JP2018146964A - Photosensitive resin composition, method for producing pattern cured product, cured product, interlayer insulation film, cover coat layer, surface protective film and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can form a cured product having excellent adhesiveness and flux resistance even when cured at a low temperature of 200°C or less, a method for producing a pattern cured product, a cured product, an interlayer insulation film, a cover coat layer, a surface protective film and an electronic component.SOLUTION: A photosensitive resin composition contains (a) a polyimide precursor, (b) a compound having an allyl group, and (c) a photopolymerization initiator.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a method for producing a patterned cured product, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.

  Conventionally, polyimide and polybenzoxazole having both excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for the surface protective film and interlayer insulating film of semiconductor elements. In recent years, photosensitive resin compositions in which photosensitive properties are imparted to these resins themselves have been used, and using this can simplify the manufacturing process of the pattern cured product and shorten complicated manufacturing processes (for example, patent documents). 1).

  By the way, in recent years, the miniaturization of transistors, which has supported the high performance of computers, has reached the limit of the scaling law, and a laminated device structure in which semiconductor elements are three-dimensionally stacked for further high performance and high speed. Has attracted attention (see, for example, Non-Patent Document 1).

  Among the stacked device structures, the multi-die fanout wafer level packaging is a package in which a plurality of dies are encapsulated in one package and has been proposed in the past. It is attracting much attention because it can be expected to achieve lower cost and higher performance than conventional fan-out wafer level packages (which are manufactured by sealing one die in one package).

  In the production of a multi-die fan-out wafer level package, low temperature curability is strongly demanded from the viewpoint of protecting high-performance die and sealing material with low heat resistance and improving yield (for example, patents) Reference 2).

  It has been proposed to introduce a vinyl group capable of photopolymerization into the diamine portion of polyamic acid and to copolymerize it with a photopolymerizable compound in order to maintain the adhesiveness with copper even at a low temperature of 200 ° C. or lower. (Patent Document 3).

JP 2009-265520 A International Publication No. 2008/111470 Special table 2012-514760 gazette

“Semiconductor Technology Yearbook 2013 Packaging / Mounting”, Nikkei Business Publications, p41-p50.

  The object of the present invention is a photosensitive resin composition capable of forming a cured product excellent in adhesiveness and flux resistance even at low temperature curing of 200 ° C. or lower, a method for producing a patterned cured product, a cured product, an interlayer insulating film, It is to provide a cover coat layer, a surface protective film, and an electronic component.

  However, since the diamine structure is fixed, the polyamic acid of Patent Document 3 cannot be applied to polyamic acids having various structures.

  In CSP (chip size packaging) and the like capable of high-density mounting, the cured product has a structure in which it directly contacts the solder bump. Therefore, the cured product directly contacts the flux in the solder bump reflow process. It has been found that a higher flux resistance is required.

  As a result of intensive studies in view of the above problems, the present inventors combined a polyimide precursor, a compound having an allyl group, and a photopolymerization initiator, even at low temperature curing of 200 ° C. or lower, The present invention has been completed by finding that both practical adhesiveness and flux resistance can be achieved.

（式（１）中、Ａは下記式（２）で表される基であり、Ｂは芳香族環を少なくとも１つ含む２価の有機基であり、Ｒ_１及びＲ_２は、それぞれ独立に水素原子又は１価の有機基である。）

（式（２）中、Ｙは、酸素原子又は硫黄原子である。）
３．Ｒ_１及びＲ_２が、それぞれ独立に水素原子、下記式（３）で表される基又は炭素数１〜４のアルキル基である２に記載の感光性樹脂組成物。

（式（３）中、Ｒ_３〜Ｒ_５は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基であり、ｍは１〜１０の整数である。）
４．前記（ｂ）成分が、２以上のアリル基を有する化合物である１〜３のいずれかに記載の感光性樹脂組成物。
５．前記（ｂ）成分が複素環を有する１〜４のいずれかに記載の感光性樹脂組成物。
６．１〜５のいずれかに記載の感光性樹脂組成物を基板上に塗布、乾燥して感光性樹脂膜を形成する工程と、
前記感光性樹脂膜をパターン露光して、樹脂膜を得る工程と、
前記パターン露光後の樹脂膜を、有機溶剤を用いて、現像し、パターン樹脂膜を得る工程と、
前記パターン樹脂膜を加熱処理する工程と、を含むパターン硬化物の製造方法。
７．前記加熱処理の温度が２００℃以下である６に記載のパターン硬化物の製造方法。
８．１〜５のいずれかに記載の感光性樹脂組成物を硬化した硬化物。
９．パターン硬化物である８に記載の硬化物。
１０．８又は９に記載の硬化物を用いて作製された層間絶縁膜、カバーコート層又は表面保護膜。
１１．１０に記載の層間絶縁膜、カバーコート層又は表面保護膜を含む電子部品。 According to the present invention, the following photosensitive resin composition and the like are provided.
1. (A) a polyimide precursor;
(B) a compound having an allyl group;
(C) a photopolymerization initiator;
Containing a photosensitive resin composition.
2. 2. The photosensitive resin composition according to 1, wherein the component (a) has a structural unit represented by the following formula (1).

(In formula (1), A is a group represented by the following formula (2), B is a divalent organic group containing at least one aromatic ring, and R ₁ and R ₂ are each independently It is a hydrogen atom or a monovalent organic group.)

(In Formula (2), Y is an oxygen atom or a sulfur atom.)
3. 3. The photosensitive resin composition according to 2, wherein R ₁ and R ₂ are each independently a hydrogen atom, a group represented by the following formula (3), or an alkyl group having 1 to 4 carbon atoms.

(In Formula (3), R < ₃ > -R < ₅ > is a hydrogen atom or a C1-C3 aliphatic hydrocarbon group each independently, and m is an integer of 1-10.)
4). The photosensitive resin composition in any one of 1-3 whose said (b) component is a compound which has a 2 or more allyl group.
5. The photosensitive resin composition in any one of 1-4 whose said (b) component has a heterocyclic ring.
A step of applying the photosensitive resin composition according to any one of 6.1 to 5 onto a substrate and drying to form a photosensitive resin film;
Pattern exposure of the photosensitive resin film to obtain a resin film;
Developing the resin film after the pattern exposure using an organic solvent, and obtaining a pattern resin film;
And a step of heat-treating the pattern resin film.
7). The manufacturing method of the pattern hardened | cured material of 6 whose temperature of the said heat processing is 200 degrees C or less.
Hardened | cured material which hardened the photosensitive resin composition in any one of 8.1-5.
9. The cured product according to 8, which is a pattern cured product.
An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured product described in 10.8 or 9.
11. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to 11.10.

  According to the present invention, a photosensitive resin composition capable of forming a cured product excellent in adhesiveness and flux resistance even at low temperature curing of 200 ° C. or less, a method for producing a patterned cured product, a cured product, an interlayer insulating film, A cover coat layer, a surface protective film, and an electronic component can be provided.

It is a manufacturing process figure of the electronic component which concerns on one Embodiment of this invention.

  Below, the photosensitive resin composition of this invention, the manufacturing method of a pattern cured material using the same, cured | curing material, an interlayer insulation film, a cover coat layer, a surface protective film, and embodiment of an electronic component are described in detail. The present invention is not limited to the following embodiments.

In this specification, “A or B” may include either one of A and B, or may include both. In addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In addition, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity. Further, the exemplary materials may be used singly or in combination of two or more unless otherwise specified.

  The photosensitive resin composition of the present invention is also referred to as (a) a polyimide precursor (hereinafter also referred to as “(a) component”) and (b) an allyl group-containing compound (hereinafter referred to as “(b) component”). And (c) a photopolymerization initiator (hereinafter also referred to as “component (c)”).

  Thereby, even if it is a low temperature hardening of 200 degrees C or less, the hardened | cured material excellent in adhesiveness and flux tolerance can be formed.

  The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

  (A) Although it does not restrict | limit especially as a component, The transmittance | permeability at the time of using i line | wire for the light source at the time of patterning is high, and the polyimide precursor which shows a hardened | cured material property also at the time of low temperature hardening below 200 degreeC is preferable.

  The component (a) preferably has a structural unit represented by the following formula (1). Thereby, the transmittance | permeability of i line | wire is high and a favorable hardened | cured material can be formed also at the time of low temperature hardening below 200 degreeC.

（式（１）中、Ａは下記式（２）で表される基であり、Ｂは芳香族環（例えば、ベンゼン環、ナフタレン環）を少なくとも１つ（好ましくは２〜４、より好ましくは２又は３）含む２価の有機基であり、Ｒ_１及びＲ_２は、それぞれ独立に水素原子又は１価の有機基である。）

(In the formula (1), A is a group represented by the following formula (2), and B is at least one aromatic ring (for example, benzene ring or naphthalene ring) (preferably 2 to 4, more preferably 2 or 3) a divalent organic group containing R ₁ and R ₂ each independently a hydrogen atom or a monovalent organic group.

（式（２）中、Ｙは、酸素原子又は硫黄原子（好ましくは酸素原子）である。）

(In Formula (2), Y is an oxygen atom or a sulfur atom (preferably an oxygen atom).)

The monovalent organic group of R ₁ and R _{2 in} the formula (1) is preferably a group represented by the following formula (3) or an alkyl group having 1 to 4 carbon atoms.

（式（３）中、Ｒ_３〜Ｒ_５は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基であり、ｍは１〜１０の整数（好ましくは２〜５の整数、より好ましくは２又は３）である。）

(In Formula (3), R < ₃ > -R < ₅ > is a hydrogen atom or a C1-C3 aliphatic hydrocarbon group each independently, m is an integer of 1-10 (preferably an integer of 2-5). , More preferably 2 or 3).)

Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 or 2) of R ₁ and R _{2 in} the formula (1) include methyl group, ethyl group, n-propyl group, 2-propyl group, n- A butyl group etc. are mentioned.

At least one of R ₁ and R ₂ in Formula (1) is preferably a group represented by Formula (3), and both are preferably groups represented by Formula (3).

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms (preferably 1 or 2) of R _{3 to} R _{5 in} the formula (3) include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. It is done. A methyl group is preferred.

  Examples of the divalent organic group containing at least one B aromatic ring of formula (1) include groups represented by the following formula (4), but are not limited thereto.

（式（４）中、Ｒ_６〜Ｒ_１３は、それぞれ独立に水素原子、１価の脂肪族炭化水素基又はハロゲン原子を有する１価の有機基である。）

(In formula (4), R _{6 to} R ₁₃ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent organic group having a halogen atom.)

Examples of the monovalent aliphatic hydrocarbon group represented by R _{6 to} R _{13 in} Formula (4) (preferably having 1 to 5 carbon atoms, more preferably 1 to 2 carbon atoms) include a methyl group, an ethyl group, and an n-propyl group. , 2-propyl group, n-butyl group and the like, and methyl group and ethyl group are preferable.

The monovalent organic group having a halogen atom (preferably a fluorine atom) represented by R _{6 to} R _{13 in} Formula (4) is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 5 carbon atoms). The number of carbon atoms is preferably 1 to 2), and examples thereof include a trifluoromethyl group.

A polyimide precursor having a structural unit represented by the formula (1) includes, for example, a tetracarboxylic dianhydride represented by the following formula (5) and a diamino compound represented by the following formula (6). -By reacting in an organic solvent such as methyl-2-pyrrolidone to obtain a polyamic acid, adding a compound represented by the following formula (7), reacting in an organic solvent and partially introducing an ester group Can be obtained.
The tetracarboxylic dianhydride represented by Formula (5) and the diamino compound represented by Formula (6) may be used individually by 1 type, and may combine 2 or more types.

（式（５）中、Ａは式（１）で定義した通りである。）

(In formula (5), A is as defined in formula (1).)

（式（６）中、Ｂは式（１）で定義した通りである。）

(In formula (6), B is as defined in formula (1).)

（式（７）中、Ｒ_１は式（１）で定義した通りである。ただし、Ｒ_１が水素原子の場合を除く。）

(In formula (7), R ₁ is as defined in formula (1), except for the case where R ₁ is a hydrogen atom.)

  The component (a) may have a structural unit other than the structural unit represented by the formula (1).

  Structural units other than the structural unit represented by Formula (1) may be used alone or in combination of two or more.

  The content of structural units other than the structural unit represented by the formula (1) is preferably less than 50 mol% with respect to all structural units of the component (a).

  In the component (a), the ratio of the carboxy group esterified with the group represented by the formula (3) with respect to all carboxy groups and all carboxy esters is preferably 50% or more, and 60 to 100% Is more preferable, and 70 to 90% is more preferable.

Although there is no restriction | limiting in particular in the molecular weight of (a) component, It is preferable that it is 10,000-200,000 in a number average molecular weight.
The number average molecular weight is determined by measuring by gel permeation chromatography and converting using a standard polystyrene calibration curve.

  The photosensitive resin composition of this invention contains (b) component. Thereby, since the possibility of hydrolysis is low and the hardened | cured material which cannot be easily deteriorated with a flux can be formed, the hardened | cured material with high flux tolerance can be obtained.

  Component (b) is a compound having an allyl group of 2 or more (preferably an integer of 2 to 4, more preferably 2 or 3) in order to improve the crosslinking density and photosensitivity and to suppress the swelling of the pattern after development. Preferably there is.

  The component (b) preferably has a heterocyclic ring.

  Examples of the heterocyclic ring (preferably having 3 to 20 ring forming atoms, more preferably 5 to 8 ring forming atoms) include a cyanuric acid ring, an isocyanuric acid ring, and a triazine ring.

  As the component (b), specifically, triallyl isocyanurate, triallyl cyanurate, 1,3,5-triallylhexahydro-1,3,5-triazine, BANI-M (Maruzen Petrochemical Co., Ltd., Product name), BANI-X (Maruzen Petrochemical Co., Ltd., product name), tetraallyloxyethane, diallylpropyl isocyanurate, diallyl 1,4-cyclohexanedicarboxylate, 9,9-bis (4-allyloxyphenyl) fluorene 2,2-bis (allyloxymethyl) -1-butanol, triallylamine, and the like, but are not limited thereto.

  (B) A component may be used individually by 1 type and may combine 2 or more types.

(B) As for content of a component, 1-50 mass parts is preferable with respect to 100 mass parts of (a) component. From a heat resistant viewpoint of hardened | cured material, More preferably, it is 5-50 mass parts, More preferably, it is 5-30 mass parts.
When it is within the above range, a practical relief pattern is likely to be obtained, and the post-development residue in the unexposed area is likely to be suppressed.

Examples of the component (c) include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives,
Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone,
Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone,
Benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal,
Benzoin derivatives such as benzoin and benzoin methyl ether, and 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) Oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione -2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl]-, 1- (0-acetyloxime), compounds such as the following formulae Although oxime ester etc. are mentioned preferably, it is not limited to these.

  In particular, oxime esters are preferable from the viewpoint of photosensitivity.

  (C) A component may be used individually by 1 type and may combine 2 or more types.

As for content of (c) component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, More preferably, it is 0.1-10 mass parts, More preferably, it is 0.1-0.1 mass parts. 5 parts by mass.
In the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern is easily obtained.

The photosensitive resin composition of the present invention may further contain (d) a solvent (hereinafter also referred to as “component (d)”).
As the component (d), a polar solvent that easily dissolves the component (a) is preferable. Examples of polar solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimityl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, N-dimethylmorpholine and the like.

（式中、Ｒ_２１〜Ｒ_２３は、それぞれ独立に、炭素数１〜１０のアルキル基である。） As the component (d), a compound represented by the following formula (8) can also be used.

_(Wherein, R 21 _{to R 23} are each independently an alkyl group having 1 to 10 carbon atoms.)

Examples of the alkyl group having 1 to 10 carbon atoms (preferably 1 to 3, more preferably 1 or 3) of R _{21 to} R ₂₃ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, A t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like can be given.

  Examples of the compound represented by the formula (8) include “KJCMPA-100” manufactured by KJ Chemicals Corporation.

(D) A component may be used individually by 1 type and may combine 2 or more types.
Although content of (d) component is not specifically limited, Generally, it is 50-1000 mass parts with respect to 100 mass parts of (a) component.

The photosensitive resin composition of the present invention may further contain another crosslinking agent.
Examples of other cross-linking agents include triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate.
Another crosslinking agent may be used individually by 1 type, and may combine 2 or more types.
When using another crosslinking agent, the content of the other crosslinking agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of component (a), and 0.3 More preferably, it is 10 mass parts.

  The photosensitive resin composition of the present invention may further contain a sensitizer, a coupling agent, a surfactant or a leveling agent, a rust inhibitor, a polymerization inhibitor, and a compound that generates radicals upon heating.

  As sensitizers, 7-N, N-diethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin, 3,3′-carbonylbis (7-N, N-diethylamino) coumarin, 3,3′-carbonylbis ( 7-N, N-dimethoxy) coumarin, 3-thienylcarbonyl-7-N, N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-N, N-methoxycoumarin, 3- (4′-methoxybenzoyl) Coumarin, 3,3′-carbonylbis-5,7- (dimethoxy) coumarin, benzalacetophenone, 4′-N, N-dimethylaminobenzalacetophenone, 4′-acetaminobenzal-4-methoxyacetophenone, dimethyl Aminobenzophenone, diethylaminobenzophenone (EAB), 4,4′-bis (N-ethyl, N-methyl) benzophenone (MEAB) and the like.

  A sensitizer may be used individually by 1 type and may combine 2 or more types.

  When using a sensitizer, 0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, 1-10 mass parts is more preferable, and, as for content of a sensitizer, 0.3-10 Part by mass is more preferable.

  Usually, in the heat treatment after development, the coupling agent itself is polymerized in the step of reacting with the polyimide precursor as the component (a) to be crosslinked or heat-treated. Thereby, the adhesiveness of the hardened | cured material obtained and a board | substrate can be improved more.

（式（９）中、Ｒ_１４及びＲ_１５は、それぞれ独立に炭素数１〜５のアルキル基である。ｋは、１〜１０の整数であり、ｊは、１〜３の整数である。） A preferable silane coupling agent includes a compound having a urea bond (—NH—CO—NH—). Thereby, also when it hardens | cures under the low temperature of 200 degrees C or less, adhesiveness with a board | substrate can further be improved.
A compound represented by the following formula (9) is more preferable in that it exhibits excellent adhesion when cured at low temperature.

(In Formula (9), R < ₁₄ > and R < ₁₅ > are respectively independently a C1-C5 alkyl group. K is an integer of 1-10 and j is an integer of 1-3. )

  Specific examples of the compound represented by the formula (9) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, preferably 3-ureidopropyltriethoxysilane.

As the silane coupling agent, a silane coupling agent having a hydroxy group or a glycidyl group may be used. When a silane coupling agent having a hydroxy group or glycidyl group and a silane coupling agent having a urea bond in the molecule are used in combination, the adhesion of the cured product to the substrate during low-temperature curing can be further improved.
Examples of the silane coupling agent having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert- Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenyl Silanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, Sobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, , 4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) Benzene, 1,4-bis (dipropyl hydroxy silyl) benzene, 1,4-bis (dibutyl hydroxy silyl) benzene, and compounds represented by the following formula (10) below. Especially, in order to improve adhesiveness with a board | substrate more, the compound represented by Formula (10) is preferable.

（式（１０）中、Ｒ_１６はヒドロキシ基又はグリシジル基を有する１価の有機基、Ｒ_１７及びＲ_１８はそれぞれ独立に炭素数１〜５のアルキル基である。ｉは１〜１０の整数、ｈは０〜２の整数である。）

(In Formula (10), R ₁₆ is a monovalent organic group having a hydroxy group or a glycidyl group, R ₁₇ and R ₁₈ are each independently an alkyl group having 1 to 5 carbon atoms. I is an integer of 1 to 10) , H is an integer of 0-2.)

  Examples of the compound represented by the formula (10) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyl Silane and the like.

The silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a nitrogen atom, and a silane coupling agent having an amino group or an amide bond is preferred.
Examples of the silane coupling agent having an amino group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, and bis (2-glycidoxy). And methyl) -3-aminopropyltriethoxysilane and bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane.

As the silane coupling agent having an amide bond, R ₃₆ — (CH ₂ ) _e —CO—NH— (CH ₂ ) _f —Si (OR ₃₇ ) ₃ (R ₃₆ is a hydroxy group or a glycidyl group, and e and f is an integer of 1 to 3 each independently, and R ₃₇ is a methyl group, an ethyl group or a propyl group).

  A silane coupling agent may be used individually by 1 type, and may combine 2 or more types.

  When a silane coupling agent is used, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (a), and 0.3 More preferably, it is 10 mass parts.

  By including the surfactant or the leveling agent, coating properties (for example, suppression of striation (film thickness unevenness)) and developability can be improved.

  Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. "F171", "F173", "R-08" (above, manufactured by DIC Corporation), trade names "Florard FC430", "FC431" (above, manufactured by 3M Japan), trade names "organosiloxane polymer KP341", “KBM303”, “KBM403”, “KBM803” (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  Surfactants and leveling agents may be used alone or in combination of two or more.

  When the surfactant or the leveling agent is included, the content of the surfactant or the leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the component (a). Preferably, 0.05 to 3 parts by mass is more preferable.

By containing a rust preventive agent, it is possible to suppress corrosion and discoloration of copper and copper alloy.
Examples of the rust inhibitor include triazole derivatives and tetrazole derivatives.
A rust preventive may be used individually by 1 type, and may combine 2 or more types.

  When using a rust preventive agent, 0.01-10 mass parts is preferable with respect to 100 mass parts of (a) component, 0.1-5 mass parts is more preferable, and 0.5- 3 parts by mass is more preferable.

By containing a polymerization inhibitor, good storage stability can be ensured.
Examples of the polymerization inhibitor include radical polymerization inhibitors and radical polymerization inhibitors.

  Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2- Examples include naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like.

  A polymerization inhibitor may be used individually by 1 type, and may combine 2 or more types.

  When the polymerization inhibitor is contained, the content of the polymerization inhibitor is 0 with respect to 100 parts by mass of component (a) from the viewpoint of the storage stability of the photosensitive resin composition and the heat resistance of the resulting cured product. 0.01 to 30 parts by mass is preferable, 0.01 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is even more preferable.

The shrinkage | contraction at the time of hardening can be suppressed by including the compound which generate | occur | produces a radical by heating.
Examples of compounds that generate radicals upon heating include organic peroxides.

  Specific examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexyl). Peroxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane and other peroxyketals, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide Hydroperoxides such as dicumyl peroxide, dialkyl peroxides such as di-t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, and di (4-t-butylcyclohexyl) peroxy Dicarbonate, di ( -Ethylhexyl) peroxydicarbonate such as peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxybenzoate, 1,1,3,3 -Peroxyesters such as tetramethylbutylperoxy-2-ethylhexanoate, bis (1-phenyl-1-methylethyl) peroxide and the like. Examples of commercially available products include “Percumml D”, “Percumyl P”, “Percumyl H” (manufactured by NOF CORPORATION) and the like.

  When using the compound which generate | occur | produces a radical by heating, 0.1-10 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for content of the compound which generate | occur | produces a radical by heating, 0.5-5 mass Part is more preferable, and 1 to 3 parts by mass is further preferable.

The photosensitive resin composition of the present invention is essentially the components (a) to (c), and optionally other crosslinking agents, sensitizers, and coupling agents, except for the solvent (component (d)). , A surfactant, a leveling agent, a rust inhibitor, a polymerization inhibitor, and a compound that generates radicals upon heating, and may contain other inevitable impurities as long as the effects of the present invention are not impaired.
Of the photosensitive resin composition of the present invention, for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more. Or 100% by weight, excluding the solvent (component (d))
(A) to (c) component, or (a) to (c) component, and optionally other crosslinking agents, sensitizers, coupling agents, surfactants, leveling agents, rust inhibitors, polymerization inhibitors, You may consist of the compound which generate | occur | produces a radical by heating.

The cured product of the present invention can be obtained by curing the above-described photosensitive resin composition.
The cured product of the present invention may be used as a pattern cured product or a cured product having no pattern.
As for the film thickness of the hardened | cured material of this invention, 5-40 micrometers is preferable.

In the method for producing a patterned cured product of the present invention, the above-described photosensitive resin composition is applied on a substrate and dried to form a photosensitive resin film, and the photosensitive resin film is subjected to pattern exposure to form a resin film. A step of obtaining the pattern resin film by developing the resin film after pattern exposure using an organic solvent, and a step of heat-treating the pattern resin film.
Thereby, a pattern hardened | cured material can be obtained.

  A method for producing a cured product having no pattern includes, for example, a step of forming the above-described photosensitive resin film and a step of heat treatment. Furthermore, you may provide the process of exposing.

Examples of the substrate include a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), a metal oxide insulator substrate such as a TiO ₂ substrate and a SiO ₂ substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

  Although there is no restriction | limiting in particular in the application method, It can carry out using a spinner etc.

Drying can be performed using a hot plate, an oven, or the like.
The drying temperature is preferably 90 to 150 ° C, and more preferably 90 to 120 ° C from the viewpoint of ensuring dissolution contrast.
The drying time is preferably 30 seconds to 5 minutes.
Drying may be performed twice or more.
Thereby, the photosensitive resin film which formed the above-mentioned photosensitive resin composition in the film form can be obtained.

  The film thickness of the photosensitive resin film is preferably 5 to 100 μm, more preferably 6 to 50 μm, and even more preferably 7 to 40 μm.

In pattern exposure, for example, a predetermined pattern is exposed through a photomask.
Actinic rays to be irradiated include ultraviolet rays such as i-rays, visible rays, and radiation, but i-rays are preferable.
As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine, or the like can be used.

By developing, a patterned resin film (pattern resin film) can be obtained. Generally, when the photosensitive resin composition is used, the unexposed portion is removed with a developer.
As the organic solvent used as the developer, a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be appropriately mixed as the developer.
Good solvents include N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, α-acetyl-gammabutyrolactone, cyclopentanone, cyclohexanone Etc.
Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and water.

  A surfactant may be added to the developer. The addition amount is preferably 0.01 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developer.

The development time can be set to, for example, twice the time until the photosensitive resin film is immersed and completely dissolved.
The development time varies depending on the component (a) to be used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 20 seconds to 5 minutes from the viewpoint of productivity.

You may wash | clean with a rinse solution after image development.
As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in combination as appropriate, or may be used in a stepwise combination. Good.

A patterned cured product can be obtained by heat-treating the pattern resin film.
The polyimide precursor of component (a) may undergo a dehydration ring-closure reaction by a heat treatment step to become a corresponding polyimide.

  When a compound that generates radicals by heating is included, by performing a heat treatment on the pattern resin film, a cross-linked structure is formed between the functional groups of component (b) or between component (a) and component (b), A pattern cured product may be obtained.

The temperature of the heat treatment is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., and further preferably 200 ° C. or lower or 160 to 200 ° C.
By being within the above range, damage to the substrate and the device can be suppressed, the device can be produced with a high yield, and energy saving of the process can be realized.

The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
By being within the above range, the crosslinking reaction or dehydration ring-closing reaction can sufficiently proceed.
The atmosphere for the heat treatment may be in the air or in an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the pattern resin film.

  Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

The cured product of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, or a surface protective film.
Using one or more selected from the group consisting of the above passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protective film, etc., a highly reliable semiconductor device, multilayer wiring board, various electronic devices, etc. Electronic parts and the like can be manufactured.

An example of a manufacturing process of a semiconductor device which is an electronic component of the present invention will be described with reference to the drawings.
FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure as an electronic component according to an embodiment of the present invention.
In FIG. 1, a semiconductor substrate 1 such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. It is formed. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film 4, and a window 6A is formed so that a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. Provided.

The interlayer insulating film 4 from which the window 6A is exposed is selectively etched to provide the window 6B.
Next, the photosensitive resin layer 5 is removed using an etching solution that does not corrode the first conductor layer 3 exposed from the window 6B and corrodes the photosensitive resin layer 5.

Further, the second conductor layer 7 is formed by using a known photolithography technique, and electrical connection with the first conductor layer 3 is performed.
When a multilayer wiring structure having three or more layers is formed, each of the layers can be formed by repeating the above-described steps.

Next, using the above-described photosensitive resin composition, the window 6C is opened by pattern exposure, and the surface protective film 8 is formed. The surface protective film 8 protects the second conductor layer 7 from external stress, α rays, etc., and the obtained semiconductor device is excellent in reliability.
In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

  Hereinafter, based on an Example and a comparative example, it demonstrates further more concretely about this invention. In addition, this invention is not limited to the following Example.

Synthesis Example 1 (Synthesis of A1)
7.07 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2′-dimethylbiphenyl-4,4′-diamine (DMAP) were added to N-methyl- The product was dissolved in 30 g of 2-pyrrolidone (NMP) and stirred at 30 ° C. for 4 hours and then at room temperature overnight to obtain polyamic acid. 9.45g of trifluoroacetic anhydride was added there under water cooling, and it stirred at 45 degreeC for 3 hours, and 7.08g of 2-hydroxyethyl methacrylate (HEMA) was added. This reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor A1.
The number average molecular weight was calculated | required on condition of the following by standard polystyrene conversion using the gel permeation chromatograph (GPC) method. The number average molecular weight of A1 was 35,000.

  Measurement was performed using a solution of 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)] with respect to 0.5 mg of A1.

Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm

  Moreover, the esterification rate of A1 (reaction rate of the carboxy group of ODPA with HEMA) was calculated by performing NMR measurement under the following conditions. The esterification rate was 80% with respect to all carboxy groups of the polyamic acid (the remaining 20% was carboxy groups).

Measuring instrument: AV400M manufactured by Bruker BioSpin
Magnetic field strength: 400MHz
Reference material: Tetramethylsilane (TMS)
Solvent: Dimethyl sulfoxide (DMSO)

Examples 1-10 and Comparative Examples 1-2
(Preparation of photosensitive resin composition)
Photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2 were prepared using the components and blending amounts shown in Table 1. The compounding quantity of Table 1 is a mass part of (b)-(d) component with respect to 100 mass parts of (a) component.

  Each component used is as follows. As component (a), A1 obtained in Synthesis Example 1 was used.

(B) Component B1: triallyl cyanurate (Tokyo Chemical Industry Co., Ltd., compound represented by the following formula B1)
B2: triallyl isocyanurate (Tokyo Chemical Industry Co., Ltd., compound represented by the following formula B2)

(B ′) Component B3: Tetraethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
B4: A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., a compound represented by the following formula B4)

(C) Component C1: NCI-930 (manufactured by ADEKA Corporation, O-acyloxime compound, compound represented by the following formula C1)

(D) Component D1: N-methyl-2-pyrrolidone D2: Compound represented by the following formula (“KJCMPA-100” manufactured by KJ Chemicals Co., Ltd.)

(Manufacture of patterned cured products)
The obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating apparatus Act8 (manufactured by Tokyo Electron Ltd.), dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to obtain a dried film. A photosensitive resin film having a thickness of 7 to 15 μm was formed.
The development time was set to twice the time required for the obtained photosensitive resin film to be immersed in cyclopentanone and completely dissolved.
In addition, a photosensitive resin film was prepared in the same manner as described above, and i-line stepper FPA-3000iW (manufactured by Canon Inc.) was used for the obtained photosensitive resin film, and i-line was applied at an irradiation amount of 500 mJ / cm ^2. Then, exposure was performed by irradiating a predetermined pattern.
The exposed resin film was subjected to paddle development on cyclopentanone with Act 8 using Act8, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.
The obtained pattern resin film was heated at 175 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo System Co., Ltd.), and a pattern cured product (film thickness after curing 10 μm) was obtained. Obtained.

(Evaluation of flux resistance)
Water-soluble flux WS-600 (manufactured by Arend Japan Co., Ltd.) was applied to the above-mentioned pattern cured product and heated at 245 ° C. for 1 minute on a hot plate. After cooling, it was washed with water heated to 60 ° C. to remove the flux and dried.
The film thickness of the pattern cured product after drying is measured, and the absolute value of (film thickness before flux immersion−film thickness of pattern cured product after drying) is divided by the film thickness before flux immersion to obtain a percentage. Thus, the film thickness change rate was calculated. The results are shown in Table 1.
Moreover, the pattern hardened | cured material after drying was observed with the optical microscope, and the damage of the pattern was evaluated. The case where there was no film roughening was indicated as “◯”, and the case where the film was roughened was indicated as “X”. The results are shown in Table 1.

(Adhesive evaluation)
The above-mentioned photosensitive resin composition was spin-coated on a copper substrate, dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to form a photosensitive resin film.
The obtained photosensitive resin film was exposed to 500 mJ / cm ² using a proximity exposure machine mask aligner MA8 (manufactured by SUSS Microtec).
The exposed resin film was heated at 173 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo System Co., Ltd.) to obtain a cured product (film thickness after curing: 10 μm). .
The obtained cured product is placed in a saturated pressure cooker apparatus (manufactured by Hirayama Seisakusho Co., Ltd.) and treated for 100 hours under a PCT (pressure cooker test) condition at a temperature of 121 ° C., a relative humidity of 100%, and 2 atm. Was taken out.

  Moreover, the hardened | cured material was created similarly to the above and PCT process was carried out except having made processing time of PCT conditions 200 hours, 300 hours, 400 hours, or 500 hours.

A sample piece obtained by cutting the cured product after PCT processing into 1 cm square is prepared, and an epoxy resin layer at the tip of an aluminum stud is fixed to the surface of the cured product, and heated in an oven at 150 ° C. for 1 hour for epoxy. The resin layer and the cured product were adhered. Then, using a thin film adhesion strength measuring apparatus ROMUS (manufactured by QUAD Group), the load was increased at 5 kg / min, the stud was pulled in the vertical direction, and the presence or absence of peeling was observed.
The case where the cured product was not peeled off from the copper substrate even after 500 hours of PCT treatment was marked as ◯. A case where the cured product was peeled off from the copper substrate after 300 hours, 400 hours, or 500 hours of the PCT treatment was evaluated as Δ. The case where the cured product was peeled off from the copper substrate in the PCT treatment for 100 hours or 200 hours was evaluated as x.
The results are shown in Table 1.

  The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer, or a surface protective film, and the interlayer insulating film, the cover coat layer, or the surface protective film of the present invention is used for an electronic component or the like. Can do.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film 5 Photosensitive resin layer 6A, 6B, 6C Window 7 2nd conductor layer 8 Surface protective film

Claims (11)

(A) a polyimide precursor;
(B) a compound having an allyl group;
(C) a photopolymerization initiator;
Containing a photosensitive resin composition. The photosensitive resin composition of Claim 1 in which the said (a) component has a structural unit represented by following formula (1).

(In formula (1), A is a group represented by the following formula (2), B is a divalent organic group containing at least one aromatic ring, and R ₁ and R ₂ are each independently It is a hydrogen atom or a monovalent organic group.)

(In Formula (2), Y is an oxygen atom or a sulfur atom.) The photosensitive resin composition according to claim 2, wherein R ₁ and R ₂ are each independently a hydrogen atom, a group represented by the following formula (3), or an alkyl group having 1 to 4 carbon atoms.

(In Formula (3), R < ₃ > -R < ₅ > is a hydrogen atom or a C1-C3 aliphatic hydrocarbon group each independently, and m is an integer of 1-10.)   The photosensitive resin composition according to claim 1, wherein the component (b) is a compound having two or more allyl groups.   The photosensitive resin composition according to claim 1, wherein the component (b) has a heterocyclic ring. Applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate and drying to form a photosensitive resin film;
Pattern exposure of the photosensitive resin film to obtain a resin film;
Developing the resin film after the pattern exposure using an organic solvent, and obtaining a pattern resin film;
And a step of heat-treating the pattern resin film.   The method for producing a patterned cured product according to claim 6, wherein the temperature of the heat treatment is 200 ° C. or less.   Hardened | cured material which hardened the photosensitive resin composition in any one of Claims 1-5.   The cured product according to claim 8, which is a pattern cured product.   An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured product according to claim 8 or 9.   An electronic component comprising the interlayer insulating film according to claim 10, a cover coat layer, or a surface protective film.

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