CN113168101A

CN113168101A - Photosensitive resin composition, method for producing patterned cured film, interlayer insulating film, cover coat, surface protective film, and electronic component

Info

Publication number: CN113168101A
Application number: CN201980065135.7A
Authority: CN
Inventors: 东绫香; 阿部悟志; 山崎范幸
Original assignee: Actri Microsystems Co ltd
Current assignee: Actri Microsystems Co ltd; HD MicroSystems Ltd
Priority date: 2018-10-03
Filing date: 2019-10-02
Publication date: 2021-07-23
Also published as: TW202028864A; KR20210068420A; WO2020071422A1; JP7459797B2; TWI819110B; JPWO2020071422A1

Abstract

A photosensitive resin composition comprising: (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a compound represented by the following formula (1), (C) a photopolymerization initiator, and (D) a thermal radical generator. (in the formula (1), A is a 2-valent organic group and does not contain CAlkenoyl or methacryloyl. R¹～R⁴Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. n1 and n2 are each independently an integer of 1 to 20. m1 and m2 are each independently 0 or 1. ).

Description

Photosensitive resin composition, method for producing patterned cured film, interlayer insulating film, cover coat, surface protective film, and electronic component

Technical Field

The invention relates to a photosensitive resin composition, a method for manufacturing a pattern cured film, a cured film, an interlayer insulating film, a cover coat, a surface protection film and an electronic component.

Background

Conventionally, polyimide or polybenzazole having excellent heat resistance, electrical properties, mechanical properties and the like has been used as a surface protective film and an interlayer insulating film of a semiconductor device

And (3) azole. In recent years, a photosensitive resin composition having photosensitive characteristics imparted to these resins itself has been used, and if this photosensitive resin composition is used, the production process of a pattern cured film can be simplified, and a complicated production process can be shortened (for example, see patent document 1).

In recent years, however, miniaturization of transistors supporting high performance of computers has approached the limit of the rule of proportionality, and a stacked device structure in which semiconductor elements are three-dimensionally stacked has attracted attention for further improvement in performance and high speed.

Among the stacked device structures, a Multi-die Fanout Wafer Level package (Multi-die Fanout Wafer Level Packaging) is a package manufactured by collectively sealing a plurality of chips in one package, and is drawing attention because it can be expected to reduce the cost and improve the performance as compared with a fan-out Wafer Level package (manufactured by sealing one chip in one package) proposed in the related art.

In the fabrication of a multi-chip fan-out type wafer level package, from the viewpoint of protecting a high-performance chip, protecting a sealing material having low heat resistance, and improving yield, low temperature curability at 200 ℃ or lower, for example, is strongly required (for example, see patent document 2). However, there is a problem that the polyimide precursor is not sufficiently imidized in the curing reaction at 200 ℃ or lower.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2009-265520

Patent document 2: international publication No. 2008/111470

Disclosure of Invention

The purpose of the present invention is to provide a photosensitive resin composition which can realize a high imidization rate even when a curing reaction is carried out at 200 ℃ or lower and can produce a cured film having excellent mechanical properties. Also provided are a method for producing a patterned cured film using the photosensitive resin composition, a cured film, an interlayer insulating film and the like produced using the cured film, and an electronic component including the interlayer insulating film and the like.

In general, it is expected that a polymerizable monomer (crosslinking agent) used in a photosensitive resin composition volatilizes in a heat treatment step for curing after a pattern is formed by a crosslinking reaction by exposure. However, when cured at a low temperature of 200 ℃ or lower, the crosslinking agent may not sufficiently volatilize and remain in the film, and such a crosslinking agent is considered to be a cause of inhibiting imidization of the polyimide precursor.

The present inventors have found that the object can be achieved by using a substance having a specific structure as a crosslinking agent and further using a thermal radical generator which promotes crosslinking at the time of curing reaction in combination, and as a result, the present invention has been completed.

According to the present invention, the following photosensitive resin composition and the like can be provided.

1. A photosensitive resin composition comprising:

(A) a polyimide precursor having a polymerizable unsaturated bond,

(B) A compound represented by the following formula (1),

(C) Photopolymerization initiator, and

(D) a thermal radical generator.

[ solution 1]

(in the formula (1), A is a 2-valent organic group and does not contain acryloyl or methacryloyl R¹～R⁴Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. n1 and n2 are each independently an integer of 1 to 20. m1 and m2 are each independently 0 or 1. )

2. The photosensitive resin composition according to 1, wherein n1 and n2 in the formula (1) are each independently 1 or 2.

3. The photosensitive resin composition according to 1 or 2, wherein R in the formula (1)¹And R²Is a hydrogen atom.

4. The photosensitive resin composition according to any one of 1 to 3, wherein R in the formula (1)³And R⁴Is a hydrogen atom.

5. The photosensitive resin composition according to any one of 1 to 4, wherein A in the formula (1) is a group formed by connecting 2-valent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, 2-valent aromatic hydrocarbon groups having 6 to 20 carbon atoms, oxygen atoms (-O-) or more than 2 of the above groups.

6. The photosensitive resin composition according to any one of 1 to 5, wherein the component (D) is an organic peroxide.

7. The photosensitive resin composition according to any one of 1 to 6, wherein the component (D) is a peroxyester or a dialkyl peroxide.

8. The photosensitive resin composition according to any one of 1 to 7, wherein the component (D) is a peroxyester.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11).

[ solution 2]

(in the formula (11), X¹Is a 4-valent group having 1 or more aromatic groups. Y is¹Is a 2-valent aromatic group. R¹¹And R¹²Each independently represents a hydrogen atom, a group represented by the following formula (12) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R¹¹And R¹²At least one of them is a group represented by the following formula (12). -COOR¹¹The radicals and the-CONH-radicals being in ortho-position to one another, -COOR¹²The radicals and the-CO-radicals are in the ortho position relative to one another. )

[ solution 3]

(in the formula (12), R¹³～R¹⁵Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. m is an integer of 1 to 10. )

10. A method for manufacturing a pattern cured film, comprising the steps of:

a step of forming a photosensitive resin film by coating the photosensitive resin composition of any one of 1 to 9 on a substrate and drying the coating;

pattern-exposing the photosensitive resin film to obtain a resin film;

a step of obtaining a pattern resin film by developing the pattern-exposed resin film with an organic solvent; and

and a step of heat-treating the patterned resin film.

11. The method of manufacturing a pattern cured film according to claim 10, wherein the temperature of the heat treatment is 200 ℃ or lower.

12. A cured film obtained by curing the photosensitive resin composition of any one of claims 1 to 9.

13. The cured film according to 12, which is a pattern cured film.

14. An interlayer insulating film, a cover coat layer or a surface protective film, which is produced using the cured film described in 12 or 13.

15. An electronic part comprising the interlayer insulating film, covercoat or surface protective film of 14.

According to the present invention, it is possible to provide a photosensitive resin composition which can realize a high imidization rate even when a curing reaction is performed at 200 ℃ or lower and can produce a cured film having excellent mechanical properties. Further, a method for producing a pattern cured film using the photosensitive resin composition, a cured film, an interlayer insulating film produced using the cured film, and an electronic component including the interlayer insulating film can be provided.

Drawings

Fig. 1 is a schematic view showing a manufacturing process of an electronic component according to an embodiment of the present invention.

Detailed Description

The embodiments of the photosensitive resin composition, the method for producing a pattern cured film, the interlayer insulating film, the covercoat, the surface protective film, and the electronic component of the present invention will be described in detail below. The present invention is not limited to the following embodiments.

In the present specification, "a or" B "may include either one of a and B, or both of them. The term "step" in the present specification includes not only an independent step but also a step that can achieve a desired action of the step even when the step is not clearly distinguished from other steps.

The numerical range represented by the term "to" represents a range including the numerical values recited before and after the term "to" as the minimum value and the maximum value, respectively. In the present specification, the content of each component in the composition refers to the total amount of a plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Further, the exemplified materials may be used alone or in combination of two or more unless otherwise specified.

In the present specification, "(meth) acrylate" means "acrylate" and "methacrylate".

[ photosensitive resin composition ]

The photosensitive resin composition of the present invention contains (a) a polyimide precursor having a polymerizable unsaturated bond (hereinafter, also referred to as "component (a)"), (B) a compound represented by formula (1) (hereinafter, also referred to as "component (B)"), (C) a photopolymerization initiator (hereinafter, also referred to as "component (C)"), and (D) a thermal radical generator (hereinafter, also referred to as "component (D)"). The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

Since the photosensitive resin composition of the present invention contains the component (B) which is one of polymerizable monomers and the component (D) which promotes crosslinking during a curing reaction, the components (B) crosslink (polymerize) with each other to form a crosslinked structure during the curing reaction (heat treatment step). (B) Since the component (a) is a so-called 2-functional acrylate and the functional group has a chain structure having a certain length or more, the component (a) can form a long chain structure in which the functional groups are linearly connected by crosslinking the functional groups. This chain structure contributes to improvement in flexibility of the film, and the imidization of the polyimide precursor can be promoted because the amount of unreacted polymerizable monomer is small or no residual polymerizable monomer remains. This makes it possible to obtain a cured film having excellent mechanical properties, particularly excellent elongation at break.

In addition, since the crosslinking reaction of the component (B) is promoted during the curing reaction of the photosensitive resin composition of the present invention, the amount of volatilization of the component is small. Therefore, the cured film has less film shrinkage (shrink) and excellent dimensional accuracy.

Hereinafter, each component will be described.

(component (A): polyimide precursor having polymerizable unsaturated bond)

(A) The component (c) is not particularly limited as long as it is a polyimide precursor having a polymerizable unsaturated bond, but is preferably a polyimide precursor having a high transmittance when i-line is used as a light source in patterning and exhibiting high cured film characteristics even when cured at a low temperature of 200 ℃ or lower.

Examples of the polymerizable unsaturated bond include a double bond between carbon atoms.

(A) The component (B) is preferably a polyimide precursor having a structural unit represented by the following formula (11). Thus, the i-line has a high transmittance, and a cured film having good physical properties can be formed even when curing is performed at a low temperature of 200 ℃ or lower.

[ solution 4]

[ solution 5]

(in the formula (12), R¹³～R¹⁵Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. m is an integer of 1 to 10 (preferably an integer of 2 to 10, more preferably an integer of 2 to 5, and further preferably 2 or 3). )

X of formula (11)¹The 4-valent group having 1 or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups in (a) may be a 4-valent aromatic hydrocarbon group (having 6 to 20 carbon atoms, for example) or a 4-valent aromatic heterocyclic group (having 5 to 20 carbon atoms, for example). X¹Preferably a 4-valent aromatic hydrocarbon group.

As X¹The aromatic hydrocarbon group of (2) to (4) is a2 to (2, 3 or 4) valent group formed from a benzene ring, a2 to 4 valent group formed from naphthalene, a2 to 4 valent group formed from perylene, or the like.

As X¹Examples of the 4-valent group having 1 or more aromatic groups in (b) include, but are not limited to, the 4-valent group represented by the following formula.

[ solution 6]

(in the formula, Z¹And Z²Each independently is a 2-valent group or a single bond that is not conjugated to the benzene ring to which it is bonded. Z³Is an ether bond (-O-) or a thioether bond (-S-). )

Z¹And Z²The 2-valent group of (A) is preferably-O-, -S-, methylene, bis (trifluoromethyl) methylene, or difluoromethylene, more preferably-O-.

Z³preferably-O-.

Y of formula (11)¹The 2-valent aromatic group(s) may be a 2-valent aromatic hydrocarbon group (having 6 to 20 carbon atoms, for example) or a 2-valent aromatic heterocyclic group (having 5 to 20 carbon atoms, for example). Y is¹Preferably a 2-valent aromatic hydrocarbon group.

As Y¹Examples of the 2-valent aromatic hydrocarbon group(s) include, but are not limited to, those represented by the following formula (13).

[ solution 7]

(in the formula (13), R²¹～R²⁸Each independently a hydrogen atom, a 1-valent aliphatic hydrocarbon group, or a 1-valent organic group having a halogen atom. )

As R²¹～R²⁸The (1) -valent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) is preferably a methyl group.

R²¹～R²⁸The 1-valent organic group having a halogen atom (preferably a fluorine atom) of (a) is preferably a 1-valent aliphatic hydrocarbon group having a halogen atom (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), and is preferably a trifluoromethyl group.

In formula (13), for example, R may be²²And R²³Is a 1-valent aliphatic hydrocarbon radical (e.g. methyl), R²¹And R²⁴～R²⁸Is a hydrogen atom.

R as formula (11)¹¹And R¹²Examples of the aliphatic hydrocarbon group having 1 to 4 (preferably 1 or 2) carbon atoms include methyl, ethyl, n-propyl, 2-propyl, n-butyl and the like.

In formula (11), R¹¹And R¹²At least one of them is a group represented by the formula (12), preferably R¹¹And R¹²Both of these are groups represented by formula (12).

R as formula (12)¹³～R¹⁵Examples of the aliphatic hydrocarbon group having 1 to 3 (preferably 1 or 2) carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. Preferably methyl.

The polyimide precursor having the structural unit represented by formula (11) can be produced, for example, as follows: a tetracarboxylic dianhydride represented by the following formula (14) is reacted with a diamino compound represented by the following formula (15) in an organic solvent such as N-methylpyrrolidone to produce a polyamic acid, and a compound represented by the following formula (16) is added and reacted in the organic solvent to introduce an ester group wholly or partially.

[ solution 8]

H₂N-Y¹-NH₂ (15)

(in the formula (14), X¹Is X of formula (11)¹The corresponding groups. In the formula (15), Y¹As defined in formula (11). In the formula (16), R¹³～R¹⁵And m is as defined for formula (12). )

The tetracarboxylic dianhydride represented by the formula (14) and the diamino compound represented by the formula (15) may be used alone or in combination of two or more.

The content of the structural unit represented by formula (11) is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, based on the total structural units of component (a). The upper limit is not particularly limited, and may be 100 mol%.

(A) The component (C) may have a structural unit other than the structural unit represented by the formula (11). Examples of the structural unit other than the structural unit represented by formula (11) include a structural unit represented by the following formula (17).

[ solution 9]

(in the formula (17), X¹²Is a 4-valent group having 1 or more aromatic groups. Y is¹²Is a 2-valent aromatic group. R³¹And R³²Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. -COOR³¹The radicals and the-CONH-radicals being in ortho-position to one another, -COOR³²The radicals and the-CO-radicals are in the ortho position relative to one another. )

X as formula (17)¹²The 4-valent group having 1 or more aromatic groups of (2) includes X of the formula (11)¹The 4-valent group having 1 or more aromatic groups of (a) is the same. As Y¹²As the 2-valent aromatic group in (2), Y of the formula (11) may be mentioned¹The 2-valent aromatic group of (a) is the same. As R³¹And R³²The aliphatic hydrocarbon group having 1 to 4 carbon atoms of (A) includes R of the formula (11)¹¹And R¹²The aliphatic hydrocarbon group having 1 to 4 carbon atoms.

The content of the structural unit other than the structural unit represented by formula (11) is preferably less than 50 mol% with respect to the total structural units of component (a).

One kind of the constitutional unit other than the constitutional unit represented by formula (11) may be used alone, or two or more kinds may be combined.

In the component (a), the ratio of the esterified carboxyl groups in the group represented by the formula (12) to all the carboxyl groups and all the carboxylic acid esters in the polyimide precursor is preferably 50 mol% or more, more preferably 60 to 100 mol%, and still more preferably 70 to 100 mol%.

(A) The molecular weight of the component (A) is not particularly limited, but is preferably 10,000 to 200,000 in terms of number average molecular weight.

The number average molecular weight was measured by Gel Permeation Chromatography (GPC) and calculated in terms of a standard polystyrene standard curve. The specific measurement conditions and the like are as described in examples.

(component (B): A compound represented by the formula (1))

The component (B) used in the present invention is one of polymerizable monomers, and is crosslinked with the component (A), or the components (B) are polymerized with each other to form a crosslinked structure. This enables formation of a patterned resin film by photoreaction, and further promotes crosslinking reaction by the component (D) in the subsequent heat treatment reaction, thereby forming a long chain structure in which the components (B) are polymerized with each other. As described above, since the chain structure improves the flexibility of the film, the component (B) can be said to function as a plasticizer.

[ solution 10]

In the case where it is judged whether or not a certain compound corresponds to the compound represented by formula (1), in the case where there are a plurality of choices of A, n1 and n2, if A, n1 and n2 can be selected so as to satisfy the compound represented by formula (1), it is regarded as corresponding to the compound represented by formula (1).

In the formula (1), n1 and n2 are preferably integers of 1 to 10, more preferably integers of 1 to 5, and may be 1 or 2.

R¹And R²Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

R³And R⁴Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

A may be a 2-valent organic group containing no acryloyl group or methacryloyl group, or a 2-valent organic group containing no polymerizable unsaturated bond.

Examples of the 2-valent organic group of A include groups formed by linking 2-valent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, 2-valent aromatic hydrocarbon groups having 6 to 20 carbon atoms, oxygen atoms (-O-), or 2 or more (preferably 2,3 or 4, more preferably 3 or 4) of these groups (for example, 1 or more (preferably 1 or 2) of 2-valent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, 1 or more (preferably 1 or 2) of 2-valent aromatic hydrocarbon groups having 6 to 20 carbon atoms and oxygen atoms (-O-), examples thereof include- (2-valent aliphatic hydrocarbon group) -O- (2-valent aliphatic hydrocarbon group) -, - (2-valent aromatic hydrocarbon group) - (2-valent aliphatic hydrocarbon group) - (2-valent aromatic hydrocarbon group) -, and the like.

The number of carbon atoms of A is not particularly limited, and is, for example, 1 to 30, preferably 1 to 20.

Examples of the aliphatic hydrocarbon group having 2 valences and 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms (for example, 1 to 10 carbon atoms) (for example, a 2-valent group corresponding to a methyl group, an ethyl group, or a propyl group), a 2-valent cycloalkylene group having 3 to 20 carbon atoms (for example, a 2-valent group derived from tricyclodecane), and the like.

Examples of the 2-valent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenylene groups and the like.

Specific examples of the component (B) include triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxy-modified bisphenol a di (meth) acrylate, and propoxy-modified bisphenol a di (meth) acrylate.

The number of ethylene glycol chains of the polyethylene glycol di (meth) acrylate is, for example, 5 to 20.

The number of propylene glycol chains of the polypropylene glycol di (meth) acrylate is, for example, 5 to 20.

The ethoxy-modified compound is a compound having an ethylene oxide chain introduced into a molecule thereof, and preferably contains 2 to 10 moles of the ethylene oxide chain per 1 molecule thereof.

The propoxy group-modified compound is a compound having an epoxypropane chain introduced into a molecule thereof, and preferably contains 2 to 10 moles of the epoxypropane chain per 1 molecule thereof.

The content of the component (B) is preferably 1 to 70 parts by mass, more preferably 5 to 50 parts by mass, and still more preferably 10 to 50 parts by mass, based on 100 parts by mass of the component (A).

(component (B'): other polymerizable monomer (crosslinking agent))

The photosensitive resin composition of the present invention may contain a crosslinking agent (component (B')) other than the component (B).

Examples of the component include diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, pentaerythritol hexaacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, Ethoxylated pentaerythritol tetraacrylate, triallylisocyanurate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloxyethyl isocyanurate, methacryloxyethyl isocyanurate, and the like.

The content of the component (B') is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the component (A).

In the crosslinking agent contained in the photosensitive resin composition of the present invention, for example, 80 mass% or more, 90 mass% or more, 95 mass% or more, 98 mass% or more, 99 mass% or more, 99.5 mass% or more, 99.9 mass% or more, or 100 mass% may be the component (B).

(component (C): photopolymerization initiator)

The photopolymerization initiator as the component (C) preferably includes, for example: benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4' -methyldiphenylketone, dibenzylketone, and fluorenone; acetophenone derivatives such as 2, 2' -diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; benzil derivatives such as benzil, benzil dimethyl ketal, and benzil- β -methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1, 2-butanedione-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 ] -, and oxime esters such as 1- (O-acetyloxime) and compounds represented by the following formula, but the oxime esters are not limited thereto. From the viewpoint of sensitivity, oxime esters are preferable.

[ solution 11]

The content of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 8 parts by mass, relative to 100 parts by mass of the component (A). In the case where the amount is within the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical uneven pattern tends to be obtained.

(component (D): thermal radical-generating agent)

Since the photosensitive resin composition of the present invention contains (D) a thermal radical generator, the crosslinking reaction between the components (B) is promoted in the heat treatment step.

The component (D) is preferably an organic peroxide.

Examples of the organic peroxide include peroxyesters, dialkyl peroxides, ketone peroxides, peroxyketals, hydrogen peroxide, diacyl peroxides, peroxydicarbonates, etc., and peroxyesters and dialkyl peroxides are preferable.

The peroxyester is a compound represented by the following general formula.

R- (C ═ O) -O-O-R' or

R-O-(C＝O)-O-O-R’

Wherein R and R' are each independently a substituted or unsubstituted alkyl group. Examples of the substituent include an aryl group having 6 to 10 carbon atoms. The number of carbon atoms of the alkyl group is, for example, 1 to 20 or 1 to 10.

Specific examples of the peroxyesters include cumyl peroxyneodecanoate, 1,3, 3-tetramethylbutyl peroxyneodecanoate, tert-hexyl neodecanoate, tert-butyl peroxyneoheptanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 1,3, 3-tetramethylbutyl peroxy2-ethylhexanoate, 2, 5-dimethyl-2, 5-di (2-ethylhexanoylperoxy) hexane, tert-hexyl peroxy2-ethylhexanoate, tert-butyl peroxyisopropylmonocarbonate, tert-butylperoxymaleic acid, tert-butyl peroxy3, 5, 5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyisopropylmonocarbonate, T-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, t-butyl peroxy-3-methylbenzoate, t-butyl peroxybenzoate, and the like.

Examples of commercially available products include "Percumyl ND", "PEROCTA ND", "PERCEXYL ND", "PERBUTYL NHP", "PERXYL PV", "PERBUTYL PV", "PEROCYTA O", "PERXYL 25O", "PERXYL O", "PERBUTYL O", "PERXYL I", "PERBUTYL MA", "PERBUTYL 355", "PERBUTYL L", "PERBUTYL I-75", "PERBUTYL E", "PERXYL Z", "PERHEXA 25Z", "PERBUTYL A", "PERBUTYL ZT" and "PERBUTYL Z" (manufactured by Nippon oil Co., Ltd.).

The dialkyl peroxide is a compound represented by the following general formula.

R-O-O-R’

Specific examples of the dialkyl peroxide include dicumyl peroxide, di-t-butyl peroxide, di (2-t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3 and the like.

Commercially available products include, for example, the trade names "Percumyl D", "PERBUTYL P", "PERHEXA 25B", "PERBUTYL C", "PERHEXYL D", "PERBUTYL D", "PERHEXYNE 25B" and "PERHEXYNE 25B-40" (manufactured by Nikkiso Co., Ltd.).

(D) The component (B) is preferably a compound having a half-life temperature of 50 ℃ or more and 200 ℃ or less for 1 hour, and more preferably a compound having a half-life temperature of 50 ℃ or more and 175 ℃ or less for 1 hour, from the viewpoint of promoting the polymerization reaction at a lower temperature.

The 1 hour half-life temperature was determined as follows.

A0.1 mol/L solution was prepared by dissolving an organic peroxide in benzene, and the solution was sealed in a glass tube purged with nitrogen. Immersing it in a constant temperature bath set at a predetermined temperature to perform thermal decomposition, and plotting a relationship of time (t) ln a/(a-x) byK was determined from the slope of the obtained straight line, and the half-life (t) was determined from the following equation_1/2)。

dx/dt＝k(a-x)

ln a/(a-x)＝kt

x＝a/2

kt_1/2＝ln2

x: amount of decomposed organic peroxide

k: constant of decomposition rate

t: time of day

a: initial concentration of organic peroxide

Since k is expressed by the following equation, the activation energy Δ E is obtained from the slope of a straight line obtained by plotting the relationship lnk to 1/T for several temperature measurements k, and the frequency factor A is obtained from the y-intercept.

k＝Aexp[-ΔE/RT]

lnk＝lnA-ΔE/RT

A: frequency factor (1/h)

Δ E: activation energy (J/mol)

R: gas constant (8.314J/mol. K)

T: absolute temperature (K)

Instead of lnk, by drawing lnt_1/2The straight line obtained from the relationship of about 1/T can obtain the half-life of the organic peroxide at an arbitrary temperature, and can obtain the decomposition temperature at which an arbitrary half-life (1 hour) can be obtained.

The content of the component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 20 parts by mass, and still more preferably 0.3 to 10 parts by mass, relative to 100 parts by mass of the component (A).

(component (E): solvent)

The photosensitive resin composition of the present invention generally contains a solvent.

Examples of the solvent include organic solvents such as N-methyl-2-pyrrolidone, γ -butyrolactone, N-dimethylacetamide, dimethylsulfoxide, 3-methoxy-N, N-dimethylpropionamide (for example, "KJCMPA-100" manufactured by KJ chemical corporation), and N-dimethylmorpholine.

The content of the solvent is not particularly limited, but is generally 50 to 1000 parts by mass per 100 parts by mass of the component (A).

(other Components)

The photosensitive resin composition of the present invention may further contain, in addition to the above components, a coupling agent (bonding aid), a surfactant or leveling agent, a sensitizer, a rust inhibitor, a polymerization inhibitor, and the like.

(coupling agent)

The coupling agent is generally reacted with the component (a) to crosslink in the heat treatment after development, or the coupling agent itself is polymerized in the step of the heat treatment. This can further improve the adhesion between the obtained cured film and the substrate.

The coupling agent is preferably a silane coupling agent.

As a preferable silane coupling agent, a compound having a urea bond (-NH-CO-NH-) can be mentioned. Thereby, even when curing is performed at a low temperature of 200 ℃ or lower, the adhesiveness to the substrate can be further improved.

The compound represented by the following formula (31) is more preferable in terms of excellent adhesion when cured at a low temperature.

[ solution 12]

(in the formula (31), R⁵¹And R⁵²Each independently an alkyl group having 1 to 5 carbon atoms. j is an integer of 1 to 10, and k is an integer of 1 to 3. )

Specific examples of the compound represented by formula (31) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, and 4-ureidobutyltriethoxysilane, and 3-ureidopropyltriethoxysilane is preferable.

As the silane coupling agent, a silane coupling agent having a hydroxyl group or a glycidyl group can be used. When a silane coupling agent having a hydroxyl group or a glycidyl group is used in combination with a silane coupling agent having a urea bond in the molecule, the adhesion of the cured film to the substrate at the time of low-temperature curing can be further improved.

Examples of the silane coupling agent having a hydroxyl group or a glycidyl group include methylphenylsilane diol, ethylphenylsilane diol, n-propylphenylsilane diol, isopropylphenylsilane diol, n-butylphenyl silane diol, isobutylphenylsilane diol, tert-butylphenyl silane diol, diphenylsilane diol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butyleethylphenylsilanol, isobutylethylphenylsilanol, tert-butyleethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyl diphenylsilanol, tert-butyl diphenylsilanol, phenylsilane triol, 1, 4-bis (trihydroxysilyl) benzene, 1, 4-bis (methyldihydroxysilyl) benzene, 1, 4-bis (ethyldihydroxysilyl) benzene, 1, 4-bis (propyldihydroxysilyl) benzene, 1, 4-bis (butyldihydroxysilyl) benzene, 1, 4-bis (dimethylhydroxysilyl) benzene, 1, 4-bis (diethylhydroxysilyl) benzene, 1, 4-bis (dipropylhydroxysilyl) benzene, 1, 4-bis (dibutylhydroxysilyl) benzene, and a compound represented by the following formula (32). Among them, the compound represented by the formula (32) is particularly preferable in order to further improve the adhesiveness to the substrate.

[ solution 13]

(in the formula (32), R⁵³Is a 1-valent organic radical having a hydroxyl group or a glycidyl group, R⁵⁴And R⁵⁵Each independently an alkyl group having 1 to 5 carbon atoms. o is an integer of 1 to 10, and p is an integer of 1 to 3. )

Examples of the compound represented by the formula (32) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane and 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane and the like.

The silane coupling agent having a hydroxyl group or a glycidyl group preferably further contains a group having a nitrogen atom, and more preferably a silane coupling agent further having an amino group or an amide bond.

Examples of the silane coupling agent having a further amino group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-glycidoxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane and the like.

Examples of the silane coupling agent further having an amide bond include a compound represented by the following formula (33).

R⁵⁶-(CH₂)_q-CO-NH-(CH₂)_r-Si(OR⁵⁷)₃ (33)

(in the formula (33), R⁵⁶Is a hydroxyl group or a glycidyl group, q and R are each independently an integer of 1 to 3, R⁵⁷Is methyl, ethyl or propyl. )

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 0.3 to 10 parts by mass, and still more preferably 1 to 10 parts by mass, based on 100 parts by mass of the component (a).

(surfactant or leveling agent)

By including a surfactant or a leveling agent, coating properties (for example, suppression of streaks (uneven film thickness)) and developing properties can be improved.

Examples of the surfactant and the leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether, and examples of commercially available products include trade names "MEGAFAX F171", "F173", and "R-08" (manufactured by DIC corporation); trade names "FLUORAD FC 430" and "FC 431" (manufactured by 3M Japan K.K.); the trade names "Organosiloxane Polymer (Organosiloxane Polymer) KP 341", "KBM 303", "KBM 403" and "KBM 803" (manufactured by shin-Etsu chemical Co., Ltd.).

When the surfactant or the leveling agent is contained, 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, and further preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the component (a).

(polymerization inhibitor)

By containing a polymerization inhibitor, good storage stability can be ensured.

Examples of the polymerization inhibitor include a radical polymerization inhibitor and a radical polymerization inhibitor.

Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, Cupferron (Cupfron), 2, 5-toluenequinone, tannic acid, p-benzylaminophenol, and nitrosoamines.

When the polymerization inhibitor is contained, the content of the polymerization inhibitor is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the component (a), from the viewpoints of storage stability of the photosensitive resin composition and heat resistance of the cured film obtained.

(other Components)

The photosensitive resin composition of the present invention may contain a sensitizer.

Examples of the sensitizer include 7-N, N-diethylaminocoumarin, 7-diethylamino-3-thenoylcoumarin, 3 ' -carbonylbis (7-N, N-diethylamino) coumarin, 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 ' -carbonylbis-5, 7- (dimethoxy) coumarin, benzylideneacetophenone, 4 ' -N, N-dimethylaminobenzeneacetophenone, water-soluble salts of these compounds, and salts of these compounds with other functional groups, 4 ' -acetamidobenzylidene-4-methoxyacetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, 4 ' -bis (N-ethyl, N-methyl) benzophenone, 4 ' -bis- (diethylamino) benzophenone, and the like.

When the sensitizer is contained, the amount is more preferably 0.1 to 3.0 parts by mass, and still more preferably 0.1 to 1.0 part by mass, per 100 parts by mass of the polyimide precursor (a).

The photosensitive resin composition of the present invention may contain a rust inhibitor from the viewpoint of further improving rust inhibition. Examples of the rust inhibitor include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole, benzotriazole, 5-methylbenzotriazole, and carboxybenzotriazole. These tetrazole and triazole compounds may also be water-soluble salts thereof.

The content of the rust inhibitor is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 4.0 parts by mass, per 100 parts by mass of the component (a).

In addition, the photosensitive resin composition of the present invention may contain a stabilizer. As the stabilizer, a known compound such as 1,4, 4-trimethyl-2, 3-diazabicyclo [3.2.2] -non-2-ene-N, N-dioxide can be used.

The content of the stabilizer is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 2.0 parts by mass, per 100 parts by mass of the component (a).

The photosensitive resin composition of the present invention is essentially composed of components (a) to (D) and one or more components selected from the group consisting of component (B'), a coupling agent (adhesion promoter), a surfactant, a leveling agent, a sensitizer, a rust inhibitor and a polymerization inhibitor, in addition to a solvent, and may further contain unavoidable impurities within a range not to impair the effects of the present invention.

The photosensitive resin composition of the present invention may be prepared, for example, from 80 mass% or more, 90 mass% or more, 95 mass% or more, 98 mass% or more, 99 mass% or more, 99.5 mass% or more, 99.9 mass% or more, or 100 mass% or more of a solvent other than the solvent

(A) Components (A) to (D),

(A) Components (A) to (D) and (B'),

(A) component (c) to component (D), and at least one selected from the group consisting of component (B'), coupling agent (adhesion promoter), surfactant, leveling agent, sensitizer, rust preventive and polymerization inhibitor, or

(A) Component (a) to component (D), component (B'), and at least one component selected from the group consisting of a coupling agent (bonding aid), a surfactant, a leveling agent, a sensitizer, a rust inhibitor, and a polymerization inhibitor.

[ cured film ]

The cured film of the present invention can be obtained by curing the photosensitive resin composition. The cured film of the present invention can be used as a patterned cured film or as a non-patterned cured film. The thickness of the cured film of the present invention is preferably 5 to 20 μm.

The cured film of the present invention comprises, as described above: a polyimide derived from the component (A), and a polymer compound (polymer) derived from the chain structure of the component (B).

[ method for producing patterned cured film ]

The method for producing a pattern cured film according to the present invention comprises the steps of: a step of forming a photosensitive resin film by coating the photosensitive resin composition on a substrate and drying the composition; pattern-exposing the photosensitive resin film to obtain a resin film; a step of obtaining a pattern resin film by developing the pattern-exposed resin film with an organic solvent; and a step of performing heat treatment on the patterned resin film. Thereby, a pattern cured film can be obtained.

The method for producing a pattern cured film of the present invention can promote the crosslinking reaction of the polymerizable monomer (crosslinking agent) in the heat treatment step by using the photosensitive resin composition of the present invention, and crosslink the components (B) or the components (a) and (B) to obtain a higher order structure through the above steps. This makes it possible to produce a patterned cured film which is less impregnated with a chemical and has high chemical resistance. In addition, since the amount of volatilization of the polymerizable monomer (crosslinking agent) (B) in the heat treatment step is small, the film shrinkage (shrink) is small and the dimensional accuracy is excellent.

The method for producing a non-patterned cured film includes, for example, a step of forming the photosensitive resin film and a step of performing a heat treatment. The method may further comprise a step of performing exposure.

Examples of the substrate include a semiconductor substrate such as a glass substrate or an Si substrate (silicon wafer); TiO 2₂Substrate and SiO₂Metal oxide insulator substrates such as substrates; silicon nitride substrates, copper alloy substrates, and the like.

The coating method is not particularly limited, and can be performed using a spin coater or the like.

Drying can be performed using a hot plate, an oven, or the like.

The drying temperature is preferably 90 to 150 ℃, and more preferably 90 to 120 ℃ from the viewpoint of ensuring the solubility contrast, in order to suppress the reaction between the component (A) and the component (B).

The drying time is preferably 30 seconds to 5 minutes.

The drying may be carried out 2 or more times.

Thus, a photosensitive resin film formed by forming the photosensitive resin composition into a film shape can be obtained.

The thickness of the photosensitive resin film is preferably 1 to 100 μm, more preferably 3 to 50 μm, and still more preferably 5 to 30 μm.

The pattern exposure is, for example, exposure to a predetermined pattern through a photomask.

The active light to be irradiated includes ultraviolet rays such as i-rays, visible rays, and radiation, and i-rays are preferable.

As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper exposure machine, a scanner exposure machine, or the like can be used.

By performing development, a patterned resin film (pattern resin film) can be obtained. In general, when a negative photosensitive resin composition is used, unexposed portions are removed with a developer.

The organic solvent used as the developer can be a good solvent for the photosensitive resin film alone or a good solvent and a poor solvent can be appropriately mixed and used.

Examples of the good solvent include N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, α -acetyl- γ -butyrolactone, cyclopentanone, and cyclohexanone.

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 amount of the additive 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.

The developing time can be, for example, 2 times the time taken for the photosensitive resin film to be immersed and dissolved.

The developing time is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and still more preferably 20 seconds to 5 minutes from the viewpoint of productivity, depending on the components (a) and (B) used.

After development, washing may be performed by a washing solution.

The rinse solution may be used alone or in a suitable mixture of distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and the like, or may be used in combination in stages.

By subjecting the pattern resin film to a heat treatment, a pattern cured film can be obtained. (A) The polyimide precursor of the component (A) undergoes a dehydration ring-closure reaction in the heat treatment step, and a part or all of the reaction product becomes polyimide.

The temperature of the heat treatment is preferably not more than 250 ℃, more preferably 120 to 250 ℃, and further preferably not more than 200 ℃ or 150 to 200 ℃.

By setting the range to the above range, damage to the substrate and the device can be suppressed to a small extent, the device can be produced with a high yield, and energy saving of the process can be achieved.

The time of the heat treatment is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. When the amount is within the above range, the crosslinking reaction or the dehydration ring-closing reaction can be sufficiently performed.

The atmosphere for the heat treatment may be in the air or in an inert atmosphere such as nitrogen, and is preferably a nitrogen atmosphere from the viewpoint of preventing the pattern resin film from being oxidized.

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

[ interlayer insulating film, cover coat, surface protective film, electronic component ]

The cured film of the present invention can be used as a passivation film, a buffer coating film, an interlayer insulating film, a cover coat, a surface protective film, or the like.

By using one or more selected from the group consisting of the above-mentioned passivation film, buffer coating film, interlayer insulating film, coverlay, surface protective film, and the like, it is possible to manufacture electronic components such as a semiconductor device, a multilayer wiring board, various electronic devices, and the like with high reliability.

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 process diagram for manufacturing 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 an Si substrate having circuit elements is covered with a protective film 2 such as a silicon oxide film except for predetermined portions of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. Then, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

Next, a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolac type, or the like is formed on the interlayer insulating film 4, and a window 6A is provided by a known photolithography technique so as to expose a predetermined portion of the interlayer insulating film 4.

The interlayer insulating film 4 exposed by the window 6A is selectively etched to provide a window 6B.

Next, the photosensitive resin layer 5 is removed by using an etching solution which does not corrode the first conductor layer 3 exposed through the window 6B and corrodes the photosensitive resin layer 5.

Further, a second conductor layer 7 is formed to be electrically connected to the first conductor layer 3 using a known photolithography technique.

In the case of forming a multilayer wiring structure having 3 or more layers, the above-described steps can be repeated to form each layer.

Next, the photosensitive resin composition is used to form the surface protection film 8 by opening the window 6C by pattern exposure. The surface protective film 8 protects the second conductor layer 7 from external stress, α -rays, and the like, and the resulting semiconductor device is excellent in reliability.

In the above examples, the photosensitive resin composition of the present invention can be used to form an interlayer insulating film.

Examples

The present invention will be specifically explained below based on examples and comparative examples. The present invention is not limited to the following examples.

Synthesis example 1 (Synthesis of Polymer A1)

7.07g of 3,3 ', 4, 4' -diphenylethertetracarboxylic dianhydride (ODPA), 0.831g of 2-hydroxyethyl methacrylate (HEMA) and a catalytic amount of 1, 4-diazabicyclo [2.2.2] octane triethylenediamine were dissolved in 30g of N-methyl-2-pyrrolidone (NMP), stirred at 45 ℃ for 1 hour, and then cooled to 25 ℃. A solution prepared by dissolving 4.12g of 2,2 '-dimethylbiphenyl-4, 4' -Diamine (DMAP) in NMP was added thereto, followed by stirring at 30 ℃ for 4 hours and then at room temperature overnight to obtain a polyamic acid. After 9.45g of trifluoroacetic anhydride was added dropwise to the solution, the mixture was stirred at 45 ℃ for 3 hours, then a catalytic amount of benzoquinone was added thereto, and 7.08g of 2-hydroxyethyl methacrylate (HEMA) was further added thereto, and the mixture was stirred at 45 ℃ for 20 hours. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as polymer a 1).

The number average molecular weight of the polymer a1 was determined by Gel Permeation Chromatography (GPC) in terms of standard polystyrene under the following conditions. The number average molecular weight of the polymer a1 was 40,000. The number average molecular weight was measured using 1mL of a solution of the solvent [ Tetrahydrofuran (THF)/Dimethylformamide (DMF) ═ 1/1 (volume ratio) ] relative to 0.5mg of the polymer a 1.

A measuring device: l4000UV manufactured by Hitachi, Inc. of Detector

A pump: l6000 manufactured by Hitachi Kabushiki Kaisha

C-R4A Chromatopac, manufactured by Shimadzu corporation

The measurement conditions were as follows: column Gelpack GL-S300 MDT-5X 2

Eluent: THF/DMF 1/1 (volumetric ratio)

LiBr(0.03mol/L)，H₃PO₄(0.06mol/L)

Flow rate: 1.0 mL/min, detector: UV270nm

In addition, the esterification rate of polymer a1 (the reaction rate of carboxyl groups derived from ODPA and HEMA) was calculated by NMR measurement under the following conditions. The esterification rate was 80 mol% relative to all carboxyl groups of the polyamic acid (the remaining 20 mol% were carboxyl groups).

Measurement equipment: AV400M manufactured by Bruker BioSpin

Magnetic field strength: 400MHz

Reference substance: tetramethylsilane (TMS)

Solvent: dimethyl sulfoxide (DMSO)

The components used in the following examples and comparative examples are as follows.

(component (A): polyimide precursor having polymerizable unsaturated bond)

Polymer a 1: polymer A1 obtained in Synthesis example 1

(component (B): polymerizable monomer)

B1: "A-200" (tetraethylene glycol diacrylate, manufactured by Ningmura chemical Co., Ltd., represented by the following formula)

[ solution 14]

B2: "FA-324A" (manufactured by Hitachi chemical Co., Ltd., ethoxy-modified bisphenol A diacrylate, a compound represented by the following formula, m ═ 2, n ═ 2)

[ solution 15]

B3: "TEGDMA" (triethylene glycol dimethacrylate, manufactured by Xinzhongcun chemical industries, Compound represented by the following formula)

[ solution 16]

B4: "FA-324M" (a compound represented by the following formula, M ═ 2, n ═ 2, ethoxy-modified bisphenol A dimethacrylate, manufactured by Hitachi chemical Co., Ltd.)

[ solution 17]

B5: "FA-321A" (a compound represented by the following formula, m-5, n-5, manufactured by Hitachi chemical Co., Ltd., ethoxy-modified bisphenol A diacrylate)

[ solution 18]

B6: "FA-321M" (a compound represented by the following formula, m.times.5, n.times.5, manufactured by Hitachi chemical Co., Ltd., ethoxy-modified bisphenol A dimethacrylate)

[ solution 19]

B7: "A-400" (a compound of the following formula, polyethylene glycol diacrylate, manufactured by Ningmura chemical Co., Ltd.)

[ solution 20]

B8: "FAP-324A" (a compound represented by the following formula, m ═ 2, n ═ 2, propoxy-modified bisphenol A diacrylate, manufactured by Hitachi chemical Co., Ltd.)

[ solution 21]

(B') component

B' 1: "A-DCP" (tricyclodecane dimethanol diacrylate, manufactured by Xinzhongcun chemical industry Co., Ltd., a compound represented by the following formula)

[ solution 22]

B' 2: "ATM-4E" (a compound of ethoxylated pentaerythritol tetraacrylate, manufactured by shinkamura chemical Co., Ltd., represented by the following formula)

[ solution 23]

B' 3: "M-140" (available from Toyo Synthesis Co., Ltd., N-acryloyloxyethylhexahydrophthalimide, a compound represented by the following formula)

[ solution 24]

B' 4: "DPE-6A" (a compound of the following formula, dipentaerythritol hexaacrylate, manufactured by Kyoeisha chemical Co., Ltd.)

[ solution 25]

B' 5: "M-215" (Compound represented by the following formula, Isocyanuric acid EO-modified diacrylate, manufactured by Toyo Synthesis Co., Ltd.)

[ solution 26]

The component (B') is a component different from the component (B) used in the present invention.

(component (C): photopolymerization initiator)

C1: "IRGACURE OXE 02" (a compound represented by the following formula, manufactured by BASF Japan K.K.)

[ solution 27]

C2: "G-1820 (PDO)" (Compound represented by the following formula, manufactured by Lambson)

[ solution 28]

(component (D): thermal radical-generating agent)

D1: "Percumyl D" (manufactured by Nichioil Co., Ltd., dicumyl peroxide, a compound represented by the following formula, 1-hour half-life temperature 135.7 ℃ C.)

[ solution 29]

D2: "PERBUTYL Z" (manufactured by Nichikoku K.K., tert-butylperoxybenzoate, a compound represented by the following formula, 1-hour half-life temperature 124.7 ℃ C.)

[ solution 30]

D3: "PERBUTYL O" (tert-butyl peroxy-2-ethylhexanoate, manufactured by Nichikoku K.K., a compound represented by the following formula, 1-hour half-life temperature 92.1 ℃ C.)

[ solution 31]

(component (E): solvent)

E1: "KJCMPA-100" (a compound represented by the following formula, manufactured by KJ Chemicals Co., Ltd.)

[ solution 32]

(other Components: polymerization inhibitor)

"Taobn" (1,4, 4-trimethyl-2, 3-diazabicyclo [3.2.2] -non-2-ene-N, N-dioxide, product of Hampford Research Co., Ltd.)

(other Components: sensitizer)

"EMK" (Compound represented by the following formula, Et represents ethyl manufactured by Aldrich Co.)

[ solution 33]

(other Components: bonding auxiliary)

"UCT-801" (3-ureidopropyltriethoxysilane, manufactured by United Chemical Technologies Co., Ltd.)

(other Components: Rust preventive)

"5 ATz" (product name "5-amino-1H-tetrazole" available from Tokyo chemical Co., Ltd., and compound represented by the following formula)

[ chemical 34]

(other Components: thermokalite Generator)

"4 HP" (product name "4-hydroxypyridine" manufactured by Tokyo chemical industry Co., Ltd., compound represented by the following formula)

[ solution 35]

Examples 1 to 12 and comparative examples 1 to 7

[ preparation of photosensitive resin composition ]

Photosensitive resin compositions of examples 1 to 12 and comparative examples 1 to 7 were prepared by using the components and blending amounts shown in Table 1. The blending amount in table 1 is a part by mass of each component with respect to 100 parts by mass of the component (a).

[ evaluation of cured film ]

(measurement of imidization ratio 1)

The obtained photosensitive resin composition was spin-coated on a silicon substrate (supporting substrate),the resin film (A) was dried at 105 ℃ for 2 minutes and at 115 ℃ for 2 minutes to obtain a resin film (A) having a film thickness of 12 μm after drying. 700mJ/cm was conducted on the resin film using a "mask aligner MA-8" (manufactured by SUSS MicroTec Co., Ltd.)²Is irradiated with light. Then, the wafer with the resin film was heated at 160 ℃ for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace "μ -TF" (manufactured by mitsui Thermo systems corporation), to obtain a cured film (B). Further, the resin film-attached wafer produced in the same manner as described above was heated at 375 ℃ for 2 hours to obtain a cured film (C).

The infrared absorption spectra of the resin film (A), the cured film (B) and the cured film (C) were measured to determine the thickness at 1370cm^-1Absorbance of the peak near the imide group due to C-N stretching vibration. The infrared absorption spectrum was measured using "IRaffinity-1 s" (manufactured by Shimadzu corporation) as a measuring apparatus. The imidization ratio of the cured film (B) was calculated from the following equation, with the imidization ratio of the resin film (a) being 0% and the imidization ratio of the cured film (C) being 100%. The results are shown in Table 1 as "160 ℃ C" of the curing temperature.

The imidization ratio of the resin film (B) { (resin film (B) absorbance-cured film (a) absorbance)/(coating film (C) absorbance-cured film (a) absorbance) } × 100

(measurement of imidization ratio 2)

A cured film was produced in the same manner as in "measurement of imidization ratio 1" except that the curing temperature was changed to 180 ℃ and the imidization ratio was calculated. The results are shown in Table 1 as "180 ℃ C" of the curing temperature.

(measurement of imidization ratio 3)

A cured film was produced in the same manner as in "measurement of imidization ratio 1" except that the curing temperature was changed to 200 ℃ and the imidization ratio was calculated. The results are shown in Table 1 as the curing temperature "200 ℃.

(evaluation of mechanical Properties (elongation at Break) characteristics)

The photosensitive resin compositions obtained in examples 2 and 3 and comparative examples 1 and 2 were spin-coated on a silicon substrate, and were dried by heating at 105 ℃ for 2 minutes and 115 ℃ for 2 minutes on a hot plate, to form a photosensitive resin film having a thickness of about 12 μm. The obtained photosensitive resin film was subjected to wide band (BB) exposure using a "mask aligner MA-8" (manufactured by SUSS MicroTec corporation), and the exposed resin film was developed with cyclopentanone to obtain a 10 mm-wide long pattern resin film. The obtained patterned wafer was heated at 160 ℃ for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace "μ -TF" (manufactured by Thermo System Co., Ltd.) to obtain a patterned cured film having a thickness of about 10 μm.

The obtained pattern cured film was immersed in a 4.9 mass% hydrofluoric acid aqueous solution and peeled from the wafer. The peeled cured film was evaluated for elongation at break as follows. The elongation at break was measured under the conditions of an inter-jig distance of 2cm and a drawing speed of 5mm per minute using "AutographyAGS-100 NH" (manufactured by Shimadzu corporation). The results are shown in table 2.

[ Table 1]

[ Table 2]

	Example 2	Example 3	Comparative example 1	Comparative example 2
					Elongation at Break (%)	61	80	45	40

As is clear from tables 1 and 2, the cured film obtained from the photosensitive resin composition of the present invention has a high imidization rate and excellent elongation at break.

Industrial applicability

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

Although several embodiments and/or examples of the present invention have been described in detail, those skilled in the art will readily appreciate that many modifications are possible in the embodiments and/or examples without materially departing from the novel teachings and advantages of this invention. Accordingly, such many variations are intended to be included within the scope of the present invention.

The documents described in the present specification and the applications underlying the paris convention-based priority of the present application are incorporated herein in their entirety.

Claims

1. A photosensitive resin composition comprising:

(A) a polyimide precursor having a polymerizable unsaturated bond,

(B) A compound represented by the following formula (1),

(C) Photopolymerization initiator, and

(D) a thermal free-radical generating agent, wherein,

[ solution 36]

In the formula (1), A is 2-valentOrganic radicals, not containing acryloyl or methacryloyl radicals, R¹～R⁴Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, n1 and n2 each independently represents an integer of 1 to 20, and m1 and m2 each independently represents 0 or 1.

2. The photosensitive resin composition according to claim 1, wherein each of n1 and n2 in the formula (1) is independently 1 or 2.

3. The photosensitive resin composition according to claim 1 or 2, wherein R in the formula (1)¹And R²Is a hydrogen atom.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein R in the formula (1)³And R⁴Is a hydrogen atom.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein A in the formula (1) is a group formed by connecting 2-valent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, 2-valent aromatic hydrocarbon groups having 6 to 20 carbon atoms, oxygen atoms (-O-), or 2 or more of them.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the component (D) is an organic peroxide.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (D) is a peroxyester or a dialkyl peroxide.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (D) is a peroxyester.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11),

[ solution 37]

In formula (11), X¹Is a 4-valent radical having more than 1 aromatic group, Y¹Is a 2-valent aromatic radical, R¹¹And R¹²Each independently represents a hydrogen atom, a group represented by the following formula (12) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R¹¹And R¹²At least one of them is a group represented by the following formula (12) — COOR¹¹The radicals and the-CONH-radicals being in ortho-position to one another, -COOR¹²The radicals and the-CO-radical are in the ortho position relative to one another,

[ solution 38]

In the formula (12), R¹³～R¹⁵Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10.

10. A method for manufacturing a pattern cured film, comprising the steps of:

a step of forming a photosensitive resin film by applying the photosensitive resin composition according to any one of claims 1 to 9 to a substrate and drying the composition;

a step of obtaining a resin film by pattern-exposing the photosensitive resin film;

and a step of heat-treating the pattern resin film.

11. The method for manufacturing a pattern cured film according to claim 10, wherein the temperature of the heat treatment is 200 ℃ or lower.

12. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 9.

13. The cured film of claim 12 which is a patterned cured film.

14. An interlayer insulating film, a cover coat layer or a surface protective film, which is produced using the cured film according to claim 12 or 13.

15. An electronic component comprising the interlayer insulating film, the covercoat, or the surface protective film of claim 14.