JPWO2015118836A1 - Resin composition containing polyimide precursor, method for producing cured film, and electronic component - Google Patents

Resin composition containing polyimide precursor, method for producing cured film, and electronic component Download PDF

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JPWO2015118836A1
JPWO2015118836A1 JP2015000357A JP2015561208A JPWO2015118836A1 JP WO2015118836 A1 JPWO2015118836 A1 JP WO2015118836A1 JP 2015000357 A JP2015000357 A JP 2015000357A JP 2015561208 A JP2015561208 A JP 2015561208A JP WO2015118836 A1 JPWO2015118836 A1 JP WO2015118836A1
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resin composition
group
formula
component
cured film
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敬司 小野
敬司 小野
榎本 哲也
哲也 榎本
匡之 大江
匡之 大江
ケイ子 鈴木
ケイ子 鈴木
和也 副島
和也 副島
越晴 鈴木
越晴 鈴木
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日立化成デュポンマイクロシステムズ株式会社
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Priority to PCT/JP2015/000357 priority patent/WO2015118836A1/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031Organic compounds not covered by group G03F7/029
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/3105After-treatment
    • H01L21/311Etching the insulating layers by chemical or physical means

Abstract

(A) A resin composition comprising a polyimide precursor having a structural unit represented by the following formula (1) and (b) a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure. However, in Formula (1), R1 is a tetravalent organic group and R2 is a divalent organic group. R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond.

Description

  The present invention relates to a resin composition containing a polyimide precursor, a method for producing a cured film using the resin composition, and an electronic component.

  With the miniaturization of semiconductor integrated circuits, an interlayer insulating film called a low-k layer for reducing the dielectric constant is required. Since the low-k layer has a pore structure, there is a problem that the mechanical strength is lowered. In order to protect such an interlayer insulating film having a low mechanical strength, a cured film formed of a polyimide resin is used. This cured film is required to have characteristics such as thick film formability (for example, 5 μm or more) and high elastic modulus (for example, 4 GPa or more). However, as the film thickness and the elastic modulus increase, the stress after curing increases and the warpage of the semiconductor wafer increases, which may cause problems during transportation and wafer fixing.

  As a method for reducing the stress of a cured film formed from a polyimide resin, for example, there is a method using a polyamide obtained by copolycondensation of a phthalic acid compound having a specific functional group as an acid component (for example, Patent Document 1). However, in recent years, curing at a low temperature has been demanded, and when the polyamide is cured at a low temperature, there is room for improvement in terms of obtaining a cured film having sufficient performance.

International Publication WO2006 / 008991

In order to reduce the stress, a polyimide precursor containing fluorine having a high i-line transmittance has been studied. However, as a result of the study by the present inventors, a cured film obtained after heat curing a resin composition containing these polyimide precursors can easily absorb the organic solvent used during the resist process and swell. found. The swelling referred to here is a phenomenon in which when the polyimide cured film is immersed in N-methylpyrrolidone at a constant temperature (for example, 70 ° C.) for a certain time (for example, 20 minutes), the cured film absorbs the solvent and the volume expands. is there.
An object of the present invention is to provide a resin composition capable of obtaining a cured film having low stress and low swelling even when cured at a low temperature of 300 ° C. or lower.

According to the present invention, the following resin composition is provided.
1. The resin composition containing the following (a) component and (b) component.
(A) a polyimide precursor having a structural unit represented by the following formula (1),
(In the formula, R 1 is a tetravalent organic group, R 2 is a divalent organic group. R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 3; ˜20 cycloalkyl groups or monovalent organic groups having a carbon-carbon unsaturated double bond.)
(B) a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure; 2. The resin composition according to 1, wherein R 2 in the formula (1) is a divalent organic group represented by the following formula (2).
(In the formula, R 5 to R 12 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 5 to R 12 is a fluorine atom, a methyl group, or a trifluoromethyl group. .) 3. 3. The resin composition according to 1 or 2, wherein R 2 in the formula (1) is a divalent organic group represented by the following formula (3).
(In the formula, R 13 and R 14 are each independently a fluorine atom or a trifluoromethyl group.)
4). The resin composition in any one of 1-3 in which the said photopolymerizable compound contains the structure represented by following formula (4).
(In the formula, R 24 is a hydrogen atom or a methyl group, X is an alkylene group, and n is an integer of 1 to 25.)
5). 5. The resin composition according to 4, wherein the photopolymerizable compound is a compound represented by the following formula (5).
(In the formula, R 21 to R 23 are each independently a monovalent organic group, and at least one is a group represented by the formula (4).)
6). The resin composition according to any one of 1 to 5, wherein the component (b) is contained in an amount of 0.01 to 50 parts by mass with respect to 100 parts by mass of the component (a).
7). (C) The resin composition in any one of 1-6 which further contains the compound which generate | occur | produces a radical by irradiation with actinic light as a component.
8). 8. The resin composition according to 7, wherein the compound that generates radicals upon irradiation with actinic rays is an oxime ester compound.
9. (E) The resin composition in any one of 1-8 which further contains photopolymerizable compounds other than (b) component as a component.
10. 10. The resin composition according to 9, wherein the photopolymerizable compound is a (meth) acrylic compound.
The manufacturing method of a cured film including the process of apply | coating the resin composition in any one of 11.1-10 on a board | substrate, drying and forming a coating film, and the process of heat-processing the said coating film.
A step of applying the resin composition according to any one of 12.1 to 10 on a substrate and drying to form a coating film, and a step of irradiating the coating film with actinic rays and developing to obtain a patterned resin film And a step of heat-treating the patterned resin film.
A cured film obtained from the method for producing a cured film according to 13.11.
The pattern cured film obtained from the manufacturing method of the pattern cured film as described in 14.12.
15. An electronic component having the cured film according to 15.13 or the pattern cured film according to 14.

  ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where it hardens | cures at the low temperature of 300 degrees C or less, the resin composition from which the cured film with a low stress and a low swelling is obtained can be provided.

It is a schematic sectional drawing of one Embodiment of the electronic component (semiconductor device) manufactured using the resin composition of this invention.

  Below, the resin composition concerning this invention and the manufacturing method of the cured film using this resin composition are demonstrated. In addition, this invention is not limited by this embodiment.

The resin composition of this invention contains the following (a) component and (b) component.
[(A) component]
Polyimide precursor having a structural unit represented by the following formula (1)
(In Formula (1), R 1 is a tetravalent organic group, R 2 is a divalent organic group. R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, It is a C3-C20 cycloalkyl group or a monovalent organic group having a carbon-carbon unsaturated double bond.)
[Component (b)]
Photopolymerizable compound having ethylenically unsaturated group and isocyanuric ring structure

Conventionally, the polyimide precursor was heat-cured at a high temperature of about 370 ° C., but the resin composition of the present invention contains both the component (a) and the component (b), so that the temperature is 300 ° C. or less. Even when cured at a low temperature, a cured film having low stress and less likely to swell can be obtained. When the component (a) is not used, for example, when a polybenzoxazole precursor is used, the effect on stress and swelling is low even when the component (b) is used in combination.
Hereinafter, each component of the resin composition of this invention is demonstrated.

(A) Component: Polyimide precursor having a structural unit represented by the following formula (1) R 1 in formula (1) is a structure derived from a tetracarboxylic acid used as a raw material or a dianhydride thereof. From the viewpoint of the stress of the cured film and the i-line transmittance, R 1 is preferably any one of groups represented by the following formulas (2a) to (2e).
(In the formula (2d), X and Y each represent a divalent group or a single bond that is not conjugated to an independently bonded benzene ring. In the formula (2e), Z represents an ether bond (—O—) or a sulfide bond. (-S-).)

The “divalent group that is not conjugated with the benzene ring to be bonded” of X and Y in the formula (2d) is, for example, —O—, —S—, or a divalent group represented by the following formula.
(Wherein R 12 represents a carbon atom or a silicon atom.
R 13 is each independently a hydrogen atom or a halogen atom such as a fluorine atom. )
Among these, R 1 is derived from pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. A structure is more preferable. These can be used alone or in combination of two or more.

As long as the stress of the cured film and the i-line transmittance are not lowered, the raw material of R 1 is 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride M-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, p-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,1, 1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis {4 ′-(2,3-dicarboxyphenoxy) ) Phenyl} propane dianhydride, 2,2-bis {4 ′-(3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 1,1,1,3,3,3-hexafluoro-2, 2-bis {4 '-(2,3-dicarboxyphenoxy) phenyl} propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis {4'-(3 4-Dicarboxyphenoxy) phenyl} propane dianhydride, 4,4′-oxydiphthalic dianhydride, 4,4′-sulfonyldiphthalic dianhydride and the like may be used.

R 2 in the formula (1) is a structure derived from a diamine used as a raw material. In the component (a), R 2 in the formula (1) is preferably a divalent organic group represented by the following formula (2).
(In formula (2), R 5 to R 12 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 5 to R 12 is a fluorine atom, a methyl group, or trifluoromethyl. Group.)

Examples of the monovalent organic group represented by R 5 to R 12 include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluoroalkyl having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Groups.

In the component (a), R 2 in the formula (1) is more preferably a divalent organic group represented by the following formula (3). The swelling phenomenon at low temperature curing tends to occur easily when a polyimide precursor containing fluorine having a high i-line transmittance is used.
(In Formula (3), R 13 and R 14 are each independently a fluorine atom or a trifluoromethyl group.)

In the component (a), the ratio in which R 2 in the formula (1) is a structural unit represented by the formula (3) is preferably 1 to 100 mol%, and more preferably 10 to 100 mol%. More preferably, it is 30-100 mol%.

  Examples of the structure represented by the formula (2) or (3) include 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′-bis (fluoro) -4,4 ′. -Diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

  Moreover, the diamine compound which gives structures other than Formula (2) and (3) can also be used. For example, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4 ′-(or 3,4′-, 3,3 ′ -, 2,4'-, 2,2 '-) diaminodiphenyl ether, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenyl Sulfone, 4,4 ′-(or 3,4′-, 3,3′-, 2,4′-, 2,2 ′-) diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4 ′ -Methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenone Diamine, bi -{4- (4'-aminophenoxy) phenyl} sulfone, 2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3 , 3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, bis {4- (3′-aminophenoxy) phenyl} sulfone, 2,2-bis (4-aminophenyl) propane, diaminopoly Examples thereof include siloxane. These can be used alone or in combination of two or more.

R 3 and R 4 in Formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), and 3 to 3 carbon atoms. A cycloalkyl group having 20 (preferably 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms), or a monovalent organic group having a carbon-carbon unsaturated double bond.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n-butyl group. Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
Examples of the monovalent organic group having a carbon-carbon unsaturated double bond include an organic group having a (meth) acryl group. Specific examples include (meth) acryloxyalkyl groups having 1 to 10 carbon atoms in the alkyl group. “(Meth) acryl” means “methacryl” or “acryl”, “(meth) acryloxy” means “methacryloxy” or “acryloxy”, and “(meth) acrylate” means “methacrylate” or “ Acrylate ".
Examples of the (meth) acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group include (meth) acryloxyethyl group, (meth) acryloxypropyl group, (meth) acryloxybutyl group and the like.

When at least one of R 3 and R 4 is a monovalent organic group having a carbon-carbon unsaturated double bond, it is combined with a compound that generates radicals upon irradiation with actinic rays, thereby crosslinking between molecular chains by radical polymerization. It becomes the photosensitive resin composition which becomes possible.

The component (a) of the present invention can be synthesized by addition polymerization of tetracarboxylic dianhydride and diamine. Moreover, after making the tetracarboxylic dianhydride represented by Formula (5) into a diester derivative, it converts into the acid chloride represented by Formula (6), and makes it react with the diamine represented by Formula (7). Can be synthesized. The synthesis method can be selected from known methods.
(In formulas (5), (6) and (7), R 1 to R 4 are the same as in formula (1).)

  As for the molecular weight of the polyimide precursor as component (a), the weight average molecular weight in terms of polystyrene is preferably 10,000 to 100,000, more preferably 15,000 to 100,000, and still more preferably 20,000 to 85,000. When the weight average molecular weight is greater than 10,000, the stress after curing can be sufficiently reduced. On the other hand, if it is less than 100,000, the solubility in the solvent can be improved, the viscosity of the solution is reduced, and the handleability is improved. In addition, a weight average molecular weight can be measured by the gel permeation chromatography method, and can be calculated | required by converting using a standard polystyrene calibration curve.

  The molar ratio of tetracarboxylic dianhydride and diamine when synthesizing the component (a) is usually 1.0, but in the range of 0.7 to 1.3 for the purpose of controlling the molecular weight and terminal residue. It may be a molar ratio. When the molar ratio is 0.7 or less or 1.3 or more, the molecular weight of the obtained polyimide precursor becomes small, and the low stress property after curing may not be sufficiently exhibited.

  As heating temperature which heat-processes the polyimide precursor which is (a) component of this invention, advances imidation, and converts it into a polyimide, 80-300 degreeC is preferable, 100-300 degreeC is more preferable, 200-300 More preferably, the temperature is C. If it is less than 80 ° C., imidization does not proceed sufficiently and the heat resistance may be lowered, and if it is performed at a temperature higher than 300 ° C., the semiconductor element may be damaged.

  The residual stress of the cured film obtained by applying the polyimide precursor represented by the formula (1) to the substrate and heat-curing is preferably 30 MPa or less when the thickness of the cured film is 10 μm. The pressure is more preferably 27 MPa or less, and further preferably 25 MPa or less. If the residual stress is 30 MPa or less, when the film is formed so that the film thickness after curing is 10 μm, the warpage of the wafer can be more sufficiently suppressed, and the problems caused in the conveyance and suction fixation of the wafer can be further reduced. Can be suppressed.

  The residual stress can be measured by a method of converting the amount of warpage of the wafer into a stress after measuring the amount of warpage of the wafer using a thin film stress measuring apparatus FLX-2320 (manufactured by KLA Tencor).

  In order to form the cured film obtained in the present invention so that the film thickness after curing is 10 μm, the above-mentioned resin composition is applied onto a substrate and dried to form a coated film, Needs to be about 20 μm thick. Therefore, when combining with the compound which generate | occur | produces a radical by actinic-light irradiation and it is set as the photosensitive resin composition, it is so preferable that i line | wire transmittance of a resin composition is high.

  Specifically, when the film thickness is 20 μm, the i-line transmittance is preferably 5% or more, more preferably 8% or more, and further preferably 15% or more. If it is less than 5%, the i-line does not reach the deep part, and radicals are not generated sufficiently. Therefore, there is a possibility that the photosensitive characteristics may be deteriorated, for example, the resin oozes out from the substrate side of the film during development.

  The i-line transmittance can be measured from a transmitted UV spectrum using U-3310 spcphotometer (manufactured by HITACHI).

(B) Component: Photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure The resin composition of the present invention includes a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure as the component (b). . It is considered that the photopolymerizable compound functions as a crosslinking agent and remains in the film after curing, thereby forming a crosslinked structure in the cured polyimide film and suppressing swelling. Moreover, a photopolymerizable compound has a function which improves the orientation of a polyimide cured film, and can also improve the residual film rate after hardening.
In addition, although there exists an aluminum chelate compound as an additive which suppresses the swelling of a polyimide cured film, for example, in a low temperature curing of 300 ° C. or less, a sufficient effect cannot be obtained by adding an aluminum chelate compound. By using the component (b), a sufficient swelling suppressing effect can be obtained even at low temperature curing of 300 ° C. or lower.

As the photopolymerizable compound, triallyl isocyanurate, triallyl isocyanurate prepolymer, and a compound having a structure represented by the following formula (4) are preferable.
(In formula (4), R 24 is a hydrogen atom or a methyl group, X is an alkylene group, and n is an integer of 1 to 25.)

The compound having a structure represented by the formula (4) is preferably a compound represented by the following formula (5).
(In Formula (5), R 21 to R 23 are each independently a monovalent organic group, and at least one is a group represented by Formula (4).)

As the compound having a structure represented by the formula (4), a compound represented by the following formula (6) can also be used.
(In formula (6), R 21 to R 23 are each independently a monovalent organic group, and at least one is a group represented by the following formula (9).)
(In Formula (9), R 24 is a hydrogen atom or a methyl group, X is an alkylene group, Y is an alkylene group, n is an integer of 1 to 25, and m is 1; It is an integer of ~ 14.)

  Examples of the monovalent organic group of the formulas (5) and (6) include an alkyl group having 1 to 15 carbon atoms, a glycidyl group, and a vinyl group. The alkyl group having 1 to 15 carbon atoms may have a halogen atom such as a 2,3-dibromopropyl group.

  Although there is no restriction | limiting in particular as carbon number of the alkylene group of X and Y of Formula (4) and (9), It is preferable that it is a C2-C7 alkylene group, and it is a C2-C4 alkylene group. More preferred is an ethylene group or a propylene group.

N of Formula (4) and Formula (9) is an integer of 1-25, it is preferable that it is an integer of 1-20, and the integer of 1-15 is more preferable.
M in the formula (9) is an integer of 1 to 14, preferably an integer of 1 to 6, and more preferably an integer of 6.

Specific examples of the photopolymerizable compound as component (b) include a compound represented by the following formula (10), and the compound is commercially available as A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Is possible.

The content of the component (b) of the resin composition of the present invention is preferably 1 to 50 parts by weight, and 1 to 30 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoint of swelling suppression and film properties. More preferred is 5 to 20 parts by mass.
(B) By making content of a component into 1 mass part or more with respect to 100 weight part of (a) component, the swelling by the organic solvent of a cured film can be suppressed, and with respect to 100 weight part of (a) component By making it 50 parts by mass or less, it is possible to suppress a decrease in elongation of the cured film.

Component (c): Compound that generates radicals by actinic rays The resin composition of the present invention preferably contains a compound that generates radicals by actinic rays as component (c).
When at least part of R 3 and / or R 4 in the formula (1) of the component (a) polyimide precursor is a monovalent organic group having a carbon-carbon unsaturated double bond, the resin composition is (C) By containing a component, the resin composition of this invention can be made into the photosensitive resin composition.

Examples of the component (c) include N, N′-tetraalkyl-4,4′-, such as an oxime ester compound, benzophenone, and N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone) described later. Diaminobenzophenone;
Aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1;
Examples include quinones fused with an aromatic ring such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; and benzyl derivatives such as benzyldimethyl ketal. These may be used individually by 1 type and may be used in combination of 2 or more type.
Among these, an oxime ester compound is preferable because it is excellent in sensitivity and gives a good pattern.

  The oxime ester compound is preferably a compound represented by the following formula (9), a compound represented by the following formula (10), or a compound represented by the following formula (11).

(In the formula (9), R and R 1 each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and an alkyl group having 1 to 8 carbon atoms, It is preferably a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group, more preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group. A methyl group, a cyclopentyl group, a phenyl group, or a tolyl group is more preferable.
R 2 represents H, OH, COOH, O (CH 2 ) OH, O (CH 2 ) 2 OH, COO (CH 2 ) OH or COO (CH 2 ) 2 OH, and H, O (CH 2 ) OH O (CH 2 ) 2 OH, COO (CH 2 ) OH or COO (CH 2 ) 2 OH is preferred, and H, O (CH 2 ) 2 OH or COO (CH 2 ) 2 OH is preferred. More preferred. )

(In Formula (10), R < 3 > shows a C1-C6 alkyl group, respectively, and it is preferable that it is a propyl group.
R 4 represents NO 2 or ArCO (where Ar represents a substituted or unsubstituted aryl group), and Ar is preferably a tolyl group.
R 5 and R 6 each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and is preferably a methyl group, a phenyl group, or a tolyl group. )

(In formula (11), R 7 represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group.
R 8 is an organic group having an acetal bond, and is preferably a substituent corresponding to R 8 included in the compound represented by formula (11-1) described later. In addition, the benzene ring substituted by R 8 may further have a substituent.
R 9 and R 10 each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, preferably a methyl group, a phenyl group, or a tolyl group, and more preferably a methyl group. )

Examples of the compound represented by the formula (9) include a compound represented by the following formula (9-1) and a compound represented by the following formula (9-2). Among these, the compound represented by the following formula (9-1) is available as IRGACURE OXE-01 (trade name, manufactured by BASF Corporation).

Examples of the compound represented by the formula (10) include a compound represented by the following formula (10-1). This compound is available as DFI-091 (trade name, manufactured by Daito Chemix Co., Ltd.).

Examples of the compound represented by the formula (11) include a compound represented by the following formula (11-1). It is available as Adekaoptomer N-1919 (manufactured by ADEKA, trade name).

As other oxime ester compounds, the following compounds are preferably used.

Moreover, the following compounds can also be used as the component (c).

  (C) As content in the case of containing a component, it is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of (a) component, and it is more preferable that it is 0.05-15 mass parts. Preferably, it is 0.1-10 mass parts. If the blending amount is 0.01 parts by mass or more, the exposed part is sufficiently cross-linked, the photosensitivity becomes more favorable, and the heat resistance of the cured film tends to be improved by being 30 parts by mass or less.

(D) Component: Solvent The resin composition of the present invention may contain a solvent as the (d) component.
The solvent as component (d) is preferably a polar solvent that completely dissolves the polyimide precursor. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethyl Urea, hexamethylphosphoric triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolide Non etc. are mentioned.
These solvents may be used alone or in combination of two or more.

  The content of the component (d) in the resin composition of the present invention is preferably 50 to 500 parts by weight, more preferably 80 to 400 parts by weight, and further 100 to 300 parts by weight with respect to 100 parts by weight of the component (a). preferable.

(E) Component: Photopolymerizable Compound Other than Component (b) The resin composition of the present invention may contain a photopolymerizable compound other than the component (b) as the component (e). Examples of the photopolymerizable compound include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, styrene, divinylbenzene, 4-vinyltoluene 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, , N- dimethyl acrylamide, N- methylol acrylamide. These may be used alone or in combination of two or more.

  In the case of containing a photopolymerizable compound, the blending amount is preferably 1 to 100 parts by weight, more preferably 10 to 75 parts by weight, and more preferably 30 to 50 parts per 100 parts by weight of component (a). It is more preferable to set it as a mass part. If the blending amount is 1 part by mass or more, better photosensitive characteristics can be imparted, and if it is 100 parts by mass or less, the heat resistance of the cured film can be further improved.

In addition to the above components (a) to (e), the resin composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to ensure good storage stability.
Specifically, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cuperone 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamine compounds and the like. These may be used alone or in combination of two or more.

  As content when a resin composition contains a radical polymerization inhibitor or a radical polymerization inhibitor, it is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of (a) component, More preferably, it is 10-10 mass parts, More preferably, it is 0.05-5 mass parts. If the blending amount is 0.01 parts by mass or more, the storage stability becomes better, and if it is 30 parts by mass or less, the heat resistance of the cured film can be further improved.

The resin composition of the present invention may further contain an organosilane compound in order to further improve the adhesion to a cured silicon substrate or the like.
Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropyltri Methoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (2-hydroxyethyl) -3-amino Propyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-amino Examples include propyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
What is necessary is just to adjust suitably content of an organosilane compound so that a desired effect may be acquired.

<Method for producing cured film and patterned cured film>
The residual stress of the cured film obtained by applying the composition of the present invention to a substrate and heat-curing is preferably 30 MPa or less, and preferably 27 MPa or less when the thickness of the cured film is 10 μm. More preferably, it is more preferably 25 MPa or less. If the residual stress is 30 MPa or less, when the film is formed so that the film thickness after curing is 10 μm, the warpage of the wafer can be more sufficiently suppressed, and the problems caused in the conveyance and suction fixation of the wafer can be further reduced. Can be suppressed.

  The residual stress can be measured by a method of converting the amount of warpage of the wafer into a stress after measuring the amount of warpage of the wafer using a thin film stress measuring apparatus FLX-2320 (manufactured by KLA Tencor).

  The pattern cured film of this invention is a pattern cured film formed from the above-mentioned resin composition. The pattern cured film of this invention is formed when the above-mentioned resin composition contains (c) component.

  Further, the method for producing a cured pattern film of the present invention includes a step of applying the above resin composition onto a substrate and drying to form a coating film, and irradiating the coating film with actinic rays, followed by development to form a pattern resin. A step of obtaining a film, and a step of heat-treating the patterned resin film.

Hereinafter, each process of the manufacturing method of a pattern cured film is demonstrated first.
The manufacturing method of the pattern cured film of this invention includes the process of apply | coating the above-mentioned resin composition on a board | substrate, and drying and forming a coating film. Examples of the method for applying the resin composition on the substrate include dipping, spraying, screen printing, and spin coating. Examples of the substrate include a silicon wafer, a metal substrate, and a ceramic substrate. Since the resin composition of the present invention can form a low-stress cured film, it can be suitably used for a silicon wafer having a large diameter of 12 inches or more.

  In the drying step, a solvent-free coating can be formed by removing the solvent by heating. For the drying step, an apparatus such as DATAPLATE (Digital Hotplate, manufactured by PMC) can be used, the drying temperature is preferably 90 to 130 ° C., and the drying time is preferably 100 to 400 seconds.

  The manufacturing method of the pattern cured film of this invention includes the process of developing after irradiating the actinic ray to the coating film formed at the said process, and obtaining a pattern resin film. Thereby, a resin film on which a desired pattern is formed can be obtained. Although the resin composition of the present invention is suitable for i-line exposure, ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays, and the like can be used as the active rays to be irradiated.

  The developer is not particularly limited, but is a flame retardant solvent such as 1,1,1-trichloroethane, an aqueous alkali solution such as an aqueous sodium carbonate solution and an aqueous tetramethylammonium hydroxide solution, N, N-dimethylformamide, dimethyl sulfoxide, Good solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates, etc., and these good solvents and poor solvents such as lower alcohols, water, and aromatic hydrocarbons A mixed solvent or the like is used. After development, rinsing with a poor solvent is performed as necessary.

The manufacturing method of the pattern cured film of this invention includes the process of heat-processing a pattern resin film.
This heat treatment can be performed using an apparatus such as a vertical diffusion furnace (manufactured by Koyo Lindberg), and is preferably performed at a heating temperature of 80 to 300 ° C., and the heating time is preferably 5 to 300 minutes. By this step, imidation of the polyimide precursor in the resin composition can be advanced to obtain a patterned cured film containing a polyimide resin.

Moreover, the cured film of this invention is a cured film formed from the above-mentioned resin composition. That is, the cured film of the present invention may be a cured film that is not patterned.
The cured film or patterned cured film of the present invention thus obtained can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer or the like of a semiconductor device.

FIG. 1 is a schematic cross-sectional view of a semiconductor device having a rewiring structure according to an embodiment of the present invention.
The semiconductor device of this embodiment has a multilayer wiring structure. An A1 wiring layer 2 is formed on the interlayer insulating layer (interlayer insulating film) 1, and an insulating layer (insulating film) 3 (for example, a P-SiN layer) is further formed on the A1 wiring layer 2. A (surface protective film) 4 is formed. A rewiring layer 6 is formed from the pad portion 5 of the wiring layer 2 and extends to an upper portion of the core 8 which is a connection portion with a conductive ball 7 formed of solder, gold or the like as an external connection terminal. Further, a cover coat layer 9 is formed on the surface protective layer 4. The rewiring layer 6 is connected to the conductive ball 7 through the barrier metal 10, and a collar 11 is provided to hold the conductive ball 7. When a package having such a structure is mounted, an underfill 12 may be interposed in order to further relieve stress.

  The cured film or pattern cured film of the present invention can be used for the cover coating material, the core material for rewiring, the color material for balls such as solder, the underfill material, and the like.

  The electronic component of the present invention is particularly limited except that it has a cover coat using the cured film or pattern cured film of the present invention, a core for rewiring, a ball collar such as solder, an underfill used in flip chips, etc. Instead, it can take various structures.

  Hereinafter, the present invention will be described specifically by way of examples.

Synthesis Example 1 (Synthesis of pyromellitic acid-hydroxyethyl methacrylate diester)
In a 0.5 liter plastic bottle, pyromellitic dianhydride 43.624 g (200 mmol), 2-hydroxyethyl methacrylate 54.919 g (401 mmol) and hydroquinone 0. 220 g is dissolved in 394 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture is stirred at room temperature (25 ° C.) for 24 hours to perform esterification, whereby pyromellitic acid-hydroxy An ethyl methacrylate diester solution was obtained. This solution is designated as PMDA (HEMA) solution.

Synthesis Example 2 (Synthesis of 4,4′-oxydiphthalic acid diester)
49.634 g (160 mmol) of 4,4′-oxydiphthalic acid, 44.976 g (328 mmol) of 2-hydroxyethyl methacrylate and hydroquinone 0 which were dried in a dryer of 160 ° C. for 24 hours in a 0.5 liter plastic bottle. 176 g was dissolved in 378 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25 ° C.) for 48 hours to perform esterification, and 4,4′-oxydiphthalate. An acid-hydroxyethyl methacrylate diester solution was obtained. This solution is defined as an ODPA (HEMA) solution.

Synthesis Example 3 (Synthesis of Polymer 1)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 195.564 g of the PMDA (HEMA) solution obtained in Synthesis Example 1 and 58.652 g of the ODPA (HEMA) solution obtained in Synthesis Example 2 were placed. Thereafter, 25.9 g (217.8 mmol) of thionyl chloride was added dropwise by using a dropping funnel so as to keep the reaction solution temperature at 10 ° C. or lower under ice cooling. After the addition of thionyl chloride was completed, the reaction was carried out for 2 hours under ice cooling to obtain a solution of PMDA (HEMA) and ODPA (HEMA) acid chloride. Then, using a dropping funnel, 31.696 g (99.0 mmol) of 2,2′-bis (trifluoromethyl) benzidine, 34.457 g (435.6 mmol) of pyridine, 0.076 g (0.693 mmol) of hydroquinone -A solution of 90.211 g of methylpyrrolidone was added dropwise while cooling with ice so that the temperature of the reaction solution did not exceed 10 ° C. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. The weight average molecular weight determined by standard polystyrene conversion was 34,000. This is polymer 1. 1 g of polymer 1 is dissolved in 1.5 g of N-methylpyrrolidone, applied onto a glass substrate by spin coating, heated on a hot plate at 100 ° C. for 180 seconds to volatilize the solvent, and a 20 μm thick coating film is formed. did. At this time, the i-line transmittance of the obtained coating film was 30%.

  The measurement conditions of the weight average molecular weight calculated | required by GPC method standard polystyrene conversion of the polymer 1 are as follows, The solvent [THF / DMF = 1/1 (volume ratio)] 1mL solution was used with respect to 0.5 mg of polymers. Measured.

Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H3PO4 (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm
The i-line transmittance of polymer 1 was measured using U-3310 Spectrophotometer (manufactured by HITACHI).

Example 1-6 and Comparative Example 1-4
Each component of (a), (b), (c), and (e) was dissolved in N-methylpyrrolidone with the formulation shown in Table 1 to prepare a resin composition. And the swelling rate was evaluated. The results are shown in Table 1.
In Table 1, the numbers in parentheses in each column of the components (b) and (c) indicate the amount (parts by mass) added to 100 parts by mass of the component (a). Further, N-methylpyrrolidone was used as the solvent, and the amount used was 1.5 times (150 parts by mass) with respect to 100 parts by mass of component (a).

(Evaluation of photosensitive characteristics (resolution))
The resin composition prepared on a 6-inch silicon wafer was applied by spin coating, heated on a hot plate at 100 ° C. for 3 minutes to evaporate the solvent, and a coating film having a thickness of 10 μm was obtained. The development time was set twice as long as the coating film was immersed in a mixed solvent of γ-butyrolactone: butyl acetate = 7: 3 and completely dissolved. An i-line stepper FPA-3000iW (manufactured by Canon Inc.) is used to expose the coated film obtained in the same manner through a photomask to 300 mJ / cm 2 in terms of i-line, and the wafer is subjected to γ-butyrolactone: After dipping in butyl acetate = 7: 3 for paddle development, rinsing with cyclopentanone was performed. The minimum mask dimension of the line and space pattern that could be resolved was evaluated as the resolution.

(Measurement of residual stress)
The obtained resin composition was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100 ° C. for 3 minutes, and the solvent was evaporated to obtain a coating film having a thickness of 10 μm after curing. . This was heat-cured at 270 ° C. for 4 hours in a nitrogen atmosphere using a vertical diffusion furnace (manufactured by Koyo Lindberg) to obtain a polyimide film. The residual stress of the cured polyimide film was measured at room temperature using a thin film stress measuring apparatus FLX-2320 (manufactured by KLA Tencor).

(Measurement of swelling rate)
The obtained resin composition was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100 ° C. for 3 minutes, and the solvent was evaporated to obtain a coating film having a thickness of 10 μm after curing. . This was heat-cured at 270 ° C. for 4 hours in a nitrogen atmosphere using a vertical diffusion furnace (manufactured by Koyo Lindberg) to obtain a polyimide film. The polyimide film produced on the substrate was immersed in N-methylpyrrolidone at 70 ° C. and heated for 20 minutes. The sample immersed in N-methylpyrrolidone was rinsed with distilled water, and the film thickness was measured. The swelling ratio (%) was calculated from the change in film thickness before and after immersion in N-methylpyrrolidone.

In Table 1, the component (b) is as follows.
A9300 (ethoxylated isocyanuric acid triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)

In Table 1, component (c) is the following compound.
C1: 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (o-benzoyloxime)] (trade name “IRGACURE OXE-01” manufactured by BASF Corporation)
C2: Adeka Cruise NCI-930 (made by ADEKA, trade name)

In Table 1, component (e) is tetraethylene glycol dimethacrylate.
Aluminum chelate A (w) is aluminum trisacetylacetonate (manufactured by Kawaken Fine Chemical Co., Ltd.).

  In the examples, by adding a compound having an isocyanuric skeleton to rigid polyimide containing fluorine, the swelling rate is 10% or less while maintaining a low stress of 30 MPa or less. On the other hand, in the comparative example, when the composition does not contain a compound having an isocyanuric skeleton, the fluorine-containing polyimide has a large swelling ratio of 20% or more. In Comparative Examples 3 and 4, an aluminum chelate compound was added, but since the curing temperature was low, the effect of improving chemical resistance was not obtained.

  The resin composition of the present invention can be used for so-called package applications such as cover coat materials, core materials for rewiring, color materials for balls such as solder, underfill materials, etc., which form electronic parts such as semiconductor devices. .

Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.

Claims (15)

  1. The resin composition containing the following (a) component and (b) component.
    (A) a polyimide precursor having a structural unit represented by the following formula (1),
    (In the formula, R 1 is a tetravalent organic group, R 2 is a divalent organic group. R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 3; ˜20 cycloalkyl groups or monovalent organic groups having a carbon-carbon unsaturated double bond.)
    (B) Photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure
  2. The resin composition according to claim 1, wherein R 2 in the formula (1) is a divalent organic group represented by the following formula (2).
    (In the formula, R 5 to R 12 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 5 to R 12 is a fluorine atom, a methyl group, or a trifluoromethyl group. .)
  3. The resin composition according to claim 1, wherein R 2 in the formula (1) is a divalent organic group represented by the following formula (3).
    (In the formula, R 13 and R 14 are each independently a fluorine atom or a trifluoromethyl group.)
  4. The resin composition in any one of Claims 1-3 in which the said photopolymerizable compound contains the structure represented by following formula (4).
    (In the formula, R 24 is a hydrogen atom or a methyl group, X is an alkylene group, and n is an integer of 1 to 25.)
  5. The resin composition according to claim 4, wherein the photopolymerizable compound is a compound represented by the following formula (5).
    (In the formula, R 21 to R 23 are each independently a monovalent organic group, and at least one is a group represented by the formula (4).)
  6.   The resin composition according to any one of claims 1 to 5, wherein the component (b) is contained in an amount of 0.01 to 50 parts by mass with respect to 100 parts by mass of the component (a).
  7.   (C) The resin composition in any one of Claims 1-6 which further contains the compound which generate | occur | produces a radical by actinic ray irradiation as a component.
  8.   The resin composition according to claim 7, wherein the compound that generates radicals upon irradiation with active light is an oxime ester compound.
  9.   The resin composition according to any one of claims 1 to 8, further comprising a photopolymerizable compound other than the component (b) as the component (e).
  10.   The resin composition according to claim 9, wherein the photopolymerizable compound is a (meth) acrylic compound.
  11.   The manufacturing method of a cured film including the process of apply | coating and drying the resin composition in any one of Claims 1-10 on a board | substrate, and the process of heat-processing the said coating film.
  12.   The process of apply | coating the resin composition in any one of Claims 1-10 on a board | substrate, and drying and forming a coating film, The process of developing after irradiating the said coating film with actinic light, and obtaining a pattern resin film And a step of heat-treating the patterned resin film.
  13.   The cured film obtained from the manufacturing method of the cured film of Claim 11.
  14.   The pattern cured film obtained from the manufacturing method of the pattern cured film of Claim 12.
  15.   An electronic component having the cured film according to claim 13 or the patterned cured film according to claim 14.
JP2015000357A 2014-02-10 2015-01-28 Resin composition containing polyimide precursor, method for producing cured film, and electronic component Granted JPWO2015118836A1 (en)

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US20190072850A1 (en) * 2015-08-21 2019-03-07 Asahi Kasei Kabushiki Kaisha Photosensitive resin composition, polyimide production method, and semiconductor device

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JP2007241195A (en) * 2006-03-13 2007-09-20 Asahi Kasei Electronics Co Ltd Photosensitive resin composition
WO2008123053A1 (en) * 2007-03-30 2008-10-16 Toray Industries, Inc. Positive photosensitive resin composition
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JP2011116848A (en) * 2009-12-02 2011-06-16 Kaneka Corp Novel polyimide precursor composition and use of the same
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KR20160124082A (en) 2016-10-26

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