain; in the molecular structure of the aliphatic poly (meth) acrylate compound (poly).
  • Acrylate compound A (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the hydroxyl group-containing (meth) acrylate compound (poly). ) Oxyalkylene modified product; A lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the hydroxyl group-containing (meth) acrylate compound; 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis.
  • Isocyanate group-containing (meth) acrylate compounds such as (acryloyloxymethyl) ethyl isocyanate; glycidyl group-containing (meth) groups such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate.
  • Epoxy group-containing (meth) acrylate compounds such as acrylate monomers, mono (meth) acrylates of diglycidyl ether compounds such as droxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. Can be mentioned.
  • the various (meth) acrylate monomers may be used alone or in combination of two or more.
  • the various (meth) acrylate monomers When the various (meth) acrylate monomers are used, it is preferable to use them in an amount that does not impair the effects of the present invention.
  • the amount of the various (meth) acrylate monomers used with respect to 100 parts by mass of the polymerizable compound of the present invention is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and 10 parts by mass. It is particularly preferable that the amount is less than or equal to a part.
  • the active energy ray-curable resin composition is a uniform liquid obtained by stirring and mixing the polymerizable compound, the photopolymerization initiator, the organic solvent, and various additives added as necessary by a usual method. It can be prepared by.
  • the cured product of the present embodiment is obtained by curing the active energy ray-curable resin composition.
  • the cured product can be used, for example, as a resist underlayer film.
  • the substrate (processed substrate) on which the resist underlayer film is formed include a silicon wafer and a wafer coated with aluminum.
  • the active energy ray-curable resin composition is applied to the surface of the substrate to be processed or another underlayer film described later, and then the organic solvent is removed to form a coating film. It can be formed by curing the coating film by irradiating it with active energy rays and heat-treating it.
  • Examples of the method for applying the active energy ray-curable resin composition include a spin coating method, a roll coating method, and a dip method.
  • the heating temperature is usually in the range of 50 to 450 ° C, preferably in the range of 150 to 300 ° C.
  • the heating time is usually in the range of 5 to 600 seconds.
  • Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • ultraviolet rays When ultraviolet rays are used as the active energy rays, they may be irradiated in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently carry out the curing reaction by the ultraviolet rays.
  • g-line (wavelength 436 nm), h-line (wavelength 405 nm) i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), etc.
  • Examples include an EUV laser (wavelength 13.5 nm) and the like.
  • the integrated light amount of the active energy rays is not particularly limited, but is preferably in the range of 10 to 5,000 mJ / cm 2 , and more preferably in the range of 50 to 1,000 mJ / cm 2 .
  • the integrated light amount is in the above range, it is preferable because the generation of the uncured portion can be prevented or suppressed.
  • the irradiation of the active energy beam may be performed in one step or may be divided into two or more steps.
  • the film thickness of the resist underlayer film is usually in the range of 10 to 1,000 nm, preferably in the range of 10 nm to 500 nm.
  • the resist composition of the present embodiment contains the polymerizable compound. By curing the resist composition, it can be used as a resist film.
  • 13 C-NMR was measured under the following conditions.
  • FD-MS was measured using a double-focusing mass spectrometer AX505H (FD505H) manufactured by JEOL Ltd.
  • Synthesis Example 2 Synthesis of epoxidized product (A-2) 63 g (0.75 mol) of 1,2,3-trihydroxybenzene and 1 in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a nitrogen introduction tube, and a stirrer. A mixture of 63 g (0.75 mol) of 2,4-trihydroxybenzene and 1388 g (15 mol) of epichlorohydrin were added and the temperature was raised to 50 ° C. Then, 11.2 g (0.06 mol) of benzyltrimethylammonium chloride was added, and the mixture was stirred at 50 ° C. for 15 hours.
  • Synthesis Example 3 Synthesis of epoxidized product (A-3) In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a nitrogen introduction tube, and a stirrer, 126 g (1.50 mol) of 1,2,4-trihydroxybenzene was added. 1388 g (15 mol) of epichlorohydrin was added, and the temperature was raised to 50 ° C. Then, 11.2 g (0.06 mol) of benzyltrimethylammonium chloride was added, and the mixture was stirred at 50 ° C. for 15 hours. 1000 mL of distilled water was poured into the obtained reaction solution and stirred, and the upper layer was removed after standing.
  • Example 1 Synthesis of polymerizable compound (1) 128 g of epoxide (A-1) (equivalent to 1.00 mol of epoxy group), 4 in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a nitrogen introduction tube, and a stirrer. -Add 134 g (1.00 mol) of isopropenylphenol, 18.6 g (0.05 mol) of ethyltriphenylphosphonium bromide (manufactured by Hokuko Kagaku Kogyo Co., Ltd.), 0.6 g (0.005 mol) of hydroquinone, and 656 g of methoxypropanol. , 70 ° C. for 10 hours.
  • A-1 epoxide
  • A-1 equivalent to 1.00 mol of epoxy group
  • the obtained polymerizable compound (1) had a number average molecular weight (Mn of 1043, a weight average molecular weight (Mw) of 1143, and a polydispersity (Mw / Mn) of 1.10.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mn polydispersity
  • the GPC chart is shown in FIG. 1, the 1 H-NMR chart is shown in FIG. 2, the 13 C-NMR chart is shown in FIG. 3, and the FD-MS chart is shown in FIG. The formation of the following compounds was confirmed by 1 H-NMR and 13 C-NMR.
  • Example 2 Synthesis of polymerizable compound (2) Same as Example 1 except that the epoxidized compound (A-1) of Example 2 was changed to 121 g of the epoxidized compound (A-2) (equivalent to 1.00 mol of epoxy group).
  • the polymerizable compound (2) was obtained by the method.
  • the obtained polymerizable compound (2) had a number average molecular weight (Mn) of 1125, a weight average molecular weight (Mw) of 1246, and a polydispersity (Mw / Mn) of 1.11.
  • the GPC chart of the polymerizable compound (2) is shown in FIG.
  • Example 3 Synthesis of polymerizable compound (3) The same as in Example 1 except that the epoxide (A-1) in Example 1 was changed to 114 g (equivalent to 1.00 mol of epoxy group) of the epoxide (A-3).
  • the polymerizable compound (3) was obtained by the method.
  • the obtained polymerizable compound (3) had a number average molecular weight (Mn) of 1244, a weight average molecular weight (Mw) of 1409, and a polydispersity (Mw / Mn) of 1.13.
  • the GPC chart of the polymerizable compound (3) is shown in FIG.
  • Example 4 Synthesis of polymerizable compound (4) 128 g of epoxide (A-1) (equivalent to 1.00 mol of epoxy group), 4 in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a nitrogen introduction tube, and a stirrer.
  • -(Hydroxy) methacrylanilide manufactured by Osaka Organic Chemical Co., Ltd.
  • 177 g (1.00 mol
  • ethyltriphenylphosphonium bromide manufactured by Hokuko Chemical Industry Co., Ltd.
  • the obtained polymerizable compound (4) had a number average molecular weight (Mn) of 1053, a weight average molecular weight (Mw) of 1157, and a polydispersity (Mw / Mn) of 1.10.
  • the GPC chart of the polymerizable compound (4) is shown in FIG. 7, the 1 H-NMR chart is shown in FIG. 8, the 13 C-NMR chart is shown in FIG. 9, and the FD-MS chart is shown in FIG. The formation of the following compounds was confirmed by the peak of 825.3 in the FD-MS spectrum and 1 H-NMR and 13 C-NMR.
  • Example 5 Synthesis of Polymerizable Compound (5) Same as Example 4 except that the epoxidized compound (A-1) of Example 4 was changed to 121 g of the epoxidized compound (A-2) (equivalent to 1.00 mol of epoxy group).
  • the polymerizable compound (5) was obtained by the method.
  • the obtained polymerizable compound (B-2) had a number average molecular weight (Mn) of 1136, a weight average molecular weight (Mw) of 1258, and a polydispersity (Mw / Mn) of 1.11.
  • the GPC chart of the polymerizable compound (5) is shown in FIG.
  • Example 6 Synthesis of polymerizable compound (6) The same as in Example 4 except that the epoxide (A-1) in Example 4 was changed to 114 g (equivalent to 1.00 mol of epoxy group) of the epoxide (A-3).
  • the resin (6) was obtained by the method.
  • the obtained resin (6) had a number average molecular weight (Mn) of 1256, a weight average molecular weight (Mw) of 1423, and a polydispersity (Mw / Mn) of 1.13.
  • the GPC chart of the polymerizable compound (6) is shown in FIG.
  • Example 7 Synthesis of polymerizable compound (7) 128 g of epoxidized product (A-1) (equivalent to 1.00 mol of epoxy group), 6 in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a nitrogen introduction tube, and a stirrer. 188 g (1.00 mol) of -hydroxy-2-naphthoic acid, 11.4 g (0.05 mol) of benzyltrimethylammonium chloride, and 512 g of dimethylformamide were added, and the mixture was stirred at 100 ° C. for 6 hours.
  • the obtained polymerizable compound (7) had a number average molecular weight (Mn) of 1166, a weight average molecular weight (Mw) of 1259, and a polydispersity (Mw / Mn) of 1.08.
  • the GPC chart of the polymerizable compound (7) is shown in FIG. 13, the 1 H-NMR chart is shown in FIG. 14, the 13 C-NMR chart is shown in FIG. 15, and the FD-MS chart is shown in FIG.
  • the formation of the following compounds was confirmed by the peak of 97.3 in the FD-MS spectrum and 1 H-NMR and 13 C-NMR.
  • Example 8 Synthesis of Polymerizable Compound (8) Same as Example 7 except that the epoxidized compound (A-1) of Example 7 was changed to 121 g of the epoxidized compound (A-2) (equivalent to 1.00 mol of epoxy group).
  • the polymerizable compound (8) was obtained by the method.
  • the obtained polymerizable compound (8) had a number average molecular weight (Mn) of 1136, a weight average molecular weight (Mw) of 1258, and a polydispersity (Mw / Mn) of 1.11.
  • the GPC chart of the polymerizable compound (8) is shown in FIG.
  • Example 9 Synthesis of polymerizable compound (9) The same as in Example 7 except that the epoxide (A-1) in Example 7 was changed to 114 g (equivalent to 1.00 mol of epoxy group) of the epoxide (A-3).
  • the polymerizable compound (9) was obtained by the method.
  • the obtained polymerizable compound (9) had a number average molecular weight (Mn) of 1339, a weight average molecular weight (Mw) of 1552, and a polydispersity (Mw / Mn) of 1.11.
  • the GPC chart of the polymerizable compound (9) is shown in FIG.
  • Comparative Example 1 Synthesis of Polymerizable Compound (1') Same as Example 1 except that the epoxy compound (A-1) of Example 1 was changed to an epoxy compound (epoxy equivalent 209 g / equivalent) of tert-butylcatechol 209 g.
  • a polymerizable compound (1') was obtained by the method.
  • the obtained polymerizable compound (1') had a number average molecular weight (Mn) of 1000, a weight average molecular weight (Mw) of 1050, and a polydispersity (Mw / Mn) of 1.05.
  • the GPC chart of the polymerizable compound (1') is shown in FIG.
  • Example 3 Comparative Example 3 Synthesis of Polymerizable Compound (3')]
  • a polymerizable compound (3') was obtained in the same manner as in Example 7 except that the epoxie (A-1) of Example 7 was changed to an epoxy of tertiary butylcatechol (epoxy equivalent 209 g / equivalent) 209 g. ..
  • the obtained polymerizable compound (3') had a number average molecular weight (Mn) of 1044, a weight average molecular weight (Mw) of 1100, and a polydispersity (Mw / Mn) of 1.05.
  • the GPC chart of the polymerizable compound (3') is shown in FIG.
  • n value (refractive index) and k value (attenuation coefficient) of the obtained coating film were measured at a wavelength of 193 and 248 nm using a spectroscopic ellipsometer (“VUV-VASE GEN-1” manufactured by JA Woollam). did.
  • composition for resist underlayer film for evaluation of etching resistance and infiltration into fine spaces 5 parts by mass of the polymerizable compound obtained in each Example and Comparative Example was added to 95 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was mixed and dissolved to obtain a solution.
  • the obtained resist underlayer film composition was applied onto a silicon wafer having a diameter of 5 inches using a spin coater, and then heated at 180 ° C. for 60 seconds in a hot plate having an oxygen concentration of 20% by volume. Further, it was heated at 350 ° C. for 120 seconds to obtain a silicon wafer with a resist underlayer film having a film thickness of 0.3 ⁇ m.
  • the formed resist underlayer film was subjected to CF 4 / Ar / O 2 (CF 4 : 40 mL / min, Ar: 20 mL / min, O 2 : 5 mL / min) using an etching device (“EXAM” manufactured by Shinko Seiki Co., Ltd.).
  • Etching was performed under the conditions of pressure: 20 Pa, RF power: 200 W, processing time: 40 seconds, and temperature: 15 ° C.). The film thickness before and after the etching treatment at this time was measured, the etching rate was calculated, and the etching resistance was evaluated.
  • the evaluation criteria are as follows. A: When the etching rate is 150 nm / min or less B: When the etching rate exceeds 150 nm / min
  • a silicon wafer with a resist underlayer film was obtained in the same manner as described above, except that a silicon wafer having a diameter of 5 inches and a hole pattern having a diameter of 110 nm and a depth of 300 nm was formed.
  • a silicon wafer was divided on a hole pattern line, and a cross-sectional observation was performed with a scanning electron microscope (“SU-3500” manufactured by Hitachi High-Technologies Corporation) to evaluate the infiltration property into a fine space.
  • the evaluation criteria are as follows. A: When the hardened material is filled to the bottom of the hole B: When the hardened material is not filled to the bottom of the hole or there is a gap in a part
  • Table 1 shows the results of each evaluation.
  • the composition containing the polymerizable compound represented by the general formula (1) has excellent infiltration into fine spaces, as well as optical properties, etching resistance, and curability. It can be seen that it is also excellent in solvent solubility and the like. On the other hand, it can be seen that the resins of Comparative Examples 1 to 3 have not solved the problem of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Materials For Photolithography (AREA)
PCT/JP2021/043093 2020-12-15 2021-11-25 重合性化合物、活性エネルギー線硬化性樹脂組成物、硬化物、レジスト用組成物、及びレジスト膜 Ceased WO2022130921A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2022569817A JP7288233B2 (ja) 2020-12-15 2021-11-25 重合性化合物、活性エネルギー線硬化性樹脂組成物、硬化物、レジスト用組成物、及びレジスト膜
KR1020237009036A KR102906921B1 (ko) 2020-12-15 2021-11-25 중합성 화합물, 활성 에너지선 경화성 수지 조성물, 경화물, 레지스트용 조성물, 및 레지스트막
CN202180084130.6A CN116670184B (zh) 2020-12-15 2021-11-25 聚合性化合物、活性能量射线固化性树脂组合物、固化物、抗蚀剂用组合物和抗蚀膜

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020207389 2020-12-15
JP2020-207389 2020-12-15

Publications (1)

Publication Number Publication Date
WO2022130921A1 true WO2022130921A1 (ja) 2022-06-23

Family

ID=82058785

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/043093 Ceased WO2022130921A1 (ja) 2020-12-15 2021-11-25 重合性化合物、活性エネルギー線硬化性樹脂組成物、硬化物、レジスト用組成物、及びレジスト膜

Country Status (5)

Country Link
JP (1) JP7288233B2 (https=)
KR (1) KR102906921B1 (https=)
CN (1) CN116670184B (https=)
TW (1) TWI884320B (https=)
WO (1) WO2022130921A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115279815A (zh) * 2020-03-10 2022-11-01 Dic株式会社 (甲基)丙烯酸酯树脂、活性能量射线固化性(甲基)丙烯酸酯树脂组合物、和抗蚀下层膜、以及(甲基)丙烯酸酯树脂的制造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000007758A (ja) * 1998-06-27 2000-01-11 Nagase Chiba Kk Ｂ−ステージ化できる液状エポキシ樹脂組成物
JP2007162027A (ja) * 2002-03-29 2007-06-28 Taiyo Ink Mfg Ltd 不飽和基含有多分岐化合物、それを含有する硬化性組成物及びその硬化物
WO2019017013A1 (ja) * 2017-07-21 2019-01-24 Dic株式会社 エポキシ樹脂、およびこれを含むエポキシ樹脂組成物、並びに前記エポキシ樹脂組成物を用いた硬化物
JP2020117612A (ja) * 2019-01-23 2020-08-06 Dic株式会社 エポキシ（メタ）アクリレート樹脂、硬化性樹脂組成物、硬化物及び物品
JP2021008410A (ja) * 2019-06-28 2021-01-28 Dic株式会社 エポキシ化合物、組成物、硬化物及び積層体
WO2021181958A1 (ja) * 2020-03-10 2021-09-16 Dic株式会社 （メタ）アクリレート樹脂、活性エネルギー線硬化性（メタ）アクリレート樹脂組成物、及びレジスト下層膜、並びに（メタ）アクリレート樹脂の製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3309339A (en) * 1963-11-12 1967-03-14 Allied Chem New trisphenols and epoxide resins prepared therefrom
AU2003221053A1 (en) * 2002-03-29 2003-10-27 Taiyo Ink Manufacturing Co., Ltd. Unsaturated polybranched compounds, curable compositions containing the same and cured articles thereof
JP2010285403A (ja) 2009-06-15 2010-12-24 Nissan Chem Ind Ltd 架橋剤及び該架橋剤を含有するレジスト下層膜形成組成物
CN103694430B (zh) 2014-01-02 2016-02-10 河北大学 聚不饱和酸没食子酸环氧酯医用高分子材料制备方法
JP6402968B2 (ja) * 2014-03-03 2018-10-10 Dic株式会社 （メタ）アクリロイル基含有樹脂、（メタ）アクリロイル基含有樹脂の製造方法、硬化性樹脂材料、その硬化物、及びレジスト材料
JP6575838B2 (ja) * 2017-07-14 2019-09-18 Dic株式会社 エポキシ樹脂、およびこれを含むエポキシ樹脂組成物、並びに前記エポキシ樹脂組成物を用いた硬化物
WO2020137309A1 (ja) * 2018-12-26 2020-07-02 Dic株式会社 レジスト組成物
JP7192521B2 (ja) * 2019-01-23 2022-12-20 Dic株式会社 酸基含有（メタ）アクリレート樹脂、硬化性樹脂組成物、硬化物、絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000007758A (ja) * 1998-06-27 2000-01-11 Nagase Chiba Kk Ｂ−ステージ化できる液状エポキシ樹脂組成物
JP2007162027A (ja) * 2002-03-29 2007-06-28 Taiyo Ink Mfg Ltd 不飽和基含有多分岐化合物、それを含有する硬化性組成物及びその硬化物
WO2019017013A1 (ja) * 2017-07-21 2019-01-24 Dic株式会社 エポキシ樹脂、およびこれを含むエポキシ樹脂組成物、並びに前記エポキシ樹脂組成物を用いた硬化物
JP2020117612A (ja) * 2019-01-23 2020-08-06 Dic株式会社 エポキシ（メタ）アクリレート樹脂、硬化性樹脂組成物、硬化物及び物品
JP2021008410A (ja) * 2019-06-28 2021-01-28 Dic株式会社 エポキシ化合物、組成物、硬化物及び積層体
WO2021181958A1 (ja) * 2020-03-10 2021-09-16 Dic株式会社 （メタ）アクリレート樹脂、活性エネルギー線硬化性（メタ）アクリレート樹脂組成物、及びレジスト下層膜、並びに（メタ）アクリレート樹脂の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115279815A (zh) * 2020-03-10 2022-11-01 Dic株式会社 (甲基)丙烯酸酯树脂、活性能量射线固化性(甲基)丙烯酸酯树脂组合物、和抗蚀下层膜、以及(甲基)丙烯酸酯树脂的制造方法
CN115279815B (zh) * 2020-03-10 2024-02-20 Dic株式会社 (甲基)丙烯酸酯树脂、活性能量射线固化性(甲基)丙烯酸酯树脂组合物、和抗蚀下层膜、以及(甲基)丙烯酸酯树脂的制造方法

Also Published As

Publication number Publication date
CN116670184B (zh) 2025-12-09
TW202231614A (zh) 2022-08-16
CN116670184A (zh) 2023-08-29
KR102906921B1 (ko) 2026-01-05
KR20230051687A (ko) 2023-04-18
JPWO2022130921A1 (https=) 2022-06-23
JP7288233B2 (ja) 2023-06-07
TWI884320B (zh) 2025-05-21

Similar Documents

Publication Publication Date Title
JP7283515B2 (ja) 化合物、樹脂、組成物並びにレジストパターン形成方法及び回路パターン形成方法
KR101569955B1 (ko) 경화성 공중합체 및 경화성 수지 조성물
JP7194356B2 (ja) 化合物、樹脂及び組成物、並びにレジストパターン形成方法及び回路パターン形成方法
JP7069530B2 (ja) 化合物、樹脂、組成物及びパターン形成方法
TWI883152B (zh) 感光性樹脂組成物、硬化膜、基板、基板的製造方法及顯示裝置
JP6506732B2 (ja) ネガ感光型樹脂組成物及びそれから製造される光硬化パターン
WO2018016615A1 (ja) 化合物、樹脂、組成物並びにレジストパターン形成方法及び回路パターン形成方法
US20200354501A1 (en) Composition for film formation for lithography, film for lithography, method for forming resist pattern, and method for forming circuit pattern
JP7024929B2 (ja) （メタ）アクリレート樹脂、活性エネルギー線硬化性（メタ）アクリレート樹脂組成物、及びレジスト下層膜、並びに（メタ）アクリレート樹脂の製造方法
JP7205716B2 (ja) 化合物、樹脂、組成物並びにレジストパターン形成方法及び回路パターン形成方法
JP7288233B2 (ja) 重合性化合物、活性エネルギー線硬化性樹脂組成物、硬化物、レジスト用組成物、及びレジスト膜
TWI848061B (zh) 含酸基之(甲基)丙烯酸酯樹脂、硬化性樹脂組成物、硬化物、絕緣材料、阻焊用樹脂材料及阻焊構件
JP7331853B2 (ja) 下層膜形成組成物
KR20190085002A (ko) 화합물, 수지, 조성물 그리고 레지스트패턴 형성방법 및 회로패턴 형성방법
JP2020166255A (ja) 硬化膜付き基板の製造方法、硬化膜付き基板、感光性樹脂組成物、感光性樹脂組成物を硬化してなる硬化膜および硬化膜または硬化膜付き基板を有する表示装置
KR20170113287A (ko) 층간 절연막 형성용 조성물, 층간 절연막 및 층간 절연막 패턴의 형성 방법, 그리고 디바이스
WO2019230364A1 (ja) （メタ）アクリレート化合物、硬化性組成物、硬化物及び物品
JP6541016B2 (ja) 酸基含有（メタ）アクリレート樹脂及びソルダーレジスト用樹脂材料
WO2016175160A1 (ja) アルカリ可溶性樹脂
WO2021085262A1 (ja) ケイ素化合物、反応性材料、樹脂組成物、感光性樹脂組成物、硬化膜、硬化膜の製造方法、パターン硬化膜およびパターン硬化膜の製造方法
TWI917320B (zh) 附硬化膜的基板之製造方法、附硬化膜的基板、感光性樹脂組成物、使感光性樹脂組成物硬化而成的硬化膜以及具有硬化膜或附硬化膜的基板之顯示裝置
JP2016166351A (ja) 硬化性組成物及びその硬化物並びに硬度向上方法
JP2017082193A (ja) 不飽和基含有アルカリ現像性樹脂及びソルダーレジスト用樹脂材料
KR20230020332A (ko) 에폭시 수지, 감광성 수지 조성물, 레지스트막, 경화성 조성물 및 경화막
JP2017149818A (ja) 不飽和基含有アルカリ現像性樹脂及びソルダーレジスト用樹脂材料

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21906284

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022569817

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20237009036

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202180084130.6

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21906284

Country of ref document: EP

Kind code of ref document: A1