WO2020226052A1 - Composition de résine photosensible, film de résine et dispositif électronique - Google Patents

Composition de résine photosensible, film de résine et dispositif électronique Download PDF

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Publication number
WO2020226052A1
WO2020226052A1 PCT/JP2020/017228 JP2020017228W WO2020226052A1 WO 2020226052 A1 WO2020226052 A1 WO 2020226052A1 JP 2020017228 W JP2020017228 W JP 2020017228W WO 2020226052 A1 WO2020226052 A1 WO 2020226052A1
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Prior art keywords
group
carbon atoms
resin composition
photosensitive resin
copolymer
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PCT/JP2020/017228
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English (en)
Japanese (ja)
Inventor
陽雄 池田
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住友ベークライト株式会社
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Priority to JP2020541468A priority Critical patent/JP6777275B1/ja
Priority to KR1020217039734A priority patent/KR20220007629A/ko
Priority to CN202080034214.4A priority patent/CN113811556B/zh
Publication of WO2020226052A1 publication Critical patent/WO2020226052A1/fr

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    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a photosensitive resin composition, a resin film, and an electronic device. More specifically, the present invention relates to a photosensitive resin composition, a resin film made of a cured product of the photosensitive film-forming composition, and an electronic device including the resin film as a permanent film.
  • Patent Document 1 describes a monomer having a cyclic hydrocarbon group, an unsaturated polybasic acid anhydride such as maleic anhydride, a copolymerizable monomer such as vinyl toluene, and a monomer having a hydroxyl group.
  • a photosensitive resin composition containing a polymer and a color filter formed from a cured film of the resin composition are disclosed.
  • the present inventors have found that by using a copolymer containing a specific structural unit as a base resin, a photosensitive resin composition in which the cured product has high transparency and excellent heat-resistant discoloration can be obtained.
  • the present invention has been reached.
  • l and m indicate the molar content of A and B in the copolymer, respectively.
  • l + m 1
  • X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
  • Y is ⁇ SR 5a
  • S is a sulfur atom, and R 5a is an organic group having 1 or more and 30 or less carbon atoms.
  • A includes a structural unit represented by the following formula (A1).
  • B comprises at least one of the structural units represented by the formulas (B1)-(B6):
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 or more and 30 or less carbon atoms or an ethylenic double bond having 1 or more and 30 or less carbon atoms. It is an organic group, and n is 0, 1 or 2.
  • R 5 is the number 1 to 30 of the organic group having a carbon having an organic group or ethylenic double bond of 1 to 30 carbon atoms.
  • R 6 and R 7 are independent organic groups having 1 or more and 30 or less carbon atoms or organic groups having 1 or more and 30 or less carbon atoms having an ethylenic double bond.
  • R 8 is an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond and having 1 to 30 carbon atoms.
  • at least one of the structural unit represented by the formula (A1) and the structural unit represented by the formulas (B1) to (B6) contained in the formula (1) has an ethylenic double bond. It has 1 or more and 30 or less organic groups. ).
  • a resin film made of a cured film of the above-mentioned photosensitive resin composition is provided.
  • an electronic device provided with the above resin film is provided.
  • an electronic device including a photosensitive resin composition in which the cured product has excellent transparency, a resin film made of the cured product of the photosensitive resin composition, and the resin film as a permanent film.
  • electronic device refers to an element to which electronic engineering technology is applied, such as a semiconductor chip, a semiconductor element, a printed wiring board, an electric circuit display device, an information communication terminal, a light emitting diode, a physical battery, and a chemical battery. , Devices, final products, etc.
  • the photosensitive resin composition of the present embodiment contains a copolymer represented by the general formula (1), a cross-linking agent, and a photosensitive agent.
  • l and m indicate the molar content of A and B in the copolymer, respectively.
  • l + m 1
  • X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
  • Y is ⁇ SR 5a
  • R 5a is an organic group having 1 or more and 30 or less carbon atoms.
  • A includes a structural unit represented by the following formula (A1).
  • B contains at least one of the structural units represented by the formulas (B1) to (B6).
  • R 1 , R 2 , R 3 and R 4 are independently hydrogen or an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond having 1 to 30 carbon atoms.
  • n is 0, 1 or 2.
  • R 5 is 1 to 30 organic group having a carbon number having an organic group or ethylenic double bond of 1 to 30 carbon atoms.
  • R 6 and R 7 are independent organic groups having 1 or more and 30 or less carbon atoms or organic groups having 1 or more and 30 or less carbon atoms having an ethylenic double bond.
  • R 8 is an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond and having 1 to 30 carbon atoms.
  • at least one of the structural unit represented by the formula (A1) included in the general formula (1) and the structural unit represented by the formulas (B1) to (B6) has an ethylenic double bond and has 1 carbon atom. It has more than 30 organic groups.
  • the copolymer of the present embodiment contains a structural unit having an ethylenic double bond and having an organic group having 1 to 30 carbon atoms as an essential component.
  • the photosensitive resin composition of the present embodiment has various properties required for the photosensitive resin composition such as adhesion to a support, resolution, and heat resistance, and also has various properties.
  • the cured product has excellent transparency, and the transparency is maintained without coloring or clouding when used in a high temperature environment.
  • a photosensitive resin composition applied to a photolithography method a composition containing a cyclic olefin monomer and a copolymer obtained by polymerizing a plurality of types of monomers including maleic anhydride has been known.
  • a conventional photosensitive resin composition has functions as a photosensitive material such as alkali solubility, processability, and heat resistance, the resin film obtained by curing the composition is colored.
  • the present inventor has found that the cause of coloring of the cured product is due to the structural unit derived from maleic anhydride in the copolymer.
  • the copolymer used in the present embodiment contains a structural unit derived from norbornene monomer or maleic anhydride having an organic group having an ethylenic double bond and having 1 to 30 carbon atoms, and -SR 5a at the end thereof. It has a group (S represents a sulfur atom).
  • a copolymer having such a structure it has functions as a photosensitive material such as alkali solubility, processability, and heat resistance, and the cured product has high transparency, and is subjected to heat treatment or a high temperature environment. It is possible to obtain a photosensitive resin composition having excellent heat-resistant discoloration property in which a decrease in transparency due to use in the above is reduced.
  • the copolymer used in the photosensitive resin composition of the present embodiment has a structure represented by the general formula (1).
  • l and m indicate the molar content of A and B in the copolymer, respectively.
  • l + m 1
  • X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
  • Y is ⁇ SR 5a
  • S is a sulfur atom, and R 5a is an organic group having 1 or more and 30 or less carbon atoms.
  • A includes a structural unit represented by the following formula (A1).
  • B contains at least one of the structural units represented by the formulas (B1) to (B6).
  • the arrangement of the structural units A and B in the above-mentioned copolymer is not limited, and may take the form of a random copolymer, a cross-polymer, a block copolymer, or a periodic copolymer.
  • composition ratio of the structural unit A and the structural unit B in the above copolymer will be described.
  • molar content (mol%) of the structural unit of A in the copolymer is l and the molar content (mol%) of the structural unit of B is m
  • l + m 1, for example, a numerical value of l.
  • the range is preferably 0.1 ⁇ l ⁇ 0.9.
  • the numerical range of m is preferably 0.1 ⁇ m ⁇ 0.9.
  • the structural unit A includes a structural unit derived from the norbornene monomer represented by the formula (A1).
  • R 1 , R 2 , R 3 and R 4 are independently hydrogen or an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond having 1 to 30 carbon atoms.
  • n is 0, 1 or 2.
  • the organic groups having 1 to 30 carbon atoms or the organic groups having an ethylenic double bond and having 1 to 30 carbon atoms constituting R 1 to R 4 in the general formula (A1) are independent of each other.
  • the structure may contain one or more atoms selected from O (oxygen atom), N (nitrogen atom), S (sulfur atom), P (phosphorus atom) and Si (silicon atom).
  • none of the organic groups constituting R 1 , R 2 , R 3 and R 4 can have an acidic functional group. This makes it possible to easily control the acid value in the copolymer.
  • R 1 to R 4 in the above formula (A1) are independently hydrogen, an organic group having 1 or more and 30 or less carbon atoms, or an organic group having an ethylenic double bond and having 1 or more and 30 carbon atoms or less. It is an organic group, preferably hydrogen or an organic group having 1 or more and 15 or less carbon atoms or an organic group having an ethylenic double bond having 1 or more and 15 or less carbon atoms, and hydrogen or an organic group having 1 or more and 10 or less carbon atoms. Alternatively, it is more preferably an organic group having an ethylenic double bond and having 1 or more and 10 or less carbon atoms.
  • examples of the organic group having 1 or more and 30 or less carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group and a heterocyclic group. Can be mentioned.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , Octyl group, nonyl group, and decyl group.
  • Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
  • alkynyl group examples include an ethynyl group.
  • alkylidene group examples include a methylidene group and an ethylidene group.
  • Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group.
  • Examples of the alkaline group include a tolyl group and a xylyl group.
  • Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group and a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
  • N-hexyloxy group examples include an epoxy group and an oxetanyl group.
  • organic group having an ethylenic double bond having 1 to 30 carbon atoms include an allyl group, an acrylic group, a methacryl group, a maleimide group, a styryl group, an aromatic vinyl group such as an indenyl group, and the like. ..
  • n in the above formula (A1) is 0, 1 or 2, and may be 0 or 1, or may be 0.
  • the structural unit B includes at least one of the structural units represented by the formulas (B1) to (B6).
  • R 5 is 1 to 30 organic group having a carbon number having an organic group or ethylenic double bond of 1 to 30 carbon atoms.
  • R 6 and R 7 are independent organic groups having 1 or more and 30 or less carbon atoms or organic groups having 1 or more and 30 or less carbon atoms having an ethylenic double bond.
  • R 8 is an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond and having 1 to 30 carbon atoms.
  • the general formula (B1), the general formula (B2) and the general formula (B6) R 5 ⁇ having 1 or more carbon atoms with organic groups or ethylenic double bond of one to 30 carbon atoms constituting the R 8 in 30
  • the following organic groups may contain one or more atoms selected from O, N, S, P and Si in their structure. Further, in the present embodiment, none of the organic groups constituting R 5 to R 8 can have an acidic functional group such as a carboxyl group. This makes it possible to easily control the acid value in the copolymer.
  • R 5 to R 8 in the general formula (B1), the general formula (B2) and the general formula (B6) are independently organic groups having 1 or more and 30 or less carbon atoms or ethylenic di. It is preferably an organic group having a heavy bond having 1 or more and 30 or less carbon atoms, preferably an organic group having 1 or more and 15 carbon atoms or less, or an organic group having an ethylenic double bond and having 1 or more carbon atoms and 15 or less carbon atoms.
  • the organic group has 1 or more and 10 or less or an ethylenic double bond and has 1 or more and 10 or less carbon atoms, and the organic group has 1 or more and 6 or less carbon atoms or an ethylenic double bond. It is more preferable that the number of organic groups is 1 or more and 6 or less.
  • examples of the organic group constituting R 5 to R 8 in the above formula (B1), formula (B2) and formula (B6) include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group and an aryl group.
  • examples include groups, aralkyl groups, alkaline groups, cycloalkyl groups, alkoxy groups and heterocyclic groups.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , Octyl group, nonyl group, and decyl group.
  • Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
  • alkynyl group examples include an ethynyl group.
  • alkylidene group examples include a methylidene group and an ethylidene group.
  • Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group.
  • Examples of the alkaline group include a tolyl group and a xylyl group.
  • Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
  • alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
  • heterocyclic group examples include an epoxy group and an oxetanyl group.
  • the above formula (B1), specific examples of the formula (B2) and the number 1 to 30 of the organic group having a carbon having an ethylenic double bond which constitutes the R 5 ⁇ R 8 in the formula (B6) examples include aromatic vinyl groups such as allyl group, acrylic group, methacryl group, maleimide group, styryl group and indenyl group.
  • At least one of the structural units represented by the formula (A1) and the structural units represented by the formulas (B1) to (B6) contained in the formula (1) has an ethylenic double bond. It has an organic group having 1 or more and 30 or less carbon atoms.
  • X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
  • the organic group having 1 or more and 30 or less carbon atoms is the same as the above-mentioned organic group having 1 or more and 30 or less carbon atoms constituting R 1 to R 4 or R 5 to R 8 .
  • Y is a group represented by ⁇ SR 5a
  • S is a sulfur atom
  • R 5a is an organic group having 1 or more and 30 or less carbon atoms.
  • the organic group having 1 or more and 30 or less carbon atoms may contain one or more atoms selected from O, N, S, P and Si.
  • Examples of the organic group having 1 to 30 carbon atoms constituting R 5 include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group and a heterocyclic group. Can be mentioned.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , Octyl group, nonyl group, and decyl group.
  • Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
  • alkynyl group examples include an ethynyl group.
  • alkylidene group examples include a methylidene group and an ethylidene group.
  • Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group.
  • Examples of the alkaline group include a tolyl group and a xylyl group.
  • Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
  • alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
  • heterocyclic group examples include an epoxy group and an oxetanyl group.
  • Y may include a structural unit derived from a radical polymerization initiator, hydrogen, or a structural unit derived from a chain transfer agent, and is derived from a structural unit derived from a radical polymerization initiator, hydrogen, or a chain transfer agent. It may be a structural unit. This is because when a radical polymerization initiator is used as the polymerization initiator when synthesizing the copolymer represented by the general formula (1), Y can be formed by the termination reaction of the radical chain reaction which is a polymerization reaction. Because.
  • Y derived from the chain transfer agent is -SR 5a .
  • S represents a sulfur atom
  • R 5a is a linear or branched hydrocarbon group having 1 to 15 carbon atoms or an organic group having 1 to 15 carbon atoms.
  • -SR 5a is a compound represented by the formula (Y1-a) or the formula (Y2-a); alkanethiols such as 1-butanethiol, 1-octanethiol, 1-decanethiol; mercaptoacetic acid, 3-mercapto.
  • Thiocarboxylic acids such as propionic acid; thiocarboxylic acid esters such as ethyl mercaptoacetate, 2-ethylhexyl mercaptoacetate, 2-ethylhexyl 3-mercaptopropionic acid; polyvalent thiols such as trimethylpropanthris (3-mercaptopropionate) It can be introduced into the copolymer of the formula (1) by using the above.
  • Y in the formula (1) when a copolymer is prepared by using the compound represented by the above formula (Y1-a) as a chain transfer agent, Y in the formula (1) has a structure represented by the formula (Y1). Coalescence is obtained. Further, when a copolymer is prepared by using the compound represented by the above formula (Y2-a) as a chain transfer agent, Y in the formula (1) has a structure represented by the formula (Y2). Coalescence is obtained.
  • the lower limit of Mw (weight average molecular weight) of the copolymer may be, for example, 1500 or more, 2000 or more, preferably 2500 or more, and preferably 3000 or more, from the viewpoint of forming an appropriate crosslinked structure. The above is more preferable.
  • the upper limit of Mw of the copolymer may be, for example, 30,000 or less, preferably 25,000 or less, and more preferably 20,000 or less.
  • the upper limit of the polydispersity of the copolymer according to the present embodiment makes the physical properties of each molecular chain of the copolymer uniform, and the shape of the resin film made of the photosensitive resin composition containing the copolymer is good.
  • it is preferably 2.5 or less, preferably 2.2 or less, more preferably 2.0 or less, and even more preferably 1.5 or less.
  • the lower limit value of the polydispersity of the copolymer is preferably 1.0 or more, for example.
  • the degree of polydispersity is represented by Mw (weight average molecular weight) / Mn (number average molecular weight), and means the degree of dispersion indicating the width of the molecular weight distribution.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw / Mn molecular weight distribution
  • PS standard polystyrene
  • the peak area at a molecular weight of 1000 or less may be 1% or less of the whole.
  • the ratio of the peak area of the molecular weight distribution curve obtained by GPC to the molecular weight of 1000 or less within the above range the pattern shape of the film made of the resin composition containing the copolymer can be improved. it can. Therefore, it is possible to improve the operation reliability of a liquid crystal display device and a solid-state image sensor having the film as a permanent film.
  • the lower limit of the amount of the low molecular weight component in the copolymer is not limited.
  • the copolymer according to the present embodiment allows a case where the peak area at a molecular weight of 1000 or less is 0.01% or more of the whole in the molecular weight distribution curve obtained by GPC.
  • the amount of the low molecular weight component in the copolymer is calculated from the ratio of the total area of the components corresponding to the molecular weight of 1000 or less to the total area of the molecular weight distribution based on the data on the molecular weight obtained by, for example, GPC measurement. ..
  • the alkali dissolution rate of the copolymer in this embodiment is, for example, 300 ⁇ / sec or more and 20,000 ⁇ / sec or less, more preferably 500 ⁇ / sec or more and 25,000 ⁇ / sec or less.
  • the alkali dissolution rate of the copolymer in this embodiment is, for example, 20,000 ⁇ / sec or less.
  • the alkali dissolution rate of the copolymer is, for example, a copolymer solution prepared by dissolving the copolymer in propylene glycol monomethyl ether acetate and adjusting the solid content to 20% by weight, and applying the copolymer solution on a silicon wafer by a spin method.
  • the copolymer film obtained by soft-baking at 110 ° C. for 100 seconds is impregnated with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C., and the time until the copolymer film is visually erased is allowed. Calculated by measuring
  • the alkali dissolution rate of the copolymer By setting the alkali dissolution rate of the copolymer to the above lower limit or higher, the throughput in the developing process using the alkaline developer can be improved. Further, by setting the alkali dissolution rate of the copolymer to the above upper limit or less, the residual film ratio after the development step with the alkaline developer can be improved. Therefore, it is possible to suppress film loss due to the lithography process.
  • a monomer is polymerized by a polymerization step to prepare a copolymer, and then a low molecular weight component is removed by a low molecular weight component removing step, and the copolymer is the main component. It is prepared by the method of obtaining the copolymer. It will be described in detail below.
  • a norbornene-type monomer (A) and one or more selected from the group consisting of maleic anhydride (B), maleimide (C), and maleimide derivative (D) are prepared. Further, one type of norbornene type monomer may be prepared, or two or more types may be prepared.
  • the structural unit A is derived from the norbornene-type monomer (A)
  • the structural unit B is maleic anhydride (B), maleimide (C) or maleimide derivative (D).
  • norbornene-type monomer represented by the formula (A) include bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), and more specifically, the norbornene type monomer.
  • Alkenyl groups such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, etc. have an alkyl group.
  • alkynyl group such as 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, etc.
  • 5-Ethynyl-2-norbornene and the like having an aralkyl group include 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene and the like.
  • the norbornene-type monomer an organic group having the above-mentioned ethylenic double bond and having 1 to 30 carbon atoms or less is used in the structure of the groups of R 1 , R 2 , R 3 , and R 4 of the formula (A). What you have can be adopted.
  • the monomer represented by the formula (A) and the monomer represented by the formula (B), the monomer represented by the formula (C), or the monomer represented by the formula (D) are subjected to the above-mentioned chain transfer agent. Addition polymerization with.
  • a copolymer of these monomers (copolymer 1) is formed by radical polymerization.
  • the polymerization method for example, a method of polymerizing using a radical polymerization initiator and, if necessary, a molecular weight modifier is preferable.
  • methods such as suspension polymerization, solution polymerization, dispersion polymerization, and emulsion polymerization can be used.
  • solution polymerization is preferable.
  • all the monomers may be charged in a batch, or a part thereof may be charged in a reaction vessel and the rest may be dropped.
  • a monomer represented by the formula (A), a monomer represented by the formula (B), a monomer represented by the formula (C), and a monomer represented by the formula (D) are used as a solvent with a polymerization initiator.
  • a polymerization initiator By dissolving and then heating for a predetermined time, the norbornene-type monomer represented by the formula (A), maleic anhydride, and maleimide are solution-polymerized.
  • the heating temperature is, for example, 50 to 80 ° C., and the heating time is 10 to 20 hours.
  • solvent used for the polymerization examples include diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate and the like, and any one or more of these can be used.
  • radical polymerization initiator examples include azo compounds and organic peroxides, and any one or more of these can be used.
  • examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis (2-methylpropionate), and 1,1'-azobis (cyclohexanecarbonitrile) (ABCN). , Any one or more of these can be used.
  • examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Of these, any one or more can be used.
  • the amount (number of moles) of the radical polymerization initiator is preferably 1 mol% to 10 mol% with respect to the total amount of the monomers used.
  • the structural unit represented by the following formula (A1), the structural unit represented by the following formula (B3), the structural unit represented by the following formula (B5), and the following formula (B6) are represented.
  • the copolymer 1 having the structural unit to be polymerized can be polymerized.
  • R 1 having the structure of the formula (A1) is common to each repeating unit, but it may be different for each repeating unit. The same applies to R 2 ⁇ R 4, R 8 .
  • n, R 1 ⁇ R 4 and R 8 are the same as defined above.
  • the copolymer 1 may have the structural units (A1), (B3), (B5) and (B6) randomly arranged, or may be alternately arranged. .. Further, the structural units (A1), (B3), (B5) and (B6) may be block copolymerized.
  • the copolymer 1 is preferably an alternating copolymer from the viewpoint of obtaining uniform solubility of the photosensitive resin composition.
  • the copolymer By reducing the amount of low molecular weight components in the copolymer, it is possible to suppress the deformation of the pattern of the film formed by the copolymer at the time of curing, and the film made of a photosensitive resin composition containing the copolymer.
  • the pattern shape of the above can be made good. It is possible to improve the operation reliability of a liquid crystal display device or a solid-state image sensor that includes the film as a permanent film.
  • the repeating units derived from maleic anhydride of the copolymer 1 for example, it is preferable to open the ring of 60% or less of the repeating unit, and open the ring of 50% or less of the repeating unit. Is more preferable. Within the above range, it becomes easy to impart a sufficient alkaline developer to the copolymer 1 and to allow the cross-linking reaction by the photoradical generator to proceed more efficiently.
  • an alcohol represented by R 5- OH (where R 5 is synonymous with the above) or water is allowed to act on the structural unit derived from maleic anhydride, and the above formula (2) is used.
  • the maleic anhydride moiety of the indicated structural unit is opened to form a carboxyl group or a salt thereof in the precursor polymer.
  • R 5 is 1 to 30 organic group having a carbon number having an organic group or ethylenic double bond of 1 to 30 carbon atoms.
  • the structure represented by the formula (B2) may be formed.
  • R 6 and R 7 are independent organic groups having 1 or more and 30 or less carbon atoms or organic groups having 1 or more and 30 or less carbon atoms having an ethylenic double bond.
  • This step can be performed, for example, by adding a predetermined amount of alcohol or water to the solution containing the copolymer 1 and heating the solution.
  • the alcohol can be R 5 OH, and the organic group R 5 can be the one described above.
  • examples of the alcohol include allyl alcohol, metallic alcohol, 3-butene-1-ol, 3-methyl-3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 6 -Heptene-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decene-1-ol, 10-undecene-1-ol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate , Hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, and 1,4-cyclohexanedimethanol monomethacrylate, any of these.
  • One or more can be used.
  • the solvent for dissolving the precursor polymer can be appropriately selected from those that do not inhibit the reaction, and the heating conditions can be set, for example, in the range of 50 to 100 ° C.
  • the reaction time can be appropriately set while observing the degree of change in the chemical structure of the polymer.
  • the solvent used in this step include diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate and the like as highly versatile solvents, and any one or more of these can be used. ..
  • a catalyst can be appropriately added from the viewpoint of accelerating the reaction, and for example, a base catalyst or an acid catalyst can be added.
  • a base catalyst pyridine, alkylamines such as triethylamine, amine compounds such as dimethylaniline, urotropin and dimethylaminopyridine, and metal salts such as sodium acetate can be used.
  • the acid catalyst mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as paratoluenesulfonic acid, and Lewis acids such as boron trifluoride etherate can be used.
  • the copolymer obtained by the present embodiment can be preferably used for forming a photosensitive resin film because of the specificity of the chemical performance contained in this structural unit.
  • the “photosensitive resin film” refers to a resin film that is subjected to an exposure process in the manufacturing process of an electronic device or the like.
  • a negative type photosensitive resin in which a portion irradiated with light is cured, while a portion not irradiated is dissolved and removed in a developing solution.
  • a developing solution for example, an alkaline solution
  • the cross-linking agent is not limited as long as it is a compound containing a functional group that reacts with the active hydrogen of the copolymer.
  • the functional group that reacts with the active hydrogen of the copolymer preferably contains, for example, one or more selected from the group consisting of a glycidyl group, an oxetanyl group, and a blocked isocyanate group, and includes a glycidyl group or an oxetanyl group. It is more preferable, and it is more preferable to contain a glycidyl group. Thereby, an appropriate crosslinked structure can be formed.
  • the photosensitive resin composition one kind or two or more kinds selected from a compound having a blocked isocyanate group, an epoxy compound and an oxetane compound can be used in combination.
  • Examples of the compound having a glycidyl group used as a cross-linking agent include allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and bisphenol A.
  • glycidyl ether such as glycidyl ether, adipic acid diglycidyl ester, glycidyl ester such as o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, 3 , 4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis (2) , 3-Epoxycyclopentyl) Ether and alicyclic epoxy such as Celoxide 2021, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, Epolide GT401, 2,2'-(((((1- (1-(1-) 4- (2- (4- (Oxylan-2-yl)
  • Aromatic glycidyl ether, 1,1,3,3,5,5-hexamethyl-1,5-bis (3- (oxylan-2-ylmethoxy) propyl) trisiloxane (for example, DMS-E09 (manufactured by Gerest)) Etc. can be used.
  • bisphenol A such as LX-01 (manufactured by Daiso), jER1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, jER825 (trade name; manufactured by Mitsubishi Chemical Corporation).
  • Type epoxy resin bisphenol F type epoxy resin such as jER807 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), jER152, 154 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.)
  • Phenolic novolac type epoxy resin such as EOCN102, 103S, 104S, 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), jER157S70 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.)
  • Araldite CY179, 184 (trade name; manufactured by Huntsman Advanced Materials), ERL-4206, 4221, 4234, 4299 (trade name; manufactured by Dow Chemical), Epicron 200,
  • Examples of the compound having an oxetane group used as a cross-linking agent include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene and bis [1-ethyl (3-oxetanyl)] methyl ether.
  • the compound having a blocked isocyanate group used as a cross-linking agent is not limited, and examples thereof include a compound in which the isocyanate group of a polyfunctional isocyanate is protected by a blocking agent.
  • the polyfunctional isocyanate is an organic compound having a plurality of isocyanate groups in one molecule.
  • examples of the polyfunctional isocyanate include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4.
  • the blocking agent examples include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, urea compounds, and oximes. Examples thereof include one or more selected from system compounds, amine compounds, imine compounds, heavy sulfites, pyridine compounds and the like.
  • blocking agent examples include oxime, ethanol, propanol, butanol, 2-ethylhexanol, methylcellosolve, butylcellosolve, methylcarpitol, benzyl alcohol, cyclohexanol and the like.
  • Alcor compounds such as phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester; malonic acid Active methylene compounds such as dimethyl, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; acetoanilide, acetate, ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam Oxime-based compounds such as; oxyimide-based compounds such as succinateimide and maleateimide; imidazole-based compounds such as imidazole and 2-methylimidazole; urea-based compounds such as urea, thiourea and ethyleneurea.
  • malonic acid Active methylene compounds such as dimethyl, diethyl mal
  • Oxime compounds such as formaldehyde, acetoaldoxime, acetooxime, methylethylketooxime, cyclohexanone oxime; amine compounds such as diphenylamine, aniline, and carbazole; imide compounds such as ethyleneimine and polyethyleneimine; Das and other heavy sulfites; pyridine compounds such as 2-hydroxypyridine and 2-hydroxyquinoline can be mentioned.
  • Specific examples of the compound having a blocked isocyanate group used as a cross-linking agent include Barnock D-500 (tolylene diisocyanate blocked product) and Barnock D-550 (1,6) manufactured by Dainippon Ink and Chemicals. -Hexamethylene diisocyanate block), Vernock D-980K (1,6-hexamethylene diisocyanate block); Takenate B-830 (trilened isocyanate block) manufactured by Mitsui Takeda Chemical Co., Ltd.
  • a photoactive compound can be used as the photosensitizer, and for example, a diazoquinone compound can be used.
  • a diazoquinone compound can be used.
  • any one or more of the following compounds can be used.
  • N2 is an integer of 1 or more and 5 or less.
  • Q is any of the structures shown below or a hydrogen atom.
  • at least one of the Qs of each compound is any of the following.
  • an o-naphthoquinonediazide sulfonic acid derivative having a Q of (a) or (b) is preferable from the viewpoint of transparency and dielectric constant of the photosensitive resin composition.
  • the positive photosensitive resin composition may contain an acid generator that generates an acid by light or heat.
  • an acid generator that generates an acid by light or heat.
  • the cross-linking reaction of the cross-linking agent can be promoted by exposing and developing the photosensitive resin composition and then irradiating or heating with light.
  • the amount of the acid generator is preferably 3 parts by mass or less with respect to 100 parts by mass of the cross-linking agent.
  • the photoacid generator that generates acid by light those described later can be used.
  • the content of the thermoacid generator is preferably 0.1% by mass or more and 5% by mass or less, for example, when the total solid content of the photosensitive resin composition is 100% by mass.
  • the total solid content of the photosensitive resin composition means a component excluding the solvent.
  • a photoacid generator can be used as the photosensitive agent.
  • the photoacid generator may be any agent that absorbs the energy of light to produce blended acid or Lewis acid. For example, triphenylsulfonium trifluoromethanesulfonate and tris (4-t-butylphenyl) sulfonium-trifluo.
  • Sulfonium salts such as lomethanesulfonate; diazonium salts such as p-nitrophenyldiazonium hexafluorophosphate; ammonium salts; phosphonium salts; diphenyliodonium trifluoromethanesulfonates, iodonium salts such as (tricmill) iodonium-tetrakis (pentafluorophenyl) borate; quinonediazide , Diazomethanes such as bis (phenylsulfonyl) diazomethane; sulfonic acid esters such as 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, N-hydroxynaphthalimide-trifluoromethanesulfonate; diphenyl Disulfons such as disulfones; tris (2,4,6-trichloromethyl) -s-triazin
  • the second cross-linking agent may contain a material that cross-links the copolymer by the action of an acid.
  • This second cross-linking agent cross-links the copolymer using the acid generated by the photo-acid generator as a catalyst, and is different from the compound used for the cross-linking agent.
  • a melamine-based cross-linking agent, a urea-based cross-linking agent, and the like can be mentioned.
  • Examples of the melamine-based cross-linking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like, and among them, hexamethoxymethylmelamine is preferable.
  • Examples of the urea-based cross-linking agent include methylated urea resin, bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, and among them, methylated urea resin is preferable.
  • Examples of commercially available methylated urea resins include MX-270, MX-280, and MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
  • the ratio of the second cross-linking agent in the negative type photosensitive resin composition is preferably 5% by mass or more and 40% by mass or less when the total solid content of the resin composition is 100% by mass, and the resolution is high. From the viewpoint, it is more preferably 5% by mass or more and 30% by mass or less, and further preferably 10 to 25% by mass.
  • the ratio of each component is, for example, as follows.
  • the total solid content of the photosensitive resin composition is 100% by mass, it is preferable that the above-mentioned copolymer is contained in an amount of, for example, 30% by mass or more and 70% by mass or less, and above all, 40% by mass or more and 60% by mass or less. It is preferable to contain it.
  • the cross-linking agent is preferably contained, for example, 15% by mass or more and 50% by mass or less, and above all, 20% by mass or more and 50% by mass or less. Is preferable.
  • the photoactive compound as a photosensitive agent is contained, for example, 5% by mass or more and 40% by mass or less, and 10% by mass or more and 30% by mass. It is more preferably contained in an amount of% by mass or less.
  • the ratio of each component is as follows, for example.
  • the above-mentioned copolymer is preferably contained in an amount of, for example, 30% by mass or more and 70% by mass, particularly 40% by mass or more and 60% by mass or less. It is preferable to do so.
  • the total solid content of the photosensitive resin composition is 100% by mass, it is preferable to contain a cross-linking agent (excluding the second cross-linking agent), for example, 15% by mass or more and 50% by mass or less, and among them, 20. It is preferably contained in an amount of% by mass or more and 50% by mass or less.
  • the amount of the photoacid generator is, for example, 0.1% by mass or more and 40% by mass or less, forming a high-resolution pattern film. It is more preferably 1% by mass or more and 30% by mass or less from the viewpoint that it can be used.
  • Additives such as a solvent, an antioxidant, a surfactant, an adhesion aid, a dissolution accelerator, a filler, a sensitizer, and polyphenols may be further added to the photosensitive resin composition.
  • a solvent such as a solvent, an antioxidant, a surfactant, an adhesion aid, a dissolution accelerator, a filler, a sensitizer, and polyphenols.
  • solvent The photosensitive resin composition described in this embodiment can be used as a varnish by dissolving each of the above-mentioned components in a solvent.
  • solvents include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, and dipropylene glycol.
  • Monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, and methyl -3-methoxypropionate and the like can be mentioned.
  • the photosensitive resin composition of the present embodiment contains a filler, a binder resin other than the above-mentioned polymer, a cross-linking agent, an acid generator, a heat resistance improver, a developing aid, a plasticizer, and the like, depending on the purpose and required characteristics of each application.
  • Polymerizers, UV absorbers, antioxidants, matting agents, defoaming agents, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, rocking agents, rocking aids, surfactants , Silane-based, aluminum-based, titanium-based coupling agents, polyhydric phenol compounds, and other components other than the above essential components may be blended.
  • the method for preparing the photosensitive resin composition in the present embodiment is not limited, and it can be prepared by using a conventionally known method.
  • each of the above components can be prepared by mixing and dissolving in a solvent. Thereby, a photosensitive resin composition as a varnish can be obtained.
  • the photosensitive resin composition of the present embodiment can be used as a cured product to obtain a resin film.
  • a resin film can be used, for example, as a resist, and can also form, for example, a protective film for an electronic device, an interlayer film, or a permanent film such as a dam material.
  • the photosensitive resin composition of the present embodiment preferably has a transmittance of 95% or more, more preferably 98% or more, as measured under the following conditions.
  • (conditions) A photosensitive resin composition is applied onto a glass substrate, dried at 100 ° C. for 120 seconds, and exposed to an exposure amount of 300 mJ / cm 2 , and the resin film A having a thickness of 3 ⁇ m is exposed to light having a wavelength of 400 nm. the light transmittance was evaluated with a spectrophotometer, and the pre-heat resistance test transmittance T a%.
  • the photosensitive resin composition of the present embodiment preferably has a heat-resistant discoloration property of the resin film of 95% or more, more preferably 96% or more, as measured under the following conditions.
  • (conditions) A photosensitive resin composition is applied onto a glass substrate, dried at 100 ° C. for 120 seconds, and exposed to an exposure amount of 300 mJ / cm 2 , and the resin film A having a thickness of 3 ⁇ m is exposed to light having a wavelength of 400 nm. the light transmittance was evaluated with a spectrophotometer, and the pre-heat resistance test transmittance T a%.
  • the permanent film obtained by curing the photosensitive resin composition of the present invention is a permanent film having excellent transmittance and heat-resistant discoloration. Therefore, it is not colored even when it is heated, especially in applications requiring transparency. It is preferable to apply it to a coloring pattern, a black matrix, an overcoat, a rib, and a spacer of an electronic device having various display devices such as a liquid crystal display device and an organic EL element.
  • the solution after the reaction was poured into a large amount of methanol to precipitate a polymer.
  • the polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours.
  • the yield of the polymer was 145.3 g, and the yield was 97%.
  • the polymer had a weight average molecular weight Mw of 3,500 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.62.
  • the yield of the polymer was 56.0 g and the yield was 64%.
  • the polymer had a weight average molecular weight Mw of 4,500 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.59.
  • the polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours.
  • the yield of the polymer was 92.5 g and the yield was 93%.
  • the polymer had a weight average molecular weight Mw of 6,900 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.76.
  • the polymer had a weight average molecular weight Mw of 7,600 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.88.
  • the polymer had a weight average molecular weight Mw of 4,900 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 2.11. Table 1 shows the blending amounts of the components used in Synthesis Examples 1 to 5, and the weight average molecular weight and dispersity of the obtained precursor polymer.
  • the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
  • the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
  • Synthesis Example 7 Synthesis of Polymer B-1) 20.0 g of the precursor polymer B synthesized in Synthesis Example 2 was dissolved in 30.0 g of MEK. Further, 11.6 g of 2-hydroxyethyl acrylate (HEA) and 2.0 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and the reaction was carried out for 6 hours. The reaction mixture was then cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer.
  • HOA 2-hydroxyethyl acrylate
  • TEA triethylamine
  • the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
  • the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
  • the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
  • the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
  • Synthesis Example 9 Synthesis of Polymer D-1) 20.0 g of the precursor polymer D synthesized in Synthesis Example 4 was dissolved in 30.0 g of MEK. Further, 9.0 g of 2-hydroxyethyl acrylate (HEA) and 2.0 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and then the reaction was carried out for 6 hours. The reaction mixture was then cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer.
  • HOA 2-hydroxyethyl acrylate
  • TEA triethylamine
  • the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
  • the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
  • Synthesis Example 10 Synthesis of Polymer E-1) 5.0 g of the precursor polymer D synthesized in Synthesis Example 5 was dissolved in 7.5 g of MEK. Further, 2.9 g of 2-hydroxyethyl acrylate (HEA) and 0.5 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and the reaction was carried out for 6 hours. The reaction mixture was then cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer.
  • HOA 2-hydroxyethyl acrylate
  • TEA triethylamine
  • the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
  • the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
  • the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) are converted to polystyrene obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement. Use the value.
  • the measurement conditions are as follows. Equipment: Tosoh gel permeation chromatography equipment HLC-8320GPC Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C Solvent: THF Sample concentration: 2.0 mg / ml
  • the double bond equivalent of the polymer was measured by the following method. First, about 50 mg of the polymer which was dried under reduced pressure to remove the solvent and about 5 mg of dimethyl terephthalate as an internal standard substance were weighed and dissolved in DMSO-d6. This solution was measured by 1H-NMR using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL Ltd.). From the integral ratio of the signal derived from the (meth) acrylic group (5-7 ppm) of the obtained spectrum chart and the signal (4H, 8.1 ppm) of the phenyl group of the internal standard substance, the polymer weight per mole of the double bond ( g / mol, double bond equivalent) was calculated.
  • ⁇ Preparation of photosensitive resin composition For each 100 parts by mass of the polymers obtained in Synthesis Examples 6 to 10, 50 parts by mass of dipentaerythritol hexaacrylate (crosslinking agent 1, DPHA) as a cross-linking agent and a photoradical initiator as a photosensitizer (manufactured by BASF). , Irgacure OXE01) 10 parts by mass, adhesion aid (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd., KBM-403) 1 part by mass, surfactant (DIC Co., Ltd., F556) 0.
  • crosslinking agent 1 dipentaerythritol hexaacrylate
  • photoradical initiator as a photosensitizer
  • Crosslinking agent -Crosslinking agent 1: An acrylic crosslinking agent represented by the following formula (12) (DPHA manufactured by Daicel Cytec).
  • Photosensitive agent Photosensitizer 1: A photoradical polymerization initiator (Irgaceure OXE02 manufactured by BASF) represented by the following formula (11) was used.
  • Adhesion aid 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Surfactant 1 Megafuck F-556 (manufactured by DIC Corporation)
  • the obtained photosensitive resin composition was evaluated according to the following.
  • Light transmittance T A For each Example and each Comparative Example, the light transmittance of the resin film A formed by using the photosensitive resin composition was measured as follows. First, the obtained photosensitive resin composition was applied to a glass substrate using a spin coater, and then baked on a hot plate at 110 ° C. for 110 seconds. As the glass substrate, a 1737 glass substrate manufactured by Corning Inc. having a size of 100 mm in length and 100 mm in width was used. Then, the entire photosensitive resin composition was exposed with g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. at 300 mJ / cm 2 . Then, of the resin film A, and measured for light transmittance T A (%) with respect to light having a wavelength of 400 nm. Light transmittance T A was measured using an ultraviolet-visible spectrophotometer. The results are shown in Table 3.

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Abstract

L'invention concerne une composition de résine photosensible qui comprend un copolymère représenté par la formule générale (1), un agent de réticulation et un photosensibilisateur.
PCT/JP2020/017228 2019-05-08 2020-04-21 Composition de résine photosensible, film de résine et dispositif électronique WO2020226052A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022065225A1 (fr) * 2020-09-23 2022-03-31 住友ベークライト株式会社 Polymère, solution de polymère et composition de résine photosensible

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10111569A (ja) * 1996-02-09 1998-04-28 Japan Synthetic Rubber Co Ltd 感放射線性樹脂組成物
JP2014102503A (ja) * 2012-11-19 2014-06-05 Rohm & Haas Electronic Materials Llc 自己組織化構造、その製造方法およびそれを含む物品
JP2014517087A (ja) * 2011-04-21 2014-07-17 エルジー・ケム・リミテッド 高分子およびそれを含む感光性樹脂組成物｛ｐｏｌｙｍｅｒａｎｄｐｈｏｔｏｓｅｎｓｉｔｉｖｅｒｅｓｉｎｃｏｍｐｏｓｉｔｉｏｎｃｏｍｐｒｉｓｉｎｇｔｈｅｓａｍｅ｝
WO2018131351A1 (fr) * 2017-01-10 2018-07-19 住友ベークライト株式会社 Composition de résine photosensible négative, film de résine et dispositif électronique
JP2018124502A (ja) * 2017-02-03 2018-08-09 住友ベークライト株式会社 感光性樹脂組成物とそれにより生成される樹脂膜及び樹脂膜を備える電子装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10111569A (ja) * 1996-02-09 1998-04-28 Japan Synthetic Rubber Co Ltd 感放射線性樹脂組成物
JP2014517087A (ja) * 2011-04-21 2014-07-17 エルジー・ケム・リミテッド 高分子およびそれを含む感光性樹脂組成物｛ｐｏｌｙｍｅｒａｎｄｐｈｏｔｏｓｅｎｓｉｔｉｖｅｒｅｓｉｎｃｏｍｐｏｓｉｔｉｏｎｃｏｍｐｒｉｓｉｎｇｔｈｅｓａｍｅ｝
JP2014102503A (ja) * 2012-11-19 2014-06-05 Rohm & Haas Electronic Materials Llc 自己組織化構造、その製造方法およびそれを含む物品
WO2018131351A1 (fr) * 2017-01-10 2018-07-19 住友ベークライト株式会社 Composition de résine photosensible négative, film de résine et dispositif électronique
JP2018124502A (ja) * 2017-02-03 2018-08-09 住友ベークライト株式会社 感光性樹脂組成物とそれにより生成される樹脂膜及び樹脂膜を備える電子装置

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022065225A1 (fr) * 2020-09-23 2022-03-31 住友ベークライト株式会社 Polymère, solution de polymère et composition de résine photosensible
JPWO2022065225A1 (fr) * 2020-09-23 2022-03-31
JP7173380B2 (ja) 2020-09-23 2022-11-16 住友ベークライト株式会社 ポリマー、ポリマーの製造方法、ポリマー溶液および感光性樹脂組成物

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