WO2014185303A1 - Composé de thioxanthène, amplificateur de base, et composition de résine pouvant réagir avec une base contenant un amplificateur de base - Google Patents

Composé de thioxanthène, amplificateur de base, et composition de résine pouvant réagir avec une base contenant un amplificateur de base Download PDF

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WO2014185303A1
WO2014185303A1 PCT/JP2014/062198 JP2014062198W WO2014185303A1 WO 2014185303 A1 WO2014185303 A1 WO 2014185303A1 JP 2014062198 W JP2014062198 W JP 2014062198W WO 2014185303 A1 WO2014185303 A1 WO 2014185303A1
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base
carbon atoms
formula
group
compound
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PCT/JP2014/062198
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Japanese (ja)
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信彦 酒井
有光　晃二
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和光純薬工業株式会社
学校法人東京理科大学
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Priority to JP2015517037A priority Critical patent/JP6280919B2/ja
Publication of WO2014185303A1 publication Critical patent/WO2014185303A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition

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  • the present invention relates to a thioxanthene compound, a base proliferating agent, and a base-reactive resin composition containing the base proliferating agent. More specifically, the present invention relates to a thioxanthene compound capable of decomposing by the action of a base to generate a new base, a base proliferating agent, and a base-reactive resin composition containing the base proliferating agent.
  • a photosensitive resin composition containing an acid generator that generates an acid by light irradiation is applied as a photoresist material, a photo-curing material, or the like.
  • the acid generated from the acid generator acts as a catalyst or a polymerization initiator.
  • a photosensitive resin composition containing an acid generator or the like is used as a photoresist material to form a pattern, for example, acid generation
  • the agent is irradiated with light to generate a strong acid serving as a catalyst, and the resin component is chemically modified. Then, a pattern is formed by the change in solubility of the chemically modified resin component.
  • Such a photoresist material is required to have a high resolution and sensitivity and to be able to form a pattern having high etching resistance.
  • a pattern having resistance to oxygen plasma etching is formed.
  • materials to obtain Various photoresist materials comprising a photosensitive resin composition containing an acid generator have been provided for the purpose of high sensitivity, high resolution, etc., but a combination of a photoacid generator and a resin material is provided. Since the types are limited to some extent, a new photosensitive system that does not use an acid generator has been demanded.
  • a method using a polymerization reaction or chemical reaction by a base catalyst for example, a method of generating a base by the action of light and chemically denaturing a resin using this as a catalyst
  • a means for applying a photosensitive resin composition using a base generated by the above as a catalyst to a photoresist material, a photocuring material or the like has been studied.
  • the compound having an epoxy group is cured by causing a crosslinking reaction by the action of a base to generate amines as initiators or catalysts in the epoxy resin layer by the action of light or heat, and then heated. Methods of curing by processing are provided.
  • a base proliferating agent that secondarily amplifies a base generated by the action of light.
  • a photosensitive resin is proposed.
  • a composition is obtained.
  • a resin composition that is improved in performance by adding a base proliferating agent that increases the base in a proliferative manner is also known, and contains a base proliferating agent that is a urethane compound that causes a base proliferating reaction.
  • a photosensitive resin composition is disclosed (see, for example, Patent Document 1 and Patent Document 2).
  • the base proliferating agent has low sensitivity, and has poor solubility in organic solvents and low compatibility with base-reactive compounds. It was difficult to make the proliferation reaction proceed efficiently.
  • the present invention has been made in view of the above problems, and can be used for, for example, a crosslinking reaction of an epoxy compound, can generate a new base by the presence of a base, and can be dissolved in an organic solvent. Since it is highly heat-resistant and has higher heat resistance than conventional base proliferating agents, when it is contained in a base-reactive compound, the compound, base proliferating agent, and the base proliferating agent that efficiently undergo a base proliferating reaction It is in providing the base reactive resin composition containing this.
  • the compound according to the present invention is represented by the following formula (A).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl having 6 to 14 carbon atoms.
  • Q is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 7 carbon atoms
  • X 1 represents SO or SO 2 and Y 1 , Y 2 , Y 3 , Y 4 , Z 1 , Z 2 , Z 3 and Z 4 are each independently a hydrogen atom or an alkyl having 1 to 12 carbon atoms.
  • D 1 represents the following formula (V 1 ) or the following formula (V 2 ), and D 2 represents the following formula (V 1 ) or the following formula (V 3 ):
  • R 8 , R 9 and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. it is shown.
  • D 1 is represented by the following formula (V 2) R 4 m 1 pieces of when it is and R 5, D 2 is m 2 when it is the following formula (V 3)
  • R 6 and R 7 , and R 8 may be bonded to each other to form a ring structure, and n 1 represents an integer of 0 to 20, and X 2 represents SO or SO 2, Y 5, Y 6 , Y 7, Y 8, Z 5, Z 6, Z 7 and Z 8 are each And a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, and 1 to 12 carbon atoms. Represents a haloalkyl group, a halogen atom or a nitro group.
  • D 1 represents the following formula (V 1 ) or the following formula (V 2 )
  • D 2 represents the following formula (V 1 ) or the following formula (V 3 )
  • D 3 represents Formula (V 1 ) or the following formula (V 4 ) is shown:
  • R 8 , R 9 , R 10 , R 13 , R 14 and R 15 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms, wherein R 3 and D 1 in the formula (A) are represented by the following formula (V 2 ):
  • m 1 R 4 and R 5 and D 2 are the following formula (V 3 )
  • m 2 R 6 and R 7 , R 8 and D 3 are the following formula (V 4 ) m 3 pieces of R 11 and R 12 when and R 13, are, among
  • m 1 R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. And an arylalkyl group having 7 to 15 carbon atoms, and m 1 represents an integer of 1 to 7)
  • m 2 R 6 and R 7 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. Or an arylalkyl group having 7 to 15 carbon atoms, and m 2 represents an integer of 1 to 7.
  • m 3 R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. And an arylalkyl group having 7 to 15 carbon atoms, m 3 represents an integer of 1 to 7)
  • the compound according to the present invention is characterized in that, in the above-described present invention, the compound represented by the formula (A) is represented by the following formula (A 1 ).
  • R 1 , R 2 and R 3 , X 1 , Y 1 , Y 2 , Y 3 and Y 4 , and Z 1 , Z 2 , Z 3 and Z 4 are the same as those in the formula (A).
  • R 3 ′ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms.
  • R 3 and R 3 ′ may be bonded to each other to form a ring structure.
  • the compound according to the present invention is characterized in that the compound represented by the formula (A) is represented by the following formula (A 2 ).
  • D 1 and D 2 , R 1 , R 2 , R 3 , R 8 , R 9 and R 10 , n 1 , X 1 and X 2 , Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 , and Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 and Z 8 are defined by the above formula (A) and the above formula ( Same as B 1 ).
  • the compound according to the present invention is characterized in that, in the above-described present invention, the compound represented by the formula (A) is represented by the following formula (A 3 ).
  • D 1 , D 2 and D 3 , R 1 , R 2 , R 3 , R 8 , R 9 , R 10 , R 13 , R 14 and R 15 , n 1 , n 2 and n 3 , w, X 1 , X 2 and X 3 , Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 , Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 , Z 10 , Z 11 and Z 12 are the same as those in the above formula (A) and the above formula (B 2 ). Is the same.)
  • the base proliferating agent according to the present invention is characterized by comprising the aforementioned compound of the present invention.
  • the base-reactive resin composition according to the present invention contains the above-described base proliferating agent according to the present invention and a base-reactive compound.
  • the base-reactive resin composition according to the present invention is characterized by containing the base proliferating agent according to the present invention, a base generator and a base-reactive compound.
  • the base-reactive resin composition according to the present invention is characterized in that, in the above-described present invention, the base generator is a photobase generator.
  • the base-reactive resin composition according to the present invention is characterized in that, in the above-described present invention, the base-reactive compound is at least one selected from the group consisting of an epoxy compound, a silicon compound, and an oxetane compound.
  • the compound and the base proliferating agent according to the present invention have high sensitivity, can be decomposed by the action of a base to generate a base in a chain, and have a heterocycle (heterocycle).
  • the base growth reaction rate can be freely controlled, and a compound capable of generating bases in a chain and a base proliferating agent are obtained.
  • the compounds of the present invention, base proliferating agents, Coexisting with a base-reactive compound such as an epoxy compound that reacts with the base enables the base-reactive compound to be efficiently cured by the base generated by growth.
  • the base-reactive compound according to the present invention contains the base proliferating agent of the present invention or the base proliferating agent of the present invention and a base generating agent, thereby generating a base generated from the base proliferating agent and a base such as an epoxy compound.
  • the reaction with the reactive compound proceeds in a chain, resulting in an excellent curing rate and reaction efficiency, resulting in a base-reactive resin composition that is rapidly cured and sufficiently cured.
  • the base-reactive resin composition of the present invention that exhibits this effect can be suitably used for, for example, a highly sensitive photocuring material, resist material (pattern forming material), and the like.
  • FIG. 3 is a diagram showing a synthesis scheme of the formula (A 2 ) when the base moiety is 1,2-bis (4-piperidyl) ethane.
  • FIG. 3 is a diagram showing a synthesis scheme of the formula (A 2 ) when the base moiety is 1,2-bis (4-piperidyl) ethane.
  • FIG. 5 is a diagram showing a synthesis scheme of the formula (A 2 ) when the base part is isophoronediamine (1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane). It is a diagram illustrating a synthetic scheme for formula (A 3). It is the figure which showed the relationship between a heating time, the conversion rate of a base growth agent, and the production
  • the base proliferating agent according to the present invention is a compound represented by the following formula (A).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl having 6 to 14 carbon atoms.
  • Q is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 7 carbon atoms
  • X 1 represents SO or SO 2 and Y 1 , Y 2 , Y 3 , Y 4 , Z 1 , Z 2 , Z 3 and Z 4 are each independently a hydrogen atom or an alkyl having 1 to 12 carbon atoms.
  • D 1 represents the following formula (V 1 ) or the following formula (V 2 ), and D 2 represents the following formula (V 1 ) or the following formula (V 3 ):
  • R 8 , R 9 and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. it is shown.
  • D 1 is represented by the following formula (V 2) R 4 m 1 pieces of when it is and R 5, D 2 is m 2 when it is the following formula (V 3) R 6 and R 7 , and R 8 may form a ring structure by combining at least two of these R.
  • N 1 represents an integer of 0 to 20
  • 2 represents SO or SO 2
  • Y 5, Y 6 , Y 7, Y 8, Z 5, Z 6, Z 7 and Z 8 it Independently, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, and 1 to 12 carbon atoms
  • D 1 represents the following formula (V 1 ) or the following formula (V 2 )
  • D 2 represents the following formula (V 1 ) or the following formula (V 3 )
  • D 3 represents Formula (V 1 ) or the following formula (V 4 ) is shown:
  • R 8 , R 9 , R 10 , R 13 , R 14 and R 15 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms, wherein R 3 and D 1 in the formula (A) are represented by the following formula (V 2 ):
  • m 1 R 4 and R 5 and D 2 are the following formula (V 3 )
  • m 2 R 6 and R 7 , R 8 and D 3 are the following formula (V 4 ) m 3 pieces of R 11 and R 12 when and R 13, are, among
  • m 1 R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. And an arylalkyl group having 7 to 15 carbon atoms, and m 1 represents an integer of 1 to 7)
  • m 2 R 6 and R 7 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. Or an arylalkyl group having 7 to 15 carbon atoms, and m 2 represents an integer of 1 to 7)
  • m 3 R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. And an arylalkyl group having 7 to 15 carbon atoms, and m 3 represents an integer of 1 to 7)
  • the formula (A) has a Q group
  • the Q group is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms.
  • the Q group is the following R 3 ′ group (A 1 )
  • the Q group is a group represented by the formula (B 1 )
  • the following formula (A 2 ) is obtained and the Q group is a group represented by the formula (B 2 )
  • the following formula (A 3 ) is obtained.
  • Formula (A 1 ), Formula (A 2 ), and Formula (A 3 ) are given as specific embodiments of Formula (A).
  • Two of R 6, R 7 , and R 8 may be bonded to each other to form a ring structure.
  • m 1 R 4 and R 5 and D 2 are the formula (V 3 ).
  • m 2 pieces of R 6 and R 7, R 8, D 3 is m 3 pieces of R 11 and R 12 in the case where formula (V 4), and R 13, of these R, at least two R May be bonded to each other to form a ring structure.
  • R 1 , R 2 and R 3 , X 1 , Y 1 , Y 2 , Y 3 and Y 4 , and Z 1 , Z 2 , Z 3 and Z 4 are the same as those in the formula (A).
  • R 3 ′ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms.
  • R 3 and R 3 ′ may be bonded to each other to form a ring structure.
  • D 1 and D 2 , R 1 , R 2 , R 3 , R 8 , R 9 and R 10 , n 1 , X 1 and X 2 , Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 , and Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 and Z 8 are defined by the above formula (A) and the above formula ( Same as B 1 ).
  • D 1 , D 2 and D 3 , R 1 , R 2 , R 3 , R 8 , R 9 , R 10 , R 13 , R 14 and R 15 , n 1 , n 2 and n 3 , w, X 1 , X 2 and X 3 , Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 , Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 , Z 10 , Z 11 and Z 12 are the same as those in the above formula (A) and the above formula (B 2 ). Is the same.)
  • the difference between the formula (A 3 ′) and the formula (A 3 ′′) is the presence of the following structure.
  • the nitrogen atom between — (CH 2 ) n 1 — and — (CH 2 ) n 2 — and the carbon atom on the carbonyl group near the thioxanthene ring containing X 3 are directly bonded.
  • the alkyl group preferably has 1 to 6 carbon atoms, and the cycloalkyl group has carbon atoms. Is preferably 6 to 8, and when it is an aryl group, it preferably has 6 to 10 carbon atoms, and when it is an arylalkyl group, it preferably has 7 to 11 carbon atoms.
  • R 1 , R 2 , R 9 , R 10 , R 14 and R 15 include, for example, methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, phenyl group, tolyl group, naphthyl group, benzyl Group, phenethyl group, naphthylmethyl group and the like.
  • R 3 , R 3 ′, R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 and Q in the above formula are alkyl groups
  • the number of carbon atoms is 2 to 6 is preferable, and examples thereof include an ethyl group, a propyl group, a butyl group, and a hexyl group.
  • the carbon number is preferably 6 to 8, and examples thereof include a cyclohexyl group and a cyclooctyl group.
  • the number of carbon atoms is preferably 6 to 10, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
  • the carbon number is preferably 7 to 11, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 , Z 10 , Z 11 and Z 12 are alkyl groups, preferably 1 to 6 carbon atoms, and cycloalkyl groups In this case, the number of carbon atoms is preferably 6 to 8. When an aryl group is used, the number of carbon atoms is preferably 6 to 10.
  • the number of carbon atoms is preferably 7 to 11. In this case, the number of carbon atoms is preferably 1 to 6, and when a halogen atom is used, a fluorine atom or a chlorine atom is preferable.
  • 5 , Z 6 , Z 7 , Z 8 , Z 9 , Z 10 , Z 11 and Z 12 include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a phenyl group.
  • the above alkyl group, cycloalkyl group, aryl group, arylalkyl group and haloalkyl group may have a substituent.
  • substituents include an amino group, an alkoxy group, an alkoxycarbonyl group, an acyl group. Group, acyloxy group, hydroxy group and the like.
  • R 3 and Q may be bonded to each other to form a ring structure” and “R 3 and R 3 ′ may be bonded to each other to form a ring structure”.
  • the ⁇ structure '' may be any ring structure such as a saturated aliphatic ring, an unsaturated aliphatic ring, and an aromatic ring.
  • a hydrogen atom bonded to a carbon atom constituting these rings is, for example, Ring structure substituted with alkyl group such as methyl group, ethyl group, propyl group, hydroxy group, mercapto group, cyano group, nitro group, for example, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom
  • a ring structure having a hetero atom (oxygen atom, sulfur atom, etc.) other than a nitrogen atom in the chain is also included in the concept of “ring structure” in the above formula.
  • ring structures include, for example, aziridine ring (3-membered ring), azetidine ring (4-membered ring), pyrrolidine ring (5-membered ring), piperidine ring (6-membered ring), hexamethyleneimine ring (azepane).
  • a nitrogen-containing saturated aliphatic ring having 2 to 10 carbon atoms such as (11-membered ring); for example, 2-methylaziridine ring (3-membered ring), 2-methylazetidine ring (4-membered ring), 3-methylazetidine Ring (4-membered ring), 2,5-dimethylpyrrolidine ring (5-membered ring), 2,5-diethylpyrrolidine ring (5-membered ring), 2,5-dipropylpyrrolidine ring (5-membered ring), 2,6 -Dimethylpiperidine ring (6-membered ring), 2 6-diethylpipe
  • a substituted nitrogen-containing saturated aliphatic ring having 2 to 10 carbon atoms for example, an oxazolidine ring (5-membered ring), a thiazolidine ring (5-membered ring), a morpholine ring (6-membered ring), a thiomorpholine ring ( A nitrogen-containing saturated aliphatic ring having 3 to 10 carbon atoms and having a hetero atom other than the nitrogen atom (oxygen atom, sulfur atom, etc.) in the chain, such as a 2,6-dimethylmorpholine ring (6-membered ring) ), 2,6-diethylmorpholine ring (6-membered ring), 2,6-dipropylmorpholine ring (6-membered ring), 2,6-dimethylthiomorpholine ring (6-membered ring), 2,6-diethylthiomorpholine Rings (6-membered rings), 2,6-dipropylthiomorpho
  • Nitrogen unsaturated aliphatic ring or aromatic ring such as 2,5-dimethylpyrrole ring (5-membered ring), 2,5-diethylpyrrole ring (5-membered ring), 2,5-dipropylpyrrole ring (5-membered ring) 2,5-dimethylimidazole ring (5-membered ring), 2,5-diethylimidazole ring (5-membered ring), 2,5-dipropylimidazole ring (5-membered ring), 3,5-dimethylpyrazole ring (5 Member), 3,5-diethylpyrazole ring (5-membered ring), 3,5-dipropylpyrazole ring (5-membered ring), etc., and hydrogen bonded to carbon atoms constituting the unsaturated aliphatic ring or aromatic ring Atom is alkyl such as methyl, ethyl, propyl , A hydroxy group, a mercapto group,
  • n 1 in formula (A 2 ) and formula (B 1 ), and n 1 , n 2 , and n 3 in formula (A 3 ) and formula (B 2 ) are each independently an integer of 0 to 20. Is preferably an integer of 0 to 8.
  • n 1 in Formula (V 2), m 2 in the formula (V 3), m 3 in the formula (V 4) is independently an integer of 1-7, and an integer of 1 to 3 It is preferable to do.
  • R 3 and Q are bonded to each other to form a ring structure (formula (G-3) Formula (G-4) and Formula (G-5)).
  • R 3 and R 8 are both hydrogen atoms
  • D 1 is Formula (V 2 )
  • m 1 in Formula (V 2 ) is 1.
  • R 4 and R 5 are both hydrogen atoms
  • D 2 is the formula (V 3 )
  • m 2 in the formula (V 3 ) is 1, and both R 6 and R 7 are hydrogen.
  • n 1 is 4 (or R 3 and R 8 are both hydrogen atoms
  • D 1 is the formula (V 2 )
  • m 1 is 5, and all five R 4 and R 5 are hydrogen atoms
  • D 2 is the formula (V 3 )
  • m 2 in the formula (V 3 ) is 1, and Specific examples in which R 6 and R 7 are both hydrogen atoms and n 1 is 0.) (Formula (G-6)).
  • Q is the formula (B 1 ).
  • D 1 is the formula (V 2 ), m 1 in the formula (V 2 ) is 1, and R 4 and R 5 are both hydrogen atoms, and D 2 Is the formula (V 3 ), m 2 in the formula (V 3 ) is 1, and R 6 and R 7 are both hydrogen atoms.
  • R 3 and R 8 are both hydrogen atoms
  • D 1 is formula (V 1 )
  • D 2 is (V 3 )
  • Q is the formula (B 1 ).
  • D 1 is the formula (V 2 )
  • m 1 in the formula (V 2 ) is 3
  • the formula in that case is the following formula (V 2A )
  • R 4a , R 4b , R 5a , R 5b and R 5c in the (V 2A ) are all hydrogen atoms, and R 3 and R 4C are bonded via a dimethylene chain having 2 carbon atoms.
  • D 2 is the formula (V 3 ), m 2 in the formula (V 3 ) is 3, and the formula in that case is represented by the following formula ( V 3A ), and R 6b , R 6c , R 7a , R 7b and R 7c in the formula (V 3A ) are all hydrogen atoms, and R 6a and R 8 have 2 carbon atoms. and via a dimethylene chain be those which combine to form a ring structure, examples of when n 1 is 2 (formula (G -8)).
  • Q is the formula (B 1 ).
  • D 1 is the formula (V 2 )
  • m 1 in the formula (V 2 ) is 3, and the formula in that case is the following formula (V 2A )
  • R 4a , R 4b , R 5a , R 5b and R 5c are all hydrogen atoms
  • R 3 and R 4C represent a dimethylene chain having 2 carbon atoms.
  • D 2 is the formula (V 3 ), m 2 in the formula (V 3 ) is 3, and the formula in that case is the following formula are those represented by (V 3A), R 6b in the formula (V 3A), R 6c, R 7a, an R 7b and R 7c are all hydrogen atoms, carbon atoms in the R 6a and R 8 A specific example (Formula (G-8b)) in the case where they are bonded to each other via two dimethylene chains to form a ring structure.
  • Q is the formula (B 1 ).
  • D 1 is Formula (V 2 ), m 1 in Formula (V 2 ) is 1, and both R 4 and R 5 are hydrogen atoms.
  • D 2 is the formula (V 3 ), m 2 in the formula (V 3 ) is 1, R 6 and R 7 are both hydrogen atoms, n 1 is 0,
  • Q is the formula (B 1 ).
  • the structure of the following formula is a specific example in which R 3 and R 8 jump over (CH 2 ) n1 and bond to form a ring structure.
  • R 3 , R 8, and R 13 are all hydrogen atoms
  • D 1 is formula (V 2 )
  • the formula (V 2 ) m 1 is 1
  • R 4 and R 5 are both hydrogen atoms
  • D 2 is the formula (V 3 )
  • m 2 in the formula (V 3 ) is 1.
  • R 6 and R 7 are both hydrogen atoms
  • D 3 is the formula (V 4 )
  • m 3 in the formula (V 4 ) is 1
  • both R 11 and R 12 are hydrogen.
  • Q is the formula (B 2 ).
  • R 3 and R 8 are all hydrogen atoms
  • D 1 is Formula (V 2 )
  • M 1 is 1 and R 4 and R 5 are both hydrogen atoms
  • D 2 is the formula (V 3 )
  • m 2 in the formula (V 3 ) is 1
  • R 2 6 and R 7 are both hydrogen atoms
  • n 1 and n 2 are all 1 and w is 0 (D 3 , R 13 and n 3 do not exist) (formula (G-11
  • Q becomes Formula (B 2 ).
  • Such a base proliferating agent according to the present invention has a property of decomposing by the action of a base to generate a base (amine).
  • the reaction scheme for the formula (A 1 ) is shown in FIG. 1
  • the reaction scheme for the formula (A 2 ) is shown in FIG. 2
  • the reaction scheme for the formula (A 3 ) is shown in FIG. 3, FIG. Show.
  • the base proliferating agent of the present invention decomposes in a self-proliferating manner only by allowing a smaller equivalent amount of base to act on a certain amount, and finally the entire amount decomposes, A large amount of base corresponding to the amount of the base proliferating agent is generated.
  • HNR′R ′′ is an arbitrary base (amine).
  • the base proliferating agent represented by the formula (A) has high sensitivity and has a heterocycle (heterocycle). Therefore, the base proliferative reaction rate can be freely controlled by changing the oxidation number of the heteroatom.
  • the X 1 , X 2 and X 3 groups that are atoms are SO or SO 2 , but the decomposition rate is faster when the hetero atom is SO 2 . Therefore, the growth reaction rate can be easily adjusted by selecting such heteroatoms.
  • a decomposition intermediate in the decomposition of the formula (A) is shown in the following formula. Since the base proliferating agent according to the present invention becomes a decomposition intermediate having the following structure, the stronger the electron withdrawing property of the X group, the more the anion is stabilized. That is, the ease with which anions are generated can be controlled by the oxidation number of heteroatoms.
  • the base proliferating agent according to the present invention is highly soluble in an organic solvent, when mixed with a base-reactive compound to form a base-reactive resin composition, it can be easily compatible with the base-reactive compound. it can.
  • the base proliferating agent according to the present invention is such that Y 1 , Y 2 , Y 3 , Y 4 , Z 1 , Z 2 , Z 3, Z 4, etc., at least one of Y group and Z group is not a hydrogen atom. Therefore, the solubility in organic solvents is excellent.
  • the base proliferating agent represented by the formula (A 2 ) and the formula (A 3 ) is a base proliferating agent in which all of the Y group and the Z group are hydrogen atoms. Compared with, it is a preferable base proliferating agent because of its excellent solubility in organic solvents. That is, since the base proliferating agent represented by the formula (A 2 ) and the formula (A 3 ) has two or more asymmetric points, it becomes a diastereomeric mixture, and thus has a higher solubility in organic solvents than the conventional one. It is thought that the price will rise dramatically.
  • the base proliferating agent according to the present invention since it has high heat resistance, when it is mixed with a base-reactive compound to form a base-reactive resin composition, it becomes a resin composition with high thermal stability. Therefore, when forming a pattern using the said resin composition, a favorable pattern can be formed. That is, the base proliferating agent according to the present invention has higher heat resistance than the base proliferating agent in which all of the Y group and the Z group are hydrogen atoms. Therefore, when the base proliferating agent according to the present invention is mixed with a base-reactive compound to form a base-reactive resin composition, the exposed portion is cured during baking in pattern formation, but the unexposed portion. Since is not cured, a good pattern can be formed.
  • the base that acts on the base proliferating agent is not particularly limited, and conventionally known bases can be used.
  • bases such as primary amines, secondary amines, tertiary amines, and pyridyl groups can be used.
  • a compound to be contained, a hydrazine compound, an amide compound, a quaternary ammonium hydroxide salt, a mercapto compound, a sulfide compound, a phosphine compound and the like can be used.
  • Examples of bases generated by decomposition of the base proliferating agent represented by the formula (A) include the following formulas (Am-1), (Am -2) or an amine represented by the formula (Am-3).
  • R 3 , R 3 ′, R 8 , R 13 , D 1 , D 2 , D 3 , n 1 , n 2, and n 3 , and w are the formulas (A) and (A 1 ), the formula (A 2 ) and the formula (A 3 ).
  • FIG. 10 shows a synthesis scheme for the formula (A 3 ).
  • R 1 , R 2 , R 9 , R 10 , R 14 , and R 15 are sometimes shown as hydrogen atoms.
  • (1) to (4) or (1) to (3), (5) and (6) may be followed, but not particularly limited thereto.
  • a carbonyl group of a thioxanthone derivative is reduced with lithium aluminum hydride to obtain a 9H-thioxanthene derivative.
  • 9H-thioxanthene derivative such a commercially available product may be used as it is.
  • the sulfur atom of the thioxanthene ring is oxidized with metachloroperbenzoic acid (mCPBA) to be converted into a sulfinyl group or a sulfonyl group.
  • mCPBA metachloroperbenzoic acid
  • An amide bond is formed by diisocyanic acid (limited to those in which R 3 , R 8 and R 13 are hydrogen atoms). (5) React with chloroformate-4-nitrophenyl or triphosgene to activate the carbonyl group. (6) The active carbonyl compound is reacted with an amine to obtain the target product.
  • the base proliferating agent according to the present invention is preferably used as a base proliferating agent composition in combination with a base generator.
  • the base generator is generally a substance that generates a base when irradiated with active energy rays such as light or heated.
  • the base generator is not particularly limited, but a photobase generator that generates a base upon irradiation with active energy rays such as light, or a thermal base generator (thermal latent base generator) that generates a base by heating is used. It is preferable to do. Among these, it is particularly preferable to use a photobase generator because it is not necessary to perform heat treatment at a high temperature in order to generate a base.
  • the photobase generator is not particularly limited, but conventionally known o-nitrobenzyl type photobase generators, (3,5-dimethoxybenzyloxy) carbonyl type photobase generators, amyloxyimino group type photobase generators. And dihydropyridine type photobase generators.
  • an o-nitrobenzil type photobase generator is preferably used because of its excellent base generation efficiency and ease of synthesis.
  • photobase generator for example, oxime ester compounds, ammonium compounds, benzoin compounds, dimethoxybenzyl urethane compounds, o-nitrobenzyl urethane compounds and the like disclosed in JP 2000-330270 A are used. You may do it.
  • base generators disclosed in JP2009-280785A, JP2010-84144A, and JP2011-236416A can be used. These are carboxylates composed of carboxylic acids and bases that are decarboxylated by light irradiation.
  • equation can also be used.
  • —R— represents — (CH 2 ) 6 — or —CH 2 CH 2 CH 2 CH (CH 3 ) CH 2 —.
  • the —OMe group represents —OCH 3 (methoxy group).
  • the thermal base generator is not particularly limited, but is decomposed by a salt of an organic acid and a base that is decarboxylated and decomposed by heating, an intramolecular nucleophilic substitution reaction, a Rossen rearrangement reaction, a Beckmann rearrangement reaction, etc.
  • a compound to be released or a compound which causes some reaction by heating to release a base is preferably used.
  • disassembles by heating is used preferably.
  • thermal base generator examples include salts of trichloroacetic acid described in British Patent No. 998949, salts of alpha-sulfonylacetic acid described in US Pat. No. 4,060,420, salts of propylic acids described in JP-A-59-157737, 2 -Carboxyl carboxamide derivatives, salts of base components described in JP-A-59-168440 with thermally decomposable acids using an alkali metal or alkaline earth metal in addition to an organic base, described in JP-A-59-180537 Hydroxam carbamates utilizing the Lossen rearrangement, aldoxime carbamates described in JP-A-59-195237, which generate nitriles by heating, British Patent No.
  • JP-A No. 2000-330270 a compound that generates a base by heating as disclosed in JP-A No. 2000-330270 may be used.
  • thermal base generators include guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, guanidine phenylsulfonylacetate, guanidine p-chlorophenylsulfonylacetate, guanidine p-methanesulfonylphenylsulfonylacetate, phenylpropiol.
  • Examples include potassium acid, guanidine phenylpropiolate, cesium phenylpropiolate, guanidine p-chlorophenylpropiolate, guanidine p-phenylene-bis-phenylpropiolate, tetramethylammonium phenylsulfonylacetate and tetramethylammonium phenylpropiolate.
  • the bases constituting the base proliferating agent and the bases constituting the base generating agent may be made common. Since the bases are common, the base proliferating agent is efficiently decomposed.
  • the base proliferating agent may be used alone or in combination of two or more.
  • the base-reactive resin composition of the present invention is a base proliferating agent represented by at least one of the above formula (A), formula (A 1 ), formula (A 2 ), and formula (A 3 ), or such a base.
  • a proliferation agent and a base generator (base proliferation agent composition) and a base-reactive compound that undergoes a curing reaction in the presence of a base are contained as essential components.
  • the base-reactive compound constituting the base-reactive resin composition of the present invention reacts with the action of a base generated by a base proliferating agent or a base proliferating agent and a base generator (base proliferating agent composition), and crosslinks.
  • a base generated by a base proliferating agent or a base proliferating agent and a base generator base proliferating agent composition
  • crosslinks can be used, and various compounds can be used.
  • Such base-reactive compounds may be used alone or in combination of two or more.
  • Usable epoxy compounds include, for example, diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol poly Glycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Lysidyl ether, glycerin polyglycidyl
  • an alkoxysilane compound or a silane coupling agent can be used as the silicon-based compound (silicon-based resin).
  • alkoxysilane compounds include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, phenyl Examples include trimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. These alkoxysilane compounds may be used alone or in combination of two or more.
  • silane coupling agent examples include vinyl silane, acrylic silane, epoxy silane, amino silane, and the like.
  • vinyl silane examples include vinyl trichlorosilane, vinyl tris ( ⁇ -methoxyethoxy) silane, vinyl triethoxysilane, vinyl trimethoxysilane, and the like.
  • acrylic silane examples include ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, and the like.
  • epoxy silane examples include ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and the like.
  • aminosilanes N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltrimethoxysilane, N-phenyl- Examples thereof include ⁇ -aminopropyltrimethoxysilane.
  • silane coupling agents examples include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, and ⁇ -chloropropylmethyldiethoxysilane. These silane coupling agents may be used alone or in combination of two or more.
  • oxetane resin a monomeric oxetane compound, a dimer oxetane compound, or the like can be used.
  • Usable oxetane compounds include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylate bis [(3-ethyl-3-oxetanyl) Methyl] ester, xylylene oxetane such as 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3-((((3-ethyloxetane-3-yl) methoxy) methyl ) Oxetane (or 3-(((3-ethyloxetane-3-yl) methoxy) methyl) -3-ethyloxe
  • R and R ′ are, for example, alkyl groups having 1 to 12 carbon atoms, but are not particularly limited thereto.
  • the base-reactive compound As hereinafter, specific examples of the base-reactive compound will be given.
  • the polymer compound 2-5 undergoes elimination and decarboxylation by the action of a base.
  • the polymer compound 2-8 causes a elimination reaction by the action of a base to produce a carboxylic acid.
  • the above-mentioned base reactive compound No. 2-1. 2-8 is a polymer group that undergoes elimination reaction by the action of a base and changes polarity, and is applied as a material (resist material) that performs patterning using the fact that solubility changes before and after decomposition. can do.
  • the base-reactive compound constituting the base-reactive resin composition of the present invention can be an epoxy compound having at least one epoxy group.
  • an epoxy compound can be made into a polymer by ring-opening polymerization of an epoxy group by allowing a base to act on an epoxy compound having at least two epoxy groups.
  • such an epoxy compound can be chemically modified by adding a base to the epoxy compound.
  • An example of an epoxy compound showing polymerization reactivity is shown below.
  • a silicon compound having at least one silanol group or alkoxysilyl group can be used as the base-reactive compound. Further, by causing a base to act on a silicon compound having at least two silanol groups or alkoxysilyl groups, such a silicon compound can be made into a polymer by condensation polymerization of silanol groups or alkoxysilyl groups. Specific examples of silicon compounds showing polymerization reactivity (No. 5-2 to No. 5-4 are polymers) are shown below.
  • the range of the irradiation light wavelength and the exposure amount in the product) depends on the type and amount of the photobase generator and the type of the base reactive compound constituting the base reactive resin composition (photosensitive resin composition).
  • the wavelength may be selected from the range of 190 to 400 nm and the exposure amount may be selected from the range of 100 to 10000 mJ / cm 2 , and the higher wavelength region can be obtained by using a sensitizer described later. Can also be used.
  • the irradiation time of irradiation light may be possible even for several seconds, it may be approximately 10 seconds or more, and preferably 1.5 to 20 minutes.
  • the heating conditions in the case of using a thermal base generator may be appropriately determined according to the type and amount of the thermal base generator used, the type of the base reactive compound constituting the base reactive resin composition, and the like.
  • the heating temperature may be about 50 to 150 ° C. and the heating time may be 1 to 1800 minutes.
  • a base-reactive resin composition when used with a base proliferating agent and a base-reactive compound without using a base generator, a desired base that can be decomposed by the base proliferating agent should be added. It is preferable to add a base common to the base proliferating agent.
  • the content of the base proliferating agent in the base-reactive resin composition of the present invention is based on 100 parts by weight of the base-reactive compound in consideration of the case where the molecular weight of the base-reactive compound such as an epoxy compound is relatively low. It is desirable to select from the range of approximately 0.1 to 350 parts by mass, and preferably 0.1 to 60 parts by mass. Further, the content of the base proliferating agent is preferably 1 to 60 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the base-reactive compound, and 2 to 20 parts by mass. More preferably, the content is 2 to 15 parts by mass.
  • the base proliferating agent may be selected from the range of 10 to 90 mol% in terms of the amine functional group ratio of the base proliferating agent to 100 mol of the epoxy group in the base reactive compound, and it should be 40 to 80 mol%. Is preferred.
  • the amine functional group ratio is expressed as mol% of the number of amino groups in the base proliferating agent with respect to the number of epoxy groups in the epoxy compound when the target base reactive compound is an epoxy compound, for example.
  • an amine functional group ratio of 10 mol% means that 10 amino groups (10 mol) are generated from the base proliferating agent with respect to 100 epoxy groups (100 mol) in the base-reactive compound. It refers to a base proliferating agent (the same applies to the amine functional group ratio for the base generator described later).
  • an epoxy compound having an epoxy group is taken as an example of the base-reactive compound, but the same applies to other base-reactive compounds such as silicon compounds.
  • the content of the base generating agent is the amount of the base proliferating agent and the base generating agent described above. It is preferable to include a base generator so as to correspond to the blending ratio (mass ratio). Further, the content of the base generator is preferably 0.5 to 40 parts by mass with respect to 100 parts by mass of the base-reactive compound. If the content of the base generator is less than 0.5 parts by mass, it may not act on the base proliferating agent and the base reactive compound may not be allowed to react rapidly, whereas the content of the base generator is 40.
  • the content of the base generator is preferably 0.5 to 35 parts by weight, more preferably 2 to 35 parts by weight with respect to 100 parts by weight of the base-reactive compound, and 5 to 20 parts by weight. It is particularly preferable to do this. Further, it may be selected from the range of 0.1 to 50 mol per monomer unit of the base reactive compound (epoxy compound or silicon compound). The base generator may be selected from the range of 5 to 90 mol% in terms of the amine functional group ratio of the base generator to 100 mol of the epoxy group in the base-reactive compound. Is preferred.
  • the base-reactive resin composition of the present invention has the above-described No. 1 as a base-reactive compound. 4-1. No. 4-14 and other epoxy compounds exhibiting polymerization reactivity (polymerizable epoxy compounds), 5-1. A silicon compound (polymerizable silicon compound) exhibiting polymerization reactivity such as 5-6 is preferable.
  • a base-reactive resin composition is polymerized by the action of light or heat to give a polymer.
  • the base-reactive resin composition of the present invention preferably further contains a thiol compound.
  • the thiol compound acts as a curing functional group such as epoxy when used in combination with an epoxy compound or the like.
  • a polythiol compound having two or more thiol groups is preferably used.
  • These thiol compounds may be used alone or in combination of two or more.
  • the ratio is 0.8 / 1.2 to 1.2 / 0.8. If this ratio is in the range of 0.3 / 1.7 to 1.7 / 0.3, a large amount of unreacted thiol groups and epoxy groups (or oxetane groups) remain in the cured product. This can be prevented, and the tendency for the mechanical properties of the cured product to decrease can be suppressed.
  • the resin composition is dissolved in an organic solvent to prepare a coating solution, and the prepared coating solution is used as a suitable substrate or the like. Apply to a solid surface and dry to form a coating. And after performing pattern exposure with respect to the formed coating film and generating a base, it heat-processes on predetermined conditions, The polymerization reaction of the base reactive compound contained in a base reactive resin composition To encourage.
  • the pattern can be obtained by immersing this in a solvent that causes a difference in solubility between the exposed part and the unexposed part and developing.
  • the base-reactive resin composition of the present invention contains the base proliferating agent of the present invention, the polymerization reaction proceeds even at room temperature, but it is preferable to perform a heat treatment in order to allow the polymerization reaction to proceed efficiently.
  • the heat treatment conditions may be appropriately determined depending on the exposure energy, the type of base generated from the base proliferating agent to be used, and the type of base-reactive compound such as an epoxy compound or silicon compound. It is preferably in the range of 150 ° C., particularly preferably in the range of 60 ° C. to 130 ° C.
  • the heating time is preferably 10 seconds to 60 minutes, particularly preferably 60 seconds to 30 minutes.
  • a sensitizer can be added to expand the photosensitive wavelength region and increase the sensitivity.
  • the sensitizer that can be used is not particularly limited.
  • the addition amount of the sensitizer is appropriately determined depending on the photobase generator and base-reactive compound used, the sensitivity required, and the like. However, it is preferably in the range of 1 to 30% by mass relative to the whole base-reactive resin composition. If the sensitizer is less than 1% by mass, the sensitivity may not be sufficiently increased. On the other hand, if the sensitizer exceeds 30% by mass, the sensitivity may be excessive.
  • the addition amount of the sensitizer is particularly preferably in the range of 5 to 20% by mass with respect to the whole base-reactive resin composition.
  • a solvent When applying the base-reactive resin composition of the present invention to a predetermined base material, a solvent may be appropriately contained as necessary. By including a solvent in the base-reactive resin composition, the coating ability can be increased and workability is improved.
  • the solvent is not particularly limited.
  • aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene; cyclohexane, methylcyclohexane, ethylcyclohexane, cyclohexene, dipentene, n-pentane, Isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane, p-menthane, o-menthane, m-menthane, etc.
  • the content of the solvent is uniform when, for example, the base-reactive resin composition is applied on a predetermined substrate to form a layer of the base-reactive resin composition. What is necessary is just to select suitably so that it may be applied to.
  • additives suitably to the base reactive resin composition of this invention in the range which does not inhibit the objective and effect of this invention.
  • additives that can be used include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, Examples thereof include a plasticizer, a plastic accelerator, an anti-sagging agent, and a curing accelerator. One of these may be used alone, or two or more may be used in combination.
  • the base-reactive resin composition of the present invention described above is a base generated from a base proliferating agent by containing the base proliferating agent of the present invention or the base proliferating agent of the present invention, a base generator and a base-reactive compound.
  • -Reactive resin composition in which the reaction between the compound and a base-reactive compound such as an epoxy-based compound proceeds in a chain, has excellent curing speed and reaction efficiency, is quickly cured, and is sufficiently cured It becomes.
  • the base-reactive resin composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material (pattern forming material), and the like.
  • the molded body applied as a photo-curing material can be used as a member in a field where characteristics such as heat resistance, dimensional stability, and insulation are effective, for example, paint or printing ink, color filter, film for flexible display, semiconductor, etc.
  • characteristics such as heat resistance, dimensional stability, and insulation are effective, for example, paint or printing ink, color filter, film for flexible display, semiconductor, etc.
  • a semiconductor device, an electronic component, an interlayer insulating film, a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, a building member, or the like is provided.
  • the formed pattern has heat resistance and insulation, for example, color filters, flexible display films, electronic components, semiconductor devices, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, reflective It can be advantageously used as a protective film, other optical member or electronic member.
  • Example 1 Production of base proliferating agent (1): 50mL egg plant flask was charged with Formula intermediates represented by (H-4) 0.22g (0.74 ⁇ 10 -3 mol) and pyridine 0.05g (0.74 ⁇ 10 -3 mol) , anhydrous tetrahydrofuran 10ml was added. While stirring, 0.15 g (0.74 ⁇ 10 ⁇ 3 mol) of chloroformate-4-nitrophenyl (NP-Cl) dissolved in 15 mL of dehydrated tetrahydrofuran was slowly added dropwise and stirred at room temperature for 4 hours.
  • Formula intermediates represented by (H-4) 0.22g (0.74 ⁇ 10 -3 mol) and pyridine 0.05g (0.74 ⁇ 10 -3 mol)
  • anhydrous tetrahydrofuran 10ml was added. While stirring, 0.15 g (0.74 ⁇ 10 ⁇ 3 mol) of chloroformate-4-nitrophenyl (NP-Cl) dissolved in 15
  • Example 2 Production of base proliferating agent (2): In a 50 mL eggplant flask, 0.50 g (1.0 ⁇ 10 ⁇ 3 mol) of the intermediate represented by the formula (H-6) was dissolved in 20 mL of dehydrated tetrahydrofuran. To this solution, a solution prepared by dissolving 0.09 g (1.0 ⁇ 10 ⁇ 3 mol) of piperidine in 1 mL of dehydrated tetrahydrofuran was added dropwise and stirred at room temperature for 12 hours.
  • the base proliferating agent 70 ⁇ 10 ⁇ 3 mol / L obtained in Example 2, piperidine 13 ⁇ 10 ⁇ 3 mol / L as a base, dioxane-d 8 as a solvent, and mesitylene 13 as an internal standard solution.
  • ⁇ 10 ⁇ 3 mol / L was added, sealed, and heated at 100 ° C. for a predetermined time. Then, by analyzing the olefin peak produced by 1 H-NMR, the decomposition behavior (olefin production) of the base proliferating agent was confirmed, and compared with the case where no base was added.
  • FIG. 11 shows the relationship between the heating time, the conversion rate of the base proliferating agent, and the olefin production rate.
  • the production rate of olefin was calculated from 1 H-NMR spectrum.
  • the solid line represents the conversion rate of the base proliferating agent, and the broken line represents the olefin production rate.
  • FIG. 12 shows the relationship between the heating time and the olefin production rate.
  • a nonlinear reaction curve peculiar to the proliferative reaction is obtained including a system to which a base (piperidine) common to the base constituting the base proliferating agent is added. It was confirmed that a base growth reaction was produced and olefin was produced. In the system to which the base was added, the base proliferating agent decomposed faster and the olefin was also generated faster.
  • FIG. 13 shows the relationship between the heating time, the conversion rate of the base proliferating agent, and the olefin production rate.
  • the production rate of olefin was calculated from 1 H-NMR spectrum.
  • the solid line represents the conversion rate of the base proliferating agent, and the broken line represents the olefin production rate.
  • Example 3 Example 4, Comparative Example 1 and Comparative Example 2, the thermal decomposition temperature (T d 5) were measured and compared.
  • FIG. 14 is a view showing the solubility in an organic solvent such as a base proliferating agent.
  • the base proliferating agents of Example 3 and Example 4 showed better solubility in organic solvents, and the base proliferating agent of Example 3 was better than the base proliferating agent of Comparative Example 1 and It was confirmed that the base proliferating agent of Example 4 exhibited superior solubility than the base proliferating agent of Comparative Example 2, respectively.
  • the thermal decomposition temperature (T d 5 ) is higher than the thermal decomposition temperature of the base proliferating agent of Comparative Example 1, and the excellent thermal resistance. Indicated. Similarly, the thermal decomposition temperature of the base proliferating agent of Example 4 was higher than that of Comparative Example 2 and showed excellent heat resistance.
  • Example 6 Production of resin composition (1) In Example 6, a resin composition was obtained using the same method as in Example 6 except that the base proliferating agent obtained in Example 5 was not added.
  • the curing progresses as the heating time is increased.
  • the exposure amount is 10,000 mJ / cm 2
  • the heating time is 20 minutes, 40 minutes, 3H, 60 minutes. A hardness of 4H was obtained.
  • Example 10 Production of base-reactive resin composition (photosensitive resin composition) (2): The bisphenol diglycidyl ether oligomer (jER828 (registered trademark) / manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), which is an epoxy compound represented by the formula (No. 4-11), is used with respect to 0.1 g. -4) 0.017 g (17 parts by mass with respect to 100 parts by mass of the epoxy compound) of the photobase generator, and 0.16 g (amine functional group ratio) of the base proliferator obtained in Example 9
  • the base-reactive resin composition of the present invention was obtained by containing 80 mol% (vs. epoxy group).
  • the present invention can be advantageously used as a material for providing a highly sensitive photocuring material, resist material (pattern forming material) and the like.

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Abstract

L'invention concerne: un amplificateur de base qui peut être utilisé dans la réaction de réticulation d'un composé époxy ou similaire, qui est susceptible de générer une nouvelle base du fait de la présence d'une base, qui est très soluble par rapport à des solvants organiques et qui peut favoriser efficacement une réaction de prolifération de la base lorsqu'il est ajouté à un composé pouvant réagir avec une base, en raison de sa résistance à la chaleur plus élevée que celle d'amplificateurs de bases conventionnels; et une composition de résine pouvant réagir avec une base contenant l'amplificateur de base. La présente invention concerne un composé de thioxanthène représenté par la formule (A), un amplificateur de base et une composition de résine pouvant réagir avec une base et contenant l'amplificateur de base.
PCT/JP2014/062198 2013-05-13 2014-05-02 Composé de thioxanthène, amplificateur de base, et composition de résine pouvant réagir avec une base contenant un amplificateur de base WO2014185303A1 (fr)

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Cited By (2)

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CN110382597A (zh) * 2017-05-10 2019-10-25 学校法人东京理科大学 活性能量线硬化型组合物、硬化膜的制造方法及硬化物
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