CN111630454A

CN111630454A - Photosensitive resin composition, resin, cured film, laminate, method for producing cured film, and semiconductor device

Info

Publication number: CN111630454A
Application number: CN201980009370.2A
Authority: CN
Inventors: 川端健志; 吉田健太; 岩井悠
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2018-01-29
Filing date: 2019-01-23
Publication date: 2020-09-04
Anticipated expiration: 2039-01-23
Also published as: JPWO2019146611A1; KR20200093077A; CN111630454B; WO2019146611A1; TWI802640B; TW201934614A; JP7008732B2; KR102313182B1

Abstract

A photosensitive resin composition, a resin, a cured film, a laminate, a method for producing a cured film, and a semiconductor device, wherein the photosensitive resin composition comprises a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and a photoactive compound, and the polymer precursor has at least one of a sulfonic acid group bonded to a side chain of the polymer precursor comprising a structural unit derived from at least one of tetracarboxylic acid, a tetracarboxylic acid derivative, dicarboxylic acid, and a dicarboxylic acid derivative and a structural unit derived from at least one of diamine via a linking group, and a sulfonic acid group bonded to an end of the polymer precursor.

Description

Photosensitive resin composition, resin, cured film, laminate, method for producing cured film, and semiconductor device

Technical Field

The invention relates to a photosensitive resin composition, a resin, a cured film, a laminated body, a manufacturing method of the cured film and a semiconductor device.

Background

Polyimide resins and polybenzoxazole resins obtained by cyclizing and curing a polyimide precursor, a polybenzoxazole precursor, or the like have excellent heat resistance, insulation properties, or the like, and thus can be suitably used for various applications (see, for example, non-patent documents 1 and 2). The use thereof is not particularly limited, but in the field of mounting semiconductor devices, materials used for insulating films, protective films thereof, and sealing materials are exemplified. Further, the film can be used as a base film or a cover layer of a flexible substrate.

In general, the polyimide resin and polybenzoxazole resin have low solubility in a solvent. Therefore, there can be mentioned an example of a method generally applied by dissolving a polymer precursor (polyimide precursor or polybenzoxazole precursor) before cyclization reaction in a solvent and applying the solution to a substrate or the like. Then, the polymer precursor is heated to cyclize the polymer precursor, whereby a cured resin layer (cured film) can be formed.

The above-mentioned polymer precursor is described in patent document 1, for example. Patent document 1 discloses that the amount of the halogenating agent, water contained in the reaction system, and the amount of the raw material are adjusted by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with the halogenating agent and then reacting the resulting product with a diamine. This can increase the cyclization speed of the polymer precursor. The same document further discloses that a specific acid group is added to a polymer precursor.

Prior art documents

Patent document

Patent document 1: international publication WO2017/104672 pamphlet

Non-patent document

Non-patent document 1: science & technology co, ltd. "high functionalization and application technology of polyimide" 2008 4 months

Non-patent document 2: basis and development of persimmon beng Yaming/Main edition CMC Technical Library polyimide material

Disclosure of Invention

Technical problem to be solved by the invention

The polymer precursor can be cured by cyclization as described above, but due to its characteristics, cyclization may proceed during storage, and the stability of the resin may be poor.

Accordingly, an object of the present invention is to provide a photosensitive resin composition, a resin, a cured film, a laminate, a method for producing a cured film, and a semiconductor device, which have excellent storage stability.

Means for solving the technical problem

As a result of intensive studies based on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by introducing a sulfonic acid group into a polymer precursor constituting a photosensitive resin composition in a specific manner. Specifically, the above object is achieved by the following means < 1 >, preferably < 2 > - < 18 >.

< 1 > a photosensitive resin composition comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and a photoactive compound, wherein the polymer precursor has at least one of a sulfonic acid group bonded to a side chain of the polymer precursor via a linking group, the side chain being composed of a structural unit derived from at least one of tetracarboxylic acid, a tetracarboxylic acid derivative, a dicarboxylic acid and a dicarboxylic acid derivative, and a structural unit derived from at least one of diamine, and a sulfonic acid group bonded to an end of the polymer precursor.

< 2 > the photosensitive resin composition according to < 1 >, wherein,

the polymer precursor contains a structural unit represented by the following formula (1) or a structural unit represented by the following formula (2),

[ chemical formula 1]

In the formula (1), A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents an organic group having a valence of 2, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group,

[ chemical formula 2]

In the formula (2), R¹²¹Represents an organic group having a valence of 2, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group.

< 3 > the photosensitive resin composition according to < 2 >, wherein,

the polymer precursor contains a structural unit represented by formula (1).

< 4 > the photosensitive resin composition according to any one of < 1 > -3 >, wherein,

the polymer precursor has a moiety represented by any one of the formulae (1-1), (1-2), (1-3), (2-1), (2-2) and (2-3),

[ chemical formula 3]

In the formula, A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents an organic group having a valence of 2, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group, X¹、X²And X³Each independently represents a linking group, represents a bonding position to the main chain of the polyimide precursor, ns represents an integer of 1 to 4,

[ chemical formula 4]

In the formula, R¹²¹Represents an organic group having a valence of 2, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group, X⁴、X⁵And X⁶Each independently represents a linking group, represents a bonding position to the main chain of the polybenzoxazole precursor, and ns represents an integer of 1 to 4.

< 5 > the photosensitive resin composition according to any one of < 1 > -4 >, wherein,

the total number of sulfonic acid groups contained in the polymer precursor is 0.05% to 15.0% of the total number of structural units.

< 6 > the photosensitive resin composition according to any one of < 1 > -5 >, further comprising a radical polymerizable compound.

< 7 > the photosensitive resin composition according to any one of < 1 > -6 >, which further comprises a curing accelerator.

< 8 > the photosensitive resin composition according to any one of < 1 > -7 >, wherein,

the above photoactive compound contains a photo radical polymerization initiator.

< 9 > the photosensitive resin composition according to any one of < 1 > - < 8 > for use in development.

< 10 > the photosensitive resin composition according to any one of < 1 > to < 9 > for use in development using a developer containing an organic solvent.

< 11 > the photosensitive resin composition according to any one of < 1 > -10 > for forming an interlayer insulating film for a rewiring layer.

< 12 > a resin which is a resin comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, wherein,

[ chemical formula 5]

[ chemical formula 6]

< 13 > a cured film obtained by curing the photosensitive resin composition described in any one of < 1 > -11 >.

< 14 > a laminate having 2 or more layers of < 13 > the cured film.

< 15 > the laminate according to < 14 > having a metal layer between the above cured films.

< 16 > a method for producing a cured film, which comprises a step of using the photosensitive resin composition as defined in any one of < 1 > to < 11 >.

< 17 > the method for producing a cured film according to < 16 > which comprises:

a photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer;

an exposure step of exposing the photosensitive resin composition layer; and

and a developing treatment step of performing a developing treatment on the exposed photosensitive resin composition layer.

< 18 > a semiconductor device having < 13 > said cured film or < 14 > or < 15 > said laminate.

Effects of the invention

The present invention can provide a photosensitive resin composition, a resin, a cured film, a laminate, a method for producing a cured film, and a semiconductor device, which have excellent storage stability. In addition, the present invention can provide a novel resin to enrich the material.

Detailed Description

In the present specification, "to" are used to define a range including numerical values before and after the range as a lower limit value and an upper limit value.

The description of the constituent elements of the present invention may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

In the present specification, the label of a group (atomic group) indicates that the label which is not substituted and the label which is not substituted include both a label having no substituent and a label having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" is not particularly limited, and in addition to exposure using light, drawing using a particle beam such as an electron beam or an ion beam is also included in exposure. Examples of the light used for exposure generally include actinic rays or radiation such as far ultraviolet rays represented by a bright line spectrum of a mercury lamp or excimer laser, extreme ultraviolet rays (EU V light), X-rays, and electron beams.

In the present specification, "(meth) acrylate" represents both or either of "acrylate" and "methacrylate", "meth (acrylic acid)" represents both or either of "acrylic acid" and "methacrylic acid", and "(meth) acryloyl group" represents both or either of "acryloyl group" and "methacryloyl group".

In the present specification, the term "step" is included in the term not only for an independent step but also for achieving an action expected for the step even when the step is not clearly distinguished from other steps.

In the present specification, the solid content is a mass percentage of the components other than the solvent in the total mass of the composition. The solid content concentration is a concentration at 25 ℃ unless otherwise specified.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as styrene equivalent values based on gel permeation chromatography (GPC measurement). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by using HLC-8220 (manufactured by TOSOH CORPOR ATION), and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORP ORATION) as columns. Unless otherwise specified, the eluent was a liquid measured with THF (tetrahydrofuran). Unless otherwise stated, the detection is performed by a 254nm wavelength detector using UV rays (ultraviolet rays).

The photosensitive resin composition of the present invention (hereinafter, may be simply referred to as "the composition of the present invention" or "the resin composition of the present invention") is characterized by comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and a photoactive compound, wherein the polymer precursor has at least one of a sulfonic acid group bonded to a side chain (a side chain of a main chain structure) of the polymer precursor composed of a structural unit derived from at least one of a tetracarboxylic acid, a tetracarboxylic acid derivative, a dicarboxylic acid and a dicarboxylic acid derivative and a structural unit derived from at least one of a diamine via a linking group, and a sulfonic acid group bonded to an end (an end of the main chain structure) of the polymer precursor. Hereinafter, the present invention will be described in detail mainly with respect to the component composition constituting a preferred embodiment of the present composition.

< Polymer precursor >

The photosensitive resin composition of the present invention contains a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor. The polymer precursor is composed of a structural unit derived from at least one of tetracarboxylic acid, a tetracarboxylic acid derivative, a dicarboxylic acid, and a dicarboxylic acid derivative, and a structural unit derived from at least one of diamines. The structural unit derived from a tetracarboxylic acid or the like and a diamine means that these structural units account for the majority of the structural units of the polymer precursor, and the total structural unit of the polymer precursor is not required to be composed of these structural units. For example, the above requirements are satisfied if 70 mol% or more, further 80 mol% or more, and particularly 90 mol% or more of the total structural units are the structural units.

Examples of the structure derived from a tetracarboxylic acid or a tetracarboxylic acid derivative include R represented by the following formula (1)¹¹⁵And 4 adjacent carbonyl groups, and examples of the structural unit derived from a dicarboxylic acid or a dicarboxylic acid derivative include R of the formula (2)¹²¹And adjacent 2 carbonyl moieties. Examples of the structure of the diamine include R of the formula (1) described later¹¹¹And adjacent 2 NH structural units and R comprising the formula (2)¹²²And adjacent 2 NH groups. That is, in one embodiment of the photosensitive resin composition of the present invention, the compound represented by formula R is preferably represented by formula R¹¹⁵、R¹²²、R¹¹¹、R¹²¹Is at least partially connected viaThe linker group introduces a sulfonic acid group. The linking group in this case may be represented by the formula (Ls) described later¹-Li-Lt-*²An example of the method. Wherein¹Is the side of the main chain structure²Is the sulfonic acid group side. Among the polymer precursors, polyimide precursors are preferable.

In the present invention, the polymer precursor has a sulfonic acid group at least at any one of the terminal and the side chain thereof. Wherein the sulfonic acid group is (i) a sulfonic acid group bonded to a side chain of the polymer precursor via a linking group or (ii) a sulfonic acid group bonded to a terminal of the polymer precursor. The above-described definition is assumed to have the following technical significance. That is, regarding (i) the sulfonic acid group, in the aspect that the side chain is bonded via the linker, effects such as good mobility of the sulfonic acid group and a large effect on storage stability can be expected as compared with the case where the sulfonic acid group is not introduced via the linker. With respect to (ii) the sulfonic acid group bonded to the terminal of the polymer precursor, similarly, an effect such as good mobility of the sulfonic acid group and a large effect on storage stability can be expected. In the present invention, "sulfonic acid group" is a sulfonic acid group in a narrow sense, that is, a group having-SO bonded to a carbon skeleton₃The structure of the H group is different from a sulfamic acid structure or a sulfonic acid monoester structure. The resin has a sulfonic acid group as a strong acid group, and thus can be expected to function as a high acid group. In addition, the above-mentioned polymer precursor may have-SO bonded in addition to the carbon skeleton₃H groups, but preferably no-SO groups bound other than the carbon skeleton₃And (4) an H group.

Hereinafter, a site satisfying the above conditions may be referred to as a "site including a sulfonic acid group".

Preferred examples of the site containing the sulfonic acid group include a structure represented by the following formula (Ls).

*¹-Li-Lt-(SO₃H) ns type (Ls)

*¹Is a bonding position on the side of a structure (for example, an aromatic ring) which becomes the main chain. Li and Lt are each independently a linking group or a single bond, at least one of which is a linking group. In addition, a specific relationship may exist between the structure which becomes the main chain and the site of the formula (Ls)The details are given for the linking group L or even the linking group Lh described below, but preferably are absent. The formula (Ls) may be bonded to 1 side chain and/or 1 terminal of 1 structural unit by only 1, or may be bonded by 2 or more. When 2 or more bonds are bonded, each formula (Ls) may be the same or different. In the present invention, it is preferable that formula (Ls) is bonded to only 1 side chain and/or 1 terminal of 1 structural unit.

In particular, when the formula (Ls) is bonded to a side chain, it is preferable that the formula (Ls) is bonded to at least one structural unit derived from a tetracarboxylic acid, a tetracarboxylic acid derivative, a dicarboxylic acid, or a dicarboxylic acid derivative.

An example of the main chain is — C (═ O) -R in formula (1) described later¹¹⁵-C(＝O)-NH-R¹¹¹-NH-or-NH-R in the formula (2) described later¹²²-NH-C(＝O)-R¹²¹-C (═ O) -. More specifically, the formulae (Ls) and R can be exemplified¹¹⁵、R¹¹¹、R¹²²、R¹²¹Any of the above bonding modes.

Li is a heteroatom or a heteroatom-containing linking group, preferably a heteroatom-containing linking group. Examples of the linking group having a hetero atom include an amide group (CONH), an ester group (COO), an urea group (NHCONH), a carbamate group (NHCOO), and an imide group (CONHCO). These hydrogen atoms may be substituted with a substituent (e.g., substituent T described later), but are preferably unsubstituted. In addition, Li is not limited by the order of labeling of the linking groups, and for example, CONH may be NHCO, COO may be OCO, and NHCOO may be OCONH with respect to a specific linking direction.

Examples of Lt include a linking group composed of a carbon atom and a hydrogen atom. Lt is preferably a linking group composed of a carbon atom and a hydrogen atom in the linking group L described later in detail. Lt is preferably a linking group having 1 to 22 carbon atoms, more preferably 1 to 18, and further preferably 1 to 10. Further, Lt is preferably a hydrocarbon group, more preferably an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms), an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), an arylalkylene group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms), and even more preferably an arylene group.

The linking group Lt may or may not have a linking group Lh having a heteroatom. The linking group Lt does not interfere with the substituent group such as a hydroxyl group, a carboxylic acid, an amino group, or a halogen atom in the range where the effects of the present invention are exhibited. Details of Lh will be described later.

ns is an integer of 1 to 4, preferably 1 or 2, more preferably 1.

The formula weight of the formula (Ls) is preferably 14 to 300, more preferably 50 to 200.

Polyimide precursor

The polyimide precursor preferably contains a structural unit represented by the following formula (1).

[ chemical formula 7]

A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents an organic group having a valence of 2, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

A¹And A²Each independently an oxygen atom or NH, preferably an oxygen atom.

R¹¹¹Represents an organic group having a valence of 2. Examples of the organic group having a valence of 2 include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group including a combination thereof, and the organic group having a valence of 2 to 20 is preferably a linear aliphatic group having a carbon number of 2 to 20, a branched aliphatic group having a carbon number of 3 to 20, a cyclic aliphatic group having a carbon number of 3 to 20, an aromatic group having a carbon number of 6 to 20, or a group including a combination thereof, and more preferably an aromatic group having a carbon number of 6 to 20.

＜＜＜R¹¹¹＞＞＞

Preferably R¹¹¹Derived from a diamine. The diamine used for producing the polyimide precursor includes a linear or branched aliphatic, cyclic aliphatic or aromatic diamine, and the like. Only one kind of diamine may be used, or 2 or more kinds may be used.

Specifically, the diamine preferably contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and more preferably contains an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[ chemical formula 8]

In the formula, A is preferably a single bond or a group selected from aliphatic hydroxyl groups having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C (═ O) -, -S-, -S (═ O)₂-, -NHCO-and combinations thereof, more preferably a single bond or a group selected from C1-3 alkylene groups which may be substituted with fluorine atoms, -O-, -C (-O) -, -S-, -SO₂-is further preferably selected from the group consisting of-CH₂-、-O-、-S-、-SO₂-、-C(CF₃)₂-and-C (CH)₃)₂A 2-valent radical of the group (A-b).

Specific examples of the diamine include those selected from the group consisting of 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-or 1, 4-diaminocyclohexane, 1, 2-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane and isophoronediamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4 '-diaminobiphenyl and 3, 3' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenylmethane and 3, 3' -diaminodiphenylmethane, 4 '-diaminodiphenyl sulfone and 3, 3-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide and 3,3 '-diaminodiphenyl sulfide, 4' -diaminobenzophenone and 3,3 '-diaminobenzophenone, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dimethoxy-4, 4 ' -diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4 ' -diaminoterphenyl, 4 ' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis (4-aminophenoxy) phenyl) sulfone, bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-hydroxyphenyl, Bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (2-aminophenoxy) phenyl ] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 9, 10-bis (4-aminophenyl) anthracene, 3 ' -dimethyl-4, 4 ' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3 ' -diethyl-4, 4 ' -diaminodiphenylmethane, 3 ' -dimethyl-4, 4 ' -diaminodiphenylmethane, 4 ' -diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, methyl ether, ethyl ether, 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3 ', 4,4 ' -tetraaminobiphenyl, 3 ', 4,4 ' -tetraaminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4 ' -diaminobiphenyl, 9 ' -bis (4-aminophenyl) fluorene, 4,4 ' -dimethyl-3, 3 ' -diaminodiphenyl sulfone, 3 ', 5,5 ' -tetramethyl-4, 4 ' -diaminodiphenylmethane, ethyl 2- (3 ', 5 ' -diaminobenzoyloxy) methacrylate, 2, 4-diaminocumene and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzotrifluoride, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecafluoroheptane, 2, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4 ' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4 ' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4 ' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4 '-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3', 5,5 '-tetramethyl-4, 4' -diaminobiphenyl, 4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2 ', 5, 5', 6,6 '-hexafluorotolidine and 4, 4' -diaminotetrabiphenyl.

Also, diamines (DA-1) to (DA-18) shown below are preferable.

[ chemical formula 9]

[ chemical formula 10]

Further, as a preferable example, a diamine having at least 2 or more alkylene glycol units in the main chain can be cited. The diamine is preferably a diamine containing 2 or more ethylene glycol chains or propylene glycol chains or a combination of both chains in one molecule, and more preferably a diamine containing no aromatic ring. Specific examples thereof include, but are not limited to, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, and D-4000 (the above are product names, manufactured by HUNTSMAN corporation), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine.

The following shows the structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176.

[ chemical formula 11]

In the above, x, y and z are average values.

From the viewpoint of flexibility of the obtained cured film, R is preferable¹¹¹from-Ar⁰-L⁰-Ar⁰-represents. Wherein Ar is⁰Each independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L is⁰Represents a single bond or is selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C (═ O) -, -S (═ O)₂-, -NHCO-and combinations of these. Preferred ranges are defined as above for A.

From the viewpoint of i-ray transmittance, R is preferable¹¹¹Is a 2-valent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and ready availability, a 2-valent organic group represented by formula (61) is more preferable.

[ chemical formula 12]

R⁵⁰～R⁵⁷Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R⁵⁰～R⁵⁷At least one of which is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

When R is⁵⁰～R⁵⁷An organic radical having a valence of 1Examples thereof include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.

[ chemical formula 13]

R⁵⁸And R⁵⁹Each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound to which the structure of formula (51) or (61) is imparted include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, 4' -diaminooctafluorobiphenyl, and the like. One of them may be used, or 2 or more of them may be used in combination.

＜＜＜R¹¹⁵＞＞＞

R in the formula (1)¹¹⁵Represents a 4-valent organic group. The organic group having a valence of 4 is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

[ chemical formula 14]

R¹¹²The same definition as in A applies to the preferred ranges.

With respect to R in the formula (1)¹¹⁵Specific examples of the organic group having a valence of 4 include tetracarboxylic acid residues remaining after removing an acid dianhydride group from a tetracarboxylic acid dianhydride. Only one tetracarboxylic dianhydride may be used, or 2 or more tetracarboxylic dianhydrides may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[ chemical formula 15]

R¹¹⁵Represents a 4-valent organic group. R¹¹⁵Is defined as in formula (1) and R¹¹⁵The same is true.

Specific examples of the tetracarboxylic acid dianhydride include tetracarboxylic acid dianhydrides selected from the group consisting of pyromellitic acid, pyromellitic acid dianhydride (PM DA), 3,3 ', 4,4 ' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenyl sulfide tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylmethane tetracarboxylic acid dianhydride, 2 ', 3,3 ' -diphenylmethane tetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -biphenyltetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -benzophenonetetracarboxylic acid dianhydride, 4,4 ' -oxydiphthalic acid dianhydride, 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 1,4,5, 7-naphthalenetetracarboxylic acid dianhydride, 1,4, 7-naphthalenetetracarboxylic acid dianhydride, and mixtures thereof, 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 3,4, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,8,9, 10-phenanthrenetetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzenetetracarboxylic dianhydride, and at least one of C1-6 alkyl derivatives and C1-6 alkoxy derivatives thereof.

Further, as preferable examples, tetracarboxylic dianhydrides (DAA-1) to (D AA-5) shown below can be given.

[ chemical formula 16]

＜＜＜R¹¹³And R¹¹⁴＞＞＞

R in the formula (1)¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group. Preferably R¹¹³And R¹¹⁴At least one of (a) and (b) contains a radical polymerizable group, and more preferably both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and the radical polymerizable group isA preferable example thereof is a group having an ethylenically unsaturated bond.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, a group represented by the following formula (III), and the like.

[ chemical formula 17]

R²⁰⁰Represents a hydrogen atom or a methyl group, more preferably a methyl group.

R²⁰¹An alkylene group having 2 to 12 carbon atoms, -CH₂CH(OH)CH₂Or a (poly) oxyalkylene group having 4 to 30 carbon atoms (as the alkylene group, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms; the number of repetitions is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms). In addition, (poly) oxyalkylene means oxyalkylene or polyoxyalkylene.

Preferred R²⁰¹Examples of the "C" group include ethylene, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene and-CH₂CH(OH)CH₂-, more preferably ethylene, propylene, trimethylene, -CH₂CH(OH)CH₂-。

Particularly preferred is R²⁰⁰Is methyl, R²⁰¹Is an ethylene group.

A preferred embodiment of the polyimide precursor includes R¹¹³Or R¹¹⁴The 1-valent organic group in (1) includes an aliphatic group, an aromatic group, an aralkyl group, and the like having 1,2, or 3, preferably 1, acid groups in addition to the sulfonic acid group described later. Specifically, the aromatic group has 6 to 20 carbon atoms and has an acid group, and the aralkyl group has 7 to 25 carbon atoms and has an acid group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group are exemplified. The acid group is preferably a hydroxyl group. Namely, R¹¹³Or R¹¹⁴Preferred is a group having a hydroxyl group.

As a group consisting of R¹¹³Or R¹¹⁴The 1-valent organic group may preferably be a substituent which improves the solubility of the developer.

From the viewpoint of solubility in an aqueous developer, R is more preferably¹¹³Or R¹¹⁴Is hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in organic solvents, R is preferred¹¹³Or R¹¹⁴Is a 1-valent organic group. The organic group having a valence of 1 preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic group). The alkyl group may be any of linear, branched, and cyclic. Examples of the straight-chain or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group and a 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, bornyl, camphene, decahydronaphthyl, tricyclodecanyl, tetracyclodecyl, camphoryl, dicyclohexyl, and pinenyl (pinenyl). Among these, cyclohexyl is most preferable from the viewpoint of achieving both high sensitivity and high sensitivity. The alkyl group substituted with an aromatic group is preferably a straight-chain alkyl group substituted with an aromatic group described later.

Examples of the aromatic group include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, tetracene ring, perylene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, perylene ring, acenaphthylene ring, perylene ring, acenaphthylene ring, anthracene ring, and acen,

Cyclic, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiopheneA ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thiophene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. Most preferred is a benzene ring.

Further, in the polyimide precursor, it is also preferable that the constituent unit has a fluorine atom. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. The upper limit is not particularly limited, and is actually 50% by mass or less.

In addition, an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by formula (1) for the purpose of improving adhesion to the substrate. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.

The structural unit represented by formula (1) is preferably a structural unit represented by formula (1-A).

[ chemical formula 18]

A¹¹And A¹²Represents an oxygen atom or NH, R¹¹¹And R¹¹²Each independently represents a 2-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group, R¹¹³And R¹¹⁴At least one of them is a radical polymerizable group-containing group, and preferably a radical polymerizable group.

A¹¹、A¹²、R¹¹¹、R¹¹³And R¹¹⁴Are each independently defined as A in the formula (1)¹、A²、R¹¹¹、R¹¹³And R¹¹⁴Similarly, the preferred ranges are also the same.

R¹¹²Is determined byR in the formula (5)¹¹²Similarly, the preferred ranges are also the same.

In the polyimide precursor, the number of the structural units represented by the formula (1) may be 1, but may be 2 or more. Further, the structural isomer of the structural unit represented by the formula (1) may be contained. The polyimide precursor may contain other types of structural units in addition to the structural unit of formula (1).

The polyimide precursor preferably has a site (structural unit or terminal structure) represented by any one of the formulae (1-1a), (1-2a) and (1-3 a).

[ chemical formula 19]

In the formula, A¹、A²、R¹¹¹、R¹¹³、R¹¹⁴、R¹¹⁵The definition of (2) is the same as that in the formula (1), and the preferable range is also the same. Denotes a bonding position to the main chain of the polyimide precursor. Ls is the above formula (Ls). In this case, Li of the formula (Ls) is preferably represented by formula (1-1a)¹-NHCO. In the formulae (1-2a) and (1-3a), preferably¹-COO or¹-CONH。

More preferably, the polyimide precursor has a site represented by any one of the formulae (1-1), (1-2) and (1-3).

[ chemical formula 20]

In the formula, A¹、A²、R¹¹¹、R¹¹³、R¹¹⁴、R¹¹⁵The definition of (2) is the same as that in the formula (1), and the preferable range is also the same. X¹、X²And X³Each independently represents a linking group, represents a bonding position to the main chain of the polyimide precursor, and ns is defined as the formula Ls.

X¹、X²And X³Each independently represents a group having a carbon atomA linking group of (3), preferably X¹、X²And X³Bonded to the sulfonic acid group via a carbon atom.

Preferably X¹、X²And X³Is a group having the above-mentioned linking group Lt or an oxygen atom, a carbonyl group and-NR^N-at least one of the groups in combination with a linking group Lt. At this time, a sulfonic acid group is bonded to the side of the linking group Lt. R^NThe details of (A) are described later, but among them, R is preferable^NIs a hydrogen atom.

X in the formula (1-3) is preferable³Is a linking group Lt. On the other hand, X in the formula (1-1) is preferable¹Having a carbonyl group attached to the NH of the backbone in addition to the linking group Lt. X in the formula (1-2) is preferable²Likewise and in addition to the linking group Lt, has an oxygen atom or-NR attached to a carbonyl group of the main chain^N-。

As an embodiment of the present invention, there can be exemplified A in which a structural unit of the main chain of the formula (1-1), the formula (1-2) or the formula (1-3) is bonded¹、A²、R¹¹¹、R¹¹³、R¹¹⁴、R¹¹⁵And A in formula (1-1), formula (1-2) and formula (1-3)¹、A²、R¹¹¹、R¹¹³、R¹¹⁴、R¹¹⁵The same group or the same atom.

X¹、X²、X³Lt and Lt may have a substituent T in a range in which the effects of the present invention are exhibited. When the substituent T is plural, it may be bonded to each other or bonded to the ring in the formula via the linking group L or not via the linking group L to form a ring. However, it preferably has no substituent.

Aromatic ring (R) as a main chain constituting a polyimide precursor¹¹⁵、R¹¹¹Preferred structure of (2) a reagent for introducing a site containing a sulfonic acid group, preferably having a structure¹-Lt-(SO₃H)_nsA compound of the structure (1). Examples of the introduction reagent include sulfobenzoic acid, aminobenzenesulfonic acid, aminoethanesulfonic acid, hydroxyethanesulfonic acid, hydroxypropanesulfonic acid, propane sultone, and butane sultone. The method of introducing a site containing a sulfonic acid group is not particularly limitedBut can be obtained by reacting the above-mentioned reagent with a polyimide precursor together with a catalyst or reacting the reagent during the synthesis thereof, if necessary. The same applies to polybenzoxazole precursors described later.

In the present invention, the structural unit of the polyimide precursor may or may not include a structural unit in which a sulfonic acid group is directly introduced into an aromatic ring in the main chain. In the range in which the effects of the present invention are exhibited, it is understood that the effects of the present invention can be sufficiently exhibited even if the polyimide precursor having such directly linked sulfonic acid groups in the constituent unit is, for example, 10% or less, further 1% or less, depending on the conditions and applications.

Examples of the substituent T include a cyclic or linear or branched alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms), a cyclic or linear or branched alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, even more preferably 2 to 6 carbon atoms), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, even more preferably 7 to 11 carbon atoms), a hydroxyl group, an amino group (preferably having 0 to 24 carbon atoms, more preferably 0 to 12 carbon atoms, even more preferably 0 to 6 carbon atoms), a thiol group, a carboxyl group, an acyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 3 carbon atoms), an acyloxy group (preferably having 2 to 12 carbon atoms, even more preferably 2 to 6, particularly preferably 2 to 3), an aroyl group (preferably 7 to 23, more preferably 7 to 19, particularly preferably 7 to 11), an aralkyl group (preferably 7 to 23, more preferably 7 to 19, particularly preferably 7 to 11), a (meth) acryloyl group, a (meth) acryloyloxy group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an oxo group (═ O), an imino group (═ NR)^N) Alkylene (═ C (R)^N)₂) And the like. Heteroatoms may also be present in the alkylene chain of the substituent T. The alkyl, alkenyl, aryl, and aralkyl groups in the substituent T may be further substituted with other substituents.

R^NThe organic group is preferably an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), or an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms). The organic group may further have a substituent T.

The linking group L is a cyclic or linear or branched alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), a cyclic or linear or branched alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an arylalkylene group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms), a heteroarylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms), and examples of a hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, an oxygen atom, a carbonyl group, a-NR group^N-or groups related to combinations thereof. The number of atoms constituting the linking group L is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6, in addition to a hydrogen atom. The number of connecting atoms of the linking group is preferably 10 or less, more preferably 8 or less. The lower limit is 1 or more. The number of the connecting atoms is the smallest number of atoms which are located between the structures defined by the connection and which are involved in the connection. For example, -CH₂In the case of — C (═ O) -O —, the number of atoms constituting the linking group excluding hydrogen atoms is 4, but the number of linking atoms is 3.

Examples of the heteroatom-containing linking group Lh include an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group and-NR^NOr a linking group comprising a combination of these. The number of atoms constituting the heteroatom-containing linking group Lh is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The number of atoms present in a specific group of the heteroatom-containing linking group Lh is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 121～3。R^NThe definitions of (a) are the same as above.

The total number of sulfonic acid groups contained in the polyimide precursor is preferably 0.05% or more, more preferably 0.1% or more, even more preferably 0.2% or more, even more preferably 0.3% or more, even more preferably 0.35% or more, even more preferably 0.4% or more, and may be 50 mol% or more, 70 mol% or more, or 90 mol% or more of the total number of structural units. The upper limit may be 100% or less, but is preferably 20.0% or less, more preferably 15.0% or less, still more preferably 10.0% or less, yet more preferably 8.0% or less, yet more preferably 6.0% or less, and particularly preferably 5.0% or less. By setting the ratio of the sulfonic acid group in the above range, both the storage stability and the copper corrosiveness can be more effectively exhibited.

In the polyimide precursor, the structural unit having the sulfonic acid group (preferably, the group of the formula (Ls)) may occupy the whole of the structural units constituting the polyimide precursor, but may have a locally different structural unit. The structural unit having a site containing the sulfonic acid group (preferably a group of the formula (Ls)) is preferably 0.05% or more, more preferably 0.1% or more, further preferably 0.2% or more, further preferably 0.3% or more, further preferably 0.35% or more, particularly preferably 0.4% or more, and may be 50 mol% or more, 70 mol% or more, or 90 mol% or more of the total structural unit. The upper limit may be 100% or less, but is preferably 20.0% or less, more preferably 15.0% or less, still more preferably 10.0% or less, yet more preferably 8.0% or less, yet more preferably 6.0% or less, and particularly preferably 5.0% or less.

An example of the structure having a sulfonic acid group in the polyimide precursor is shown below. It goes without saying that the present invention is not limited to these.

< mode in which sulfonic acid group is bonded to the end of polyimide precursor (end of main chain)

[ chemical formula 21]

[ chemical formula 22]

< mode in which sulfonic acid group is bonded to side chain (side chain of main chain structure) of polyimide precursor

[ chemical formula 23]

As an embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of the total structural units is the structural unit represented by the formula (1) or a structural unit having a sulfonic acid group in a side chain can be exemplified. The upper limit is actually 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.

The dispersion degree (Mw/Mn) of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or dicarboxylic acid derivative is halogenated with a halogenating agent and then can be reacted with a diamine.

In the method for producing a polyimide precursor, an organic solvent is preferably used when the reaction is carried out. The organic solvent may be one kind or 2 or more kinds.

The organic solvent can be appropriately set according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

The production of the polyimide precursor preferably includes a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid deposition can be performed.

Precursor of polybenzoxazole

The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).

[ chemical formula 24]

R¹²¹Represents an organic group having a valence of 2, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group.

R¹²¹Represents an organic group having a valence of 2. The 2-valent organic group is preferably a group containing at least one of an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms). As a constituent R¹²¹Examples of the aromatic group of (3) include R of the above formula (1)¹¹¹An example of the method. The aliphatic group is preferably a straight-chain aliphatic group. Preferably R¹²¹From 4, 4' -oxodibenzoyl chloride.

R¹²²Represents a 4-valent organic group. As the 4-valent organic group, the same as defined for R in the above formula (1)¹¹⁵Similarly, the preferred ranges are also the same. Preferably R¹²²From 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group, which is as defined above for R in the formula (1)¹¹³And R¹¹⁴Similarly, the preferred ranges are also the same.

The polybenzoxazole precursor preferably has a site represented by the following formulae (2-1a), (2-2a) and (2-3 a).

[ chemical formula 25]

In the formula, R¹²¹、R¹²²、R¹²³、R¹²⁴The definition of (3) is the same as that in the formula (2), and the preferable range is also the same. Denotes the bonding position to the main chain of the polybenzoxazole precursor. Ls is a radical of the above formula (Ls). Among them, in the case of formula (2-1a), Li of formula (Ls) is preferably 1-NHCO. In the case of the formula (2-2a), 1-COO or CONH is preferable. In the case of formula (2-3a), Li is preferably 1-OCO. In the formula (Ls), the definitions of the other Lt or ns are the same as those in the case of the formula (1). In addition, where 1 is R¹²¹Or R¹²²Lateral bonding position.

The polybenzoxazole precursor further preferably has a site represented by the following formula (2-1), (2-2) or (2-3).

[ chemical formula 26]

In the formula, R¹²¹、R¹²²、R¹²³And R¹²⁴The definition of (3) is the same as that of the formula (2). X⁴、X⁵And X⁶Each independently represents a linking group, represents a bonding position to the main chain of the polybenzoxazole precursor, and ns represents an integer of 1 to 4.

X⁴、X⁵And X⁶Each independently represents a linking group having a carbon atom, preferably X⁴、X⁵And X⁶Bonded to the sulfonic acid group via a carbon atom.

Preferably X⁴、X⁵And X⁶Is a linking group Lt or an oxygen atom, a carbonyl group and-NR^N-at least one group in combination therewith. ns is preferably 1 or 2, more preferably 1.

X⁴、X⁵、X⁶Lt and Lt may have a substituent T in a range in which the effects of the present invention are exhibited.

The ratio of the number of sulfonic acid group-containing sites in the polybenzoxazole precursor is the same as the ratio defined in the polyimide precursor. The reagent for introducing a sulfonic acid group-containing site into the polybenzoxazole precursor or the method for introducing the same is the same as the method described for the polyimide precursor.

An example of the structure having a sulfonic acid group in the polybenzoxazole precursor is shown below. It goes without saying that the present invention is not limited to these.

< mode of bonding sulfonic acid group to end of polybenzoxazole precursor >

[ chemical formula 27]

< mode of bonding sulfonic acid group to side chain of polybenzoxazole precursor >

[ chemical formula 28]

The polybenzoxazole precursor may contain other kinds of structural units in addition to the structural unit of the above formula (2).

From the viewpoint of suppressing the occurrence of warpage in the cured film accompanying ring closure, it is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another type of structural unit.

[ chemical formula 29]

Z has a structure a and a structure b, R^1sIs a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R^2sIs a C1-10 hydrocarbon group (preferably C1-6, more preferably C1-3), R^3s、R^4s、R^5s、R^6sAt least one of which is an aromatic group (preferably a carbon atom)The number of the carbon atoms is 6 to 22, more preferably 6 to 18, and particularly preferably 6 to 10, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), and the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, the a structure is preferably 5 to 95 mol%, the b structure is preferably 95 to 5 mol%, and a + b is preferably 100 mol%.

In the formula (SL), preferable Z is R in the structure of b^5sAnd R^6sZ being phenyl. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by gel permeation chromatography which is generally used. By setting the molecular weight in the above range, the effects of reducing the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, suppressing warpage, and improving solubility can be achieved at the same time.

When the other type of structural unit contains a diamine residue represented by the formula (SL), it is preferable that the precursor further contains, as a structural unit, a tetracarboxylic acid residue remaining after removing an acid dianhydride group from the tetracarboxylic acid dianhydride, from the viewpoint of improving the alkali solubility. As an example of such tetracarboxylic acid residues, R in the formula (1) can be mentioned¹¹⁵An example of the method.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.

The molecular weight dispersity (Mw/Mn) of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The content of the polymer precursor in the photosensitive resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on the total solid content of the composition. In the upper limit, the content of the polymer precursor in the photosensitive resin composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 95% by mass or less, and further preferably 95% by mass or less, based on the total solid content of the composition.

The photosensitive resin composition may contain only 1 kind of polymer precursor, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably in the above range.

< solvent >

The photosensitive resin composition of the present invention preferably contains a solvent. The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, -caprolactone, -valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.) (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) Alkyl esters of 2-alkoxypropionic acid (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate and the like are preferred esters.

Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene, which are preferable aromatic hydrocarbons.

As the sulfoxide, for example, dimethyl sulfoxide is cited as a preferable sulfoxide.

Examples of the amide include preferable amides such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.

From the viewpoint of improvement of the properties of the coated surface, it is also preferable to mix 2 or more solvents.

In the present invention, it is preferable that the solvent is one or a mixture of 2 or more solvents selected from the group consisting of methyl 3-ethoxypropionate, ethyl ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate. Particularly preferably, dimethyl sulfoxide and gamma-butyrolactone are used simultaneously.

The content of the solvent is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass, of the total solid content concentration of the photosensitive resin composition of the present invention, from the viewpoint of coatability. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method.

The solvent may contain only one kind, or may contain 2 or more kinds. When 2 or more solvents are contained, the total amount thereof is preferably in the above range.

< photoactive Compound >

In the present invention, the photosensitive resin composition contains a photoactive compound. Examples of the photoactive compound include a photopolymerization initiator, a photoacid generator, and a photocuring accelerator.

[ photopolymerization initiator ]

The photosensitive resin composition of the present invention may contain a photopolymerization initiator. Preferably, the photopolymerization initiator is a photo radical polymerization initiator.

The photo radical polymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light from an ultraviolet region to a visible region is preferable. And may be an active agent that exerts some action with the photo-excited photosensitizer and generates active radicals.

Preferably, the photo radical polymerization initiator contains at least one compound having an absorption coefficient of at least about 50 mol in the range of about 300 to 800nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferable to perform measurement by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian corporation) at a concentration of 0.01g/L using an ethyl acetate solvent.

When the photosensitive resin composition of the present invention contains a photo-radical polymerization initiator, curing due to radicals generated by applying the photosensitive resin composition of the present invention to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer and then irradiating the photosensitive resin composition layer with light can be caused, and the solubility in a light irradiated portion can be reduced. Therefore, there is an advantage that, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern for masking only the electrode portion, regions having different solubilities can be easily produced according to the pattern of the electrode.

As the photo radical polymerization initiator, known compounds can be arbitrarily used, and examples thereof include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference can be made to the descriptions in paragraphs 0165 to 0182 of japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.

Examples of the ketone compound include those described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, which are incorporated herein by reference. Among commercially available products, KAYA CURE DETX (manufactured by nippon kayaku co., ltd.) is also preferably used.

As the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese patent laid-open No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184(IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names, both manufactured by BASF corporation) can be used.

As the aminoacetophenone initiator, commercially available IRGACURE 907, IRGACU RE 369 and IRGACURE 379 (product names, both manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, a compound described in Japanese patent laid-open publication No. 2009-191179, which has a maximum absorption wavelength matching a light source having a wavelength of 365nm or 405nm, can also be used.

Examples of the acylphosphine initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 or IRGACURE-TPO (product name, manufactured by BASF) can be used as a commercially available product.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF corporation).

The photo radical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be further effectively improved. Among oxime compounds, oxime compounds are particularly preferable because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

Specific examples of the oxime compound include compounds described in Japanese patent application laid-open Nos. 2001-233842, 2000-080068, and 2006-342166.

Preferred examples of the oxime compounds include compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the photosensitive resin composition of the present invention, an oxime compound (oxime-based photopolymerization initiator) is particularly preferably used as the photo radical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of > C — N — O — C (═ O) -in the molecule.

[ chemical formula 30]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE03, IRGACURE OXE 04 (manufactured by BASF Co., Ltd.), and ADEKA OPTOMER N-1919 (photo radical polymerization initiator 2 disclosed in ADEKA CORPORATION, Japanese patent application laid-open No. 2012 and 014052) can also be preferably used. Also, TR-PBG-304 (manufactured by Changzhou Tronly New electronic Materials Co., Ltd.), ADEKA ARKLSNCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Also, DFI-091 (manufactured by DAITO cheimix co., ltd.) can be used.

Further, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24, 36 to 40 described in section 0345 of Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in section 0101 of Japanese patent application laid-open No. 2013-164471.

Most preferred oxime compounds include those having a specific substituent as shown in Japanese patent laid-open Nos. 2007-269779 and 2009-191061.

From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

More preferred photo radical polymerization initiators are trihalomethyl triazine compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, further preferably at least one compound selected from the group consisting of trihalomethyl triazine compounds, α -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, still further preferably metallocene compounds or oxime compounds are used, and still further preferably oxime compounds are used.

Further, as the photo radical polymerization initiator, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone such as benzophenone and N, N ' -tetramethyl-4, 4 ' -diaminobenzophenone (Michler's ketone)), aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, and quinones obtained by condensing alkylanthraquinone with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal can be used. Further, a compound represented by the following formula (I) can also be used.

[ chemical formula 31]

In the formula (I), R^I00Is a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, R is^I01Is a group represented by the formula (II), or with R^I00Same radicals, R^I02～R^I04Each independently is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a halogen.

[ chemical formula 32]

In the formula, R^I05～R^I07With R of the above formula (I)^I02～R^I04The same is true.

Further, as the photo radical polymerization initiator, a compound described in paragraphs 0048 to 0055 of International publication WO2015/125469 can be used.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The photopolymerization initiator may include only 1 kind, or may include 2 or more kinds. When 2 or more photopolymerization initiators are contained, the total amount thereof is preferably in the above range.

Photoacid generators

In the present invention, a photoacid generator can be used as the photoactive compound. Specifically, known compounds and mixtures thereof that generate an acid upon irradiation with actinic rays or radiation used for photocationic polymerization, photoradical polymerization initiators, dye-based photobleaches, photochromic agents, photoresists, and the like can be suitably selected and used. Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. When the photoacid generator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, even more preferably 0.5 to 10% by mass, and even more preferably 0.5 to 5% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The photoacid generator may contain only 1 species, or may contain 2 or more species. When 2 or more types of photoacid generators are contained, the total amount thereof is preferably in the above range.

(photo-curing accelerator)

The photosensitive resin composition used in the present invention may contain a photo-curing accelerator. The photocurable accelerator in the present invention is an accelerator that generates an alkali upon exposure to light and does not exhibit activity under normal conditions at normal temperature and pressure, but is not particularly limited as long as it generates an alkali (basic substance) when electromagnetic waves are irradiated and heated as an external stimulus. The base generated by exposure can be preferably used because it acts as a catalyst when the polymer precursor is cured by heating.

In the present invention, a known photo-curing accelerator can be used as the photo-curing accelerator. Examples of the compound include nonionic compounds, such as transition metal compound complexes, complexes having a structure of ammonium salts or the like, ionic compounds neutralized by salt formation of a base component, which are latent by salt formation of an amidine moiety and carboxylic acids, and photocuring accelerators in which a base component is latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.

Examples of the photocuring accelerator according to the present invention include a photocuring accelerator having a cinnamamide structure as disclosed in japanese patent laid-open publication No. 2009-080452 and international publication No. 2009/123122, a photocuring accelerator having a urethane structure as disclosed in japanese patent laid-open publication nos. 2006-189591 and 2008-247747, and a photocuring accelerator having an oxime structure or a carbamoyl oxime structure as disclosed in japanese patent laid-open publication nos. 2007-249013 and 2008-003581, but the present invention is not limited thereto, and a known photocuring accelerator may be used in addition to these.

Examples of the photo-curing accelerator include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese patent laid-open No. 2012-093746, compounds described in paragraphs 0022 to 0069 of Japanese patent laid-open No. 2013-194205, compounds described in paragraphs 0026 to 0074 of Japanese patent laid-open No. 2013-204019, and compounds described in paragraph 0052 of International publication No. WO 2010/064631.

As commercially available products of the photo-curing accelerator, WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used.

When the photo-curing accelerator is used, the content of the photo-curing accelerator in the composition is preferably 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.

The photo-curing accelerator can be used in 1 kind or 2 or more kinds. When 2 or more species are used, the total amount is preferably in the above range.

< thermal radical polymerization initiator >

The photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator within a range not departing from the gist of the present invention.

The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates a polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, cyclization of the polymer precursor can be performed, and the polymerization reaction of the polymer precursor can be performed, so that higher heat resistance can be achieved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063554.

When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 5 to 15% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The thermal radical polymerization initiator may contain only 1 species, or may contain 2 or more species. When 2 or more thermal radical polymerization initiators are contained, the total amount thereof is preferably in the above range.

< polymerizable Compound >

< radically polymerizable compound >

The photosensitive resin composition of the present invention preferably contains a radical polymerizable compound.

As the radical polymerizable compound, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinylphenyl group, a vinyl group, a (meth) acryloyl group, and an allyl group. The radical polymerizable group is preferably a (meth) acryloyl group.

The number of radical polymerizable groups of the radical polymerizable compound may be 1 or 2 or more, but the radical polymerizable compound preferably has 2 or more radical polymerizable groups, and more preferably 3 or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

The molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one 2-or more-functional radical polymerizable compound having 2 or more polymerizable groups, and more preferably contains at least one 3-or more-functional radical polymerizable compound. Further, a mixture of a 2-functional radical polymerizable compound and a 3-or more-functional radical polymerizable compound may be used. The number of functional groups of the radically polymerizable compound means the number of radically polymerizable groups in one molecule.

Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyhydric amine compounds. Further, addition reaction products of unsaturated carboxylic acid esters or amides having an affinity substituent such as a hydroxyl group, an amino group, or a mercapto group with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, and the like can also be preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanate group or epoxy group with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having releasable substituent groups such as halogen group or tosyloxy group with monofunctional or polyfunctional alcohols, amines, and thiols are also preferable. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with an unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether, or the like can be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese patent laid-open No. 2016-027357, which are incorporated herein by reference.

Further, the radical polymerizable compound is preferably a compound having a boiling point of 100 ℃ or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane and the like, urethane (meth) acrylates described in Japanese patent publication Sho-48-041708, Japanese patent publication Sho-50-006034, Japanese patent laid-open publication Sho-51-037193, urethane (meth) acrylates described in Japanese patent publication Sho-51-037193, urethane (meth) acrylates, urethane acrylates, and urethane acrylates, The polyester acrylates described in JP-A-48-064183, JP-A-49-043191 and JP-A-52-030490, and the polyfunctional acrylates or methacrylates such as epoxy acrylates as a reaction product of an epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also preferable. Further, there can be mentioned a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate.

Further, as a preferable radical polymerizable compound other than the above, a compound having a fluorene ring and having 2 or more ethylenically unsaturated bond-containing groups or a cardo resin described in japanese patent application laid-open nos. 2010-160418, 2010-129825, 4364216, and the like can be used.

Further, as other examples, specific unsaturated compounds described in Japanese patent publication No. 46-043946, Japanese patent publication No. 1-040337, and Japanese patent publication No. 1-040336, vinylphosphonic acid compounds described in Japanese patent publication No. 2-025493, and the like can be cited. Furthermore, a compound containing a perfluoroalkyl group as described in Japanese patent application laid-open No. 61-022048 can also be used. Further, compounds described as photopolymerizable monomers and oligomers in Journal of the administration Society of Japan, vol.20, No.7, pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 can be preferably used, and these contents are incorporated in the present specification.

Further, compounds obtained by (meth) acrylating after addition of ethylene oxide or propylene oxide to polyfunctional alcohols described as the formula (1) and the formula (2) and specific examples thereof in Japanese patent application laid-open No. 10-062986 can also be used as radical polymerizable compounds.

The compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can also be used as other radical polymerizable compounds, and these contents are incorporated in the present specification.

As the radical polymerizable compound, dipentaerythritol triacrylate (KaYARAD-330; Nippon Kayaku Co., manufactured by Ltd., as a commercial product), dipentaerythritol tetraacrylate (KaYARAD-320; Nippon Kayaku Co., manufactured by Ltd., as a commercial product), dipentaerythritol penta (meth) acrylate (KaYARAD-310; Nippon Kayaku Co., manufactured by Ltd., as a commercial product), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; Nippon Kayaku Co., manufactured by Ltd., as a commercial product), dipentaerythritol hexa (meth) acrylate (A-DPH; Shin-Nakamura Co., manufactured by Ltd., as a commercial product) and a structure in which (meth) acryloyl groups thereof are bonded via ethylene glycol residues or propylene glycol residues are preferable. Their oligomer type can also be used.

Commercially available products of the radical polymerizable compound include, for example, SR-494 (manufactured by Sartomer Company, Inc.) as a 4-functional acrylate having 4 vinylene chains, SR-209, 231, 239 (manufactured by Sartomer Company, Inc.) as a 2-functional acrylate having 4 vinylene chains, SR-209, 231, 239 (manufactured by Nippon Kayaku Co., Ltd.), DPCA-60 (manufactured by Ltd.) as a 6-functional acrylate having 6 pentenyloxy chains, TPA-330 (manufactured by 3-functional acrylate having 3 isobutoxy chains), urethane oligomer UAS-10, urethane oligomer UAB-140(NIPPON PAPENNDUSES CO., manufactured by LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NKESTER A-9300, NK NAkaura-7200 (manufactured by Shin-Co., Lklu Co., manufactured by Shi Chemical Co., LTP 40 HA (manufactured by Nippon Co., Ltd.), Nippon Kayaku Co., Japan). Ltd, manufactured), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600(Kyoeisha chemical co., ltd, manufactured), BLEMMER PME400(NOF corporation, manufactured), and the like.

As the radical polymerizable compound, urethane acrylates such as those disclosed in JP-B-48-041708, JP-B-51-037193, JP-B-2-032293 and JP-B-2-016765, urethane compounds having an ethylene oxide skeleton as disclosed in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also preferable. Further, as the radical polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 1-105238 can be used.

The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphoric group. Among the radical polymerizable compounds having an acid group, an ester of an aliphatic polyhydroxyl compound and an unsaturated carboxylic acid is preferable, and a radical polymerizable compound having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxyl compound with a non-aromatic carboxylic acid anhydride is more preferable. In particular, among the radical polymerizable compounds having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, the aliphatic polyhydroxy compound is preferably a compound of pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as the polybasic acid-modified acrylic oligomer produced by TOAGOSEI CO., Ltd.

The acid value of the radical polymerizable compound having an acid group is preferably 0.1 to 40mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the radical polymerizable compound is within the above range, the production and handling properties are excellent, and the developability is excellent. Further, the polymerizability is good.

The photosensitive resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as a radical polymerizable compound from the viewpoint of suppressing warpage associated with elastic modulus control of a cured film. As the monofunctional radical polymerizable compound, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, (meth) acrylic acid derivatives such as glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate. The monofunctional radical polymerizable compound is preferably a compound having a boiling point of 100 ℃ or higher under normal pressure in order to suppress volatilization before exposure.

< polymerizable Compound other than the above-mentioned radically polymerizable Compound >

The photosensitive resin composition of the present invention may further contain a polymerizable compound other than the above radical polymerizable compound. Examples of the polymerizable compound other than the radical polymerizable compound include compounds having a methylol group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; an oxetane compound; benzo (b) is

An oxazine compound.

(Compound having hydroxymethyl group, alkoxymethyl group or acyloxymethyl group)

As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.

[ chemical formula 33]

(wherein t represents an integer of 1 to 20, R¹⁰⁴A t-valent organic group having 1 to 200 carbon atoms, R¹⁰⁵Is represented by-OR¹⁰⁶or-OCO-R¹⁰⁷A group represented by R¹⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms¹⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

[ chemical formula 34]

(in the formula, R⁴⁰⁴R is a 2-valent organic group having 1 to 200 carbon atoms⁴⁰⁵Is represented by-OR⁴⁰⁶or-OCO-R⁴⁰⁷A group represented by R⁴⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁴⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

[ chemical formula 35]

(wherein u represents an integer of 3 to 8, R⁵⁰⁴A u-valent organic group having 1 to 200 carbon atoms, R⁵⁰⁵Is represented by-OR⁵⁰⁶or-OCO-R⁵⁰⁷A group represented by R⁵⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁵⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (hereinafter referred to as "ASAHI ORGANIC CHEMICALS INDUSTRY CO", LTD "), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (hereinafter referred to as" product "or" Honshu Chemical INDUSTRY Co., Ltd. "), NIKALAC MX-290 (hereinafter referred to as" product "or" Sanewa Chemical Co., Ltd. "), 2, 6-dimethylymethyl-4-t-butanol, 2, 6-dimethylmethane-p-4-diol, 2, 6-dimethylmethane-p-diol, 2-6-dimethylmethane-4-diol, 2-dimethylmethane-c-diol, and 2-dimethylmethane-p-2, 6-methane-diol.

Specific examples of the compound represented by the formulｃA (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (product name, manufactured by AHI ORGANIC CHEMICALS INDUSTRY CO., LTD.), NIKALAC MX-280, KANILAC MX-270, NIKALAC MW-100LM (product name, manufactured by SanwｃA Chemical Co., Ltd.).

(epoxy Compound (Compound having epoxy group))

The epoxy compound is preferably a compound having 2 or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200 ℃ or lower, and film shrinkage is difficult to occur because a dehydration reaction due to crosslinking does not occur. Therefore, by containing the epoxy compound, low-temperature curing and warpage of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warpage. The polyethylene oxide group is a compound having an ethylene oxide structural unit number of 2 or more, and the structural unit number is preferably 2 to 15.

Examples of the epoxy compound include bisphenol a type epoxy resins; bisphenol F type epoxy resins; alkylene glycol-based epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol-based epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicone such as polymethyl (glycidoxypropyl) siloxane, but the epoxy group-containing silicone is not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (above, product name DIC S, EP, product name RIKARESIN (registered trademark) EXO-60, product name Corporation, product name 4000, product name Lpan-4000, product name 4000, EP-40052, manufactured by adekakoroporation), and the like. Among them, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppression of warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain a polyethylene oxide group, and are therefore preferable.

(Oxetane Compound (Compound having an Oxetanyl group))

Examples of the oxetane compound include a compound having 2 or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester, and the like. As a specific example, ARON oxoetane series (for example, OXT-121, OXT-221, OXT-191, and OXT-223) can be preferably produced using TOAGOSEI co.

(benzo

Oxazine compound (compound having polybenzoxazole group)

Benzo (b) is

Oxazine compound factorThe crosslinking reaction by the ring-opening addition reaction is preferable because degassing does not occur during curing, and further, the occurrence of warpage is suppressed by reducing thermal shrinkage.

As benzene

As a preferred example of the oxazine compound, B-a type benzo

Oxazine, B-m type benzo

Benzoxazine (product name, Shikoku Chemicals Corporation), polyhydroxystyrene resin

Oxazine adduct and novolak-type dihydrobenzo

An oxazine compound. These may be used alone, or 2 or more kinds may be mixed.

When the polymerizable compound is contained, the content thereof is preferably more than 0 mass% and 60 mass% or less with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and still more preferably 30% by mass or less.

The polymerizable compound may be used alone in 1 kind, but may be used in combination with 2 or more kinds. When 2 or more kinds are used simultaneously, the total amount thereof is preferably in the above range.

< migration inhibitor >

Preferably, the photosensitive resin composition of the present invention further comprises a migration inhibitor. By including the migration inhibitor, it is possible to effectively inhibit the metal ions from the metal layer (metal wiring) from migrating into the photosensitive resin composition layer.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, and triazine ring), compounds having a thiourea group and a mercapto group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as 1,2, 4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Further, an ion scavenger for scavenging anions such as halide ions can also be used.

As other migration inhibitors, there can be used rust inhibitors described in paragraph 0094 of Japanese patent application laid-open No. 2013-015701, compounds described in paragraphs 0073-0076 of Japanese patent application laid-open No. 2009-283711, compounds described in paragraph 0052 of Japanese patent application laid-open No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese patent application laid-open No. 2012-194520, and the like.

Specific examples of the migration inhibitor include the following compounds.

[ chemical formula 36]

When the photosensitive resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of the photosensitive resin composition.

The number of migration inhibitors may be only 1, or may be 2 or more. When the number of migration inhibitors is 2 or more, the total number thereof is preferably in the above range.

< polymerization inhibitor >

The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, thiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, glycoletherdiamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, pyrogallol, and the like can be preferably used, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-tert-butyl) phenylmethane and the like. Further, the polymerization inhibitor described in paragraph 0060 of Japanese patent laid-open publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International publication WO2015/125469 can also be used.

Further, the following compound (Me is methyl) can also be used.

[ chemical formula 37]

When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.05 to 2.5% by mass, based on the total solid content of the photosensitive resin composition of the present invention.

The polymerization inhibitor may be one kind only, or 2 or more kinds. When the number of polymerization inhibitors is 2 or more, the total amount thereof is preferably in the above range.

< modifier for improving adhesion of Metal >

The photosensitive resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to a metal material used for an electrode, a wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent and the like.

Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International publication No. WO2011/080992A1, compounds described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-041264, and compounds described in paragraphs 0055 of International publication No. WO 2014/097594. Further, it is preferable to use 2 or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358. Further, the following compounds are preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.

[ chemical formula 38]

Further, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese patent application laid-open No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese patent application laid-open No. 2013-072935 can be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polymer precursor. When the lower limit value is not less than the lower limit value, the adhesion between the cured film and the metal layer after the curing step is good, and when the upper limit value is not more than the upper limit value, the heat resistance and the mechanical properties of the cured film after the curing step are good. The metal adhesion improver may be one type, or 2 or more types. When 2 or more species are used, the total amount thereof is preferably in the above range.

< curing Accelerator >

The photosensitive resin composition of the present invention may also contain a curing accelerator. The curing accelerator may be a thermal curing accelerator or a photo-curing accelerator. The curing accelerator in the present invention is preferably an accelerator that generates a base (base generator) by heat, exposure, or the like.

(Heat curing accelerator)

The thermal curing promoter is preferably a salt of a quaternary ammonium cation with a carboxylic acid anion. The quaternary ammonium cation is preferably represented by any one of the following formulae (Y1-1) to (Y1-4).

[ chemical formula 39]

R^Y1Represents n^YValence (n)^YIs an integer of 1 to 12), preferably n^YA hydrocarbyl group. Examples of the hydrocarbon group include n containing alkane^YA valence group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), n containing an olefin^YA valence group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 3 carbon atoms), n containing an aromatic hydrocarbon^YA valence group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), or a combination thereof. R^Y1Among them, aromatic hydrocarbon groups are preferable. Within a range not impairing the effects of the present invention, R^Y1May have the aforementioned substituent T.

In the formula, R is preferred^Y2～R^Y5Each independently represents a hydrogen atom or a hydrocarbon group (preferably 1 to 36, more preferably 1 to 24, further preferably 1 to 12 carbon atoms), an alkyl group (preferably 1 to 36, more preferably 1 to 24, further preferably 1 to 23 carbon atoms), an alkenyl group (preferably 2 to 36, more preferably 2 to 24, further preferably 2 to 23 carbon atoms), an alkynyl group (preferably 1 to 36, more preferably 1 to 24, further preferably 1 to 23 carbon atoms), an aryl group (preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 10 carbon atoms). The alkyl group, alkenyl group and alkynyl group may be cyclic or linear, or in the case of a linear, branched.

R^Y6The compound is an alkyl group (preferably having 1 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, further preferably 4 to 18 carbon atoms), an alkenyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, further preferably 4 to 18 carbon atoms), an alkynyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, further preferably 4 to 18 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms). The alkyl, alkenyl and alkynyl groups may be cyclic or cyclicThe polymer may be linear or branched in the case of being linear or chain. In the alkyl group, alkenyl group, alkynyl group and aryl group, a linker group Lh containing a hetero atom may be present in the middle of the group or in the bond to the parent nucleus.

n^YRepresents an integer of 1 to 12, more preferably an integer of 1 to 6, and still more preferably an integer of 1 to 3.

n^XRepresents an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.

R^Y2～R^Y6The 2 or more of (2) may be bonded to each other to form a ring.

R^Y7～R^Y16Is with R^NThe same groups as defined above. In the formula (Y1-2), R is preferred^Y7And R^Y8Is a carboxyalkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms; the number of carboxyl groups is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms). Preferably R^Y9Is an aromatic group or an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms). Alternatively, an alkoxycarbonyl group substituted with an aromatic group is preferable (the alkoxy group is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms, and the aromatic group is preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 14 carbon atoms). In the formula (Y1-3), R is preferred^Y11And R^Y13Is a hydrogen atom. R^Y14And R^Y15The combination of 2 (a) or (b) may be ═ C (NR)^N ₂)₂A substituent of (1) is a substituent (means bonded to a nitrogen atom through a double bond). In the formula (Y1-4), R is preferred^Y13Is a hydrogen atom, preferably R^Y10、R^Y11、R^Y12、R^Y16Is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms). In this case, R is preferably^Y11And R^Y16、R^Y10And R^Y12Bonded to form a ring to form a bicyclic compound. Specific examples thereof include diazabicyclononene and diazabicycloundecene.

In the present embodiment, it is preferable that the carboxylic acid anion pairing with the quaternary ammonium cation of the formula (Y1-1), the formula (Y1-3) or the formula (Y1-4) is represented by the following formula (X1).

[ chemical formula 40]

In the formula (X1), EWG represents an electron-withdrawing group.

In the present embodiment, the electron-withdrawing group means an electron group having a positive hammett substituent constant σ m. Among them, σ m is described in detail in general, Journal of Synthetic Organic Chemistry, Japan, Vol.23, No. 8 (1965), p.631-642. The electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.

An example of a substituent in which σ m represents a positive value is CF₃Base (. sigma.m.0.43), CF₃CO group (σ m ═ 0.63), HC ≡ C group (σ m ≡ 0.21), CH group₂CH (σ m) group 0.06, Ac (σ m) group 0.38, MeOCO (σ m) group 0.37, MeCOCH (σ m) CH group 0.21, PhCO (σ m) group 0.34, H₂NCOCH₂And a group (σ m ═ 0.06). In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

The EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6).

[ chemical formula 41]

In the formulae (EWG-1) to (EWG-6), R^x1～R^x3Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), a hydroxyl group or a carboxyl group. Ar represents an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms). When R is^x1～R^x3When the alkyl, alkenyl or aryl is used,a ring may be formed, and the above-mentioned linking group L or the linking group Lh having the above-mentioned hetero atom may be interposed in the ring formation. These alkyl groups, alkenyl groups, aryl groups, and Ar may have a substituent T within a range not impairing the effects of the present invention. Among them, Ar particularly preferably has a carboxyl group (preferably 1 to 3). Denotes the bonding site.

Np represents an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2.

The molecular weight of the thermosetting accelerator in the present invention is preferably 100 or more and less than 2000, more preferably 200 to 1000.

Specific examples of the heat-curing accelerator in the present invention include, in addition to D-1 to D-3 used in examples, acidic compounds which generate a base when heated to 40 ℃ or higher as described in WO2015/199219, and ammonium salts having an anion and an ammonium cation with a pKa1 of 0 to 4, which are incorporated herein.

When a thermosetting accelerator is used, the content of the thermosetting accelerator in the composition is preferably 0.01 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. The upper limit is more preferably 10% by mass or less, and still more preferably 5% by mass or less.

The heat-curing accelerator can be used in 1 kind or 2 or more kinds. When 2 or more species are used, the total amount is preferably in the above range. The composition of the present invention may be a composition that does not substantially contain a thermosetting accelerator. Substantially not included means less than 0.01% by mass, more preferably less than 0.005% by mass, relative to the total solid content of the composition.

< other additives >

The photosensitive resin composition of the present invention can be blended with various additives, for example, a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like, as necessary, within a range not to impair the effects of the present invention. When these additives are blended, the total blending amount thereof is preferably 3% by mass or less of the solid content of the composition.

Thermal acid generator

The photosensitive resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, and promotes cyclization of the polymer precursor to further improve mechanical properties of the cured film. Examples of the thermal acid generator include compounds described in paragraph 0059 of Japanese patent laid-open publication No. 2013-167742.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the polymer precursor. The mechanical properties and chemical resistance of the cured film can be further improved by containing 0.01 parts by mass or more of the thermal acid generator to promote the crosslinking reaction and the cyclization of the polymer precursor. The content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint of electrical insulation of the cured film.

The thermal acid generator may be used alone or in combination of 2 or more. When 2 or more species are used, the total amount is preferably within the above range.

Sensitizing dye

The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active ray to become an electron excited state. The sensitizing dye in an electron excited state is brought into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, and functions such as electron transfer, energy transfer, heat generation, and the like are generated. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases. For details of the sensitizing dye, reference can be made to the descriptions in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The sensitizing dye can be used singly or in combination of 2 or more.

Chain transfer agent

The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in page 683-684 of The third edition of The Polymer dictionary (The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. They supply hydrogen to low-activity radicals to generate radicals, or after oxidation, can generate radicals by deprotonation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, and the like) can be preferably used.

When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. The chain transfer agent may be one type or 2 or more types. When the number of the chain transfer agents is 2 or more, the total amount thereof is preferably in the above range.

Surface active agent

In order to further improve coatability, various surfactants may be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Further, the following surfactants are also preferable.

[ chemical formula 42]

When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The surfactant may be one kind only, or 2 or more kinds. When the number of the surfactants is 2 or more, the total amount thereof is preferably in the above range.

Higher fatty acid derivatives

In order to prevent inhibition of polymerization by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the photosensitive resin composition of the present invention so as to be locally present on the surface of the composition during drying after application.

When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition of the present invention. The number of the higher fatty acid derivatives may be only one, or may be 2 or more. When the number of the higher fatty acid derivatives is 2 or more, the total amount thereof is preferably in the above range.

< restrictions on other contained substances >

The moisture content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass, from the viewpoint of the properties of the coated surface.

The metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulation properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are contained, the total of these metals is preferably in the above range.

As a method for reducing metal impurities which are not intended to be contained in the photosensitive resin composition of the present invention, there can be mentioned a method in which a raw material having a small metal content is selected as a raw material constituting the photosensitive resin composition of the present invention, the raw material constituting the photosensitive resin composition of the present invention is filtered through a filter, and the inside of the apparatus is lined with polytetrafluoroethylene and distilled under conditions in which contamination is suppressed as much as possible.

In view of the use as a semiconductor material, the content of the halogen atom in the photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm, from the viewpoint of the corrosiveness of wiring. Among them, the amount of the composition existing in the state of a halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably in the above-mentioned range.

As the container for the photosensitive resin composition of the present invention, a conventionally known container can be used. Further, for the purpose of suppressing the contamination of impurities into the raw material or the composition, a multilayer bottle having an inner wall of the container made of 6 kinds of 6-layer resins, or a bottle having a 7-layer structure made of 6 kinds of resins is preferably used as the storage container. Examples of such containers include those described in Japanese patent laid-open publication No. 2015-123351.

< preparation of the composition >

The photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

Further, filtration using a filter is preferably performed for the purpose of removing foreign matter such as dust and fine particles in the composition. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one previously washed with an organic solvent. In the filtration step of the filter, a plurality of filters may be connected in parallel or in series for use. When a plurality of filters are used, filters having different pore sizes or different materials may be used in combination. Also, various materials may be filtered multiple times. When the filtration is performed a plurality of times, it may be a circulation filtration. Further, the filtration may be performed under pressure. When filtration is performed under pressure, the pressure to be applied is preferably 0.05MPa or more and 0.3MPa or less.

In addition to filtration using a filter, an impurity removal process using an adsorbent material may be performed. The filtration by the filter and the impurity removal treatment using the adsorbent may be combined. As the adsorbing material, a known adsorbing material can be used. Examples thereof include inorganic adsorbing materials such as silica gel and zeolite, and organic adsorbing materials such as activated carbon.

In the photosensitive resin composition of the present invention, the polymer precursor has a sulfonic acid group, and therefore, the photosensitive resin composition can be stored at high temperatures. More preferably from-60 ℃ to 40 ℃, and still more preferably from-20 ℃ to 10 ℃.

< cured film, laminate, semiconductor device, and method for producing same

Next, the cured film, the laminate, the semiconductor device, and methods for manufacturing these will be described.

The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The thickness of the cured film of the present invention can be set to, for example, 0.5 μm or more and 1 μm or more. The upper limit value may be 100 μm or less, and may be 30 μm or less.

The cured film of the present invention may be laminated in 2 or more layers, and further in 3 to 7 layers to form a laminate. The laminate having 2 or more layers of the cured films of the present invention preferably has a metal layer between the cured films. These metal layers can be preferably used as metal wirings of a rewiring layer or the like.

Examples of the field to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Further, a sealing film, a substrate material (a base film, a coverlay film, or an interlayer insulating film of a flexible printed wiring board), or an insulating film for mounting as described above may be patterned by etching. For these applications, for example, reference can be made to Science & tech immunology co., ltd. "high-functionalization and application technology of polyimide" 4 months 2008, kaki benaying/master edition, base and development of CMC Technical Library "polyimide material" 11 months 2011 release, japan polyimide aromatic polymer research institute/edition "latest polyimide base and application" NTS, 8 months 2010, and the like.

The cured film of the present invention can also be used for the production of printing plates such as offset printing plates and screen printing plates, the use of molded parts, and the production of protective paints and dielectric layers for electronics, particularly microelectronics.

The method for producing a cured film of the present invention includes a method using the photosensitive resin composition of the present invention. Specifically, the method comprises the following steps: a layer forming step of applying the photosensitive resin composition of the present invention to a substrate to form a layer; and a heating step of heating the photosensitive resin composition in a layer form at 50 to 500 ℃. Preferably, the method for producing a cured film further comprises: an exposure step of exposing the layer after the layer forming step; and a developing treatment step of performing a developing treatment on the exposed photosensitive resin composition layer (resin layer). After the development, the exposed resin layer can be further cured by heating (preferably, heating at 50 to 500 ℃). In addition, in the case of using the photosensitive resin composition as described above, the composition is cured by exposure to light in advance, and then, if necessary, a desired process (for example, lamination described below) is performed, whereby the composition can be further cured by heating.

The method for producing a laminate of the present invention includes the method for producing a cured film of the present invention. In the method for producing a laminate of the present invention, in the case where the layer forming step and the heating step or the photosensitivity is further provided to the photosensitive resin composition again after the cured film is formed according to the method for producing a cured film, the layer forming step, the exposure step, and the development treatment step (the heating step if necessary) are preferably performed in this order. In particular, it is preferable to sequentially perform each step 2 to 5 times (i.e., 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the upper part of the portion provided with the cured film, between the cured films, or between both of them.

The details of these will be described below.

< layer Forming Process >

The production method according to a preferred embodiment of the present invention includes a layer forming step of applying a photosensitive resin composition to a substrate to form a layer.

The type of the substrate may be appropriately set according to the application, but is not particularly limited, and examples thereof include a semiconductor substrate such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, a metal substrate such as quartz, glass, an optical thin film, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, Ni, Cu, Cr, and Fe, paper, sog (spin On glass), a TFT (thin film transistor) array substrate, and an electrode plate of a Plasma Display Panel (PDP). In the present invention, a semiconductor substrate is particularly preferable, and a silicon substrate is more preferable.

When the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.

As a method for applying the photosensitive resin composition to a substrate, coating is preferable.

Specifically, examples of suitable methods include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and an ink jet method. From the viewpoint of the thickness uniformity of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. By adjusting the solid content concentration and the coating conditions appropriately according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected according to the shape of the substrate, and a spin coating method, a spray coating method, an ink jet method, and the like are preferable if the substrate is a circular substrate such as a wafer, and a slit coating method, a spray coating method, an ink jet method, and the like are preferable if the substrate is a rectangular substrate. In the case of spin coating, the coating can be applied at a rotation speed of 500 to 2000rpm for about 10 seconds to 1 minute, for example.

(drying process)

The production method of the present invention may further include a step of drying the photosensitive resin composition layer after the layer formation step in order to remove the solvent. The preferable drying temperature is 50 to 150 ℃, more preferably 70 to 130 ℃, and further preferably 90 to 110 ℃. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

Exposure process

The production method of the present invention may include an exposure step of exposing the photosensitive resin composition layer. The exposure amount is not particularly limited within the range capable of curing the photosensitive resin composition, and for example, the exposure energy at a wavelength of 365nm is preferably 100 to 10000mJ/cm²More preferably, the irradiation is 200 to 8000mJ/cm²。

The exposure wavelength can be set appropriately within the range of 190 to 1000nm, and is preferably 240 to 550 nm.

The exposure wavelength is described in relation to a light source, and examples thereof include (1) a semiconductor laser (having a wavelength of 830nm, 532nm, 488nm, 405nm etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, a g-ray (having a wavelength of 436nm), an h-ray (having a wavelength of 405nm), an i-ray (having a wavelength of 365nm), a broad (3 wavelengths of g, h, and i-rays), (4) an excimer laser, a KrF excimer laser (having a wavelength of 248nm), an ArF excimer laser (having a wavelength of 193nm), an F2 excimer laser (having a wavelength of 157nm), and (5) an extreme ultraviolet ray; EUV (wavelength 13.6nm), (6) electron beam, and the like. The photosensitive resin composition of the present invention is particularly preferably exposed to light from a high-pressure mercury lamp, and particularly preferably exposed to i-rays. This makes it possible to obtain particularly high exposure sensitivity.

Development processing procedure

The production method of the present invention may include a development treatment step of performing a development treatment on the exposed photosensitive resin composition layer. By performing development, an unexposed portion (unexposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as spin immersion, spraying, dipping, or ultrasonic waves can be used.

The development is performed using a developer. The developing solution can be used without particular limitation as long as the unexposed portion (unexposed portion) can be removed. The developer preferably comprises an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of-1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be determined as a calculated value by inputting the structural formula by chembidraw (chemibiological diagram).

As the organic solvent, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, -caprolactone, -valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.) (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate (example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate and the like, and ethers such as diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, propylene glycol, Tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and as sulfoxides, dimethyl sulfoxide, etc., may be appropriately cited.

In the present invention, cyclopentanone and γ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.

The developer is preferably an organic solvent in an amount of 50% by mass or more, more preferably an organic solvent in an amount of 70% by mass or more, and still more preferably an organic solvent in an amount of 90% by mass or more. Further, 100% by mass of the developer may be an organic solvent.

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, but can be generally carried out at 20 to 40 ℃.

After the treatment with the developer, rinsing may be further performed. Preferably, the rinsing is performed with a different solvent than the developer. For example, the solvent contained in the photosensitive resin composition can be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

Heating process

The production method of the present invention preferably includes a step of heating after the layer forming step, the drying step, or the developing step. In the heating step, a cyclization reaction of the polymer precursor proceeds. The composition of the present invention may contain a radical polymerizable compound other than the polymer precursor, but curing of a radical polymerizable compound other than the unreacted polymer precursor and the like may be performed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 to 500 ℃, more preferably 50 to 450 ℃, even more preferably 140 to 400 ℃, and even more preferably 160 to 350 ℃.

The heating is preferably performed at a temperature rise rate of 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and still more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is set to 1 ℃/min or more, whereby excessive volatilization of the amine can be prevented while ensuring productivity, and the temperature increase rate is set to 12 ℃/min or less, whereby the residual stress of the cured film can be relaxed.

The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, and further preferably 25 to 120 ℃. The temperature at the start of heating is the temperature at the start of the heating step to the maximum heating temperature. For example, when the photosensitive resin composition is applied to a substrate and then dried, the temperature of the layer after drying is preferably gradually increased from a temperature 30 to 200 ℃ lower than the boiling point of the solvent contained in the photosensitive resin composition.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

In particular, in the case of forming a multilayer laminate, from the viewpoint of adhesion between the layers of the cured film, the heating is preferably performed at a heating temperature of 180 to 320 ℃, and more preferably at 180 to 260 ℃. The reason for this is not clear, but it is considered that the ethynyl groups of the polymer precursors between the layers are crosslinked with each other at this temperature.

The heating may be performed in stages. As an example, a pretreatment process of raising the temperature from 25 ℃ to 180 ℃ at 3 ℃/min and holding at 180 ℃ for 60 minutes, raising the temperature from 180 ℃ to 200 ℃ at 2 ℃/min and holding at 200 ℃ for 120 minutes may be performed. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform treatment by irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. The film characteristics can be improved by such a pretreatment step. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be carried out in two or more stages, for example, the pretreatment step 1 may be carried out at a temperature of 100 to 150 ℃ and the pretreatment step 2 may be carried out at a temperature of 150 to 200 ℃.

Further, the heating and the cooling may be performed, and the cooling rate in this case is preferably 1 to 5 ℃/min.

In the heating step, it is preferable to perform the heating step in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, in order to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50ppm (by volume) or less, more preferably 20ppm (by volume) or less.

Metal layer forming process

The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.

The metal layer is not particularly limited, and conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and still more preferably copper.

The method for forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in Japanese patent laid-open Nos. 2007-157879, 2001-521288, 2004-214501 and 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, there are a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined.

The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

Lamination process

The production method of the present invention preferably further comprises a lamination step.

The laminating step is a series of steps including the above-described layer forming step and heating step again on the surface of the cured film (resin layer) or the metal layer in the above-described order, or the above-described layer forming step, the above-described exposure step, and the above-described developing treatment step on the photosensitive resin composition. Of course, the laminating step may include the drying step, the heating step, or the like.

In the case where the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment may be exemplified.

The laminating step is preferably performed 2 to 5 times, and more preferably 3 to 5 times.

For example, a structure in which the resin layer is 3 layers or more and 7 layers or less, such as resin layer/metal layer/resin layer/metal layer, is preferable, and 3 layers or more and 5 layers or less is more preferable.

That is, in the present invention, it is particularly preferable that after the metal layer is provided, the layer forming step and the heating step of the photosensitive resin composition are further performed in the above order as covering the metal layer, or the layer forming step, the exposure step and the development treatment step (the heating step is further performed as necessary) are performed on the photosensitive resin composition. The photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the laminating step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step.

Also disclosed is a semiconductor device having the cured film or laminate of the invention. As a specific example of a semiconductor device in which the photosensitive resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer, reference can be made to the descriptions in paragraphs 0213 to 0218 of japanese patent application laid-open No. 2016-.

Examples

The present invention will be described in further detail below with reference to examples. The materials, amounts, ratios, processing contents, processing steps, and the like shown in the following examples can be appropriately modified within a range not departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

< Synthesis of Polymer precursor composition (photosensitive resin composition) >

(Synthesis example 1)

[ Synthesis of Polymer precursor A-1 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 11.0g of pyridine and 50mL of tetrahydrofuran were mixed and stirred at 60 ℃ for 4 hours. Subsequently, the reaction mixture was cooled to-10 ℃, a solution in which 28.1g of dicyclohexylcarbodiimide was dissolved in 40mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 30 minutes. Subsequently, a solution prepared by dissolving 6.9g of 1, 4-phenylenediamine in 100mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 30 minutes, and after the mixture was stirred for 1 hour, 6.0g of 4-aminobenzenesulfonic acid, 10mL of ethanol, and 100mL of γ -butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. To the resulting reaction solution, 6L of water was added to precipitate a polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45 ℃ for 2 days under reduced pressure. In the obtained polyimide precursor, the weight average molecular weight was 19500, the number average molecular weight was 8100, and the number of sulfonic acid groups was 7.54% of the total number of the structural units.

(Synthesis example 2)

[ Synthesis of Polymer precursor A-2 ]

14.9g of pyromellitic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 100mL of diethylene glycol dimethyl ether were mixed and stirred at 60 ℃ for 4 hours. Next, the reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃₂. After dilution with 50mL of N-methylpyrrolidinone, a solution of 20.3g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl and 0.2g of 2-sulfobenzoic anhydride in 100mL of N-methylpyrrolidinone is added dropwise to the reaction mixture at-5 ℃ over 30 minutes, and after the mixture has been stirred for 1 hour, 20mL of ethanol is added. To the obtained reaction solution, 6L of water was added to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400mL of tetrahydrofuran. 6L of water was added to the resulting solution to precipitate a polyimide precursor at a rate of 500rpmThe water-polyimide precursor mixture was vigorously stirred for 60 minutes. The solid of the polyimide precursor was filtered again and dried under reduced pressure at 45 ℃ for 2 days. In the obtained polyimide precursor, the weight average molecular weight was 22400, the number average molecular weight was 8600, and the number of sulfonic acid groups was 0.15% of the total number of the structural units.

(Synthesis example 3)

[ Synthesis of Polymer precursor A-3 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 100mL of diethylene glycol dimethyl ether were mixed and stirred at 60 ℃ for 4 hours. Next, the reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃₂. After dilution with 50mL of N-methylpyrrolidinone, a solution of 12.7g of 4, 4' -diaminodiphenyl ether in 100mL of N-methylpyrrolidinone was added dropwise to the reaction mixture over 30 minutes at-5 ℃ and after stirring the mixture for 1 hour, 0.6g of 2-aminobenzenesulfonic acid and 20mL of ethanol were added. To the obtained reaction solution, 6L of water was added to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400mL of tetrahydrofuran. To the resulting solution, 6L of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered again and dried under reduced pressure at 45 ℃ for 2 days. In the obtained polyimide precursor, the weight average molecular weight was 26400, the number average molecular weight was 9600, and the number of sulfonic acid groups was 1.05% of the total number of the structural units.

(Synthesis example 4)

[ Synthesis of Polymer precursor A-4 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 11.0g of pyridine and 50mL of tetrahydrofuran were mixed and stirred at 60 ℃ for 4 hours. Next, the reaction mixture was cooled to-10 ℃, a solution in which 17.2g of diisopropylcarbodiimide was dissolved in 40mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 30 minutes. Then, a solution prepared by dissolving 12.7g of 4, 4' -diaminodiphenyl ether and 1.2g of 2-sulfobenzoic anhydride in 100mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 30 minutes, and after stirring the mixture for 1 hour, 10mL of ethanol and 100mL of γ -butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. To the resulting reaction solution, 6L of water was added to precipitate a polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45 ℃ for 2 days under reduced pressure. In the obtained polyimide precursor, the weight average molecular weight was 20900, the number average molecular weight was 8200, and the number of sulfonic acid groups was 0.44% of the total number of the structural units.

(Synthesis example 5)

[ Synthesis of Polymer precursor A-5 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 100mL of diethylene glycol dimethyl ether were mixed and stirred at 60 ℃ for 4 hours. Next, the reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃₂. After dilution with 50mL of N-methylpyrrolidinone, a solution of 20.29g of 2, 2' -bis (trifluoromethyl) benzidine dissolved in 100mL of N-methylpyrrolidinone is added dropwise to the reaction mixture over 30 minutes at-5 ℃ and after the mixture has been stirred for 1 hour, 1.0g of 2-aminoethanesulfonic acid and 20mL of ethanol are added. To the obtained reaction solution, 6L of water was added to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400mL of tetrahydrofuran. To the resulting solution, 6L of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered again and dried under reduced pressure at 45 ℃ for 2 days. In the obtained polyimide precursor, the weight average molecular weight was 27100, the number average molecular weight was 10100, and the number of sulfonic acid groups was 3.21% of the total number of the structural units.

(Synthesis example 6)

[ Synthesis of Polymer precursor A-6 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 100mL of diethylene glycol dimethyl ether were mixed and stirred at 60 ℃ for 4 hours. Next, the reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃₂. After dilution with 50mL of N-methylpyrrolidinone, a solution of 20.29g of 2, 2' -bis (trifluoromethyl) benzidine dissolved in 100mL of N-methylpyrrolidinone is added dropwise to the reaction mixture over 30 minutes at-5 ℃ and after stirring the mixture for 1 hour, 0.1g of 2-aminoethanesulfonic acid and 20mL of ethanol are added. To the obtained reaction solution, 6L of water was added to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400mL of tetrahydrofuran. To the resulting solution, 6L of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered again and dried under reduced pressure at 45 ℃ for 2 days. In the obtained polyimide precursor, the weight average molecular weight was 27500, the number average molecular weight was 9900, and the number of sulfonic acid groups was 0.07% of the total number of the structural units.

(Synthesis example 7)

[ Synthesis of Polymer precursor A-7 ]

28.0g of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 200mL of N-methylpyrrolidinone. Then, 25.0g of 4, 4' -oxodibenzoyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ℃, and then 3.0g of 3-hydroxypropanesulfonic acid (about 80 mass% aqueous solution) was added thereto and the mixture was stirred for 60 minutes. To the resulting reaction solution, 6L of water was added to precipitate a polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ℃ for 2 days. In the obtained polybenzoxazole precursor, the weight average molecular weight was 21800, the number average molecular weight was 8300, and the number of sulfonic acid groups was 4.20% of the total number of the structural units.

(Synthesis example 8)

[ Synthesis of Polymer precursor A-8 ]

28.0g of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 200mL of N-methylpyrrolidinone. Then, 25.0g of 4, 4' -oxodibenzoyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ℃, and then 10.0g of 2-sulfobenzoic anhydride was added thereto and the mixture was stirred for 60 minutes. To the resulting reaction solution, 6L of water was added to precipitate a polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ℃ for 2 days. In the obtained polybenzoxazole precursor, the weight average molecular weight was 18800, the number average molecular weight was 7300, and the number of sulfonic acid groups was 12.48% of the total number of the structural units.

(Synthesis example 9)

[ Synthesis of Polymer precursor A-9 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 10.0g of 4-aminobenzenesulfonic acid, 23.9g of pyridine, and 100mL of diethylene glycol dimethyl ether were mixed and stirred at 60 ℃ for 4 hours. Next, the reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃₂. After dilution with 50mL of N-methylpyrrolidinone, a solution of 20.29g of 2, 2' -bis (trifluoromethyl) benzidine dissolved in 100mL of N-methylpyrrolidinone is added dropwise to the reaction mixture over 30 minutes at-5 ℃ and after stirring the mixture for 1 hour, 20mL of ethanol is added. To the obtained reaction solution, 6L of water was added to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400mL of tetrahydrofuran. To the resulting solution, 6L of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered again and dried under reduced pressure at 45 ℃ for 2 days. In the polyimide precursor, the weight average molecular weight was 24300, the number average molecular weight was 9200, and the number of sulfonic acid groups was 17.20% of the total number of structural units.

(Synthesis example 10)

[ Synthesis of Polymer precursor A-10 ]

21.2g of 4, 4' -oxydiphthalic dianhydride and 18.2g of 2-hydroxyethylmethane were mixedThe acrylic ester, 5.0g of 4-aminobenzenesulfonic acid, 23.9g of pyridine and 100mL of diethylene glycol dimethyl ether were stirred at 60 ℃ for 4 hours. Next, the reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃₂. After dilution with 50mL of N-methylpyrrolidinone, a solution of 20.29g of 2, 2' -bis (trifluoromethyl) benzidine dissolved in 100mL of N-methylpyrrolidinone is added dropwise to the reaction mixture over 30 minutes at-5 ℃ and after stirring the mixture for 1 hour, 20mL of ethanol is added. To the obtained reaction solution, 6L of water was added to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400mL of tetrahydrofuran. To the resulting solution, 6L of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered again and dried under reduced pressure at 45 ℃ for 2 days. In the polyimide precursor, the weight average molecular weight was 22700, the number average molecular weight was 9400, and the number of sulfonic acid groups was 3.21% of the total number of the structural units.

(Synthesis example 11)

[ Synthesis of Polymer precursor A-11 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 3.0g of 4-aminobenzenesulfonic acid, 11.0g of pyridine and 50mL of tetrahydrofuran were mixed and stirred at 60 ℃ for 4 hours. Next, the reaction mixture was cooled to-10 ℃, a solution in which 17.2g of diisopropylcarbodiimide was dissolved in 40mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 30 minutes. Then, a solution prepared by dissolving 12.7g of 4, 4' -diaminodiphenyl ether in 100mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 30 minutes, and after the mixture was stirred for 1 hour, 10mL of ethanol and 100mL of γ -butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. To the resulting reaction solution, 6L of water was added to precipitate a polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45 ℃ for 2 days under reduced pressure. In the polyimide precursor, the weight average molecular weight was 25100, the number average molecular weight was 9800, and the number of sulfonic acid groups was 4.32% of the total number of structural units.

(Synthesis example 12)

[ Synthesis of Polymer precursor A-12 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 2.0g of 3-hydroxypropanesulfonic acid (about 80% by mass aqueous solution), 11.0g of pyridine, and 50mL of tetrahydrofuran were mixed and stirred at 60 ℃ for 4 hours. Subsequently, the reaction mixture was cooled to-10 ℃, a solution in which 28.1g of dicyclohexylcarbodiimide was dissolved in 40mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 30 minutes. Then, a solution prepared by dissolving 12.7g of 4, 4' -diaminodiphenyl ether in 100mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 30 minutes, and after the mixture was stirred for 1 hour, 10mL of ethanol and 100mL of γ -butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. To the resulting reaction solution, 6L of water was added to precipitate a polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45 ℃ for 2 days under reduced pressure. In the polyimide precursor, the weight average molecular weight was 18100, the number average molecular weight was 7100, and the number of sulfonic acid groups was 2.20% of the total number of the structural units.

(Synthesis example 13)

[ Synthesis of Polymer precursor A-13 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 0.2g of 2-aminoethanesulfonic acid, 11.0g of pyridine and 50mL of tetrahydrofuran were mixed and stirred at 60 ℃ for 4 hours. Subsequently, the reaction mixture was cooled to-10 ℃, a solution in which 28.1g of dicyclohexylcarbodiimide was dissolved in 40mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 30 minutes. Then, a solution prepared by dissolving 12.7g of 4, 4' -diaminodiphenyl ether in 100mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 30 minutes, and after the mixture was stirred for 1 hour, 10mL of ethanol and 100mL of γ -butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. To the resulting reaction solution, 6L of water was added to precipitate a polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45 ℃ for 2 days under reduced pressure. In the polyimide precursor, the weight average molecular weight was 22400, the number average molecular weight was 8900, and the number of sulfonic acid groups was 0.04% of the total number of the structural units.

(Synthesis example 14)

[ Synthesis of Polymer precursor A-14 ]

28.0g of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 200mL of N-methylpyrrolidinone. Then, while maintaining the temperature at 0 to 5 ℃, 25.0g of 4, 4' -oxodibenzoyl chloride was added dropwise over 30 minutes, and then 5.0g of 2-sulfoacetic acid and 8.0g of dicyclohexylcarbodiimide were added thereto and the mixture was stirred for 60 minutes. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. To the resulting reaction solution, 6L of water was added to precipitate a polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ℃ for 2 days. In the polybenzoxazole precursor, the weight average molecular weight was 22800, the number average molecular weight was 8900, and the number of sulfonic acid groups was 6.21% of the total number of the structural units.

(Synthesis example 15)

[ Synthesis of Polymer precursor A-15 ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 11.0g of pyridine and 50mL of tetrahydrofuran were mixed and stirred at 60 ℃ for 4 hours. Subsequently, the reaction mixture was cooled to-10 ℃, a solution in which 28.1g of dicyclohexylcarbodiimide was dissolved in 40mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 30 minutes. Subsequently, a solution prepared by dissolving 6.9g of 1, 4-phenylenediamine in 100mL of γ -butyrolactone was added dropwise to the reaction mixture at-10 ℃ over 30 minutes, and after the mixture was stirred for 1 hour, 10mL of ethanol and 100mL of γ -butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. To the resulting reaction solution, 6L of water was added to precipitate a polyimide precursor, and the water-polyimide precursor mixture was vigorously stirred at 500rpm for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45 ℃ for 2 days under reduced pressure. In the polyimide precursor, the weight average molecular weight was 22800, the number average molecular weight was 9100, and no sulfonic acid group was present.

(Synthesis example 16)

[ Synthesis of Polymer precursor A-16 ]

28.0g of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 200mL of N-methylpyrrolidinone. Then, 25.0g of 4, 4' -oxodibenzoyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ℃, and then stirring was continued for 60 minutes. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. To the resulting reaction solution, 6L of water was added to precipitate a polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ℃ for 2 days. In the polybenzoxazole precursor, the weight average molecular weight was 21400, the number average molecular weight was 8500, and a sulfonic acid group was not present.

(Synthesis example 17)

[ Synthesis of Polymer precursor A-17 ]

A mixture of 14.9g (68.3mmol) of pyromellitic dianhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine, 0.10g of water and 250mL of diethylene glycol dimethyl ether was stirred at 60 ℃ for 4 hours to prepare a diester of pyromellitic anhydride and 2-hydroxyethyl methacrylate. The water content of the obtained reaction solution was measured, and it contained 6.9 mmol. Next, the reaction mixture was cooled to-10 ℃ and 16.9g (142.1mmol) of SOCl was added over 60 minutes while maintaining the temperature at-10. + -. 5 ℃₂. Diluting with 50mL of N-methylpyrrolidone, and then carrying out reaction at-10 +/-5 DEG CA solution of 20.1g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl dissolved in 100mL of N-methylpyrrolidinone was added dropwise to the reaction mixture over 60 minutes, and the mixture was stirred for 2 hours. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred at 5000rpm for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380g of tetrahydrofuran. With respect to the resulting solution, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred at 5000rpm for 15 minutes. The solid of the polyimide precursor was again filtered and dried at 45 ℃ for 3 days under reduced pressure. The polyimide precursor had a weight average molecular weight of 26,800 and a number average molecular weight of 8400, and-SO bonded thereto except for a carbon skeleton₃The number of H groups was 4.52% of the total number of structural units.

< measurement of weight average molecular weight and number average molecular weight >

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer precursor are polystyrene-converted values measured based on Gel Permeation Chromatography (GPC), and were measured by the following methods.

HLC-8220 (manufactured by TOSOH CORPORATION) was used as a measuring device, and protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were used as columns. Further, the elution reagent was measured at 40 ℃ at a flow rate of 0.35 mL/min using THF (tetrahydrofuran). An Ultraviolet (UV)254nm detector was used for detection. The measurement sample used was a sample prepared by diluting the heterocycle-containing polymer precursor with THF to 0.1 mass%.

< preparation of photosensitive resin compositions of examples and comparative examples >

Each of the components described in table 1 below was mixed, and the mixture was pressure-filtered through a Polytetrafluoroethylene (PTFE) filter having a pore width of 0.8 μm at a pressure of 0.3MPa to obtain a uniform solution, thereby obtaining each photosensitive resin composition.

< storage stability >

10g of the photosensitive resin composition was sealed in a container (container material: light-shielding glass, volume: 100mL), and allowed to stand at 25 ℃ under an atmosphere of 65% relative humidity for 1 week. The viscosity of each composition was measured at 25 ℃ using RE-85L (TOKI SANGYO co., ltd., product) to calculate the change rate of viscosity (η r ═ η 2- η 1|/η 1, η r: the change rate of viscosity,. eta.1: the viscosity before the lapse of time,. eta.2: the viscosity after the lapse of time). The smaller the change rate, the higher the stability of the photosensitive resin composition, which is a preferable result. Setting of the apparatus, measurement conditions, and the like, and other matters are measured according to JIS Z8803: 2011 is a reference.

A: more than 0 percent and less than 5 percent

B: more than 5 percent and less than 8 percent

C: more than 8 percent and less than 10 percent

D: more than 10 percent and less than 15 percent

E: over 15 percent

< copper corrosiveness >

The photosensitive resin composition is spin-molded on a copper substrate having a thickness of 250 μm. The copper substrate to which the photosensitive resin composition was applied was dried on a hot plate at 100 ℃ for 5 minutes to form a film having a thickness of 10 μm on the copper substrate. Subsequently, the temperature was increased at a rate of 10 ℃/min under a nitrogen atmosphere to 230 ℃ and then held for 3 hours. After cooling, the film on the copper substrate was scraped off with a blade. The copper corrosion was evaluated by visually observing the copper substrate and calculating the area ratio of the colored, oxidized and oxidized portions. The less area ratio, the less corrosive the copper.

A: 5% or less.

B: more than 5% and less than 10%.

C: more than 10% and less than 20%.

D: greater than 20%.

[ Table 1]

As shown in Table 1, the resin having the sulfonic acid group-containing site introduced thereinto was storedBoth stability and copper corrosion show high performance (examples 1 to 23). In contrast, the comparative examples using a resin having no sulfonic acid group-containing site had particularly poor storage stability (comparative examples 1 and 2). And, even with-SO₃H radicals, to which-SO is bound only, other than the carbon skeleton₃In the case of H group, the storage stability is also poor. In examples, examples 6 to 10(A-3 to A-5), example 12(A-7) and examples 16 to 21(A-10 to A-12) in which the introduction ratio of the sulfonic acid group-containing site was medium showed relatively high performance.

From the above results, according to the present invention, storage stability can be achieved. Further, it is found that a balance between storage stability and copper corrosiveness can be achieved. Further, the present invention can provide a novel polyimide precursor and a polybenzoxazole precursor which are different from those of the conventional polyimide and polybenzoxazole precursors.

(A) Polymer precursor

A-1 to A-16: polymer precursors produced in Synthesis examples 1 to 16

(B) Radical polymerizable compound

B-1: NK ESTER M-40G (Shin-Nakamura Chemical Co., Ltd.; manufactured by Ltd.)

B-2: SR-209 (manufactured by Sartomer Company, Inc.)

B-3: NK ESTER A-9300(Shin-Nakamura Chemical Co., Ltd.; manufactured by Ltd.)

B-4: A-TMMT (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)

B-5: A-DPH (dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)

(C) Photo-radical polymerization initiator

C-1: IRGACURE OXE 01 (manufactured by BASF corporation)

C-2: IRGACURE OXE 02 (manufactured by BASF corporation)

C-3: IRGACURE OXE 04 (manufactured by BASF corporation)

C-4: IRGACURE-784 (manufactured by BASF corporation)

C-5: NCI-831 (manufactured by ADEKA CORPORATION)

(D) Curing accelerator (alkali generating agent)

D-1: the following compounds

D-2: the following compounds

D-3: the following compounds

[ chemical formula 43]

(E) Polymerization inhibitor

E-1: 1, 4-benzoquinones

E-2: 4-methoxyphenol

(F) Additive (migration inhibitor)

F-1: 1,2, 4-triazoles

F-2: 1H-tetrazole

(G) Silane coupling agent (Metal adhesion improver)

G-1: the following compounds

G-2: the following compounds

G-3: the following compounds

[ chemical formula 44]

(H) Solvent(s)

H-1: gamma-butyrolactone

H-2: dimethyl sulfoxide

H-3: n-methyl-2-pyrrolidone

H-4: lactic acid ethyl ester

The solvent in Table 1 means that 48 mass% of H-1 and 12 mass% of H-2 are contained, for example, when the column of the type is "H-1/H-2" and the column of the mass% is "48 + 12".

< example 100 >

The photosensitive resin composition of example 1 was pressure-filtered through a filter having a pore width of 0.8 μm, and then coated on a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition layer was dried at 100 ℃ for 5 minutes on a hot plate to form a uniform photosensitive layer having a thickness of 15 μm on the silicon waferA resin composition layer. Using a stepper (Nikon NSR 2005i9C), at 500mJ/cm²The photosensitive resin composition layer on the silicon wafer was exposed to light with the exposure energy of (1), and the exposed photosensitive resin composition layer (resin layer) was developed with cyclopentanone for 60 seconds to form a hole having a diameter of 10 μm. Subsequently, the temperature was increased at a rate of 10 ℃/min to 250 ℃ in a nitrogen atmosphere, and then the temperature was maintained for 3 hours. After cooling to room temperature, a copper thin layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by a vapor deposition method so as to cover the hole portion. Further, the same kind of photosensitive resin composition was used again on the surfaces of the metal layer and the photosensitive resin composition layer, and the process from the filtration of the photosensitive resin composition to the heating of the patterned film for 3 hours was performed again in the same manner as described above to produce a laminate composed of a resin layer/a metal layer/a resin layer.

The resin layer (interlayer insulating film for rewiring layer) has excellent insulating properties.

Then, as a result of manufacturing a semiconductor device using the rewiring layer interlayer insulating film, it was confirmed that the operation was normal.

Claims

1. A photosensitive resin composition comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor and a photoactive compound,

the polymer precursor has at least one of the group consisting of a sulfonic acid group bonded via a linking group at a side chain of the polymer precursor and a sulfonic acid group bonded to a terminal of the polymer precursor,

the polymer precursor is composed of a structural unit derived from at least one of tetracarboxylic acid, a tetracarboxylic acid derivative, a dicarboxylic acid, and a dicarboxylic acid derivative, and a structural unit derived from at least one of diamines.

2. The photosensitive resin composition according to claim 1,

the polymer precursor comprises a structural unit represented by the following formula (1) or a structural unit represented by the following formula (2),

3. The photosensitive resin composition according to claim 2,

the polymer precursor includes a structural unit represented by formula (1).

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

the polymer precursor has a structure represented by any one of formula (1-1), formula (1-2), formula (1-3), formula (2-1), formula (2-2), and formula (2-3),

in the formula, A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents an organic group having a valence of 2, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group, X¹、X²And X³Each independently represents a linking group, before the polyimideThe bonding position of the main chain of the body, ns represents an integer of 1 to 4,

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

the total number of sulfonic acid groups contained in the polymer precursor is 0.05% or more and 15.0% or less of the total number of structural units.

6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a radical polymerizable compound.

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising a curing accelerator.

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

the photoactive compound comprises a photo radical polymerization initiator.

9. The photosensitive resin composition according to any one of claims 1 to 8, which is used for development.

10. The photosensitive resin composition according to any one of claims 1 to 9, for use in development using a developer containing an organic solvent.

11. The photosensitive resin composition according to any one of claims 1 to 10, which is used for forming an interlayer insulating film for a rewiring layer.

12. A resin which is a resin comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, wherein,

the polymer precursor has a moiety represented by any one of formula (1-1), formula (1-2), formula (1-3), formula (2-1), formula (2-2), or formula (2-3),

13. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 11.

14. A laminate having 2 or more layers of the cured film of claim 13.

15. The laminate of claim 14, having a metal layer between the cured films.

16. A method for producing a cured film, comprising a step of using the photosensitive resin composition according to any one of claims 1 to 11.

17. The method for manufacturing a cured film according to claim 16, comprising:

an exposure step of exposing the photosensitive resin composition layer; and

18. A semiconductor device having the cured film according to claim 13 or the laminate according to claim 14 or 15.