Classifications

• • 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
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • 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
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • 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
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • 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

Definitions

• the present invention relates to a negative photosensitive resin composition.
• Patent Document 1 describes a cyclic olefin resin having a functional group having a polymerizable double bond in a side chain and a polymerization initiator. A resin composition containing the same has been proposed.
• the photosensitive resin composition is required to be excellent in pattern forming property by development. Further, the resin film obtained by using the photosensitive resin composition is required to be excellent in electrical properties such as dielectric loss tangent, chemical resistance, and extensibility.
• the conventional photosensitive resin composition as described in Patent Document 1 improves the pattern forming property by development, lowers the dielectric loss tangent of the obtained resin film, and further improves the chemical resistance and extensibility. There was room for improvement in terms of making it work.
• the present invention is a negative photosensitive resin capable of improving the pattern forming property by development, reducing the dielectric loss tangent of the obtained resin film, and further improving the chemical resistance and extensibility. It is an object of the present invention to provide a composition.
• the present inventor has made diligent studies to achieve the above object. Then, the present inventor can improve the pattern forming property by development by using a resin composition containing a polymer containing a predetermined structural unit and a photoradical generator as a negative photosensitive resin composition. I found it possible. It has also been found that by forming a resin film using the resin composition, the dielectric loss tangent of the obtained resin film can be reduced, and chemical resistance and extensibility can be improved. Then, based on these findings, the present invention was completed.
• the present invention is intended to advantageously solve the above problems, and the negative photosensitive resin composition of the present invention contains a polymer and a photoradical generator, and the polymer is ,
• the structural unit (I) represented by the following formula (I) and the structural unit (II) represented by the following formula (II) are included.
• R 1 to R 3 independently represent a hydrogen atom, an alkyl group or an aromatic ring group, and R 1 to R 3 may be bonded to form a ring, and R 4 may be formed. Indicates a hydrogen atom or an alkyl group, X indicates an alkylene group having 1 to 10 carbon atoms, and m indicates 0, 1 or 2.
• R 5 to R 8 each independently represent a hydrogen atom, an alkyl group or an aromatic ring group, and R 5 to R 8 may be bonded to form a ring, where n is. Indicates 0, 1 or 2.
• the pattern forming property by development can be improved. ..
• the photoradical generator is an acylphosphine oxide-based or oxime ester-based photoradical generator. If an acylphosphine oxide-based or oxime ester-based photoradical generator is used as the photoradical generator, the pattern forming property by development can be further improved, and the dielectric loss tangent of the obtained resin film can be further lowered. can.
• the content of the photoradical generator is preferably more than 0.5 parts by mass and 25 parts by mass or less per 100 parts by mass of the polymer.
• the content of the photoradical generator is not less than the above lower limit, the cross-linking reaction of the functional group of the structural unit of the above formula (I) can be sufficiently proceeded, so that the pattern forming property by development is further excellent. Can be.
• the content of the photoradical generator is not more than the above upper limit, the dielectric loss tangent of the obtained resin film can be further reduced.
• the content ratio of the structural unit (I) in the polymer is preferably 3 mol% or more and 70 mol% or less.
• the content ratio of the structural unit (I) in the polymer is within the above range, the extensibility of the obtained resin film becomes excellent.
• the content ratio of the structural unit (I) in the polymer is not less than the above lower limit, the chemical resistance of the resin film can be improved, and when it is not more than the above upper limit, the dielectric loss tangent of the resin film is increased. It can be suppressed.
• the "content ratio of structural units” can be measured by using a nuclear magnetic resonance (NMR) method such as 1 H-NMR or 13 C-NMR.
• a negative photosensitive resin capable of improving pattern formation by development, reducing the dielectric loss tangent of the obtained resin film, and improving chemical resistance and extensibility.
• the composition can be provided.
• the negative photosensitive resin composition of the present invention is not particularly limited, and is used when forming a resin film that can be provided for electronic components such as integrated circuit elements, organic EL elements, and semiconductor packages. Can be done.
• the negative photosensitive resin composition of the present invention can be particularly preferably used when producing an insulating organic film such as an organic EL or a semiconductor package.
• the active energy ray used when patterning the resin film formed by using the negative photosensitive resin composition of the present invention is not particularly limited, and is a single beam such as ultraviolet rays, g-rays, h-rays, and i-rays.
• the negative photosensitive resin composition of the present invention can be particularly preferably used in the wavelength range of 200 nm to 500 nm, for example.
• the negative photosensitive resin composition of the present invention needs to contain a polymer containing the structural units described below and a photoradical generator, and may optionally contain a solvent and an additive component. Further, according to the negative photosensitive resin composition of the present invention, the pattern forming property by development can be improved, and the dielectric loss tangent of the resin film formed by using the negative photosensitive resin composition is lowered. And it is possible to improve chemical resistance and extensibility.
• the polymer contained in the negative photosensitive resin composition of the present invention is a polymer having a functional group in which a cross-linking reaction can proceed by radicals generated by irradiation with active energy rays in the presence of a photoradical generator.
• the polymer of the present invention contains a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II).
• the polymer may contain a structural unit other than the structural unit (I) and the structural unit (II).
• R 1 to R 3 independently represent a hydrogen atom, an alkyl group or an aromatic ring group, and R 1 to R 3 are bonded and rings. May be formed.
• the alkyl group that can form R 1 to R 3 is not particularly limited, and examples thereof include an unsubstituted alkyl group having 1 to 5 carbon atoms. Of these, as the alkyl group that can constitute R 1 to R 3 , a methyl group or an ethyl group is preferable.
• the aromatic ring group that can form R 1 to R 3 is not particularly limited, and examples thereof include aromatic rings having 4 to 30 carbon atoms, and examples thereof include a benzene ring and a naphthalene ring.
• the ring formed by combining R 1 to R 3 may be a monocyclic ring or a polycyclic ring.
• X represents an alkylene group having 1 to 10 carbon atoms.
• the alkylene group having 1 to 10 carbon atoms that can constitute X is not particularly limited, but is a chain having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, an n-butylene group, and an isobutylene group.
• An alkylene group is preferable, a linear alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group and an n-butylene group is more preferable, and a linear alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group and a propylene group is more preferable.
• the linear alkylene group of the above is more preferable, and the methylene group is particularly preferable.
• m represents 0, 1 or 2, and is more preferably 0 or 1.
• R4 represents a hydrogen atom or an alkyl group.
• the alkyl group that can constitute R 4 is not particularly limited, and examples thereof include an unsubstituted alkyl group having 1 to 5 carbon atoms. Of these, as the alkyl group that can constitute R 4 , a methyl group or an ethyl group is preferable.
• the structural unit (I) is a functional group because the substituted or unsubstituted acryloyl group as a functional group is bonded to the cyclic olefin structure via the alkylene group represented by X.
• the motility of is enhanced. Therefore, the polymer containing the structural unit (I) having such a functional group improves the cross-linking reactivity of the functional group in the presence of radicals.
• the negative photosensitive resin composition of the present invention containing the polymer containing the structural unit (I) and the above-mentioned structural unit (II) and the photoradical generator can improve the pattern forming property by development. At the same time, it is possible to reduce the dielectric loss tangent of the obtained resin film and improve the extensibility of the resin film.
• the content ratio of the structural unit (I) in the polymer is preferably 3 mol% or more, preferably 10 mol%, based on the total of 100 mol% of the structural unit (I) and the structural unit (II).
• the above is more preferable, 15 mol% or more is further preferable, 70 mol% or less is preferable, 50 mol% or less is more preferable, and 40 mol% or less is further preferable. ..
• the content ratio of the structural unit (I) in the polymer is within the above range, the extensibility of the obtained resin film is excellent.
• the content ratio of the structural unit (I) in the polymer is not less than the above lower limit, the chemical resistance of the resin film can be improved, and when it is not more than the above upper limit, the dielectric loss tangent of the resin film is increased. It can be suppressed.
• R 5 to R 8 independently represent a hydrogen atom, an alkyl group or an aromatic ring group, and R 4 to R 8 are bonded and rings. May be formed.
• the alkyl group that can form R 4 to R 8 is not particularly limited, and examples thereof include the same alkyl groups that can form R 1 to R 3 .
• the aromatic ring group that can form R 4 to R 8 is not particularly limited, and examples thereof include the same aromatic ring groups that can form R 1 to R 3 .
• the ring formed by binding R 4 to R 8 is not particularly limited, and examples thereof include the same ring formed by binding R 1 to R 3 .
• n 0, 1 or 2, and is preferably 0 or 1.
• the content ratio of the structural unit (II) in the polymer is preferably 3 mol% or more, preferably 5 mol%, based on the total of 100 mol% of the structural unit (I) and the structural unit (II). More preferably, it is more preferably 10 mol% or more, further preferably 30 mol% or more, further preferably 50 mol% or more, and particularly preferably 60 mol% or more. It is preferably 97 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less.
• the weight average molecular weight (Mw) of the above-mentioned polymer is preferably 3000 or more, more preferably 5000 or more, further preferably 10,000 or more, preferably 500,000 or less, and preferably 300,000. It is more preferably less than or equal to, and even more preferably 100,000 or less.
• the weight average molecular weight of the polymer is at least the above lower limit, the mechanical properties can be improved. Further, when the weight average molecular weight of the polymer is not more than the above upper limit, the solvent solubility can be improved.
• the molecular weight distribution (Mw / Mn) of the above-mentioned polymer is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. If the molecular weight distribution of the polymer is not more than the upper limit, the resolution can be improved.
• the "molecular weight distribution (Mw / Mn)" refers to the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). Then, in the present invention, the weight average molecular weight of the polymer is determined as a polystyrene-equivalent value by gel permeation chromatography (GPC).
• the method for preparing the above-mentioned polymer is not particularly limited, and for example, a ring-opening polymer is synthesized by a ring-opening polymerization reaction of a norbornene-based monomer, and the obtained ring-opening polymer is hydrogenated.
• Ring-opening polymer hydrogenation is carried out by performing a modification reaction with the step of obtaining the ring-opening polymer hydrogen additive (hereinafter referred to as "ring-opening polymerization step") and the obtained ring-opening polymer hydrogen additive. It can be efficiently synthesized by a method including a step of obtaining a modified product of a substance (hereinafter, referred to as a "modification step").
• a modification step a modified product of a substance
• a norbornene-based monomer (I) capable of forming the above-mentioned structural unit (I) and a norbornene-based monomer (II) capable of forming the above-mentioned structural unit (II) are used.
• a ring-opening polymer is synthesized by a ring-opening polymerization reaction.
• Examples of the norbornene-based monomer (I) include 2-norbornene-5-methanol, 2-methyl-2-hydroxymethylbicyclo [2.2.1] hept-5-ene, and 2,3-ene.
• Dodeca-9-ene 4-hydroxymethyltetracyclo [6.2.1.1 3,6 .
• the norbornene-based monomer (I) can be used alone or in combination of two or more.
• Nonbornene-based monomer (II) examples include tetracyclo [4.4.0.1 2,5 . 1 7 , 10] Dodeca-3-ene (trivial name: tetracyclododecene), 8-ethylidene-tetracyclo [4.4.0.1 2,5 .
• dodeca-3-ene (trivial name: ethylidenetetracyclododecene), tricyclo [5.2.1.0 2,6 ] deca-3,8-diene (trivial name: dicyclopentadiene), 1,4-Metano-1,4,4a-9a-Tetrahydrofluorene (trivial name: methanotetrahydrofluorene), 5-Etylidene bicyclo [2.2.1] hept-2-ene (trivial name: etylidene norbornene), Bicyclo [2.2.1] hept-2-ene (also referred to as "norbornene”), 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.
• the derivative refers to a derivative having a substituent in the ring structure.
• the substituent that can be contained in the ring structure include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group.
• the ring structure of the derivative may have one or more of these substituents.
• the norbornene-based monomer (II) can be used alone or in combination of two or more.
• the ring-opening polymerization reaction can be carried out in a solvent according to a known method.
• the solvent is not particularly limited, and for example, an organic solvent such as tetrahydrofuran or toluene can be used.
• an organic solvent such as tetrahydrofuran or toluene
• the ring-opening polymerization catalyst a metal catalyst containing a metal such as molybdenum, tungsten, or ruthenium can be used, and among them, a metal catalyst containing ruthenium is preferable.
• the ring-opening polymerization time is usually 1 hour or more and 10 hours or less, and preferably 2 hours or more and 5 hours or less.
• the ring-opening polymerization temperature is usually 20 ° C. or higher and 100 ° C. or lower, preferably 90 ° C. or lower.
• the hydrogenation reaction can be carried out according to a known method.
• the hydrogenation reaction time, hydrogenation reaction temperature, and hydrogenation pressure in the hydrogenation reaction are not particularly limited, but the hydrogenation reaction time is usually 1 hour or more and 10 hours, preferably 5 hours or less. ..
• the hydrogenation reaction temperature is usually 100 ° C. or higher and 200 ° C. or lower, preferably 180 ° C. or lower.
• the hydrogenation pressure is usually 1 MPa or more and 10 MPa or less, preferably 5 MPa or less.
• the terminal portion of the ring-opening polymer hydrogenated product obtained in the ring-opening polymerization step is subjected to a modification reaction using a modifying agent to carry out a modification reaction of the ring-opening polymer hydrogenated product (that is, that is).
• the polymer containing the structural unit (I) and the structural unit (II) described above) is synthesized.
• the denaturing agent for example, a compound having a methacryloyl group or an acryloyl group can be used.
• the compound having a methacrylic acid group include methacrylic acid chloride, methacrylic acid anhydride and the like.
• the compound having an acryloyl group include acrylic acid chloride and acrylic acid anhydride. Among these, it is more preferable to use methacrylic acid chloride or acrylic acid chloride from the viewpoint of efficiently performing the modification reaction.
• the modification reaction is not particularly limited, and for example, the modification reaction can be carried out by reacting the ring-opening polymer hydrogen additive and the modification agent in a solvent in the presence of a modification reaction catalyst.
• the modification reaction catalyst is not particularly limited, and for example, triethylamine, pyridine and the like can be used.
• the solvent is not particularly limited, and for example, the same solvent as that used in the ring-opening polymerization reaction can be used.
• the denaturation reaction temperature and the denaturation reaction time are not particularly limited, but the denaturation reaction temperature is usually ⁇ 10 ° C. or higher and 15 ° C. or lower, and the denaturation reaction time is usually 1 hour or longer and 15 hours or lower.
• an acylphosphine oxide-based, oxime ester-based, aromatic ketone-based photoradical generator or the like can be used.
• the photoradical generator may be used alone or in combination of two or more.
• an acylphosphine oxide-based or oxime ester-based photoradical generator is used from the viewpoint of further improving the pattern forming property by development and further reducing the dielectric loss tangent of the obtained resin film. It is preferable to use it.
• acylphosphine oxide-based photoradical generator examples include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 2,4. 6-trimethylbenzoylphenylethoxyphosphine oxide and the like can be used.
• Examples of the oxime ester-based photoradical generator include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), etanone, 1- [9-ethyl. -6- (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc. can be used.
• aromatic ketone radical generator examples include benzophenone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, and 1-hydroxycyclohexylphenylketone. , 2,2-Dimethoxy-1,2-diphenylethan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1- Phenyl-Propane-1-one, 2-Methyl-1 [4-Methylthio] phenyl] -2-morpholinopropane-1-one, o-Methyl benzoyl benzoate, [4- (Methylphenylthio) phenyl] Phenylmethane , 1,4 dibenzoylbenzene, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, benzyl
• the content of the photoradical generator is usually 0.3 parts by mass or more, preferably more than 0.5 parts by mass, and preferably 1 part by mass or more per 100 parts by mass of the polymer. It is more preferably 25 parts by mass or less, preferably less than 20 parts by mass, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.
• the content of the photoradical generator is not less than the above lower limit, the cross-linking reaction of the functional groups in the above-mentioned structural unit (I) can be sufficiently proceeded, so that the pattern forming property by development is further excellent. can do.
• the content of the photoradical generator in the negative photosensitive resin composition is not more than the above upper limit, the dielectric loss tangent of the obtained resin film can be further reduced.
• the solvent that can be contained in the negative photosensitive resin composition of the present invention is not particularly limited, and is, for example, toluene, o-xylene, m-xylene, p-xylene, 1,2,4-trimethylbenzene, 1 , 3,5-trimethylbenzene, aromatic solvents such as tetralin, hydrocarbons such as cyclohexane and decalin, ether solvents such as dibutyl ether, diisoamyl ether, tetrahydrofuran, cyclopentylmethyl ether, butyl acetate, hexyl acetate, propylene glycol.
• ester solvents such as monomethyl ether acetate
• ketone solvents such as methyl ethyl ketone, diisobutyl ketone and cyclopentanone. These solvents may be used alone or in combination of two or more.
• the total mass of the solvent in the negative photosensitive resin composition other than the solvent is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the negative photosensitive resin composition.
• the amount is preferably 60% by mass or less, more preferably 50% by mass or less.
• the additive component that can be contained in the negative photosensitive resin composition of the present invention is not particularly limited, and examples thereof include a surfactant, an antioxidant, a sensitizer, and an adhesion aid. These additive components may be used alone or in combination of two or more. Above all, from the viewpoint of improving the coatability of the negative photosensitive resin composition of the present invention and further improving the uniformity of the film thickness of the obtained resin film, a surfactant may be contained as an additive component. preferable.
• the surfactant is not particularly limited, and a known silicone-based surfactant, fluorine-based surfactant, or the like can be used.
• the content ratio of the surfactant in the negative photosensitive resin composition is preferably 0.1% by mass or less, preferably 0.05% by mass or less, based on the total mass of the negative photosensitive resin composition. Is more preferable.
• the negative photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned essential components and various optional components by a known method.
• the negative photosensitive resin composition of the present invention is used as a negative photosensitive resin composition obtained by dissolving each component in a solvent and filtering the components, for example.
• a known mixer such as a stirrer, a ball mill, a sand mill, a bead mill, a pigment disperser, a grinder, an ultrasonic disperser, a homogenizer, a planetary mixer, or a fill mix can be used.
• a general filtration method using a filter medium such as a filter can be adopted.
• the negative photosensitive resin composition of the present invention can be used to form a resin film by using a known film forming method (see, for example, International Publication No. 2015/033901). Then, the obtained resin film is not particularly limited, and is desired by performing an exposure step of irradiating an arbitrary active energy ray, for example, an exposure light having a wavelength of 200 nm or more and 500 nm or less, and a development step. It is possible to form a resin film having the pattern of. Further, if necessary, the pre-bake step may be carried out prior to the exposure step, or the post-exposure bake (PEB) step may be carried out at a desired timing after the start of the exposure step.
• PEB post-exposure bake
• a post-baking step may be carried out after the development step is completed.
• the developing solution used in the above-mentioned developing step is not particularly limited, and for example, those listed as the solvent that can be contained in the negative photosensitive resin composition of the present invention may be used as the developing solution. can.
• One of these developers can be used alone, or two or more of them can be used in combination.
• ⁇ Dissipation factor> Resin composition prepared in each Example and each comparative example on a 4-inch silicon wafer on which an aluminum film having a film thickness of 50 nm was formed using a sputtering device (“i-Miller CFS-4EP-LL” manufactured by Shibaura Eletech). After spin-coating the material, it was prebaked at 90 ° C. for 2 minutes using a hot plate to form a resin film composed of the resin composition. Then, after exposure with a mask aligner (manufactured by Canon, "PLA501F”) using a g-hi mixed line at an irradiation amount of 1000 mJ / cm 2 , the resin film is cured by heating in nitrogen at 180 ° C. for 1 hour.
• a mask aligner manufactured by Canon, "PLA501F”
• a silicon wafer with a resin film having a thickness of 10 ⁇ m was obtained.
• the obtained silicon wafer with a resin film was immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours to etch aluminum, whereby the resin film was peeled off from the silicon wafer. After drying in an oven at 110 ° C. for 1 hour, the dried resin film was cut into strips having a width of 2 mm and a length of 50 mm to form test pieces, and the dielectric loss tangent at 10 GHz was measured for this test piece by the cavity resonator method. gone.
• C Dissipation factor is 0.01 or more
• ⁇ Development residual film ratio> The resin compositions prepared in each Example and each Comparative Example were applied onto a silicon wafer by a spin coating method, and heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate to obtain a film thickness of 5.0 ⁇ m. A resin film was formed. Then, using a mask aligner (“PLA501F” manufactured by Canon Inc.), the g—i mixed line was exposed to an irradiation amount of 1000 mJ / cm 2 through a photomask having a line and space pattern of 100 ⁇ m.
• PLA501F mask aligner
• a laminate consisting of a resin film having a line-and-space pattern and a silicon wafer was obtained by performing a developing treatment using toluene as a developing solution for 60 seconds and then shaking off and drying.
• the film thickness of the line pattern portion of the resin film after the development process was measured using an optical interferometry film thickness measuring device (“Lambda Ace VM-1210” manufactured by Dainippon Screen Co., Ltd.), and the developed residual film ratio was measured according to the following formula. (%) Was calculated.
• the larger the value of the development residual film ratio the better the pattern formation property by development, which is preferable.
• Development residual film ratio (%) (film thickness of line pattern portion of resin film after development treatment) / (film thickness of resin film before development) ⁇ 100
• ⁇ Tensile elongation rate> Resin composition prepared in each Example and each comparative example on a 4-inch silicon wafer on which an aluminum film having a film thickness of 50 nm was formed using a sputtering device (“i-Miller CFS-4EP-LL” manufactured by Shibaura Eletech). After spin-coating the material, it was prebaked at 90 ° C. for 2 minutes using a hot plate to form a resin film composed of the resin composition. Then, using a mask aligner (“PLA501F” manufactured by Canon Inc.), the g—i mixed line was exposed with an irradiation amount of 1000 mJ / cm 2 . Then, the resin film was cured by heating in nitrogen at 180 ° C.
• a sputtering device (“i-Miller CFS-4EP-LL” manufactured by Shibaura Eletech). After spin-coating the material, it was prebaked at 90 ° C. for 2 minutes using a hot plate to form a resin film composed of the resin
• the obtained silicon wafer with a resin film is immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours to etch aluminum to peel off the resin film from the wafer with a resin film, and then placed in an oven at 110 ° C. for 1 hour. It was dried. The dried resin film was cut into strips having a width of 5 mm and a length of 40 mm to form test pieces, and a tensile test was performed on the test pieces to measure the tensile elongation of the resin film. Specifically, a tensile test was performed at 23 ° C.
• modified ring-opening polymer hydrogenated product 200 parts of tetrahydrofuran as a solvent was added to the reaction solution, the mixture was cooled to 0 ° C., and 0.5 times by mass of methanol was added to the reaction solution while keeping the temperature of the reaction solution at 10 ° C. or lower. The temperature was raised to room temperature at 0 ° C. for 1 hour, and the mixture was further stirred for 1 hour. The reaction solution was added dropwise to 8000 parts of methanol, and the generated precipitate was recovered by filtration. The precipitate is washed with methanol three times and then dried under reduced pressure at 50 ° C. to modify the hydrogenated ring-opening polymer (hereinafter referred to as "modified ring-opening polymer hydrogenated product”) (B-1.
• modified ring-opening polymer hydrogenated product hereinafter referred to as "modified ring-opening polymer hydrogenated product
• the weight average molecular weight of the modified ring-opening polymer hydrogenated product (B-1) measured by GPC was 14600, and the molecular weight distribution was 1.7.
• the methacryloyl modification rate of the ring-opening polymer hydrogenated product (A-1) was 100%, and the methacryloyl-modified NBMOH in the modified ring-opening polymer hydrogenated product (B-1) was found.
• the content was confirmed to be 65 mol%.
• the modified ring-opening polymer hydrogenated product (B-1) has a structural unit represented by the following formula (I-1) of 65 mol% and a structural unit represented by the following formula (II-1). It was confirmed that the polymer contained 35 mol%.
• Synthesis Example 2 The same operation as in Synthesis Example 1 was carried out except that NBMOH was changed to 40 mol%, TCD was changed to 60 mol% and the solvent was changed to toluene in Synthesis Example 1 to obtain a ring-opening polymer hydrogenated product (A-2). Then, the hydrogenated ring-opening polymer (A-1) was changed to the hydrogenated ring-opening polymer (A-2), triethylamine was 229.9 parts, methacrylic acid chloride was 176.2 parts, and the solvent was toluene. The same operation as in Synthesis Example 1 was carried out except that the hydrogenation was changed to the modified ring-opening polymer hydrogenated product (B-2).
• the weight average molecular weight of the modified ring-opening polymer hydrogenated product (B-2) measured by GPC was 13,800, and the molecular weight distribution was 1.6.
• the methacryloyl modification rate of the ring-opening polymer hydrogenated product (A-2) was 100%, and the methacryloyl-modified NBMOH in the modified ring-opening polymer hydrogenated product (B-2) was found. The content was confirmed to be 40 mol%.
• the modified ring-opening polymer hydrogenated product (B-2) has a structural unit represented by the following formula (I-2) in an amount of 40 mol% and a structural unit represented by the following formula (II-2) in an amount of 40 mol%. It was confirmed that the polymer contained 60 mol%.
• Synthesis Example 3 The same operation as in Synthesis Example 1 was carried out except that NBMOH was changed to 5 mol%, TCD was changed to 95 mol% and the solvent was changed to toluene in Synthesis Example 1 to obtain a ring-opening polymer hydrogenated product (A-3). Then, the hydrogenated ring-opening polymer (A-1) was changed to the hydrogenated ring-opening polymer (A-3), 22.4 parts of triethylamine, 19.8 parts of methacrylic acid chloride, and the solvent were toluene. The same operation as in Synthesis Example 1 was carried out except that the hydrogenation was changed to the modified ring-opening polymer hydrogenated product (B-3).
• the weight average molecular weight of the modified ring-opening polymer hydrogenated product (B-3) measured by GPC was 13,500, and the molecular weight distribution was 1.6.
• the methacryloyl modification rate of the ring-opening polymer hydrogenated product (A-3) was 100%, and the methacryloyl-modified NBMOH in the modified ring-opening polymer hydrogenated product (B-3) was found. The content was confirmed to be 5 mol%.
• the modified ring-opening polymer hydrogenated product (B-3) has a structural unit represented by the following formula (I-3) in an amount of 5 mol% and a structural unit represented by the following formula (II-3) in an amount of 5 mol%. It was confirmed that the polymer contained 95 mol%.
• Synthesis Example 4 NBMOH was changed from 15 mol% and TCD was changed from 90 mol% to 85 mol% ethylidenetetracyclododecene (hereinafter abbreviated as "ETD"), and 3.0 parts of 1,5-hexadiene was changed to 1 part.
• ETD ethylidenetetracyclododecene
• the methacryloyl modification rate of the ring-opening polymer hydrogenated product (A-4) was 100%, and the methacryloyl-modified NBMOH in the modified ring-opening polymer hydrogenated product (B-4) was found. The content was confirmed to be 15 mol%. Further, the modified ring-opening polymer hydrogenated product (B-4) has a structural unit represented by the following formula (I-4) in an amount of 15 mol% and a structural unit represented by the following formula (II-4) in an amount of 15 mol%. It was confirmed that the polymer contained 85 mol%.
• Synthesis Example 5 In Synthesis Example 1, the same operation as in Synthesis Example 1 was carried out except that NBMOH was changed from 10 mol% to 30 mol% and TCD 90 mol% was changed to ETD 70 mol%, and the ring-opening polymer hydrogenated product (A-5) was carried out. ) was obtained. Then, except that the hydrogenated ring-opening polymer (A-1) was changed to the hydrogenated ring-opening polymer (A-5), triethylamine was changed to 126.4 parts, and methacrylic acid chloride was changed to 111.2 parts. Performed the same operation as in Synthesis Example 1 to obtain a modified ring-opening polymer hydrogenated product (B-5).
• the weight average molecular weight of the modified ring-opening polymer hydrogenated product (B-5) measured by GPC was 14700, and the molecular weight distribution was 1.7. 1
• the methacryloyl modification rate of the ring-opening polymer hydrogenated product (A-5) was 100%, and the methacryloyl-modified NBMOH in the modified ring-opening polymer hydrogenated product (B-5) was found. The content was confirmed to be 30 mol%.
• the modified ring-opening polymer hydrogenated product (B-5) has a structural unit represented by the following formula (I-5) in an amount of 30 mol% and a structural unit represented by the following formula (II-5) in an amount of 30 mol%. It was confirmed that the polymer contained 70 mol%.
• Synthesis Example 6 In Synthesis Example 1, the same operation as in Synthesis Example 1 was carried out except that NBMOH was changed from 10 mol% to 25 mol%, TCD 90 mol% was changed to dicyclopentadiene 75 mol%, and the solvent was changed to toluene. (A-6) was obtained. Then, the hydrogenated ring-opening polymer (A-1) was changed to the hydrogenated ring-opening polymer (A-6), and the triethylamine was 136.0 parts, the methacrylic acid chloride was 120.4 parts, and the solvent was toluene. The same operation as in Synthesis Example 1 was carried out except that the hydrogenation was changed to the modified ring-opening polymer hydrogenated product (B-6).
• the weight average molecular weight of the modified ring-opening polymer hydrogenated product (B-6) measured by GPC was 15,000, and the molecular weight distribution was 1.6.
• the methacryloyl modification rate of the ring-opening polymer hydrogenated product (A-6) was 100%, and the methacryloyl-modified NBMOH in the modified ring-opening polymer hydrogenated product (B-6) was found. The content was confirmed to be 25 mol%.
• the modified ring-opening polymer hydrogenated product (B-6) has a structural unit represented by the following formula (I-6) in an amount of 25 mol% and a structural unit represented by the following formula (II-6) in an amount of 25 mol%. It was confirmed that the polymer contained 75 mol%.
• Synthesis Example 7 In Synthesis Example 1, the same operation as in Synthesis Example 1 was carried out except that NBMOH was changed from 10 mol% to 35 mol% and TCD 90 mol% was changed to ETD 65 mol%, and the ring-opening polymer hydrogenated product (A-7) was carried out. ) Was obtained. Then, the hydrogenated ring-opening polymer (A-1) was changed to the hydrogenated ring-opening polymer (A-7), and triethylamine was changed to 136.0 parts and methacrylic acid chloride was changed to 120.4 parts of acrylic acid chloride. The same operation as in Synthesis Example 1 was carried out except for the change, to obtain a modified ring-opening polymer hydrogenated product (B-7).
• the weight average molecular weight of the modified ring-opening polymer hydrogenated product (B-7) measured by GPC was 13300, and the molecular weight distribution was 1.6. 1 From the H-NMR measurement, the acryloyl modification rate of the ring-opening polymer hydrogenated product (A-7) was 100%, and the acryloyl-modified NBMOH in the modified ring-opening polymer hydrogenated product (B-7) was found. The content was confirmed to be 35 mol%. Further, in the modified ring-opening polymer hydrogenated product (B-7), the structural unit represented by the following formula (I-7) is 35 mol%, and the structural unit 65 represented by the following formula (II-7). It was confirmed that the polymer contained mol%.
• Synthesis Example 8 Same as Synthesis Example 1 except that NBMOH was changed from 10 mol% to 40 mol% and TCD 90 mol% to 30 mol% of etilidennobornene (ENB) and 30 mol% of methanotetrahydrofluorene (MTF) in Synthesis Example 1.
• a ring-opening polymer hydrogenated product (A-8) was obtained. Then, except that the ring-opening polymer hydrogenated product (A-1) was changed to the ring-opened polymer hydrogenated product (A-8), triethylamine was changed to 201.8 parts, and methacrylic acid chloride was changed to 154.7 parts.
• the structural unit represented by the following formula (I-8) is 40 mol%
• the structural unit 30 represented by the following formula (II-8a) is 30. It was confirmed that the polymer contained mol% and 30 mol% of the structural unit represented by the following formula (II-8b).
• Synthesis Example 9 In Synthesis Example 1, 10 mol% of NBMOH was changed to 40 mol% of norborneneol, 90 mol% of TCD was changed to 60 mol%, 3.0 parts of 1,5-hexadien was changed to 1.0 part, and the solvent was changed. The same operation as in Synthesis Example 1 was carried out except that the toluene was changed, to obtain a ring-opening polymer hydrogenated product (A-9). Then, the ring-opening polymer hydrogenated product (A-1) was changed to the ring-opened polymer hydrogenated product (A-9), triethylamine was changed to 326.4 parts, and methacrylic acid chloride was changed to 250.3 parts.
• the modified ring-opening polymer hydrogenated product (B-9) has a structural unit represented by the following formula (I-9) in an amount of 40 mol% and a structural unit represented by the following formula (II-9) in an amount of 60 mol%. It was confirmed that the polymer contained mol%.
• a norbornene / norbornene methanol copolymer as an addition polymer was synthesized by an addition polymerization reaction of norbornene (NB) as a norbornene-based monomer and NBMOH.
• NB norbornene
• the NB / NBMOH copolymer was synthesized according to the method described in Macromolecules 29,2761 (1996) except that the scale was increased by 20 times. Further, by 1 H-NMR measurement, the content of NBMOH in the NB / NBMOH copolymer was 15 mol%.
• the ring-opening polymer hydrogenated additive (A-1) was changed to the addition polymer (A-10), triethylamine was added to 107.7 parts, methacrylic acid chloride to 82.6 parts, and the reaction solvent was totoluene.
• the same operation as in Synthesis Example 1 was carried out except that the modification was changed to, to obtain a modified addition polymer (B-10).
• the methacryloyl modification rate of the addition polymer (A-10) is 100%, and the content of methacryloyl-modified NBMOH in the modified addition polymer (B-10) is 15 mol%. It was confirmed that.
• the weight average molecular weight of the modified ring-opening polymer hydrogenated product (B-9) measured by GPC was 28100, and the molecular weight distribution was 1.8. Further, the modified addition polymer (B-10) has a structural unit represented by the following formula (I-10) in an amount of 15 mol% and a structural unit represented by the following formula (II-10) in an amount of 85 mol%. It was confirmed that the polymer contained.
• a surfactant manufactured by Shin-Etsu Silicone Co., Ltd., manufactured by Shin-Etsu Silicone Co., Ltd.
• surfactant (1) a polytetrafluoroethylene filter having a pore size of 0.45 ⁇ m
• Example 2 100 parts of the modified ring-opening polymer hydrogenated product (B-2) obtained in Synthesis Example 2, 5 parts of the oxime ester-based photoradical generator (1), and toluene as a solvent (relative to the total amount of the resin composition). (Amount in which the total amount other than the solvent is 30%) was mixed and dissolved. Next, a surfactant (1) was added so as to be 0.03% with respect to the total amount of the resin composition, and then the mixture was filtered through the filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• Example 3 100 parts of the modified ring-opening polymer hydrogenated product (B-3) obtained in Synthesis Example 3, 5 parts of the oxime ester-based photoradical generator (1), and toluene as a solvent (relative to the total amount of the resin composition). (Amount in which the total amount other than the solvent is 30%) was mixed and dissolved. Next, a surfactant (1) was added so as to be 0.03% based on the total weight of the resin composition, and then the mixture was filtered through the filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• Example 4 100 parts of the modified ring-opening polymer hydrogenated product (B-4) obtained in Synthesis Example 4 and an oxime ester-based photoradical generator (BASF, "IrgacureOEX02", chemical formula: etanone, 1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), hereinafter referred to as "oxime ester-based photoradical generator (2)”) 5 parts , And toluene as a solvent (amount in which the total amount other than the solvent is 30% with respect to the total amount of the resin composition) was mixed and dissolved.
• BASF "IrgacureOEX02"
• etanone 1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), hereinafter referred to as "oxi
• a surfactant (1) was added so as to be 0.03% with respect to the total amount of the resin composition, and then the mixture was filtered through the filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• Example 5 100 parts of the modified ring-opening polymer hydrogenated product (B-5) obtained in Synthesis Example 5, an acylphosphine oxide-based photoradical generator (BASF, "Omnirad 819", chemical formula: bis (2, 4,) 10 parts of 6-trimethylbenzoyl) phenylphosphine oxide) and toluene as a solvent (amount in which the total amount other than the solvent is 30% with respect to the total amount of the resin composition) were mixed and dissolved. Next, a surfactant (1) was added so as to be 0.03% with respect to the total amount of the resin composition, and then the mixture was filtered through a filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• Example 6 100 parts of the modified ring-opening polymer hydrogenated product (B-5) obtained in Synthesis Example 5, 20 parts of the oxime ester-based photoradical generator (1), and toluene as a solvent (relative to the total amount of the resin composition). (Amount in which the total amount other than the solvent is 30%) was mixed and dissolved. Next, a surfactant (1) was added so as to be 0.03% with respect to the total amount of the resin composition, and then the mixture was filtered through the filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• Example 7 100 parts of the modified ring-opening polymer hydrogenated product (B-6) obtained in Synthesis Example 6, 5 parts of the oxime ester-based photoradical generator (2), and toluene as a solvent (relative to the total amount of the resin composition). (Amount in which the total amount other than the solvent is 30%) was mixed and dissolved. Next, a surfactant (1) was added so as to be 0.03% by weight based on the total amount of the resin composition, and then the mixture was filtered through the filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• Example 8 100 parts of the modified ring-opening polymer hydrogenated product (B-6) obtained in Synthesis Example 6, 0.5 part of the oxime ester-based photoradical generator (2), and toluene as a solvent (total amount of the resin composition). (Amount in which the total amount other than the solvent is 30%) was mixed and dissolved. Next, a surfactant (1) was added so as to be 0.03% with respect to the total amount of the resin composition, and then the mixture was filtered through the filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• Example 9 100 parts of the modified open cyclic polymer hydrogenated product (B-7) obtained in Synthesis Example 7, 3 parts of the oxime ester-based photoradical generator (1), and toluene as a solvent (relative to the total amount of the resin composition). (Amount in which the total amount other than the solvent is 30%) was mixed and dissolved. Next, a surfactant (1) was added so as to be 0.03% with respect to the total amount of the resin composition, and then the mixture was filtered through the filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• Example 10 100 parts of the modified ring-opening polymer hydrogenated product (B-2) obtained in Synthesis Example 2, 5 parts of benzophenone as an aromatic ketone-based photoradical generator, and toluene as a solvent (in the total amount of the resin composition). (Amount in which the total amount other than the solvent is 30%) was mixed and dissolved. Next, a surfactant (1) was added so as to be 0.03% with respect to the total amount of the resin composition, and then the mixture was filtered through the filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• Example 11 100 parts of the modified ring-opening polymer hydrogenated product (B-8) obtained in Synthesis Example 8, 5 parts of the oxime ester-based photoradical generator (2), and toluene as a solvent (relative to the total amount of the resin composition). (Amount in which the total amount other than the solvent is 30%) was mixed and dissolved. Next, a surfactant (1) was added so as to be 0.03% with respect to the total amount of the resin composition, and then the mixture was filtered through the filter (1) to prepare a resin composition. Then, various evaluations were carried out according to the above using the obtained resin composition. The results are shown in Table 1.
• the resin compositions (negative photosensitive resin compositions) of Examples 1 to 11 containing the polymer containing a predetermined structural unit and the photoradical generator have dielectric loss tangent, development residual film ratio, and resistance to development. It can be seen that it is excellent in both chemical properties and tensile elongation. On the other hand, even if the polymer contains a structural unit having a functional group, the resin of Comparative Example 1 using a polymer having a structure in which the functional group is directly bonded to the ring-opening polymer hydrogenated product. It can be seen that the composition could not increase both the development residual film ratio and the tensile elongation.
• a resin composition can be provided.

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