TW201841992A - Photosensitive resin composition, method for manufacturing pattern cured film, cured product, interlayer insulation film, cover coating layer, surface protective film, and electronic component - Google Patents

Abstract

Provided is a photosensitive resin composition containing: (a) a polyimide precursor; (b) a radically polymerizable compound having an aliphatic cyclic structure; and (c) a compound represented by formula (1). (In formula (1), R1 is an organic group represented by formula (2), R2 is a hydrogen atom or a C1-C10 alkyl group, and R3 is a C1-C3 alkyl group, a C1-C3 alkoxy group, or a C6-C10 aryl group. In formula (2), R4 is a monovalent organic group, X is a carbon atom, a sulfur atom, or a carbonyl group, and s is an integer of 0-5).

Description

Photosensitive resin composition, method for producing pattern cured film, cured product, interlayer insulating film, cover layer, surface protective layer, and electronic component

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

Conventionally, polyimide or polybenzoxazole, which has excellent heat resistance, electrical properties, and mechanical properties, has been used as a surface protection film and an interlayer insulating film of a semiconductor device. In recent years, a photosensitive resin composition that imparts photosensitive properties to these resins has been used. If the photosensitive resin composition is used, the manufacturing steps of the pattern cured film can be simplified, and complicated manufacturing steps can be shortened (for example, refer to Patent Document 1).

However, in recent years, miniaturization of transistors that have brought about high performance of computers has faced the limit of the law of proportionality. In order to further increase the performance or speed, it is considered that a technology of a three-dimensionally laminated semiconductor element is required. Based on this background, a three-dimensional package using Through Silicon Via (TSV), a 2.5-dimensional package using an interposer, or a 2.1-dimensional package are proposed, and the structure of the multilayer device represented by these packages has attracted attention (For example, refer to Non-Patent Document 1.)

In a multilayer device structure, a multi-die fanout wafer level package (Multi-die Fanout Wafer Level Packaging) is a package manufactured to seal multiple wafers in one package, and a previous package manufactured to seal one wafer in one package. Compared with the fan-out wafer-level package, it can be expected to be lower in cost and higher in performance, so it has attracted attention.

In addition, in the production of a multi-wafer fan-out wafer-level package, heat treatment at a high temperature cannot be performed from the viewpoint of protecting a high-performance wafer or protecting a sealing material with low heat resistance and improving the yield. Therefore, the polyimide precursor used as a redistribution forming layer for redistribution of copper is also strongly required for low-temperature curability (see Patent Document 2). However, when it is cured at a low temperature of 200 ° C or lower, it also has high adhesion to copper, which is difficult for a photosensitive resin composition using a polyimide precursor and cannot handle the package. Production.

Furthermore, from the standpoint of miniaturization and high integration of electronic devices, there is a demand for higher resolution of a pattern cured film formed by heating and curing a patterned resin film. There is a limit to high resolution (for example, Patent Document 3). [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2009-265520 [Patent Literature 2] International Publication No. 2008/111470 [Patent Literature 3] Japanese Patent Laid-Open No. 2010-266843 [Non-Patent Literature]

[Non-Patent Document 1] "Semiconductor Technology Yearbook 2013 Packaging / Installation", Nikkei Business Publications (BP) Co., Ltd., December 2012, p.41-50

An object of the present invention is to provide a photosensitive resin composition and a method for producing a pattern cured film using the photosensitive resin composition, a cured product, an interlayer insulating film, a cover layer, a surface protective film, and an electronic component. When the resin composition is cured at 200 ° C. or lower, a cured film exhibiting high adhesion to a copper substrate can also be obtained, and the resolution is excellent.

The inventors of the present invention conducted diligent research in view of the problems described above, and found that by combining a radically polymerizable compound having an aliphatic cyclic structure and a compound having a specific structure in a polyimide precursor, Both the resolution and the coherence are taken into consideration, and the present invention has been completed.

According to the present invention, the following photosensitive resin composition and the like are provided. A photosensitive resin composition comprising: (a) a polyimide precursor; (b) a radical polymerizable compound having an aliphatic cyclic structure; and (c) represented by the following formula (1) compound of. [Chemical 1] (In formula (1), R ¹ is an organic group represented by the following formula (2), R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ³ is an alkyl group or carbon having 1 to 3 carbon atoms. Alkoxy having 1 to 3 or aryl having 6 to 10 carbons] [Chemical 2] (In the formula (2), R ⁴ is a monovalent organic group, X is an oxygen atom, a sulfur atom, or a carbonyl group, and s is an integer of 0 to 5.) 2. The photosensitive resin composition according to 1, wherein ( a) The component is a polyimide precursor having a structural unit represented by the following formula (3). [Chemical 3] (In formula (3), A is a tetravalent organic group represented by the following formula (4), B is a divalent organic group containing at least one aromatic ring, and R ⁵ and R ⁶ are each independently a hydrogen atom or a Valent organic group) (In formula (4), Y is an oxygen atom or a sulfur atom) 3. The photosensitive resin composition according to 2, wherein R ⁵ and R ^{6 in} the formula (3) are each independently a hydrogen atom, and the following A group represented by formula (5) or an alkyl group having 1 to 4 carbon atoms. [Chemical 5] (In formula (5), R ⁷ to R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m is an integer of 1 to 10) 4. The photosensitivity according to any one of 1 to 3 The (b) component contains a radical polymerizable compound having two or more radical polymerizable groups and an aliphatic cyclic structure. 5. The photosensitive resin composition according to any one of 1 to 4, wherein the component (b) contains a group selected from the group consisting of tricyclodecane, adamantane, cyclohexane, and norbornene. A radically polymerizable compound having one or more of these structures. 6. A method for producing a pattern cured film, comprising: a step of applying a photosensitive resin composition according to any one of 1 to 5 on a substrate and drying the photosensitive resin composition to form a photosensitive resin film; A step of pattern-exposing the photosensitive resin film; a step of developing a patterned resin film by developing the resin film subjected to the pattern exposure using an organic solvent; and a step of heating the patterned resin film. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 5. 8. An interlayer insulating film, a cover layer, or a surface protective film, which is manufactured using the hardened body according to 7. 9. An electronic component having the interlayer insulating film, the cover layer, or the surface protective film according to 8.

According to the present invention, it is possible to provide a photosensitive resin composition and a method for producing a pattern cured film using the photosensitive resin composition, a cured product, an interlayer insulating film, a cover layer, a surface protective film, and an electronic component. When the resin composition is cured at 200 ° C. or lower, a cured film exhibiting high adhesion to a copper substrate can also be obtained, and the resolution is excellent.

Hereinafter, the form for implementing this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. In this specification, "A or B" may include any one of A and B, and may include both. In addition, in this specification, the term "step" includes not only an independent step, but even if it cannot be clearly distinguished from other steps, as long as the desired effect of the step is achieved, it may be included in the term. The numerical ranges shown using "~" are ranges in which the numerical values described before and after "~" are included as the minimum and maximum values, respectively. In addition, in this specification, regarding the content of each component in the photosensitive resin composition, when there are many kinds of substances corresponding to each component in the photosensitive resin composition, unless otherwise specified, it means that it is present in the photosensitive resin composition. The total amount of the plurality of substances in the resin composition. Furthermore, the exemplified materials may be used alone or in combination of two or more of them unless otherwise specified. "(Meth) acrylic acid" means "methacrylic acid" or "acrylic acid".

[Photosensitive resin composition] The photosensitive resin composition of the present invention includes (a) a polyimide precursor, (b) a radical polymerizable compound having an aliphatic cyclic structure, and (c) the following formula (1) ). [Chemical 6] (In formula (1), R ¹ is an organic group represented by the following formula (2), R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ³ is an alkyl group or carbon having 1 to 3 carbon atoms. Alkoxy having 1 to 3 or aryl having 6 to 10 carbons) [Chem. 7] (In formula (2), R ⁴ is a monovalent organic group, X is an oxygen atom, a sulfur atom, or a carbonyl group, and s is an integer of 0 to 5)

The photosensitive resin composition of the present invention exhibits a high resolution by including the above-mentioned components, and therefore can form a fine pattern, and can be preferably used for further miniaturization of a semiconductor expected in the future. In addition, high adhesion between the cured film and the substrate can be achieved. In particular, by providing hydrophobicity to the cured film, excellent adhesion can be exhibited even under high temperature and humidity conditions. The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

Hereinafter, each component used in a photosensitive resin composition is demonstrated. Each component may be abbreviated as (a) component, (b) component, and (c) component.

((A) Component: Polyimide precursor) The polyimide precursor is not particularly limited, and it is preferable that the i-rays used as the light source during patterning have high transmittance and low-temperature curing at 200 ° C or lower. It also shows high cured film characteristics. Therefore, a polyfluorene imide precursor having a structural unit represented by the following formula (3) is preferred. [Chemical 8] (In formula (3), A is a tetravalent organic group represented by the following formula (4), B is a divalent organic group containing at least one aromatic ring, and R ⁵ and R ⁶ are each independently a hydrogen atom or a Valent organic group) (In formula (4), Y is an oxygen atom or a sulfur atom)

Examples of the monovalent organic group represented by R ⁵ and R ^{6 in} the formula (3) include a monovalent organic group represented by the following formula (5) or an alkyl group having 1 to 4 carbon atoms. [Chemical 10] (In formula (5), R ⁷ to R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m is an integer of 1 to 10)

In formula (5), R ⁷ and R ^{8 are} preferably hydrogen atoms, R ^{9 is} preferably an alkyl group having 1 to 3 carbon atoms (preferably methyl), and m is preferably an integer of 1 to 3 (compared with Preferably 2).

In the formula (3), as the divalent organic group containing at least one aromatic ring of B, a structure represented by the following formula (6) can be mentioned. [Chemical 11] (In formula (6), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a monovalent hydrocarbon group, or a monovalent organic group having a halogen atom.)

Examples of the monovalent hydrocarbon group in the formula (6) include an alkyl group having 1 to 4 carbon atoms, and examples of the monovalent organic group having a halogen atom include a halogenated alkyl group having 1 to 4 carbon atoms. R ¹⁰ to R ¹⁷ are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. For example, R ¹⁰ and R ¹³ to R ^{17 may} be hydrogen atoms, and R ¹¹ and R ^{12 may} be 1 to carbon atoms. 4 alkyl (eg methyl).

The polyfluorene imide precursor having a structural unit represented by the formula (3) can be obtained by using, for example, a tetracarboxylic dianhydride represented by the following formula (7) and a diamine compound represented by the following formula (8). As raw materials to manufacture. [Chemical 12] (In formula (7), A is the same as A in formula (3); in formula (8), B is the same as B of formula (3))

Specifically, the polyfluorene imide precursor (polyamino acid) can be obtained by dissolving a tetracarboxylic dianhydride represented by Formula (7) and a diamine compound represented by Formula (8) in an organic solvent (for example, N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamidamine, dimethylsulfinium, etc.). In addition, the obtained polyfluorenic acid is modified into isofluorenimine using a catalyst such as trifluoroanhydride, and then an appropriate amount of an alcohol represented by the following formula (9) or formula (10) is added, and the The reaction is performed in an organic solvent to introduce an ester group and perform esterification, thereby obtaining at least one of R ⁵ and R ⁶ in formula (3) as a monovalent organic group represented by formula (5) or a carbon number of 1 to 4-alkyl polyimide precursor. (In formula (9), R ¹⁸ is an alkyl group having 1 to 4 carbons; in formula (10), m, R ⁷ to R ⁹ are the same as R ⁷ to R ^{9 in} formula (5))

Examples of the alkyl group having 1 to 4 carbon atoms of R ¹⁸ include methyl, ethyl, n-propyl, isopropyl, and n-butyl.

In the polyfluorene imide precursor having the structural unit represented by the formula (3), all of R ⁵ and R ⁶ are introduced into the monovalent organic group represented by the formula (5) by the esterification. The ratio (esterification rate) is preferably 50 mol% to 90 mol%, and more preferably 70 mol% to 90 mol%. The esterification ratio was calculated by nuclear magnetic resonance (NMR) measurement.

A polyimide precursor having a structural unit represented by the formula (3) may have a structural unit other than the structural unit represented by the formula (3) in a part thereof. In this case, the proportion is preferably less than 50 mol% in all the structural units.

The molecular weight of the polyfluorene imide precursor of the component (a) is not particularly limited, but is preferably 10,000 to 200,000 in terms of the number average molecular weight. The number average molecular weight is measured by a gel permeation chromatography (GPC), and is calculated by polystyrene conversion.

((B) component: a radically polymerizable compound having an aliphatic cyclic structure) (b) the component is a radically polymerizable compound, and preferably contains one or more polymerizable compounds that can be polymerized by a photopolymerization initiator. A group of unsaturated double bonds (such as (meth) acrylic). The number of the group having a polymerizable unsaturated double bond is preferably two or more, and preferably three or less. If it is this range, when a crosslinking structure is formed, a crosslinking density will be moderate, a favorable light sensitivity can be acquired, and the swelling of the pattern after image development can be suppressed.

Examples of the aliphatic cyclic structure include tricyclodecane, adamantane, cyclohexane, and norbornene. The component (b) is preferably a compound having at least one structure selected from these.

As the component (b), compounds represented by the following formulae (11) to (14) can be used. [Chemical 13] In the formulae (11) to (14), R ¹⁹ to R ²² are each independently an aliphatic group having 1 to 4 carbon atoms or a monovalent organic group represented by the following formula (15). a is an integer from 1 to 6 (preferably an integer from 1 to 3), b is an integer from 1 to 12 (preferably an integer from 1 to 3), and c is an integer from 1 to 16 (preferably from 1 to 3) Is preferably an integer of 2), and d is an integer of 1 to 16 (preferably an integer of 1 to 3, more preferably 2). Each compound represented by Formula (11) to Formula (14) has at least one (preferably two or three) monovalent organic group represented by Formula (15). In addition, R ¹⁹ to R ²² may be bonded to all possible substitution positions in each compound represented by Formula (11) to Formula (14). [Chemical 14] (In formula (15), R ²⁹ to R ³¹ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (preferably a methyl group), and l is an integer of 0 to 10 (preferably 0 or 1). )

The photosensitive resin composition of the present invention may contain a radical polymerizable compound other than a radical polymerizable compound having an aliphatic cyclic structure. Examples of the compound include tetraethylene glycol dimethacrylate.

The addition amount of the component (b) in the photosensitive resin composition is usually 1 to 50 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 parts by mass based on 100 parts by mass of the (a) component. Parts to 30 parts by mass. If it is 1 part by mass to 50 parts by mass, the crosslinking density during photopolymerization is moderate, so that the swelling of the pattern after development can be suppressed, and a practical relief pattern can be obtained. In addition, it can effectively improve the hydrophobicity of the cured film. Furthermore, the influence on the unexposed portion caused by the scattered light from the substrate surface during exposure can be reduced, and the generation of residues after development in the unexposed portion can be suppressed.

(Component (c): compound represented by formula (1)) The compound represented by formula (1) used as component (c) usually generates radicals by light and is used as a light source for patterning I-ray with high sensitivity. [Chemical 15] (In formula (1), R ¹ is an organic group represented by the following formula (2), R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ³ is an alkyl group or carbon having 1 to 3 carbon atoms. Alkoxy having 1 to 3 or aryl having 6 to 10 carbons] [Chem. 16] (In formula (2), R ⁴ is a monovalent organic group, X is an oxygen atom, a sulfur atom, or a carbonyl group, and s is an integer of 0 to 5)

In formula (1), R ^{2 is} preferably an alkyl group having 1 to 10 carbon atoms (preferably 1 to 8), and more preferably a methyl group or a hexyl group. R ^{3 is} preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group or a phenyl group. In the formula (2), X is preferably a sulfur atom. R ^{4 is} preferably a hydroxyalkoxy group having 1 to 4 carbon atoms. s is preferably 0 or 1. In addition, the formula (2) may be a group represented by the following formula (2 '). [Chemical 17]

The photosensitive resin composition of the present invention may include a compound that generates a radical by light other than the compound represented by the formula (1). Examples of such a compound include dibenzophenone, methyl benzophenylidenebenzoate, 4-benzylidene-4'-methyldiphenylketone, dibenzylketone, and fluorenone. Acetophenone derivatives; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone; thioanthone, Derivatives of thioanthrone such as 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; Benzophenone, Benzophenone dimethylketal, Benzophenone -Benzozone derivatives such as β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether; 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-benzoylfluorenyl) oxime, 1,3-diphenylglycerone-2- (o-ethoxycarbonyl) oxime, 1-phenyl- The oxime esters such as 3-ethoxyglycerone-2- (o-benzoylfluorenyl) oxime and the like are not limited thereto.

The addition amount of the component (c) in the photosensitive resin composition is usually 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.1 part by mass based on 100 parts by mass of the (a) component. Parts to 5 parts by mass. When it is 0.1 to 20 parts by mass, the absorption amount of the exposure light near the surface of the coating film is moderate, and the exposure light sufficiently reaches the substrate. Therefore, light-crosslinking can be performed uniformly in the film thickness direction, and a good relief pattern can be obtained.

In the photosensitive resin composition of the present invention, for example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, 99.5% by mass or 99.9% by mass or more may be (a) Component-(c) component, the solvent mentioned later, and any other components. The photosensitive resin composition of the present invention may essentially include the components (a) to (c), a solvent described later, and any other components. In this case, unavoidable impurities may be contained. Moreover, the photosensitive resin composition of this invention may contain only (a) component-(c) component, the solvent mentioned later, and any other components.

The photosensitive resin composition of the present invention contains, in addition to the components (a) to (c), (1) a solvent, (2) a coupling agent, (3) a surfactant or a leveling agent, and (4) ) Rust inhibitors, (5) polymerization inhibitors, (6) compounds that generate free radicals by heating, etc. Hereinafter, each component is demonstrated.

((1) Solvent) The solvent is preferably a polar solvent from the viewpoint of dissolving the polyfluorene imide precursor as the component (a). Examples of the polar solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamidamine, N, N-dimethylformamidine, dimethylsulfine, tetramethylene Methyl urea, trimethylamine hexamethyl phosphate, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene glycol carbonate, Ethyl lactate, 1,3-dimethyl-2-imidazolidone, and the like.

((2) Coupling agent (compounds other than (b) component)) As for the coupling agent, the photosensitive resin composition is usually coated, exposed, and developed, and then used as a component (a) in a heat treatment step. The polyfluorene imide precursor reacts for crosslinking, or the coupling agent itself polymerizes. This can further improve the adhesion between the cured film and the substrate. In addition, by using a silane coupling agent having a urea bond (-NH-CO-NH-) in the molecule, the adhesiveness with the substrate can be further improved even when the curing is performed at a low temperature of 200 ° C or lower.

The silane coupling agent having a urea bond is more preferably a compound represented by the following formula (20) in terms of excellent adhesion development when curing at a low temperature. [Chemical 18] (In formula (20), R ³² and R ³³ are each independently an alkyl group having 1 to 5 carbon atoms; k is an integer of 1 to 10, and j is an integer of 1 to 3)

Specific examples of the compound represented by the formula (20) include urethanemethyltrimethoxysilane, urethanemethyltriethoxysilane, 2-ureaethyltrimethoxysilane, and 2-ureaethyltriethyl Oxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 4-ureabutyltrimethoxysilane, 4-ureabutyltriethoxysilane, etc., preferably 3-Ureapropyltriethoxysilane.

In addition to the silane coupling agent having a urea bond, when a silane coupling agent having a hydroxyl group or a glycidyl group is used in combination, it is further effective in improving the adhesion of the cured film to the substrate during low-temperature curing. Examples of the silane coupling agent having a hydroxyl group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n- Butylphenylsilanediol, isobutylphenylsilanediol, third butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenyl Silanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, third butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethyl Isopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, third butylethylphenylsilanol, methyldiphenylsilanol, ethyldiyl Phenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, third butyldiphenylsilanol , Phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis ( Dihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) ) Benzene, 1,4-bis (dibutylhydroxysilyl) benzene and the like or a compound represented by the following formula (21). [Chemical 19] (In formula (21), R ³⁴ is a monovalent organic group having a hydroxyl group or a glycidyl group, R ³⁵ and R ³⁶ are each independently an alkyl group having 1 to 5 carbon atoms; i is an integer of 1 to 10, and h is An integer from 0 to 2)

Among the silane coupling agents having a hydroxyl group or a glycidyl group, a compound represented by the formula (21) is more preferred from the viewpoint of further improving the adhesion to the substrate. Examples of such a silane coupling agent include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, and 3- Hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidyloxymethyltrimethoxysilane , Glycidyloxymethyltriethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxy Silane, 3-glycidyloxypropyltriethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltriethoxysilane, etc.

The silane coupling agent having a hydroxyl group or a glycidyl group is preferably a silane coupling agent having a group containing a nitrogen atom together with a hydroxyl group or a glycidyl group, specifically, an amine group or an amidine bond. Examples of the silane coupling agent having an amine group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, and bis (2-hydroxymethyl) -3-aminopropyltrimethoxy Silyl, bis (2-glycidyloxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, and the like. Examples of the silane coupling agent having a amide bond include a silane coupling agent having a amide bond, such as a compound represented by the following formula. Z- (CH ₂ ) _e -CO-NH- (CH ₂ ) _f -Si (OR ³⁷ ) ₃ (where Z is a hydroxyl group or a glycidyl group, e and f are each independently an integer of 1 to 3, R ³⁷ is methyl, ethyl or propyl)

The content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 0.3 to 10 parts by mass based on 100 parts by mass of the component (a).

((3) Surfactant or leveling agent) By adding a surfactant or leveling agent to the photosensitive resin composition, coating properties (such as suppression of streaks (unevenness in film thickness)) and development can be improved. Sex. Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like as commercially available products. Examples include "Megafac F171", "F173", "R-08" (above, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), trade names "Fluorad FC430", and "FC431" "(Above, manufactured by Sumitomo 3M Co., Ltd.), trade names" organic siloxane polymer KP341 "," KBM303 "," KBM403 "," KBM803 "(above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) )Wait.

The content of the surfactant or leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.05 to 3 parts by mass, with respect to 100 parts by mass of the component (a). Parts by mass.

((4) Rust inhibitor) By adding a rust inhibitor, it is possible to prevent corrosion and discoloration of copper and copper alloys. Examples of the rust inhibitor include triazole derivatives and tetrazole derivatives. The content when the rust inhibitor is used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the component (a). .

((5) Polymerization inhibitor) By including a polymerization inhibitor (radical polymerization inhibitor, radical polymerization inhibitor), good storage stability can be ensured. Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, and o-dinitrobenzene , P-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, cupferron, 2,5-methylbenzoquinone (2,5-toluquinone), Dan Ninamic acid, p-benzylaminophenol, nitrosoamines, etc.

The content of the polymerization inhibiting agent is preferably from 0.01 to 30 parts by mass relative to 100 parts by mass of the component (a) from the viewpoint of the storage stability of the photosensitive resin composition and the heat resistance of the obtained cured film. Parts, more preferably 0.01 parts by mass to 10 parts by mass, and even more preferably 0.05 parts by mass to 5 parts by mass.

((6) Compounds that generate radicals by heating) By including compounds that generate radicals by heating, it is possible to suppress shrinkage of the photosensitive resin composition when curing. Examples of the compound that generates a radical upon heating include organic peroxides. Specific examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide, and 1,1-bis (third hexylperoxy) -3,3,5-trimethylcyclohexyl. Peroxal ketals such as alkane, 1,1-bis (third hexylperoxy) cyclohexane, 1,1-bis (third butylperoxy) cyclohexane; 1,1,3,3-tetramethyl Hydroperoxides such as butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide; dialkyl peroxides such as dicumyl peroxide, di-third butyl peroxide Dioxinyl peroxides, such as dilauryl fluorenyl peroxide, dibenzyl fluorenyl peroxide; bis (4-third butylcyclohexyl) peroxydicarbonate, bis (2-ethylhexyl) ) Peroxydicarbonates such as peroxydicarbonate; third butylperoxy-2-ethylhexanoate, third hexylperoxyisopropyl monocarbonate, third butylperoxybenzoate , 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and other peroxyesters. Examples of commercially available products include "Percuml D", "Percumyl P", and "Percumy H" (above, manufactured by Nippon Oil Corporation), etc. .

The content of the compound that generates a radical by heating is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 part by mass with respect to 100 parts by mass of the component (a). ~ 3 parts by mass.

[Manufacturing method of pattern cured film] The pattern cured film can be manufactured by a manufacturing method including a step of forming a photosensitive resin film by applying the photosensitive resin composition of the present invention on a substrate and drying the photosensitive resin composition. A step of pattern-exposing the photosensitive resin film; a step of developing the pattern-exposed resin film using an organic solvent to form a pattern resin film; and a step of performing a heat treatment on the pattern resin film. Each step will be described below.

(Step of Forming Photosensitive Resin Film) Examples of raw materials for the substrate include glass; semiconductors; metal oxide insulators such as TiO ₂ and SiO ₂ ; silicon nitride; copper; copper alloys; The coating method is not particularly limited and can be performed using a spinner or the like.

Drying can be performed using a hot plate, an oven, or the like. The heating temperature is preferably 90 ° C to 150 ° C, and more preferably 90 ° C to 120 ° C from the viewpoint of ensuring the dissolution contrast. The heating time is preferably 30 seconds to 5 minutes. Thereby, the photosensitive resin film which formed the photosensitive resin composition of this invention into a film shape can be obtained. The film thickness of the photosensitive resin film is preferably 5 μm to 100 μm, more preferably 5 μm to 50 μm, and even more preferably 5 μm to 30 μm.

(Exposure Step) In the exposure step, exposure can be performed in a predetermined pattern through a mask. Examples of actinic rays to be irradiated include ultraviolet rays, visible rays, and radiation including i rays, and i rays are preferred. As an exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanning exposure machine, etc. can be used.

(Developing Step) By subjecting the obtained resin film to a developing process, a patterned resin film (patterned resin film) can be obtained. When a negative-type photosensitive resin composition is used, the unexposed part is usually removed with a developing solution. Examples of the developing solution include an organic solvent, and a good solvent may be used alone or a good solvent and a poor solvent may be appropriately mixed and used. As a good vehicle, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide , Dimethyl sulfene, γ-butyrolactone, α-ethylfluorenyl-γ-butyrolactone, cyclopentanone, cyclohexanone, etc. As the poor solvent, toluene, xylene, methanol, ethanol, Propanol, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether and water.

The development time varies depending on the type of the (a) component used, but it is preferably from 10 seconds to 15 minutes, more preferably from 10 seconds to 15 minutes, and from the viewpoint of productivity, more preferably from 20 seconds to 5 minutes. .

A surfactant may also 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 based on 100 parts by mass of the developer.

After the development is completed, the developing solution is removed by washing with the eluent to obtain a patterned resin film. As the eluent, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or the like may be used alone or in a suitable mixture, or may be used in combination in stages.

(Heat treatment step) By subjecting the pattern resin film to heat treatment, a pattern cured film can be obtained. (A) The component is a polyfluorene imide precursor, and therefore, a dehydration ring-closing reaction can be caused by a heat treatment step, thereby preparing a corresponding polyfluorene imine.

In addition, when the photosensitive resin composition includes the compound (6) which generates a radical by heating, the pattern resin film may be subjected to a heat treatment, and the functional groups of the component (b) may be added to each other, or ( A crosslinked structure is formed between the a) component and the (b) component, etc., thereby obtaining a pattern cured film.

The heating temperature is preferably 250 ° C or lower, more preferably 120 ° C to 250 ° C, and even more preferably 160 ° C to 200 ° C. By being within the above range, it is possible to suppress damage to the substrate or the device to be small, to produce the device with a good yield, and to save energy in the manufacturing process.

The heating time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. By being in the range, a crosslinking reaction or a dehydration ring-closing reaction can be sufficiently performed. The heat treatment environment may be in the air or in an inert environment such as nitrogen. From the viewpoint of preventing the pattern resin film from being oxidized, the environment is preferably a nitrogen environment.

Examples of the device used in the heat treatment step include a quartz tube furnace, a heating plate, a rapid annealing furnace, a vertical diffusion furnace, an infrared hardening furnace, an electron beam hardening furnace, and a microwave hardening furnace.

[Hardened product] By applying the heat treatment step to the photosensitive resin composition of the present invention, a hardened product can be obtained. The hardened | cured material of this invention may be the said pattern hardened film, and may be a hardened film which does not have a pattern.

[Electronic Parts] The pattern cured film or cured product can be used as an interlayer insulating film, a cover layer, or a surface protective film. By using this interlayer insulating film, a cover layer, a surface protective film, etc., electronic components such as semiconductor devices, multilayer wiring boards, and various electronic devices with high reliability can be manufactured.

[Manufacturing Process of Semiconductor Device] An example of a manufacturing process of a semiconductor device as 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. 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 and the like except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. Thereafter, the spin-coating method is used to form an interlayer insulating film 4 on the semiconductor substrate 1.

Next, a photosensitive resin film 5 such as a chlorinated rubber system, a phenol novolak system, or the like is formed on the interlayer insulating film 4 by a spin coating method, and a predetermined portion of the interlayer insulating film 4 is formed by a known photo etching technique. A window 6A is provided in an exposed manner. The interlayer insulating film 4 exposed on the window 6A is selectively etched by a dry etching method using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin film 5 is removed using an etching solution that does not corrode the first conductive layer 3 exposed from the window 6B and only etches the photosensitive resin film 5.

Furthermore, the second conductive layer 7 is formed using a well-known photo etching technique, and electrical connection with the first conductive layer 3 is performed. In the case of forming a multilayer wiring structure of three or more layers, the above steps can be repeated to form each layer.

Then, a surface protection film 8 is formed. In the example shown in FIG. 1, the photosensitive resin composition of the present invention is applied by a spin coating method, dried, and irradiated with light from a mask depicting a pattern forming a window 6C on a predetermined portion, and then developed by an organic solvent to form It is patterned and heated to form a surface protection film 8. The surface protection film 8 protects the conductor layer from external stress, alpha rays, and the like, and the obtained semiconductor device has excellent reliability. Furthermore, in the above-mentioned example, the photosensitive resin composition of the present invention may be used to form the interlayer insulating film 4. Examples

Hereinafter, the present invention will be described more specifically based on examples and comparative examples. The present invention is not limited to the following examples.

Synthesis Example 1 [(a) Component: Synthesis of polyimide precursor a1] 7.07 g of 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) was dissolved in 30 g of N-methyl-2-pyrrolidone (NMP), and stirred at 30 ° C for 4 hours, and thereafter , And stirred at room temperature overnight to obtain polyamic acid. Under water cooling, 9.45 g of trifluoroacetic anhydride was added thereto, stirred at 45 ° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a target polyfluorene imine precursor (polyamino acid derivative) a1. The number average molecular weight of the polyfluorene imide precursor a1, which is calculated by GPC standard polystyrene conversion, is 35,000. In addition, the esterification rate by HEMA calculated by NMR measurement was 80 mol% (the remaining 20 mol% was a carboxyl group). The measurement conditions for NMR measurement are as follows. Measuring equipment: "AV400M" manufactured by Bruker BioSpin Company Magnetic field strength: 400 MHz Reference material: Tetramethylsilane (TMS) Solvent: Dimethyl sulfonium (DMSO)

The measurement conditions of the number average molecular weight obtained by GPC method standard polystyrene conversion are as follows. The 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 the polyfluorene imide precursor a1. Measuring device: Detector L4000UV manufactured by Hitachi Manufacturing Co., Ltd .: L6000 manufactured by Hitachi Manufacturing Co., Ltd. C-R4A Chromatopac manufactured by Shimadzu Manufacturing Co., Ltd. Measuring conditions: Gelpack GL-S300MDT-5 × 2 roots : 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

Examples 1 to 6 and Comparative Examples 1 to 2 [Preparation of photosensitive resin composition] Examples 1 to 6 and Comparative Examples 1 to Comparative Examples were prepared using the components and blending amounts shown in Table 1. 2 is a photosensitive resin composition. This photosensitive resin composition is a negative type. The compounding quantity of Table 1 is a mass part of each component with respect to 100 mass parts of (a) component. The components used are as follows.

<(A) component: polyimide precursor> × a1: polyimide precursor a1 obtained in Synthesis Example 1

<(B) component: radical polymerizable compound having an aliphatic cyclic structure> × b1: tricyclodecane dimethanol diacrylate (made by Shin Nakamura Chemical Industry Co., Ltd., trade name "A-DCP", below A compound represented by the formula) × b2: Adamantane-1,3-diacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "ADDA", compound represented by the following formula) [Chem. 21]

<(B ') component> × b'1: Tetraethylene glycol dimethacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "TEGDMA", compound represented by the following formula) [Chem. 22]

<(C) component: compound represented by formula (1)> × c1: compound represented by the following formula (manufactured by ADEKA Corporation, trade name "NCI-930") [Chem. 23] × c2: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzylidene oxime)] (manufactured by BASF Japan, trade name "IRUGCUREOXE 01 ", a compound represented by the following formula) [Chem. 24] <(C ') component> × c'1: Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- ( O-acetylamoxime) (manufactured by BASF Co., Ltd., trade name "IRUGCUREOXE 02", compound represented by the following formula) [Chem. 25]

<Solvent> × NMP

The (b ') component refers to a component different from the (b) component used in the present invention, and the (c') component refers to a component different from the (c) component used in the present invention .

[Evaluation of Photosensitive Resin Composition] The following evaluations were performed on the photosensitive resin composition obtained in Examples 1 to 6 and Comparative Examples 1 to 2. The results are shown in Table 1.

<Evaluation of resolution> A photosensitive resin composition was spin-coated on a silicon substrate using a coating device (manufactured by Tokyo Electronics Co., Ltd., "Act8"), dried at 100 ° C for 2 minutes, and then dried at 110 ° C. In 2 minutes, a photosensitive resin film having a dry film thickness of 7 μm to 15 μm was formed. The obtained photosensitive resin film was exposed using an i-ray stepper (manufactured by Canon Co., Ltd., trade name "FPA-3000iW") (exposure amount: 400 mJ / cm ² ). When an unexposed photosensitive resin film of the same thickness is immersed in cyclopentanone, twice the time until complete dissolution is set as the development time, and the exposed resin film is immersed in cyclopentanone and covered. Liquid development and rinsing with PGMEA to obtain a patterned resin film. With respect to the obtained patterned resin film, the smallest diameter capable of being patterned without peeling or residue in the pattern of the circular hole shape was set as the resolution.

<Evaluation of Residual Film Rate> For a pattern resin film obtained by the same method as that of <Resolution Evaluation>, the residual film rate (remaining film rate after development) was calculated by the following formula. Residual film rate after development = (film thickness after development / film thickness before exposure) × 100

The patterned resin film was subjected to heat treatment under a nitrogen atmosphere at 175 ° C. for 1 hour in a vertical diffusion furnace (manufactured by Thermo System Co., Ltd.) to produce a patterned cured film. For the obtained pattern cured film, the residual film ratio (remaining film ratio after curing) was calculated by the following formula. Residual film rate after curing = (Film thickness after curing / Film thickness before exposure) × 100

Regarding the film thickness before exposure, the film thickness after development, and the film thickness after curing, the substrate was exposed by scrubbing a resin film or a part of the cured film, and a pin profiler (Ulvac Corporation Limited) Manufactured by the company under the trade name "Dektak 150") to measure the height from the exposed substrate surface to the film surface.

[Evaluation of cured product] The cured product (cured film) obtained from the photosensitive resin composition of Examples 1 to 6 and Comparative Examples 1 to 2 was evaluated as follows. The results are shown in Table 1.

<Evaluation of adhesiveness> A photosensitive resin composition was applied on a copper substrate, and spin-coated so that the film thickness after curing became 10 μm. After drying at 100 ° C for 2 minutes, it was dried at 110 ° C for 2 minutes to form a photosensitive resin film. The obtained photosensitive resin film was exposed using a mask alignment exposure device (manufactured by SUSS MicroTec, trade name "MA8"). This resin film was heated in a nitrogen atmosphere at 173 ° C. for 1 hour using a vertical diffusion furnace (manufactured by Thermo System Co., Ltd.) to obtain a cured film. Then, a pressure cooker test (PCT) was performed on the obtained hardened film. The PCT conditions were set to 121 ° C, 100% RH, and 2 atm, and the test time was set to 100 hours, 200 hours, 300 hours, 400 hours, and 500 hours.

A stud pull evaluation method (measurement of the tensile and peeling strength of the column plug) using a film pull strength tester (manufactured by Quad Group, Inc., trade name "Romulus") was used. The adhesiveness of the cured film after PCT was measured. Specifically, each copper substrate on which a cured film is formed is cut into 1 cm squares to produce a sample piece. An epoxy pin pin is erected at the center of the copper substrate and fixed with a jig, and heated and cured in an oven at 150 ° C The stud pin with epoxy resin was fixed to the cured film for 1 hour to prepare a sample for evaluation. The sample for evaluation was set on a film adhesion strength measuring machine (Romulus), the load was increased to 100 kg at 5 kg / sec, and a tensile load was applied to the stud pin in a vertical direction, and The presence or absence of peeling of the cured film was observed. Based on the PCT processing time of the evaluation sample for peeling the cured film from the copper substrate, the adhesiveness was evaluated by the following criteria. ：: In the sample test piece for evaluation for 500 hours, the cured film did not peel off. (Triangle | delta): The hardened film peeled in the sample piece for evaluation of 300 hours, 400 hours, or 500 hours. X: In the sample piece for evaluation for 100 hours or 200 hours, the cured film was peeled.

[Table 1]

As can be seen from Table 1, the photosensitive resin composition of the present invention has excellent resolution, and the cured film obtained from the photosensitive resin composition has high adhesion to a copper substrate. [Industrial availability]

The photosensitive resin composition of the present invention can be used to form a heat-resistant relief pattern such as a passivation film, a buffer coating film, an interlayer insulation film, a cover layer, a surface protection film, and the like in an insulating material for electronic parts or a semiconductor device.

The embodiments and / or examples of the present invention are described in detail in the foregoing, but those skilled in the art can easily implement the embodiments and / or examples as examples without substantially departing from the novel teachings and effects of the present invention. Various modifications may be made to the embodiments. Therefore, these various modifications are included in the scope of the present invention. The contents of the documents described in this specification are all incorporated in this specification.

1‧‧‧ semiconductor substrate

2‧‧‧ protective film

3‧‧‧ 1st conductor layer

4‧‧‧ interlayer insulation film

5‧‧‧ photosensitive resin film

6A, 6B, 6C‧‧‧ windows

7‧‧‧ 2nd conductor layer

8‧‧‧ surface protection film

FIG. 1 is a schematic cross-sectional view illustrating a manufacturing process of a semiconductor device as an electronic component having a multilayer wiring structure.

Claims (9)

A photosensitive resin composition comprising: (a) a polyimide precursor; (b) a radical polymerizable compound having an aliphatic cyclic structure; and (c) a compound represented by the following formula (1) ; In formula (1), R ¹ is an organic group represented by the following formula (2), R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ³ is an alkyl group having 1 to 3 carbon atoms and carbon number 1 to 3 alkoxy groups or 6 to 10 carbon aryl groups; In the formula (2), R ⁴ is a monovalent organic group, X is an oxygen atom, a sulfur atom, or a carbonyl group, and s is an integer of 0 to 5. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the component (a) is a polyimide precursor having a structural unit represented by the following formula (3); In formula (3), A is a tetravalent organic group represented by the following formula (4), B is a divalent organic group containing at least one aromatic ring, and R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent Organic In the formula (4), Y is an oxygen atom or a sulfur atom. The photosensitive resin composition according to item 2 of the scope of patent application, wherein R ⁵ and R ^{6 in} the formula (3) are each independently a hydrogen atom, and the group or carbon number 1 represented by the following formula (5) is 1 ~ 4 alkyl; In the formula (5), R ⁷ to R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m is an integer of 1 to 10. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (b) contains a free radical having two or more radical polymerizable groups and an aliphatic cyclic structure. Radical polymerizable compound. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (b) contains a photosensitive resin composition selected from the group consisting of tricyclodecane, adamantane, cyclohexane, and norbornene. A radically polymerizable compound having one or more structures in the formed group. A method for manufacturing a pattern cured film, comprising: applying a photosensitive resin composition according to any one of claims 1 to 5 on a substrate and drying the photosensitive resin composition to form a photosensitive resin film; A step of pattern-exposing the photosensitive resin film; a step of developing a pattern resin film by developing the resin film subjected to the pattern exposure using an organic solvent; and a step of heating the pattern resin film . A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5 of the scope of patent application. An interlayer insulation film, a cover layer or a surface protection film is manufactured by using a hardened material as described in item 7 of the scope of patent application. An electronic component has an interlayer insulating film, a cover layer, or a surface protective film as described in item 8 of the scope of patent application.