WO2022270541A1 - ネガ型感光性樹脂組成物、ネガ型感光性ポリマー、硬化膜および半導体装置 - Google Patents

ネガ型感光性樹脂組成物、ネガ型感光性ポリマー、硬化膜および半導体装置 Download PDF

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WO2022270541A1
WO2022270541A1 PCT/JP2022/024894 JP2022024894W WO2022270541A1 WO 2022270541 A1 WO2022270541 A1 WO 2022270541A1 JP 2022024894 W JP2022024894 W JP 2022024894W WO 2022270541 A1 WO2022270541 A1 WO 2022270541A1
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general formula
carbon atoms
group
negative photosensitive
resin composition
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PCT/JP2022/024894
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English (en)
French (fr)
Japanese (ja)
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啓太 今井
数矢 中島
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住友ベークライト株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C08G73/16—Polyester-imides
    • 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

Definitions

  • the present invention relates to a negative photosensitive resin composition, a negative photosensitive polymer, a cured film and a semiconductor device.
  • Polyimide resin has high mechanical strength, heat resistance, insulation, and solvent resistance, so it is widely used as a protective material for liquid crystal display elements and semiconductors, as an insulating material, and as a thin film for electronic materials such as color filters.
  • Patent Document 1 discloses a block copolyimide that is soluble in a dipolar aprotic solvent, and states that a predetermined acid anhydride can be used to obtain the block copolyimide.
  • Patent Document 2 discloses a polyimide resin composed of structural units having a predetermined structure. This document describes an example of synthesizing a polyimide resin using 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane.
  • Patent Document 3 discloses an aromatic tetracarboxylic dianhydride, 4,4'-diaminodiphenylmethane having at least one or more alkyl groups in an aromatic ring having an amino group, and p-aminobenzoic acid ester groups at both ends.
  • a polyimide elastomer resin is disclosed which is a terpolymer obtained from a polyether oligomer having a specific molecular weight.
  • the document describes that the resin has excellent heat and humidity resistance.
  • Patent Document 4 discloses a block copolymer consisting of a polyimide structural unit formed from an aromatic tetracarboxylic dianhydride and a 4,4'-diaminodiphenylmethane derivative and a dimethylsiloxane structural unit.
  • the document mentions bis(4-amino-3-ethyl-5-methylphenyl)methane as 4,4'-diaminodiphenylmethane.
  • the literature describes that the resin is excellent in heat resistance and solvent solubility.
  • the film containing polyimide obtained from the photosensitive resin composition has room for improvement in mechanical strength such as elongation.
  • the present inventors have found that the above problems can be solved by using a polyimide having a specific structure, and completed the present invention. That is, the present invention can be shown below.
  • A polyimide
  • B a cross-linking agent comprising a polyfunctional (meth)acrylate
  • C a photoinitiator; including Polyimide
  • A) is a structural unit (a1) represented by the following general formula (a1); a structural unit (a2) represented by the following general formula (a2); a structural unit (a3) represented by the following general formula (a3);
  • a negative photosensitive resin composition comprising: (In general formula (a1), Y is a divalent organic group.
  • R 1 to R 4 each independently represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R 1 and R 2 are different groups; R3 and R4 are different groups.
  • Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different.
  • R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
  • n1 and m2 each independently represent an integer of 1 to 3;
  • Y is a divalent organic group.
  • R 1 to R 4 each independently represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R 1 and R 2 are different groups; R3 and R4 are different groups.
  • Y in the general formula (a1) is a divalent group containing an alkylene group or a divalent group containing at least one aromatic ring type photosensitive resin composition.
  • Y in the general formula (a1) is a divalent organic group selected from the following general formula (a1-1), the following general formula (a1-2) and the following general formula (a1-3).
  • the negative photosensitive resin composition according to any one of [1] to [4].
  • R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R 7 and a plurality of R 8 may be the same or different, R 9 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; may be the same or different, and * indicates a bond.
  • each of R 10 and R 11 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R 11 may be the same or different. * indicates a bond.
  • Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group. * indicates a bond.
  • the polyimide (A) is a negative photosensitive according to any one of [1], [2], and [4] to [6], which contains a structural unit represented by the following general formula (2) elastic resin composition.
  • Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different.
  • R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
  • n1 and m2 each independently represent an integer of 1 to 3;
  • Y is a divalent organic group.
  • R 1 to R 4 each independently represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R 1 and R 2 are different groups; R3 and R4 are different groups.
  • Y in the general formula (a1) is a divalent group containing an alkylene group or a divalent group containing at least one aromatic ring type photosensitive polymer.
  • Y in the general formula (a1) is a divalent organic group selected from the following general formula (a1-1), the following general formula (a1-2) and the following general formula (a1-3).
  • the negative photosensitive polymer according to any one of [8] to [11].
  • R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R 7 and a plurality of R 8 may be the same or different
  • R 9 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; may be the same or different
  • * indicates a bond.
  • each of R 10 and R 11 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R 11 may be the same or different. * indicates a bond.
  • Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group. * indicates a bond.
  • FIG. 1 is a schematic cross-sectional view of a semiconductor device according to an embodiment
  • the negative photosensitive resin composition of the present embodiment contains (A) a polyimide, (B) a cross-linking agent containing a polyfunctional (meth)acrylate, and (C) a photopolymerization initiator.
  • polyimide (A) The polyimide (A) (negative photosensitive polymer) of the present embodiment can be explained according to the first embodiment or the second embodiment.
  • the polyimide (A) (negative photosensitive polymer) of the present embodiment includes a structural unit (a1) represented by the following general formula (a1), and a structural unit (a2) represented by the following general formula (a2). , and a structural unit (a3) represented by the following general formula (a3).
  • Y is a divalent organic group.
  • the divalent organic group a known organic group can be used as long as the effect of the present invention is exhibited. From the viewpoint of the effect of the present invention, Y is a divalent group containing an alkylene group, or at least one A divalent group containing an aromatic ring is preferred.
  • the alkylene group is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms.
  • the aromatic ring includes a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring, a divalent biphenyl group and the like, preferably a divalent benzene ring or a divalent biphenyl group.
  • Y in general formula (a1) is preferably a divalent organic group selected from general formula (a1-1), general formula (a1-2) and general formula (a1-3) below.
  • R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple R 7 , multiple R 8 may be the same or different. From the viewpoint of the effects of the present invention, R 7 and R 8 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 9 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R 9 may be the same or different. From the viewpoint of the effects of the present invention, R 9 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom. * indicates a bond.
  • each of R 10 and R 11 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R 11 may be the same or different.
  • R 10 and R 11 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably at least one of R 10 and at least one of R 11 an alkyl group having 1 to 3 carbon atoms, more preferably three R 10 are alkyl groups having 1 to 3 carbon atoms, one R 10 is a hydrogen atom, and three R 11 are alkyl groups having 1 to 3 carbon atoms one R 11 is a hydrogen atom, particularly preferably three R 10 are methyl groups and one R 10 is a hydrogen atom, and three R 11 are methyl groups and one R 11 is It is a hydrogen atom. * indicates a bond.
  • Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group, preferably a divalent aromatic group.
  • the divalent aromatic group includes a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring, and a divalent biphenyl group, with a divalent benzene ring being preferred. * indicates a bond.
  • R 1 to R 4 each independently represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R 1 and R 2 are different groups; R3 and R4 are different groups. From the viewpoint of the effects of the present invention, R 1 to R 4 are preferably alkyl groups having 1 to 3 carbon atoms.
  • X 1 is preferably a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, and more A linear or branched alkylene group having 1 to 5 carbon atoms or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms is preferred.
  • the polyimide (A) of the present embodiment suppresses the influence of the imide ring on the electrons, suppresses the hydrolysis of the polyimide, and improves mechanical properties such as elongation. Excellent strength and excellent solubility in organic solvents.
  • the polyimide (A) of the present embodiment and the negative photosensitive resin composition containing the polyimide (A) have an excellent balance of these properties.
  • Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different.
  • Examples of the divalent to tetravalent organic group having 1 to 10 carbon atoms include an ester group, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a divalent to tetravalent carbon number of 3 to 10.
  • Alicyclic hydrocarbon groups and the like may be mentioned, and these hydrocarbon groups may contain heteroatoms such as oxygen, nitrogen, and sulfur atoms, and ester bonds, thioester bonds, urethane bonds, thiourethane bonds, urea bonds etc. in the structure.
  • R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
  • m1 and m2 each independently represent an integer of 1 to 3;
  • X 2 is preferably a linear or branched alkylene group having 1 to 5 carbon atoms or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms.
  • the polyimide (A) of the present embodiment can contain a structural unit represented by the following general formula (1).
  • R 1 to R 4 and X 1 have the same meanings as in general formula (a2), and Y has the same meaning as in general formula (a1).
  • the polyimide (A) of the present embodiment can contain a structural unit represented by the following general formula (2) together with the structural unit represented by the general formula (1).
  • the polyimide (A) of the present embodiment can contain the structural unit represented by the general formula (3).
  • the polyimide (A) of the present embodiment contains the structural units described above, and may further partially contain the following structural units.
  • Q, R 5 , R 6 , m1, m2, and X 2 are synonymous with general formula (a3), and Y is synonymous with general formula (a1).
  • at least one of both ends of the polyimide (A) is preferably a (meth)acrylate group. By including the group, it is superior in mechanical strength such as elongation. Having a (meth)acrylate group can be analyzed by 1 H-NMR.
  • the polyimide (A) has at least one terminal structure (a4) to terminal structure (a12) represented by the following general formulas (a4) to (a12) at least one of both ends
  • the terminal structure (a4) is provided.
  • Q has the same meaning as in general formula (a3), and Y has the same meaning as in general formula (a1).
  • R7 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
  • m3 represents an integer of 1-3. * indicates a bond.
  • Q has the same meaning as in general formula (a3), and X 1 and R 1 to R 4 have the same meanings as in general formula (a2).
  • R 7 and m3 are synonymous with general formula (a4). * indicates a bond.
  • the weight average molecular weight of the polyimide (A) of this embodiment is 5,000 to 200,000, preferably 10,000 to 100,000.
  • the polyimide (A) of the present embodiment Hydrolysis of the polyimide (A) of the present embodiment is suppressed, and the polyimide (A) and the negative photosensitive resin composition containing the polyimide (A) are excellent in mechanical strength such as elongation, and can be used as a film or the like. A cured product can be obtained.
  • the polyimide (A) of the present embodiment has excellent solubility in solvents and does not need to be varnished in a precursor state, a varnish containing the polyimide (A) can be prepared. A cured product such as a film can be obtained from the varnish.
  • a method for producing a polyimide (A) (negative photosensitive polymer) having a structural unit An acid anhydride (a1′) represented by the following general formula (a1′), a diamine (a2′) represented by the following general formula (a2′), and a bis represented by the following general formula (a3′)
  • a compound having a (meth)acrylate group is reacted with the hydroxyl group of the structural unit derived from the bisaminophenol (a3′) of the general formula (a3′) of the polymer obtained in step 1 to convert the (meth)acrylate group.
  • a polyimide (A) having excellent solubility in organic solvents can be synthesized by a simple method.
  • Y has the same meaning as in general formula (a1) and is preferably selected from groups represented by general formulas (a1-1), (a1-2) or (a1-3). be.
  • R 1 to R 4 and X 1 have the same meanings as in general formula (a2).
  • acid anhydrides that are end capping agents include phthalic anhydride, maleic anhydride, and nadic anhydride
  • aromatic amines include p-methylaniline, p-methoxyaniline, p-phenoxyaniline, and the like.
  • the amount of acid anhydride or aromatic amine added as the end capping agent is preferably 5 mol % or less. If it exceeds 5 mol %, the molecular weight of the resulting polyhydroxyimide is significantly lowered, causing problems in heat resistance and mechanical properties.
  • the equivalent ratio of acid anhydride (a1'), diamine (a2') and bisaminophenol (a3') in the imidization reaction in step 1 is an important factor that determines the molecular weight of the resulting polymer.
  • the equivalent ratio of the acid anhydride (a1′), the diamine (a2′) and the bisaminophenol (a3′) to be used is not particularly limited.
  • bisaminophenol (a3′) is preferably in the range of 0.70 to 1.30. If the corresponding amount ratio is within the above range, the mechanical strength is excellent and the manufacturing stability is excellent.
  • Step 1 imidization reaction step
  • Step 1 can be performed in an organic solvent by a known method.
  • organic solvents include aprotic polar solvents such as ⁇ -butyl lactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane. , and one type or two or more types may be used in combination. At this time, a nonpolar solvent compatible with the aprotic polar solvent may be mixed and used.
  • aprotic polar solvents such as ⁇ -butyl lactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane.
  • a nonpolar solvent compatible with the aprotic polar solvent may be mixed and used.
  • nonpolar solvents examples include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene and solvent naphtha, and ether solvents such as cyclopentyl methyl ether.
  • the ratio of the non-polar solvent in the mixed solvent is set arbitrarily according to the resin properties such as the stirring device capacity and solution viscosity, as long as the solubility of the solvent decreases and the polyamic acid resin obtained by the reaction does not precipitate. can do.
  • the reaction temperature is 0° C. or higher and 100° C. or lower, preferably 20° C. or higher and 80° C. or lower, for about 30 minutes to 2 hours. React for some time.
  • step 1 a polyhydroxyimide having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2′), or a structural unit represented by the following general formula (3′) It is possible to obtain a polyhydroxyimide containing structural units having In step 1, the polyhydroxyimide can be purified by a known method. can be done.
  • R 1 to R 4 and X 1 have the same definitions as in general formula (a2), X 2 has the same meaning as in general formula (a3), Y has the same meaning as in general formula (a1), It is preferably selected from groups represented by the general formulas (a1-1), (a1-2) and (a1-3).
  • step 2 the hydroxyl groups of the polyhydroxyimide obtained in step 1 are reacted with a compound having (meth)acrylate groups to introduce cross-linking groups containing (meth)acrylate groups.
  • the cross-linking group introduced into the polyimide (A) reacts with the cross-linking agent (B) described later in the exposure step, and the exposed area becomes insoluble in the organic solvent.
  • Compounds having a (meth)acrylate group include 2-isocyanatoethyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate , glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and the like.
  • polyhydroxyimide and a compound having a (meth)acrylate group are mixed in an organic solvent at 60° C. to 150° C. for 2 hours. React for about 10 hours. Although the reaction is not particularly limited, it can be carried out at normal pressure.
  • the compound having a (meth)acrylate group can be appropriately selected according to the amount of cross-linking groups to be introduced into the polyhydroxyimide. It can be added so as to double, preferably 2.0 to 3.0 mol times. In addition, when the polyhydroxyimide has a group capable of introducing a cross-linking group, the group can be added in a molar amount.
  • organic solvents include aprotic polar solvents such as ⁇ -butyl lactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane. , and one type or two or more types may be used in combination. At this time, a nonpolar solvent compatible with the aprotic polar solvent may be mixed and used.
  • aprotic polar solvents such as ⁇ -butyl lactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane.
  • a nonpolar solvent compatible with the aprotic polar solvent may be mixed and used.
  • non-polar solvents examples include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene and solvent naphtha, and ether solvents such as cyclopentyl methyl ether.
  • a base such as triethylamine or 1,1,3,3-tetramethylguanidine may be added during the reaction.
  • step 2 a polyimide (A) having a structural unit represented by general formula (1) and a structural unit represented by general formula (2), or a polyimide having a structural unit represented by general formula (3) ( A) can be obtained.
  • step 2 the polyhydroxyimide obtained by purifying the reaction solution containing polyhydroxyimide obtained in step 1 by reprecipitation or the like can be used. can be used.
  • a reaction solution containing the polyimide (A) (negative photosensitive polymer) of the present embodiment can be obtained, and further diluted with an organic solvent or the like as necessary, and the polymer solution ( It can be used as a varnish for coating.
  • organic solvent those exemplified in the reaction step can be used, and the same organic solvent as in the reaction step may be used, or a different organic solvent may be used.
  • this reaction solution can be put into a poor solvent to reprecipitate the polyimide (A) resin to remove unreacted monomers, dry and solidify, and dissolve again in an organic solvent to be used as a purified product.
  • the polyimide (A) of the present embodiment is a structural unit (a1) represented by the general formula (a1); a structural unit (a2) represented by the general formula (a2); and at least one of both ends thereof is a (meth)acrylate group.
  • the polyimide (A) is a (meth)acrylate group.
  • the group By including the group, it is excellent in mechanical strength such as elongation. Having a (meth)acrylate group can be analyzed by 1 H-NMR.
  • the polyimide (A) has a terminal structure (a4) represented by the general formula (a4) or a terminal structure (a5) represented by the general formula (a5) at least one of both ends. It is preferred to have at least one, preferably a terminal structure (a4).
  • the polyimide (A) of the present embodiment preferably contains a structural unit represented by the following general formula (1).
  • R 1 to R 4 and X 1 have the same meanings as in general formula (a2), and Y has the same meaning as in general formula (a1).
  • the weight average molecular weight of the polyimide (A) of this embodiment is 5,000 to 200,000, preferably 10,000 to 100,000.
  • the polyimide (A) of the present embodiment Hydrolysis of the polyimide (A) of the present embodiment is suppressed, and the polyimide (A) and the negative photosensitive resin composition containing the polyimide (A) are excellent in mechanical strength such as elongation, and can be used as a film or the like. A cured product can be obtained.
  • the polyimide (A) of the present embodiment has excellent solubility in solvents and does not need to be varnished in a precursor state, a varnish containing the polyimide (A) can be prepared. A cured product such as a film can be obtained from the varnish.
  • the polyimide (A) of this embodiment can be produced by the same method as in the first embodiment, except that the bisaminophenol (a3') represented by the general formula (a3') is not used.
  • the equivalent ratio of the acid anhydride (a1′) and the diamine (a2′) to be used is not particularly limited, but the equivalent ratio of the diamine (a2′) to the acid anhydride (a1′) is 0. It is preferably in the range of 0.70 to 1.30. If it is less than 0.70, the molecular weight is low and the material becomes brittle, resulting in low mechanical strength. On the other hand, if it exceeds 1.30, the molecular weight is low and the material becomes brittle, resulting in a weak mechanical strength. That is, when the equivalent ratio is within the above range, excellent mechanical strength and excellent production stability are obtained.
  • the polyimide (A) (negative photosensitive polymer) of the present embodiment has excellent hydrolysis resistance, and the weight average molecular weight reduction rate measured under the following conditions is 15% or less, preferably 12% or less. be.
  • (conditions) 400 parts by mass of ⁇ -butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water are added to 100 parts by mass of the negative photosensitive polymer, and the mixture is stirred at 100°C for 6 hours.
  • the negative photosensitive polymer of the present embodiment has a weight-average molecular weight reduction rate within the above range, so that a cured product such as a film having excellent mechanical strength such as elongation can be obtained.
  • Table A below shows preferred formulation examples of the negative photosensitive polymer of the present embodiment.
  • ⁇ MED-J 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane
  • ⁇ HFBAPP 4,4′-(hexafluoroisopropylidene)bis[(4-aminophenoxy)benzene]
  • BAPA 2,2-bis (3-amino-4-hydroxyphenyl) propane
  • BAFA 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
  • TMPBP-TME 4-[4- (1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate
  • TMHQ p-phenylene bis(trimellitate anhydride)
  • ⁇ AOI 2-isocyanatoethyl acrylate
  • ⁇ MOI 2-isocyanatoe
  • a cross-linking agent (B) contains a polyfunctional (meth)acrylate.
  • the polyfunctional (meth)acrylate is a compound having two or more (meth)acryloyl groups, and conventionally known compounds can be used as long as the effects of the present invention can be exhibited.
  • a (meth)acryl group indicates an acryl group or a methacryl group.
  • Specific polyfunctional (meth)acrylates include bifunctional (meth)acrylates such as diethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, polyethylene glycol #400 di(meth)acrylate, and trimethylolpropane.
  • tri(meth)acrylate pentaerythritol tri(meth)acrylate, trifunctional (meth)acrylate such as ethoxylated isocyanuric acid triacrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate and other tetrafunctional ( Hexafunctional (meth)acrylates such as meth)acrylates, dipentaerythritol hexa(meth)acrylate, octafunctional (meth)acrylates such as tripentaerythritol octa(meth)acrylate, and deca(meth)acrylates such as tetrapentaerythritol deca(meth)acrylate.
  • Methodh)acrylates are mentioned. You may use 1 type(s) or 2 or more types among these.
  • the amount of the cross-linking agent (B) with respect to 100 parts by mass of the polyimide (A) is 1 part by mass or more and 30 parts by mass or less, preferably 2 parts by mass or more and 20 parts by mass or less, preferably 3 parts by mass, from the viewpoint of the effect of the present invention. parts or more and 15 parts by mass or less. Within this range, elongation is further improved.
  • the photo-radical generator includes a photo-radical generator that generates radicals upon irradiation with actinic rays such as ultraviolet rays and functions as a photopolymerization initiator for the polyimide (A) described above.
  • Examples of the photoradical generator include alkylphenone type initiators, oxime ester type initiators, acylphosphine oxide type initiators, and the like.
  • alkylphenone type initiators For example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1[4-(methylthio)phenyl]-2-morifolinopropan-1-one , 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)), ethanone, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]
  • the amount of the polymerization initiator (C) added is not particularly limited, but it is preferably about 0.3 to 20% by mass of 100% by mass of the non-volatile components of the negative photosensitive resin composition excluding the solvent, and 0.5% by mass. About 15% by mass is more preferable, and about 1 to 10% by mass is even more preferable.
  • the negative photosensitive resin composition according to this embodiment can contain a solvent. Thereby, a uniform photosensitive resin film can be formed on various substrate surfaces.
  • An organic solvent is preferably used as the solvent.
  • one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.
  • solvents examples include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma-butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl- Mention may be made of n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof.
  • the amount of solvent used is not particularly limited. For example, it is used in such an amount that the concentration of non-volatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.
  • the negative photosensitive resin composition according to this embodiment may further contain a surfactant.
  • the surfactant is not limited, and specifically polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Ftop EF301, Ftop EF303, Ftop EF352 (manufactured by Shin-Akita Kasei), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (DIC Corporation
  • a fluorine-based surfactant having a perfluoroalkyl group As the specific examples of the perfluoroalkyl group-containing fluorosurfactant, Megafac F171, Megafac F173, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, and Megafac
  • F477 manufactured by DIC
  • Surflon S-381, Surflon S-383, Surflon S-393 manufactured by AGC Seimi Chemical Co., Ltd.
  • Novec FC4430 and Novec FC4432 manufactured by 3M Japan
  • a silicone-based surfactant eg, polyether-modified dimethylsiloxane, etc.
  • silicone surfactants include SH series, SD series and ST series from Dow Corning Toray Co., Ltd., BYK series from BYK Chemie Japan, KP series from Shin-Etsu Chemical Co., Ltd., Disfoam from NOF CORPORATION ( (registered trademark) series, TSF series of Toshiba Silicone Co., Ltd., and the like.
  • the upper limit of the content of the surfactant in the negative photosensitive resin composition is preferably 1% by mass (10000 ppm) or less with respect to the entire negative photosensitive resin composition (including the solvent), It is more preferably 0.5% by mass (5000 ppm) or less, and even more preferably 0.1% by mass (1000 ppm) or less.
  • the content of the surfactant in the negative photosensitive resin composition is 0.001% by mass (10 ppm) or more with respect to the whole (including the solvent). Applicability and uniformity of the coating film can be improved while maintaining other properties by appropriately adjusting the amount of the surfactant.
  • the negative photosensitive resin composition according to this embodiment may further contain an antioxidant.
  • an antioxidant one or more selected from phenol-based antioxidants, phosphorus-based antioxidants and thioether-based antioxidants can be used.
  • the antioxidant can suppress oxidation of the resin film formed from the negative photosensitive resin composition.
  • Phenolic antioxidants include pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis ⁇ 2-[3-(3 -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl ⁇ 2,4,8,10-tetraoxaspiro[5,5]undecane, octadecyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5 -trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t -butyl-4
  • Phosphorus antioxidants include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenylphosphite), tetrakis(2 ,4-di-t-butyl-5-methylphenyl)-4,4′-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis-(2,6 -dicumylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, tris(mixed mono and di-nonylphenylphosphite), bis(2, 4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6
  • Thioether antioxidants include dilauryl-3,3′-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl)sulfide , distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis(3-lauryl)thiopropionate, and the like.
  • the negative photosensitive resin composition according to this embodiment may further contain an adhesion aid.
  • adhesion aids include silane coupling agents such as aminosilane, epoxysilane, (meth)acrylsilane, mercaptosilane, vinylsilane, ureidosilane, acid anhydride-functional silane, and sulfidesilane. Silane coupling agents may be used alone or in combination of two or more.
  • epoxysilanes i.e., compounds containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in one molecule
  • anhydride-functional silanes i.e., in one molecule, an anhydride and a group that generates a silanol group by hydrolysis
  • aminosilanes include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ -amino propylmethyldimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldiethoxysilane, N-phenyl- ⁇ -amino-propyltrimethoxysilane, and the like.
  • epoxysilanes include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and ⁇ -glycidylpropyltrimethoxysilane. Silane etc. are mentioned.
  • acrylic silanes include ⁇ -(methacryloxypropyl)trimethoxysilane, ⁇ -(methacryloxypropyl)methyldimethoxysilane, ⁇ -(methacryloxypropyl)methyldiethoxysilane, and the like.
  • Mercaptosilanes include, for example, 3-mercaptopropyltrimethoxysilane.
  • Vinylsilanes include, for example, vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like.
  • Ureidosilanes include, for example, 3-ureidopropyltriethoxysilane.
  • acid anhydride-functional silanes examples include X-12-967C (product name: 3-trimethoxysilylpropylsuccinic anhydride) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
  • sulfide silanes include bis(3-(triethoxysilyl)propyl)disulfide and bis(3-(triethoxysilyl)propyl)tetrasulfide.
  • the amount of the adhesion aid added is not particularly limited, but is 0.1 to 5% by mass, preferably 0.5 to 3% by mass, based on the total solid content of the negative photosensitive resin composition.
  • a method for preparing the negative photosensitive resin composition in the present embodiment is not limited, and a known method can be used depending on the components contained in the negative photosensitive resin composition. For example, it can be prepared by mixing and dissolving the above components in a solvent.
  • the negative photosensitive resin composition according to the present embodiment is formed by applying the negative photosensitive resin composition to a surface comprising a metal such as Al or Cu, and then pre-baking to dry it to form a resin film. Then, the resin film is patterned into a desired shape by exposure and development, and then the resin film is cured by heat treatment to form a cured film.
  • the pre-baking conditions may be, for example, heat treatment at a temperature of 90° C. or higher and 130° C. or lower for 30 seconds or longer and 1 hour or shorter.
  • the heat treatment conditions are, for example, heat treatment at a temperature of 150° C. to 250° C. for 30 minutes to 10 hours, preferably about 170° C. for 1 to 6 hours.
  • the film obtained from the negative photosensitive resin composition of the present embodiment has a maximum elongation of 15 to 200%, preferably 20 to 150%, and an average elongation of 10 as measured by a tensile test using a Tensilon tester. ⁇ 150%, preferably 15-120%.
  • the film obtained from the negative photosensitive resin composition of the present embodiment preferably has a tensile strength of 20 MPa or more, more preferably 30 to 300 MPa, as measured by a tensile test using a Tensilon tester.
  • the negative photosensitive resin composition of the present embodiment contains polyimide (A) (negative photosensitive polymer) having excellent hydrolysis resistance, it can be , Even after performing a HAST test (unsaturated pressurized steam test) for 96 hours, the rate of decrease in the elongation rate (maximum value, average value) represented by the following formula is 20% or less, preferably 15% or less, More preferably, it is 12% or less. [(Elongation before test - Elongation after test) / Elongation before test)] ⁇ 100
  • the negative photosensitive resin composition of this embodiment is excellent in low-temperature curability.
  • the cured product obtained by curing the negative photosensitive resin composition of the present embodiment at 170°C for 4 hours has a glass transition temperature (Tg) of 200°C or higher, preferably 210°C or higher, more preferably 220°C. °C or higher.
  • the cured product obtained by curing the negative photosensitive resin composition of the present embodiment at 170° C. for 4 hours has a storage elastic modulus E′ at 30° C. of 2.0 GPa or more, preferably 2.5 GPa or more, More preferably, it can be 3.0 GPa or more.
  • the storage elastic modulus E' at 200°C can be 0.5 GPa or more, preferably 0.7 GPa or more, and more preferably 0.8 GPa or more.
  • the viscosity of the negative photosensitive resin composition according to this embodiment can be appropriately set according to the desired thickness of the resin film.
  • the viscosity of the negative photosensitive resin composition can be adjusted by adding a solvent.
  • a cured product such as a film obtained from the negative photosensitive resin composition of the present embodiment has excellent chemical resistance.
  • the film is immersed in a solution of less than 99% by mass of dimethyl sulfoxide and less than 2% by mass of tetramethylammonium hydroxide at 40° C. for 10 minutes, then thoroughly washed with isopropyl alcohol and air-dried. to measure.
  • the film thickness change rate between the film thickness after treatment and the film thickness before treatment is calculated from the following formula and evaluated as the reduction rate of the film.
  • the film thickness change rate is preferably 40% or less, more preferably 30% or less.
  • the negative photosensitive resin composition of the present embodiment has suppressed curing shrinkage, and is spin-coated on the surface of a silicon wafer so that the film thickness after drying becomes 10 ⁇ m, pre-baked at 120° C. for 3 minutes, and placed under a high-pressure mercury lamp.
  • the film thickness after the pre-bake is the film thickness A
  • the film thickness after the heat treatment. is the film thickness B
  • the cure shrinkage calculated from the following formula is preferably 12% or less, more preferably 10% or less.
  • Cure shrinkage rate [%] ⁇ (film thickness A - film thickness B) / film thickness A ⁇ x 100
  • the negative photosensitive resin composition of the present embodiment has high heat resistance, and the resulting film has a weight loss temperature (Td5) measured by simultaneous thermogravimetric differential thermal measurement of 200° C. or higher, preferably 300° C. or higher. be able to.
  • Td5 weight loss temperature measured by simultaneous thermogravimetric differential thermal measurement of 200° C. or higher, preferably 300° C. or higher. be able to.
  • the film made of the negative photosensitive resin composition of the present embodiment has suppressed shrinkage on curing, and can have a linear thermal expansion coefficient (CTE) of 200 ppm/°C or less, preferably 100 ppm/°C or less.
  • CTE linear thermal expansion coefficient
  • the film made of the negative photosensitive resin composition of the present embodiment has excellent mechanical strength, and has an elastic modulus at 25° C. of 1.0 to 5.0 GPa, preferably 1.5 to 3.0 GPa. can do.
  • the negative photosensitive resin composition of the present embodiment is used for forming resin films for semiconductor devices such as permanent films and resists.
  • resin films for semiconductor devices such as permanent films and resists.
  • Use of a permanent film from the viewpoint of improving the adhesion between the cured film of the negative photosensitive resin composition and the metal, and also from the viewpoint of improving the chemical resistance of the negative photosensitive resin composition after heat treatment. It is preferably used for
  • the resin film includes a cured film of a negative photosensitive resin composition. That is, the resin film according to this embodiment is obtained by curing a negative photosensitive resin composition.
  • the permanent film is composed of a resin film obtained by pre-baking, exposing, and developing a negative photosensitive resin composition, patterning it into a desired shape, and then curing it by heat treatment. Permanent films can be used as protective films, interlayer films, dam materials, and the like for semiconductor devices.
  • the above-mentioned resist can be obtained, for example, by applying a negative photosensitive resin composition to an object to be masked by the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, and negative photosensitive resin composition. It is composed of a resin film obtained by removing the solvent from a flexible resin composition.
  • the semiconductor device 100 according to this embodiment can be a semiconductor device including the resin film.
  • one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 in the semiconductor device 100 can be a resin film containing the cured product of the present embodiment.
  • the resin film is preferably the permanent film described above.
  • the semiconductor device 100 is, for example, a semiconductor chip.
  • a semiconductor package is obtained by mounting the semiconductor device 100 on the wiring substrate via the bumps 52 .
  • the semiconductor device 100 includes a semiconductor substrate provided with semiconductor elements such as transistors, and a multilayer wiring layer (not shown) provided on the semiconductor substrate.
  • An interlayer insulating film 30 and a top layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layers.
  • the uppermost layer wiring 34 is made of aluminum Al, for example.
  • a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34 . A portion of the passivation film 32 is provided with an opening through which the uppermost layer wiring 34 is exposed.
  • a rewiring layer 40 is provided on the passivation film 32 .
  • the rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, have An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42 .
  • the rewiring 46 is formed on the insulating layer 42 and in openings provided in the insulating layer 42 and connected to the uppermost layer wiring 34 .
  • the insulating layer 44 is provided with an opening connected to the rewiring 46 .
  • a bump 52 is formed in the opening provided in the insulating layer 44 via a UBM (Under Bump Metallurgy) layer 50, for example.
  • Semiconductor device 100 is connected to a wiring substrate or the like via bumps 52, for example.
  • MED-J 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane
  • BAPA 2,2-bis(3-amino-4-hydroxyphenyl)propane
  • BAFA 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane
  • TFMB 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl
  • HFBAPP 4,4′-(hexafluoroisopropylidene)bis[(4-aminophenoxy)benzene]
  • TMHQ p-phenylene bis(trimellitate anhydride)
  • Example 1 First, 29.01 g (102.7 mmol) of MED-J, 26.53 g (102.7 mmol) of BAPA, and 151.29 g (244 mmol) of TMPBP-TME were added to an appropriately sized reaction vessel equipped with a stirrer and condenser. .6 mmol) was added. An additional 620.49 g of GBL was then added to the reaction vessel. After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was further carried out at 180° C. for 3 hours to polymerize the bisaminophenol and the acid anhydride to prepare a polymerization solution.
  • GPC measurement of the polymer revealed a weight average molecular weight Mw of 20,000 and a polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of 1.98.
  • AOI 2-isocyanatoethyl acrylate
  • GBL ⁇ -butyl lactone
  • the resulting reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to methanol to precipitate a white solid.
  • the resulting white solid was collected and vacuum dried at a temperature of 40° C. to obtain 212.35 g of polymer.
  • GPC measurement of the polymer revealed a weight average molecular weight Mw of 26,100 and a polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of 2.30. Further, 1 H-NMR measurement confirmed a peak in the aromatic region (6.8 ppm to 8.8 ppm) with an area ratio corresponding to the number of protons.
  • the ratio of the area of the aromatic region (6.8 ppm to 8.8 ppm) and the alkene region (5.8 ppm to 6.3 ppm) was 83%.
  • a part of the polymer into which the cross-linking group was introduced contained repeating units represented by the following formula.
  • Example 2 First, 9.67 g (34.2 mmol) of MED-J, 2.95 g (11.4 mmol) of BAPA, and 33.62 g (54 mmol) of TMPBP-TME were added to an appropriately sized reaction vessel equipped with a stirrer and condenser. .3 mmol) was added. An additional 138.71 g of GBL was then added to the reaction vessel. After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was further carried out at 180° C. for 3 hours to polymerize the bisaminophenol and the acid anhydride to prepare a polymerization solution.
  • GPC measurement of the polymer revealed a weight average molecular weight Mw of 21,500 and a polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of 2.02.
  • AOI 2-isocyanatoethyl acrylate
  • GBL ⁇ -butyl lactone
  • the resulting reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to methanol to precipitate a white solid.
  • the resulting white solid was collected and vacuum dried at a temperature of 40° C. to obtain 43.73 g of polymer.
  • GPC measurement of the polymer revealed a weight average molecular weight Mw of 22,800 and a polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of 2.15. Further, 1 H-NMR measurement confirmed a peak in the aromatic region (6.8 ppm to 8.8 ppm) with an area ratio corresponding to the number of protons.
  • the introduction rate of the cross-linking group was 100%.
  • a part of the polymer into which the cross-linking group was introduced contained the repeating unit represented by the above formula.
  • Example 3 First, 12.89 g (45.7 mmol) of MED-J and 33.62 g (54.3 mmol) of TMPBP-TME were placed in an appropriately sized reaction vessel equipped with a stirrer and condenser. An additional 125.58 g of GBL was then added to the reaction vessel. After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was further carried out at 180° C. for 3 hours to polymerize the bisaminophenol and the acid anhydride to prepare a polymerization solution.
  • the resulting reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to methanol to precipitate a white solid.
  • the obtained white solid was collected and vacuum-dried at a temperature of 40° C. to obtain 41.73 g of polymer.
  • GPC measurement of the polymer revealed a weight average molecular weight Mw of 23,100 and a polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of 2.09. Further, when 1 H-NMR measurement was performed, a peak was confirmed in the aromatic region (6.9 ppm to 8.9 ppm) with an area ratio corresponding to the number of protons.
  • the obtained polymer partially contained a repeating unit represented by the following formula, and had a cross-linking group introduced at its end.
  • Examples 4 to 7 and Comparative Examples 1 to 4 were synthesized in the same manner as in Example 1 except for the conditions described in Table 1. In Comparative Examples 1 and 2, gelation occurred during the polymerization reaction, making it difficult to continue the reaction.
  • the tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. Ten test pieces were measured, the tensile elongation was calculated from the breaking distance and the initial distance, and the maximum value of the elongation was obtained. Table 1 shows the results.
  • the negative photosensitive polymers of the present invention obtained in Examples are excellent in solubility in organic solvents and elongation. It was inferred that the decrease in physical strength was suppressed.
  • Photoradical generator 2-(dimethylamino)-1-(4-(4-morpholino)phenyl)-2-(phenylmethyl)-1-butanone (Irgacure Oxe01, manufactured by BASF Japan)
  • Thermal radical generator Dicumyl peroxide (Perkadox BC, peroxide, manufactured by Kayaku Akzo Co., Ltd.)
  • Adhesion aid 1 3-methacryloxypropyltrimethoxysilane (KBM-503P, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Example 8 (Preparation of negative photosensitive resin composition) A photosensitive resin composition was prepared by mixing the polymer of Example 5 (100 parts by mass of polymer) and the components shown in Table 2 pre-dissolved so as to form a 22 wt % GBL solution. The obtained negative photosensitive resin composition was spin-coated on the surface of a silicon wafer so that the film thickness after drying was 10 ⁇ m, prebaked at 120° C. for 3 minutes, and then exposed to light at 600 mJ/cm 2 with a high-pressure mercury lamp. After that, heat treatment was performed at 170° C. for 120 minutes in a nitrogen atmosphere to prepare a film. The obtained film was measured for glass transition temperature (Tg) and elongation by the following methods to evaluate the patterning properties. Table 2 shows the results.
  • Tg glass transition temperature
  • Glass transition temperature (Tg) A test piece of 8 mm ⁇ 40 mm was cut out from the film obtained in Example 8, and the test piece was subjected to dynamic viscoelasticity measurement (DMA device, manufactured by TA Instruments, Q800) at a heating rate of 5. A dynamic viscoelasticity measurement was performed at °C/min and a frequency of 1 Hz, and the temperature at which the loss tangent tan ⁇ showed the maximum value was measured as the glass transition temperature.
  • Example 8 A test piece (6.5 mm ⁇ 60 mm ⁇ 10 ⁇ m thick) cut out from the film obtained in Example 8 was subjected to a tensile test (stretching speed: 5 mm/min) in an atmosphere of 23° C.
  • the tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. The strength was obtained by measuring five test pieces and averaging the stress at the breaking point. The tensile elongation was calculated from the breaking distance and the initial distance, and the average and maximum values of the elongation were obtained.
  • test piece cut out from the film obtained in Example 8 was subjected to HAST (unsaturated pressurized steam test) for 96 hours under conditions of a temperature of 130 ° C. and a relative humidity of 85% RH. Similarly, the average value and maximum value of the elongation rate were obtained.
  • HAST unsaturated pressurized steam test
  • Example 8 [Evaluation of patterning characteristics] It was confirmed as follows that the photosensitive resin composition of Example 8 could be sufficiently patterned by exposure and development.
  • the photosensitive resin composition of Example 8 was applied onto an 8-inch silicon wafer using a spin coater. After the application, it was pre-baked on a hot plate at 110° C. for 3 minutes in the atmosphere to obtain a coating film having a thickness of about 5.0 ⁇ m.
  • This coating film was irradiated with an i-line through a mask having a via pattern with a width of 20 ⁇ m.
  • An i-line stepper (NSR-4425i manufactured by Nikon Corporation) was used for irradiation.
  • the film obtained from the negative photosensitive resin composition containing the negative photosensitive polymer of the present invention has excellent elongation and excellent hydrolysis resistance. Since it contains a polymer, it has become clear that the mechanical strength is excellent even after the HAST test. Moreover, it was confirmed that the patterning property was also favorable and it was suitably used as a negative photosensitive resin composition.
  • interlayer insulating film 32 passivation film 34 top layer wiring 40 rewiring layer 42 insulating layer 44 insulating layer 46 rewiring 50 UBM layer 52 bump

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WO2024190733A1 (ja) * 2023-03-15 2024-09-19 富士フイルム株式会社 感光性樹脂組成物、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
WO2025142647A1 (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
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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