WO2018131351A1 - ネガ型感光性樹脂組成物、樹脂膜及び電子装置 - Google Patents

ネガ型感光性樹脂組成物、樹脂膜及び電子装置 Download PDF

Info

Publication number
WO2018131351A1
WO2018131351A1 PCT/JP2017/044142 JP2017044142W WO2018131351A1 WO 2018131351 A1 WO2018131351 A1 WO 2018131351A1 JP 2017044142 W JP2017044142 W JP 2017044142W WO 2018131351 A1 WO2018131351 A1 WO 2018131351A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
negative photosensitive
structural unit
formula
Prior art date
Application number
PCT/JP2017/044142
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
陽雄 池田
Original Assignee
住友ベークライト株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友ベークライト株式会社 filed Critical 住友ベークライト株式会社
Priority to JP2018509928A priority Critical patent/JP6332583B1/ja
Priority to CN201780083437.8A priority patent/CN110178085B/zh
Priority to KR1020197023189A priority patent/KR102614402B1/ko
Publication of WO2018131351A1 publication Critical patent/WO2018131351A1/ja

Links

Images

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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • 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
    • C08F290/02—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 end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a negative photosensitive resin composition, a resin film, and an electronic device.
  • Patent Document 1 a radiation-sensitive resin composition containing a [A] polymer and a [B] acid generator is described. And, because the [A] polymer has the structural unit (I) and the structural unit (II), it is excellent in LWR (Line Width Roughness) performance and defect suppression property, which indicates a small variation in line width.
  • LWR Line Width Roughness
  • the structural unit (I) is N- (t-butyloxycarbonylmethyl) maleimide, N- (1-methyl-1-cyclopentyloxycarbonylmethyl) maleimide, or N- (2-ethyl-2-adamantyloxy) It is described that it is a structural unit derived from (carbonylmethyl) maleimide. Further, it is described that the structural unit (II) is a structural unit derived from 2-norbornene.
  • the inventor produced a resin film made of a negative photosensitive resin composition, and examined the durability of the resin film such as heat resistance and solvent resistance, and developability such as the remaining film ratio after development. As a result, it has been found that the resin film made of the radiation-sensitive resin composition described in Patent Document 1 has room for further improvement in terms of durability and developability. Then, this invention makes it a subject to provide the negative photosensitive resin composition which can improve durability and developability with sufficient balance, without impairing alkali developability.
  • the present inventor In order to improve the durability such as heat resistance and solvent resistance of a resin film made of a negative photosensitive resin composition and the developability such as the remaining film ratio after development, the present inventor The structural unit with As a result, the copolymer has a norbornene-type structural unit substituted with a functional group containing a terminal carbon unsaturated double bond, a norbornene-type structural unit substituted with a carboxyl group, maleic anhydride, maleic anhydride It has been found that by including a derivative, a maleimide or a structural unit derived from a maleimide derivative, durability and developability can be improved in a balanced manner without impairing alkali developability. As described above, the present inventors include a copolymer containing a specific structural unit, so that the durability and developability of the resin film using the negative photosensitive resin composition can be obtained without impairing alkali developability. The present invention has been completed.
  • a polymer which is a copolymer represented by the following formula (1); A crosslinking agent; A negative photosensitive resin composition containing a photosensitive agent is provided.
  • A is a structural unit represented by the following formula (A1);
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and at least R 1 , R 2 , R 3 and R 4 Contains one terminal unsaturated carbon double bond, n is 0, 1 or 2)
  • R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.
  • R 8 is independently an organic group having 1 to 30 carbon atoms.
  • R 9 and R 10 are each independently an organic group having 1 to 30 carbon atoms.
  • R 11 is independently an organic group having 1 to 30 carbon atoms.
  • a resin film comprising the above negative photosensitive resin composition.
  • an electronic device including the resin film is provided.
  • a negative photosensitive resin composition capable of improving the durability and developability of a resin film comprising a negative photosensitive resin composition without impairing alkali developability.
  • a to B mean A or more and B or less.
  • summary of the negative photosensitive resin composition of this embodiment is demonstrated.
  • the negative photosensitive resin composition of the present embodiment is A polymer which is a copolymer represented by the following formula (1); A crosslinking agent; And a photosensitizer.
  • A is a structural unit represented by the following formula (A1);
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and at least R 1 , R 2 , R 3 and R 4 Contains one terminal unsaturated carbon double bond, n is 0, 1 or 2)
  • R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.
  • R 8 is independently an organic group having 1 to 30 carbon atoms.
  • R 9 and R 10 are each independently an organic group having 1 to 30 carbon atoms.
  • R 11 is independently an organic group having 1 to 30 carbon atoms.
  • the copolymer comprises a norbornene-type structural unit substituted with a functional group containing a terminal unsaturated carbon double bond, a norbornene-type structural unit substituted with a carboxyl group, and maleic anhydride. And structural units derived from maleic anhydride derivatives, maleimides or maleimide derivatives.
  • the negative photosensitive resin composition according to this embodiment is cured by the radical chain reaction caused by the photosensitizer generating radicals upon exposure.
  • the negative photosensitive resin composition according to the present embodiment it is considered that the terminal unsaturated carbon double bond of the norbornene side chain of the copolymer contributes to the radical chain reaction.
  • the negative photosensitive resin composition according to the present embodiment has a crosslinked structure formed by radical chain reaction as compared with the conventional negative photosensitive resin composition. It is estimated that the density can be improved and the mobility of the molecular chain can be more limited. Therefore, durability such as heat resistance and solvent resistance of a cured film of the negative photosensitive resin composition and developability such as a remaining film ratio after development can be improved.
  • the negative photosensitive resin composition according to the present embodiment is, for example, partially exposed and cured as described above, while the portion is not exposed and not cured. And the unexposed part which is not hardened
  • the norbornene-type structural unit substituted with a functional group containing a terminal unsaturated carbon double bond substitutes a part of the norbornene-type structural unit substituted with a carboxyl group. Formed by. And the norbornene-type structural unit substituted by a part of carboxyl group remains in a copolymer as it is.
  • the copolymer which concerns on this embodiment contains the norbornene-type structural unit provided with a carboxyl group.
  • alkali solubility can be improved.
  • the alkali solubility of the copolymer can be appropriately controlled by including a structural unit derived from maleic anhydride, a maleic anhydride derivative, a maleimide or a maleimide derivative.
  • the alkali solubility is lowered simply by making the structure easy to crosslink. There was an inconvenience that it would end up.
  • the negative photosensitive resin composition according to this embodiment includes a norbornene type structural unit in which the copolymer is substituted with a functional group containing a terminal unsaturated carbon double bond, and a norbornene type substituted with a carboxyl group.
  • a norbornene type structural unit in which the copolymer is substituted with a functional group containing a terminal unsaturated carbon double bond
  • a norbornene type substituted with a carboxyl group By improving the durability and developability of the cured film without deteriorating alkali solubility, it is possible to include the structural unit of the above and the structural unit derived from maleic anhydride, maleic anhydride derivative, maleimide or maleimide derivative. can do.
  • the negative photosensitive resin composition according to this embodiment can improve the durability and developability of the resin film made of the negative photosensitive resin composition without impairing the alkali developability. .
  • the negative photosensitive resin composition according to the present embodiment includes a polymer, a crosslinking agent, and a photosensitive agent.
  • the polymer according to this embodiment is a copolymer represented by the following formula (1).
  • following formula (1) does not limit the arrangement
  • a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, or the like can be selected.
  • A is a structural unit represented by the following formula (A1);
  • the composition ratio between the structural unit A and the structural unit B in the copolymer will be described.
  • the molar content (mol%) of the structural unit of A is 1
  • the numerical range of 1 is 0.1 ⁇ l ⁇ 0.9
  • the numerical range of m is 0.1 ⁇ m ⁇ 0.9.
  • A is a structural unit derived from a norbornene-type monomer substituted by a functional group containing a terminal unsaturated carbon double bond represented by the following formula (A1): And a structural unit derived from a norbornene-type monomer substituted with a carboxyl group represented by the following formula (A2).
  • A1 a structural unit derived from a norbornene-type monomer substituted by a functional group containing a terminal unsaturated carbon double bond represented by the following formula (A1):
  • A2 a structural unit derived from a norbornene-type monomer substituted with a carboxyl group represented by the following formula (A2).
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and at least R 1 , R 2 , R 3 and R 4 Contains one terminal unsaturated carbon double bond, n is 0, 1 or 2)
  • R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.
  • R 1 to R 4 in the above formula (A1) and R 5 to R 7 in the above formula (A2) are hydrogen or an organic group having 1 to 30 carbon atoms in the structure. May contain one or more atoms selected from O, N, S, P and Si. Furthermore, in this embodiment, the organic group which comprises R ⁇ 1 >, R ⁇ 2 >, R ⁇ 3 > and R ⁇ 4 > does not have any acidic functional group. Thereby, control of the acid value in a polymer can be made easy.
  • R 1 to R 4 in the above formula (A1) and R 5 to R 7 in the above formula (A2) are each independently hydrogen or an organic compound having 1 to 30 carbon atoms.
  • Each of which is independently hydrogen or an organic group having 1 to 10 carbon atoms, more preferably independently hydrogen or an organic group having 1 to 5 carbon atoms. More preferred is hydrogen or an organic group having 1 to 3 carbon atoms.
  • examples of the organic group constituting R 1 to R 4 in the above formula (A1) and R 5 to R 7 in the above formula (A2) include an alkyl group, an alkenyl group, and an alkynyl group. , Alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, and heterocyclic group.
  • 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, heptyl group, An octyl group, a nonyl group, and a decyl group are mentioned.
  • alkenyl group examples include allyl group, pentenyl group, and vinyl group. An ethynyl group is mentioned as an alkynyl group.
  • Examples of the alkylidene group include a methylidene group and an ethylidene group.
  • Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group.
  • Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
  • R 1 , R 2 , R 3 and R 4 include at least one terminal unsaturated carbon double bond.
  • the structural unit which is radicalized at the time of exposure and contributes to a crosslinked structure can be increased.
  • the side chain of the norbornene-type structural unit contributes to the crosslinked structure, so that the movement of the polymer chain can be more firmly limited.
  • the heat resistance of a negative photosensitive resin composition, solvent resistance, and the remaining film rate after image development can be improved with sufficient balance.
  • one containing a terminal unsaturated carbon double bond is preferably any one of R 1 to R 4 .
  • the functional group containing a terminal unsaturated carbon double bond does not become a steric hindrance, and is preferable from the viewpoint that a suitable crosslinked structure can be formed.
  • n is independently 0, 1 or 2
  • n is 0 or 1
  • n is 0.
  • R 1 , R 2 , R 3 and R 4 preferably contain a structure represented by the following formula (E1) in order to contain a terminal unsaturated carbon double bond.
  • E1 a structure represented by the formula (E1)
  • E2 a structure represented by the following formula (E2).
  • R e is independently hydrogen or an organic group having 1 to 10 carbon atoms.
  • R e is independently hydrogen or an organic group having 1 to 10 carbon atoms.
  • R e is independently hydrogen or an organic group having 1 to 10 carbon atoms, preferably hydrogen or an organic group having 1 to 7 carbon atoms, It is more preferably an organic group having 1 to 5 carbon atoms, more preferably hydrogen or an organic group having 1 to 3 carbon atoms, and particularly preferably hydrogen or an organic group having 1 carbon atom.
  • R 1 , R 2 , R 3 and R 4 containing a terminal unsaturated carbon double bond include vinyl group, vinylidene group, acrylic group, methacryl group, acrylate group, methacrylate group and the like.
  • R 1 , R 2 , R 3 and R 4 including a terminal unsaturated carbon double bond may be at least one selected from the group consisting of an acryl group, a methacryl group, an acrylate group and a methacrylate group. Preferably, it is an acrylate group or a methacrylate group.
  • the lower limit of the content of the structural unit represented by the above formula (A1) in the copolymer is preferably 0.1 mol or more with respect to 1 mol of the structural unit represented by the above formula (A2), More preferably, it is 0.2 mol or more. Thereby, a suitable crosslinked structure can be formed.
  • the upper limit of the content of the structural unit represented by the above formula (A1) in the copolymer is, for example, 3.0 mol or less with respect to 1 mol of the structural unit represented by the above formula (A2). It is preferably 2.0 mol or less, more preferably 1.0 mol or less, and even more preferably 0.7 mol or less. Thereby, alkali solubility can be expressed suitably.
  • the content of the structural unit represented by the above formula (A1) with respect to 1 mol of the structural unit represented by the above formula (A1) in the polymer is, for example, a nuclear magnetic resonance apparatus (for example, JEOL Ltd.). Can be evaluated by 1H-NMR measurement.
  • a nuclear magnetic resonance apparatus for example, JEOL Ltd.
  • B represents the following formula (B1), the following formula (B2), the following formula (B3), the following formula (B4), the following formula (B5), or the following formula.
  • Including at least one of the structural units represented by (B6) it is preferable to include a structural unit represented by the following formula (B5) or the following formula (B6).
  • the following formula (B6) is included in the following formula (B5) or the following formula (B6).
  • R 8 is independently an organic group having 1 to 30 carbon atoms.
  • R 9 and R 10 are each independently an organic group having 1 to 30 carbon atoms.
  • R 11 is independently an organic group having 1 to 30 carbon atoms.
  • B preferably further includes a structural unit represented by the above formula (B5) in addition to the structural unit represented by the above formula (B6).
  • the organic group having 1 to 30 carbon atoms constituting R 8 to R 11 in the above formulas (B1), (B2), and (B6) has O, N, S, One or more atoms selected from P and Si may be included. Further, in the present embodiment, any of organic groups constituting R 8 to R 11 may not have an acidic functional group. Thereby, control of the acid value in a polymer can be made easy.
  • R 8 to R 11 in the above formulas (B1), (B2), and (B6) are each independently an organic group having 1 to 30 carbon atoms, and each independently It is preferably an organic group having 1 to 10 carbon atoms, more preferably independently an organic group having 1 to 5 carbon atoms, and each independently an organic group having 1 to 3 carbon atoms. Is more preferable.
  • the organic groups constituting R 8 to R 11 in the above formulas (B1), (B2), and (B6) include R 1 to R 4 in the above formula (A1), and An organic group similar to the organic group constituting R 5 to R 7 in the above formula (A2) can be used.
  • the upper limit value of Mw (weight average molecular weight) of the polymer according to this embodiment is, for example, 30000 or less, preferably 20000 or less, more preferably 14000 or less, and even more preferably 10,000 or less. preferable. Thereby, the mobility of a molecular chain improves and a more suitable crosslinked structure can be made.
  • the lower limit value of the polymer Mw is, for example, 1500 or more, preferably 2000 or more, and more preferably 3000 or more. Thereby, when exposing a negative photosensitive resin composition, it becomes possible to form a crosslinked structure rapidly. Therefore, the sensitivity of the negative photosensitive resin composition can be improved.
  • the degree of dispersion of the polymer according to the present embodiment that is, the upper limit value of Mw (weight average molecular weight) / Mn (number average molecular weight) is, for example, 2.5 or less and 2.2 or less. Preferably, it is 2.0 or less.
  • variety of the molecular weight distribution of a polymer can be reduced, and the same crosslinked structure can be formed in the whole negative photosensitive resin composition. Therefore, the physical properties can be made uniform throughout the cured product of the negative photosensitive resin composition.
  • the lower limit of Mw / Mn may be 1.0 or more, for example, and can be 1.5 or more. Mw / Mn is preferably closer to monodispersion.
  • Mw / Mn is a 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
  • a polystyrene conversion value obtained from a standard polystyrene (PS) calibration curve obtained by GPC measurement is used.
  • the measurement conditions are, for example, as follows.
  • Tosoh gel permeation chromatography device HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
  • Solvent THF Sample concentration: 2.0 mg / ml
  • the alkali dissolution rate of the polymer in the present embodiment is, for example, not less than 500 kg / sec and not more than 20,000 kg / sec.
  • the alkali dissolution rate of the polymer can be determined by, for example, dissolving a polymer in propylene glycol monomethyl ether acetate and applying a polymer solution adjusted to a solid content of 20% by weight on a silicon wafer by a spin method, followed by soft baking at 110 ° C. for 100 seconds.
  • the polymer film thus obtained is impregnated with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C., and the time until the polymer film is visually erased is calculated.
  • the alkali dissolution rate of the polymer By setting the alkali dissolution rate of the polymer to 500 kg / second or more, it is possible to improve the throughput in the development step using an alkali developer. Moreover, the residual film rate after the image development process by an alkali developing solution can be improved by making the alkali dissolution rate of a polymer into 20,000 kg / sec or less. For this reason, it is possible to suppress film loss due to the lithography process.
  • the polymer according to this embodiment is produced, for example, as follows.
  • a ring-opening step (treatment) S′1) and then a cleaning step (processing S′2) for removing residual metal components may be included. Details of each step will be described below.
  • a norbornene type monomer substituted with a carboxyl group and maleic anhydride, maleimide or a maleimide derivative are prepared.
  • the norbornene type monomer substituted with the carboxyl group (hereinafter referred to as monomer A) is derived from the structural unit represented by A.
  • one or more monomers selected from the group consisting of maleic anhydride, maleimide and maleimide derivatives (hereinafter referred to as monomer B) are derived from the structural unit represented by B.
  • Monomer A is represented by the following formula (2).
  • R 5 to R 7 can be the same as those in the above-described formula (A2).
  • R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.
  • norbornene-type monomer substituted by the carboxyl group represented by the above formula (2) include 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and tetracyclododecenecarboxylic acid. An acid etc. are mentioned.
  • the norbornene type monomer substituted with a carboxyl group one or more of these can be used. Of these, 5-norbornene-2-carboxylic acid is preferably used from the viewpoint of improving heat resistance.
  • Monomer B is one or more monomers selected from the group consisting of maleic anhydride, maleimide and maleimide derivatives, and one or more monomers selected from the group consisting of maleimide and maleimide derivatives.
  • a maleimide derivative By using a maleimide derivative, the heat resistance, the remaining film ratio after curing, and the solvent resistance can be improved. Further, by using maleimide and a maleimide derivative in combination, the alkali dissolution rate of the negative photosensitive resin composition can be improved, and further the sensitivity can be improved.
  • the maleimide derivative is represented by the following formula (3).
  • R 11 is independently an organic group having 1 to 30 carbon atoms.
  • maleimide derivatives represented by the above formula (3) include N-linear alkylmaleimides such as N-methylmaleimide and N-ethylmaleimide; N-branched alkylmaleimides such as N-isopropylmaleimide; N-cyclohexylmaleimide And N-arylmaleimide such as N-phenylmaleimide and N-naphthylmaleimide.
  • N-linear alkylmaleimides such as N-methylmaleimide and N-ethylmaleimide
  • N-branched alkylmaleimides such as N-isopropylmaleimide
  • N-arylmaleimide such as N-phenylmaleimide and N-naphthylmaleimide.
  • linear N-alkylmaleimide, branched alkylmaleimide or N-cycloalkylmaleimide is preferably used, and N-cycloalkylmaleimide
  • the copolymer 1 is synthesized by addition polymerization of the monomer A and the monomer B.
  • the method of addition polymerization is not particularly limited, but in this embodiment, the copolymer 1 is synthesized by radical polymerization.
  • copolymer 1 having a structural unit derived from monomer A and a structural unit derived from monomer B can be synthesized.
  • the structural unit derived from the monomer A is represented by the following formula (A2).
  • R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.
  • R 11 is independently an organic group having 1 to 30 carbon atoms.
  • the molar ratio of monomer A to monomer B is preferably 0.5: 1 to 1: 0.5. Among these, from the viewpoint of controlling the molecular structure, the molar ratio is preferably 1: 1. Monomer A, monomer B, and a polymerization initiator are dissolved in a solvent, and then heated for a predetermined time to cause addition polymerization to proceed.
  • the heating temperature is, for example, 50 to 80 ° C., and the heating time is 10 to 20 hours.
  • azo compounds and organic peroxides can be used as the polymerization initiator.
  • the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis (2-methylpropionate), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN). Any one or more of these can be used.
  • the organic peroxide include hydrogen peroxide, ditertiary butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Any one or more of them can be used.
  • the amount (number of moles) of the polymerization initiator is 1% to the total number of moles of the norbornene-type monomer substituted with the carboxyl group derived from the structural unit A and the monomer derived from the structural unit B. 10% is preferable.
  • the weight average molecular weight (Mw) of the resulting polymer can be adjusted to 5000-30000 by appropriately setting the amount of the polymerization initiator within the above range and appropriately setting the reaction temperature and reaction time.
  • solvent for example, one or more of diethyl ether, tetrahydrofuran, toluene and the like can be used.
  • copolymer 1 which is a copolymer of monomer A and monomer B can be polymerized.
  • sequence of the copolymer 1 is not specifically limited, Any of a random copolymer, an alternating copolymer, a block copolymer, and a periodic copolymer may be sufficient.
  • the copolymer 1 is represented by the following formula (4). A copolymer having a structural unit is formed.
  • R 5 to R 7 are the same as the above formula (A2). Also, R 11 is the same as the above formula (3).
  • the functional groups of R 5 to R 7 derived from the monomer A may be different in each repeating unit or may be common. Among these, it is preferable that they are common. Thereby, the patterning precision of a negative photosensitive resin composition can be improved.
  • the method for substituting the copolymer 1 and synthesizing the copolymer 2 is not particularly limited, for example, the following method can be used.
  • the copolymer 1 and the compound having a terminal unsaturated carbon double bond are dissolved in a solvent and heated for a predetermined time, whereby the substitution reaction proceeds to synthesize the copolymer 2.
  • the heating temperature is, for example, 50 to 100 ° C.
  • the heating time is 2 to 20 hours.
  • a common unit comprising a repeating unit derived from the monomer A, a repeating unit in which the monomer A is substituted with a compound having a terminal unsaturated carbon double bond, and a structural unit derived from the monomer B.
  • Polymer 2 can be obtained.
  • a structural unit in which the monomer A is substituted with a compound having a terminal unsaturated carbon double bond is shown in the following formula (A1).
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and at least R 1 , R 2 , R 3 and R 4 Contains one terminal unsaturated carbon double bond, n is 0, 1 or 2)
  • an acrylic compound is preferably used as the compound having a terminal unsaturated carbon double bond.
  • the acrylic compound include methacrylic acid methacrylic acid (glycidyl methacrylate), glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, hydroxyethyl methacrylate, and the like. Among these, it is preferable to use glycidyl methacrylate.
  • solvent for example, one or more of diethyl ether, tetrahydrofuran, toluene and the like can be used.
  • the copolymer 2 for example, it is preferable to replace 5 mol% or more of structural units with the structural unit represented by the above formula (A1) with respect to all the structural units represented by A, and to replace 10 mol% or more. It is more preferable to substitute 15 mol% or more, and it is more preferable to substitute 20 mol% or more.
  • substitution rate By setting the substitution rate in this way, the terminal unsaturated carbon double bond derived from the norbornene unit can be appropriately crosslinked. Thereby, the heat resistance of the negative photosensitive resin composition containing the copolymer 2 and a residual film rate and solvent resistance can be improved.
  • substitution of some of the repeating units derived from the norbornene-type monomer substituted with a carboxyl group can be identified by spectral data of 1H-NMR measurement.
  • substitution rate which substituted the carboxyl group with the acrylic compound can be measured as follows.
  • the polymer solution of copolymer 2 is subjected to 1H-NMR measurement.
  • the signal integral value X per unit proton derived from the carboxyl group and the signal per unit proton derived from the terminal unsaturated carbon double bond formed by the added acrylic compound An integral value Y is calculated.
  • the extraction operation is preferably repeated until the content of low nuclei having a molecular weight of 1000 or less in the copolymer 2 is 1% or less. Thereby, the amount of the low molecular weight component in the first polymer can be reduced to a degree sufficient to suppress the deformation of the film pattern during curing.
  • the ring-opening step (S′1) and the washing step (S′2) are performed after the polymerization step (S1) and before the low molecular weight component removal step (S3). You may go. This will be described below.
  • the ring-opening rate of the repeating unit derived from maleic anhydride can be measured as follows.
  • the IR absorption intensity (A1) of (C ⁇ O) in the acid anhydride structure of copolymer 1 or copolymer 2 before ring opening was measured, and (C ⁇ O) in the acid anhydride structure after ring opening was measured.
  • the ring opening rate is calculated from the IR absorption intensity (A2) by the following formula.
  • Ring-opening rate (%) ((A1-A2) / A1) ⁇ 100 Acetonitrile is used as an internal standard substance.
  • reaction liquid L1 a part of the anhydride ring of the repeating unit derived from the maleic anhydride of the copolymer 1 is opened, and a part of the terminal formed by the ring opening is esterified. The remaining terminals are not esterified and have a metal salt structure.
  • the number of moles of metal alkoxide or alkali metal hydroxide is preferably 50% or less of the number of moles of maleic anhydride used in the polymerization step.
  • the number of moles of metal alkoxide or alkali metal hydroxide is preferably 40% or less, 10% or more, and more preferably 30% or less of the number of moles of maleic anhydride used in the polymerization step. It is preferable. By doing so, the amount of metal alkoxide or alkali metal hydroxide can be reduced, and the alkali metal concentration in the finally obtained polymer can be reduced. By reducing the alkali metal concentration in the polymer, migration of metal ions can be suppressed when a device using this polymer is formed.
  • the metal alkoxide described above is preferably one represented by M (OR 8 ) (M is a monovalent metal and R 8 is an organic group having 1 to 18 carbon atoms).
  • M is a monovalent metal and R 8 is an organic group having 1 to 18 carbon atoms.
  • the metal M include alkali metals, and sodium is preferable from the viewpoint of handleability.
  • the R 8, are the same as those for R 8 in example above formula (B1). Two or more different metal alkoxides may be used. However, from the viewpoint of production stability, it is preferable to use one kind of metal alkoxide.
  • the maleic anhydride-derived structure of copolymer 1 or copolymer 2 may be ring-opened in the presence of (B) an alcohol and an alkali metal hydroxide as a base.
  • an alcohol As the alkali metal hydroxide, sodium hydroxide is preferable from the viewpoint of handleability.
  • the alcohol monovalent alcohol (R 8 OH) is preferable. What was mentioned above can be used for R ⁇ 8 > which is an organic group. R 8 preferably has 30 or less carbon atoms.
  • the repeating unit derived from maleic anhydride opened in this ring-opening step (treatment S′1) has a structure represented by the following formula (6), and has a structure having a carboxyl group salt moiety.
  • this ring-opening step (treatment S′1) it is preferable that 50% or more of the repeating units derived from maleic anhydride of Copolymer 1 or Copolymer 2 are not opened.
  • a metal for example, Na
  • the amount of metal contained in the product polymer can be reduced.
  • the quantity of the alkali metal in the polymer finally obtained by this embodiment can be reduced, and a desired characteristic can be exhibited in the negative photosensitive resin composition using this polymer.
  • the above-described cleaning step (processing S′2) is repeated, for example, 5 times or more, more preferably 10 times. Further, it is preferable to remove 85% or more of the remaining sodium and more preferably 90% or more by one washing step by adjusting the addition amount of water and organic solvent used in the washing step. Thereby, the density
  • the negative photosensitive resin composition can contain the polymer, a photosensitive agent, and a crosslinking agent. Furthermore, an additive such as a solvent and an adhesion improving agent or a surfactant can be contained.
  • the upper limit of the polymer content is 80 parts by mass or less, preferably 75 parts by mass or less, with respect to 100 parts by mass of the total solid content of the negative photosensitive resin composition. It is still more preferable that it is below mass parts.
  • the lower limit of the content of the polymer is 5 parts by mass or more, preferably 10 parts by mass or more, and 20 parts by mass or less with respect to 100 parts by mass of the total solid content of the negative photosensitive resin composition. More preferably.
  • a radical photopolymerization initiator can be used as the photosensitive agent.
  • the radical photopolymerization initiator include alkylphenone type initiators, oxime ester type initiators, acylphosphine oxide type initiators, and the like.
  • a radical photopolymerization initiator one or a combination of two or more of the above specific examples can be used. Among these, it is preferable to use an oxime ester type radical photopolymerization initiator. Thereby, the photosensitive agent can be radicalized with a low exposure amount, and the sensitivity can be increased.
  • Specific photo radical polymerization initiators include, for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-Morifolinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- Methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetylo Shim), and the like. Among these, you may use 1 type, or 2
  • the upper limit of the content of the photosensitive agent may be 1 part by mass or more, preferably 1.5 parts by mass or more, and preferably 2 parts by mass or more with respect to 100 parts by mass of the polymer. More preferably it is.
  • the reaction rate by exposure can be improved. Therefore, sensitivity can be improved.
  • the lower limit of the content of the photosensitive agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less. Thereby, in a negative photosensitive resin composition, appropriate reactivity with respect to a polymer can be expressed.
  • a known crosslinking agent can be used as the crosslinking agent.
  • the crosslinking agent for example, an acrylic crosslinking agent containing a (meth) acryl group is preferably used.
  • the acrylic crosslinking agent is, for example, a polyfunctional acrylic compound.
  • the polyfunctional acrylic compound is a compound having two or more (meth) acryl groups.
  • a (meth) acryl group shows an acryl group or a methacryl group, ie, a methacryl group.
  • the acrylic group includes an acrylate group.
  • the methacryl group includes a methacrylate group, that is, a methacrylate group.
  • the crosslinking agent is preferably an acrylic crosslinking agent
  • the functional group having a terminal unsaturated carbon double bond of the copolymer preferably includes a structure represented by the general formula (E1) or the general formula (E2).
  • Specific polyfunctional acrylic compounds include trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth).
  • trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth).
  • examples include tetrafunctional (meth) acrylates such as acrylate and hexafunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate. Among these, you may use 1 type, or 2 or more types.
  • the lower limit value of the content of the crosslinking agent may be 20 parts by mass or more, preferably 25 parts by mass or more, and 30 parts by mass or more with respect to 100 parts by mass of the polymer. Is more preferable.
  • the upper limit of the content of the crosslinking agent may be 80 parts by mass or less, preferably 75 parts by mass or less, and more preferably 70 parts by mass or less with respect to 100 parts by mass of the polymer. .
  • the negative photosensitive resin composition described in the present embodiment can be used as a varnish by dissolving the above-described components in a solvent.
  • solvents include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, 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, and ethyl and methyl pyruvate -3-Methoxypropionate and the like.
  • ⁇ -butyrolaclone dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether are among these compounds from the viewpoint of significantly suppressing the occurrence of cracks in the resin film. It is preferable to use a compound selected from the group consisting of propylene glycol monomethyl ether acetate.
  • the negative photosensitive resin composition is added as necessary, such as an adhesion improving agent, a surfactant, an antioxidant, a filler, a sensitizer, a silane coupling agent, and a terminal blocking agent.
  • An agent may be included.
  • the resin film according to the present embodiment is made of a cured product of a negative photosensitive resin composition.
  • the resin film of this embodiment consists of the said negative photosensitive resin composition, and can be comprised with these dry films or cured films.
  • the negative photosensitive resin composition of this embodiment is used for forming a resin film such as a resist or a permanent film.
  • a resin film such as a resist or a permanent film.
  • the resist is, for example, a resin obtained by applying a negative photosensitive resin composition by spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, or the like, and removing the solvent. Consists of a membrane.
  • the permanent film is composed of a cured film obtained by exposing and developing the resin film, patterning it into a desired shape, and curing it by heat treatment or the like.
  • the permanent film can be used, for example, as a protective film, an interlayer film, or a dam material.
  • the resin film is used in the electronic device according to the present embodiment.
  • the electronic device 100 of the present embodiment can include the above resin film.
  • An electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip.
  • a semiconductor package can be obtained by mounting the electronic device 100 on the wiring board via the bumps 52.
  • the electronic device 100 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer provided on the semiconductor substrate (not shown).
  • An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layer.
  • the uppermost layer wiring 34 is made of, for example, Al.
  • a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening through which the uppermost layer wiring 34 is exposed is provided in a part of the passivation film 32.
  • a rewiring layer 40 is provided on the passivation film 32.
  • the rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, Have An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42.
  • the rewiring 46 is formed on the insulating layer 42 and in an opening provided in the insulating layer 42, and is connected to the uppermost layer wiring 34.
  • the insulating layer 44 is provided with an opening connected to the rewiring 46.
  • one or more of the passivation film 32, the insulating layer 42, and the insulating layer 44 may be formed of a resin film formed by curing, for example, the above-described negative photosensitive resin composition. it can.
  • the coating film formed of a negative photosensitive resin material is exposed to ultraviolet light, patterned by performing development, and then heated and cured to thereby passivate the passivation film 32, the insulating layer 42, or the insulating layer. 44 is formed.
  • a bump 52 is formed via a UBM (Under Bump Metallurgy) layer 50.
  • the electronic device 100 is connected to a wiring board or the like via bumps 52, for example.
  • Synthesis Example 1 A copolymer is prepared by charging 5-norbornene-2-carboxylic acid and N-cyclohexylmaleimide at a molar ratio of 50/50, and adding glycidyl methacrylate to the copolymer. A polymer was synthesized and designated as Synthesis Example 1. Details will be described below.
  • a polymer which is a copolymer of the above-mentioned 5-norbornene-2-carboxylic acid and N-cyclohexylmaleimide, is weighed into a reaction vessel of an appropriate size equipped with a stirrer and a condenser. (140.0 g).
  • glycidyl methacrylate (GMA, manufactured by Tokyo Chemical Industry Co., Ltd., 20.7 g, 0.146 mol) and triethylamine (1.8 g) were added and heated at 80 ° C. for 5 hours.
  • GMA glycidyl methacrylate
  • triethylamine (1.8 g) were added and heated at 80 ° C. for 5 hours.
  • formic acid was added to the reaction solution for acid treatment, the solution was added dropwise to a large amount of methanol / water mixture (weight ratio 8/2) to precipitate the polymer of Synthesis Example 1.
  • the solid collected by filtration was dried in a vacuum dryer at 40 ° C. for 40 hours to obtain the polymer of Synthesis Example 1.
  • the yield was 50.5 g, Mw was 5,500, and Mw / Mn was 1.65.
  • the obtained polymer of Synthesis Example 1 was dissolved in heavy DMSO, and 1H-NMR measurement was performed using a nuclear magnetic resonance apparatus manufactured by JEOL. From the spectrum obtained by 1H-NMR measurement, a signal derived from the methacryloyl group of the added GMA was confirmed at ⁇ 5.68 and ⁇ 6.07, and a signal derived from the carboxyl group in the polymer was confirmed at ⁇ 12.13. In addition, from the integration ratio of each signal, it was confirmed that the molar ratio of the carboxyl group to the methacryloyl group was 1: 0.3.
  • the dissolved solution was purged with nitrogen for 10 minutes to remove oxygen, and then reacted at 70 ° C. for 6 hours with stirring.
  • a mixed solution of maleimide (14.9 g, 0.154 mol), CMI (50.1 g, 0.279 mol) and MEK 91.0 g was continuously added to the reaction vessel over 6 hours.
  • the mixture was further reacted at 70 ° C. for 3 hours.
  • 200 g of MEK was added to the reaction solution for dilution, it was added dropwise to a large amount of methanol / water mixture (weight ratio 5/5) to precipitate a solid.
  • the solid collected by filtration was dried in a vacuum dryer at 50 ° C.
  • a polymer which is a copolymer of 5-norbornene-2-carboxylic acid, maleimide and N-cyclohexylmaleimide.
  • the yield was 124.3 g, Mw was 4,500, and Mw / Mn was 1.75.
  • glycidyl methacrylate (GMA, manufactured by Tokyo Chemical Industry Co., Ltd., 24.3 g, 0.171 mol) and triethylamine (1.5 g) were added and heated at 90 ° C. for 4 hours.
  • formic acid was added to the reaction solution for acid treatment, it was dropped into a large amount of methanol / water mixture (weight ratio 5/5) to precipitate the polymer of Synthesis Example 2.
  • the solid collected by filtration was dried in a vacuum dryer at 40 ° C. for 40 hours to obtain the polymer of Synthesis Example 2.
  • the yield was 31.2 g, Mw was 4,900, and Mw / Mn was 1.72.
  • the obtained polymer of Synthesis Example 2 was dissolved in heavy DMSO, and 1H-NMR measurement was performed using a nuclear magnetic resonance apparatus manufactured by JEOL. Similar to Synthesis Example 1, a peak derived from the carboxyl group and a peak derived from the structure of the methacryloyl group were confirmed. As a result, it was confirmed that the carboxyl groups in some structural units derived from 5-norbornene-2-carboxylic acid were substituted with glycidyl methacrylate. Therefore, in Synthesis Example 2, it was confirmed that a copolymer having each structural unit represented by the following formula (10) was obtained.
  • the solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated to 60 ° C. with stirring. After 16 hours, MEK (320 g) was added to dilute and cool.
  • the reaction mixture was added dropwise to a large amount of methanol to precipitate a solid, which was filtered using a Nutsche, further washed with methanol, and the solid was collected by filtration.
  • the obtained solid was vacuum dried at 70 ° C. to obtain a copolymer of 2-norbornene and maleic anhydride.
  • the yield was 208.1 g, the weight average molecular weight (Mw) was 11,100, and the dispersity (Mw / Mn) was 2.25.
  • the above-mentioned copolymer of 2-norbornene and maleic anhydride (10.0 g) was weighed and dissolved in MEK (30.0 g) in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Further, 2-hydroxyethyl methacrylate (HEMA, Nippon Shokubai Co., Ltd., 8.5 g, 65 mmol) and sodium acetate (1.0 g) were added and heated at 70 ° C. for 8 hours. To this reaction solution, glycidyl methacrylate (GMA, 1.5 g, 10 mmol) was added, and the mixture was further stirred at 70 ° C. for 16 hours.
  • HEMA 2-hydroxyethyl methacrylate
  • GMA glycidyl methacrylate
  • Table 1 shows the evaluation results of acid value and alkali dissolution rate for the polymers of each synthesis example.
  • Photosensitive agent Photosensitizer 1: A photoradical polymerization initiator represented by the following formula (11) (Irgacure OXE02 manufactured by BASF) was used.
  • Crosslinking agent 1 An acrylic crosslinking agent (DPHA manufactured by Daicel Cytec Co., Ltd.) represented by the following formula (12) was used.
  • Adhesion improver 1 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Surfactant 1 Megafac F-556 (manufactured by DIC Corporation)
  • the cured film of the photosensitive resin composition was peeled from the wafer using hydrofluoric acid, and dried under conditions of 60 ° C. and 10 hours. In this way, a cured film cured at a curing temperature of 200 ° C. was obtained for each of the examples and comparative examples. Next, the 5% weight loss temperature (° C.) of the sample was measured.
  • the measurement was performed on a sample obtained by weighing 10 mg of the cured film using a thermogravimetric / differential calorimeter (TG / DTA), a starting temperature of 30 ° C., a measuring temperature range of 30 to 500 ° C., and a heating rate of 5 The measurement was performed under the conditions of ° C / min. The temperature at which the weight of the weighed sample was reduced by 5% was defined as a 5% weight reduction temperature.
  • TG / DTA thermogravimetric / differential calorimeter
  • the remaining film rate after hardening was evaluated as follows using the obtained negative photosensitive resin composition.
  • the obtained negative photosensitive resin composition was spin-coated on a 4-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 110 ° C. for 100 seconds to obtain a thin film A having a thickness of about 3.0 ⁇ m. .
  • HMDS Hexamethyldisilazane
  • solvent resistance About each Example and each comparative example, solvent resistance was evaluated as follows using the obtained negative photosensitive resin composition.
  • the obtained negative photosensitive resin composition was spin-coated on a 1737 glass substrate made by Corning 100 mm long and 100 mm wide, baked on a hot plate at 110 ° C. for 100 seconds, and with a thin film having a thickness of about 3.0 ⁇ m.
  • a glass substrate was obtained.
  • the glass substrate with a thin film was immersed in N-methylpyrrolidone (Kanto Chemical Co., Inc.) at room temperature (25 ° C.) for 10 minutes, and then rinsed with pure water.
  • the sensitivity evaluation was performed as follows using the obtained negative photosensitive resin composition.
  • the obtained negative photosensitive resin composition was spin-coated on a 4-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 90 ° C. for 120 seconds to obtain a thin film having a thickness of about 3.0 ⁇ m.
  • This thin film was exposed with a g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. using a mask having a 10 ⁇ m line and a space width of 1: 1.
  • PPA-501F g + h + i line mask aligner

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/JP2017/044142 2017-01-10 2017-12-08 ネガ型感光性樹脂組成物、樹脂膜及び電子装置 WO2018131351A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2018509928A JP6332583B1 (ja) 2017-01-10 2017-12-08 ネガ型感光性樹脂組成物、樹脂膜及び電子装置
CN201780083437.8A CN110178085B (zh) 2017-01-10 2017-12-08 负型感光性树脂组合物、树脂膜和电子装置
KR1020197023189A KR102614402B1 (ko) 2017-01-10 2017-12-08 네거티브형 감광성 수지 조성물, 수지막 및 전자 장치

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-002022 2017-01-10
JP2017002022 2017-01-10

Publications (1)

Publication Number Publication Date
WO2018131351A1 true WO2018131351A1 (ja) 2018-07-19

Family

ID=62840203

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/044142 WO2018131351A1 (ja) 2017-01-10 2017-12-08 ネガ型感光性樹脂組成物、樹脂膜及び電子装置

Country Status (4)

Country Link
KR (1) KR102614402B1 (ko)
CN (1) CN110178085B (ko)
TW (1) TWI759378B (ko)
WO (1) WO2018131351A1 (ko)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020023654A (ja) * 2018-07-27 2020-02-13 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、感光性樹脂組成物、パターン、カラーフィルタ、ブラックマトリクス、液晶表示装置および固体撮像素子
JP6777275B1 (ja) * 2019-05-08 2020-10-28 住友ベークライト株式会社 感光性樹脂組成物、樹脂膜および電子装置
WO2020226052A1 (ja) * 2019-05-08 2020-11-12 住友ベークライト株式会社 感光性樹脂組成物、樹脂膜および電子装置
WO2022065225A1 (ja) * 2020-09-23 2022-03-31 住友ベークライト株式会社 ポリマー、ポリマー溶液および感光性樹脂組成物
KR102705672B1 (ko) 2019-05-08 2024-09-12 스미또모 베이크라이트 가부시키가이샤 감광성 수지 조성물, 수지막 및 전자 장치

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021060080A1 (ja) * 2019-09-26 2021-04-01 住友ベークライト株式会社 ポリマー、感光性樹脂組成物、樹脂膜、および電子装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01217453A (ja) * 1988-02-26 1989-08-31 Tosoh Corp 感光性組成物
JPH02146045A (ja) * 1988-02-17 1990-06-05 Tosoh Corp フォトレジスト組成物
JP2015007762A (ja) * 2013-05-29 2015-01-15 住友ベークライト株式会社 ネガ型感光性樹脂組成物、電子装置およびポリマー
WO2016175103A1 (ja) * 2015-04-30 2016-11-03 住友ベークライト株式会社 ポリマーの製造方法、感光性樹脂組成物および電子装置
WO2016194619A1 (ja) * 2015-05-29 2016-12-08 住友ベークライト株式会社 着色感光性樹脂組成物、着色パターンまたはブラックマトリクス、カラーフィルタ、液晶表示装置または固体撮像素子およびカラーフィルタの製造方法
JP2017025223A (ja) * 2015-07-23 2017-02-02 住友ベークライト株式会社 ポリマー、感光性樹脂組成物、樹脂膜および電子装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6065750B2 (ja) * 2013-05-29 2017-01-25 住友ベークライト株式会社 感光性樹脂組成物および電子装置
JP6369132B2 (ja) * 2013-06-28 2018-08-08 住友ベークライト株式会社 ネガ型感光性樹脂組成物、硬化膜、電子装置およびポリマー

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02146045A (ja) * 1988-02-17 1990-06-05 Tosoh Corp フォトレジスト組成物
JPH01217453A (ja) * 1988-02-26 1989-08-31 Tosoh Corp 感光性組成物
JP2015007762A (ja) * 2013-05-29 2015-01-15 住友ベークライト株式会社 ネガ型感光性樹脂組成物、電子装置およびポリマー
WO2016175103A1 (ja) * 2015-04-30 2016-11-03 住友ベークライト株式会社 ポリマーの製造方法、感光性樹脂組成物および電子装置
WO2016194619A1 (ja) * 2015-05-29 2016-12-08 住友ベークライト株式会社 着色感光性樹脂組成物、着色パターンまたはブラックマトリクス、カラーフィルタ、液晶表示装置または固体撮像素子およびカラーフィルタの製造方法
JP2017025223A (ja) * 2015-07-23 2017-02-02 住友ベークライト株式会社 ポリマー、感光性樹脂組成物、樹脂膜および電子装置

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020023654A (ja) * 2018-07-27 2020-02-13 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、感光性樹脂組成物、パターン、カラーフィルタ、ブラックマトリクス、液晶表示装置および固体撮像素子
JP7255166B2 (ja) 2018-07-27 2023-04-11 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、感光性樹脂組成物、パターン、カラーフィルタ、ブラックマトリクス、液晶表示装置および固体撮像素子
JP6777275B1 (ja) * 2019-05-08 2020-10-28 住友ベークライト株式会社 感光性樹脂組成物、樹脂膜および電子装置
WO2020226052A1 (ja) * 2019-05-08 2020-11-12 住友ベークライト株式会社 感光性樹脂組成物、樹脂膜および電子装置
CN113811556A (zh) * 2019-05-08 2021-12-17 住友电木株式会社 感光性树脂组合物、树脂膜和电子装置
TWI833014B (zh) * 2019-05-08 2024-02-21 日商住友電木股份有限公司 感光性樹脂組成物、樹脂膜以及電子裝置
CN113811556B (zh) * 2019-05-08 2024-05-28 住友电木株式会社 感光性树脂组合物、树脂膜和电子装置
KR102705672B1 (ko) 2019-05-08 2024-09-12 스미또모 베이크라이트 가부시키가이샤 감광성 수지 조성물, 수지막 및 전자 장치
WO2022065225A1 (ja) * 2020-09-23 2022-03-31 住友ベークライト株式会社 ポリマー、ポリマー溶液および感光性樹脂組成物
JPWO2022065225A1 (ko) * 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

Also Published As

Publication number Publication date
CN110178085A (zh) 2019-08-27
CN110178085B (zh) 2022-10-21
KR102614402B1 (ko) 2023-12-15
KR20190101460A (ko) 2019-08-30
TW201835128A (zh) 2018-10-01
TWI759378B (zh) 2022-04-01

Similar Documents

Publication Publication Date Title
WO2018131351A1 (ja) ネガ型感光性樹脂組成物、樹脂膜及び電子装置
KR101914409B1 (ko) 폴리머의 제조 방법, 감광성 수지 조성물 및 전자 장치
JP6398310B2 (ja) ネガ型感光性樹脂組成物、電子装置、ネガ型感光性ポリマーの製造方法、およびネガ型感光性樹脂組成物の製造方法
JP7074051B2 (ja) ポリマーの製造方法、ネガ型感光性樹脂組成物の製造方法、樹脂膜の製造方法、電子装置の製造方法およびポリマー
TWI841797B (zh) 聚合物及樹脂組成物
JP6332583B1 (ja) ネガ型感光性樹脂組成物、樹脂膜及び電子装置
CN113366029B (zh) 感光性树脂组合物、聚合物、图案、滤色器、黑矩阵、显示装置及摄像元件
JP6661929B2 (ja) ネガ型感光性樹脂組成物、樹脂膜および電子装置
JP7200532B2 (ja) 感光性樹脂組成物、及び、電子装置
JP2023100610A (ja) 感光性樹脂組成物、パターン、カラーフィルタ、ブラックマトリクス、表示装置、撮像素子、および、表示装置または撮像素子の製造方法
JP6930679B1 (ja) 樹脂組成物、ならびに感光性樹脂組成物およびその硬化物
JP2019167496A (ja) 耐熱性樹脂組成物
JP2014136720A (ja) ポリマーの製造方法
WO2022270546A1 (ja) ネガ型感光性ポリマー、ポリマー溶液、ネガ型感光性樹脂組成物、硬化膜および半導体装置
WO2023140257A1 (ja) ポリマー、ポリマー溶液、感光性樹脂組成物、および硬化物
JP2017044860A (ja) ポジ型感光性樹脂組成物、硬化膜および電子装置
JP2023091961A (ja) ポリマー、ポリマー溶液、感光性樹脂組成物、および硬化物
JP2021140133A (ja) カラーフィルタまたはブラックマトリクス形成用ポリマー溶液
CN114450318A (zh) 聚合物、感光性树脂组合物、树脂膜和电子装置
JP2023091438A (ja) ポリマー、ポリマー溶液、感光性樹脂組成物、および硬化物
JP2023004156A (ja) ネガ型感光性ポリマー
JP2021063222A (ja) ポリマー、ポリマーの製造方法、感光性樹脂組成物、および硬化物
JP2021175784A (ja) ポリマー溶液、感光性樹脂組成物
JP2017057262A (ja) ポリマーの製造方法、ポリマー、感光性樹脂組成物、樹脂膜および電子装置

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018509928

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 17891730

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20197023189

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 17891730

Country of ref document: EP

Kind code of ref document: A1