WO2022202098A1 - 感光性樹脂組成物 - Google Patents

感光性樹脂組成物 Download PDF

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Publication number
WO2022202098A1
WO2022202098A1 PCT/JP2022/007899 JP2022007899W WO2022202098A1 WO 2022202098 A1 WO2022202098 A1 WO 2022202098A1 JP 2022007899 W JP2022007899 W JP 2022007899W WO 2022202098 A1 WO2022202098 A1 WO 2022202098A1
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Prior art keywords
bond
photosensitive resin
group
resin composition
formula
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PCT/JP2022/007899
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English (en)
French (fr)
Japanese (ja)
Inventor
貴文 遠藤
秀則 石井
崇洋 坂口
浩司 荻野
有輝 星野
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日産化学株式会社
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Priority to JP2023508841A priority Critical patent/JPWO2022202098A1/ja
Priority to CN202280019418.XA priority patent/CN116982003A/zh
Priority to KR1020237030944A priority patent/KR20230160249A/ko
Publication of WO2022202098A1 publication Critical patent/WO2022202098A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Definitions

  • the present invention provides a photosensitive resin composition, a resin film obtained from the composition, a photosensitive resist film using the composition, a method for producing a substrate with a cured relief pattern, a substrate with a cured relief pattern, and a cured relief pattern. semiconductor device.
  • polyimide resin which has excellent heat resistance, electrical properties, and mechanical properties, has been used as an insulating material for electronic parts, and as a passivation film, surface protective film, interlayer insulating film, etc. for semiconductor devices.
  • these polyimide resins those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by thermal imidization treatment by applying, exposing, developing, and curing the precursor. be able to.
  • Such a photosensitive polyimide precursor has the feature of enabling a significant process reduction compared to conventional non-photosensitive polyimide resins.
  • Patent Documents 1 and 2 propose a photosensitive resin composition containing polyamic acid or polyimide using a diamine having a (meth)acryloyloxy group.
  • the photosensitive resin used to obtain the hardened relief pattern is divided into two types: the positive type, in which the photosensitive resin in the exposed areas is dissolved in the developer by exposure and development, leaving the photosensitive resin in the unexposed areas, and the photosensitive resin in the unexposed areas. is dissolved in the developer, and the photosensitive resin in the exposed areas remains.
  • the negative type is inferior to the positive type in resolution, but is easy to form a thick film or a film, and is excellent in reliability.
  • an object of the present invention is to provide a photosensitive resin composition that can be developed with an organic solvent, has a low dielectric loss tangent in the resulting cured film and has a high tensile elongation, and a photosensitive resin composition obtained from the composition.
  • the object of the present invention is to provide a resin film obtained by the composition, a photosensitive resist film using the composition, a method for producing a substrate with a cured relief pattern, a substrate with a cured relief pattern, and a semiconductor device having a cured relief pattern.
  • a photosensitive resin composition contains an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid having three or more aromatic rings.
  • organic solvent development is possible, and a photosensitive resin composition having a low dielectric loss tangent and a high tensile elongation in the resulting cured film can be obtained.
  • the present invention has been completed.
  • a photosensitive resin composition comprising a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, and a solvent.
  • the polyamic acid has at least a structural unit represented by the following formula (1)
  • the photosensitive resin composition according to [2], wherein the polyimide has at least a structural unit represented by the following formula (2).
  • Ar 1 represents a divalent organic group having a photopolymerizable group and an aromatic ring
  • Ar 2 represents a tetravalent organic group having three or more aromatic rings.
  • Ar 3 represents a divalent organic group having a photopolymerizable group and an aromatic ring
  • Ar 4 represents a tetravalent organic group having three or more aromatic rings.
  • X 1 and X 2 each independently represent a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, or a sulfonyl bond.
  • R 1 and R 2 each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms.
  • Y represents a divalent organic group represented by the following formula (3-1) or (3-2).
  • n1 and n2 each independently represent an integer of 0 to 3; When there are multiple R 1 s, the multiple R 1s may be the same or different. When there are multiple R 2 s, the multiple R 2s may be the same or different. * represents a bond.
  • Z 1 represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, or a sulfonyl bond.
  • R 3 and R 4 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms.
  • m1 represents an integer of 0 to 3;
  • n3 and n4 each independently represent an integer of 0 to 4;
  • Z 1 is plural, the plural Z 1 may be the same or different.
  • n4 is plural, the plural n4 may be the same or different.
  • R 3 is plural, the plural R 3 may be the same or different.
  • R 4 is plural, the plural R 4 may be the same or different.
  • Z 2 represents a divalent organic group represented by formula (4) or (5) below.
  • R 5 and R 6 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms.
  • n5 and n6 each independently represent an integer of 0 to 4; When R 5 is plural, the plural R 5 may be the same or different. When R 6 is plural, the plural R 6 may be the same or different.
  • * represents a bond.
  • R 7 and R 8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents a bond.
  • R 9 and R 10 each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond.
  • Ar 1 in the formula (1) and Ar 3 in the formula (2) are divalent organic groups represented by the following formula (6): A photosensitive resin composition.
  • Z3 represents an ether bond , an ester bond, an amide bond, a urethane bond or a urea bond
  • Z4 represents a direct bond, an ester bond or an amide bond.
  • Z5 represents a direct bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, or sulfonyl bond.
  • m2 represents an integer of 0 to 1;
  • R 11 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and
  • R 12 represents a hydrogen atom or a methyl group. * represents a bond.
  • [6] The photosensitive resin composition according to [ 5 ], wherein Z3 and Z4 in formula ( 6 ) are ester bonds.
  • [7] The photosensitive resin composition according to [5] or [6], wherein R 11 in formula (6) is a 1,2-ethylene group.
  • a photosensitive resist film comprising a substrate film, a photosensitive resin layer formed from the photosensitive resin composition according to any one of [1] to [11], and a cover film.
  • [15] (1) A step of applying the photosensitive resin composition according to any one of [1] to [11] onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) A method for producing a substrate with a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.
  • the method for producing a cured relief patterned substrate according to [15] wherein the developer used for the development is an organic solvent.
  • a substrate with a cured relief pattern produced by the method according to [15] or [16].
  • a semiconductor device comprising a semiconductor element and a cured film provided above or below the semiconductor element, wherein the cured film comprises the photosensitive resin composition according to any one of [1] to [11].
  • a semiconductor device that is a cured relief pattern formed from a material.
  • a photosensitive resin composition that can be developed with an organic solvent and has a low dielectric loss tangent and a high tensile elongation in the resulting cured film, a resin film obtained from the composition, A photosensitive resist film using the composition, a method for producing a substrate with a cured relief pattern, a substrate with a cured relief pattern, and a semiconductor device having a cured relief pattern are obtained.
  • the photosensitive resin composition of the present invention contains at least a reaction product and a solvent, and further contains other components as necessary.
  • the reaction product is a reaction product between an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings.
  • the reaction product contains, as constituent components, an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, and if necessary, other diamines as constituent components. compounds, and other tetracarboxylic acid derivatives.
  • the reaction product is, for example, polyamic acid or polyimide obtained by dehydration ring closure of polyamic acid.
  • Photosensitivity is imparted to the resin composition containing the reaction product by including the aromatic diamine compound having a photopolymerizable group in the reaction product.
  • the reaction product contains an aromatic diamine compound and a tetracarboxylic acid derivative having three or more aromatic rings as constituent components, the obtained cured film has a low dielectric loss tangent and a high tensile elongation. .
  • aromatic diamine compound having a photopolymerizable group two amino groups may be bonded to one aromatic ring or may be bonded to each of the two aromatic rings.
  • Aromatic rings include aromatic hydrocarbon rings, aromatic heterocycles, and the like.
  • the aromatic diamine compound may have an aromatic ring to which no amino group is bonded.
  • photopolymerizable groups examples include radically polymerizable groups, cationic polymerizable groups, and anionically polymerizable groups. Among these, a radically polymerizable group is preferred.
  • examples of radically polymerizable groups include acryloyl groups, methacryloyl groups, propenyl ether groups, vinyl ether groups, and vinyl groups.
  • the reaction product contains an aromatic diamine compound having three or more aromatic rings as a diamine compound other than the aromatic diamine compound having a photopolymerizable group in the resulting cured film. It is preferable in that dielectric loss tangent and higher tensile elongation can be obtained.
  • the number of aromatic rings in the aromatic diamine compound having 3 or more aromatic rings is not particularly limited as long as it is 3 or more, but may be 4 or more, for example.
  • the upper limit of the number of aromatic rings is not particularly limited, but may be, for example, 8 or less, or 6 or less.
  • aromatic rings in "3 or more aromatic rings” polycyclic aromatic rings formed by condensing two or more aromatic rings such as naphthalene ring and anthracene ring are counted as one aromatic ring. . Therefore, a naphthalene ring is counted as one aromatic ring.
  • a biphenyl ring is not a fused ring and counts as two aromatic rings.
  • a perylene ring is regarded as a structure formed by bonding two naphthalene rings and counted as two aromatic rings.
  • Aromatic rings include aromatic hydrocarbon rings, aromatic heterocycles, and the like.
  • tetracarboxylic acid derivatives examples include tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide.
  • Carboxylic dianhydrides are preferred.
  • Aromatic tetracarboxylic acids refer to compounds having a total of four carboxy groups attached to the same or different aromatic rings.
  • the number of aromatic rings in the tetracarboxylic acid derivative having 3 or more aromatic rings is not particularly limited as long as it is 3 or more, but may be 4 or more, for example.
  • the upper limit of the number of aromatic rings is not particularly limited, but may be, for example, 8 or less, or 6 or less.
  • the ratio of the aromatic diamine compound having a photopolymerizable group to the total diamine compound constituting the reaction product is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, 10 to 100 mol% is preferable, and 50 to 50 mol%. 100 mol % is more preferred.
  • the ratio of the aromatic tetracarboxylic acid derivative having three or more aromatic rings to the total tetracarboxylic acid derivative constituting the reaction product is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is 20. ⁇ 100 mol% is preferred, and 50 to 100 mol% is more preferred.
  • the reaction product is preferably a polyamic acid or a polyimide obtained by dehydrating and ring-closing a polyamic acid. From the viewpoint of obtaining a finer relief pattern, polyimide obtained by dehydrating and ring-closing a polyamic acid is more preferable.
  • the imidization rate of polyimide need not be 100%.
  • the imidization rate may be, for example, 90% or more, 95% or more, or 98% or more.
  • Polyamic acid preferably has at least a structural unit represented by the following formula (1).
  • Polyimide preferably has at least a structural unit represented by the following formula (2).
  • Ar 1 represents a divalent organic group having a photopolymerizable group and an aromatic ring
  • Ar 2 represents a tetravalent organic group having three or more aromatic rings.
  • Ar 3 represents a divalent organic group having a photopolymerizable group and an aromatic ring
  • Ar 4 represents a tetravalent organic group having three or more aromatic rings.
  • Ar 1 and Ar 3 are divalent organic groups having a photopolymerizable group and an aromatic ring, and are not particularly limited as long as the effects of the present invention are exhibited.
  • the divalent organic group having a photopolymerizable group and an aromatic ring is a residue obtained by removing two amino groups from an aromatic diamine compound having a photopolymerizable group. Examples of the photopolymerizable group include the photopolymerizable groups described above.
  • Ar 1 and Ar 3 are preferably divalent organic groups represented by the following formula (6).
  • Z 3 is an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-) or a urea bond (-NHCONH-).
  • Z 4 represents a direct bond, an ester bond (--COO--) or an amide bond (--NHCO--).
  • Z 5 is a direct bond, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond (-NHCONH-), thioether bond (- S—) or a sulfonyl bond (—SO 2 —).
  • m2 represents an integer from 0 to 1;
  • R 11 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and
  • R 12 represents a hydrogen atom or a methyl group. * represents a bond.
  • alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group
  • examples of the alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group include 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group, 2,3-butylene group, 1,2-pentylene group, 2,4-pentylene group, 1,2-hexylene group, 1,2-cyclopropylene group , 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, alkylene in which at least part of these hydrogen atoms are substituted with hydroxyl groups groups (eg, 2-hydroxy-1,3-propylene group) and the like.
  • hydroxyl groups groups eg, 2-hydroxy-1,3-propylene group
  • Z3 is preferably an ester bond.
  • Z4 is preferably an ester bond.
  • R 11 is preferably a 1,2-ethylene group.
  • Examples of the divalent organic group represented by Formula (6) include the following divalent organic groups.
  • * represents a bond. The two bonds are, for example, positioned meta to a substituent having a photopolymerizable group.
  • Ar 2 in formula (1) and Ar 4 in formula (2) are not particularly limited as long as they are tetravalent organic groups having three or more aromatic rings and exhibiting the effect of the present invention. , is preferably a divalent organic group represented by the following formula (3) from the viewpoint of suitably obtaining the effects of the present invention.
  • X 1 and X 2 are each independently a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-) , represents a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO 2 -).
  • R 1 and R 2 each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms.
  • Y represents a divalent organic group represented by the following formula (3-1) or (3-2).
  • n1 and n2 each independently represent an integer of 0 to 3; When there are multiple R 1 s, the multiple R 1s may be the same or different. When there are multiple R 2 s, the multiple R 2s may be the same or different. * represents a bond. ]
  • Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms for R 1 and R 2 include alkyl groups having 1 to 6 carbon atoms.
  • Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
  • an alkyl group unless otherwise specified for its structure, may be linear, branched, cyclic, or two or more of these.
  • substituents on the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
  • “1 to 6 carbon atoms" in “optionally substituted alkyl group having 1 to 6 carbon atoms” refers to the number of carbon atoms in the "alkyl group” excluding substituents. Also, the number of substituents is not particularly limited.
  • Z 1 is a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond ( -NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO 2 -).
  • R 3 and R 4 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms.
  • m1 represents an integer of 0 to 3;
  • n3 and n4 each independently represent an integer of 0 to 4;
  • Z 1 is plural, the plural Z 1 may be the same or different.
  • n4 When n4 is plural, the plural n4 may be the same or different.
  • R 3 When R 3 is plural, the plural R 3 may be the same or different.
  • R 4 When R 4 is plural, the plural R 4 may be the same or different.
  • * represents a bond.
  • Z 2 represents a divalent organic group represented by formula (4) or (5) below.
  • R 5 and R 6 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms.
  • n5 and n6 each independently represent an integer of 0 to 4; When R 5 is plural, the plural R 5 may be the same or different.
  • R 6 When R 6 is plural, the plural R 6 may be the same or different. * represents a bond. ]
  • Examples of the optionally substituted hydrocarbon group having 1 to 6 carbon atoms in R 3 , R 4 , R 5 and R 6 include an optionally substituted alkyl group having 1 to 6 carbon atoms, An optionally substituted phenyl group is included.
  • Substituents include, for example, a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thioxy group, and 1 carbon atom. alkoxy groups of 1 to 6, and the like.
  • the "1 to 6 carbon atoms" of the "optionally substituted hydrocarbon group having 1 to 6 carbon atoms” refers to the number of carbon atoms in the "hydrocarbon group” excluding substituents. Also, the number of substituents is not particularly limited.
  • R 3 , R 4 , R 5 and R 6 include, for example, the substituted alkyl group exemplified in the description of R 1 and R 2 A good alkyl group having 1 to 6 carbon atoms is exemplified.
  • R 7 and R 8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents a bond.
  • R 9 and R 10 each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond.
  • the hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R 7 and R 8 includes, for example, an alkyl group having 1 to 6 carbon atoms and a halogenated alkyl group having 1 to 6 carbon atoms. groups, phenyl groups, halogenated phenyl groups, and the like.
  • alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
  • Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include fluorine atom, chlorine atom, bromine atom and iodine atom.
  • the halogenated alkyl group having 1 to 6 carbon atoms and the halogenated phenyl group may be partially or wholly halogenated.
  • substituents on the optionally substituted alkylene group having 1 to 6 carbon atoms in R 9 and R 10 include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, sulfo group, amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
  • the optionally substituted alkylene group having 1 to 6 carbon atoms includes, for example, an alkylene group having 1 to 6 carbon atoms and a halogenated alkylene group having 1 to 6 carbon atoms.
  • alkylene group having 1 to 6 carbon atoms examples include methylene group, ethylene group, propylene group, and butylene group.
  • the "1 to 6 carbon atoms" of the "optionally substituted alkylene group having 1 to 6 carbon atoms” refers to the number of carbon atoms in the "alkylene group” excluding substituents. Also, the number of substituents is not particularly limited.
  • substituents on the optionally substituted arylene group having 6 to 10 carbon atoms in R 9 and R 10 include a halogen atom, an optionally halogenated C 1 to 6 alkyl group, halogen alkoxy groups having 1 to 6 carbon atoms which may be substituted, and the like. Halogenation may be partially or wholly.
  • the arylene group includes, for example, a phenylene group and a naphthylene group.
  • the "6 to 10 carbon atoms" of the "optionally substituted arylene group having 6 to 10 carbon atoms" refers to the number of carbon atoms in the "arylene group” excluding substituents. Also, the number of substituents is not particularly limited.
  • Examples of the divalent organic group represented by formula (4) include divalent organic groups represented by the following formulae.
  • * represents a bond.
  • Examples of the divalent organic group represented by formula (5) include divalent organic groups represented by the following formulae.
  • R 13 to R 15 are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom represents an alkoxy group.
  • n13 represents an integer of 0 to 5;
  • n14 and n15 each independently represent an integer of 0 to 4;
  • R 13 is plural, the plural R 13 may be the same or different.
  • R 14 is plural, the plural R 14 may be the same or different.
  • R 15 is plural, the plural R 15 may be the same or different.
  • * represents a bond.
  • alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms for R 13 to R 15 include alkyl groups having 1 to 6 carbon atoms and halogen having 1 to 6 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
  • the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include fluorine atom, chlorine atom, bromine atom and iodine atom.
  • a halogenated alkyl group having 1 to 6 carbon atoms may be partially or completely halogenated.
  • alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R 13 to R 15 are an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom. based on.
  • Ar 2 and Ar 4 include, for example, tetravalent organic groups represented by the following formulas.
  • * represents a bond.
  • the polyamic acid may have structural units other than the structural unit represented by formula (1).
  • Other structural units include, for example, structural units represented by the following formula (1′).
  • Polyimide may have structural units other than the structural unit represented by formula (2).
  • Other structural units include, for example, structural units represented by the following formula (2′).
  • Ar 1 ' is a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring or a divalent organic group having a photopolymerizable group and an aromatic ring
  • Ar 2′ represents a tetravalent organic group having 3 or more aromatic rings or a tetravalent organic group having no 3 or more aromatic rings.
  • Ar 1' is a divalent organic group having a photopolymerizable group and an aromatic ring and Ar 2' is a tetravalent organic group having 3 or more aromatic rings is excluded.
  • Ar 3′ is a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring or a divalent organic group having a photopolymerizable group and an aromatic ring and Ar 4′ represents a tetravalent organic group having 3 or more aromatic rings or a tetravalent organic group having no 3 or more aromatic rings.
  • Ar 3' is a divalent organic group having a photopolymerizable group and an aromatic ring and Ar 4' is a tetravalent organic group having 3 or more aromatic rings is excluded.
  • Combinations of Ar 1′ and Ar 2′ include the following combinations (i) to (iii). (i): A combination in which Ar 1′ represents a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar 2′ represents a tetravalent organic group having no three or more aromatic rings (ii) ): Ar 1′ represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar 2′ is a tetravalent organic group having no three or more aromatic rings (iii): Ar 1 ' represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar 2 ' has three or more aromatic rings 4 a combination representing a valent organic group
  • Combinations of Ar 3′ and Ar 4′ include the following combinations (iv) to (vi).
  • Ar 3' represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring
  • Ar 4' is a tetravalent organic group having no three or more aromatic rings
  • Ar 3 ' represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring
  • Ar 4 ' has three or more aromatic rings 4 a combination representing a valent organic group
  • ⁇ Ar 1′ and Ar 3′ As the divalent organic group having a photopolymerizable group and an aromatic ring in Ar 1' and Ar 3' , for example, the divalent organic group having a photopolymerizable group and an aromatic ring exemplified in the description of Ar 1 and Ar 3 organic group.
  • the divalent organic group other than the photopolymerizable group and the divalent organic group having an aromatic ring in Ar 1' and Ar 3' is not particularly limited, but the resulting cured film has a lower dielectric loss tangent and a higher A divalent organic group having three or more aromatic rings is preferred because it provides high tensile elongation.
  • the divalent organic group having three or more aromatic rings is not particularly limited, it is preferably a divalent organic group represented by the following formula (13).
  • X 21 and X 22 are each independently a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-) , represents a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO 2 -).
  • R 21 and R 22 each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms.
  • Y 20 represents a divalent organic group represented by the following formula (13-1) or (13-2).
  • n21 and n22 each independently represent an integer of 0 to 4; When R 21 is plural, the plural R 21 may be the same or different. When R 22 is plural, the plural R 22 may be the same or different. * represents a bond. ]
  • optionally substituted alkyl group having 1 to 6 carbon atoms for R 21 and R 22 include the optionally substituted alkyl groups having 1 to 6 carbon atoms exemplified in the description of R 1 and R 2 .
  • An alkyl group is mentioned.
  • “1 to 6 carbon atoms" of “optionally substituted alkyl group having 1 to 6 carbon atoms” refers to the number of carbon atoms in the "alkyl group” excluding substituents. Also, the number of substituents is not particularly limited.
  • Z 21 is a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond ( -NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO 2 -).
  • R 23 and R 24 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms.
  • m21 represents an integer of 0 to 3;
  • n23 and n24 each independently represent an integer of 0 to 4;
  • the plural Z 21 may be the same or different.
  • n24 When n24 is plural, the plural n24 may be the same or different.
  • R 23 When R 23 is plural, the plural R 23 may be the same or different.
  • R 24 When R 24 is plural, the plural R 24 may be the same or different.
  • * represents a bond.
  • Z 22 represents a divalent organic group represented by formula (14) or (15) below.
  • R 25 and R 26 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms.
  • n25 and n26 each independently represent an integer of 0 to 4;
  • R 25 When R 25 is plural, the plural R 25 may be the same or different.
  • R 26 When R 26 is plural, the plural R 26 may be the same or different. * represents a bond. ]
  • optionally substituted hydrocarbon group having 1 to 6 carbon atoms in R 23 , R 24 , R 25 and R 26 are those in the description of R 3 , R 4 , R 5 and R 6 Examples include optionally substituted hydrocarbon groups having 1 to 6 carbon atoms.
  • “1 to 6 carbon atoms" of “optionally substituted hydrocarbon group having 1 to 6 carbon atoms” refers to the number of carbon atoms in the "hydrocarbon group” excluding substituents. Also, the number of substituents is not particularly limited.
  • R 23 , R 24 , R 25 and R 26 include, for example, the substituted alkyl group exemplified in the description of R 1 and R 2 A good alkyl group having 1 to 6 carbon atoms is exemplified.
  • R 27 and R 28 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents a bond.
  • R 29 and R 30 each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond.
  • hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R 27 and R 28 are optionally substituted with the halogen atoms exemplified in the description of R 7 and R 8
  • a hydrocarbon group having 1 to 6 carbon atoms can be mentioned.
  • optionally substituted alkylene group having 1 to 6 carbon atoms for R 29 and R 30 include the optionally substituted alkylene groups having 1 to 6 carbon atoms exemplified in the description of R 9 and R 10 .
  • An alkylene group is mentioned.
  • the "1 to 6 carbon atoms" of the "optionally substituted alkylene group having 1 to 6 carbon atoms” refers to the number of carbon atoms in the "alkylene group” excluding substituents. Also, the number of substituents is not particularly limited.
  • optionally substituted arylene group having 6 to 10 carbon atoms for R 29 and R 30 include the optionally substituted arylene groups having 6 to 10 carbon atoms exemplified in the description of R 9 and R 10 .
  • An arylene group is mentioned.
  • the "6 to 10 carbon atoms" of the "optionally substituted arylene group having 6 to 10 carbon atoms” refers to the number of carbon atoms in the "arylene group” excluding substituents. Also, the number of substituents is not particularly limited.
  • Examples of the divalent organic group represented by formula (14) include divalent organic groups represented by the following formulae.
  • * represents a bond.
  • Examples of the divalent organic group represented by formula (15) include divalent organic groups represented by the following formulas.
  • R 33 to R 35 are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom represents an alkoxy group.
  • n33 represents an integer of 0 to 5;
  • n34 and n35 each independently represent an integer of 0 to 4;
  • R 33 is plural, the plural R 33 may be the same or different.
  • R 34 is plural, the plural R 34 may be the same or different.
  • R 35 is plural, the plural R 35 may be the same or different.
  • * represents a bond.
  • alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms for R 33 to R 35 include the carbon atoms optionally substituted by halogen atoms exemplified in the description of R 13 to R 15 Examples include alkyl groups having 1 to 6 atoms.
  • Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R 33 to R 35 are an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, based on.
  • Ar 1' and Ar 3' include, for example, divalent organic groups represented by the following formulas.
  • * represents a bond.
  • Ar 1′ and Ar 3′ include, for example, divalent organic groups represented by the following formulas.
  • * represents a bond.
  • ⁇ Ar 2′ and Ar 4′ Examples of the tetravalent organic group having 3 or more aromatic rings for Ar 2' and Ar 4' include the tetravalent organic groups having 3 or more aromatic rings exemplified in the description of Ar 2 and Ar 4 . groups.
  • the tetravalent organic group having no three or more aromatic rings in Ar 2' and Ar 4' is, for example, a tetravalent organic group having one or two aromatic rings or an aromatic ring.
  • a tetravalent organic group that does not have A tetravalent organic group having one or two aromatic rings is derived, for example, from an aromatic tetracarboxylic dianhydride derivative.
  • the tetravalent organic group having no aromatic ring is derived from, for example, an aliphatic tetracarboxylic anhydride derivative.
  • examples of such a tetravalent organic group include, but are not particularly limited to, the following tetravalent organic groups.
  • * represents a bond.
  • the ratio of the structural unit represented by formula (1) in the total structural units of the polyamic acid is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is preferably 10 to 100 mol%, and 50 to 100 mol%. more preferred.
  • a structural unit is also a repeating unit.
  • the proportion of the structural unit represented by the formula (1′) in the total structural units of the polyamic acid is not particularly limited, but is 1 to 90 mol. %, more preferably 1 to 50 mol %.
  • the polyimide may have a structural unit represented by formula (1) in addition to the structural unit represented by formula (2).
  • the total ratio of the structural units represented by the formula (1) and the structural units represented by the formula (2) in the total structural units of the polyimide is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is 10 ⁇ 100 mol% is preferred, and 50 to 100 mol% is more preferred.
  • the structural unit represented by the formula (1') in all the structural units of the polyimide and the structural unit represented by formula (2′) is not particularly limited, but is preferably 1 to 90 mol %, more preferably 1 to 50 mol %.
  • the weight average molecular weight of the reaction product is not particularly limited. 0000 is preferred, 7,000 to 50,000 is more preferred, 10,000 to 50,000 is even more preferred, and 10,000 to 40,000 is particularly preferred.
  • the reaction product comprises an aromatic diamine compound having a photopolymerizable group, a tetracarboxylic acid derivative having three or more aromatic rings, and optionally other diamine compounds and other tetracarboxylic acid derivatives. Obtained by reaction.
  • the method for producing the reaction product is not particularly limited, and includes, for example, a known method for obtaining polyamic acid or polyimide by reacting a diamine compound and a tetracarboxylic acid derivative.
  • Polyamic acid and polyimide can be synthesized by a known method as described in WO2013/157586, for example.
  • the reaction product is produced, for example, by reacting (condensation polymerization) a diamine component containing an aromatic diamine compound having a photopolymerizable group with a tetracarboxylic acid derivative component having three or more aromatic rings in a solvent. It is done by reacting (condensation polymerization) a diamine component containing an aromatic diamine compound having a photopolymerizable group with a tetracarboxylic acid derivative component having three or more aromatic rings in a solvent. It is done by reacting (condensation polymerization) a diamine component containing an aromatic diamine compound having a photopolymerizable group with a tetracarboxylic acid derivative component having three or more aromatic rings in a solvent. It is done by reacting (condensation polymerization) a diamine component containing an aromatic diamine compound having a photopolymerizable group with a tetracarboxylic acid derivative component having three or more aromatic rings in a solvent.
  • solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid amide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone.
  • the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] Any of the indicated solvents can be used.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • -3 represents an alkyl group having 1 to 4 carbon atoms.
  • solvents may be used alone or in combination. Furthermore, even a solvent that does not dissolve the reaction product may be used by mixing with the above solvent within the range that the reaction product does not precipitate.
  • the reaction can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the reaction may be carried out at a high concentration, and then the solvent may be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid derivative component is preferably 0.8 to 1.2. As in a normal polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the reaction product produced.
  • thermal polymerization inhibitor When reacting the diamine component and the tetracarboxylic acid derivative component, a thermal polymerization inhibitor may be added to the reaction system in order to avoid polymerization of the photopolymerizable group.
  • thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, and glycol ether.
  • diaminetetraacetic acid 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-( N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like.
  • the amount of the thermal polymerization inhibitor used is not particularly limited.
  • Polyimide is obtained by dehydrating and ring-closing the polyamic acid, which is the reaction product obtained in the above reaction.
  • Methods for obtaining polyimide include thermal imidization in which the polyamic acid solution, which is the reaction product obtained in the above reaction, is heated as it is, and chemical imidization in which a catalyst is added to the polyamic acid solution.
  • the temperature for thermal imidization in a solution is 100 to 400° C., preferably 120 to 250° C. It is preferable to perform the imidization reaction while removing water produced by the imidization reaction from the system.
  • the chemical imidization can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution obtained by the reaction and stirring at -20 to 250°C, preferably 0 to 180°C. .
  • the amount of the basic catalyst is 0.1 to 30 mol times, preferably 0.2 to 20 mol times the amount of the amic acid groups, and the amount of the acid anhydride is 1 to 50 mol times the amount of the amic acid groups, preferably 1. 5 to 30 mol times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, triethylamine is preferred because it hardly produces polyisoimide as a by-product.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the rate of imidization by chemical imidization (ratio of repeating units to be ring-closed to all repeating units of the polyimide precursor, also referred to as rate of ring closure) can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. can.
  • the reaction solution may be put into a solvent to precipitate.
  • Solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
  • the polymer precipitated by putting it into a solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure.
  • polyimide In polyimide, some or all of the repeating units are ring-closed.
  • the imidization rate of polyimide is preferably 20 to 99%, preferably 30 to 99%, more preferably 50 to 99%.
  • the polyimide may be end-sealed.
  • a method for terminal blocking is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.
  • solvent contained in the photosensitive resin composition it is preferable to use an organic solvent from the viewpoint of the solubility of the reaction product.
  • an organic solvent from the viewpoint of the solubility of the reaction product.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • -3 represents an alkyl group having 1 to 4 carbon atoms.
  • the solvent is in the range of, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the reaction product, depending on the desired coating thickness and viscosity of the photosensitive resin composition. can be used in the range of
  • the photosensitive resin composition may further contain components other than the reaction product and the solvent.
  • Other components include, for example, photoradical polymerization initiators (also referred to as “photoradical initiators”), crosslinkable compounds (also referred to as “crosslinkers”), thermosetting agents, other resin components, fillers, and sensitizers. , adhesion aids, thermal polymerization inhibitors, azole compounds, hindered phenol compounds, and the like.
  • the photoradical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used for photocuring. benzoyldioxy)hexane, 1,4-bis[ ⁇ -(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene Hydroperoxide, ⁇ -(iso-propylphenyl)-iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4- Bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2′,5,5′-tetra(tert-butylperoxycarbonyl)benz
  • Radical photopolymerization initiators are commercially available, for example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, OXE03, OXE04, 250, 1173, MBF, TPO, 4265, TPO (manufactured by BASF), KAYACURE [registered trademark] DETX-S, MBP, DMBI, EPA, OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (manufactured by STAUFFER Co.
  • IRGACURE registered trademark
  • the content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the reaction product, and from the viewpoint of photosensitivity characteristics, 0.5 parts by mass to 15 parts by mass. part is more preferred. If it contains 0.1 parts by mass or more of the photoradical polymerization initiator with respect to 100 parts by mass of the reaction product, the photosensitivity of the photosensitive resin composition is likely to be improved, on the other hand, if it contains 20 parts by mass or less is likely to improve the thick-film curability of the photosensitive resin composition.
  • a monomer having a photoradical polymerizable unsaturated bond (a crosslinkable compound) can be arbitrarily included in the photosensitive resin composition.
  • a crosslinkable compound a (meth)acrylic compound that undergoes a radical polymerization reaction with a photoradical polymerization initiator is preferable.
  • acrylate ethylene glycol or polyethylene glycol mono or di (meth) acrylate, propylene glycol or polypropylene glycol mono or di (meth) acrylate, glycerol mono, di or tri (meth) acrylate, 1,4-butanediol di (Meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di( meth)acrylate, cyclohexane di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, bisphenol A mono- or di(meth)acrylate ) acrylate, di(meth)acrylate of bisphenol F, di(me
  • the content of the crosslinkable compound is not particularly limited, it is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the reaction product.
  • heat curing agent examples include hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis ( butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea and 1, 1,3,3-tetrakis(methoxymethyl)urea and the like.
  • the content of the thermosetting agent in the photosensitive resin composition is not particularly limited.
  • fillers include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, and the like.
  • the content of the filler in the photosensitive resin composition is not particularly limited.
  • the photosensitive resin composition may further contain a resin component other than the reaction product.
  • resin components that can be contained in the photosensitive resin composition include polyoxazoles, polyoxazole precursors, phenol resins, polyamides, epoxy resins, siloxane resins, and acrylic resins.
  • the content of these resin components is not particularly limited, but is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the reaction product.
  • the photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity.
  • Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzo
  • the content of the sensitizer is not particularly limited, it is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the reaction product.
  • an adhesion promoter can optionally be added to the photosensitive resin composition in order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate.
  • adhesion promoters include ⁇ -aminopropyldimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(meth)acryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3 -diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)
  • adhesion aids it is more preferable to use a silane coupling agent in terms of adhesion.
  • the content of the adhesion aid is not particularly limited, but is preferably in the range of 0.5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the reaction product.
  • thermal polymerization inhibitor can be arbitrarily blended in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, particularly during storage in the state of a solution containing a solvent.
  • thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, and glycol ether.
  • diaminetetraacetic acid 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-( N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like are used.
  • the content of the thermal polymerization inhibitor is not particularly limited, but is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the reaction product.
  • Azole compound when using a substrate made of copper or a copper alloy, an azole compound can optionally be added to the photosensitive resin composition in order to suppress discoloration of the substrate.
  • Azole compounds include, for example, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-
  • the content of the azole compound is not particularly limited, but it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the reaction product, and from the viewpoint of photosensitivity characteristics, 0.5 to 5 parts by mass. Part is more preferred.
  • the content of the azole compound with respect to 100 parts by mass of the reaction product is 0.1 parts by mass or more, discoloration of the copper or copper alloy surface when the photosensitive resin composition is formed on copper or copper alloy is suppressed, and on the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.
  • a hindered phenolic compound can optionally be incorporated into the photosensitive resin composition to inhibit discoloration on copper.
  • Hindered phenol compounds include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6
  • 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione is particularly preferred.
  • the content of the hindered phenol compound is not particularly limited, but it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the reaction product, and from the viewpoint of photosensitivity characteristics, 0.5 to 20 parts by mass It is more preferably 10 parts by mass.
  • the content of the hindered phenol compound with respect to 100 parts by mass of the reaction product is 0.1 parts by mass or more, for example, when a photosensitive resin composition is formed on copper or a copper alloy, discoloration of copper or copper alloy - Corrosion is prevented, and on the other hand, when it is 20 parts by mass or less, it is preferable because it is excellent in photosensitivity.
  • the photosensitive resin composition can be suitably used as a negative photosensitive resin composition for producing a cured relief pattern, which will be described later.
  • the resin film of the present invention is a baked product of the coating film of the photosensitive resin composition of the present invention.
  • a method conventionally used for coating a photosensitive resin composition for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. can be used.
  • a baking method for obtaining a baked product various methods can be selected such as, for example, using a hot plate, using an oven, and using a heating oven in which a temperature program can be set. Firing can be performed, for example, at 130° C. to 250° C. for 30 minutes to 5 hours.
  • Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.
  • the thickness of the resin film is not particularly limited, but is preferably 1 ⁇ m to 100 ⁇ m, more preferably 2 ⁇ m to 50 ⁇ m.
  • the resin film is, for example, an insulating film.
  • the photosensitive resin composition of the present invention can be used for photosensitive resist films (so-called dry film resists).
  • the photosensitive resist film has a base film, a photosensitive resin layer (photosensitive resin film) formed from the photosensitive resin composition of the present invention, and a cover film.
  • a photosensitive resin layer and a cover film are laminated in this order on a base film.
  • a photosensitive resist film is produced, for example, by coating a base film with a photosensitive resin composition, drying it to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer.
  • a method conventionally used for coating a photosensitive resin composition for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. can be used.
  • the drying method includes, for example, conditions of 20° C. to 200° C. for 1 minute to 1 hour.
  • the thickness of the resulting photosensitive resin layer is not particularly limited, but is preferably 1 ⁇ m to 100 ⁇ m, more preferably 2 ⁇ m to 50 ⁇ m.
  • a known base film can be used, and for example, a thermoplastic resin film or the like is used.
  • the thermoplastic resin include polyester such as polyethylene terephthalate.
  • the thickness of the base film is preferably 2 ⁇ m to 150 ⁇ m.
  • a known cover film can be used, for example, a polyethylene film, a polypropylene film, or the like.
  • As the cover film a film having adhesive strength to the photosensitive resin layer smaller than that of the base film is preferable.
  • the thickness of the cover film is preferably 2 ⁇ m to 150 ⁇ m, more preferably 2 ⁇ m to 100 ⁇ m, particularly preferably 5 ⁇ m to 50 ⁇ m.
  • the base film and the cover film may be made of the same film material, or may be made of different films.
  • the method for producing a cured relief patterned substrate of the present invention comprises: (1) a step of applying the photosensitive resin composition according to the present invention onto a substrate to form a photosensitive resin layer (photosensitive resin film) on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a cured relief pattern.
  • the photosensitive resin composition according to the present invention is applied onto the substrate. Then, if necessary, it is dried to form a photosensitive resin layer.
  • a method conventionally used for coating a photosensitive resin composition for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. can be used.
  • the coating film made of the photosensitive resin composition can be dried, and drying methods include, for example, air drying, heat drying using an oven or hot plate, vacuum drying, and the like. Specifically, when air drying or heat drying is performed, drying can be performed at 20° C. to 200° C. for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on the substrate.
  • Step of exposing the photosensitive resin layer the photosensitive resin layer formed in the above step (1) is exposed using an exposure device such as a contact aligner, a mirror projection, a stepper, or the like to form a photomask having a pattern. Alternatively, it is exposed to an ultraviolet light source or the like through a reticle or directly.
  • Light sources used for exposure include, for example, g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser.
  • the exposure amount is desirably 25 mJ/cm 2 to 2000 mJ/cm 2 .
  • post-exposure baking PEB
  • pre-development baking may be performed at any combination of temperature and time, if necessary.
  • the temperature is preferably 50° C. to 200° C.
  • the time is preferably 10 seconds to 600 seconds. is not limited to
  • Step of developing the exposed photosensitive resin layer to form a relief pattern an unexposed portion of the exposed photosensitive resin layer is removed by development.
  • a developing method for developing the photosensitive resin layer after exposure any of conventionally known photoresist developing methods such as a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like can be used. method can be selected and used.
  • rinsing may be performed for the purpose of removing the developer.
  • post-development baking may be performed at any combination of temperature and time, if necessary. Organic solvents are preferred as the developer used for development.
  • organic solvents examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, ⁇ -butyrolactone, ⁇ - Acetyl- ⁇ -butyrolactone and the like are preferred.
  • two or more kinds of each solvent can be used, for example, several kinds can be used in combination.
  • the rinsing liquid used for rinsing an organic solvent that is miscible with the developer and has low solubility in the photosensitive resin composition is preferable.
  • Preferred examples of the rinse liquid include methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene.
  • two or more kinds of each solvent can be used, for example, several kinds can be used in combination.
  • Step of Heating the Relief Pattern to Form a Hardened Relief Pattern the relief pattern obtained by the development is heated and converted into a hardened relief pattern.
  • the reaction product is a polyamic acid
  • this heating results in thermal imidization resulting in a cured relief pattern comprising polyimide.
  • various methods can be selected, for example, a method using a hot plate, a method using an oven, and a method using a heating oven capable of setting a temperature program. Heating can be performed, for example, at 130° C. to 250° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.
  • the thickness of the cured relief pattern is not particularly limited, it is preferably 1 ⁇ m to 100 ⁇ m, more preferably 2 ⁇ m to 50 ⁇ m.
  • Embodiments also provide a semiconductor device comprising a semiconductor element and a cured film provided over or under the semiconductor element.
  • a cured film is a cured relief pattern formed from the photosensitive resin composition of the present invention.
  • the cured relief pattern can be obtained, for example, by steps (1) to (4) in the method for producing a substrate with a cured relief pattern described above.
  • the present invention can also be applied to a method of manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-described method of manufacturing a substrate with a cured relief pattern as part of the steps.
  • the semiconductor device of the present invention forms a cured relief pattern as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a semiconductor device having a bump structure, or the like. It can be manufactured by combining with a manufacturing method of a semiconductor device.
  • a display device comprising a display element and a cured film provided on top of the display element, wherein the cured film is the cured relief pattern described above.
  • the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween.
  • the cured film includes a surface protective film, an insulating film, and a flattening film for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, projections for MVA (Multi-domain Vertical Alignment) type liquid crystal display devices, and A partition wall for an organic EL (Electro-Luminescence) device cathode can be mentioned.
  • the photosensitive resin composition of the present invention in addition to application to the semiconductor device as described above, is also used for applications such as interlayer insulating films of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Useful.
  • the weight-average molecular weight (Mw) shown in the synthesis examples below is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification).
  • GPC gel permeation chromatography
  • HPC-8320GPC manufactured by Tosoh Corporation
  • Chemical imidization rate a proton derived from a structure that does not change before and after imidization is determined as a reference proton, and the peak integrated value of this proton and the proton derived from the NH group of amic acid appearing around 9.5 ppm to 11.0 ppm. It was calculated by the following formula using the peak integrated value.
  • Chemical imidization rate (%) (1- ⁇ x/y) x 100
  • x is the proton peak integrated value derived from the NH group of the amic acid
  • y the peak integrated value of the reference proton
  • ⁇ is one NH group proton of the amic acid in the case of polyamic acid (imidization rate is 0%). is the number ratio of reference protons to
  • the resulting polyamic acid had a repeating unit structure represented by (P-2) below, and had a weight average molecular weight (Mw) of 25,273 as measured by GPC in terms of polystyrene.
  • the resulting polyamic acid had a repeating unit structure represented by (P-5) below, and had a weight average molecular weight (Mw) of 27,852 as measured by GPC in terms of polystyrene.
  • the resulting polyamic acid had a repeating unit structure represented by (P-6) below, and had a weight average molecular weight (Mw) of 56,737 as measured by GPC in terms of polystyrene.
  • the resulting polyamic acid had a repeating unit structure represented by (P-15) below, and had a weight average molecular weight (Mw) of 24,559 as measured by GPC in terms of polystyrene.
  • Example 1 27.75 g of the solution containing the polyamic acid (P-1) obtained in Synthesis Example 1 (solid content concentration: 30% by weight), NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.67 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.42 g and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.17 g were mixed and dissolved.
  • a solution of a negative photosensitive resin composition was prepared by filtering with a filter.
  • Example 2 32.24 g of the solution (solid content concentration: 30% by weight) containing the polyamic acid (P-2) obtained in Synthesis Example 2, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.93 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.48 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6(1H,3H,5H)-Trione, BASF Japan Co., Ltd.) 0.15 g, and KBM-5103 (3-
  • Example 3 33.16 g of a solution containing the polyamic acid (P-2) obtained in Synthesis Example 2 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 1.93 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.48 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.15 g, and KBM-5103 (3-acryloxypropy
  • Example 4 22.08 g of the solution (solid content concentration: 30% by weight) containing the polyamic acid (P-3) obtained in Synthesis Example 3, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.33 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., Ltd.) 0.10 g, KBM-5103 (3
  • Example 5 32.49 g of a solution containing the polyamic acid (P-3) obtained in Synthesis Example 3 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.97 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.49 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.15 g, KBM-5103 (3-acryloxypropyl
  • Example 6 33.16 g of a solution containing the polyamic acid (P-4) obtained in Synthesis Example 4 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.99 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.50 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.15 g, and KBM-5103 (3-acryloxypropy
  • Example 7 29.96 g of the solution containing the polyamic acid (P-5) obtained in Synthesis Example 5 (solid content concentration: 30% by weight), NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.80 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.45 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., Ltd.) 0.13 g, KBM-5103 (3
  • Example 8 23.89 g of a solution containing the polyamic acid (P-5) obtained in Synthesis Example 5 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.72 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.36 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.11 g, KBM-5103 (3-acryloxypropyl
  • Example 9 37.84 g of the solution (solid content concentration: 20% by weight) containing the polyamic acid (P-6) obtained in Synthesis Example 6, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.51 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.38 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, BASF Japan Co., Ltd.) 0.11 g, and KBM-5103 (3-
  • Example 11 22.08 g of the solution (solid content concentration: 30% by weight) containing the polyamic acid (P-8) obtained in Synthesis Example 8, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.33 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., Ltd.) 0.10 g, KBM-5103 (3
  • Example 12 31.50 g of a solution containing the polyamic acid (P-8) obtained in Synthesis Example 8 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.95 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.47 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.14 g, KBM-5103 (3-acryloxypropyl
  • Example 13 Solution containing polyamic acid (P-9) obtained in Synthesis Example 9 (solid content concentration: 20% by weight) 33.11 g, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.33 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6(1H,3H,5H)-trione, BASF Japan Co., Ltd.) 0.10 g, and KBM-5103 (3-acryloxy
  • Example 14 20.75 g of the solution (solid content concentration: 30% by weight) containing the polyamic acid (P-10) obtained in Synthesis Example 10, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.25 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.31 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., Ltd.) 0.09 g, KBM-5103 (3
  • Example 15 Solution containing polyamic acid (P-11) obtained in Synthesis Example 11 (solid concentration: 25% by weight) 23.66 g, N-ethyl-2-pyrrolidone 0.99 g, NK ester A-DOD- as a cross-linking agent N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.59 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) Phenyl-,2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) 0.30 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl- 4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Ltd.) 0.09
  • Example 16 24.78 g of a solution (solid concentration: 25% by weight) containing the polyamic acid (P-12) obtained in Synthesis Example 12, NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.62 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.31 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.09 g, and KBM-5103 (3-acryloxypropy
  • Example 17 > 27.64 g of the solution (solid content concentration: 30% by weight) containing the polyamic acid (P-13) obtained in Synthesis Example 13, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.66 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.41 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6(1H,3H,5H)-trione, BASF Japan Co., Ltd.) 0.12 g, and KBM-5103 (3-
  • Example 18 28.42 g of a solution containing the polyamic acid (P-13) obtained in Synthesis Example 13 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.85 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.43 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.13 g, and KBM-5103 (3-acryloxypropy
  • Example 19 27.64 g of the solution (solid content concentration: 30% by weight) containing the polyamic acid (P-14) obtained in Synthesis Example 14, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.66 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.41 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6(1H,3H,5H)-trione, BASF Japan Co., Ltd.) 0.12 g, and KBM-5103 (3-
  • Example 20 28.42 g of a solution containing the polyamic acid (P-14) obtained in Synthesis Example 14 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.85 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.43 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.13 g, and KBM-5103 (3-acryloxypropy
  • Example 21 21.40 g of a solution containing the polyamic acid (P-15) obtained in Synthesis Example 15 (solid content concentration: 30% by weight), NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.28 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.32 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., Ltd.) 0.10 g, KBM-5103
  • Example 22 37.81 g of a solution containing the polyamic acid (P-16) obtained in Synthesis Example 16 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 2.27 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.57 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.17 g, and KBM-5103 (3-acryloxypropy
  • Example 23 65.34 g of a solution containing the polyamic acid (P-17) obtained in Synthesis Example 17 (solid concentration: 25% by weight), NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 3.27 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.82 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4 , 6(1H,3H,5H)-Trione, BASF Japan Co., Ltd.) 0.25 g, and KBM-5103 (3-
  • Example 24 38.23 g of a solution containing the polyamic acid (P-18) obtained in Synthesis Example 18 (solid concentration: 25% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.96 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.48 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.14 g, and KBM-5103 (3-acryloxypropy
  • Example 25 38.23 g of a solution containing the polyamic acid (P-19) obtained in Synthesis Example 19 (solid concentration: 25% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.96 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.48 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.14 g, and KBM-5103 (3-acryloxypropy
  • Example 26 38.57 g of a solution (solid concentration: 20% by weight) containing the polyamic acid (P-20) obtained in Synthesis Example 20, NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.77 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.39 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.12 g, and KBM-5103 (3-acryloxypropy
  • Example 27 38.57 g of a solution containing the polyamic acid (P-21) obtained in Synthesis Example 21 (solid concentration: 20% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.77 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.39 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.12 g, and KBM-5103 (3-acryloxypropy
  • Example 28 Powder 11.02 g of the solvent-soluble polyimide (P-22) obtained in Synthesis Example 22, N-ethyl-2-pyrrolidone 25.71 g, NK ester A-DOD-N (1,10-decane Diol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 2.20 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-( O-benzoyloxime)], manufactured by BASF Japan Ltd.) 0.55 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1 , 3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.17 g, and KBM-5103 (3-acryloxypropyltri
  • NK Ester A-200 polyethylene glycol diacrylate, Shin
  • NK Ester A-200 polyethylene glycol diacrylate, Shin
  • NK Ester A-200 polyethylene glycol diacrylate, Shin
  • NK Ester A-200 polyethylene glycol diacrylate,
  • NK Ester A-200 polyethylene glycol diacrylate,
  • the negative photosensitive resin compositions of Examples 1 to 30 fully dissolved (developed) the photosensitive resin film in the unexposed area (0 mJ/cm 2 ) after development, and the exposed area (300 mJ/cm 2 ) of the photosensitive resin film remained without being dissolved (developed). That is, since a clear dissolution difference (dissolution contrast) of the photosensitive resin film was obtained in the exposed and unexposed areas, the relief pattern creation process using general-purpose organic solvents such as cyclopentanone for development It can be suitably used as a negative photosensitive resin composition for.
  • the negative photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 were spin-coated onto a 4-inch silicon wafer coated with an aluminum foil having a thickness of 20 ⁇ m, and heated at 115 degrees on a hot plate. C. for 180 seconds or 270 seconds to form a photosensitive resin film on the aluminum foil.
  • an i-line aligner PLA-501, manufactured by Canon Inc.
  • the entire surface of the wafer was exposed at 500 mJ/cm 2 , then in a nitrogen atmosphere at 160° C. for 1 hour, then at 230° C. for 1 hour. Baked.
  • the film was obtained by immersing the baked aluminum foil in 6N hydrochloric acid to dissolve the aluminum foil.
  • the dielectric loss tangent measurement conditions are as follows.
  • ⁇ Measurement method Perturbation cavity resonator method
  • ⁇ Vector network analyzer FieldFox N9926A (manufactured by Keysight Technologies Inc.)
  • ⁇ Cavity resonator TMR-1A (manufactured by Keycom Co., Ltd.)
  • ⁇ Cavity volume 1192822 mm 3
  • ⁇ Measurement frequency about 1 GHz
  • Sample tube made of PTFE, inner diameter: 3 mm, length of about 30 mm (manufactured by Keycom Co., Ltd.)
  • the aluminum wafer was immersed in 6N hydrochloric acid to dissolve the aluminum, thereby obtaining a film with a width of 5 mm. rice field.
  • the tensile elongation of the obtained film was measured using a desktop precision universal testing machine (Autograph AGS-10kNX, manufactured by Shimadzu Corporation). The conditions for measuring the tensile elongation are as follows.
  • ⁇ Desktop precision universal testing machine Autograph AGS-10kNX (manufactured by Shimadzu Corporation) ⁇ Film width: 5mm ⁇ Distance between grips: 25mm
  • the tensile elongation of 50% means that the film is stretched up to 1.5 times, in other words, the film breaks when the distance between the grips is 1.5 times (37.5 mm).
  • Table 2 shows the measurement results of dielectric loss tangent and tensile elongation.
  • the dielectric loss tangent values at 1 GHz of the films obtained from the negative photosensitive resin compositions of Examples 1 to 30 were lower than those of Comparative Examples 1 to 5.
  • the films obtained from the negative photosensitive resin compositions of Examples 1 to 30 had higher tensile elongation values than those of Comparative Examples 1 to 6. That is, the negative photosensitive resin compositions of Examples 1 to 30 can form a relief pattern, have a low dielectric loss tangent, and have a high tensile elongation at the same time. It can be suitably used for the production of electronic materials that require properties.

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CN115626989A (zh) * 2022-10-28 2023-01-20 嘉兴瑞华泰薄膜技术有限公司 光敏聚酰亚胺、光敏聚酰亚胺薄膜及其制备方法和应用
JP2023143861A (ja) * 2021-03-26 2023-10-06 財團法人工業技術研究院 感光性組成物およびこれにより作製されるフィルム
WO2024185652A1 (ja) * 2023-03-08 2024-09-12 富士フイルム株式会社 樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス
WO2025142645A1 (ja) * 2023-12-26 2025-07-03 住友ベークライト株式会社 感光性樹脂組成物、硬化物および半導体装置
JP7736225B1 (ja) 2023-12-26 2025-09-09 住友ベークライト株式会社 感光性樹脂組成物、硬化物および半導体装置

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WO1999051662A1 (fr) * 1998-04-01 1999-10-14 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Compositions de polyimides
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JPH01118514A (ja) * 1987-11-02 1989-05-11 Hitachi Chem Co Ltd 感光性樹脂組成物
WO1999051662A1 (fr) * 1998-04-01 1999-10-14 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Compositions de polyimides
WO2021107024A1 (ja) * 2019-11-27 2021-06-03 富士フイルム株式会社 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、樹脂

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Publication number Priority date Publication date Assignee Title
JP2023143861A (ja) * 2021-03-26 2023-10-06 財團法人工業技術研究院 感光性組成物およびこれにより作製されるフィルム
JP7456038B2 (ja) 2021-03-26 2024-03-26 財團法人工業技術研究院 感光性組成物およびこれにより作製されるフィルム
CN115626989A (zh) * 2022-10-28 2023-01-20 嘉兴瑞华泰薄膜技术有限公司 光敏聚酰亚胺、光敏聚酰亚胺薄膜及其制备方法和应用
WO2024185652A1 (ja) * 2023-03-08 2024-09-12 富士フイルム株式会社 樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス
WO2025142645A1 (ja) * 2023-12-26 2025-07-03 住友ベークライト株式会社 感光性樹脂組成物、硬化物および半導体装置
JP7736225B1 (ja) 2023-12-26 2025-09-09 住友ベークライト株式会社 感光性樹脂組成物、硬化物および半導体装置

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