JP6837063B2 - Negative photosensitive resin composition, cured film, method for producing cured film, semiconductor device, method for manufacturing laminate, method for manufacturing semiconductor device and polyimide precursor - Google Patents

Description

The present invention relates to a negative photosensitive resin composition, a cured film, a method for producing a cured film, a semiconductor device, a method for producing a laminate, a method for producing a semiconductor device, and a polyimide precursor.

Thermosetting resins that are cyclized and cured, such as polyimide resins, are used as insulating layers of semiconductor devices because they have excellent heat resistance and insulating properties. In addition, since the polyimide resin has low solubility in a solvent, it is used in the state of a precursor (polyimide precursor) before the cyclization reaction, applied to a substrate or the like, and then heated to cyclize the polyimide precursor. A cured film is also formed.

For example, Patent Document 1 describes a substituent having a repeating unit represented by the general formula (1) in the main chain (A) and having a photopolymerizable carbon-carbon double bond at both ends of the molecule. A polyimide precursor having a chemical linear functional group having a structure terminal-modified with an aminobenzene or a trimellitic acid derivative, (B) a photosensitizer having a photopolymerizable functional group, and (C) N-aryl. A resin composition containing a photopolymerization initiator containing −α-amino acids and thioxanthones, wherein the content of the photopolymerization initiator is 7 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor. The photosensitive resin composition which is a part is described.
In the formula, R ¹ is a tetravalent organic group and R ² is a divalent organic group.

Japanese Unexamined Patent Publication No. 2013-76845

Since Patent Document 1 has a polyamic acid structure, it is easily hydrolyzed by water. Therefore, the stability over time is low, and the synthesized resin cannot be purified in an aqueous system, so that it is difficult to apply to semiconductor applications that require high quality.

Therefore, an object of the present invention is to provide a negative photosensitive resin composition having excellent resolution. Another object of the present invention is to provide a cured film, a method for producing a cured film, a semiconductor device, a method for producing a laminate, a method for producing a semiconductor device, and a polyimide precursor using the above-mentioned negative photosensitive resin composition.

As a result of diligent studies, the present inventors can improve the resolution by providing a polymerizable group at the end of the polyimide precursor and setting the weight average molecular weight of the polyimide precursor to 50,000 or less. This has led to the completion of the present invention. Therefore, the present invention provides the following.
<1> Containing a polyimide precursor, a photopolymerization initiator, and a solvent,
The polyimide precursor has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at at least one end, and has a weight average molecular weight of 50,000 or less. Resin composition;
In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and R ¹ and R ² are independently non-polymerizable organic groups;
(A) _l- L ^1- * (2)
In formula (2), A represents a polymerizable group, L ¹ represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a binding site with another site.
<2> The negative photosensitive resin composition according to <1>, wherein l in the formula (2) is an integer of 2 to 5.
<3> The negative photosensitive resin composition according to <1> or <2>, wherein ^{R 1} and R ^{2 are independently non-polymerizable organic groups having 1 to 4 carbon atoms.}
<4> The negative photosensitive resin composition according to any one of <1> to <3>, wherein A in the formula (2) is a group containing a carbon-carbon unsaturated double bond.
<5> The negative photosensitive resin according to any one of <1> to <4>, wherein the structure represented by the formula (2) is a structure represented by the formula (3) or the formula (4). Composition;
In formula (3), R ³ represents a hydrogen atom or a methyl group, Z represents an oxygen atom or NH, L ² represents a single bond or an m + 1 valent organic group, and m represents an integer of 1-10. , * Indicates the site of connection with other sites;
In formula (4), L ³ represents a single bond or an n + 1 valent organic group, n represents an integer of 1 to 10, and * represents a binding site with another site.
<6> The negative photosensitive resin composition according to any one of <1> to <5>, wherein the polyimide precursor has a weight average molecular weight of 5000 or more.
<7> The negative photosensitive resin composition according to any one of <1> to <6>, which further contains a polyfunctional radically polymerizable monomer.
<8> The negative photosensitive resin composition according to any one of <1> to <7>, further comprising a thermal base generator.
<9> The negative photosensitive resin composition according to any one of <1> to <8>, wherein the photopolymerization initiator is at least one selected from an oxime compound and a metallocene compound.
<10> The negative photosensitive resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a rewiring layer.
<11> A cured film obtained by curing the negative photosensitive resin composition according to any one of <1> to <10>.
<12> The cured film according to <11>, which has a film thickness of 1 to 30 μm.
<13> A photosensitive resin composition layer forming step of applying the negative photosensitive resin composition according to any one of <1> to <10> to a substrate to form a layer.
An exposure process that exposes the negative photosensitive resin composition layer,
A developing process that performs a developing process on the exposed photosensitive resin composition layer,
A method for producing a cured film having.
<14> The method for producing a cured film according to <13>, which comprises a heating step of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500 ° C. after the development treatment step.
<15> A semiconductor device having the cured film according to <11> or <12>.
<16> A method for producing a laminate, which comprises the method for producing a cured film according to <13> or <14>.
<17> A method for manufacturing a semiconductor device, which comprises the method for manufacturing a cured film according to <13> or <14>.
<18> A polyimide precursor having a repeating unit represented by the formula (1), having a structure represented by the formula (2) at at least one end, and having a weight average molecular weight of 50,000 or less;
In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and R ¹ and R ² are independently non-polymerizable organic groups;
(A) _l- L ^1- * (2)
In formula (2), A represents a polymerizable group, L ¹ represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a binding site with another site.
<19> ^{The polyimide precursor according to <18>, wherein R 1} and R ² are independently non-polymerizable organic groups having 1 to 4 carbon atoms.
<20> The polyimide precursor according to <18> or <19>, wherein A in the formula (2) is a group containing a carbon-carbon unsaturated double bond.
<21> The polyimide precursor according to any one of <18> to <20>, wherein l in the formula (2) is an integer of 2 to 5.

According to the present invention, it has become possible to provide a negative photosensitive resin composition having excellent resolution. Further, it has become possible to provide a cured film, a method for producing a cured film, a semiconductor device, a method for producing a laminate, a method for producing a semiconductor device, and a polyimide precursor using the above-mentioned negative photosensitive resin composition. ..

It is a schematic diagram which shows the structure of one Embodiment of a semiconductor device.

The description of the components in the present invention described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation can be mentioned.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. Representing either, "(meth) acryloyl" represents both "acryloyl" and "methacryloyl", or either.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
As used herein, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition. Further, the solid content concentration refers to the concentration at 25 ° C. unless otherwise specified.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC) measurement unless otherwise specified. In the present specification, HLC-8220 (manufactured by Tosoh Corporation) is used as the weight average molecular weight (Mw) and the number average molecular weight (Mn), and the guard columns TSKgradevolume SuperAW-H and TSK SuperAWM-H (Tosoh Corporation) are used as columns. ) Can be obtained. Unless otherwise specified, the eluate shall be measured using N-methyl-2-pyrrolidone (NMP). Unless otherwise specified, a differential refractive index (RI) detector is used for detection.

<Negative photosensitive resin composition>
The negative photosensitive resin composition of the present invention (hereinafter, also referred to as the composition of the present invention) contains a polyimide precursor, a photopolymerization initiator, and a solvent, and the polyimide precursor is represented by the formula (1) described later. It has a repeating unit represented by, has a structure represented by the formula (2) described later at at least one end, and has a weight average molecular weight of 50,000 or less.

According to the composition of the present invention, a negative photosensitive resin composition having excellent resolution can be obtained. It is presumed that the mechanism for obtaining such an effect is as follows.
According to the studies by the present inventors, it has been found that the glass transition temperature (Tg) can be improved by providing a polymerizable group at the end of the polyimide precursor. Until now, the polyimide precursor has generally been provided with a polymerizable group in the side chain because the polymerizable group can be introduced at a high density. However, it has been found that when a polymerizable group is added to the side chain of the polyimide precursor, the polymerizable group of the side chain may be eliminated during the cyclization of the polyimide precursor. On the other hand, when a polymerizable group is introduced at the end of the polyimide precursor, elimination of the polymerizable group does not occur even if it is cyclized.
However, it was found that the resolution at the time of development was inferior when only the polymerizable group was provided at the end. It was considered that this was because the amount of the polymerizable group with respect to the polyimide precursor was relatively small. Therefore, by setting the weight average molecular weight of the polyimide precursor to 50,000 or less, the amount of the polymerizable group with respect to the polyimide precursor can be relatively increased, and as a result, the resolution has been successfully improved. is there.
Further, according to the present invention, it is possible to improve the resolution while maintaining a high Tg of the cured film of the negative photosensitive resin composition.

In addition, in the present invention, by using R ¹ and R ² of the formula (1) as non-polymerizable groups having 1 to 4 carbon atoms, the residual film ratio after thermosetting can be improved. That is, during the cyclization of the polyimide, ^{the portions R 1} and R ² of the formula (1) were easily detached, and when they were detached, the film was thinned. In the present invention, by using ^{the portions R 1} and R ² of the formula (1) as non-polymerizable groups having 1 to 4 carbon atoms, even if these groups are eliminated by cyclization, the film is more effectively reduced. Can be suppressed. That is, the residual film ratio after thermosetting can be maintained higher.

In the composition of the present invention, the lower limit of the glass transition temperature measured by the method described in Examples described later is preferably 226 ° C. or higher, more preferably 228 ° C. or higher, and 230 ° C. or higher. Is even more preferable. When the glass transition temperature is equal to or higher than the above value, reliability can be expected to be improved in high temperature processes such as a vapor deposition process for forming metal wiring and a bonding process between electrodes. The upper limit of the glass transition temperature is not particularly defined, but for example, the desired performance is sufficiently exhibited even at 350 ° C. or lower.

In the composition of the present invention, the residual film ratio of the exposed portion is preferably 50% or more, more preferably 70% or more, and further preferably 90% or more. The exposure portion residual film ratio is a value defined as follows. For details of the measurement method, the description of Examples described later can be taken into consideration.
Exposed area residual film ratio (%) = [Thickness after development of exposed area / Film thickness before development of unexposed area] x 100

In the composition of the present invention, the residual film ratio after thermosetting is preferably 70% or more, more preferably 80% or more, and further preferably 85% or more. The residual film ratio after thermosetting is a value defined by the following. For details of the measurement method, the description of Examples described later can be taken into consideration.
Residual film ratio after thermosetting (%) = [Film thickness after thermosetting / Film thickness before thermosetting] x 100

Hereinafter, each component of the composition of the present invention will be described in detail.

<< Polyimide precursor >>
The composition of the present invention has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at at least one end, and has a weight average molecular weight of 50,000 or less. Contains. This polyimide precursor is also the polyimide precursor of the present invention.
In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and R ¹ and R ² are independently non-polymerizable organic groups;
(A) _l- L ^1- * (2)
In formula (2), A represents a polymerizable group, L ¹ represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a binding site with another site.

Examples of the divalent organic group represented by X in the formula (1) include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or linear group having 2 to 20 carbon atoms or a group containing an aromatic group. A branched aliphatic group, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and an aromatic group having 6 to 20 carbon atoms is included. Groups are more preferred. A particularly preferred embodiment includes a group represented by "-Ar-L-Ar-". Here, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −CO−, −S. -, -SO _2- or -NHCO-, and a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group. L is an aliphatic hydrocarbon group of fluorine carbon atoms which may be substituted with atoms 1 or 2, -O -, - CO - , - S- or -SO ₂ - are preferred. The aliphatic hydrocarbon group here is preferably an alkylene group.

The divalent organic group represented by X in the formula (1) is preferably a group derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, the divalent organic group represented by X is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms. It is preferably a diamine containing a group or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include the following aromatic groups.

Among the above aromatic groups, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −C (= O) −, −S−. , -S (= O) _2- , -NHCO-, and a group selected from a combination thereof, preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom. -O -, - C (= O ) -, - S -, - SO 2 - , more preferably a group selected _{from, -CH 2 -, - O -} , - S -, - SO 2 -, More preferably, it is a divalent group selected from the group consisting of −C (CF ₃ ) ₂ − and −C (CH ₃ ) _{2 −.}

Specific examples of the diamine include 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'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'-and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diaminodiphenylsulfone , 4,4'-and 3,3'-diaminodiphenyl sulfide, 4,4'-and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 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-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl ] Sulfur, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3, 3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-amino) Phenyl) 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'-Tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9 , 9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylene Esters of diamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, diaminobenzoic acid , 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4) -Aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [ 4- (2-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4) -Aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] Hexafluoropropane, Parabis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-tri) Fluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) bipheni , 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [ 4- (4-Amino-3-trifluoromethylphenoxy) phenyl] Hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4, 4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotrizine and 4,4'' '-At least one diamine selected from diaminoquaterphenyls.

Further, the diamines (DA-1) to (DA-18) shown below are also preferable.

Further, a diamine having at least two or more alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more ethylene glycol chains and / or both of propylene glycol chains in one molecule is preferable, and a diamine containing no aromatic ring is preferable. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark). ) EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2- (2-) Aminopropoxy) ethoxy) propoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propan-2-amine and the like, but are not limited thereto. ..
Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffamine® EDR-176 is shown below.

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

The divalent organic group represented by X in the formula (1) is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
Equation (51)
In formula (51), R ^{10 to} R ¹⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 10 to} R ¹⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. Is.
As ^{monovalent organic groups of R 10 to} R ¹⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a hook having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) Examples thereof include an alkylated group.
Equation (61)
In formula (61), R ¹⁸ and R ¹⁹ are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethyl-4,4'-diaminobiphenyl and 2,2'-bis (trifluoromethyl) -4,4'-diamino. Examples thereof include biphenyl, 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.

As the tetravalent organic group represented by Y in the formula (1), a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
Equation (5)
In formula (5), R ¹¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −CO−, −S−, −SO. _2- , -NHCO-, and preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO- , -S- and -SO _2- are more preferably groups selected from -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _{2-, -O-, -CO.} -, - S- and -SO ₂ - 2 divalent radical selected from the group consisting of is more preferable.

Equation (6)

Specific examples of the tetravalent organic group represented by Y in the formula (1) include tetracarboxylic acid residues remaining after removal of the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O).
Equation (O)
In formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is synonymous with the tetravalent organic group represented by Y in the formula (1), and the preferred range is also the same.

Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfide tetra. Carcarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4, 4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3 , 3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid 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-naphthalene Tetetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalene Tetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3-di) Carboxyphenyl) ethanedianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethanedianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and their carbon number 1 An example is at least one selected from an alkyl derivative of ~ 6 and an alkoxy derivative having 1 to 6 carbon atoms.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as preferable examples.

It is also preferable to have a hydroxyl group at at least one of X and Y in the formula (1).

^{The non-polymerizable organic group represented by R 1} and R ² of the formula (1) is preferably a group that does not contain a carbon-carbon unsaturated double bond. For example, linear or branched alkyl groups, cyclic alkyl groups and aromatic groups are preferred. Examples of the aromatic group include an aryl group and an aralkyl group. The ^{non-polymerizable organic group represented by R 1} and R ² is more preferably a non-polymerizable organic group having 1 to 4 carbon atoms, and is a linear or branched alkyl group having 1 to 4 carbon atoms. Is even more preferable. Preferred specific examples of the non-polymerizable organic group are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group. Groups, isopropyl groups, isobutyl groups, sec-butyl groups, t-butyl groups, 1-ethylpentyl groups, 2-ethylhexyl groups and the like include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups and isobutyls. Groups, sec-butyl groups and tert-butyl groups are preferred, methyl and ethyl groups are more preferred, and methyl groups are even more preferred.

The polyimide precursor of the present invention has a structure represented by the formula (2) at at least one end.
(A) _l- L ^1- * (2)
In formula (2), A represents a polymerizable group, L ¹ represents a single bond or an l + 1 valent organic group, l represents an integer of 1 to 10, and * represents a binding site with another site.

As the polymerizable group represented by A in the formula (2), a group containing a carbon-carbon unsaturated double bond is preferable. Specific examples thereof include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a group represented by the following formula (A-1) and a group represented by the formula (A-2).
In the above formula, * indicates a binding site with ^{L 1 from the formula (2).} R ³ represents a hydrogen atom or a methyl group, and Z represents an oxygen atom or NH.

In the formula (2), L ¹ represents a single bond or an l + 1 valent organic group, and an l + 1 valent organic group is preferable. The l + 1 valent organic group consists of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group is mentioned.
Specific examples of the l + 1-valent organic group include a group composed of the following structural units or a combination of two or more of the following structural units (which may form a ring structure).

In the formula (2), l represents an integer of 1 to 10, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and even more preferably an integer of 2 to 5. According to this aspect, the residual film ratio after development in the exposed portion can be increased.

The structure represented by the formula (2) is preferably a structure represented by the formula (3) or the formula (4), and a structure represented by the formula (3) is more preferable. According to this aspect, the residual film ratio after development in the exposed portion can be increased.
In formula (3), R ³ represents a hydrogen atom or a methyl group, Z represents an oxygen atom or NH, L ² represents a single bond or an m + 1 valent organic group, and m represents an integer of 1-10. , * Indicates a site of connection with another site.
In formula (4), L ³ represents a single bond or an n + 1 valent organic group, n represents an integer of 1 to 10, and * represents a binding site with another site.

The m + 1-valent organic group represented ^{by L 2 in the} formula (3) and the n + 1-valent organic group represented ^{by L 3 in} the formula (4) are the groups described in the l + 1-valent organic group represented ^{by L 1 in the formula (2).} The same applies to the preferred ranges.

In the formula (3), m represents an integer of 1 to 10, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and even more preferably an integer of 2 to 5. According to this aspect, the residual film ratio in the exposed portion can be increased. In the formula (4), n represents an integer of 1 to 10, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and even more preferably an integer of 2 to 5. According to this aspect, the residual film ratio in the exposed portion can be increased.

The polyimide precursor of the present invention preferably has a fluorine atom in the repeating unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

The polyimide precursor of the present invention may further contain a repeating unit containing an aliphatic group having a siloxane structure for the purpose of improving the adhesion to the substrate. Examples of the diamine component for introducing an aliphatic group having a siloxane structure include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.

In the polyimide precursor, the repeating unit represented by the formula (1) may be one kind, or two or more kinds. Further, the polyimide precursor may contain a structural isomer of a repeating unit represented by the formula (1). Further, the polyimide precursor may contain other types of repeating units in addition to the repeating unit represented by the formula (1).

The polyimide precursor of the present invention preferably contains the repeating unit represented by the formula (1) in an amount of 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more of all the repeating units. It is more preferable to do so.

The weight average molecular weight (Mw) of the polyimide precursor is 50,000 or less, preferably 40,000 or less, and more preferably 35,000 or less. The lower limit preferably exceeds 2000, more preferably 5000 or more, further preferably 6000 or more, and further preferably 7000 or more. When the weight average molecular weight of the polyimide precursor is 50,000 or less, the developability is excellent. Further, when the weight average molecular weight of the polyimide precursor is 5000 or more, the mechanical strength of the obtained cured film is good.

The dispersity (Mw / Mn) of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the dispersity of the polyimide precursor is not particularly determined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.

The content of the polyimide precursor in the composition of the present invention is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and even more preferably 70 to 96% by mass of the total solid content of the composition of the present invention. ..
Further, the composition of the present invention has a repeating unit represented by the formula (1) and has a structure represented by _{"(A) l-} L ^{1- *" at at least one end.} The content of the polyimide precursor having a weight average molecular weight of 50,000 or less is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and further 70 to 96% by mass of the total solid content of the composition of the present invention. preferable.

In the polyimide precursor of the present invention, a tetracarboxylic acid dianhydride or a derivative thereof is reacted with a diamine, and then a compound having a polymerizable group is further reacted with the reactant, and then the carboxyl group is esterified. It can be manufactured by converting it into a compound. Alternatively, as another method, a diamine is reacted with an ester of a tetracarboxylic dianhydride or the like and an alcohol, and then a compound having a polymerizable group is further reacted with the reaction product to produce the product. it can.
In the present invention, the molar ratio of the raw material molar ratio of the tetracarboxylic dianhydride or its derivative to the alcohol (tetracarboxylic dianhydride or its derivative: alcohol) is 0.9 to 1.1: 2.1 to 1. 9 is preferable.
In the present invention, the molar ratio of tetracarboxylic dianhydride or its derivative to the raw material molar ratio of diamine (tetracarboxylic dianhydride or its derivative: diamine) is 0.8 to 1.2: 1.2 to 0. .8 is preferable, and 1.001 to 1.2: 0.999 to 0.8 is more preferable. By slightly enriching the tetracarboxylic acid dianhydride or its derivative in this way, the terminal before the addition of the compound having a polymerizable group has an acid anhydride structure, and the compound having a hydroxyl group or an amino group and a polymerizable group. Therefore, the polymerizable group can be surely introduced.
The reaction temperature of the above reaction is preferably -20 to 60 ° C. The reaction time is preferably 30 minutes to 10 hours.

The molecular weight of the alcohol to be reacted with the tetracarboxylic dianhydride is preferably 30 to 150, more preferably 30 to 80, and even more preferably 30 to 65. When the molecular weight of the alcohol to be reacted with the tetracarboxylic dianhydride is within the above range, a polyimide precursor having excellent resolvability can be easily obtained.
The alcohol to be reacted with the tetracarboxylic acid dianhydride is preferably an alcohol having 1 to 8 carbon atoms, more preferably an alcohol having 1 to 4 carbon atoms, further preferably an alcohol having 1 to 3 carbon atoms, and having 1 or 2 carbon atoms. Alcohol is more preferable, and alcohol having 1 carbon atom (methanol) is even more preferable.
Specific examples of the alcohol include methanol, ethanol, propanol, and n-butanol, with methanol being particularly preferable.

The compound having a polymerizable group is preferably a compound having 1 to 10 polymerizable groups, more preferably a compound having 2 to 8 polymerizable groups, and even more preferably a compound having 2 to 5 polymerizable groups. As the polymerizable group, a group containing a carbon-carbon unsaturated double bond is preferable. Specifically, a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a styryl group, a group represented by the above-mentioned formula (A-1) and a group represented by the above-mentioned formula (A-2). Can be mentioned.
The molecular weight of the compound having a polymerizable group is preferably 100 to 2000, more preferably 100 to 1500, and even more preferably 100 to 1000. When the molecular weight of the compound having a polymerizable group is in the above range, a specific example of a compound in which a polyimide precursor having excellent resolvability can be easily obtained is a pentaerythritol tri, which is used in an excessive amount of acid dianhydride. (Meta) acrylate, glycerol di (meth) acrylate, isocyanate diethylene oxide (EO) modified di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate and 4-aminostyrene are exemplified, and when diamine is used in excess, 2-isocyanatoethyl (meth) acrylate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate are exemplified.

In the method for producing a polyimide precursor, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

In the production of polyimide precursors, one of the main chain ends of the precursor is sealed with an end sealant such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound in order to further improve storage stability. You may stop. Of these, it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 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-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.

The production of the polyimide precursor may include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution can be precipitated as a solid by precipitating it in a poor solvent such as water or alcohol. Then, the polyimide precursor can be dried to obtain a powdery polyimide precursor.

<< Photopolymerization Initiator >>
The composition of the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator include a photocationic polymerization initiator and a photoradical polymerization initiator, and a photoradical polymerization initiator is preferable. When the composition of the present invention contains a photoradical polymerization initiator, the composition of the present invention is applied to a substrate such as a semiconductor wafer to form a negative photosensitive resin composition layer, and then irradiated with light. , Curing due to radicals occurs, and the solubility in the light-irradiated portion can be reduced. Therefore, for example, by exposing the negative photosensitive resin composition layer through a photomask having a pattern that masks only the electrode portion, it is possible to easily prepare regions having different solubilitys according to the electrode pattern. There are advantages.

The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photopolymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP-A-2016-0273557 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photopolymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a thermobase generator.
As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used.
Preferred oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminovtan-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminovtan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one and the like.
Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA OPTMER N-1919 (manufactured by ADEKA Corporation, JP2012-14052). The polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA Arklus NCI-831 and ADEKA Arkuru's NCI-930 (manufactured by ADEKA) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
More preferable photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is particularly preferable.
The photopolymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and other aromatic ketones, alkylanthraquinone and the like Kinones fused with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used. Further, a compound represented by the following formula (I) can also be used.
Wherein ^{(I), R 50} is an alkyl group having 1 to 20 carbon atoms; a phenyl group; an alkoxy group having 1 to 12 carbon atoms, alkyl group of the 2 to 20 carbon atoms interrupted by one or more oxygen atoms; Alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon number 2 to interrupted by one or more oxygen atoms A phenyl group substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, where R ⁵¹ is the group represented by formula (II) or the same as ^{R 50.} The groups, R ^{52 to} R ^54, are independently alkyl having 1 to 12 carbon atoms and alkoxy or halogen having 1 to 12 carbon atoms, respectively.
In the formula, R ^{55 to} R ⁵⁷ are the same as ^{R 52 to} R ^{54 in} the above formula (I).

Further, as the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication WO2015 / 125469 can also be used.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.1 to 1% by mass, based on the total solid content of the composition of the present invention. It is 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.

<< Solvent >>
The composition of the present invention contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-Valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-) Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropionate, etc. Methyl acid and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Preferable examples thereof include propyl acid acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Preferable examples thereof include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Preferable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
Preferred examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
Preferable examples of sulfoxides include dimethyl sulfoxide.
Preferable examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.

As the solvent, a form in which two or more kinds are mixed is also preferable from the viewpoint of improving the properties of the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone. , Dimethylsulfoxide, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and a mixed solution composed of two or more selected from propylene glycol methyl ether acetate are preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the composition of the present invention is 5 to 80% by mass, more preferably 5 to 70% by mass, and 10 to 60% by mass. % Is particularly preferable. The solvent content may be adjusted according to the desired thickness and coating method. For example, if the coating method is spin coating or slit coating, the content of the solvent having a solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% by mass to 50% by mass, and preferably 1.0% by mass to 25% by mass. By adjusting the amount of the solvent according to the coating method, the photosensitive resin composition layer having a desired thickness can be uniformly formed.
Only one type of solvent may be contained, or two or more types may be contained. When two or more kinds of solvents are contained, the total is preferably in the above range.

<< Polyfunctional Radical Polymerizable Monomer >>
The composition of the present invention preferably contains a polyfunctional radically polymerizable monomer (hereinafter, also referred to as a polymerizable monomer). With such a configuration, a cured film having excellent heat resistance can be formed.

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

The polymerizable monomer preferably has two or more radically polymerizable groups, and more preferably three or more. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

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

From the viewpoint of developability, the composition of the present invention preferably contains at least one bifunctional or higher polymerizable monomer containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher functional polymerizable monomer. Is more preferable. Further, it may be a mixture of a bifunctional polymerizable monomer and a trifunctional or higher functional polymerizable monomer. The number of functional groups of the polymerizable monomer means the number of radically polymerizable groups in one molecule.

Specific examples of the polymerizable monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, which are preferably unsuitable. Esters of saturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyhydric amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogen group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the polymerizable monomer, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples include polyethylene glycol di (meth) acrylate, trimethylol ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-41708, JP-A-50-6034, and JP-A-51-37193. Urethane (meth) acrylates, such as those described in JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490, polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be mentioned.
Further, as other preferable polymerizable monomers, a group having a fluorene ring and having an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. It is also possible to use a compound having two or more of them or a cardo resin.
Further, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-4537, Japanese Patent Publication No. 1-4536, and Japanese Patent Application Laid-Open No. 2-25493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-22048 can also be used. Furthermore, the journal of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, polymerizable monomers represented by the following formulas (MO-1) to (MO-5) can also be preferably used. In the formula, when T is an oxyalkylene group, the end on the carbon atom side is bonded to R.

In each of the above equations, n is an integer from 0 to 14 and m is an integer from 0 to 8. A plurality of R and T existing in the molecule may be the same or different from each other.
In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), at least one of the plurality of Rs is -OC (= O) CH = CH ₂ or -OC. (= O) C (CH ₃ ) = represents a group represented by _{CH 2.}
As a specific example of the polymerizable monomer represented by the above formulas (MO-1) to (MO-5), the compounds described in paragraphs 0248 to 0251 of JP-A-2007-269779 can be used. ..

Further, the compound described in JP-A-10-62986 with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a polymerizable monomer.

Further, the compounds described in paragraphs 0104 to 0131 of JP2015-187211A can also be used as polymerizable monomers, and their contents are incorporated in the present specification.

As polymerizable monomers, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku Co., Ltd.) ), A-TMMT: manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (As a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues. The structure is preferred. These oligomer types can also be used.
In addition, pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2) are also mentioned as preferable examples.

Commercially available products of the polymerizable monomer include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartmer. DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 manufactured by Nippon Kayaku Co., Ltd. (Sanyo Kokusaku Pulp Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Nippon Kayaku (Nippon Kayaku) UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.) and the like.

The polymerizable monomer includes urethane acrylates as described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-Open No. 2-16765. Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Further, as the polymerizable monomer, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, are used. You can also do it.

The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. The polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The polymerizable monomer having the above is more preferable. Particularly preferably, in a polymerizable monomer obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol and / or di. It is a compound that is pentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polymerizable monomer having an acid group, one type may be used alone, or two or more types may be mixed and used. Further, if necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group may be used in combination.
The preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable monomer is within the above range, it is excellent in manufacture and handling, and further excellent in developability. Moreover, the polymerizability is good.

The content of the polymerizable monomer is preferably 1 to 50% by mass with respect to the total solid content of the composition of the present invention from the viewpoint of good polymerizable property and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. One type of polymerizable monomer may be used alone, or two or more types may be mixed and used.
The mass ratio of the polyimide precursor to the polymerizable monomer (polyimide precursor / polymerizable monomer) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90/10 to 50. / 50 is the most preferable. When the mass ratio of the polyimide precursor and the polymerizable monomer is within the above range, a cured film having better polymerizable properties and heat resistance can be formed.

In the composition of the present invention, a monofunctional polymerizable monomer can be preferably used from the viewpoint of suppressing warpage by controlling the elastic modulus of the cured film. Examples of the monofunctional polymerizable monomer include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional polymerizable monomer, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

<< Other polymerizable compounds >>
The composition of the present invention may further contain a polymerizable compound other than the above-mentioned polyimide precursor and the polymerizable monomer. Other polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.

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

(In the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and R ⁵ is a group represented by -OR ⁶ or -OCO-R ^7. R ⁶ indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁷ indicates an organic group having 1 to 10 carbon atoms.)

The content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. More preferably, it is 10 to 35 parts by mass. Further, the total amount of the other polymerizable compounds contains 10 to 90% by mass of the compound represented by the following formula (AM4) and 10 to 90% by mass of the compound represented by the following formula (AM5). Is also preferable.

(In the formula, R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom or carbon. It represents an organic group having a number of 1 to 10, and R ⁷ indicates an organic group having 1 to 10 carbon atoms.)

(In the formula, u represents an integer of 3 to 8, R ⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by -OR ⁶ or -OCO-R ^7. , R ⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

By using the above-mentioned compound having a hydroxymethyl group or the like, the occurrence of cracks can be more effectively suppressed when the composition of the present invention is applied on an uneven substrate. Further, it is possible to form a cured film having excellent pattern processability and high heat resistance having a 5% mass reduction temperature of 350 ° C. or higher, more preferably 380 ° C. or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacethoxymethyl-p-cresol, etc. Be done.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like. HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

(Epoxy compound (compound having an epoxy group))
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. Further, the flexibility of the film can be increased to obtain a cured film having excellent elongation and the like. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi). Examples include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA) and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable because it suppresses warpage and is excellent in heat resistance. For example, Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain a polyethylene oxide group.

The content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. When the content of the epoxy compound is 5 parts by mass or more, the warp of the obtained cured film can be further suppressed, and when the content is 50 parts by mass or less, the pattern filling caused by reflow during curing can be further suppressed.

(Oxetane compound (compound having an oxetanyl group))
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or individually. Two or more kinds may be mixed.

The content of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.

(Benzodizepine compound (compound having a benzoxazolyl group))
Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzoxazine. Examples include compounds. These may be used alone or in combination of two or more.

The content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.

<< Metal discoloration inhibitor >>
The composition of the present invention preferably further contains a metal discoloration inhibitor. When the composition of the present invention contains a metal discoloration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the negative photosensitive resin composition layer.
The metal discoloration inhibitor is not particularly limited, but is a heterocycle (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring. , Pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and mercapto group compound, hindered phenol system Examples thereof include compounds, salicylate derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as triazole and benzotriazole, and tetrazole-based compounds such as tetrazole and benzotriazole can be preferably used.

It is also possible to use an ion trap agent that traps anions such as halogen ions.

Examples of other metal discoloration inhibitors include rust preventives described in paragraphs 0094 of JP2013-15701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-59656A. The compounds described in paragraph 0052 of the above, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A can be used.

Specific examples of the metal discoloration inhibitor include the following compounds.

When the composition of the present invention has a metal discoloration inhibitor, the content of the metal discoloration inhibitor is preferably 0.01 to 5.0% by mass, based on the total solid content of the composition of the present invention. 05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable. The metal discoloration inhibitor may be only one kind or two or more kinds. When there are two or more types of metal discoloration inhibitor, the total is preferably in the above range.

<< Polymerization inhibitor >>
The composition of the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, para-tert-butylcatechol, parabenzoquinone, diphenyl-parabenzoquinone, 4,4'-thiobis (3-methyl). -6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, Ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol , 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy) -3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication WO2015 / 125469 can also be used.
In addition, the following compounds can be used (Me is a methyl group).
When the composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the composition of the present invention.
The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<< Thermal base generator >>
The composition of the present invention preferably contains a thermobase generator.
The type of thermal base generator is not particularly specified, but it is selected from acidic compounds that generate bases when heated to 40 ° C. or higher, and ammonium salts having an anion having pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermobase generator containing at least one of these. _{Here, pKa1 represents the logarithm (-Log 10} Ka) of the reciprocal of the dissociation constant (Ka) of the first proton of the acid, and the details will be described later.

Since the acidic compound (A1) and the ammonium salt (A2) generate bases when heated, the bases generated from these compounds can promote the cyclization reaction of the polyimide precursor or the like, and the ring of the polyimide precursor or the like can be promoted. The conversion can be carried out at a low temperature. Further, even if these compounds coexist with a polyimide precursor or the like that is cyclized and cured by a base, cyclization of the polyimide precursor or the like hardly proceeds unless heated, so that a composition having excellent storage stability can be obtained. Can be prepared.
In the present specification, the acidic compound means that 1 g of the compound is collected in a container, 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added, and the compound is added at room temperature for 1 hour. It means a compound having a value of less than 7 measured at 20 ° C. using a pH (power of hydrogen) meter for the solution obtained by stirring.

In the present embodiment, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and even more preferably 165 ° C. or lower. The lower limit of the base generation temperature is preferably 130 ° C. or higher, more preferably 135 ° C. or higher.
When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, bases are less likely to be generated during storage, so that a composition having excellent stability can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor or the like can be lowered. For the base generation temperature, for example, using differential scanning calorimetry, the compound is heated to 250 ° C. in a pressure resistant capsule at 5 ° C./min, the peak temperature of the lowest exothermic peak is read, and the peak temperature is measured as the base generation temperature. can do.

In the present embodiment, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine is highly basic, the cyclization temperature of the polyimide precursor and the polybenzoxazole precursor can be lowered. The boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The value of the molecular weight is a theoretical value obtained from the structural formula.

In the present embodiment, the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.

In the present embodiment, 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.). ) May be a compound excluding an acidic compound that generates a base when heated.

In the present embodiment, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, or may be held outside the molecule of the ammonium cation, but may be held outside the molecule of the ammonium cation. preferable. The fact that the anion is present outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the extramolecular anion of the cation part is also referred to as a counter anion.
Equation (101) Equation (102)
In formulas (101) and (102), R ^{1 to} R ⁶ independently represent 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 , and R ⁵ and R ⁷ in formulas (101) and (102) may be combined to form a ring, respectively.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ are synonymous with those in formula (101) or formula (102).
In the formulas (Y1-1) to (Y1-4), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5. ..

In the present embodiment, the ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polyimide precursor or the like can be cyclized at a low temperature, and the stability of the composition can be improved. When pKa1 is 4 or less, the stability of the thermobase generator is good, the generation of bases can be suppressed without heating, and the stability of the composition is good. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polyimide precursor or the like is good.
The type of anion is preferably one selected from carboxylic acid anion, phenol anion, phosphoric acid anion and sulfuric acid anion, and more preferably carboxylic acid anion because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to obtain a thermobase generator capable of further improving the stability, curability and developability of the composition. In particular, the use of a divalent carboxylic acid anion can further improve the stability, curability and developability of the composition.
In the present embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and is Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafli). , Nachod, F.C .; Compilation: Braude, E.A., Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: D. al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.

The carboxylic acid anion is preferably represented by the following formula (X1).
In formula (X1), EWG represents an electron-attracting group.

In the present embodiment, the electron-attracting group means that Hammett's substituent constant σm shows a positive value. Here, σm is a review article by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting group in the present embodiment is not limited to the substituents described in the above documents.
Examples of substituents in which σm shows a positive value include CF ₃ groups (σm = 0.43), CF ₃ CO groups (σm = 0.63), HC≡C groups (σm = 0.21), and the like. 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. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
In formulas (EWG-1) to (EWG-6), R ^{x1 to} R ^x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar is an aromatic group. Represents.

In the present embodiment, the carboxylic acid anion is preferably represented by the following formula (XA).
Equation (XA)
In the formula ^{(XA), L 10} represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X - represents and divalent linking group selected from these combinations, ^{R X} is a hydrogen atom , Alkyl group, alkenyl group or aryl group.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion. These can be preferably used.

Specific examples of the thermobase generator include the following compounds.

When the composition of the present invention contains a thermobase generator, the content of the thermobase generator is preferably 0.1 to 50% by mass with respect to the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
As the thermobase generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<< Metal Adhesive Improvement Agent >>
The composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesiveness improving agent include a silane coupling agent.

Examples of the silane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, the compounds described in paragraphs 0063-0071 of International Publication WO2011 / 080992A1, JP-A-2014-191252. Examples thereof include the compounds described in paragraphs 0060 to 0061, the compounds described in paragraphs 0045 to 0052 of JP-A-2014-41264, and the compounds described in paragraph 0055 of International Publication WO2014 / 0975994. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Further, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor. When the amount is 0.1 parts by mass or more, the adhesiveness between the cured film and the metal layer after the curing process is good, and when the amount is 30 parts by mass or less, the heat resistance and mechanical properties of the cured film after the curing process are good. Become. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

<< Other additives >>
The composition of the present invention contains various additives such as a photobase generator, a thermal polymerization initiator, a thermoacid generator, a sensitizing dye, and chain transfer, as required, as long as the effects of the present invention are not impaired. Agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

(Photobase generator)
The composition of the present invention may contain a photobase generator. A photobase generator is a compound that generates a base by exposure and does not show activity under normal conditions of normal temperature and pressure, but when it is irradiated with electromagnetic waves and heated as an external stimulus, it is a base (basic substance). ) Is not particularly limited as long as it is a compound that generates). Since the base generated by exposure acts as a catalyst when the polyimide precursor or the like is cured by heating, it can be suitably used in the negative type.

The content of the photobase generator is not particularly limited as long as it can form a desired resin pattern, and can be a general content. The photobase generator is preferably in the range of 0.01 parts by mass or more and less than 30 parts by mass, and is in the range of 0.05 parts by mass to 25 parts by mass with respect to 100 parts by mass of the polyimide precursor. Is more preferable, and more preferably in the range of 0.1 parts by mass to 20 parts by mass.
The photobase generator may be only one kind or two or more kinds. When there are two or more photobase generators, the total is preferably in the above range.

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

Further, as the photobase generator, a carbamate derivative, an amide derivative, an imide derivative, an α-cobalt complex, an imidazole derivative, a cinnamic acid amide derivative, an oxime derivative and the like can also be used. Further, the photobase generator having a carbamic acid amide structure described in JP-A-2009-80452 and JP-A-2009 / 123122 is described in JP-A-2006-189591 and JP-A-2008-247747. A photobase generator having a carbamate structure, an oxime structure described in JP-A-2007-249013 and JP-A-2008-003581, and a photobase generator having a carbamoyloxime structure can also be used.
Other examples of the photobase generator include the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205. Examples include the compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204319, and the compounds described in paragraph 0052 of International Publication WO2010 / 064631.

(Thermal polymerization initiator)
The composition of the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.
A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, it is possible to proceed with the polymerization reaction of the polyimide precursor as well as the cyclization of the polyimide precursor, so that a higher degree of heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

When the composition of the present invention has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, preferably 0.1 to 50% by mass, based on the total solid content of the composition of the present invention. 30% by mass is more preferable, and 0.1 to 20% by mass is particularly preferable. Further, it is preferable to contain 0.1 to 50 parts by mass of the thermal radical polymerization initiator with respect to 100 parts by mass of the polyimide precursor, and more preferably 0.5 to 30 parts by mass. According to this aspect, it is easy to form a cured film having more excellent heat resistance. The thermal radical polymerization initiator may be only one kind or two or more kinds. When there are two or more types of thermal radical polymerization initiators, the total is preferably in the above range.

(Thermal acid generator)
The composition of the present invention may contain a thermoacid generator. The thermoacid generator generates an acid by heating, promotes the cyclization of the polyimide precursor, and further improves the mechanical properties of the cured film. Examples of the thermoacid generator include the compounds described in paragraph 0059 of JP2013-167742A.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the polyimide precursor. By containing 0.01 part by mass or more of the thermal acid generator, the crosslinking reaction and the cyclization of the polyimide precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. The content of the thermoacid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less, from the viewpoint of electrical insulation of the cured film.
Only one type of thermoacid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

(Sensitizing pigment)
The composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electron-excited state. The sensitizing dye in the electron-excited state comes into contact with a base generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the base generator, the thermal radical polymerization initiator, and the photopolymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the composition of the present invention. Is more preferable, and 0.5 to 10% by mass is further preferable. The sensitizing dye may be used alone or in combination of two or more.

(Chain transfer agent)
The composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazol, etc.) can be preferably used.

When the composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass and 1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the composition of the present invention. Parts are more preferable, and 1 to 5 parts by mass are further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

(Surfactant)
Each type of surfactant may be added to the composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferable.

When the composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0, based on the total solid content of the composition of the present invention. It is .005 to 1.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When there are two or more types of surfactant, the total is preferably in the above range.

(Higher fatty acid derivative)
In the composition of the present invention, in order to prevent polymerization inhibition due to oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide are added and unevenly distributed on the surface of the composition in the process of drying after application. You may.
When the composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the composition of the present invention. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

<< Restrictions on other contained substances >>
The water content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of coating surface properties.

From the viewpoint of insulating properties, the metal content of the composition of the present invention is preferably less than 5 parts by mass (parts per million), more preferably less than 1 parts by mass, and particularly preferably less than 0.5 parts by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
Further, as a method for reducing metal impurities unintentionally contained in the composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the composition of the present invention. Examples thereof include a method of filtering the raw material to be used, and a method of lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions in which contamination is suppressed as much as possible.

The composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm, from the viewpoint of wiring corrosiveness. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom, or chloride ion and bromide ion is in the above range, respectively.

<Preparation of composition>
The composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.
Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Manufacturing method of cured film, semiconductor device, cured film, semiconductor device, method of manufacturing laminate and method of manufacturing semiconductor device>
Next, the cured film, the semiconductor device, the method for producing the cured film, the semiconductor device, the method for producing the laminate, and the method for producing the semiconductor device of the present invention will be described.
The cured film of the present invention is obtained by curing the composition of the present invention. The thickness of the cured film of the present invention can be, for example, 1 μm or more, and 5 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

Two or more layers of the cured film of the present invention may be laminated to form a laminated body. Such a laminate preferably has a metal layer between the cured films. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

Examples of the applicable field of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, and the like. In particular, since it has good resolution, it can be preferably used as an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.
Further, the cured film in the present invention can also be used as a photoresist for electronics, a galvanic resist, an etching resist, a solder top resist, and the like.
The cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention includes using the composition of the present invention. Preferably, a negative photosensitive resin composition layer forming step of applying the negative photosensitive resin composition of the present invention to a substrate to form a layer, an exposure step of exposing the negative photosensitive resin composition layer, and the like. It has a step of developing a negative type photosensitive resin composition layer that has been exposed. The production method of the present invention may include a step of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500 ° C. after the development treatment step. Since the cured film of the present invention has excellent heat resistance, good performance can be maintained even when heated at 150 to 500 ° C.

The method for producing a laminate of the present invention includes the method for producing a cured film of the present invention. In the method for producing a laminate of the present invention, after forming the cured film according to the method for producing a cured film of the present invention, the negative type photosensitive resin composition layer forming step, the exposure step, and the developing treatment step are performed again. , It is preferable to repeat in the above order. In particular, it is preferable that the negative photosensitive resin composition layer forming step, the exposure step, and the developing treatment step are further performed 2 to 5 times (that is, 3 to 6 times in total) in the above order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on a portion that has been developed after being provided with a cured film and then developed and removed.

The present invention also discloses a semiconductor device including the cured film of the present invention. Hereinafter, an embodiment of a semiconductor device in which the composition of the present invention is used as an interlayer insulating film for a rewiring layer will be described.

The semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a laminated body 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are laminated is arranged on a wiring board 120. In this embodiment, the case where the number of layers of the semiconductor element (semiconductor chip) is four is mainly described, but the number of layers of the semiconductor element (semiconductor chip) is not particularly limited, and for example, 2 It may be a layer, an 8-layer, a 16-layer, a 32-layer, or the like. Moreover, it may be one layer.

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) integrally provided with the through electrodes are provided on both sides of each semiconductor element.

The laminated body 101 has a structure in which a semiconductor element 101a having no through electrode and a semiconductor element 101b to 101d having through electrodes 102b to 102d are flip-chip connected. That is, the electrode pad of the semiconductor element 101a having no penetrating electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the penetrating electrode 102b adjacent thereto are connected by a metal bump 103a such as a solder bump and penetrated. The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c adjacent thereto by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the through electrode 102d adjacent thereto by a metal bump 103c such as a solder bump. Has been done.

An underfill layer 110 is formed in the gap between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are laminated via the underfill layer 110.

The laminated body 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 ceramics substrate, or a glass substrate as a substrate is used. Examples of the wiring board 120 to which the resin substrate is applied include a multilayer copper-clad laminate (multilayer printed wiring board) and the like.

A surface electrode 120a is provided on one surface of the wiring board 120.
An insulating layer 115 on which the rewiring layer 105 is formed is arranged between the wiring board 120 and the laminated body 101, and the wiring board 120 and the laminated body 101 are electrically connected to each other via the rewiring layer 105. It is connected. The insulating layer 115 is formed by using the composition of the present invention.
That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side via a metal bump 103d such as a solder bump. Further, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
An underfill layer 110a is formed between the insulating layer 115 and the laminated body 101. Further, an underfill layer 110b is formed between the insulating layer 115 and the wiring board 120.

In addition to the above, the cured film of the present invention can be widely used in various applications using polyimide.
Further, since polyimide is heat-resistant, the cured film or the like in the present invention is used for plastic substrates and interlayer insulating films for display devices such as liquid crystal displays, organic EL displays, and electronic papers, automobile parts, heat-resistant paints, coating agents, and films. Can also be suitably used as.
Furthermore, the polyimide precursor of the present invention can also be used in a positive photosensitive resin composition.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

Synthesis of polyimide precursor <Synthesis of polyimide precursor P-1>
2.0.00 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA, 4,4'-oxydiphthalic acid dried at 140 ° C. for 12 hours, bifunctional acid anhydride) and 4. Mix 13 g (129 mmol) of methanol (side chain compound), 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglime (diethylene glycol dimethyl ether), and stir at a temperature of 60 ° C. for 18 hours. , 4,4'-Oxydiphthalic acid dianhydride and methanol diesters were prepared. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.88 g (59.3 mmol) of 4,4'-oxydianiline (ODA, diamine) in 100 mL of N-methylpyrrolidone was added to the reaction mixture at 20 to 23 ° C. for 20 minutes. Dropped into. Then, 23.9 g (15.5 mmol) of dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku, terminal compound) was added to the reaction mixture, and the reaction mixture was stirred at room temperature overnight. The polyimide precursor was then precipitated in a mixed solvent of 3 liters of water and 3 liters of acetone. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried under reduced pressure at room temperature for 2 days to obtain a polyimide precursor (P-1). The structure of the obtained polyimide precursor (P-1 ^{) was confirmed by 1} H-NMR (nuclear magnetic resonance spectrum) (DMSO (dimethyl sulfoxide) -d6 solution).
10.6 to 10.3 ppm (m, 2H), 8.2 to 6.7 ppm (m, 14H), 6.4 to 6.2 ppm (m, 1H), 6.2 to 6.0 ppm (m, 1H) ), 6.0-5.8 ppm (m, 0.9H), 4.4-4.0 ppm (m, 3H), 3.9-3.6 ppm (s, 6H).
The weight average molecular weight of the obtained P-1 (gel permeation chromatography (eluent: polystyrene-equivalent value of NMP (N-methyl-2-pyrrolidone)) was 50,000.
The measurement conditions are as follows.
Column: 1 TSK guard AW-H (4.6 mm ID. × 35 mm) TSK SuperAWM-H (6.0 mm ID. × 150 mm) 2 developing solvent: NMP (10 mmol / L lithium bromide, 10 mmol / L phosphoric acid solution)
Column temperature: 50 ° C
Flow rate: 0.35 mL / min Sample injection volume: 20 μL
Sample concentration: 0.1% by mass
Device name: HLC-8220GPC (manufactured by Tosoh)
Calibration curve base resin: polystyrene

<Synthesis of polyimide precursors P-2 to P-16 and P-18>
In the synthesis of the polyimide precursor P-1, the bifunctional acid anhydride, the diamine, the side chain compound and the terminal compound were each changed as shown in Table 1 below, and the others were similarly subjected to the same procedure to carry out the polyimide precursor. Compounds P-2 to P-16 and P-18 were synthesized, respectively.

<Synthesis of P-17>
4,4'-Oxydiphthalic dianhydride (15.51 g) and N-methylpyrrolidone (114 g) were added to a three-necked flask equipped with a thermometer, a stirrer and a calcium chloride tube, and the mixture was stirred at room temperature. 4,4'-Oxydianiline (9.21 g) was added to this suspension, and the mixture was stirred at 30 ° C. After 1 hour, a mixed solution of N-methylpyrrolidone (15.27 g) and DPHA (18.51 g) was added, and the mixture was stirred at 30 ° C. After 6 hours, it was cooled to room temperature. The obtained mixed solution was diluted with NMP, and the weight average molecular weight measured by GPC was 50,000. The polyimide precursor was then precipitated in a mixed solvent of 3 liters of water and 3 liters of acetone. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at room temperature for 2 days. The obtained solid was dissolved in NMP, and the weight average molecular weight measured by GPC was 20000. It was considered to have decomposed in the purification process.

ODPA: Tokyo Kasei Kogyo BPDA: 3,3', 4,4'-biphenyltetracarboxylic acid dianoxide, Tokyo Kasei Kogyo ODA: Tokyo Kasei Kogyo benzidine (4,4'-diaminobiphenyl): Tokyo Kasei Kogyo Ethanol: Wako Pure Chemical Industries n-Butanol: Wako Pure Chemical Industries n-Octanol: Wako Pure Chemical Industries DPHA: Nippon Kayaku, KAYARAD DPHA
M-305: Pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd., Aronix M-305
701: Glycerol dimethacrylate, manufactured by Shin-Nakamura Chemical Industry, hydroxyethyl acrylate: manufactured by Wako Pure Chemical Industries, Ltd. M-215: Isocyanuric acid ethylene oxide (EO) modified diacrylate, manufactured by Toagosei Co., Ltd., Aronix M-215
Karenz BEI: 1,1- (bisacryloyloxymethyl) ethyl isocyanate, Showa Denko Karenz MOI: 2-isocyanatoethyl methacrylate, Showa Denko 4-aminostyrene: Tokyo Kasei Kogyo

The structure of the obtained polyimide precursor is shown below. In the following, [] means a repeating unit. Me represents a methyl group.

<Example 1>
<< Preparation of Negative Photosensitive Resin Composition >>
As shown in Table 4 below, a polyimide precursor, a photopolymerization initiator, a radically polymerizable monomer, a polymerization inhibitor, a metal discoloration inhibitor, a silane coupling agent and a solvent are mixed to prepare a negative photosensitive resin as a uniform solution. The composition was prepared.

<< Resolution >>
<<< Exposure film residual film ratio >>>
The negative photosensitive resin composition is pressure-filtered at a pressure of 3.0 MPa through a filter having a pore width of 0.8 μm, and then the negative photosensitive resin composition is formed on a silicon wafer by a spin coating method. It was applied in layers to form a negative photosensitive resin composition layer. The silicon wafer to which the obtained negative photosensitive resin composition layer is applied is dried on a hot plate at 100 ° C. for 5 minutes, and a uniform negative photosensitive resin composition layer having a thickness of 15 μm is formed on the silicon wafer. Obtained. The negative photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of ^{500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).} After allowing to stand at room temperature for 30 minutes, it was developed with cyclopentanone for 60 seconds, and the residual film ratio of the exposed portion was determined from the change in film thickness before and after development.
Exposed area residual film ratio (%) = [Thickness after development of exposed area / Film thickness before development of unexposed area] x 100
5: 90% or more 4: 70% or more and less than 90% 3: 50% or more and less than 70% 2: 30% or more and less than 50% 1: less than 30% Evaluation 3 or more is practically preferable.

<<< Remaining film ratio in unexposed area >>>
The negative photosensitive resin composition is pressure-filtered at a pressure of 3.0 MPa through a filter having a pore width of 0.8 μm, and then the negative photosensitive resin composition is formed on a silicon wafer by a spin coating method. It was applied in layers to form a negative photosensitive resin composition layer. The silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform negative photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. did. This was developed with cyclopentanone for 60 seconds, and the residual film ratio of the unexposed portion was determined from the change in film thickness before and after development.
Unexposed area residual film ratio (%) = [(Film thickness of unexposed area after development) / Film thickness of unexposed area before development] x 100
5: Less than 5% 4: 5% or more and less than 20% 3: 20% or more and less than 50% 2: 50% or more and less than 90% 1: 90% or more Evaluation 3 or more is practically preferable.

<< Remaining film ratio after thermosetting >>
The negative photosensitive resin composition is pressure-filtered at a pressure of 3.0 MPa through a filter having a pore width of 0.8 μm, and then the negative photosensitive resin composition is formed on a silicon wafer by a spin coating method. It was applied in layers to form a negative photosensitive resin composition layer. The silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform negative photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. did. The negative photosensitive resin composition layer on the silicon wafer ^{was exposed to an exposure energy of 500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C), and the exposed negative photosensitive resin composition layer (resin layer). Was heated at a heating rate of 10 ° C./min in a nitrogen atmosphere, and after reaching 230 ° C., it was held for 3 hours, and the residual film ratio after heating was determined from the change in film thickness before and after heating.
Residual film ratio after thermosetting (%) = [Film thickness after thermosetting / Film thickness before thermosetting] x 100
5: 85% or more 4: 80% or more and less than 85% 3: 70% or more and less than 80% 2: 60% or more and less than 70% 1: less than 60% Evaluation 2 or more is practically preferable.

<< Glass transition temperature (Tg) >>
The negative photosensitive resin composition is pressure-filtered at a pressure of 3.0 MPa through a filter having a pore width of 0.8 μm, and then the negative photosensitive resin composition is formed on a silicon wafer by a spin coating method. It was applied in layers to form a negative photosensitive resin composition layer. The silicon wafer to which the obtained negative photosensitive resin composition layer is applied is dried on a hot plate at 100 ° C. for 5 minutes, and a uniform negative photosensitive resin composition layer having a thickness of 15 μm is formed on the silicon wafer. Obtained. The negative photosensitive resin composition layer on the silicon wafer ^{was exposed to an exposure energy of 500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C), and the negative photosensitive resin composition layer (resin layer) was exposed. Was heated at a heating rate of 10 ° C./min in a nitrogen atmosphere, reached 230 ° C., and then held for 3 hours. The cured resin layer was immersed in a 4.9 mass% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film. The obtained resin film was set in a viscoelasticity measuring device (Rheogel E4000 manufactured by UBM), and the temperature was raised from 0 ° C. to 350 ° C. at a frequency of 1 Hz and a temperature rise rate of 10 ° C./min using a tensile method. , Tg (° C.) was determined from the peak temperature of tan δ.

<Other Examples and Comparative Examples>
In Example 1, one or more of the polyimide precursor, the photopolymerization initiator, the radically polymerizable monomer, the polymerization inhibitor, the metal discoloration inhibitor, the silane coupling agent and the solvent are modified as shown in Table 4 or Table 5. However, for some of the examples, as shown in Table 5, a thermobase generator was blended, and the others were carried out in the same manner.

The obtained results are shown in Tables 4 and 5 below.

Details of each component in Tables 4 and 5 are as follows.
<Photoradical polymerization initiator>
OXE-01: IRGACURE OXE 01 (Oxime compound, manufactured by BASF)
IRGACURE-784: IRGACURE-784 (metallocene compound, manufactured by BASF)
<Radical polymerizable monomer>
SR209: SR-209 (bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartmer)
A-9300: NK ester A-9300 (trifunctional acrylate having three isobutyleneoxy chains, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
A-TMMT: Shin Nakamura Chemical Industry Co., Ltd., pentaerythritol tetraacrylate A-DPH: Shin Nakamura Chemical Industry Co., Ltd., dipentaerythritol hexaacrylate

<Thermal base generator>
E-1: The following compound E-2: The following compound E-3: The following compound

<Polymerization inhibitor>
F-1: The following compound F-2: The following compound F-3: The following compound

<Metal discoloration inhibitor>
G-1: The following compound G-2: The following compound G-3: The following compound G-4: The following compound

<Silane coupling agent>
H-1: The following compound H-2: The following compound H-3: The following compound

<Solvent>
DMSO: Dimethyl sulfoxide GBL: γ-Butyrolactone NMP: N-Methyl-2-pyrrolidone Ethyl lactate

As is clear from the above results, when the negative photosensitive resin composition of the present invention was used, Tg was high and the resolution was excellent.
Further, in the present invention, the glass transition temperature was 230 ° C. or higher, which was 5 ° C. higher than that of Comparative Examples 1 and 2. It can be said that an increase in Tg of 5 ° C. is a very remarkable effect from the viewpoint of improving reliability in high temperature processes such as a vapor deposition process for forming metal wiring and a bonding process between electrodes.
Further, by shortening the side chain of the polyimide precursor (by making R ¹ and R ² of the formula (1) organic groups of non-polymerizable groups having 1 to 4 carbon atoms), after thermosetting. The residual film ratio was significantly improved.

Example 100
<Manufacturing of laminated body 1>
The photosensitive resin composition of Example 3 was pressure-filtered through a filter having a pore width of 0.8 μm, and then a photosensitive resin composition layer was formed on a silicon wafer by a spin coating method. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. Next, the photosensitive resin composition layer on the silicon wafer ^{was exposed to an exposure energy of 500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was subjected to. Developed with cyclopentanone for 60 seconds to form holes with a diameter of 10 μm. Then, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained for 3 hours. After cooling to room temperature, the same type of photosensitive resin composition as the photosensitive resin composition was used again on the surface of the resin layer, and the photosensitive resin composition was filtered in the same manner as described above to obtain a patterned film 3 The procedure up to time heating was carried out again to form a laminate 1 having two resin layers.

<Manufacturing of laminated body 2>
By using the photosensitive resin composition of Example 3 on the surface of the laminate 1 obtained above and performing the same procedure as the production of the laminate 1 again, the laminate 2 having four resin layers is carried out again. Was produced.

<Manufacturing of laminated body 3>
The photosensitive resin composition of Example 3 was pressure-filtered through a filter having a pore width of 0.8 μm, and then a photosensitive resin composition layer was formed on a silicon wafer by a spin coating method. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. ^{The photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was subjected to cyclopenta. The non-developed hole was developed for 60 seconds to form a hole having a diameter of 10 μm. Then, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained for 3 hours. After cooling to room temperature, a copper thin film (metal layer) having a thickness of 2 μm was applied to a part of the surface of the photosensitive resin composition layer by a vapor deposition method so as to cover the hole portion. Further, on the surfaces of the metal layer and the photosensitive resin composition layer, the photosensitive resin composition of Example 3 was used again, and the photosensitive resin composition was filtered in the same manner as described above for 3 hours of the patterned film. The procedure up to heating was carried out again to prepare a laminate 3 composed of a resin layer / metal layer / resin layer.

100: Semiconductor device 101a-101d: Semiconductor element 101: Laminated body 102b-102d: Through electrode 103a-103e: Metal bump 105: Rewiring layer 110, 110a, 110b: Underfill layer 115: Insulation layer 120: Wiring board 120a: Surface electrode

Claims (21)

Contains a polyimide precursor, a photopolymerization initiator, and a solvent.
The polyimide precursor has a repeating unit represented by the formula (1), has a structure represented by the formula (2) at at least one end, and has a weight average molecular weight of 50,000 or less. Negative resin composition;
In the formula (1), X represents a group represented by -Ar-L-Ar- or a group represented by the formula (51), Ar is an independently aromatic group, and L is an aromatic group. , An aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO _2- or -NHCO-, and two or more of the above. Y represents a tetravalent organic group, and R ¹ and R ² are independently non-polymerizable organic groups having 1 to 4 carbon atoms;
(A) _l- L ^1- * (2)
In formula (2), A represents a polymerizable group, L ¹ represents a single bond or an l + 1 valent organic group, l represents an integer of 2 to 10, and * represents a binding site with another site;
Equation (51)
In formula (51), R ^{10 to} R ¹⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 10 to} R ¹⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. Is. The negative photosensitive resin composition according to claim 1, wherein the polyimide precursor contains the repeating unit represented by the formula (1) in an amount of more than 90 mol% of all the repeating units. The negative photosensitive resin composition according to claim 1 or 2, wherein l in the formula (2) is an integer of 2 to 5. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein A in the formula (2) is a group containing a carbon-carbon unsaturated double bond. The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the structure represented by the formula (2) is a structure represented by the formula (3) or the formula (4);
In formula (3), R ³ represents a hydrogen atom or a methyl group, Z represents an oxygen atom or NH, L ² represents a single bond or an m + 1 valent organic group, and m represents an integer of 1-10. , * Indicates the site of connection with other sites;
In formula (4), L ³ represents a single bond or an n + 1 valent organic group, n represents an integer of 1 to 10, and * represents a binding site with another site. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the polyimide precursor has a weight average molecular weight of 5000 or more. The negative photosensitive resin composition according to any one of claims 1 to 6, further comprising a polyfunctional radically polymerizable monomer. The negative photosensitive resin composition according to any one of claims 1 to 7, further comprising a thermal base generator. The negative photosensitive resin composition according to any one of claims 1 to 8, wherein the photopolymerization initiator is at least one selected from an oxime compound and a metallocene compound. The negative photosensitive resin composition according to any one of claims 1 to 9, which is used for forming an interlayer insulating film for a rewiring layer. A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 10. The cured film according to claim 11, which has a film thickness of 1 to 30 μm. A step of forming a photosensitive resin composition layer by applying the negative photosensitive resin composition according to any one of claims 1 to 10 to a substrate to form a layer.
An exposure step for exposing the negative photosensitive resin composition layer and
A developing process for performing a developing process on the exposed photosensitive resin composition layer, and
A method for producing a cured film having. The method for producing a cured film according to claim 13, further comprising a heating step of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500 ° C. after the development treatment step. A semiconductor device having the cured film according to claim 11 or 12. A method for producing a laminate, which comprises the method for producing a cured film according to claim 13 or 14. A method for manufacturing a semiconductor device, which comprises the method for manufacturing a cured film according to claim 13 or 14. A polyimide precursor having a repeating unit represented by the formula (1), having a structure represented by the formula (2) at at least one end, and having a weight average molecular weight of 50,000 or less;
In the formula (1), X represents a group represented by -Ar-L-Ar- or a group represented by the formula (51), Ar is an independently aromatic group, and L is an aromatic group. , An aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO _2- or -NHCO-, and two or more of the above. Y represents a tetravalent organic group, and R ¹ and R ² are independently non-polymerizable organic groups having 1 to 4 carbon atoms;
(A) _l- L ^1- * (2)
In formula (2), A represents a polymerizable group, L ¹ represents a single bond or an l + 1 valent organic group, l represents an integer of 2 to 10, and * represents a binding site with another site;
Equation (51)
In formula (51), R ^{10 to} R ¹⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 10 to} R ¹⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. Is. The polyimide precursor according to claim 18, wherein the repeating unit represented by the formula (1) is contained in an amount of more than 90 mol% of all the repeating units. The polyimide precursor according to claim 18 or 19, wherein A in the formula (2) is a group containing a carbon-carbon unsaturated double bond. The polyimide precursor according to any one of claims 18 to 20, wherein l in the formula (2) is an integer of 2 to 5.