KR102021305B1

KR102021305B1 - Negative photosensitive resin composition, cured film, manufacturing method of cured film, and semiconductor device

Info

Publication number: KR102021305B1
Application number: KR1020177035505A
Authority: KR
Inventors: 유 이와이; 이치로 코야마; 타케시 카와바타; 아키노리 시부야
Original assignee: 후지필름 가부시키가이샤
Priority date: 2015-06-30
Filing date: 2016-06-29
Publication date: 2019-09-16
Also published as: JP6481032B2; WO2017002859A1; KR20180005227A; JPWO2017002859A1; TWI662367B; TW201708957A

Abstract

It is providing the negative photosensitive resin composition, cured film, the manufacturing method of a cured film, and a semiconductor device with a wide exposure latitude. At least one first polymerization inhibitor selected from a polyimide precursor, a radical polymerization initiator, and a compound having an aromatic hydroxyl group, a nitroso compound, an N-oxide compound, a quinone compound, an N-oxyl compound, and a phenocyse The negative photosensitive resin composition containing at least 1 sort (s) of 2nd polymerization inhibitor chosen from an azine compound.

Description

Negative photosensitive resin composition, cured film, manufacturing method of cured film, and semiconductor device

This invention relates to a negative photosensitive resin composition, a cured film, the manufacturing method of a cured film, and a semiconductor device. In particular, it is related with the negative photosensitive resin composition suitable for the interlayer insulation film for redistribution layers.

Thermosetting resins cyclized and cured such as polyimide are used for insulating layers of semiconductor devices because of their excellent heat resistance and insulation.

Here, since the polyimide has low solubility in a solvent, it is used in a precursor (heterocycle-containing polymer precursor) state before the cyclization reaction, is applied to a substrate or the like, and then heated to cyclize the heterocycle-containing polymer precursor to form a cured film. Is done.

As a photosensitive resin composition using such a polyimide precursor, in patent document 1, (A) following General formula (1):

[Formula 1]

(In formula (1), X <_1> is a tetravalent organic group, Y <_1> is a divalent organic group, n is an integer of 2-150, R <_1> and R <_2> is respectively independently a hydrogen atom and the following general Equation (2):

[Formula 2]

(In formula, R <_3> , R <_4> and R <_5> is respectively independently a hydrogen atom or a C1-C3 organic group, and m is an integer of 2-10.) Monovalent organic group or C1-C1 It is saturated aliphatic group of -4. However, the polyimide precursor which has a structure represented by both of R <_11> and R <_22> is a hydrogen atom at the same time): 100 mass parts,

(B) photoinitiator: 1-20 mass parts

(C) The negative photosensitive resin composition containing 0.01-10 mass parts of C2-C30 monocarboxylic acid compound which has 1 or more functional groups chosen from the group which consists of a hydroxyl group, an ether group, and an ester group is disclosed.

On the other hand, in patent document 2, the negative photosensitive material containing an aerobic polymerization inhibitor and an anaerobic polymerization inhibitor is described.

Patent Document 1: Japanese Unexamined Patent Publication No. 2011-191749 Patent Document 2: International Publication No. WO2010 / 008514

Here, the negative photosensitive resin composition which has a wide resolution appropriate range of resolution of a negative photosensitive resin composition, ie, a wide exposure latitude, etc. when using for the interlayer insulation film for redistribution layers of a semiconductor is calculated | required. However, all of the negative photosensitive resin compositions of patent document 1 and patent document 2 have a narrow exposure latitude. Here, although patent document 2 has description about high image resolution, there is neither description nor suggestion about obtaining the image which has the sharpness of the favorable edge by a wide exposure energy.

This invention aims at solving such a subject, Comprising: It aims at providing the negative photosensitive resin composition, cured film, the manufacturing method of a cured film, and a semiconductor device with a wide exposure latitude.

As a result of the inventor's examination under the said subject, it discovered that it is possible to widen the exposure latitude of a negative photosensitive resin composition by employ | adopting the polyimide precursor which has a predetermined structure for a negative photosensitive resin composition, It has been solved. Specifically, by the following <1>, Preferably the said subject was solved by <2>-<19>.

<1> at least 1 sort (s) of 1st polymerization inhibitor chosen from a polyimide precursor, a radical polymerization initiator, and the compound which has an aromatic hydroxyl group, a nitroso compound, an N-oxide compound, a quinone compound, and an N-oxyl compound And at least one second polymerization inhibitor selected from phenothiazine compounds.

The negative photosensitive resin composition as described in <1> in which a <2> polyimide precursor contains the repeating unit represented by following General formula (1);

General formula (1)

[Formula 3]

In General Formula (1), A ¹ and A ² each independently represent an oxygen atom or —NH—, R ¹¹ represents a divalent organic group, R ¹² represents a tetravalent organic group, and R ¹³ and R ¹⁴ Each independently represents a hydrogen atom or a monovalent organic group.

<3> formula (1) of, R ¹³ and R ¹⁴ of the at least one side, comprising a radically polymerizable group, the negative-type photosensitive resin composition according to <2>.

The negative photosensitive resin composition in any one of <1>-<3> which further contains a <4> radically polymerizable compound.

The negative photosensitive resin composition as described in <4> in which a <5> radically polymerizable compound has two or more radically polymerizable groups.

The negative photosensitive resin composition in any one of <1>-<5> in which a <6> 2nd polymerization inhibitor is chosen from a quinone compound and an N-oxyl compound.

The negative photosensitive resin composition in any one of <1>-<6> whose mass ratio of a <7> 1st polymerization inhibitor and a 2nd polymerization inhibitor is 10: 90-90: 10.

The negative photosensitive resin composition in any one of <1>-<7> whose mass ratio of a <8> 1st polymerization inhibitor and a radical polymerization initiator is 1: 99-10: 90.

<9> formula (1) of, R ¹² is, tetravalent group containing an aromatic ring, <1> to <8> of the negative-type photosensitive resin composition according to any one.

The negative photosensitive resin composition in any one of <1>-<9> which further contains a <10> heat base generator.

The negative photosensitive resin composition as described in <10> in which a <11> heat base generator has an ammonium cation represented with the following general formula (Y);

[Formula 4]

In General Formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring, n Represents an integer of 1 or more.

The negative photosensitive resin composition in any one of <1>-<11> which is for the interlayer insulation film for <12> redistribution layers.

<13> Cured film formed by hardening | curing the negative photosensitive resin composition in any one of <1>-<12>.

The cured film as described in <13> which is an interlayer insulation film for <14> redistribution layers.

<15> The manufacturing method of the cured film containing using the negative photosensitive resin composition in any one of <1>-<12>.

<16> applying a negative photosensitive resin composition to a substrate;

Irradiating actinic radiation or radiation to a negative photosensitive resin composition applied to a substrate, and

The manufacturing method of the cured film as described in <15> which has a process of developing image development about the exposed negative photosensitive resin composition.

The manufacturing method of the cured film as described in <16> including the process of heating the developed negative photosensitive resin composition to the temperature of 50-500 degreeC after the process of <17> image development processing.

The manufacturing method of the cured film in any one of <15>-<17> whose film thickness of a <18> cured film is 3-30 micrometers.

<19> The semiconductor device which has a cured film as described in <13> or <14>, or a cured film manufactured by the method in any one of <15>-<18>.

According to this invention, it became possible to provide the negative photosensitive resin composition, cured film, the manufacturing method of a cured film, and a semiconductor device with a wide exposure latitude.

1 is a schematic diagram illustrating a configuration of an embodiment of a semiconductor device.

Although description of the component in this invention described below may be made based on typical embodiment of this invention, this invention is not limited to such embodiment.

In the description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

In the present specification, "active light" means, for example, a light spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and the like. In addition, in this invention, light means actinic light or a radiation. Unless otherwise indicated, "exposure" in this specification is not only exposure using the ultraviolet rays represented by a mercury lamp, an excimer laser, X-rays, EUV light, etc. but also the drawing degree exposure using particle beams, such as an electron beam and an ion beam. Include it in

In this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In the present specification, "(meth) acrylate" represents both or both of "acrylate" and "methacrylate", and "(meth) allyl" represents "allyl" and "metall". It represents both or either, and "(meth) acryl" shows both "acryl" and "methacryl", or either, and "(meth) acryloyl" shows "acryloyl" and " Or both of methacryloyl ".

In the present specification, the term "process" means not only an independent process but also a case where a desired action of the process is achieved even if it cannot be clearly distinguished from other processes, and is included in the term.

In this specification, solid content concentration is the mass percentage of the mass of the other component except a solvent with respect to the gross mass of a composition. In addition, solid content concentration means the density | concentration in 25 degreeC, unless there is particular notice.

In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion value in a gel permeation chromatography (GPC) measurement unless there is particular notice. In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are guard columns HZ-L and TSKgel Super HZM-M as a column using HLC-8220 (made by Tosoh Corporation), for example. , TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) can be obtained. Eluent shall be measured using THF (tetrahydrofuran) unless it mentions specially. In addition, the detection shall use the ultraviolet (UV) 254 nm detector unless there is particular notice.

Negative photosensitive resin composition

The negative photosensitive resin composition of this invention is a polyimide precursor, a radical polymerization initiator, at least 1st polymerization inhibitor chosen from the compound which has an aromatic hydroxyl group, a nitroso compound, an N-oxide compound, And at least one second polymerization inhibitor selected from quinone compounds, N-oxyl compounds, and phenothiazine compounds. By setting it as such a structure, the negative photosensitive resin composition with a wide exposure latitude is obtained.

Although the negative photosensitive resin composition containing a polyimide precursor is exposed and hardened | cured, by mix | blending two types of polymerization inhibitors, a 1st polymerization inhibitor mainly acts on the side near a surface layer, and a side far from the surface layer of a film | membrane, It is thought that a 2nd polymerization inhibitor mainly acts, and as a result, the polymerization inhibitory effect acts substantially uniformly throughout the negative photosensitive resin composition layer, and it becomes possible to widen an exposure latitude. It is especially advantageous when the film is thick with a large difference in light irradiation system.

Moreover, resin used in the Example of the said patent document 2 is an acrylic resin, although there exists a problem also from a heat resistant viewpoint, In this invention, it can be made excellent in heat resistance from the point which uses a polyimide precursor.

The negative photosensitive resin composition of this invention contains a polyimide precursor. 1 type of polyimide precursors may be sufficient, and 2 or more types may be sufficient as it.

It is preferable that a polyimide precursor is a polyimide precursor containing the repeating unit represented by General formula (1).

General formula (1)

[Formula 5]

A ¹ and A ² each independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.

R ¹¹ represents a divalent organic group. As a divalent organic group, the group containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aryl group is illustrated, A C2-C20 linear or branched aliphatic group, a C6-C20 cyclic aliphatic group, C6 A group consisting of an aryl group of ˜20 or a combination thereof is preferable, and a group consisting of an aryl group having 6 to 60 carbon atoms is more preferable. As an example of an aryl group, the following is mentioned.

[Formula 6]

In formula, A is a C1-C10 hydrocarbon group which may be substituted by a single bond or a fluorine atom, -O-, -C (= O)-, -S-, -S (= O) _2- and It is preferable that it is group chosen from -NHCO- and its combination, A C1-C3 alkylene group which may be substituted by a single bond, a fluorine atom, -O-, -C (= O)-, -S-, -SO _2, and more preferable group is selected _{from, -CH 2 -, -O-, -S-} , -SO 2 -, -C (CF 3) 2 -, -C (CH 3) 2 - 2 is selected from It is more preferable that it is a valent group.

Specifically, R ¹¹ includes diamine residues and the like remaining after removal of the amino groups of the following diamines.

1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexyl methane Phosphorus and isophorone diamine; m- and p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'- and 3,3'-diaminodiphenylether, 4, 4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodiphenylsulfide, 4,4'- and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobi Phenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoroprop Pane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3 -Amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis ( 4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-amino Phenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3 , 3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3- Bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl -4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl , 3,3 ', 4,4'-tetraaminodiphenylether, 1,4-diaminoant Quinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-di Methyl-3,3'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene , 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylene Diamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzaniyl Ride, ester 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-amino Nyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy)- 3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2 -Trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoro Methylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoro Methylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-di Aminobipe , 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2 ', 5,5', 6,6'-hexafluorotolidine and 4,4 '' At least one diamine selected from '-diaminoquaterphenyl.

Moreover, the diamine residue remaining after removal of the amino group of diamine (DA-1)-(DA-18) shown below is also mentioned as an example of R <^11> .

[Formula 7]

[Formula 8]

Moreover, the diamine residue remaining after removal of the amino group of the diamine which has two or more alkylene glycol units in a principal chain is also mentioned as an example of R <^11> . Preferably, it is a diamine residue which contains 2 or more of any one or both of an ethylene glycol chain and a propylene glycol chain in 1 molecule, More preferably, it is a diamine residue which does not contain an aromatic ring. As an example, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (above) , HUNTSMAN Corporation), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) (Propane-2-yl) oxy) propane-2-amine etc. are mentioned, but it is not limited to this. The structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[Formula 9]

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

In General Formula (1), R ¹² represents a tetravalent organic group, preferably a tetravalent group containing an aromatic ring, and more preferably a group represented by the following General Formula (1-1) or General Formula (1-2). .

General formula (1-1)

[Formula 10]

In the general formula (1-1), R ¹¹² is a single bond, or a hydrocarbon group, -O- group having 1 to 10 carbon atoms is a fluorine atom may be substituted, -CO-, -S-, -SO ₂ - and - preferably group selected from NHCO- and combinations thereof, and a single bond, a fluorine atom or an alkylene group, having 1 to 3 carbon atoms that may be substituted with -O-, -CO-, -S- and -SO ₂ - selected from it is more preferably a divalent _{group, -CH 2 -, -C (CF} 3) 2 -, -C (CH 3) 2 -, -O-, -CO-, -S- and -SO ₂ - consisting of More preferred are divalent groups selected from the group.

General formula (1-2)

[Formula 11]

R ¹² is a tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride.

Specifically, the tetracarboxylic acid residue etc. which remain | survives after removal of anhydride group from the following tetracarboxylic dianhydride are mentioned.

Pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethane tetracarboxylic dianhydride, 2 , 2 ', 3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride Water, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride , 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4, 5,6-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5- Naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane Dianhydrides, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydrides, and 1,2,3,4-benzenetetracarboxylic dianhydrides, their C1-C6 alkyls and C1-C6 At least one tetracarboxylic dianhydride selected from alkoxy derivatives of.

Moreover, the tetracarboxylic-acid residue remaining after anhydride group removal from tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below is also mentioned as an example of R <^12> .

[Formula 12]

From the viewpoint of solubility in the alkaline developer, it is preferable that R ¹² has an OH group. More specifically, examples of R ¹² include tetracarboxylic acid residues remaining after the anhydride group is removed from the above (DAA-1) to (DAA-5).

In General formula (1), R <^13> and R <^14> represents a hydrogen atom or monovalent organic group each independently.

As a monovalent organic group which R <^13> and R <^14> represents, the substituent which improves the solubility to a developing solution is used preferably.

From the standpoint of solubility in the aqueous developer, R ¹³ and R ¹⁴ are hydrogen atoms or monovalent organic groups, and as the monovalent organic group, 1, 2 or 3 bonded to a carbon atom of an aryl group, preferably An aryl group, an aralkyl group, etc. which have one acidic group are mentioned. Specifically, the C6-C20 aryl group which has an acidic group, and the C7-C25 aralkyl group which has an acidic group are mentioned. More specifically, the benzyl group which has the phenyl group and acidic group which have an acidic group is mentioned. The acidic group is preferably an OH group.

It is preferable that R ¹³ and R ¹⁴ be a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility to an aqueous developer.

From the viewpoint of solubility in the organic solvent, R ¹³ and R ¹⁴ are preferably monovalent organic groups. As a monovalent organic group, the thing containing an alkyl group, a cycloalkyl group, and an aryl group is preferable, and the alkyl group substituted by the aryl group is more preferable.

As for carbon number of an alkyl group, 1-30 are preferable. The alkyl group may be any of linear, branched or cyclic. As a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group, iso A propyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group are mentioned. The cyclic alkyl group (cycloalkyl group) may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. As a monocyclic cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. As a polycyclic cycloalkyl group, an adamantyl group, a norbornyl group, a carbonyl group, a camphoryl group, a decahydronaphthyl group, a tricyclodecaneyl group, a tetracyclodecaneyl group, a camporoyl group, a dicyclohexyl group, and a pinenyl group are mentioned, for example. Can be. Especially, a cyclohexyl group is the most preferable from a viewpoint of compatibility with high sensitivity. Moreover, as an alkyl group substituted by the aryl group, the linear alkyl group substituted by the aryl group mentioned later is preferable.

Specifically as an aryl group, a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptylene ring, indene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring , Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, Pyridazine ring, indolin ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolysin ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, iso Quinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, cyanthrene ring, chroman ring, xanthene ring, phenoxacyin ring, phenoxyazine ring or phenazine ring. The benzene ring is most preferred.

As a polymeric group which R <^13> and R <^14> has, an epoxy group, an oxetanyl group, the group which has an ethylenically unsaturated bond, a block isocyanate group, an alkoxy methyl group, a methylol group, an amino group, etc. are mentioned.

In this invention, the aspect containing a radically polymerizable group is illustrated as preferable embodiment of R <^13> and R <^14> , and group which has an ethylenically unsaturated bond is more preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.

[Formula 13]

In the formula (III), R ²⁰⁰ is hydrogen or methyl, more preferably methyl.

In the formula (III), R ²⁰¹ is an alkylene group having 2 to _{12, -CH 2 CH (OH) CH} 2 a - represents a polyoxyalkylene or a carbon number of 4 to 30.

Examples of suitable R ²⁰¹ are ethylene, propylene, trimethylene, tetramethylene, 1,2-butenedinyl, 1,3-butenedinyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH (OH) CH ₂ -is mentioned, and ethylene, propylene, trimethylene, and -CH ₂ CH (OH) CH ₂ -are more preferable.

Especially preferably, R ²⁰⁰ is methyl and R ²⁰¹ is ethylene.

When R <^13> and R <^14> in General formula (1) contains a polymeric group (preferably radically polymerizable group), the molar ratio of polymeric group: polymeric group-free content becomes like this. Preferably it is 100: 0-5: 95. More preferably, it is 100: 0-20: 80, More preferably, it is 100: 0-50: 50.

In general formula (1), when A <^2> is an oxygen atom and R <^13> is a hydrogen atom, or / and A <^1> is an oxygen atom and R <^14> is a hydrogen atom, the tertiary amine compound which has an ethylenically unsaturated bond, and You may form an opposite salt. As an example of the tertiary amine compound which has such ethylenically unsaturated bond, N, N- dimethylaminopropyl methacrylate is mentioned.

Moreover, in the case of alkali image development, in terms of improving resolution, it is preferable that a polyimide precursor has a fluorine atom in a structural unit. By the fluorine atom, water repellency is imparted to the surface of the film at the time of alkali development, and absorption from the surface can be suppressed. 10 mass% or more is preferable, and, as for the fluorine atom content in a polyimide precursor, 20 mass% or less is preferable at the point of the solubility to aqueous alkali solution.

Moreover, for the purpose of improving adhesiveness with a board | substrate, a polyimide precursor may copolymerize the aliphatic group which has a siloxane structure. Specifically, bis (3-aminopropyl) tetramethyl disiloxane, bis (p-aminophenyl) octamethyl pentasiloxane, etc. are mentioned as a diamine component.

In addition, in order to improve the storage stability of the negative photosensitive resin composition, it is preferable that the polyimide precursor is sealed with a terminal sealant such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a mono-active ester compound. . It is more preferable to use monoamine among these. Preferred compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy- 6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid , 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-a No phenol, there may be mentioned 4-aminophenol, 2-amino-thio phenol, 3-amino-thio phenol, 4-amino-thio phenol and the like. You may use 2 or more types of these and may introduce several other terminal group by making a some terminal sealant react.

The polyimide precursor used by this invention may consist of the repeating unit represented by General formula (1), and the other repeating unit which is another imide precursor.

When it contains another repeating unit, it is preferable that it is 1-60 mol%, and, as for the ratio of the other repeating unit in a polyimide precursor, it is more preferable that it is 5-50 mol%.

The negative photosensitive resin composition of this invention can also be set as the structure which does not contain substantially other polyimide precursors other than the polyimide precursor containing the repeating unit represented by General formula (1). Substantially not included means that content of the polyimide precursor of that excepting the above contained in the negative photosensitive resin composition of this invention is 3 mass% or less of content of a polyimide precursor, for example.

The weight average molecular weight (Mw) of a polyimide precursor becomes like this. Preferably it is 20000-28000, More preferably, it is 22000-27000, More preferably, it is 23000-25000.

Although the dispersion degree (Mw / Mn) of a polyimide precursor is not specifically determined, It is preferable that it is 1.0 or more, It is more preferable that it is 2.5 or more, It is more preferable that it is 2.8 or more. Although the upper limit of the dispersion degree of a polyimide precursor is not specifically determined, For example, 4.5 or less are preferable and it can also be 3.4 or less.

As for content of the polyimide precursor in the negative photosensitive resin composition of this invention, 20-100 mass% is preferable with respect to the total solid of a negative photosensitive resin composition, 50-99 mass% is more preferable, 60- 99 mass% is more preferable, and 70-99 mass% is especially preferable.

The negative photosensitive resin composition of this invention may contain the other resin component in the range which does not deviate from the meaning of this invention. As another resin component, a polybenzoxazole precursor and a polyimide resin are illustrated. Moreover, in this invention, it can also be set as the structure which does not contain resin other than a polyimide precursor substantially. Substantially not included means that content of resin other than the polyimide precursor contained in the negative photosensitive resin composition of this invention is 3 mass% or less of content of a polyimide precursor, for example.

The negative photosensitive resin composition of this invention contains a radical polymerization initiator. A negative development can be performed by a radical polymerization initiator initiating superposition | polymerization of the radically polymerizable group which a polyimide precursor can have, or the radically polymerizable compound mentioned later. The radical polymerization initiator may be an optical radical polymerization initiator or a thermal radical polymerization initiator, but is preferably an optical radical polymerization initiator. More specifically, after applying a negative photosensitive resin composition to a semiconductor wafer etc., and forming a layered composition layer, hardening by a radical arises by irradiating light and the solubility in a light irradiation part can be reduced. For this reason, for example, by exposing the said composition layer through the photomask which has the pattern which masked only the electrode part, there exists an advantage that the area | region which differs in solubility can be easily produced according to the pattern of an electrode.

As an optical radical polymerization initiator, there is no restriction | limiting in particular as long as it has the ability to start polymerization reaction (crosslinking reaction), such as a radically polymerizable compound, It can select suitably from well-known radical photopolymerization initiator. For example, it is preferable to have photosensitivity with respect to the light ray of a visible region from an ultraviolet region. Moreover, the active agent which produces | generates an active radical by generating some action with a photoexcited sensitizer may be sufficient.

It is preferable that the radical photopolymerization initiator contains at least 1 type of compound which has a molar extinction coefficient of at least about 50 in the range of about 300-800 nm (preferably 330-500 nm). The molar extinction coefficient of a compound can be measured using a well-known method. For example, it is preferable to measure it by the ultraviolet visible spectrophotometer (Cary-5 spectrophotometer by Varian company) at the density | concentration of 0.01 g / L using an ethyl acetate solvent.

As a radical photopolymerization initiator, a well-known compound can be used without a restriction | limiting, For example, a halogenated hydrocarbon derivative (for example, having a triazine skeleton, having an oxadiazole skeleton, a trihalomethyl group Oxime compounds such as acyl phosphine compounds such as acyl phosphine oxide, hexaaryl biimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoximether, aminoaceto Phenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes and the like.

As a halogenated hydrocarbon derivative which has a triazine skeleton, Wakabayashi et al., Bull. Chem. Soc. J. Org by the compounds described in Japan, 42, 2924 (1969), the compounds described in British Patent Publication No. 1388492, the compounds described in JP-A-53-133428, the compounds described in JP 3337024, FC Schaefer and the like. . Chem .; 29, 1527 (1964), the compound of JP-A-62-58241, the compound of JP-A-5-281728, the compound of JP-A-5-34920, United States And the compounds described in Patent Publication No. 4212976.

As the compound described in US Patent No. 4212976, for example, a compound having an oxadiazole skeleton (eg 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2- Trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4- Chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tribromo Methyl-5-styryl-1,3,4-oxadi Azole etc.) etc. are mentioned.

Moreover, an acridine derivative (for example, 9-phenyl acridine, 1,7-bis (9,9'- acrydinyl) heptane etc.), N-phenyl as an optical radical polymerization initiator of that excepting the above is mentioned. Polyhalogen compounds, such as glycine (for example, carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuran oil) -7- Diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7- Diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3'- Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamyl)- 7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipe Ropoxy coumarin, 7-benzotriazole-2-ylcoumarin, Japanese Unexamined Patent Publication No. 5-19475, Japanese Unexamined Patent Publication No. 7-271028, Japanese Unexamined Patent Publication No. 2002-363206, Japanese Unexamined Patent Publication 2002 Coumarin compounds and the like described in -363207, Japanese Unexamined Patent Publication No. 2002-363208, Japanese Unexamined Patent Publication No. 2002-363209 and the like), and acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl)). -Phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, LucirinTPO and the like), metallocenes (for example, Japanese Patent Laid-Open No. 2011) The titanocene compound described in Paragraph No. 0076 of -13602, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1- (I) -phenyl) titanium,? 5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), Japanese Patent Application Laid-open No. 53-133428, Japanese Patent Publication There may be mentioned the air beam bovine No. 57-1819, No. 57-6096 copper, and compounds such as described in U.S. Patent No. 3,615,455 calls.

As a ketone compound, For example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bro Mobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethylester thereof, 4,4'-bis (dialkylamino) benzophenones (e.g., 4, 4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dihydro Oxyethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, Anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2 - Jyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (e.g., benzoin methyl ether, benzoin ethyl ether, benzoinpropyl) Ether, benzoin isopropyl ether, benzoin phenyl ether, benzyldimethyl ketal), acridon, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloro Acridon etc. are mentioned.

In a commercial item, Kayakure DETX (made by Nippon Kayaku Co., Ltd.) is used suitably.

As the radical photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, the amino acetophenone series initiator of Unexamined-Japanese-Patent No. 10-291969, and the acyl phosphine oxide type initiator of Unexamined-Japanese-Patent No. 4225898 can also be used, for example.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used. IRGACURE is a registered trademark.

As an aminoacetophenone type initiator, the compound of Unexamined-Japanese-Patent No. 2009-191179 which the absorption wavelength matched to light sources, such as 365 nm or 405 nm, can also be used.

As an acyl phosphine type initiator, IRGACURE-819 which is a commercial item, and DAROCUR-TPO (all are brand name: BASF Corporation make) can be used.

As an optical radical polymerization initiator, More preferably, an oxime compound is mentioned. As a specific example of an oxime system initiator, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

As a preferable oxime compound, 3-benzoyloxy iminobutan-2-one, 3-acetoxy iminobutan-2-one, 3-propionyloxy iminobutan-2-one, 2-acetoxy iminopentane-3, for example -One, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

As the oxime compound, J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, and Journal of Photopolymer Science and Technology (1995) pp. The compound described in 202-232, the compound of Unexamined-Japanese-Patent No. 2000-66385, Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2004-534797, Unexamined-Japanese-Patent No. 2006-342166, etc. Can be mentioned.

In a commercial item, IRGACURE-OXE01 (made by BASF Corporation), IRGACURE-OXE02 (made by BASF Corporation), and N-1919 (made by ADEKA Corporation) are used suitably.

Moreover, the compound of Unexamined-Japanese-Patent No. 2009-519904 by which oxime is connected to the N position of a carbazole ring, the compound of Unexamined-Japanese-Patent No. 7626957 in which the hetero substituent was introduce | transduced in the benzophenone site, and the Japanese publication which introduced the nitro group in the pigment | dye site | part The compounds described in JP 2010-15025 and US 2009-292039, the ketoxime compounds described in WO2009 / 131189, U.S. Patent Publication No. 7556910 which includes a triazine skeleton and an oxime skeleton in the same molecule. You may use the compound described in Unexamined-Japanese-Patent No. 2009-221114, etc. which have the absorption maximum in 405 nm and the favorable sensitivity with respect to a g-ray light source.

Moreover, the cyclic oxime compound of Unexamined-Japanese-Patent No. 2007-231000 and Unexamined-Japanese-Patent No. 2007-322744 can also be used suitably. Among the cyclic oxime compounds, the cyclic oxime compounds condensed with carbazole dyes described in JP 2010-32985 and JP 2010-185072 are particularly preferred from the viewpoint of high sensitivity. Do.

Moreover, the compound of Unexamined-Japanese-Patent No. 2009-242469 which is a compound which has an unsaturated bond in the specific site of an oxime compound can also be used suitably.

Moreover, it is also possible to use the oxime compound which has a fluorine atom. As a specific example of such an initiator, the compound described in Unexamined-Japanese-Patent No. 2010-262028, the compound 24, 36-40 which are described in Paragraph No. 0345 of Unexamined-Japanese-Patent No. 2014-500852, Unexamined-Japanese-Patent No. 2013- The compound (C-3) described in Paragraph No. 0101 of 164471 can be mentioned. As a specific example, the following compounds are mentioned.

[Formula 14]

As an most preferable oxime compound, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269779, the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned.

The radical photopolymerization initiator is, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metal Rosene compound, oxime compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, halomethyloxadia Preferred are compounds selected from the group consisting of sol compounds and 3-aryl substituted coumarin compounds.

More preferably, the trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triarylimidazole dimer, onium compound, benzophenone compound, acetophenone compound More preferably, they are a trihalomethyl triazine compound, the (alpha)-amino ketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound, Most preferably, they are an oxime compound.

As for content of a radical polymerization initiator, 0.1-30 mass% is preferable with respect to the total solid of a negative photosensitive resin composition, More preferably, it is 0.1-20 mass%, More preferably, it is 0.1-10 mass%. Moreover, it is preferable to contain 1-20 mass parts of radical polymerization initiators with respect to 100 mass parts, and it is more preferable to contain 3-10 mass parts.

1 type of radical polymerization initiators may be sufficient, and 2 or more types may be sufficient as it. When there are 2 or more types of radical polymerization initiators, it is preferable that the sum total is the said range.

<1st polymerization inhibitor>

The negative photosensitive resin composition of this invention contains at least 1 sort (s) of 1st polymerization inhibitor chosen from the compound which has an aromatic hydroxyl group. Such a polymerization inhibitor has a strong polymerization inhibitory effect of a compound having a radically polymerizable group mainly in the presence of oxygen.

It is preferable that the compound which has an aromatic hydroxyl group is a compound shown by Formula (101).

Formula (101)

[Formula 15]

In Formula (101), m represents the integer of 1-5, n represents the integer of 1-4, n R <^101> respectively independently represents a halogen atom (a fluorine atom, a chlorine atom, a bromine atom) , Iodine atom), a cyano group, a hydroxyl group, an alkyl group which may have a branch of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkenyl group of 1 to 5 carbon atoms, or carbon atoms The alkynyl group of 1-5 may be represented, These groups may couple | bond with the benzene ring shown by Formula (101), and as a coupling group, a carbonyl group, a carbonyloxy group (-COO-), an oxycarbonyl group (-OCO- ), Thio group, sulfonyl group, sulfinyl group, oxy group, imino group (-NH-), amide group, C1-C6 alkylene group, C6-C12 arylene group, phosphonic acid ester group, phosphate ester group, 3-8 membered polyvalent polyvalent ring having two or more hydrogen atoms removed from heterocycles such as triazine and dioxane The polyvalent linking group chosen from the combination of a heterocyclic group, an alkylamino group, and these linking groups is mentioned. Moreover, the group represented by two or more R <^101> may combine with each other, and may form the ring structure.

The group represented by R ¹⁰¹ may have a substituent on the carbon atom to be introduced. As a substituent which can be introduced, a C1-C6 alkyl group, a hydroxyl group, a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an amino group, an alkylamino group, an alkoxy group, and (meth) Acryloyl group etc. can be illustrated.

X ¹⁰¹ does not exist when m is 1, and when m is 2 or more, m represents a linking group, and specifically, a single bond, a carbonyl group, a carbonyloxy group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, Phosphonic acid ester group, C1-C6 alkylene group, C6-C12 arylene group, imino group, C1-C6 aliphatic hydrocarbon group which removed m hydrogen atoms, m-valent C6 which removed m hydrogen atoms 6-12 membered heterocyclic group which removed m hydrogen atoms from heterocycles, such as -12 aromatic hydrocarbon group, a triazine, and dioxane, the combination of these coupling groups, etc. are mentioned, and a substituent is introduced into a carbon atom which can be introduced. You may have As for a substituent, the substituent similar to R <^101> is preferable.

When m is 1 in the formula (101), needless to say it does not have a linking group X ^101. In this case, it may have a monovalent substituent instead of X ¹⁰¹ , and the same group as R ¹⁰¹ is exemplified as the monovalent substituent, may be bonded to R ¹⁰¹ substituted with a benzene ring to form a ring structure, and a benzene ring and a linking group You may combine.

Specifically as a 1st polymerization inhibitor, 4-methoxy phenol, 2, 6- di-tert- butyl- 4-methyl phenol, pentaerythritol tetrakis [3- (3, 5- di-tert- butyl-] 4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl ) Propionamide], 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri- p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] , Hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy Roxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert -Butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, catechol, tert-butyl-catechol, 4,4 ', 4 " -(1-methylpropanyl-3-iridene) tris (6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetra Oxaspiro [5,5] undecane, hydroquinone, methylhydroquinone, t-butylhydroquinone, di-t-butyl-p-cresol, pyrogallol, 4,4-thiobis (3-methyl-6 -t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), phenol resins, and cresol resins are illustrated.

Moreover, a 3- (3,5-di-tert- butyl- 4-hydroxyphenyl) propionic acid alkyl ester is also mentioned as a preferable example. As for carbon number of the part of the alkyl chain which an alkyl ester here has, 7-9 are preferable.

As for content of the 1st polymerization inhibitor in a negative photosensitive resin composition, 0.01-5 mass% is preferable with respect to the total solid of a negative photosensitive resin composition. As for the minimum of content of a 1st polymerization inhibitor, 0.02 mass% or more is more preferable, and 0.03 mass% or more is more preferable. As an upper limit, 3 mass% or less is more preferable, and 1 mass% or less is more preferable.

1 type of 1st polymerization inhibitors may be sufficient, and 2 or more types may be sufficient as it. When a 1st polymerization inhibitor is 2 or more types, it is preferable that the sum total is the said range.

<2nd polymerization inhibitor>

The negative photosensitive resin composition of this invention contains at least 1 sort (s) of 2nd polymerization inhibitor chosen from a nitroso compound, an N-oxide compound, a quinone compound, an N-oxyl compound, and a phenothiazine compound. Such a polymerization inhibitor has a strong polymerization inhibitory effect of a compound having a radically polymerizable group mainly in the presence of non-oxygen.

As the nitroso compound of the second polymerization inhibitor, nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitroso-diphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitrosopy Lolidine, Nt-butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperidine, 4-nitrosomorpholine, N-nitroso -N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N-nitrosophenylhydroxyamine cerium salt and N-nitrosophenylhydroxyamine Aluminum salts, 2,4,6-Tris-t-butyl-nitrosobenzene, N-nitrosodiphenylamine are exemplified.

Examples of the N-oxide compound include phenyl-t-butylnitron, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl-1-pyrroline N-oxide, 4 -Methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isicotinic acid N-oxide Is illustrated.

Examples of the quinone compound include p-benzoquinone, p-xyloquinone, p-toluquinone, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone and 2-tert-butyl- p-benzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-1,4-benzoquinone, thymoquinone, 2,5-di-tert-amyl Benzoquinone, 2-bromo-1,4-benzoquinone, 2,5-dibromo-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro- 1,4-benzoquinone, 2-bromo-5-methyl-1,4-benzoquinone, tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone, 2-chloro-5 -Methyl-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2,5-dihydroxy-1,4-benzoquinone, 2,5-di Methoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, tetrahydroxy-1, 4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-anthraquinone, 2-methyl-1,4-naphthoquinone, 5,8- Daiha Doxy-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 5-hydroxy-2-methyl-1,4- Naphthoquinone, 1-nitroanthraquinone, anthraquinone, 1-aminoanthraquinone, 1,2-benzoanthraquinone, 1,4-diaminoanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthra Quinones, 2-methylanthraquinones, 5,12-naphthacequinones are exemplified.

Examples of the N-oxyl compound include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2 , 2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy-2,2,6,6- Tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpi Ferridine 1-oxyl, piperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamide-2,2,6,6 Tetramethylpiperidine 1-oxyl free radical, 4-maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonooxy-2,2,6,6 -Tetramethylpiperidine 1-oxyl free radicals, pyrrolidine 1-oxyl free radical compounds, 3-carboxyoxyl free radicals (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1- Oxyl free radicals).

Examples of the phenothiazine compound include phenothiazine, 10-methylphenothiazine, 2-methylthiophenothiazine, 2-chlorophenothiazine, 2-ethylthiophenothiazine, and 2- (trifluoromethyl) Phenothiazines, 2-methoxyphenothiazines are exemplified.

In addition, the compound belonging to any of the structure of a 1st polymerization inhibitor and a 2nd polymerization inhibitor is considered a 2nd polymerization inhibitor because polymerization can be inhibited both in the vicinity of the surface layer of a film | membrane, and inside of a film | membrane.

As a 2nd polymerization inhibitor, it is preferable to select from a quinone compound and an N-oxyl compound.

As for content of the 2nd polymerization inhibitor in a negative photosensitive resin composition, 0.01-5 mass% is preferable with respect to the total solid of a negative photosensitive resin composition. As for the minimum of content of a 2nd polymerization inhibitor, 0.02 mass% or more is more preferable, and 0.03 mass% or more is more preferable. As an upper limit, 3 mass% or less is more preferable, and 1 mass% or less is more preferable.

1 type of 2nd polymerization inhibitors may be sufficient, and 2 or more types may be sufficient as it. In the case where two or more second polymerization inhibitors are used, the total sum thereof is preferably within the above range.

Although the mass ratio of a 1st polymerization inhibitor and a 2nd polymerization inhibitor is not specifically determined, It is preferable that it is 1: 99-99: 1, It is more preferable that it is 90: 10-10: 90, 70: 30- It is more preferable that it is 30:70. By setting it as such a range, there exists a tendency for exposure latitude to become wider.

Moreover, in this invention, polymerization inhibitors other than the said 1st polymerization inhibitor and the 2nd polymerization inhibitor may be included. Moreover, in this invention, it can also be set as the structure which does not substantially contain polymerization inhibitors other than the said 1st polymerization inhibitor and the 2nd polymerization inhibitor. Substantially not included means that in the polymerization inhibitor contained in the photosensitive resin composition of this invention, the quantity of another polymerization inhibitor is 5 mass% or less of the quantity of all the polymerizable inhibitors.

Moreover, it is preferable that it is 0.01: 99.99-20: 80, and, as for the mass ratio of a 1st polymerization inhibitor and a radical polymerization initiator, 1: 99-10: 90 are more preferable. By setting it as such a range, there exists a tendency for exposure latitude to become wider.

The negative photosensitive resin composition of this invention may contain radically polymerizable compounds other than the said polyimide precursor. By containing a radically polymerizable compound, the cured film excellent in heat resistance can be formed. Furthermore, pattern formation can also be performed by the photolithographic method.

As a radically polymerizable compound, the compound which has an ethylenically unsaturated bond is preferable, and it is more preferable that it is a compound containing two or more ethylenically unsaturated groups.

The radically polymerizable compound may be any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof and multimers thereof.

In the present invention, the monomeric radical polymerizable compound (hereinafter also referred to as radical polymerizable monomer) is a compound different from the high molecular compound. The radically polymerizable monomer is typically a low molecular compound, preferably a low molecular weight compound having a molecular weight of 2000 or less, more preferably a low molecular weight compound having a molecular weight of 1500 or less, and even more preferably a low molecular weight compound having a molecular weight of 900 or less. In addition, the molecular weight of a radically polymerizable monomer is 100 or more normally.

Moreover, it is preferable that an oligomer type radically polymerizable compound is a polymer of relatively low molecular weight typically, and the polymer which ten to 100 radically polymerizable monomers couple | bonded. As molecular weight, it is preferable that the weight average molecular weight of polystyrene conversion in a gel permeation chromatography (GPC) method is 2000-20000, 2000-15000 are more preferable, It is more preferable that it is 2000-10000.

The number of functional groups of the radically polymerizable compound in the present invention means the number of radically polymerizable groups in one molecule.

It is preferable that a radically polymerizable compound contains at least 1 sort (s) or more bifunctional or more radically polymerizable compounds containing two or more radically polymerizable groups from a resolution viewpoint, and at least 1 sort (s) of 2-4 functional radically polymerizable compounds. It is more preferable to include.

<< compound having ethylenically unsaturated bond >>

As a group which has an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group, and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable.

Specific examples of the compound having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and multimers thereof. And esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds and their multimers. Moreover, the addition reaction product of the ester or amide of unsaturated carboxylic acid which has nucleophilic substituent, such as a hydroxyl group, an amino group, and a mercapto group, and monofunctional or polyfunctional isocyanate or epoxy, or monofunctional or polyfunctional carboxylic acid Dehydration condensation reactants with and the like are also suitably used. Moreover, addition reaction product of ester or amide of unsaturated carboxylic acid which has electrophilic substituents, such as an isocyanate group and an epoxy group, with monofunctional or polyfunctional alcohol, amines, and thiol, and also a halogen group and a tosyl jade Substitution reaction products of esters or amides of unsaturated carboxylic acids having a leaving substituent such as a period and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. As another example, a compound group substituted with a vinylbenzene derivative such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, or the like may be used instead of the above unsaturated carboxylic acid.

As a specific example of the monomer of the ester of a polyhydric alcohol compound and an unsaturated carboxylic acid, as an acrylic acid ester, ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 3- butanediol diacrylate, tetramethylene glycol Glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol Ethane triacrylate, hexanediol diacrylate, 1, 4- cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, di Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, pen Erythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide Modified triacrylate, polyester acrylate oligomer and the like.

As methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol ether Trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate Late, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-metha Krilloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, etc. have.

As the itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol Diitaconate, pentaerythritol diitaconate, and sorbitol tetrataconate.

Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

As examples of the other esters, for example, the aliphatic alcohol esters described in JP-A-46-27926, JP-A-51-47334 and JP-A-57-196231, and JP-A-JP The compound which has the aromatic skeleton of Unexamined-Japanese-Patent No. 59-5240, Unexamined-Japanese-Patent No. 59-5241, and Unexamined-Japanese-Patent No. 2-226149, and the amino group of Unexamined-Japanese-Patent No. 1-165613 are included. Compounds etc. are also used suitably.

Moreover, as a specific example of the monomer of the amide of a polyamine compound and an unsaturated carboxylic acid, methylene bis- acrylamide, methylene bis- methacrylamide, 1, 6- hexamethylene bis- acrylamide, 1, 6- hexamethylene bis- methacryl Amide, diethylene triamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As an example of another preferable amide monomer, the monomer which has the cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Moreover, the urethane-type addition polymerizable monomer manufactured using addition reaction of an isocyanate and a hydroxyl group is also suitable, As such a specific example, 1 as described in Unexamined-Japanese-Patent No. 48-41708 is mentioned. And vinylurethane compounds containing two or more polymerizable vinyl groups in one molecule in which a vinyl monomer containing a hydroxyl group is added to a polyisocyanate compound having two or more isocyanate groups in a molecule thereof. .

Moreover, urethane acrylates as described in Japanese Unexamined Patent Publication No. 51-37193, Japanese Unexamined Patent Publication No. Hei 2-32293, and Japanese Unexamined Patent Publication No. Hei 2-16765, and Japanese Patent Publication No. 58 Also suitable are urethane compounds having an ethylene oxide-based skeleton described in -49860, JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418.

Moreover, as a compound which has an ethylenically unsaturated bond, Paragraph No. 0095 of Unexamined-Japanese-Patent No. 2009-288705-the compound of 0108 can be used suitably also in this invention.

Moreover, as a compound which has an ethylenically unsaturated bond, the compound which has a boiling point of 100 degreeC or more under normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; 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 (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, and Japanese Patent Publication No. 48 Urethane (meth) as described in JP-A-41708, JP-A-50-6034, and JP-A-51-37193; Polyester acrylates, epoxy resins and the like described in each of acrylates, Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Application Laid-open No. 49-43191 and Japanese Patent Application Laid-open No. 52-30490; And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of) acrylic acid, and mixtures thereof. Moreover, Paragraph No. 0254 of Unexamined-Japanese-Patent No. 2008-292970-the compound of 0257 are also suitable. Moreover, the polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and ethylenically unsaturated group, react with polyfunctional carboxylic acid are mentioned.

Moreover, as a compound which has another preferable ethylenically unsaturated bond, it has a fluorene ring as described in Unexamined-Japanese-Patent No. 2010-160418, Unexamined-Japanese-Patent No. 2010-129825, Unexamined-Japanese-Patent No. 4364216, etc., and is ethylenically unsaturated. It is also possible to use the compound which has two or more groups which have a bond, and cardo resin.

Other examples include the specific unsaturated compounds described in Japanese Patent Application Laid-Open No. 46-43946, Japanese Patent Application Laid-open No. Hei 1-40337, Japanese Patent Application Laid-open No. Hei 1-40336, and Japanese Patent Application Laid-Open No. 2-25493. The vinyl phosphonic acid type-compound etc. which were described in the head are mentioned, for example. In any case, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is suitably used. In addition, Japan Adhesion Society vol. 20, No. 7, 300 to 308 (1984), which are introduced as radically polymerizable monomers and oligomers, can also be used.

In addition to the above, a compound having an ethylenically unsaturated bond represented by the following General Formulas (MO-1) to (MO-5) can also be suitably used. In addition, in formula, when T is an oxyalkylene group, the terminal at the side of a carbon atom couple | bonds with R.

[Formula 16]

[Formula 17]

In general formula, n is an integer of 0-14, m is an integer of 1-8. Two or more R and T in one molecule may be same or different, respectively.

In each of the polymerizable compounds represented by General Formulas (MO-1) to (MO-5), at least one of the plurality of R's is -OC (= 0) CH = CH ₂ , or -OC (= 0) Group represented by C (CH ₃ ) = CH ₂ .

As a specific example of the compound which has an ethylenically unsaturated bond represented by said general formula (MO-1)-(MO-5), Paragraph No. 0248 of Unexamined-Japanese-Patent No. 2007-269779-the compound of 0025-1 are disclosed in this invention. Also, it can use suitably.

Moreover, (meth) acrylated after adding ethylene oxide or a propylene oxide to the polyfunctional alcohol described in Unexamined-Japanese-Patent No. 10-62986 with the specific example as General formula (1) and (2). One compound can also be used as a polymeric compound.

As a compound which has an ethylenically unsaturated bond, it is a dipentaerythritol triacrylate (as a commercial item, KAYARAD D-330; the Nippon Kayaku Co., Ltd. make), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; Nippon Kayaku Co., Ltd., dipentaerythritol penta (meth) acrylate (as a commercial item, KAYARAD D-310; made by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial item) Nippon Kayaku Co., Ltd.), and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.

The compound which has an ethylenically unsaturated bond may be a polyfunctional monomer which has acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. As for the polyfunctional monomer which has an acidic radical, the ester of an aliphatic polyhydroxy compound and unsaturated carboxylic acid is preferable, and the polyfunctional monomer which made non-reactive hydroxyl group of the aliphatic polyhydroxy compound react with a non-aromatic carboxylic anhydride to give an acidic radical is more preferable. In this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. As a commercial item, M-510, M-520, etc. which are Toagosei Co., Ltd. polybasic acid modified acryl oligomer are mentioned, for example.

Although the polyfunctional monomer which has an acidic radical may be used individually by 1 type, you may mix and use 2 or more types. Moreover, you may use together the polyfunctional monomer which does not have an acidic radical, and the polyfunctional monomer which has an acidic radical as needed.

As a preferable acid value of the polyfunctional monomer which has an acidic radical, it is 0.1-40 mgKOH / g, Especially preferably, it is 5-30 mgKOH / g. If the acid value of a polyfunctional monomer is the said range, it is excellent in manufacture and handling property, and also excellent in developability. Moreover, radical polymerization property is favorable.

The compound which has a caprolactone structure can also be used for the compound which has an ethylenically unsaturated bond.

The compound having a caprolactone structure and an ethylenically unsaturated bond is not particularly limited as long as it has a caprolactone structure in the molecule, but for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethyl Ε-capro obtained by esterifying polyhydric alcohols such as olpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, and (meth) acrylic acid and ε-caprolactone Lactone modified polyfunctional (meth) acrylate is mentioned. Especially, the polymeric compound which has the caprolactone structure represented by the following general formula (C) is preferable.

General formula (C)

[Formula 18]

(In formula, all 6 R is group represented by the following general formula (D), or 1-5 of 6 R is group represented by the following general formula (D), and remainder is a following general formula (E) It is a flag that appears.)

General formula (D)

[Formula 19]

(Wherein R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond).

General formula (E)

[Formula 20]

(In formula, R <^1> represents a hydrogen atom or a methyl group, and "*" represents a bond.)

The polymeric compound which has such a caprolactone structure is marketed as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., for example, and m = 1, in DPCA-20 (the said general formula (C)-(E)), Number of groups represented by General Formula (D) = 2, R ¹ are all hydrogen atoms), DPCA-30 (same formula, m = 1, number of groups represented by General Formula (D) = 3, R ¹ is The compound which is all a hydrogen atom), DPCA-60 (the same formula, m = 1, the number of groups represented by general formula (D) = 6, the compound in which R <^1> is all a hydrogen atom), DPCA-120 (m in the same formula) = 2, the number of groups represented by general formula (D) = 6, the compound whose R <^1> is all hydrogen atoms), etc. are mentioned.

In this invention, the compound which has a caprolactone structure and ethylenically unsaturated bond can be used individually or in mixture of 2 or more types.

It is also preferable that the compound which has an ethylenically unsaturated bond is at least 1 sort (s) chosen from the group of the compound represented by the following general formula (i) or (ii).

[Formula 21]

In General Formulas (i) and (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-, y represents the integer of 0-10 each independently, and X represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group each independently.

In general formula (i), the sum total of a (meth) acryloyl group is three or four, m respectively independently represents the integer of 0-10, and the sum of each m is an integer of 0-40. However, when the sum of each m is 0, any one of X is a carboxyl group.

In general formula (ii), the sum total of a (meth) acryloyl group is five or six, n represents the integer of 0-10 each independently, and the sum of each n is an integer of 0-60. However, when the sum of each n is 0, any one of X is a carboxyl group.

In general formula (i), the integer of 0-6 is preferable and, as for m, the integer of 0-4 is more preferable.

Moreover, the integer of 2-40 is preferable, as for the sum total of each m, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.

In general formula (ii), the integer of 0-6 is preferable and, as for n, the integer of 0-4 is more preferable.

Moreover, the integer of 3-60 is preferable, as for the sum total of each n, the integer of 3-24 is more preferable, and the integer of 6-12 is especially preferable.

-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-in general formula (i) or general formula (ii) has X as the terminal Forms of bonding are preferred. In particular, in general formula (ii), the form whose all 6 X is acryloyl group is preferable.

The compound represented by the general formula (i) or (ii) is a step of linking the ring-opening skeleton by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known step, and the ring-opening skeleton. (Meth) acryloyl chloride is made to react, for example by the terminal hydroxyl group of, and it can synthesize | combine by the process of introduce | transducing a (meth) acryloyl group. Each step is a well known step, and a person skilled in the art can easily synthesize a compound represented by formula (i) or (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and dipentaerythritol derivatives are more preferable.

Specifically, the compound (henceforth "exemplified compound (a)-(f)") represented by following formula (a)-(f) is mentioned, Especially, exemplary compound (a), (b) , (e) and (f) are preferred.

[Formula 22]

[Formula 23]

As a commercial item of the polymeric compound represented by General formula (i) and (ii), it is SR-494 which is a tetrafunctional acrylate which has four ethyleneoxy chains made by Satomer, and a pen by Nippon Kayaku Co., Ltd. DPCA-60 which is a 6-functional acrylate which has 6 thylene oxy chains, and TPA-330 which is a trifunctional acrylate which has 3 isobutylene oxy chains, etc. are mentioned.

As a compound which has an ethylenically unsaturated bond, it is described in Unexamined-Japanese-Patent No. 48-41708, Unexamined-Japanese-Patent No. 51-37193, Unexamined-Japanese-Patent No. 2-32293, and Unexamined-Japanese-Patent No. 2-16765. Urethane acrylates, Japanese Patent Laid-Open No. 58-49860, Japanese Patent Laid-Open No. 56-17654, Japanese Patent Laid-Open No. 62-39417, Japanese Patent Laid-Open No. 62-39418 Also suitable are urethane compounds having the ethylene oxide skeleton described in the above. As the polymerizable compound, an addition having an amino structure or a sulfide structure in a molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-105238. Polymerizable monomers can also be used.

As a commercial item of the compound which has an ethylenically unsaturated bond, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku pulp company), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A- 9300, UA-7200 (made by Shin-Nakamura Kagaku Kogyo Co., Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, And AI-600 (manufactured by Kyoeisha Kagaku Co., Ltd.) and Blemmer PME400 (manufactured by Nichiyu Co., Ltd.).

It is preferable that the compound which has an ethylenically unsaturated bond has a partial structure represented by a following formula from a heat resistant viewpoint. Where * in the formula is a connecting hand.

[Formula 24]

As a specific example of the compound which has an ethylenically unsaturated bond which has the said partial structure, For example, trimethylol propane tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, and isocyanur Acid ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth ) Acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylol methane tetra (meth) acrylate, and the like. In the present invention, these polymerizable compounds can be particularly preferably used.

In a negative photosensitive resin composition, 1-50 mass% of content of a radically polymerizable compound is preferable with respect to the total solid of a negative photosensitive resin composition from a viewpoint of favorable radical polymerization property and heat resistance. As for a minimum, 5 mass% or more is more preferable. As for an upper limit, 30 mass% or less is more preferable. Although a radically polymerizable compound may be used individually by 1 type, you may mix and use 2 or more types.

Moreover, as for the mass ratio (polyimide precursor / radically polymerizable compound) of the compound which has a polyimide precursor and a radically polymerizable compound, 98 / 2-10 / 90 are preferable, 95 / 5-30 / 70 are more preferable , 90/10-50/50 are more preferable. If the mass ratio of a polyimide precursor and a radically polymerizable compound is the said range, the cured film excellent in curability and heat resistance can be formed.

1 type of radically polymerizable compounds may be used and may be used 2 or more types. When using 2 or more types, it is preferable that a total amount becomes said range.

The negative photosensitive resin composition of this invention may contain the photobase generator. The photobase generator generates a base by exposure, and exhibits no activity under normal conditions of normal temperature and normal pressure, but is particularly limited as long as it generates a base (basic substance) when irradiation and heating of electromagnetic waves are performed as an external stimulus. It doesn't happen. Since the base which generate | occur | produced by exposure acts as a catalyst at the time of hardening a polyimide precursor by heating, it can use suitably in a negative type.

The content of the photobase generator is not particularly limited as long as the desired pattern can be formed, and can be made into a general content. It is preferable that content of a photobase generator exists in the range of 0.01 mass part or more and less than 30 mass parts with respect to 100 mass parts of negative photosensitive resin composition, It is more preferable to exist in the range of 0.05 mass part-25 mass parts, 0.1 mass It is more preferable to exist in the range of part-20 mass parts.

In this invention, a well-known thing can be used as a photobase generator. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Tsunooka Masahiro, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. As described in Technol., 19, 81 (2006), the base component is a salt having a structure such as a transition metal compound complex, an ammonium salt, or the like, and the amidine moiety is latent by forming a salt with a carboxylic acid. And nonionic compounds whose base components are latent by urethane bonds, oxime bonds such as carbamate derivatives, oxime ester derivatives, acyl compounds, and the like, which are neutralized by forming the amine compounds.

The photobase generator that can be used in the present invention is not particularly limited and known ones can be used, and examples thereof include carbamate derivatives, amide derivatives, imide derivatives, α cobalt complexes, imidazole derivatives and cinnamic acid amide derivatives. And oxime derivatives.

Although the basic substance which generate | occur | produces from a photobase generator is not specifically limited, Polyamine, such as a compound which has an amino group, especially monoamine, diamine, amidine, etc. are mentioned.

The basic substance which generate | occur | produces the compound which has an amino group with higher basicity is preferable. This is because the catalytic action against the dehydration condensation reaction in imidation of the polyimide precursor is strong, and the addition of a smaller amount enables the expression of the catalytic effect in the dehydration condensation reaction at a lower temperature and the like. That is, since the catalytic effect of the generated basic substance is large, the sensitivity of the external appearance as a negative photosensitive resin composition improves.

It is preferable that it is amidine and an aliphatic amine from a viewpoint of the said catalyst effect.

It is preferable that a photobase generator is a photobase generator which does not contain a salt in a structure. It is preferable that there is no electric charge on the nitrogen atom of the base part which arises in a photobase generator. It is preferable that the photobase generator is latent using a covalent bond, and the base generating mechanism cut | disconnects a covalent bond between the nitrogen atom of the base part to generate | occur | produces, and an adjacent atom, It is more preferable that it is a compound which arises. If it is a photobase generator which does not contain a salt in a structure, since a photobase generator can be made neutral, solvent solubility is favorable and a pot life is improved. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

Moreover, for the same reason as above, it is preferable that the base generated as mentioned above is latent using a covalent bond. Moreover, it is more preferable that the generated base is latent using an amide bond, a carbamate bond, and an oxime bond.

As a base generator which concerns on this invention, the base generator which has a cinnamic acid amide structure as disclosed, for example in Unexamined-Japanese-Patent No. 2009-80452 and WO2009 / 123122, Unexamined-Japanese-Patent No. 2006-189591 And base generators having a carbamate structure as disclosed in JP-A-2008-247747, oxime structures as disclosed in JP-A-2007-249013 and JP-A-2008-003581, and carbamoyl oxime structures Although the base generator which has is mentioned, etc. are mentioned, It is not limited to these, In addition, the structure of a well-known base generator can be used.

Hereinafter, the photobase generator which can be used for the present invention will be described with reference to specific examples.

As an ionic compound, the thing of the following structural formula is mentioned, for example.

[Formula 25]

As an acyl compound, the compound shown by following formula is mentioned, for example.

[Formula 26]

Moreover, as a photobase generator, the compound represented by following General formula (PB-1) is mentioned, for example.

[Formula 27]

(In General Formula (PB-1), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an organic group, and may be the same or different. However, at least one of R ⁴¹ and R ⁴² is an organic group. Or , R ⁴¹ and R ⁴² may be bonded to each other to form a ring structure, or may include a bond of hetero atoms, R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercap; Earthenware, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, and a nitrate Rosso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosph Group, a phosphonate group, an amino group, an import ammonia or an organic group, be the same or different, or, R ^45, R ^46, R ⁴⁷ and R ⁴⁸ is, by a combination of them two or more may form a ring structure And R ⁴⁹ may be a protecting group that can be deprotected by irradiation of a hydrogen atom or heating and / or electromagnetic waves.

Although the specific example of general formula (PB-1) is given to the following, it is not limited to this.

[Formula 28]

[Formula 29]

[Formula 30]

In addition, as a photobase generator, Paragraph No. 0185 of Unexamined-Japanese-Patent No. 2012-93746, 0199-0200, the compound of 0202, Paragraph No. 0022 of Unexamined-Japanese-Patent No. 2013-194205, 0069, Japan The compound of Paragraph No. 0026 of Unexamined-Japanese-Patent No. 2013-204019-00074, and the compound of Paragraph No. 0052 of WO2010 / 064631 are mentioned as an example.

The negative photosensitive resin composition of this invention may contain the heat base generator.

Although the kind etc. of a heat base generating agent are not specifically determined, At least 1 sort (s) chosen from an acidic compound which generate | occur | produces a base when heated to 40 degreeC or more, and an ammonium salt which has an anion and an ammonium cation whose pKa1 is 0-4 are included. It is preferable to include a heat base generator. Here, pKa1 represents the logarithmic representation (-Log ₁₀ Ka) of the dissociation constant Ka of the 1st proton of a polyvalent acid.

By mix | blending such a compound, the cyclization reaction of a polyimide precursor can be performed at low temperature, and it can be set as the negative photosensitive resin composition which is more excellent in stability. Moreover, since a heat base generator does not generate a base unless it heats, even if it coexists with a polyimide precursor, cyclization of the polyimide precursor in storage can be suppressed and it is excellent in storage stability.

The heat base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C or higher, and an ammonium salt (A2) having an anion and an ammonium cation of pKa1 of 0 to 4 It includes.

Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the cyclization reaction of the polyimide precursor can be accelerated by the base generated from these compounds, and the cyclization of the polyimide precursor can be performed at low temperature. Can be. Moreover, even if these compounds coexist with the polyimide precursor which cyclizes and hardens with a base, since the cyclization of a polyimide precursor hardly advances unless it heats, the negative photosensitive resin composition excellent in stability can be prepared.

In addition, in this specification, with an acidic compound, 1 g of compounds are extract | collected to the container, 50 mL of mixed liquids (mass ratio of water / tetrahydrofuran = 1/4) of ion-exchange water and tetrahydrofuran are added, and it is 1 hour at room temperature. By stirring, the solution obtained means the compound whose value measured at 20 degreeC using a pH (potential hydrogen) meter is less than 7.

In this invention, 40 degreeC or more is preferable and, as for the base generation temperature of an acidic compound (A1) and an ammonium salt (A2), 120-200 degreeC is more preferable. 190 degrees C or less is more preferable, as for the upper limit of base generation temperature, 180 degrees C or less is more preferable, and 165 degrees C or less is more preferable. 130 degreeC or more is more preferable, and, as for the minimum of base generation temperature, 135 degreeC or more is more preferable.

If the base generation temperature of an acidic compound (A1) and an ammonium salt (A2) is 120 degreeC or more, since a base will hardly generate | occur | produce during storage, the negative photosensitive resin composition excellent in stability can be prepared. If the base generation temperature of an acidic compound (A1) and an ammonium salt (A2) is 200 degrees C or less, the cyclization temperature of a polyimide precursor can be made low. The base generation temperature is, for example, using a differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in an internal pressure capsule, reading the peak temperature of the lowest exothermic peak, and reading the peak temperature. Can be measured as the base generation temperature.

In the present invention, the base generated by the heat base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a polyimide precursor can be made lower. In addition, the boiling point of the base generated by the heat base generator is preferably 80 ° C or higher, more preferably 100 ° C or higher, and most preferably 140 ° C or higher. Moreover, as for the molecular weight of the base to generate | occur | produce, 80-2000 are preferable. As for a minimum, 100 or more are more preferable. As for an upper limit, 500 or less are more preferable. In addition, the value of molecular weight is a theoretical value calculated | required from structural formula.

In this invention, it is preferable that the said acidic compound (A1) contains 1 or more types chosen from the compound represented by an ammonium salt and general formula (A1) mentioned later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C or higher (preferably 120 to 200 ° C), or 40 ° C or higher (preferably 120 to 200 ° C). It may be a compound other than an acidic compound that generates a base when heated.

<< ammonium salt >>

In this invention, an ammonium salt means the salt of the ammonium cation represented by following General formula (1) or General formula (2), and an anion. The anion may be bonded to a part of any one of the ammonium cations via a covalent bond or may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation. In addition, an anion outside the molecule | numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple | bonded through a covalent bond. Hereinafter, the anion out of the molecule of a cation part is also called counter anion.

[Formula 31]

In said general formula (1), (2), R <^1> -R <^6> respectively independently represents a hydrogen atom or a hydrocarbon group, and R <^7> represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁷ may be bonded to each other to form a ring.

In the present invention, the ammonium salt preferably has an anion and an ammonium cation having a pKa1 of 0 to 4. 3.5 or less are more preferable, and, as for the upper limit of pKa1 of an anion, 3.2 or less are more preferable. 0.5 or more are more preferable, and, as for a minimum, 1.0 or more are more preferable. When pKa1 of an anion is the said range, a polyimide precursor can be cyclized at low temperature, and also the stability of a negative photosensitive resin composition can be improved. If pKa1 is 4 or less, the stability of a heat base generator is favorable, it can suppress generation of a base without heating, and the stability of a negative photosensitive resin composition is favorable. When pKa1 is 0 or more, the generated base is hardly neutralized, and the cyclization efficiency of the polyimide precursor is good.

As for the kind of anion, 1 type chosen from a carboxylic acid anion, a phenol anion, a phosphate anion, and a sulfate anion is preferable, and a carboxylic acid anion is more preferable from the reason that both the stability of a salt and thermal decomposition property are compatible. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.

The anion of the divalent or higher carboxylic acid having two or more carboxyl groups is preferably an carboxylic acid anion, and more preferably the anion of the divalent carboxylic acid. According to this aspect, it can be set as the heat base generator which can improve the stability, curability, and developability of a negative photosensitive resin composition further. In particular, by using the anion of divalent carboxylic acid, the stability, curability, and developability of a negative photosensitive resin composition can be improved more.

In the present invention, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. 3.5 or less are more preferable, and, as for pKa1, 3.2 or less are more preferable. According to this aspect, the stability of a negative photosensitive resin composition can be improved more.

Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compilation: Braude, EA , Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.

In the present invention, the carboxylic acid anion is preferably represented by the following General Formula (X1).

[Formula 32]

In General Formula (X1), EWG represents an electron withdrawing group.

In the present invention, the electron withdrawing group means that Hammet's substituent constant sigma m represents a positive value. Here, sigma m is described in detail in the general summary by Lake Tsuno, Vol. 23 No. 8 (1965) P. 631-642. In addition, the electron-withdrawing group of this invention is not limited to the substituent as described in the said document.

Examples of substituents in which sigma m represents a positive value include, for example, a CF ₃ group (σm = 0.43), a CF ₃ CO group (σm = 0.63), a HC = C group (σm = 0.21), and a CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group (σm = 0.06), and the like. Can be. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

In the present invention, EWG preferably represents a group represented by the following General Formulas (EWG-1) to (EWG-6).

[Formula 33]

In the formula, each of R ^x1 to R ^x3 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aryl group.

1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be any of linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent and may be unsubstituted. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have. As a substituent, a carboxyl group is preferable.

2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are more preferable. The alkenyl group may be any of linear, branched or cyclic, linear or branched, and more preferably linear. The alkenyl group may have a substituent and may be unsubstituted. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have. As a substituent, a carboxyl group is preferable.

6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are more preferable. The aryl group may have a substituent and may be unsubstituted. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have. As a substituent, a carboxyl group is preferable.

In the present invention, the carboxylic acid anion is also preferably represented by the following General Formula (X).

[Formula 34]

In General Formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, -NR ^X -and a combination thereof, and R ^X represents a hydrogen atom, An alkyl group, an alkenyl group, or an aryl group is represented.

1-30 are preferable, as for carbon number of the alkylene group which L <^10> represents, 1-20 are more preferable, and 1-10 are more preferable. The alkylene group may be any of linear, branched or cyclic, linear or branched, and more preferably linear. The alkylene group may have a substituent and may be unsubstituted. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have.

2-30 are preferable, as for carbon number of the alkenylene group which L <^10> represents, 2-20 are more preferable, and its 2-10 are more preferable. The alkenylene group may be any of linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkenylene group may have a substituent and may be unsubstituted. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have.

6-30 are preferable, as for carbon number of the arylene group which L <^10> represents, 6-20 are more preferable, and 6-12 are more preferable. The arylene group may have a substituent and may be unsubstituted. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have.

1-30 are preferable, as for carbon number of the alkyl group which R ^X represents, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be any of linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent and may be unsubstituted. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have.

2-30 are preferable, as for carbon number of the alkenyl group which R ^X represents, 2-20 are more preferable, and its 2-10 are more preferable. The alkenyl group may be any of linear, branched or cyclic, linear or branched, and more preferably linear. The alkenyl group may have a substituent and may be unsubstituted. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have.

6-30 are preferable, as for carbon number of the aryl group which R ^X represents, 6-20 are more preferable, and 6-12 are more preferable. The aryl group may have a substituent and may be unsubstituted. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have.

Specific examples of the carboxylic acid anion include maleic anion, phthalic anion, N-phenylimino diacetate anion and oxalic acid anion. These can be used preferably.

It is preferable that an ammonium cation is represented by either of the following general formula (Y1-1) (Y1-6).

[Formula 35]

In the above general formula, R ¹⁰¹ represents an n-valent organic group,

R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group,

R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group,

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring,

Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group,

n represents an integer of 1 or more,

m represents the integer of 0-5.

R ¹⁰¹ represents an n-valent organic group. As monovalent organic group, an alkyl group, an alkylene group, an aryl group, etc. are mentioned. Examples of the divalent or more organic group include those in which one or more hydrogen atoms are removed from the monovalent organic group to form an n-valent group.

R ¹⁰¹ is preferably an aryl group. Specific examples of the aryl group, there may be mentioned later that described in Ar ^10.

R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group.

As the hydrocarbon group represented by R ¹⁰² to R ¹¹¹ , R ¹⁵⁰ and R ¹⁵¹ , an alkyl group, an alkenyl group or an aryl group is preferable. The alkyl group, alkenyl group and aryl group may further have a substituent. As a substituent, it may be mentioned organic groups represented by A ¹ to be described later is described in the substituent which may optionally have.

1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be any of linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent and may be unsubstituted.

2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are more preferable. The alkenyl group may be any of linear, branched or cyclic, linear or branched, and more preferably linear. The alkenyl group may have a substituent and may be unsubstituted.

6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are more preferable. The aryl group may have a substituent and may be unsubstituted.

Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group.

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. As a ring, an aliphatic ring (non-aromatic hydrocarbon ring), an aromatic ring, a heterocyclic ring, etc. are mentioned. The ring may be monocyclic or may be cyclic. Examples of the linking group in the case where the above groups bond to form a ring include a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group, and a combination thereof. have. As a specific example of the ring formed, for example, a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, a thiazine ring, an indole ring , Isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.

In the present invention, the ammonium cation preferably has a structure represented by General Formula (Y1-1) or (Y1-2), is represented by General Formula (Y1-1) or (Y1-2), and R ¹⁰¹ is an aryl group. The structure is more preferable, and the structure wherein R ¹⁰¹ is an aryl group is particularly preferable. That is, in this invention, it is more preferable that an ammonium cation is represented with the following general formula (Y).

[Formula 36]

Ar ¹⁰ represents an aryl group. Specifically as an aryl group, a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptylene ring, indencene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridine Polyazine ring, indolin ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolysin ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline Ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, cyanthrene ring, chromen ring, xanthene ring, phenoxacyine ring, phenoxyazine ring, and phenazine ring. Especially, a benzene ring, a naphthalene ring, an anthracene ring, a phenothiazine ring, or a carbazole ring are preferable from a viewpoint of storage stability and high sensitivity, and a benzene ring or a naphthalene ring is the most preferable.

Examples of the substituent which may have an aryl group, can be represented by A ¹ to be described later that is mentioned in the substituent group which may contain organic groups.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group. Although there is no limitation in particular as a hydrocarbon group, An alkyl group, an alkenyl group, or an aryl group is preferable.

R ¹¹ and R ¹² are preferably hydrogen atoms.

1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be any of linear, branched or cyclic.

As a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group, iso A propyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group are mentioned.

The cyclic alkyl group (cycloalkyl group) may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. As a monocyclic cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. As a polycyclic cycloalkyl group, an adamantyl group, a norbornyl group, a carbonyl group, a camphoryl group, a decahydronaphthyl group, a tricyclodecaneyl group, a tetracyclodecaneyl group, a camporoyl group, a dicyclohexyl group, and a pinenyl group are mentioned, for example. Can be. Especially, a cyclohexyl group is the most preferable from a viewpoint of compatibility with high sensitivity.

2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are more preferable. The alkenyl group may be any of linear, branched or cyclic, linear or branched, and more preferably linear.

6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are more preferable.

R <^13> -R <^15> represents a hydrogen atom or a hydrocarbon group.

As the hydrocarbon groups, there may be mentioned hydrocarbon groups described in the above-described R ^11, R ^12. An alkyl group is particularly preferable for R ¹³ to R ¹⁵ , and preferred embodiments thereof are also the same as those described for R ¹¹ and R ¹² .

R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of the ring include cyclic aliphatic (non-aromatic hydrocarbon rings), aromatic rings, heterocycles, and the like. The ring may be monocyclic or may be cyclic. Examples of the linking group in the case where R ¹⁴ and R ¹⁵ combine to form a ring include a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aryl group, and a combination thereof. Can be mentioned. As a specific example of the ring formed, for example, a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, a thiazine ring, an indole ring , Isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.

R <^14> -R <^15> R <^14> and R <^15> combine with each other, they form the ring, or R <^13> is a C5-C30 (more preferably C6-C18) linear alkyl group, R <^14> and R ^It is preferable that ¹⁵ is a C1-C3 (more preferably C1-C2) alkyl group each independently. According to this aspect, amine species with a high boiling point can be easily generated.

Moreover, it is preferable that the total number of carbon atoms of R <^13> , R <^14> and R <^15> is 7-30, and, as for R <^13> -R <^15> from a basic and boiling point of the amine species which generate | occur | produce, it is more preferable that it is 10-20. Do.

In addition, the reason is liable to generate a high-boiling amine species, the formula "-NR ¹³ R ¹⁴ R ^15" of the formula weight of the (Y) is 80 to 2000, more preferably 100 to 500 Do.

On the other hand, as an embodiment for further improving adhesiveness with a copper wiring, in general formula (Y), R <^13> and R <^14> is a methyl group or an ethyl group, R <^15> is a C5 or more linear, branched or cyclic alkyl group, The form which is an aryl group is mentioned. In this embodiment, R ¹³ and R ¹⁴ is a methyl group, and, R ¹⁵ is preferably a straight chain alkyl group, a cyclic alkyl group or a phenyl group having 6 to 17 branched alkyl group, having 6 to 10 of a carbon number of 5-20, and R ¹³ And it is more preferable that R <^14> is a methyl group, R <^15> is a C5-C10 linear alkyl group, a C6-C10 branched alkyl group, a C6-C8 cyclic alkyl group, or a phenyl group. By lowering the hydrophobicity of the amine species in this manner, even when the amine adheres on the copper wiring, the affinity between the copper surface and the polyimide can be more effectively suppressed. In this embodiment, the preferable range of Ar <^10> , R <^11> , R <^12> and n is the same as the above-mentioned.

In this invention, it is also preferable that an acidic compound is a compound represented with the following general formula (A1). Although the compound is acidic at room temperature, the carboxyl group is decarboxylated or dehydrated and disappeared by heating, and the amine moiety that has been neutralized and inactivated until then becomes active, thereby becoming basic. Hereinafter, general formula (A1) is demonstrated.

[Formula 37]

In General Formula (A1), A ¹ represents a pvalent organic group, R ¹ represents a monovalent organic group, L ¹ represents a (m + 1) valent organic group, m represents an integer of 1 or more, and p is 1 The above integer is shown.

In General Formula (A1), A ¹ represents a p-valent organic group. As an organic group, an aliphatic group, an aryl group, etc. are mentioned, An aryl group is preferable. By using A ¹ as an aryl group, a base having a high boiling point can be easily generated at a lower temperature. By raising the boiling point of the base to generate | occur | produce, volatilization or decomposition by the heating at the time of hardening of a polyimide precursor can be suppressed, and cyclization of a polyimide precursor can be advanced more effectively.

As monovalent aliphatic group, an alkyl group, an alkenyl group, etc. are mentioned, for example.

1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be any of linear, branched or cyclic. The alkyl group may have a substituent and may be unsubstituted. Specific examples of the alkyl group include methyl group, ethyl group, tert-butyl group, dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group and the like.

2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are more preferable. The alkenyl group may be any of linear, branched or cyclic. The alkenyl group may have a substituent and may be unsubstituted. As an alkenyl group, a vinyl group, a (meth) allyl group, etc. are mentioned.

Examples of the divalent or higher aliphatic group include groups in which at least one hydrogen atom is removed from the monovalent aliphatic group.

The aryl group may be monocyclic or polycyclic. The aryl group may be a heteroaryl group containing a hetero atom. The aryl group may have a substituent and may be unsubstituted. Unsubstituted is preferred. Specific examples of the aryl group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptylene ring, an indencene ring, a perylene ring, a pentacene ring, an acenaphthalene ring, a phenanthrene ring, anthracene ring, a naphthacene ring, a chrysene ring, Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoliazine ring , Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolysin ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenan A tridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromen ring, a xanthene ring, a phenoxa cyin ring, a phenythiazin ring, and a phenazine ring are mentioned, A benzene ring is the most preferable.

A plurality of aromatic rings may be connected via a single bond or a linking group to be described later. As a linking group, an alkylene group is preferable, for example. The alkylene group is preferably both straight chain and branched. Specific examples of the aryl group in which a plurality of aromatic rings are linked via a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenyl isopropane, triphenylmethane, tetraphenylmethane and the like. have.

As an example of the substituent which the organic group which A <^1> may have, For example, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; Aryloxy groups such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; Aryloxycarbonyl groups such as phenoxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; Acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; Alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; Arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; Halogenated alkyl groups such as alkyl fluoride groups; Cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and adamantyl group; Aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; Hydroxyl group; Carboxyl groups; Foam diary; Sulfo groups; Cyano groups; Alkylaminocarbonyl group; Arylaminocarbonyl group; Sulfonamide groups; Silyl groups; Amino group; Monoalkylamino groups; Dialkylamino group; Arylamino group; Diarylamino group; Thiooxy group; Or a combination thereof.

L ¹ represents a (m + 1) valent linking group. Linking group is not particularly limited, -COO-, -OCO-, -CO-, -O- , -S-, -SO-, -SO 2 -, an alkylene group (preferably a straight chain or branched having 1 to 10 carbon atoms An alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), an alkenylene group (preferably a straight or branched alkenylene group having 2 to 10 carbon atoms), or a linking group having a plurality thereof connected thereto; Can be mentioned. As for the total carbon number of a coupling group, 3 or less are preferable. The linking group is preferably an alkylene group, a cycloalkylene group, an alkenylene group, more preferably a straight chain or branched alkylene group, still more preferably a straight chain alkylene group, particularly preferably an ethylene group or a methylene group, and most preferably a methylene group.

R ¹ represents a monovalent organic group. As monovalent organic group, an aliphatic group, an aryl group, etc. are mentioned. Examples of the aliphatic group and the aryl group include those described above for A ¹ . The monovalent organic group represented by R ¹ may have a substituent. Examples of the substituent include those mentioned above.

It is preferable that R <^1> is group which has a carboxyl group. In other words, R ¹ is preferably a group represented by the following formula.

-L ^2- (COOH) _n

In the formula, L ² represents a (n + 1) -valent linking group, and n represents an integer of 1 or more.

L represents a ^divalent linking group is, there may be mentioned groups described in the above L ^1, and the preferred range is also the same, an ethylene group or a methylene group, and particularly preferred, and most preferably a methylene group.

n represents an integer of 1 or more, 1 or 2 is preferable and 1 is more preferable. The upper limit of n is the maximum number of substituents that the linking group represented by L ² can take. When n is 1, it is easy to generate | occur | produce a tertiary amine with a high boiling point by heating below 200 degreeC. Furthermore, the stability of a negative photosensitive resin composition can be improved.

m represents an integer of 1 or more, 1 or 2 is preferable and 1 is more preferable. The upper limit of m is the maximum number of substituents that the linking group represented by L ¹ can take. When m is 1, it is easy to generate | occur | produce tertiary amine with a high boiling point by the heating of 200 degrees C or less. Furthermore, the stability of a negative photosensitive resin composition can be improved.

p represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of p is the maximum number of substituents that the organic group represented by A ¹ can take. When p is 1, it is easy to generate | occur | produce a tertiary amine with a high boiling point by the heating of 200 degrees C or less.

In the present invention, the compound represented by General Formula (A1) is preferably a compound represented by the following General Formula (1a).

[Formula 38]

In General Formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m + 1) valent coupling group, L ² represents a (n + 1) valent coupling group, m represents an integer of 1 or more, n represents an integer of 1 or more, and p represents an integer of 1 or more.

A <^1> , L <^1> , L <^2> , m, n, and p of General formula (1a) are synonymous with the range demonstrated by General formula (A1), and its preferable range is also the same.

In the present invention, the compound represented by General Formula (A1) is preferably N-arylimino diacetic acid. N-arylimino diacetic acid is a compound in which A ¹ in General Formula (A1) is an aryl group, L ¹ and L ² are methylene groups, m is 1, n is 1, and p is 1 . N-arylimino diacetic acid is easy to generate | occur | produce tertiary amine with a high boiling point at 120-200 degreeC.

Although the specific example of the heat base generator in this invention is described below, this invention is not limited to these. These can be used individually or in mixture of 2 or more types, respectively. Me in the following formula represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18) and (A-19) are compounds represented by the formula (A1). Among the compounds shown below, (A-1) to (A-11) and (A-18) to (A-26) are more preferable, and (A-1) to (A-9) and (A-18) )-(A-21), (A-23) and (A-24) are more preferable.

Moreover, from a viewpoint of improving adhesiveness with copper, (A-18)-(A-26), (A-38)-(A-43) are preferable, (A-26) and (A-38) (A-43) is more preferable.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

As a heat base generator used by this invention, Paragraph No. 0015 of Unexamined-Japanese-Patent No. 2015-034388-the compound of 0055 are also used suitably, These content is integrated in this specification.

When using a heat base generator, 0.1-50 mass% of content of the heat base generator in a negative photosensitive resin composition is preferable with respect to the total solid of a negative photosensitive resin composition. 0.5 mass% or more is more preferable, and, as for a minimum, 1 mass% or more is more preferable. 30 mass% or less is more preferable, and, as for an upper limit, 20 mass% or less is more preferable.

The heat base generator can use 1 type (s) or 2 or more types. When using 2 or more types, it is preferable that the total amount is the said range.

The negative photosensitive resin composition of this invention may contain the thermal radical polymerization initiator. As a thermal radical polymerization initiator, a well-known thermal radical polymerization initiator can be used.

A thermal radical polymerization initiator is a compound which generate | occur | produces a radical by the energy of heat, and starts or accelerates the polymerization reaction of a polymeric compound. By adding a thermal radical polymerization initiator, when advancing the cyclization reaction of a polyimide precursor, the polymerization reaction of a polymeric compound can be advanced. Moreover, when a polyimide precursor contains an ethylenically unsaturated bond, since the polymerization reaction of a polyimide precursor can be advanced with cyclization of a polyimide precursor, higher heat resistance can be achieved.

Examples of thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, and carbon halogens. The compound which has a bond, an azo compound, etc. are mentioned. Especially, a peroxide or azo compound is more preferable, and a peroxide is especially preferable.

It is preferable that 10-hour half life temperature is 90-130 degreeC, and, as for the thermal radical polymerization initiator used by this invention, it is more preferable that it is 100-120 degreeC.

Specifically, Paragraph No. 0074 of Unexamined-Japanese-Patent No. 2008-63554-the compound described in 0018 are mentioned.

In a commercial item, perbutyl Z and Percutyl D (made by Nichi Oil Co., Ltd.) can be used suitably.

When a negative photosensitive resin composition contains a thermal radical polymerization initiator, 0.1-50 mass% is preferable with respect to the total solid of a negative photosensitive resin composition, and, as for content of a thermal radical polymerization initiator, 0.1-30 mass% is more preferable. 0.1-20 mass% is especially preferable. Moreover, it is preferable to contain 0.1-50 mass parts of thermal radical polymerization initiators with respect to 100 mass parts of polymeric compounds, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, it is easy to form the cured film excellent in heat resistance.

1 type of thermal radical polymerization initiators may be sufficient, and 2 or more types may be sufficient as it. When there are two or more types of thermal radical polymerization initiators, it is preferable that the sum total is the said range.

Anticorrosive

It is preferable to add a corrosion inhibitor to the negative photosensitive resin composition of this invention. A corrosion inhibitor is added in order to prevent the outflow of the ion from a metal wiring, As a compound, For example, the antirust agent of Paragraph No. 0094 of Unexamined-Japanese-Patent No. 2013-15701, and Paragraph No. of Unexamined-Japanese-Patent No. 2009-283711 The compound of 0073-0076, the compound of Paragraph No. 0052 of Unexamined-Japanese-Patent No. 2011-59656, the compound of Paragraph No. 0114, 0116, 0118 of Unexamined-Japanese-Patent No. 2012-194520, etc. can be used. Especially, the compound which has a triazole ring or the compound which has a tetrazole ring can be used preferably, 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole , 1H-tetrazole and 5-methyl-1H-tetrazole are more preferred, and 1H-tetrazole is most preferred.

When adding a corrosion inhibitor, the compounding quantity of a corrosion inhibitor becomes like this. Preferably it is the range of 0.1-10 mass parts with respect to 100 mass parts of polyimide precursors, More preferably, it is the range of 0.2-5 mass parts.

1 type of corrosion inhibitors may be sufficient, and 2 or more types may be sufficient as it. When using 2 or more types, it is preferable that the sum total is the said range.

It is preferable that the negative photosensitive resin composition of this invention contains the metal adhesive improving agent for improving adhesiveness with the metal material used for an electrode, wiring, etc. As an example of a metal adhesive improving agent, Paragraph No. 0046-0049 of Unexamined-Japanese-Patent No. 2014-186186, and Paragraph No. 0032-0043 of Unexamined-Japanese-Patent No. 2013-072935 are mentioned. As a metal adhesive improving agent, the following compound is also illustrated further.

[Formula 39]

When using a metal adhesive improving agent, the compounding quantity of a metal adhesive improving agent becomes like this. Preferably it is the range of 0.1-30 mass parts with respect to 100 mass parts of polyimide precursors, More preferably, it is the range of 0.5-15 mass parts. By setting it as 0.1 mass part or more, the adhesiveness of the film | membrane after thermosetting and metal becomes favorable, and by setting it as 30 mass parts or less, the heat resistance of a film | membrane after hardening, and a mechanical characteristic will become favorable.

1 type of metal adhesive improving agents may be sufficient, and 2 or more types may be sufficient as it. When using 2 or more types, it is preferable that the sum is the said range.

It is preferable that the negative photosensitive resin composition of this invention contains the silane coupling agent from the point which improves adhesiveness with a board | substrate. As an example of a silane coupling agent, Paragraph No. 0062 of Unexamined-Japanese-Patent No. 2014-191002, the compound of 0073, Paragraph No. 0063 of 002011 / 080992A1, The compound of 0091, Paragraph No. 0060 of 0061-0061 The compound of description, Paragraph No. 0045 of Unexamined-Japanese-Patent No. 2014-41264-the compound of 0005, and the compound of Paragraph No. 0055 of WO2014 / 097594 are mentioned. Moreover, it is also preferable to use another 2 or more types of silane coupling agent as described in Paragraph No. 0050 of Unexamined-Japanese-Patent No. 2011-128358-0058.

When using a silane coupling agent, the compounding quantity of a silane coupling agent becomes like this. Preferably it is the range of 0.1-20 mass parts with respect to 100 mass parts of polyimide precursors, More preferably, it is the range of 1-10 mass parts. If it is 0.1 mass part or more, more sufficient adhesiveness with a board | substrate can be provided, and if it is 20 mass parts or less, problems, such as a viscosity increase at the time of room temperature storage, can be suppressed more.

1 type may be sufficient as a silane coupling agent, and 2 or more types may be sufficient as it. When using 2 or more types, it is preferable that the sum total is the said range.

The negative photosensitive resin composition of this invention may also contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation, and becomes an electron excited state. The sensitizing dye which has become an electron-excited state comes into contact with a heat base generator, a thermal radical polymerization initiator, an optical radical polymerization initiator, or the like to cause an action such as electron transfer, energy transfer, and heat generation. As a result, the thermal base generator, the thermal radical polymerization initiator, and the radical photopolymerization initiator undergo chemical changes to decompose to generate radicals, acids or bases.

Examples of preferred sensitizing dyes include those belonging to the following compounds and those having an absorption wavelength in the 300 nm to 450 nm region. For example, polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10- dialkoxy anthracene), xanthenes (e.g., fluorescein, eosin, erythrosine , Rhodamine B, rose bengal), thioxanthones (e.g., 2,4-diethyl thioxanthone), cyanines (e.g., thiacabocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin) , Acriflavin), anthraquinones (eg, anthraquinones), squaryliums (eg, squarylium), coumarins (eg, 7-diethylamino-4-methylcoumarin), Styryl benzene, distyryl benzene, carbazole, etc. are mentioned.

Among them, in the present invention, it is preferable to use polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene), thioxanthones, distyrylbenzenes, and styrylbenzenes. In view of the above, it is preferable to use a compound having an anthracene skeleton. As a particularly preferable specific compound, 9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, etc. are mentioned.

When a negative photosensitive resin composition contains a sensitizing dye, as for content of a sensitizing dye, 0.01-20 mass% is preferable with respect to the total solid of a negative photosensitive resin composition, 0.1-15 mass% is more preferable, 0.5 10 mass% is more preferable. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

The negative photosensitive resin composition of this invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in pages 683-684 of the Polymer Dictionary, 3rd edition (Polymer Society Society, 2005). As a chain transfer agent, the compound group which has SH, PH, SiH, GeH in a molecule | numerator is used, for example. These can generate a radical by hydrogen donating to a low activity radical species, generating | generating a radical, or oxidizing and deprotoning. In particular, a thiol compound (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazols) Etc.) can be preferably used.

When a negative photosensitive resin composition contains a chain transfer agent, content of a chain transfer agent becomes like this. Preferably it is 0.01-20 mass parts, More preferably, 1-10 mass with respect to 100 mass parts of total solids of a negative photosensitive resin composition. Part, More preferably, it is 1-5 mass parts.

1 type of chain transfer agents may be sufficient, and 2 or more types may be sufficient as it. When a chain transfer agent is 2 or more types, it is preferable that the sum total is the said range.

You may add various surfactant to the negative photosensitive resin composition of this invention from a viewpoint of further improving applicability | paintability. As surfactant, various surfactant, such as a fluorochemical surfactant, nonionic surfactant, cationic surfactant, anionic surfactant, silicone type surfactant, can be used.

In particular, by including a fluorine-based surfactant, the liquid characteristics (particularly fluidity) when prepared as a coating liquid are further improved, and thus the uniformity and coating liquidity of the coating thickness can be further improved.

In the case of forming a film using a coating liquid containing a fluorine-based surfactant, by reducing the interfacial tension between the surface to be coated and the coating liquid, the wettability on the surface to be coated is improved, and the coating property on the surface to be coated is improved. For this reason, even when a thin film of about several micrometers is formed with a small amount of liquid, it is effective at the point which can form the film of uniform thickness with a small thickness variation more suitably.

3-40 mass% is suitable for the fluorine-containing rate of a fluorine-type surfactant, More preferably, it is 5-30 mass%, Especially preferably, it is 7-25 mass%. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and the liquid solution property, and the solubility is also good.

As a fluorine type surfactant, Megapak F171, copper F172, copper F173, copper F176, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437, copper F475, copper F479, copper F482 , Copper F554, copper F780, copper F781 (above, made by DIC Corporation), fluoride FC430, copper FC431, copper FC171 (or more, manufactured by Sumitomo 3M, Inc.), surflon S-382, copper SC-101, East SC-103, East SC-104, East SC-105, East SC1068, East SC-381, East SC-383, East S393, East KH-40 (above, made by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA), etc. are mentioned.

A block polymer can also be used as a fluorine-type surfactant, As a specific example, the compound of Unexamined-Japanese-Patent No. 2011-89090 is mentioned, for example.

Moreover, the following compound is also illustrated as a fluorine-type surfactant used by this invention.

[Formula 40]

The weight average molecular weight of said compound is 14,000, for example.

Specific examples of the nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate, etc.) and polyoxy. Ethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 made from BASF Corporation), Solsper 20000 (Nihon Lu Brisol Co., Ltd.) etc. are mentioned. Moreover, Pionein D-6112-W by Takeshi Yushi Co., Ltd., NCW-101, NCW-1001, NCW-1002 by Wako Junyaku Kogyo Co., Ltd. can also be used.

Specifically as a cationic surfactant, a phthalocyanine derivative (brand name: EFKA-745, the Morishita Sangyo Co., Ltd. product), organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), (meth) Acrylic acid (co) polymer polyflo no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Corporation), and the like.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Corporation).

As a silicone type surfactant, Toray Dow Corning Co., Ltd. "Toray Silicon DC3PA", "Toray Silicon SH7PA", "Toray Silicon DC11PA", "Toray Silicon SH28PA", "Toray Silicon SH28PA", "Toray Silicon SH29PA" "," Toray Silicon SH30PA "," Toray Silicon SH8400 "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4460 "," TSF-4452 "made by Momentive Performance Materials "KP341", "KF6001", "KF6002", "BYK307", "BYK323", "BYK330" by the company made from Shin-Etsu Silicone Co., Ltd., etc. are mentioned.

When a negative photosensitive resin composition contains surfactant, 0.001 to 2.0 mass% is preferable with respect to the total solid of a negative photosensitive resin composition, More preferably, it is 0.005 to 1.0 mass%.

1 type of surfactant may be sufficient and 2 or more types may be sufficient as it. When containing 2 or more types of surfactant, it is preferable that the sum total is the said range.

In order to prevent the polymerization inhibition by oxygen, a higher fatty acid derivative, such as behenic acid and behenic acid amide, is added to the negative photosensitive resin composition of the present invention, and to the surface of the negative photosensitive resin composition in the drying process after coating. You may make it ubiquitous.

When a negative photosensitive resin composition contains higher fatty acid derivatives, 0.1-10 mass% of content of higher fatty acid derivatives etc. is preferable with respect to the total solid of a negative photosensitive resin composition.

The higher fatty acid derivative may be one kind or two or more kinds. When containing 2 or more types of higher fatty acid derivatives, it is preferable that the sum total is the said range.

When making the negative photosensitive resin composition of this invention into layer shape by application | coating, it is preferable to mix | blend a solvent. As long as a solvent can form a negative photosensitive resin composition in layer shape, a well-known thing can be used without a restriction | limiting.

As a solvent used for the negative photosensitive resin composition of this invention, as ester, For example, ethyl acetate, acetic acid-n-butyl, isobutyl acetate, formic acid amyl, isoamyl acetate, butyl propionate, isopropyl butyrate, beauty Ethyl oleate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetic acid (e.g., methyl oxyacetic acid, ethyl oxyacetic acid, butyl oxyacetate ( For example, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate butyl, methyl ethoxy acetate, ethyl ethoxy acetate, etc.), 3-oxypropionic acid alkyl esters (for example, methyl 3-oxypropionate, Ethyl 3-oxypropionate and the like (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion) 2-oxypropionate alkyl esters (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionic acid, etc.) (for example, methyl 2-methoxypropionate, 2-meth) Ethyl oxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (e.g. , 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, methyl 2-oxobutanoate, and As ethyl ether, such as 2-oxobutanoic acid etc., For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methylcello Solve Acetate, Ethyl Cellosolve Acetate Tate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone And N-methyl-2-pyrrolidone and the like, and aromatic hydrocarbons include, for example, toluene, xylene, anisole, and limonene, and dimethyl sulfoxide as sulfoxides.

The form which mixes 2 or more types is also preferable from a viewpoint of improvement of a coating surface shape, etc. of a solvent. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate and 2-heptanone Selected from cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate The mixed solution which consists of 2 or more types is preferable. Particularly preferred is a combination of dimethyl sulfoxide and γ-butyrolactone.

When a negative photosensitive resin composition contains a solvent, it is preferable to make content of a solvent into the quantity which becomes 5-80 mass% of total solid content concentration of a negative photosensitive resin composition from a coatability viewpoint, and is 5-70 mass % Is more preferable, and 10-60 mass% is more preferable.

1 type of solvents may be sufficient, and 2 or more types may be sufficient as it. When containing 2 or more types of solvents, it is preferable that the sum total is the said range.

In addition, the contents of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide are negative from the viewpoint of film strength. Less than 5 mass% is preferable with respect to the total mass of a type photosensitive resin composition, Less than 1 mass% is more preferable, Less than 0.5 mass% is more preferable, Less than 0.1 mass% is especially preferable.

The negative photosensitive resin composition of this invention is various additives, for example, an inorganic particle, a hardening | curing agent, a hardening catalyst, a filler, antioxidant, a ultraviolet absorber, an aggregation inhibitor, etc. as needed, in the range which does not impair the effect of this invention. Can be blended. When mix | blending these additives, it is preferable to make the total compounding quantity into 3 mass% or less of solid content of a negative photosensitive resin composition.

From the viewpoint of application surface shape, the water content of the negative photosensitive resin composition of the present invention is preferably less than 5 mass%, more preferably less than 1 mass%, particularly preferably less than 0.6 mass%.

From the viewpoint of insulation, the metal content of the negative photosensitive resin composition of the present invention is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, particularly preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium and nickel. In the case of containing a plurality of metals, it is preferable that the sum of these metals is in the above range.

Moreover, as a method of reducing the metal impurity unintentionally contained in a negative photosensitive resin composition, as a raw material which comprises a negative photosensitive resin composition, the raw material with few metal content is selected, or the raw material which comprises a negative photosensitive resin composition is used. And filter distillation, or distillation under conditions in which the interior is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

In the negative photosensitive resin composition of the present invention, the halogen atom content is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Especially, less than 5 mass ppm is preferable, as for what exists in a halogen ion state, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is especially preferable. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the sum total of a chlorine atom and a bromine atom, or a chloride ion and a bromide ion are the said ranges, respectively.

The negative photosensitive resin composition of this invention can mix and prepare said each component. The mixing method is not particularly limited and can be performed by a conventionally known method.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances, such as dust and microparticles | fine-particles in a negative photosensitive resin composition. As a pore diameter of a filter, 1 micrometer or less is preferable, 0.5 micrometer or less is more preferable, and 0.1 micrometer or less is more preferable. As a material of a filter, the filter made from polytetrafluoroethylene, polyethylene, and nylon is preferable. You may use the filter wash | cleaned previously with the organic solvent. In the filter filtration process, you may connect and use multiple types of filter in series or in parallel. When using multiple types of filters, you may use combining the filter from which a hole diameter and / or material differs. Moreover, you may filter various materials multiple times, and a circulating filtration process may be sufficient as the process of filtering multiple times. Moreover, you may heat and perform filtration, and the pressure to pressurize is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, an adsorbent may be used to remove impurities. In addition, the removal of impurities may combine filter filtration and an adsorbent. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.

The negative photosensitive resin composition of this invention can be used as a cured film by hardening. Since the cured film excellent in heat resistance and insulation can be formed, the negative photosensitive resin composition of this invention can be used suitably for the insulating film of a semiconductor device, the interlayer insulation film for redistribution layers, etc. In particular, it can use suitably for the interlayer insulation film for redistribution layers in a three-dimensional mounting device.

It can also be used for photoresists for electronics (galvanic resist, etching resist, solder top resist) and the like.

It can also be used for the production of plate surfaces such as offset plate surfaces or screen plate surfaces, etching of molded parts, production of protective lacquers and dielectric layers in electronics, particularly microelectronics.

Next, the manufacturing method of the cured film of this invention is demonstrated. The manufacturing method of a cured film is not specifically determined as long as it is formed using the negative photosensitive resin composition of this invention. It is preferable that the manufacturing method of the cured film of this invention has the process of applying the negative photosensitive resin composition of this invention to a board | substrate, and the process of hardening the negative photosensitive resin composition applied to the board | substrate.

<< process >> which applies negative photosensitive resin composition to board | substrate >>

Examples of the application method of the negative photosensitive resin composition to the substrate include spinning, dipping, doctor blade coating, suspended casting, coating, spraying, electrostatic spraying, reverse roll coating, and the like. Roll application is preferred for the reason that it can be applied uniformly on the substrate.

As a board | substrate, an inorganic board | substrate, resin, resin composite material, etc. are mentioned.

As an inorganic substrate, the composite substrate which deposited molybdenum, titanium, aluminum, copper, etc. on the glass substrate, a quartz substrate, a silicon substrate, a silicon nitride substrate, and those substrates is mentioned, for example.

As the resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyldiglycol carbonate, polyamide , Fluorine resins such as polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, The board | substrate which consists of synthetic resins, such as a silicone resin, an ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic ether, maleimide olefin, a cellulose, an episulfide compound, is mentioned. These board | substrates are rarely used as said form, and usually, the multilayer laminated structure like a thin film transistor (TFT) element is formed according to the form of a final product.

The amount of application of the negative photosensitive resin composition (layer thickness) and the type of substrate (carrier of the layer) depend on the field of the desired use. It is particularly advantageous to be able to use the photosensitive resin composition in a widely varying layer thickness. As for the range of layer thickness, 0.5-100 micrometers is preferable, and when it is set as 3-30 micrometers, and also 5-30 micrometers in the method of this invention, it is more effective.

After applying a negative photosensitive resin composition to a board | substrate, it is preferable to dry. It is preferable to perform drying for 10 second-2 minutes, for example at 60-150 degreeC.

<< heating process >>

By heating the negative photosensitive resin composition applied to the board | substrate, the cyclization reaction of a polyimide precursor advances and the cured film excellent in heat resistance can be formed.

50-300 degreeC is preferable and 100-250 degreeC of heating temperature is more preferable.

According to this invention, since it contains many isomers with a faster cyclization rate, the cyclization reaction of a polyimide precursor can also be performed at low temperature.

It is preferable to adjust at least 1 sort (s) chosen from a heating rate, a heat time, and a cooling rate from a viewpoint of the internal stress reduction of a cured film, or curvature suppression.

As a heating rate, it is preferable that it is 3-5 degree-C / min using 20-150 degreeC as heating start temperature.

When heating temperature is 200-240 degreeC, 180 minutes or more of heating time are preferable. As for an upper limit, 240 minutes or less are preferable, for example. When heating temperature is 240-300 degreeC, 90 minutes or more of heating time are preferable. As for an upper limit, 180 minutes or less are preferable, for example. When heating temperature is 300-380 degreeC, 60 minutes or more of heating time are preferable. As for an upper limit, 120 minutes or less are preferable, for example.

It is preferable that a cooling rate is 1-5 degree-C / min.

The heating may be performed step by step. For example, the process of heating up at 5 degree-C / min from 20 degreeC to 150 degreeC, leaving it at 150 degreeC for 30 minutes, heating up at 150 degreeC to 230 degreeC at 5 degree-C / min, and leaving it at 230 degreeC for 180 minutes are mentioned. .

The heating step is preferably performed in a low oxygen concentration atmosphere by flowing an inert gas such as nitrogen, helium, argon, etc., in terms of preventing decomposition of polyimide precursors such as polyimide. 50 volume ppm or less is preferable, and, as for oxygen concentration, 20 volume ppm or less is more preferable.

In this invention, you may perform a pattern formation process between the process of applying the said negative photosensitive resin composition to a board | substrate, and the said process to heat. A pattern formation process can be performed by the photolithographic method, for example. For example, the method of performing through the process of exposing and the process of image development is mentioned.

It is preferable to perform pattern formation in the photolithographic method using the photosensitive resin composition containing a polyimide precursor and a radical polymerization initiator.

Hereinafter, the case where a pattern is formed by the photolithography method is demonstrated.

<< process to expose >>

In the process of exposing, actinic light or a radiation of a predetermined pattern is irradiated to the negative photosensitive resin composition applied to the board | substrate.

Although the wavelength of actinic light or a radiation varies with the composition of a negative photosensitive resin composition, 200-600 nm is preferable and 300-450 nm is more preferable.

As a light source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used, and 300 nm or more and 450 nm, such as i line | wire (365 nm), h line | wire (405 nm), and g line (436 nm), etc. Active rays having the following wavelengths can be preferably used. Moreover, irradiation light can also be adjusted through spectroscopic filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. Exposure dose is preferably 1 to 1000mJ / cm ^2, and more preferably, 200 ~ 800mJ / cm ^2. In this wide range, the value of this invention is high in that it can develop with high developability.

As exposure apparatus, the exposure machine of various systems, such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a micro lens array, a lens scanner, and laser exposure, can be used.

In addition, when (meth) acrylates and similar olefin unsaturated compounds are used, their photopolymerization is prevented by oxygen in the air, as is well known, especially in thin layers. This effect can be alleviated by well-known conventional methods, such as temporary film layer introduction of polyvinyl alcohol, preexposure, or preconditioning in an inert gas, for example.

<< process which performs development >>

In the process of developing, the unexposed part of a negative photosensitive resin composition is developed using a developing solution. As a developing solution, an aqueous alkaline developing solution, an organic solvent, etc. can be used.

As an alkali compound used for aqueous alkaline developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia or amine Etc. can be mentioned. As the amine, for example, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium Hydroxide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide and the like. Especially, the alkali compound which does not contain a metal is preferable. Suitable aqueous alkaline developing solutions are generally up to 0.5 definitions with respect to alkali, but may be appropriately diluted before use. For example, an aqueous alkaline developer of about 0.15 to 0.4, preferably 0.20 to 0.35, is also suitable. 1 type of alkali compounds may be sufficient and 2 or more types may be sufficient as it. When using 2 or more types of alkali compounds, it is preferable that the sum total is the said range.

As an organic solvent, the thing similar to the solvent which can be used for the negative photosensitive resin composition mentioned above can be used. For example, acetic acid-n-butyl, (gamma) -butyrolactone, cyclopentanone, and these mixed things are mentioned suitably.

Moreover, it is also preferable to include the process of heating the developed negative photosensitive resin composition to the temperature of 50-500 degreeC after the process of image development processing. By going through such a process, there is a merit that heat resistance and adhesiveness with a board | substrate improve.

As a field to which the manufacturing method of the cured film of this invention is applicable, it can use suitably for the insulating film of a semiconductor device, the interlayer insulation film for redistribution layers, etc. In particular, since resolution is favorable, it can use suitably for the interlayer insulation film for redistribution layers in a three-dimensional mounting device.

Next, one Embodiment of the semiconductor device which used the negative photosensitive resin composition for the interlayer insulation film for redistribution layers is demonstrated.

The semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a laminate 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are stacked is disposed on the wiring board 120. .

In addition, in this embodiment, the case where the number of lamination | stacking of semiconductor elements (semiconductor chip) is four layers is demonstrated mainly, The number of lamination | stacking of semiconductor elements (semiconductor chip) is not specifically limited, For example, two layers, eight layers, 16 layers, 32 layers, etc. may be sufficient. Moreover, one layer may be sufficient.

The plurality of semiconductor elements 101a to 101d are all made of a semiconductor wafer such as a silicon substrate.

The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.

The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.

The laminated body 101 has the structure which flip-chip-connected the semiconductor element 101a which does not have a through electrode, and the semiconductor element 101b-101d which has the through electrode 102b-102d.

That is, the electrode pad of the semiconductor element 101a which does not have a penetrating electrode, and the connection pad of the semiconductor element 101a side of the semiconductor element 101b which has the penetrating electrode 102b adjacent to it are metals, such as a solder bump, and the like. The connection pad on the other side of the semiconductor element 101b having the through electrode 102b connected to the bump 103a and having the through electrode 102c adjacent thereto has the semiconductor element 101b side of the semiconductor element 101c. Connection pads and metal bumps 103b such as solder bumps. Similarly, the connection pads on the other side of the semiconductor element 101c having the through electrodes 102c are connected to the connection pads and the solder bumps on the semiconductor element 101c side of the semiconductor element 101d having the through electrodes 102d adjacent thereto. It is connected by metal bump 103c, such as these.

The underfill layer 110 is formed in the space | interval of each semiconductor element 101a-101d, and each semiconductor element 101a-101d is laminated | stacked through the underfill layer 110. As shown in FIG.

The laminate 101 is laminated on the wiring board 120.

As the wiring board 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, a glass substrate, or the like is used. As a wiring board 120 to which the resin substrate was applied, a multilayer copper clad laminated board (multilayer printed wiring board) etc. are mentioned.

The surface electrode 120a is provided in one surface of the wiring board 120.

The insulating layer 115 in which the redistribution layer 105 was formed is arrange | positioned between the wiring board 120 and the laminated body 101, The wiring board 120 and the laminated body 101 are the redistribution layer 105. FIG. It is electrically connected through. The insulating layer 115 is formed by using the negative photosensitive resin composition of this invention.

That is, one end of the redistribution layer 105 is connected to an electrode pad formed on the surface of the redistribution layer 105 side of the semiconductor element 101d via a metal bump 103d such as a solder bump. The other end of the redistribution layer 105 is connected to the surface electrode 120a of the wiring board via metal bumps 103e such as solder bumps.

The underfill layer 110a is formed between the insulating layer 115 and the laminate 101. In addition, an underfill layer 110b is formed between the insulating layer 115 and the wiring board 120.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, "%" and "part" are mass references | standards unless there is particular notice. NMR is an abbreviation for nuclear magnetic resonance.

Synthesis Example 1

[Synthesis of polyimide precursor (A-1: polyimide precursor without radical polymerizable group) from pyromellitic dianhydride, 4,4′-oxydianiline and benzyl alcohol]

14.06 g (64.5 mmol) pyromellitic dianhydride (dried 12 hours at 140 ° C.) and 14.22 g (131.58 mmol) benzyl alcohol are suspended in 50 ml of N-methylpyrrolidone to provide molecular Dried over. The suspension was heated at 100 ° C. for 3 hours. A few minutes after the start of heating, a clear solution was obtained. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 ml N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl ₂ were added for 10 minutes while maintaining the temperature at −10 ± 4 ° C. While adding SOCl ₂ , the viscosity increased. After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Subsequently, a solution in which 11.08 g (58.7 mmol) of 4,4'-oxydianiline was dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23 ° C. for 20 minutes. The reaction mixture was then stirred overnight at room temperature. Subsequently, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was collected by filtration, poured into 4 liters of water again, and further stirred for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 degreeC for 3 days under reduced pressure, and the polyimide precursor (A-1) containing the structure shown by a following formula was obtained.

[Formula 41]

Synthesis Example 2

[Synthesis of polyimide precursor (A-2: polyimide precursor having a radical polymerizable group) from pyromellitic dianhydride, 4,4′-oxydianiline and 2-hydroxyethyl methacrylate]

14.06 g (64.5 mmol) pyromellitic dianhydride (dried 12 hours at 140 ° C.), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 10.7 g Pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to give a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Manufactured. Subsequently, after the obtained diester is chlorinated by SOCl ₂ , it is converted into a polyimide precursor by 4,4′-oxydianiline in the same manner as in Synthesis Example 1, and is represented by the following formula in the same manner as in Synthesis Example 1 The polyimide precursor (A-2) containing a structure was obtained.

[Formula 42]

Synthesis Example 3

[Synthesis of polyimide precursor (A-3: polyimide precursor having a radical polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried 12 hours at 140 ° C.), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone , 10.7 g of pyridine and 140 g of diglim were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Subsequently, after the obtained diester is chlorinated by SOCl ₂ , it is converted into a polyimide precursor by 4,4′-oxydianiline in the same manner as in Synthesis Example 1, and is represented by the following formula in the same manner as in Synthesis Example 1 The polyimide precursor (A-3) containing a structure was obtained.

[Formula 43]

Synthesis Example 4

[Synthesis of 4,4'-oxydiphthalic anhydride and polyimide precursor (A-4: polyimide precursor having a carboxyl group) from 4,4'-oxydianiline]

20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried 12 hours at 140 ° C.) was dissolved in 180 ml of NMP (N-methyl-2-pyrrolidone) and further 21.43 g (270.9) 1 mole of pyridine was added to dissolve 11.08 g (58.7 mmol) of 4,4'-oxydianiline in 100 ml of NMP while cooling the reaction solution to -10 ° C and maintaining the temperature at -10 ± 4 ° C. The solution was added dropwise for 30 minutes, and then the reaction mixture was stirred overnight at room temperature. Subsequently, it poured into 5 liters of water, precipitated the polyimide precursor, and stirred the water-polyimide precursor mixture for 15 minutes at the speed of 5000 rpm. The polyimide precursor was collected by filtration, poured into 4 liters of water again, stirred for 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried at 45 degreeC under reduced pressure for 3 days, and the polyimide precursor (A-4) containing the structure shown by a following formula was obtained.

[Formula 44]

Synthesis Example 5

[Synthesis of Comparative Example Polymer (RA-1)]

27.0 g (153.2 mmol) benzyl methacrylate, 20 g (157.3 mmol) N-isopropylmethacrylamide, 39 g (309.2 mmol) allyl methacrylate, 13 g (151.0 mmol) methacrylic acid, polymerization initiator ( 3.55 g (15.4 mmol) of V-601, Wako Junyaku Kogyo Co., Ltd., and 300 g of 3-methoxy-2-propanol were mixed. The liquid mixture was dripped in 300 g of 3-methoxy- 2-propanol heated at 75 degreeC under nitrogen atmosphere for 2 hours. After completion of the dropwise addition, the mixture was further stirred at 75 ° C under nitrogen atmosphere for 2 hours. After completion | finish of reaction, it poured into 5 liters of water, precipitated a polymer, and stirred for 15 minutes at the speed of 5000 rpm. The acrylic resin was collected by filtration, poured into 4 liters of water again, stirred for 30 minutes, and filtered again. Next, the obtained acrylic resin was dried for 3 days at 45 degreeC under reduced pressure, and the comparative polymer (RA-1) represented by a following formula was obtained.

[Formula 45]

The component of the following base material was mixed, and it was set as the uniform solution, and the coating liquid of the photosensitive resin composition was prepared.

<< composition >> of photosensitive resin composition

Polyimide precursor: parts by mass as listed in Table 6

Radical polymerization initiator: the mass part of Table 6

1st polymerization inhibitor: the mass part of Table 6

2nd polymerization inhibitor: the mass part of Table 6

Radical polymerizable compound: Mass part shown in Table 6

Heat base generator: parts by mass of Table 6

(Other ingredients)

γ-butyrolactone: 60.00 parts by mass

TABLE 6

Abbreviated-name of Table 6 is as follows.

(A) polyimide precursor or comparative resin

A-1 to A-4 and RA-1: Resin synthesized in Synthesis Examples 1 to 5

(B) radical photopolymerization initiator

B-1: Irgacure OXE-01 (manufactured by BASF Corporation)

B-2: Irgacure 369 (made by BASF)

B-3: Irgacure 784 (made by BASF)

(C) the first polymerization inhibitor

C-1: 4-methoxy phenol (Tokyo Kasei Kogyo Co., Ltd.)

C-2: 2,6-di-tert-butyl-4-methylphenol (Tokyo Kasei Kogyo Co., Ltd.)

C-3: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (made by BASF, Irganox 1010)

C-4: thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (made by BASF, Irganox 1035)

C-5: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF, Irganox 1076)

C-6: N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (made by BASF, Irganox 1098)

C-7: 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p Cresol (manufactured by BASF, Irganox 1330)

C-8: ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (made by BASF, Irganox 245)

C-9: hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (made by BASF, Irganox 259)

C-10: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) Trion (made by BASF, Irganox 3114)

C-11: Catechol (Tokyo Kasei High School)

C-12: tert-butyl-catechol (Tokyo Kasei High School)

(D) second polymerization inhibitor

D-1: 2,4,6-Tris-t-butyl-nitrosobenzene (Tokyo Kasei Kogyo Co., Ltd.)

D-2: phenyl-t-butyl nitrone (Tokyo Kasei Kogyo Co., Ltd.)

D-3: 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (Tokyo Kasei Kogyo Co., Ltd.)

D-4: p-benzoquinone (Tokyo Kasei Kogyo Co., Ltd.)

D-5: p-toluquinone (Tokyo Kasei High School)

D-6: 2-tert-butyl-p-benzoquinone (Tokyo Kasei Kogyo Co., Ltd.)

D-7: 2,2,6,6-tetramethylpiperidine 1-oxyl (Tokyo Kasei Kogyo Co., Ltd.)

D-8: 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tokyo Kasei Kogyo Co., Ltd.)

D-9: 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tokyo Kasei Kogyo Co., Ltd.)

D-10: N-nitrosodiphenylamine (Tokyo Kasei Kogyo Co., Ltd.)

D-11: Phenosaigin (Tokyo Kasei High School)

(E) radically polymerizable compound

E-1: NK ester M-40G (monofunctional methacrylate structure made by Shin-Nakamura Kagaku Kogyo Co., Ltd.)

[Formula 46]

E-2: NK ester 4G (Shin Nakamura Kagaku Kogyo Co., Ltd. second functional methacrylate following structure)

[Formula 47]

E-3: NK ester A-9300 (Shin Nakamura Kagaku Kogyo Co., Ltd. third functional acrylate structure below)

[Formula 48]

[Formula 49]

Comparative Example Polymer (RA-2): Polymethyl methacrylate (Mw: 15,000, manufactured by Aldrich)

Each negative photosensitive resin composition was filtered through a filter having a micropore width of 0.8 µm, and then filtered and applied onto a silicon wafer. The silicon wafer to which the negative photosensitive resin composition was applied was dried for 5 minutes at 100 degreeC on the hotplate, and the uniform polymer layer of the thickness of Table 6 was formed on the silicon wafer.

Exposure Latitude

The photosensitive resin composition layer on the silicon wafer was exposed using the stepper (Nikon NSR2005 i9C). The exposure is performed by i-line, and at a wavelength of 365 nm, each of the exposure energies of 200, 300, 400, 500, 600, 700, and 800 mJ / cm ² , using a photomask with a line and space of 1 μm intervals from 5 μm to 25 μm And exposure were performed.

The exposed photosensitive resin composition layer was developed for 60 seconds with cyclopentanone. The line width which could have the sharpness of the favorable edge was evaluated based on the following references | standards. The smaller the line width of the photosensitive resin composition layer shows that the difference in solubility in the developing solution of the light irradiating portion and the light non-irradiating portion is increased, resulting in a preferable result. Moreover, with respect to the change in exposure energy, when the change in line width is small, it shows that the exposure latitude is large, and a favorable result is obtained. The measurement limit is 5 μm. The results are shown in Table 7.

A: 5 μm or more and 8 μm or less

B: 8 μm or more and 10 μm or less

C: 10 μm or more and 15 μm or less

D: more than 15 μm and 20 μm or less

E: greater than 20 μm

[Heat resistance]

After heating the exposed photosensitive resin composition layer at 300 degreeC in nitrogen atmosphere for 3 hours, the exposed photosensitive resin composition layer is scraped, and thermal mass spectrometry measurement is performed on condition of the temperature increase rate of 10 degree-C / min in nitrogen, The pyrolysis temperature was measured and evaluated based on the following criteria. The results are shown in Table 7.

A: 5% mass reduction temperature is 300 ° C. or more

B: 5% mass reduction temperature is less than 300 ° C

TABLE 7

In Table 7, the numerical value of the exposure latitude represents the exposure energy (unit: mJ / cm ² ).

In Comparative Example 4, all components were dissolved in the developing treatment with cyclopentanone, and thus, it was impossible to measure.

After negative filtration of the negative photosensitive resin composition of Example 1 through the filter whose width | variety of a micropore is 0.8 micrometer, it spins (3500 rpm, 30 second) and applied to the resin substrate in which the copper foil layer was formed. The negative photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 5 minutes, and then exposed using an aligner (Karl-Suss MA150). Exposure was performed with the high pressure mercury lamp, and the exposure energy in wavelength 365nm was measured. After exposure, the image was developed for 75 seconds with cyclopentanone.

Then, it heated at 180 degreeC for 20 minutes. Thus, the interlayer insulation film for redistribution layers was formed.

This interlayer insulation film for redistribution layers was excellent in insulation.

Moreover, when the semiconductor device was manufactured using this interlayer insulation film for redistribution layers, it confirmed that it operated without a problem.

100: semiconductor device
101a to 101d: semiconductor device
101: laminate
102b to 102d: through electrode
103a-103e: metal bump
105: redistribution layer
110, 110a, 110b: underfill layer
115: insulation layer
120: wiring board
120a: surface electrode

Claims

At least 1 sort (s) selected from a polyimide precursor, a radical polymerization initiator, and the compound which has an aromatic hydroxyl group, and at least 1 sort (s) chosen from an N-oxide compound, a quinone compound, and an N-oxyl compound. The negative photosensitive resin composition containing a 2nd polymerization inhibitor.

The method according to claim 1,
The negative photosensitive resin composition in which the said polyimide precursor contains the repeating unit represented by following General formula (1);
General formula (1)
[Formula 1]

The method according to claim 2,
In said general formula (1), the negative photosensitive resin composition in which at least one of R <^13> and R <^14> contains a radically polymerizable group.

The method according to any one of claims 1 to 3,
The negative photosensitive resin composition which further contains a radically polymerizable compound.

The method according to claim 4,
The negative photosensitive resin composition in which the said radically polymerizable compound has two or more radically polymerizable groups.

The method according to any one of claims 1 to 3,
The negative photosensitive resin composition wherein the second polymerization inhibitor is selected from a quinone compound and an N-oxyl compound.

The method according to any one of claims 1 to 3,
The negative photosensitive resin composition whose mass ratio of a said 1st polymerization inhibitor and a 2nd polymerization inhibitor is 10: 90-90: 10.

The method according to any one of claims 1 to 3,
The negative photosensitive resin composition whose mass ratio of a said 1st polymerization inhibitor and a radical polymerization initiator is 1: 99-10: 90.

The method according to claim 2 or 3,
In said general formula (1), N12 is a negative photosensitive resin composition in which R <^12> is a tetravalent group containing an aromatic ring.

The method according to any one of claims 1 to 3,
The negative photosensitive resin composition which further contains a heat base generator.

The method according to claim 10,
A negative photosensitive resin composition in which the heat base generator has an ammonium cation represented by the following General Formula (Y);
[Formula 2]

The method according to any one of claims 1 to 3,
The negative photosensitive resin composition which is for interlayer insulation films for redistribution layers.

The cured film formed by hardening | curing the negative photosensitive resin composition of any one of Claims 1-3.

The method according to claim 13,
Cured film which is an interlayer insulation film for redistribution layers.

The manufacturing method of the cured film containing using the negative photosensitive resin composition of any one of Claims 1-3.

The method according to claim 15,
Applying the negative photosensitive resin composition to a substrate;
Irradiating actinic radiation or radiation to the negative photosensitive resin composition applied to the substrate;
The manufacturing method of the cured film which has a process of image-processing about the exposed negative photosensitive resin composition.

The method according to claim 16,
The manufacturing method of the cured film containing the process of heating the developed negative photosensitive resin composition to the temperature of 50-500 degreeC after the process of performing the said image development process.

The method according to claim 15,
The film thickness of the said cured film is a manufacturing method of the cured film whose 3-30 micrometers.

The semiconductor device which has a cured film of Claim 13.