CN116848467A

CN116848467A - Photosensitive resin composition, cured film, and semiconductor device

Info

Publication number: CN116848467A
Application number: CN202280015064.1A
Authority: CN
Inventors: 乙黑昭彦; 今井启太; 上田祐辉; 久保山俊治
Original assignee: Sumitomo Bakelite Co Ltd
Current assignee: Sumitomo Bakelite Co Ltd
Priority date: 2021-02-15
Filing date: 2022-02-10
Publication date: 2023-10-03
Also published as: TW202311368A; JPWO2022270527A1; WO2022270527A1

Abstract

The photosensitive resin composition of the present invention comprises: a polymer A having a structural unit represented by the following general formula (a); and a polymer B containing a polyimide having a group B represented by the following general formula (B).

Description

Photosensitive resin composition, cured film, and semiconductor device

Technical Field

The invention relates to a photosensitive resin composition, a cured film and a semiconductor device.

Background

Polyimide resins have high mechanical strength, heat resistance, insulation properties, and solvent resistance, and are therefore widely used as films for electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display elements and semiconductors.

Patent document 1 discloses a photosensitive composition containing a polyimide having a predetermined maleimide group at the terminal.

Patent document 2 discloses an optical waveguide having a core containing a 1 st compound having a functional group capable of dimerization by light irradiation, and an example of the 1 st compound is a cyclic olefin resin having a predetermined maleimide group at a terminal as the functional group capable of dimerization.

Prior art literature

Patent literature

Patent document 1: international publication No. 2020/181021.

Patent document 2: japanese patent application laid-open No. 2019-028115.

Disclosure of Invention

Technical problem to be solved by the invention

However, in the conventional techniques described in patent documents 1 and 2, there is room for improvement in dielectric loss tangent and mechanical strength of cured films and the like obtained from photosensitive resin compositions.

Means for solving the technical problems

The present inventors have found that the above problems can be solved by using a polyimide having a specific structure in combination with a cyclic olefin resin, and have completed the present invention.

That is, the present invention can be shown below.

According to the present invention, there can be provided a photosensitive resin composition, wherein the photosensitive resin composition comprises: a polymer A having a structural unit represented by the following general formula (a); and a polymer B containing a polyimide having a group B represented by the following general formula (B).

(in the general formula (a), R ¹ R is as follows ² Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q ¹ Represents a single bond or a 2-valent organic group, G ¹ 、G ² G ³ Each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and m is 0, 1 or 2. )

(in the general formula (b), R ³ R is as follows ⁴ Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q ² Represents an organic group of valence 2, G ⁴ Each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. * Representing a bond. )

According to the present invention, a cured film can be provided, wherein the cured film is composed of a cured product of the photosensitive resin composition.

According to the present invention, a semiconductor device including a resin film including a cured product of the photosensitive resin composition can be provided.

ADVANTAGEOUS EFFECTS OF INVENTION

The photosensitive resin composition of the present invention can obtain a cured product such as a film having excellent low dielectric loss tangent and excellent mechanical properties.

Drawings

Fig. 1 is a schematic cross-sectional view of a semiconductor device according to the present embodiment.

Detailed Description

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and description thereof is omitted as appropriate. For example, "1 to 10" means "1 or more" to "10 or less" unless otherwise specified.

The photosensitive resin composition of the present embodiment includes a polymer a and a polymer B.

Thus, the photosensitive resin composition of the present embodiment can obtain a cured product such as a film having excellent low dielectric loss tangent and excellent mechanical properties.

The components will be described below.

[ Polymer A ]

The polymer A has a structural unit (a) represented by the following general formula (a).

In the general formula (a), R ¹ R is as follows ² Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ¹ R is as follows ² At least one of them is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms is preferably an alkyl group having 1 or 2 carbon atoms, more preferably an alkyl group having 1 carbon atom, from the viewpoint of the effect of the present invention.

Q ¹ Represents a single bond or a 2-valent organic group.

The organic group having a valence of 2 may be any known organic group within a range that exhibits the effect of the present invention, and examples thereof include an alkylene group having 1 to 8 carbon atoms or a (poly) alkylene glycol chain. The alkylene group having 1 to 8 carbon atoms is preferably an alkylene group having 2 to 6 carbon atoms.

Examples of the alkylene group having 1 to 8 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene groups.

The alkylene oxide constituting the (poly) alkylene glycol chain is not particularly limited, but is preferably an alkylene oxide having 1 to 18 carbon atoms, more preferably an alkylene oxide having 2 to 8 carbon atoms, and examples thereof include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butylene oxide, 2-butylene oxide, trimethylethylene oxide, tetrahydrofuran (tetramethylene oxide), tetramethylethylene oxide, butadiene monoxide (butadiene monoxide), and octane oxide.

G ¹ 、G ² G ³ Each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.

Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an aryl group, an aralkyl group, an alkylaryl group (alkaryl) and a cycloalkyl group.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl.

Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. Examples of the alkynyl group include an ethynyl group.

Examples of the alkylene group include methylene (methylene) and ethylene (ethylene).

Examples of the aryl group include phenyl, naphthyl and anthracenyl. Examples of the aralkyl group include benzyl and phenethyl.

Examples of the alkylaryl group include tolyl and xylyl. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl.

The hydrocarbon group having 1 to 30 carbon atoms may contain at least one atom selected from O, N, S, P and Si in its structure.

In the present embodiment, the hydrocarbon group having 1 to 30 carbon atoms is preferably a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the substituent of the substituted hydrocarbon group having 1 to 30 carbon atoms include a hydroxyl group, an amino group, a cyano group, an ester group, an ether group, an amide group, and a sulfonamide group, and may be substituted with at least one group.

In the present embodiment, G is preferable ¹ 、G ² G ³ Any 1 of them is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms and the rest are hydrogen atoms, and more preferably all of them are hydrogen atoms.

m is 0, 1 or 2, preferably 0 or 1, more preferably 0.

The polymer a of the present embodiment has a structure represented by the general formula (a), and therefore has excellent low dielectric loss tangent. Further, since the polymer a has a predetermined maleimide group in a side chain and can be photodimerized without generating a radical reaction, the polyimide contained in the polymers a, a and a polymer B described later can be photopolymerized, and the mechanical strength is further excellent.

The polymer a of the present embodiment can be synthesized as follows.

First, a compound (a ') represented by the following general formula (a') is subjected to addition polymerization, and if necessary, with another norbornene compound to obtain a polymer. For example, addition polymerization is performed by coordination polymerization.

In the general formula (a'), R ¹ 、R ² 、Q ¹ 、G ¹ 、G ² 、G ³ And m has the same meaning as in formula (a).

Examples of the other norbornene compound include norbornene compounds having an alkyl group such as 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, and 5-cyclopentylnorbornene; norbornene having an alkenyl group such as 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornene, 5-cyclohexenyl norbornene, and 5-cyclopentenyl norbornene; and norbornene having an aromatic ring such as 5-phenylnorbornene, 5-phenylmethylnorbornene, 5-phenylethylnorbornene and 5-phenylpropyl norbornene.

In the present embodiment, after the above-mentioned compound and the organometallic catalyst are dissolved in the solvent, the solution polymerization can be performed by heating for a predetermined time. In this case, the heating temperature can be set to, for example, 30 to 200 ℃, preferably 40 to 150 ℃, and more preferably 50 to 120 ℃. In the present embodiment, the heating temperature is set to a high temperature as compared with the conventional one, whereby the yield of the polymer (a) can be improved.

The heating time can be, for example, 0.5 to 72 hours. Further, it is more preferable to carry out the solution polymerization after removing dissolved oxygen in the solvent by nitrogen bubbling.

Further, a molecular weight regulator or a chain transfer agent can be used as needed. Examples of the chain transfer agent include alkylsilane compounds such as trimethylsilane, triethylsilane, and tributylsilane. These chain transfer agents may be used singly or in combination of two or more.

As the solvent used in the polymerization reaction, for example, one or more of Methyl Ethyl Ketone (MEK), propylene glycol monomethyl ether, diethyl ether, tetrahydrofuran (THF), toluene, ethyl acetate, butyl acetate and other esters, methanol, ethanol, isopropanol and other alcohols can be used.

As the organometallic catalyst, it is not particularly required to select, for example, a ligand such as phosphine or diimine, which is coordinated to a palladium complex or a nickel complex, and a counter anion or the like can be used as long as addition polymerization is performed. One or two or more of them may be used.

Examples of the palladium complex include allylpalladium complexes such as (acetate-. Kappa.0) (acetonitrile) bis [ tris (1-methylethyl) phosphine ] palladium (I) tetrakis (2, 3,4,5, 6-pentafluorophenyl) borate, pi-allyl palladium chloride dimer; palladium organic carboxylates such as palladium acetate, propionate, maleate, and naphthoate; palladium organic carboxylic acid complexes such as triphenylphosphine complex of palladium acetate, tris (m-tolyl) phosphine complex of palladium acetate, and tricyclohexylphosphine complex of palladium acetate; palladium organic sulfonates such as dibutylphosphite and p-toluenesulfonate of palladium; beta-diketone compounds of palladium such as bis (acetylacetonate) palladium, bis (hexafluoroacetylacetonate) palladium, bis (ethylacetoacetate) palladium, and bis (phenylacetoacetate) palladium; palladium halide complexes such as bis (triphenylphosphine) palladium, bis [ tris (m-tolylphosphine) ] palladium, dibromobis [ tris (m-tolylphosphine) ] palladium, and acetonyl triphenylphosphine complex (acetonyltriphenylphosphonium complex).

Examples of the phosphine ligand include triphenylphosphine, dicyclohexylphenylphosphine, cyclohexyldiphenylphosphine, and tricyclohexylphosphine.

Examples of the counter anion include triphenylcarbenium tetrakis (pentafluorophenyl) borate (triphenylcarbenium tetrakis), triphenylcarbenium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, triphenylcarbenium tetrakis (2, 4, 6-trifluorophenyl) borate, triphenylcarbenium tetraphenyl borate, tributylammonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N-diphenylanilinium tetrakis (pentafluorophenyl) borate, and lithium tetrakis (pentafluorophenyl) borate.

The amount of the organometallic catalyst can be 300ppm to 5000ppm, preferably 1000ppm to 3500ppm, and more preferably 1500ppm to 2500ppm relative to the norbornene-based monomer. Thereby, the yield of the polymer a can be improved.

The reaction solution containing the obtained polymer a is added to an alcohol such as hexane or methanol, for example, to precipitate the polymer a. Then, polymer a is collected by filtration, washed with, for example, an alcohol such as hexane or methanol, and then dried.

In this embodiment, for example, the polymer a can be synthesized in this manner.

According to the production method of the present embodiment, the polymer a can be obtained with a high yield of 70% or more.

The conversion based on the dialkyl maleic anhydride is preferably 30% or more. More preferably 40% or more, and still more preferably 50% or more. If the amount is within this range, the polyimide component eluted during development can be reduced.

The polymer a of the present embodiment may contain other structural units than the structural unit (a) within the range where the effect of the present invention is exhibited, and examples of other structural units include structural units derived from the above-mentioned other norbornene-based compounds.

In the case where the polymer B described later does not contain a halogen atom in the structure, specifically, R of the general formula (B1) ⁵ R is as follows ⁶ In the case where the monomer is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, and X is a single bond, an alkylene group having 1 to 4 carbon atoms, a 2-valent ether group derived from bisphenol a, a 2-valent ether group derived from bisphenol F, or a 2-valent ether group derived from bisphenol S, the weight average molecular weight of the polymer a can be 3000 to 30000, preferably 4000 to 20000, and more preferably 4500 to 15000 from the viewpoint of compatibility of the polymer a with the polymer B.

On the other hand, in the case where the polymer B described later contains a halogen atom in the structure, specifically, R of the general formula (B1) ⁵ 、R ⁶ When any of X is a group containing a halogen atom, the polymer B is excellent in compatibility, and therefore, from the viewpoint of compatibility between the polymer a and the polymer B, the weight average molecular weight of the polymer a can be 3000 to 300000, preferably 4000 to 250000, and more preferably 4500 to 200000.

[ Polymer B ]

The polymer B contains a polyimide having a group B represented by the following general formula (B).

In the general formula (b), R ³ R is as follows ⁴ Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ³ R is as follows ⁴ At least one of them is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms is preferably an alkyl group having 1 or 2 carbon atoms, more preferably an alkyl group having 1 carbon atom, from the viewpoint of the effect of the present invention. * Representing a bond.

G ⁴ Each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. Substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms is defined as G ¹ 、G ² G ³ The same applies.

In the present embodiment, a plurality of G's are preferably present ⁴ Any 1 of them is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms and the rest are hydrogen atoms, and more preferably all of them are hydrogen atoms.

Q ² An organic group having a valence of 2.

The organic group having a valence of 2 may be any known organic group within a range that exhibits the effect of the present invention, and examples thereof include organic groups represented by the following general formula (b 1).

In the general formula (b 1), R ⁵ R is as follows ⁶ Each independently represents a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group, preferably an alkyl group having 1 to 3 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms or a haloalkyl group having 1 to 2 carbon atoms.

The haloalkyl group having 1 to 4 carbon atoms may be either a straight chain or a branched chain, examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 1, 2-trifluoroethyl, 1, 2-tetrafluoroethyl, 2-trifluoroethyl pentafluoroethyl, 3-fluoropropyl, heptafluoropropyl, 1,2, 3-hexafluoropropyl, 1,2,2,3,3,3-hexafluoropropyl, 4-fluorobutyl, nonafluorobutyl; chloromethyl, dichloromethyl, trichloromethyl, 2-chloroethyl, 1, 2-trichloroethyl, 1, 2-tetrachloroethyl, 2-trichloroethyl, pentachloroethyl, 3-chloropropyl, heptachloropropyl, hexachloropropyl, 1,2,2,3,3,3-hexachloropropyl, 4-chlorobutyl, nonachlorobutyl, and the like.

Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl and isopropyl.

Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, n-propoxy and isopropoxy.

X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a haloalkylene group having 1 to 4 carbon atoms, a 2-valent ether group derived from bisphenol A, a 2-valent ether group derived from bisphenol F, a 2-valent ether group derived from bisphenol S, or a 2-valent ether group derived from hexafluorobisphenol A, and is preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 2 carbon atoms.

Examples of the alkylene group having 1 to 4 carbon atoms include methylene, ethylene, trimethylene, propylene, and butylene.

Examples of the haloalkylene group having 1 to 4 carbon atoms include fluoromethylene group, difluoromethylene group, fluoroethylene group, 1, 2-difluoroethylene group, trifluoroethylene group, perfluoroethylene group, perfluoropropylene group, perfluorobutylene group, chloromethylene group, chloroethylene group, chloropropylene group, bromomethylene group, bromoethylene group, bromopropylene group, iodomethylene group, iodoethylene group, and iodopropylene group.

* Representing a bond.

From the viewpoint of the effect of the present invention, the polymer B preferably contains a polyimide having the group B represented by the general formula (B) at least one terminal (preferably at both terminals).

The polymer B of the present embodiment has the group B represented by the general formula (B), and thus is excellent in mechanical strength. Further, since polyimide has a predetermined maleimide group at the terminal and can be photodimerized without generating a radical reaction, the polyimide contained in the polymer B can be photopolymerized with each other and the polymer a and the polyimide, and the mechanical strength is further excellent.

The polymer (B) may contain a polyimide having a group c represented by the following general formula (c) at least one terminal.

In the general formula (c), R ⁵ 、R ⁶ X has the same meaning as that of the general formula (b 1), G ⁴ The meaning of (a) is the same as that of the general formula (b).

When the polyimide contained in the polymer (B) contains a polyimide having the above group c, the ratio (B/b+c) of the number of moles of the group B to the total number of moles of the group B and the group c can be set to 0.50 or more, preferably 0.55 or more, and more preferably 0.60 or more. If the amount is within this range, the polyimide component eluted during development can be reduced.

From the viewpoint of the effect of the present invention, the polymer B preferably contains a polyimide represented by the following general formula (d).

In the general formula (d), R ³ 、R ⁴ 、Q ² Is the same as the general formula (b), a plurality of R's are present ³ R are present in plural with each other ⁴ Q existing among each other in plurality ² G are present between each other in plural ⁴ May be the same as or different from each other.

Y is selected from the group consisting of a group represented by the following general formula (d 1), a group represented by the following general formula (d 2) and a group represented by the following general formula (d 3), and a plurality of groups of C1-C5 haloalkenes, wherein the plurality of groups of Y may be the same or different.

In the general formula (d 1), R ⁷ R is as follows ⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's present ⁷ R are present in plural with each other ⁸ May be the same or different from each other. * Representing a bond.

From the viewpoint of the effect of the present invention, R ⁷ R is as follows ⁸ Preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferablyIs R ⁷ At least 1 of (a) and R ⁸ At least 1 of them is an alkyl group having 1 to 3 carbon atoms, more preferably 3R' s ⁷ Is alkyl with 1-3 carbon atoms, 1R ⁷ Is a hydrogen atom and 3R ⁸ Is alkyl with 1-3 carbon atoms, 1R ⁸ Is a hydrogen atom, particularly preferably 3R ⁷ Is methyl, 1R ⁷ Is a hydrogen atom and 3R ⁸ Is methyl, 1R ⁸ Is a hydrogen atom.

* Representing a bond.

In the general formula (d 2), R ⁹ R is as follows ¹⁰ Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's present ⁹ R are present in plural with each other ¹⁰ May be the same or different from each other.

From the viewpoint of the effect of the present invention, R ⁹ R is as follows ¹⁰ Preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

R ¹¹ Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's present ¹¹ May be the same or different from each other.

From the viewpoint of the effect of the present invention, R ¹¹ Preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

* Representing a bond.

In the general formula (d 3), Z represents an alkylene group having 1 to 5 carbon atoms, and an aromatic group having 2 valences.

Examples of the aromatic group having a valence of 2 include phenylene group, biphenyl group having a valence of 2, and naphthylene group.

* Representing a bond.

The polyimide of the present embodiment contains a compound (polymer) having the group represented by the general formula (d 1), the general formula (d 2), and the general formula (d 3) in the main chain, and the main chain of the polymer is resistant to deformation, and further, the sliding between the polymer chains is improved, so that a cured product such as a film having significantly improved elongation, excellent mechanical strength, suppressed cure shrinkage, and excellent dimensional stability can be obtained.

In the general formula (d), Q ³ The repeating unit represented by the following general formula (d 4) is represented.

In the general formula (d 4), R ⁵ 、R ⁶ And X has the same meaning as the general formula (b 1), Y has the same meaning as the general formula (d), G ⁴ The meaning of (a) is the same as that of the general formula (b).

n represents an integer of 20 to 200, preferably an integer of 30 to 180.

* Representing a bond.

The polyimide contained in the polymer B of the present embodiment has a weight average molecular weight of 10000 to 300000, preferably 15000 to 200000.

Further, since the polyimide of the present embodiment is excellent in solubility in a solvent, a varnish is not required to be prepared in a precursor state, and thus a varnish containing the polymer B can be prepared, and a cured product such as a film excellent in dimensional stability can be obtained from the varnish.

Method for producing polyimide

The polyimide according to the present embodiment can be synthesized as follows.

A diamine represented by the following general formula (i), an acid anhydride represented by the following general formula (ii) and a maleic anhydride derivative represented by the following general formula (iii) are reacted.

In the general formula (i), X, R ⁵ 、R ⁶ The meaning of (b) is the same as that of the general formula (b 1).

The diamine (i) may be one of compounds represented by the general formula (i).

In the general formula (ii), G ⁴ The meaning of Y is the same as that of the general formula (d).

The acid anhydride (ii) may be one of compounds represented by the general formula (ii) above.

In the general formula (iii), R ³ 、R ⁴ The meaning of (a) is the same as that of the general formula (b).

The maleic anhydride derivative (iii) may be one or more compounds represented by the general formula (iii).

The equivalent ratio of diamine (i) to anhydride (ii) in this reaction is an important factor in determining the molecular weight of the polyimide obtained. In general, it is known that a polymer has a correlation between molecular weight and mechanical properties, and the larger the molecular weight is, the more excellent the mechanical properties are. Therefore, in order to obtain polyimide having practically excellent strength, a certain degree of high molecular weight is required. In the present invention, the equivalent ratio of the diamine (i) to the acid anhydride (ii) to be used is not particularly limited, but the equivalent ratio of the acid anhydride (ii) to the diamine (i) is preferably in the range of 0.80 to 1.06. When less than 0.80, the molecular weight is low and becomes weak, so that the mechanical strength becomes weak. If the amount exceeds 1.06, the unreacted carboxylic acid may be decarbonized during heating to generate gas, which may cause foaming.

The amount of the maleic anhydride derivative (iii) can be preferably 30 to 100mol%, more preferably 40 to 100mol%, and still more preferably 50 to 100mol% of the polynorbornene.

Thus, photosensitivity due to photodimerization can be imparted to polyimide, and a cured product such as a film having a more excellent low dielectric loss tangent and more excellent mechanical properties can be obtained.

The reaction can be carried out in an organic solvent by a known method.

Examples of the organic solvent include aprotic polar solvents such as γ -butyrolactone (GBL), N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1, 4-dioxane, and one or two or more of them may be used in combination. In this case, a nonpolar solvent having compatibility with the aprotic polar solvent may be used in combination. Examples of the nonpolar solvent include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene, and solvent naphtha. The proportion of the nonpolar solvent in the mixed solvent can be arbitrarily set in accordance with the resin characteristics such as the stirring device capacity and the solution viscosity, if the solubility of the solvent is reduced and the polyamide acid resin obtained by the reaction does not precipitate.

The reaction temperature is about 0 to 100 (preferably 20 to 80) for 30 minutes to 2 hours, and then about 100 to 250 (preferably 120 to 200) for 1 to 5 hours.

The maleic anhydride derivative (iii) may be present in the imidization reaction of the diamine (i) and the acid anhydride (ii), but the polyimide terminal can be blocked by adding the maleic anhydride derivative (iii) dissolved in the organic solvent to the reaction of the diamine (i) and the acid anhydride (ii) or after the completion of the reaction.

In the case of adding the maleic anhydride derivative (iii) separately, it is preferable that the reaction is carried out for about 1 to 5 hours at 100℃or more and 250℃or less (preferably 120℃or more and 200℃or less) after the addition.

Through the above steps, a reaction solution containing the polyimide (end-blocked polyimide) of the present embodiment can be obtained, and further, diluted with an organic solvent or the like as necessary, and used as a polymer solution (coating varnish). The organic solvent used in the reaction step may be the same organic solvent as in the reaction step or a different organic solvent.

The reaction solution may be put into a poor solvent to reprecipitate polyimide and remove unreacted monomers, and the dried and solidified material may be redissolved in an organic solvent to be used as a finished product. In particular, in applications where impurities or foreign matter are problematic, it is preferable to prepare a filtration-purified varnish by redissolving in an organic solvent.

The polyimide concentration in the polymer solution (100 wt%) is not particularly limited, and is about 10 to 30 wt%.

In this embodiment, from the viewpoint of the effect of the present invention, the ratio of the polymer a to the polymer B (a: B) can be set to 5:95 to 95:5, preferably 10:90 to 90:10, more preferably 20:80 to 80:20, still more preferably 30:70 to 70:30, and particularly preferably 40:60 to 60:40.

From the viewpoints of tensile strength and elongation, the molecular weight of the polymer B can be 30000 to 200000, preferably 40000 to 180000, and more preferably 50000 to 150000.

[ photosensitizer ]

The photosensitive resin composition of the present embodiment may further include a photosensitizer.

Examples of the photosensitizer include a benzophenone-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, a benzyl (benzyl) -based photopolymerization initiator, and a Michler's ketone-based photopolymerization initiator. Among these, a benzophenone-based photopolymerization initiator or a thioxanthone-based photopolymerization initiator is preferable.

Examples of the benzophenone-based photopolymerization initiator include benzophenone, 4-chlorobenzophenone, 4' -dimethoxybenzophenone, 4' -diaminobenzophenone, 4-phenylbenzophenone, m-xylylene ketone (isophthalic phenone), and 4-benzoyl-4 ' -methyl-diphenyl sulfide. These benzophenones or derivatives thereof can increase the curing rate by using tertiary amines as hydrogen donors.

Examples of commercial products of the benzophenone-based photopolymerization initiator include SPEEDCUREMBP (4-methylbenzophenone), SPEEDCUREMBB (methyl 2-benzoylbenzoate), sppedcurebs (4-benzoyl-4 '-methyldiphenyl sulfide), sppedcurebbz (4-phenylbenzophenone), sppedcuremk (4, 4' -bis (diethylamino) benzophenone) (the above is a trade name, manufactured by DKSH Japan corporation (DKSH Japan k.k.), and the like.

Examples of the thioxanthone photopolymerization initiator include thioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone. The diethylthioxanthone is preferably 2, 4-diethylthioxanthone, the isopropylthioxanthone is preferably 2-isopropylthioxanthone, and the chlorothioxanthone is preferably 2-chlorothioxanthone. Among them, a thioxanthone-based photopolymerization initiator containing diethylthioxanthone is more preferable.

Examples of commercial products of the thioxanthone photopolymerization initiator include speedcureDETX (2, 4-diethylthioxanthone), speedcureITX (2-isopropylthioxanthone), speedcureCTX (2-chlorothioxanthone), speedcureCTX (1-chloro-4-propylthioxanthone) (the above are trade names, manufactured by DKSH Japanese Co., ltd. (DKSH Japan K.K.), and kayaccureDETX (2, 4-diethylthioxanthone) (trade names, manufactured by Nippon Kayaku Co., ltd.).

The amount of the photosensitizer to be added is not particularly limited, but is preferably about 0.05 to 10% by mass, more preferably about 0.1 to 7.5% by mass, and still more preferably about 0.2 to 5% by mass of the total solid content of the photosensitive resin composition. By setting the addition amount of the photosensitive agent within the above range, the patterning property of the photosensitive resin layer containing the photosensitive resin composition can be improved, and the long-term storage property of the photosensitive resin composition can be improved.

(sealing auxiliary agent)

The photosensitive resin composition of the present embodiment may further include an adhesion promoter.

This can improve adhesion between the resin film or pattern formed from the photosensitive resin composition and the substrate.

The sealing auxiliary agent that can be used is not particularly limited. For example, silane coupling agents such as aminosilanes, epoxysilanes (epoxy silane), acrylic silanes (acrylic silane), mercapto silanes, vinyl silanes, ureido silanes, anhydride functional silanes, sulfide silanes, and the like can be used. The silane coupling agent may be used alone or in combination of two or more. Of these, epoxy silanes (i.e., compounds containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in 1 molecule) or anhydride functional silanes (i.e., compounds containing both an anhydride group and a group that generates a silanol group by hydrolysis in 1 molecule) are preferred. The adhesion between the substrate and the resin film or pattern formed of the photosensitive resin composition can be further improved by bonding the group on the side opposite to the silane of the silane coupling agent to the polymer a or polymer B, or by improving the affinity with the polymer.

Examples of aminosilanes include bis (2-hydroxyethyl) -3-aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, γ -aminopropyl methyldiethoxysilane, γ -aminopropyl methyldimethoxysilane, N- β (aminoethyl) γ -aminopropyl trimethoxysilane, N- β (aminoethyl) γ -aminopropyl triethoxysilane, N- β (aminoethyl) γ -aminopropyl methyldimethoxysilane, N- β (aminoethyl) γ -aminopropyl methyldiethoxysilane, and N-phenyl- γ -amino-propyl trimethoxysilane.

Examples of epoxysilanes include gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and gamma-glycidoxypropyl trimethoxysilane.

Examples of the acryl silane include γ - (methacryloxypropyl) trimethoxysilane, γ - (methacryloxypropyl) methyldimethoxysilane, and γ - (methacryloxypropyl) methyldiethoxysilane.

Examples of mercaptosilanes include 3-mercaptopropyl trimethoxysilane.

Examples of the vinylsilane include vinyltris (. Beta. -methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane.

Examples of the ureido silane include 3-ureido propyl triethoxy silane.

Examples of the acid anhydride functional silane include 3-trimethoxysilylpropyl succinic anhydride and the like.

Examples of the sulfide silane include bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide.

When the sealing auxiliary agent is used, only one kind may be used, or two or more kinds may be used at the same time.

The content of the adhesion promoter is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the entire solid content of the photosensitive resin composition. When the amount is within this range, it is considered that the effect of the adhesion promoter, that is, "adhesion", can be sufficiently obtained while maintaining a balance with other properties.

(solvent)

The photosensitive resin composition according to the present embodiment may contain a urea compound or an amide compound having an acyclic structure as a solvent. As the solvent, for example, a urea compound is preferably contained. This can further improve adhesion between the cured product of the photosensitive resin composition and metals such as Al and Cu.

In the present specification, the urea compound means a compound having urea bonds, that is, urea bonds. The amide compound means an amide which is a compound having an amide bond. In addition, specifically, the amide may be a primary amide, a secondary amide, or a tertiary amide.

In the present embodiment, the acyclic structure means that the structure of the compound does not have a cyclic structure such as a carbocycle, an inorganic ring, or a heterocycle. Examples of the structure of the compound having no cyclic structure include a linear structure and a branched structure.

The urea compound and the acyclic amide compound are preferably those having a large number of nitrogen atoms in the molecular structure. Specifically, the number of nitrogen atoms in the molecular structure is preferably 2 or more. Thereby, the number of lone pairs can be increased. Therefore, adhesion to metals such as Al and Cu can be improved.

The structure of the urea compound may specifically be a cyclic structure, an acyclic structure, or the like. In the above specific examples, the structure of the urea compound is preferably an acyclic structure. This can improve adhesion between the cured product of the photosensitive resin composition and a metal such as Al or Cu. The reason for this is presumed as follows. It is presumed that the urea compound having an acyclic structure is likely to form a coordinate bond as compared with the urea compound having a cyclic structure. This is considered to be because the urea compound having an acyclic structure has less restriction on molecular movement than the urea compound having a cyclic structure, and further, the degree of freedom of deformation of the molecular structure is large. Therefore, when a urea compound having an acyclic structure is used, a strong coordination bond can be formed, and adhesion can be improved.

Specific examples of the urea compound include Tetramethylurea (TMU), 1, 3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, tetrabutylurea, N, N '-dimethylpropyleneurea, 1, 3-dimethoxy-1, 3-dimethylurea, N, N' -diisopropyl-O-methyliso urea, O, N, N '-triisopropylisourea, O-tert-butyl-N, N' -diisopropylisourea, O-ethyl-N, N '-diisopropylisourea, O-benzyl-N, N' -diisopropylisourea, and the like. As the urea compound, one or two or more of the above specific examples can be used in combination. Among the above specific examples, for example, one or two or more selected from the group consisting of Tetramethylurea (TMU), tetrabutylurea, 1, 3-dimethoxy-1, 3-dimethylurea, N ' -diisopropyl-O-methyliso urea, O, N ' -triisopropylisourea, O-tert-butyl-N, N ' -diisopropylisourea, O-ethyl-N, N ' -diisopropylisourea, and O-benzyl-N, N ' -diisopropylisourea are preferably used, and Tetramethylurea (TMU) is more preferably used. This can form a strong coordination bond, and can improve adhesion.

Specific examples of the amide compound having an acyclic structure include 3-methoxy-N, N-dimethylpropionamide, N-dimethylformamide, N-dimethylpropionamide, N-diethylacetamide, 3-butoxy-N, N-dimethylpropionamide, and N, N-dibutylformamide.

The photosensitive resin composition according to the present embodiment may contain a solvent having no nitrogen atom as well as a urea compound and an amide compound having an acyclic structure.

Specific examples of the solvent having no nitrogen atom include an ether-based solvent, an acetate-based solvent, an alcohol-based solvent, a ketone-based solvent, a lactone-based solvent, a carbonate-based solvent, a sulfone-based solvent, an ester-based solvent, and an aromatic hydrocarbon-based solvent. As the solvent having no nitrogen atom, one or two or more of the above specific examples may be used in combination.

Specific examples of the ether solvent include Propylene Glycol Monomethyl Ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, and 1, 3-butanediol-3-monomethyl ether.

Specific examples of the above-mentioned acetate solvents include Propylene Glycol Monomethyl Ether Acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, and methyl-1, 3-butanediol acetate.

Specific examples of the alcohol-based solvent include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropanol.

Specific examples of the ketone solvent include cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone.

Specific examples of the lactone-based solvent include gamma-butyrolactone (GBL) and gamma-valerolactone (gamma-valerolactone).

Specific examples of the carbonate-based solvent include ethylene carbonate and propylene carbonate.

Specific examples of the sulfone-based solvent include dimethyl sulfoxide (DMSO), sulfolane, and the like.

Specific examples of the ester-based solvent include methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, and the like.

Specific examples of the aromatic hydrocarbon solvent include mesitylene, toluene, and xylene.

Among the above solvents, PGMEA and cyclopentanone are more preferable. By using these, the solubility of the polymer a (polynorbornene) and the polymer B (polyimide) can be improved.

The lower limit value of the content of the urea compound and the amide compound having an acyclic structure in the solvent is, for example, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, and particularly preferably 70 parts by mass or more, based on 100 parts by mass of the solvent. This can further improve adhesion between the cured product of the photosensitive resin composition and metals such as Al and Cu.

The lower limit of the content of the urea compound and the amide compound having an acyclic structure in the solvent may be set to 100 parts by mass or less, for example, when the solvent is set to 100 parts by mass. From the viewpoint of improving adhesion, it is preferable that the content of the urea compound and the amide compound having an acyclic structure in the solvent is large.

(surfactant)

The photosensitive resin composition according to the present embodiment may further include a surfactant.

The surfactant is not limited, and specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters, e.g., polyoxyethylene dilaurate and polyoxyethylene distearate; a commercially available surface active agent such as F-TOP EF301, F-TOP EF303, F-TOP EF352 (manufactured by New autumn chemical Co., ltd.), MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGAFACE F477 (manufactured by DIC Corporation), fluoro FC-430, fluoro FC-431, novec FC4430, novec FC4432 (manufactured by 3M Japanese Limited), surflon S-381, surflon S-382, surflon S-383, surflon S-393, surflon SC-101, surflon SC-102, surflon SC-103, surflon SC-104, surflon SC-105, surflon SC-106 (manufactured by SurfSC-106, manufactured by SurfD Corporation); organosiloxane copolymer KP341 (Shin-Etsu Chemical co., ltd.); and (meth) acrylic copolymers Polyflow No.57 and 95 (manufactured by Kyowa Kagaku Co., ltd.).

Among these, a fluorinated surfactant having a perfluoroalkyl group is preferably used. The fluorinated surfactant having a perfluoroalkyl group is preferably one or two or more selected from the group consisting of MEGAFACE F171, MEGAFACE F173, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGAFACE F477 (manufactured by DIC Corporation), surflon S-381, surflon S-383, surflon S-393 (manufactured by AGC cleaning science (AGC SEIMI CHEMICAL co., ltd)), novec FC4430 and Novec FC4432 (manufactured by 3M Japan Limited) in the above specific examples.

Also, as the surfactant, a silicone surfactant (for example, polyether modified dimethylsiloxane or the like) can be preferably used. Specific examples of the Silicone surfactant include SH series, SD series, and ST series of oridacorning CORPORATION (Dow Corning Toray co., ltd.), BYK series of Japan pick chemistry (BYK Japan k.k.), KP series of singe Chemical industry CORPORATION (Shin-Etsu Chemical co., ltd.), disfoam (registered trademark) series of NOF CORPORATION (NOF CORPORATION), TSF series of Toshiba Silicone CORPORATION (Toshiba Silicone co., ltd.), and the like.

The upper limit value of the content of the surfactant in the photosensitive resin composition is preferably 1 mass% (10000 ppm) or less, more preferably 0.5 mass% (5000 ppm) or less, and still more preferably 0.1 mass% (1000 ppm) or less, relative to the entire photosensitive resin composition (including the solvent).

The lower limit of the content of the surfactant in the photosensitive resin composition is not particularly limited, but is, for example, 0.001 mass% (10 ppm) or more relative to the entire photosensitive resin composition (including the solvent) from the viewpoint of sufficiently obtaining the effect of the surfactant.

By properly adjusting the amount of the surfactant, it is possible to improve the coatability, the uniformity of the coating film, and the like while maintaining other properties.

(antioxidant)

The photosensitive resin composition according to the present embodiment may further contain an antioxidant. As the antioxidant, one or more selected from a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether (thio) based antioxidant can be used. The antioxidant can inhibit oxidation of a resin film formed from the photosensitive resin composition.

Examples of the phenolic antioxidants include pentaerythritol 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, 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl 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-ethylphenol, 2, 6-diphenyl-4-octadecyl phenol, (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, (3, 5-di-t-butyl-4-hydroxyphenyl) stearyl ester, (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 3, 5-trimethyl-2, 4-di-t-butyl-4-hydroxybenzyl) benzene, 2, 6-di-t-butyl-4-butylphenyl (3, 6-di-t-butyl-4-hydroxyphenyl) propionate, 4-di-t-butyl-4-hydroxyphenyl) sulfide, 4-t-butyl-4-butylphenyl) propionate, and (3, 6-di-t-butyl-4-hydroxyphenyl) propionate, 2,2' -methylenebis (4-methyl-6-tert-butyl-6-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), bis [ 3, 3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid ] glycol ester, 4' -butylidenebis (6-tert-butyl-m-cresol), 2' -ethylenebis (4, 6-di-tert-butylphenol), 2' -ethylenebis (4-sec-butyl-6-tert-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane bis [ 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] terephthalate, 1,3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4, 6-trimethylbenzene, 1,3, 5-tris [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl ] isocyanurate, tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5,5] undecane-bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], 1' -bis (4-hydroxyphenyl) cyclohexane, 2' -methylenebis (4-methyl-6-tert-butylphenol) 2,2' -methylenebis (4-ethyl-6-tert-butylphenol), 2' -methylenebis (6- (1-methylcyclohexyl) -4-methylphenol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), 3, 9-bis (2- (3-tert-butyl-4-hydroxy-5-methylphenyl propionyloxy) -1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro (5, 5) undecane, 4' -thiobis (3-methyl-6-tert-butylphenol), 4' -bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4' -thiobis (6-tert-butyl-2-methylphenol), 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2, 4-dimethyl-6- (1-methylcyclohexyl) styrenated phenol, 2, 4-bis ((octylthio) methyl) -5-methylphenol, and the like.

Examples of the phosphorus antioxidant include bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2, 4-di-t-butylphenyl phosphite), tetrakis (2, 4-di-t-butyl-5-methylphenyl) -4,4' -biphenylene diphosphonite, 3, 5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2, 6-diisopropylphenyl) pentaerythritol diphosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, tris (mixed mono-and di-nonylphenyl) phosphite (tris (mixed mono-and dinonylphenyl) phosphorus phosphite), bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methoxycarbonylethyl-phenyl) pentaerythritol diphosphite, and bis (2, 6-di-t-butyl-4-octadecylcarbonylethyl) pentaerythritol diphosphite.

Examples of the thioether-based antioxidant include dilauryl 3,3 '-thiodipropionate, bis (2-methyl-4- (3-n-dodecyl) thiopropionyl) -5-t-butylphenyl) sulfide, distearyl 3,3' -thiodipropionate, pentaerythritol-tetra (3-lauryl) thiopropionate, and the like.

(Filler)

The photosensitive resin composition according to the present embodiment may further contain a filler. As the filler, an appropriate filler can be selected according to mechanical properties and thermal properties required for a resin film formed from the photosensitive resin composition.

Specifically, the filler may be an inorganic filler, an organic filler, or the like.

Specific examples of the inorganic filler include fused silica, fused spherical silica, crystalline silica, 2-shot silica, and silica such as fine silica; metal compounds such as aluminum oxide, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, and titanium white; talc; clay; mica; glass fiber, and the like. As the inorganic filler, one or two or more of the above specific examples can be used in combination.

Specific examples of the organic filler include an organic silicone powder and a polyethylene powder. As the organic filler, one or two or more of the above specific examples can be used in combination.

(preparation of photosensitive resin composition)

The method for producing the photosensitive resin composition of the present embodiment is not limited, and a known method can be used depending on the components contained in the photosensitive resin composition.

For example, the above-mentioned components can be prepared by mixing them in a solvent and dissolving them.

(photosensitive resin composition, cured film)

The photosensitive resin composition according to the present embodiment can be used as follows: the photosensitive resin composition is applied to a surface having a metal such as Al or Cu, and then dried to form a resin film by pre-baking (pre-baking), and then the resin film is patterned into a desired shape by exposure to light and development, and then cured to form a cured film by post-baking (post-baking).

In the case of producing the permanent film, the pre-baking condition may be, for example, a heat treatment at a temperature of 50 ℃ or more and 150 ℃ or less and 30 seconds or more and 1 hour or less. The post-baking conditions may be, for example, a heat treatment at a temperature of 150 ℃ or higher and 250 ℃ or lower and for 30 minutes or higher and 10 hours or lower.

The viscosity of the photosensitive resin composition according to the present embodiment can be appropriately set according to the desired thickness of the resin film. The viscosity of the photosensitive resin composition can be adjusted by adding a solvent. In addition, in the adjustment, it is necessary to keep the content of the urea compound and the acyclic amide compound in the solvent constant.

The upper limit of the viscosity of the photosensitive resin composition according to the present embodiment may be, for example, 5000mpa·s or less, 4000mpa·s or less, or 3000mpa·s or less. The lower limit value of the viscosity of the photosensitive resin composition according to the present embodiment may be, for example, 10mpa·s or more, or 50mpa·s or more, depending on the thickness of the desired resin film.

The maximum elongation of the film obtained from the photosensitive resin composition of the present embodiment, as measured by a tensile test by a universal tensile tester (Tensilon), is 10 to 200%, preferably 20 to 150%, and the average value is 1 to 150%, preferably 2 to 120%.

The tensile strength of the film obtained from the photosensitive resin composition of the present embodiment can be set to 30 to 300MPa, preferably 50 to 200MPa.

As described above, the photosensitive resin composition of the present embodiment can provide a cured product such as a film having excellent mechanical strength. The reason for this is not clear, but it is assumed that the excellent properties of the rigid polyimide of the present invention are attributed to the present invention.

The film formed from the photosensitive resin composition of the present embodiment is excellent in low dielectric loss tangent, and the dielectric loss tangent (tan δ) when measured at a frequency of 10GHz is 0.008 or less, preferably 0.007 or less, and more preferably 0.006 or less.

The film formed from the photosensitive resin composition of the present embodiment is suppressed in curing shrinkage, and the coefficient of linear thermal expansion (CTE) can be set to 200ppm/°c or less, preferably 150ppm/°c or less.

In the present embodiment, the polyimide contained in the polymer B preferably contains no halogen atom. Thus, a cured product such as a film formed from the photosensitive resin composition is excellent in hydrolysis resistance, and deterioration of mechanical properties and the like can be suppressed.

Specifically, since a cured product (film) formed from a photosensitive resin composition containing a polymer a and a polymer B containing a polyimide containing no halogen atom is excellent in hydrolysis resistance, the elongation (maximum value) represented by the following formula is reduced by 20% or less, preferably 15% or less, and more preferably 12% or less even after 96 hours of HAST test (unsaturated pressurized steam test) under conditions of a temperature of 130 ℃ and a relative humidity of 85% rh.

[ (elongation before test-elongation after test)/elongation before test) ]. Times.100

(use)

The photosensitive resin composition (negative photosensitive resin composition) of the present embodiment is used for forming a resin film for a semiconductor device such as a permanent film or a resist. Among these, the use for using a permanent film is preferable from the viewpoint of improving the adhesion between the photosensitive resin composition after the pre-baking and the Al pad and suppressing the generation of residues of the photosensitive resin composition at the time of development, from the viewpoint of improving the adhesion between the cured film of the photosensitive resin composition after the post-baking and the metal, and from the viewpoint of improving the chemical resistance of the photosensitive resin composition after the post-baking.

In the present embodiment, the resin film includes a cured film of the photosensitive resin composition. That is, the resin film according to the present embodiment is a film obtained by curing a photosensitive resin composition.

The permanent film is formed of a resin film obtained by patterning a photosensitive resin composition into a desired shape by prebaking, exposing and developing, and then post-baking and curing the resin film. The permanent film can be used for a protective film, an interlayer film, a dam (dammmaterial), and the like of a semiconductor device.

The resist is composed of, for example, a resin film obtained by applying a photosensitive resin composition to an object masked with the resist by spin coating, roll coating, flow coating, dip coating, spray coating, knife coating, or the like, and removing a solvent from the photosensitive resin composition.

An example of the semiconductor device according to the present embodiment is shown in fig. 1.

The semiconductor device 100 according to the present embodiment can be configured as a semiconductor device including the resin film. Specifically, 1 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 set to a resin film containing the cured product of the present embodiment. Here, the resin film is preferably the above-mentioned permanent film.

The semiconductor device 100 is, for example, a semiconductor chip. At this time, the semiconductor package is obtained by mounting the semiconductor device 100 on a wiring substrate through a bump (bump) 52, for example.

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 an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided at the uppermost layer of the multilayer wiring layers. The uppermost wiring 34 is made of aluminum Al, for example. A passivation film 32 is provided on the interlayer insulating film 30 and on the uppermost wiring 34. An opening through which the uppermost wiring 34 is exposed is provided in a part of the passivation film 32.

A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 has an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and on the rewiring 46. An opening connected to the uppermost wiring 34 is formed on the insulating layer 42. The rewiring 46 is formed on the insulating layer 42 and disposed in the opening of the insulating layer 42, and is connected to the uppermost wiring 34. An opening connected to the rewiring 46 is provided in the insulating layer 44.

Bumps 52 are formed in openings provided in the insulating layer 44, for example by means of UBM (Under Bump Metallurgy: under bump metallurgy) layer 50. The semiconductor device 100 is connected to a wiring board or the like through, for example, the bump 52.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be adopted within a range that does not impair the effects of the present invention.

Examples

The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. In this example, unless specifically indicated, all parts and percentages are by weight, all temperatures are degrees celsius, and the pressure is at or near atmospheric pressure.

Synthesis example 1

(Synthesis of maleic anhydride-modified norbornene monomer (DMMIBuNB, 1- [4- (5-2-norbornyl) butyl ] -3, 4-dimethyl-pyrrole-2, 5-dione))

200mL of toluene was added with stirring to a 1L 4-necked round-bottomed flask (RBF) equipped with a thermowell, a condenser with a nitrogen inlet, an addition funnel, and a mechanical stirrer, followed by addition of DMMI potassium (35 g, 0.21 mol) and 18-crown-6 (5.7 g, 0.021mol, 10 mol%). To the addition funnel was added 200mL of endo-exo (endo-exo) NBBuBr (45 g, 0.20 mol) in toluene, which was added over 5 minutes. The mixture was heated to 100 ℃ and an off-white slurry was observed. The mixture was stirred for a further 6.5 hours and the colour changed from the initially observed off-white colour to dark green and then to reddish brown. The reaction was monitored by GC and was completed in 73.6% of product and 15.6% of unreacted in-out NBBuBr.

Next, after cooling the reaction mixture to room temperature, 250mL of water was added for water quenching (sequence), followed by 150mL of toluene was diluted. By CH ₂ Cl ₂ (2X 200 mL) the aqueous layer was extracted and the organic layer was washed with brine (brine) over Na ₂ SO ₄ Drying above, filtration and evaporation gave 55g of crude product as a brown oil. The crude product was adsorbed to 55g of SiO ₂ On 330g of SiO ₂ Chromatography was performed above, eluting with pentane (3L), 2% etoac in pentane (5L), 3% etoac in heptane (3L), and 4% etoac in heptane (2L). From the concentrated purified fraction (fraction), 31g of the product was obtained in the form of colorless viscous oil (yield 58%) in a purity of 99.3% based on HPLC, and as another fraction, 7.0g of the product was obtained in a purity of 99.09% based on HPLC (yield 13.1%). The overall yield for the reaction was 71%. ¹ H-NMR and MS were consistent with the structure of DMMIBuNB. The following shows the reaction scheme.

(Synthesis of Polymer (DMMI-PNB (1))

The nitrogen-substituted reaction vessel was charged with 596g of 1- [4- (5-2-norbornyl) butyl ] -3, 4-dimethyl-pyrrole-2, 5-dione, 1849g of toluene and 457g of ethyl acetate obtained by the above-mentioned method. 66ml of a toluene solution of (toluene) bis (perfluorophenyl) nickel at a concentration of 10% by weight was further added, and reacted at 49℃for 2 hours. After 2 hours, the reaction was stopped by adding 11g of water, and a polymer solution was obtained. The conversion to polymer was 99%.

To 100 parts by weight of the prepared polymer solution, 150g of ethyl acetate, 463g of isopropyl alcohol, 254g of acetic acid, 481g of hydrogen peroxide (30%) and 601g of water were added, and the mixture was stirred at 160rpm while being heated to 50 ℃. After reaching 50 ℃, stirring was further performed for 30 minutes. After 30 minutes, the stirring speed was reduced to 50rpm, and 154g of isopropyl alcohol was added thereto, followed by stirring for 10 minutes and further standing at 50℃for 30 minutes. After standing, the organic phase and the aqueous phase were separated, and the aqueous phase was discarded. The obtained resin solution was reprecipitated with MeOH, filtered and dried under vacuum at 50℃to obtain 545g of a polymer (DMMI-PNB (1)). Mw was 10 ten thousand.

Synthesis example 2

In a 500mL round bottom flask, dimethyl maleic anhydride (42.6 g, 0.34 mol) was dissolved in toluene (300 mL) at room temperature. To remove oxygen, the solution was placed under a nitrogen atmosphere. The reaction flask was placed in an ice bath to prevent overheating from exothermic reactions. At the time of the dissolution of dimethyl maleic anhydride, a dropping funnel containing 5-norbornene-2-butylamine (49.6 g, 0.30 mol) was installed, and the norbornene compound was added dropwise to the reaction flask over 3 hours. The dropping funnel was removed and a Dean-Stark (Dean-Stark) tube and reflux cooler were placed in the flask. The solution was heated to reflux in an oil bath set at 125 ℃ and the reaction stirred at that temperature for 18 hours. During this time, about 6mL of water was recovered into the dean-stark tube. The flask was removed from the oil bath and cooled to room temperature. Toluene solvent was removed using an evaporator, and a yellow oily substance was obtained. The crude product was placed on a flash chromatography column (250 g of silica gel) and eluted with 1.7 liters of a solvent mixture of cyclohexane/ethyl acetate (95/5 wt). The eluting solvent was removed using an evaporator, after which it was dried under vacuum at 45 ℃ for 18 hours to give 80.4g (92.7% yield) of the desired product. The following shows the reaction scheme.

(Synthesis of Polymer (DMMI-PNB (2))

After charging a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube with nitrogen for 1 hour, 1- [4- (5-2-norbornyl) butyl ] -3, 4-dimethyl-pyrrole-2, 5-dione (NBBuDMMI) (24.60 g, 90 mmol) and triethylsilane (3.14 g, 27 mmol) were introduced. Further, cyclopentylmethyl ether (CPME) (16.04 g) and Ethyl Acetate (EA) (1.98 g) were added, whereby a reaction solution was obtained. The reaction solution was heated to 70℃under a stream of nitrogen (50 mL/min) with stirring. The catalyst ((acetonitrile) bis (triisopropylphosphine) palladium (II) acetate tetrakis (2, 3,4,5, 6-pentafluorophenyl) borate, pd-1206) (0.0434 g) and cocatalyst (N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, danaba) (0.0288 g) were dissolved in Ethyl Acetate (EA) (3.37 g) to give nbbudmi: catalyst: cocatalyst = 2500:1:1 (molar ratio) was added to the reaction solution. Then, polymerization was carried out at 70℃for 3 hours, and after polymerization, the reaction was stopped by natural cooling.

The obtained polymerization solution was diluted with tetrahydrofuran to prepare a diluted solution, and then, the diluted solution was added dropwise to a methanol solution, whereby a white solid was precipitated. The obtained white solid was recovered and dried under vacuum at a temperature of 50℃to thereby obtain 20.02g of a polymer (DMMI-PNB (2)). Mw was 6000.

The following compounds were used in synthesis examples 3 to 6.

4,4' - (hexafluoroisopropylidene) diphthalic anhydride represented by the following formula (hereinafter also referred to as 6 FDA).

2,2' -bis (trifluoromethyl) benzidine represented by the following formula (hereinafter, also referred to as TFMB).

4- [4- (1, 3-dioxoisobenzofuran-5-ylcarbonyloxy) -2,3, 5-trimethylphenyl ] -2,3, 6-trimethylphenyl-1, 3-dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME) represented by the following formula.

4, 4-diamino-3, 3-diethyl-5, 5-dimethyldiphenylmethane (hereinafter also referred to as MED-J) represented by the following formula.

A mixture of 1- (4-aminophenyl) -1, 3-trimethylphenylindan-6-amine and 1- (4-aminophenyl) -1, 3-trimethylphenylindan-5-amine represented by the following formula (hereinafter, also referred to as TMDA).

9, 9-bis (3-methyl-4-aminophenyl) fluorene represented by the following formula (hereinafter, also referred to as BTFL).

Synthesis example 3

(Synthesis of Polymer (DMMI-PI (1))

First, a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube was charged with TFMB16.09g (50.2 mmol), 6FDA11.05g (24.9 mmol), and TMPBP-TME 15.39g (24.9 mmol). Thereafter, 99.24g of gamma-butyrolactone (hereinafter, also referred to as GBL) was further charged into the reaction vessel.

After nitrogen was purged for 10 minutes, the temperature was raised to 60 ℃ with stirring, and the reaction was allowed to proceed for 1 hour. A solution of 0.38g (3.0 mmol) of dimethyl maleic anhydride in 0.78g of gamma-butyrolactone was prepared in advance, and the solution was placed in a reaction vessel and reacted for a further 30 minutes. The diamine and the acid anhydride were further polymerized by reacting them at 175℃for 3 hours, to prepare a polymer solution having a closed terminal.

The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then, the diluted solution was added dropwise to a methanol solution, whereby a white solid was precipitated. The obtained white solid was recovered and dried under vacuum at a temperature of 120℃to thereby obtain 34.78g of a polymer represented by the following formula (DMMI-PI (1)).

GPC measurement showed that weight average molecular weight Mw was 76991, polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 2.06 and terminal blocking ratio was 93%. Wherein, m is n is approximately equal to 1:1.

IR measurements of the polymers revealed 1480, 1550 and 1670cm ^-1 Nearby peaks from amide groups have disappeared, and imidization is completed.

Synthesis example 4

(Synthesis of Polymer (DMMI-PI (2))

First, MED-J43.99g (155.8 mmol) and TMPBP-TME 89.22g (144.2 mmol) were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. Thereafter, 399.64g of gamma-butyrolactone (hereinafter, also referred to as GBL) was further added to the reaction vessel.

After nitrogen was purged for 10 minutes, the temperature was raised to 60 ℃ with stirring, and the reaction was allowed to proceed for 1 hour. A solution of 8.73g (69.2 mmol) of dimethyl maleic anhydride in 26.19g of gamma-butyrolactone was prepared in advance, and the solution was placed in a reaction vessel and reacted for a further 30 minutes. The diamine and the acid anhydride were further polymerized by reacting them at 175℃for 3 hours, to prepare a polymer solution having a closed terminal.

The obtained polymerization solution was diluted with tetrahydrofuran to prepare a diluted solution, and then, the diluted solution was added dropwise to a methanol solution, whereby a white solid was precipitated. The obtained white solid was recovered and dried under vacuum at a temperature of 80℃to thereby obtain 125.88g of a polymer represented by the following formula (DMMI-PI (2)).

GPC measurement showed that weight-average molecular weight Mw was 74000, polydispersity (weight-average molecular weight Mw/number-average molecular weight Mn) was 2.62 and terminal blocking ratio was 65%.

Synthesis example 5

(Synthesis of Polymer (DMMI-PI (3))

First, a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube was charged with MED-J7.17g (25.4 mmol), TMDA 6.76g (25.4 mmol) and TMPBP-TME 30.47g (49.3 mmol). Thereafter, 159.82g of gamma-butyrolactone (hereinafter, also referred to as GBL) was further added to the reaction vessel.

After nitrogen was purged for 10 minutes, the temperature was raised to 60 ℃ with stirring, and the reaction was allowed to proceed for 1 hour. A solution of 1.12g (8.9 mmol) of dimethyl maleic anhydride in 4.47g of gamma butyrolactone was prepared in advance, and the solution was placed in a reaction vessel and further reacted for 30 minutes. The diamine and the acid anhydride were further polymerized by reacting them at 175℃for 3 hours, to prepare a polymer solution having a closed terminal.

The obtained polymerization solution was diluted with tetrahydrofuran to prepare a diluted solution, and then, the diluted solution was added dropwise to a methanol solution, whereby a white solid was precipitated. The obtained white solid was recovered and dried under vacuum at a temperature of 80℃to thereby obtain 40.62g of a polymer (DMMI-PI (3)).

GPC measurement showed that weight-average molecular weight Mw was 77000, polydispersity (weight-average molecular weight Mw/number-average molecular weight Mn) was 2.07, and terminal blocking ratio was 98%.

Synthesis example 6

(Synthesis of Polymer (DMMI-PI (4))

First, a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube was charged with MED-J7.17g (25.4 mmol), BTFL 9.55g (25.4 mmol), and TMPBP-TME 30.47g (49.3 mmol). Thereafter, 169.88g of gamma-butyrolactone (hereinafter, also referred to as GBL) was further added to the reaction vessel.

The obtained polymerization solution was diluted with tetrahydrofuran to prepare a diluted solution, and then, the diluted solution was added dropwise to a methanol solution, whereby a white solid was precipitated. The obtained white solid was recovered and dried under vacuum at a temperature of 80℃to thereby obtain 43.69g of a polymer (DMMI-PI (4)).

GPC measurement showed that weight-average molecular weight Mw was 83000, polydispersity (weight-average molecular weight Mw/number-average molecular weight Mn) was 2.10 and terminal blocking ratio was 86%.

The following ingredients were used in the examples below.

And (3) a photosensitizer: 1-chloro-4-propoxythioxanthone (manufactured by Lambson, UK, SPEEDCURE CPTX (trade name)).

Solvent: propylene glycol monomethyl ether acetate.

Sealing auxiliary agent: 3-trimethoxysilylpropyl succinic anhydride (trade name "X-12-967C", manufactured by Xinyue Chemical Co., ltd.).

Examples 1 to 7 and comparative examples 1 to 2

The components described in table 1 were mixed to prepare photosensitive resin compositions.

The obtained photosensitive resin composition was spin-coated on the surface of a silicon wafer so that the film thickness became 10 μm after drying, and after 3 minutes of prebaking at 120℃the film was subjected to 2000mJ/cm by a high-pressure mercury lamp ² After which the film was prepared by curing under nitrogen at 200℃for 120 minutes. In example 5, the pre-baking was performed at 150℃for 3 minutes, and the exposure was changed to 800mJ/cm ² Except for this, a film was produced in the same manner as in example 1.

(tensile Strength, elongation and elastic modulus)

A tensile test (stretching speed: 5 mm/min) was performed on a test piece (6.5 mm. Times.60 mm. Times.10 μm thickness) cut out from the obtained film in an atmosphere at 23 ℃. The tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Nippon sea Meter Co., LTD. The 5 test pieces were measured, and the stress at the breaking point was averaged as strength. The tensile elongation was calculated from the distance at break and the initial distance, and the maximum elongation was obtained. From the initial slope of the obtained stress-strain curve, each tensile elastic modulus was calculated, and the value obtained by averaging the tensile elastic modulus was used as the elastic modulus. The results are shown in Table 1.

Further, after the test piece cut out from the obtained film was subjected to HAST (unsaturated pressurized steam test) for 96 hours at a temperature of 130 ℃ and a relative humidity of 85% rh, the maximum value of elongation was obtained in the same manner as described. The results are shown in Table 1.

(coefficient of Linear thermal expansion (CTE))

From the obtained film, a long test piece having a length of 13mm by a width of 4mm was cut. The thermal mechanical measurement in the stretching mode was performed at a collet spacing of 10mm, and the average linear thermal expansion coefficient (CTE, 50 to 100℃or 100 to 200 ℃) was determined from the thermal expansion curve. The results are shown in Table 1.

(glass transition temperature: tg)

From the obtained film, a long test piece having a length of 50mm by a width of 10mm was cut. Dynamic viscoelasticity measurement was performed with a collet spacing of 20mm, and the peak temperature of the loss tangent (tan δ) obtained was taken as the glass transition temperature (Tg). The measurement conditions were set to a nitrogen flow of 30 ml/min, an application frequency of 1Hz, and a heating rate of 5 ℃/min. The results are shown in Table 1.

(dielectric loss tangent Df)

The photosensitive resin compositions of examples 1 to 7 and comparative examples 1 to 2 were applied to a substrate, the applied film was dried at 120℃for 10 minutes, and PLA exposure (540 mJ) was performed, and the film was cured for 2 hours under a nitrogen atmosphere at 200℃to obtain a film having a film thickness of 100. Mu.m. The dielectric loss tangent at 10GHz was measured for the obtained film by the cavity resonance method. The results are shown in Table 1.

From the results of table 1, it is clear that since the photosensitive resin composition of the present application comprises a predetermined cyclic olefin resin and polyimide in combination, a resin film excellent in low dielectric loss tangent and excellent in mechanical properties can be obtained. Further, it is estimated that the resin film is also excellent in hydrolysis resistance, and the deterioration of mechanical properties and the like is suppressed.

Further, as a result of conducting a photosensitivity test on the photosensitive resin compositions of examples 1 to 7, it was confirmed that holes having a diameter of 20 μm could be formed.

This application claims priority based on japanese patent application publication nos. 2021-021545 of 15/2/2021 and 2021-105687 of 25/6/2021, and the disclosures of which are incorporated herein in their entirety.

Description of the reference numerals

30: an interlayer insulating film; 32: a passivation film; 34: an uppermost wiring; 40: a rewiring layer; 42: an insulating layer; 44: an insulating layer; 46: rewiring; 50: a UBM layer; 52: a bump; 100: a semiconductor device.

Claims

1. A photosensitive resin composition, wherein,

the photosensitive resin composition comprises:

a polymer A having a structural unit represented by the following general formula (a); and

a polymer B comprising a polyimide having a group B represented by the following general formula (B),

In the general formula (a), R ¹ R is as follows ² Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q ¹ Represents a single bond or a 2-valent organic group, G ¹ 、G ² G ³ Independently represent a hydrogen atomSubstituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, m is 0, 1 or 2,

in the general formula (b), R ³ R is as follows ⁴ Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q ² Represents an organic group of valence 2, G ⁴ Each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and represents a bond.

2. The photosensitive resin composition according to claim 1, wherein,

Q ¹ the organic group having 2 valences of (C) 1-8 is an alkylene group or a (poly) alkylene glycol chain.

3. The photosensitive resin composition according to claim 1 or 2, wherein,

the polymer B contains a polyimide having a group B represented by the general formula (B) at both ends.

4. The photosensitive resin composition according to any one of claim 1 to 3, wherein,

said Q of said formula (b) ² The organic group having a valence of 2 in (b 1) is represented by the following general formula,

in the general formula (b 1), R ⁵ R is as follows ⁶ Each independently represents a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group, X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a haloalkylene group having 1 to 4 carbon atoms, a 2-valent ether group derived from bisphenol A, a 2-valent ether group derived from bisphenol F Ether group of valence 2 derived from bisphenol S, ether group of valence 2 derived from hexafluorobisphenol a.

5. The photosensitive resin composition according to claim 1 or 2, wherein,

the polymer (B) comprises a polyimide having a group c represented by the following general formula (c) at least one terminal,

in the polyimide contained in the polymer (B), the ratio of the number of moles of the group B to the total number of moles of the group B and the group c, i.e., B/b+c, is 0.5 or more,

in the general formula (c), R ⁵ R is as follows ⁶ Each independently represents a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group, X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a haloalkylene group having 1 to 4 carbon atoms, a 2-valent ether group derived from bisphenol A, a 2-valent ether group derived from bisphenol F, a 2-valent ether group derived from bisphenol S, a 2-valent ether group derived from hexafluorobisphenol A, G ⁴ Each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and represents a bond.

6. The photosensitive resin composition according to any one of claims 1 to 4, wherein,

the polymer B contains polyimide represented by the following general formula (d),

In the general formula (d), R ³ 、R ⁴ 、Q ² 、G ⁴ Is the same as the general formula (b), a plurality of R's are present ³ R are present in plural with each other ⁴ Each other and store a plurality ofQ at ² G are present between each other in plural ⁴ Each of which is the same as or different from the other,

y is selected from the group consisting of a group represented by the following general formula (d 1), a group represented by the following general formula (d 2), a group represented by the following general formula (d 3) and a haloalkylene having 1 to 5 carbon atoms, and a plurality of Y's present are the same or different,

in the general formula (d 1), R ⁷ R is as follows ⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's present ⁷ R are present in plural with each other ⁸ Are identical or different from each other, denote bonding bonds,

in the general formula (d 2), R ⁹ R is as follows ¹⁰ Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's present ⁹ R are present in plural with each other ¹⁰ Identical or different from each other, R ¹¹ Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's present ¹¹ Are identical or different from each other, denote bonding bonds,

in the general formula (d 3), Z represents an alkylene group having 1 to 5 carbon atoms, an aromatic group having 2 valences, a bond is represented by,

Q ³ Represents a repeating unit represented by the following general formula (d 4),

in the general formula (d 4), R ⁵ 、R ⁶ And X has the same meaning as the general formula (b 1), G ⁴ The meaning of Y is the same as the general formula (d), n represents an integer of 20-200, and x represents a bonding bond.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein,

the photosensitive resin composition further comprises a photosensitizer.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein,

the photosensitive resin composition further comprises a silane coupling agent.

9. A cured film, wherein,

the cured film is composed of a cured product of the photosensitive resin composition according to any one of claims 1 to 8.

10. A semiconductor device, wherein,

the semiconductor device is provided with a resin film,

the resin film contains a cured product of the photosensitive resin composition according to any one of claims 1 to 8.

11. The semiconductor device according to claim 10, wherein,

the semiconductor device includes:

an interlayer insulating film;

a resin film provided on the interlayer insulating film and containing a cured product of the photosensitive resin composition according to any one of claims 1 to 8; and

And rewiring embedded in the resin film.