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

Abstract

This disclosure related to a polyimide precursor comprising composition that includes at least one resin; and at least one acyl germanium compound, as well as related processes, films, cured film structures, and articles such as laminates or semiconductors. Further, said precursor is a heterocycle-forming polymer precursor, wherein the heterocycle-forming polymer precursor is selected from a polyimide (PI) precursor comprising Formula (1).

Description

[0001] PHOTOSENSITIVE POLYIMIDE PRECURSOR COMPOSITION, CURED FILM, LAMINATE, METHOD FOR PRODUCING CURED FILM AND SEMICONDUCTOR DEVICE

[0002] FIELD OF THE DISCLOSURE

[0003] The present disclosure relates to polyimide precursor resin comprising formulations containing an acyl germanium compound, as well as related processes, films, dry film structures, and articles.

[0004] BACKGROUND OF THE DISCLOSURE

[0005] Polyimide precursor resin comprising formulations for redistribution layer application in semiconductor packaging are continuously evolving. The trend in electronic packaging continues to move towards faster processing speeds, increased complexity and higher packing density while maintaining a high level of reliability. As electronic packaging technology advances and chips continue to shrink in size, the demand for innovative and high-performance resin composition is growing. In order to cope with high resolution, various proposals have been made for a photosensitive polyimide precursor composition. A photoinitiator having high sensitivity in longer wavelengths may be beneficial in some cases when used in photosensitive composition using lamp or Laser Direct Imaging (LDI) technique.

[0006] SUMMARY OF THE DISCLOSURE

[0007] This disclosure is based on the unexpected discovery that certain acyl germanium compounds can be used as a photoinitiator or a photosensitizer in a photosensitive polyimide precursor comprising formulation or composition such that the composition can be developed at a relatively long UV wavelength to form a film. Long UV wavelengths include, but are not limited to: 375nm lasers, 405nm lasers, the output spectrum of a mercury-vapor lamps: 365nm (l-line), 405nm (H-line), 435nm (G-line). The term a polyimide precursor containing formulation (composition) refers to a formulation comprising a not fully imidized polyimide resin in this application. The acyl germanium compounds are non-toxic and can significantly improve the resolution of the film thus formed. This improved resolution directly improves the total exposure latitude (EL) for the material. Furthermore, the high efficiency of the acyl germanium compounds adds to the improved sensitivity. As such, the film thus formed can have excellent pattern shape and film hardness.

[0008] According to an aspect of the present invention there is provided a polyimide precursor comprising composition comprising: at least one resin, and at least one acyl germanium compound. Further, the at least one resin in the polyimide precursor comprising composition is the polyimide precursor itself. The polyimide precursor comprising composition is preferably a film forming composition. As used herein, the terms 'film-forming composition(s)' and 'polyimide precursor-comprising composition(s)' are interchangeable.

[0009] Advantageously, the polyimide precursor comprising composition described above may comprise a polyimide precursor selected from one or more compounds of formula (1),

[0010] Formula (1) wherein A1 and A2 each independently represent an oxygen atom or NH, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 each independently represent a hydrogen atom or a monovalent organic group.

[0011] Advantageously, the polyimide precursor being inherently a heterocycle-forming polymer precursor used in the above-described composition may comprise a compound of Formula (1).

[0012] In some embodiments, the polyimide precursor is a heterocycle-forming polymer precursor, wherein the heterocycle-forming polymer precursor is selected from a polyimide (PI) precursor comprising (a compound of) Formula (1):

[0013] Formula (1) wherein A1 and A2 each independently represent an oxygen atom or NH, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 each independently represent a hydrogen atom or a monovalent organic group.

[0014] Preferably, the divalent organic group R111 in Formula (1) is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, one or more aromatic group(s) having 6 to 20 carbon atoms, or a group composed of a combination thereof. In some embodiments, R115 in Formula (1) is selected from (X-1), (X-2), and (X-3). In some embodiments, R111 in Formula (1) is selected from (Y-1) and (Y-3). Further, in some embodiments R115 in Formula (1) can be selected from (X-1), (X-2) and (X-3), and R111 can be selected from (Y-1) and (Y-3).

[0015] In some embodiments, the polyimide precursor is heterocycle-forming precursor, wherein the heterocycle-forming precursor a heterocycle-forming polyimide precursor comprising a compound of Formula (1).

[0016] In some embodiments, the polyimide precursor of formula (1) comprises at least one methacryloyl alkyl group as side chain.

[0017] Advantageously, the acyl germanium compound in the above-described polyimide comprising composition, may comprise a compound of structure (I): structure (I) in which

[0018] R1is C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, or C6-C22 heteroaryl; each of R2, R3, and R4, independently, is C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, C6-C22 heteroaryl, or -C(O)R, in which R is C1-C4 alkyl, C5-C12 cycloalkyl, Ce-Cis aryl, or Ce- C18 heteroaryl; and each of alkyl, alkenyl, cycloalkyl, aryl, or heteroaryl, independently, is optionally substituted by at least one C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR5, -OC(O)R5, or -COOR5, where R5is H, Ci- 04 alkyl, C5-C12 cycloalkyl, Ce-Cis aryl, or Ce-Cis heteroaryl.

[0019] In some embodiments, the at least one acyl germanium compound is a diacylgermanium compound.

[0020] According to a further aspect of the present invention, there is provided a cured film that is obtained by curing the polyimide precursor comprising composition comprising: at least one resin (polyimide precursor), and at least one acyl germanium compound.

[0021] According to yet another aspect, the present invention provides the use of a polyimide precursor comprising composition, as described above or in any embodiment herein, for forming a cured film.

[0022] According to yet another aspect of the present invention, there is provided a laminate comprising: two or more layers consisting of the cured film obtained as described above; and a metal layer between any layers consisting of the cured film.

[0023] According to yet another aspect of the present invention, there is provided a manufacturing method for a cured film, comprising: a film forming step of applying the polyimide precursor comprising composition comprising at least one resin, and at least one acyl germanium compound onto a substrate to form a film; an exposure step of selectively exposing the film; and a development step of developing, by using a developer, the film exposed in the exposure step to form a pattern. In some embodiments, the above-described manufacturing method for a cured film, further comprises a heating step of heating the film at 50°C to 450°C.

[0024] In still another aspect of the present invention describes a semiconductor device comprising the cured film that is obtained by curing the polyimide precursor comprising composition comprising: at least one resin (polyimide precursor), and at least one acyl germanium compound, or the laminate comprising: two or more layers consisting of the cured film obtained as described above; and a metal layer between any layers consisting of the cured film.

[0025] In another aspect, the present invention describes the use of the polyimide precursor comprising composition comprising at least one resin, and at least one acyl germanium compound for forming a cured film.

[0026] DETAILED DESCRIPTION OF THE DISCLOSURE

[0027] In general, the present disclosure relates to film forming photosensitive polyimide precursor compositions, also referred to as polyimide precursor comprising composition. The film forming compositions described herein can be sensitive to electromagnetic or actinic radiation in the wavelength range from about 150 nm to 450 nm (e.g. 355nm, 365nm, 375nm, 405 nm, 435nm), electron beam, or X-ray, thereby resulting in solubility change (e.g., solubility increase or decrease) in a suitable developer (e.g., cyclopentanone).

[0028] The film forming composition (i.e. the polyimide precursor comprising composition) comprises the polyimide precursor itself as the resin compound and at least one acyl germanium compound.

[0029] Further, the polyimide precursor is preferably a heterocycle-forming polymer precursor that can undergo cyclization reaction to form the fully imidized polyimide structure.

[0030] In some embodiments, the present disclosure provides film forming compositions comprising at least one (e.g., two, three, or four) resin (e.g., a polyimide precursor polymer), and at least one (e.g., two, three, or four) acyl germanium compound according to structure (I), wherein R1is C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, or C6-C22 heteroaryl; each of R2, R3, R4, independently, is C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, C6-C22 heteroaryl, or -C(O)R, in which R is C1-C4 alkyl, C5-C12 cycloalkyl, Ce-Cis aryl, or Ce-Cis heteroaryl; and each of alkyl, alkenyl, cycloalkyl, aryl, or heteroaryl, independently, is optionally substituted by at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR5, - OC(O)R5, or -COOR5, where R5is H, C1-C4 alkyl, C5-C12 cycloalkyl, Ce-Cis aryl, or Ce-Cis heteroaryl. In some embodiments, the acyl germanium compounds described herein can include one acyl group (i.e. , monoacyl germanium compounds), two acyl groups (i.e. , diacyl germanium compounds), three acyl groups (i.e., triacyl germanium compounds), or four acyl groups (i.e., tetraacyl germanium compounds). In some embodiments the acyl germanium compound according to structure (I) may comprise non-identical acyl groups. In the preferred embodiment the germanium compound is a diacyl germanium compound wherein R2 = R1- C(O).

[0031] Examples of alkyl groups described herein include methyl, ethyl, propyl, isopropyl, and butyl. Examples of alkenyl groups described herein include vinyl and allyl. Examples of cycloalkyl groups described herein include cyclopentyl and cyclohexyl. Examples of aryl groups described herein include phenyl, naphthyl, pyrenyl, anthryl, and phenanthryl. Examples of heteroaryl groups described herein include furyl, furylene, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, quinazolinyl, quinolyl, isoquinolyl, and indolyl.

[0032] Suitable examples of the acyl germanium compounds of structure (I) include, but not limited to, (2,4,6-trimethylbenzoyl)triethylgermanium, (2,4,6- trimethylbenzoyl)tripropylgermanium, (2,4,6-trimethylbenzoyl)tributylgermanium, (2,6- dimethoxybenzoyl)triethylgermanium, (2.6-dimethoxybenzoyl)tripropylgermanium, (2,6- dimethoxybenzoyl)tributylgermanium, bisbenzoyldiethylgermanium, benzoyltrimethylgermanium, bisbenzoyldipropylgermanium, bis(4-methoxybenzoyl)diethylgermanium, bis(2,4,6- trimethylbenzoyl)diethylgermanium, trisbenzoylethylgermanium, tris(2,4,6- trimethylbenzoyl)ethylgermanium and the like. A commercial example of an acyl germanium compound is Ivocerin (i.e., bis(4-methoxybenzoyl) diethylgermanium). Commercial examples of these can be obtained by Synthon (e.g. Ivocerin). Other examples of such acyl germanium compounds are disclosed in, e.g., U.S. Patent Nos. 7,605,190 and 9,532,930, the entire contents of which are hereby incorporated by reference.

[0033] In some embodiments, the polyimide precursor comprising composition comprises at least one acyl germanium compound is selected from one or more of (2,4,6- trimethylbenzoyl)triethylgermanium, (2,4,6-trimethylbenzoyl)tripropylgermanium, (2,4,6- trimethylbenzoyl)tributylgermanium, (2,6-dimethoxybenzoyl)triethylgermanium, (2.6- dimethoxybenzoyl)tripropylgermanium, (2,6-dimethoxybenzoyl)tributylgermanium, bisbenzoyldiethylgermanium, benzoyltrimethylgermanium, bisbenzoyldipropylgermanium, bis(4- methoxybenzoyl)diethylgermanium, bis(2,4,6-trimethylbenzoyl)diethylgermanium, trisbenzoylethylgermanium, and tris(2,4,6-trimethylbenzoyl)ethylgermanium.

[0034] In some embodiments, the acyl germanium compound is in an amount of from at least about 0.05 wt% (e.g., at least about 0.1 wt%, at least about 0.2 wt%, at least about 0.4 wt%, at least about 0.5 wt%, at least about 0.6 wt%, at least about 0.8 wt%, at least about 1 wt%, at least about 1.5 wt%, or at least about 2 wt%) to at most about 20 wt% (e.g., at most about 18 wt%, at most about 16 wt%, at most about 15 wt%, at most about 14 wt%, at most about 12 wt%, at most about 10 wt%, at most about 8 wt%, at most about 6 wt%, at most about 5 wt%, at most about 4 wt%, at most about 2 wt%, or at most about 1 wt%) of the solid weight of a polyimide precursor comprising composition described herein. In the most preferred embodiment, the acyl germanium compound ranges from 0.05 wt% up to 5 wt% based on the solid weight of the polyimide precursor comprising composition. As used herein, the solid weight of a film forming composition refers to the total weight of the solids in such a composition (i.e. , without any solvent).

[0035] In some embodiments, the film forming compositions (i.e. polyimide precursor comprising compositions) described herein can optionally contain at least one (e.g., two, three, or four) radical initiator different from the acyl germanium described herein. As used herein, a radical initiator refers to a compound capable of generating free radicals that can initiate radical polymerization or crosslinking upon heating or irradiation with light at a certain wavelength range (e.g., from about 150 nm (e.g., about 157 nm) or about 600 nm). In some embodiments, the wavelength range is selected such that the radical initiator has absorption and the radically polymerizable monomer does not have substantial absorption. A photo-radical initiator (also referred to herein as a photoinitiator) and a thermal-radical initiator (also referred to herein as a thermal initiator) are examples of a radical initiator. In some embodiments, a photo-radical initiator is preferable.

[0036] In some embodiments, the amount of the radical initiator (e.g., a photoinitiator) is from at least about 0.1 wt% (e.g., at least about 0.2 wt%, at least about 0.5 wt%, at least about 0.8 wt%, at least about 1 wt%, at least about 1.5 wt%, at least about 2 wt%, at least about 3 wt%, at least about 4 wt%, or at least about 5 wt%) to at most about 10 wt% (e.g., at most about 9 wt%, at most about 8 wt%, at most about 7 wt%, at most about 6 wt%, at most about 5 wt%, at most about 4 wt%, at most about 3 wt%, at most about 2 wt%, or at most about 1 wt%) of the solid weight of a dielectric film forming composition described herein. In some embodiments, a photoinitiator has photosensitivity to rays ranging from an ultraviolet ray region to a visible region. In some embodiments, the photoinitiator can be an activator which produces a free radical by some action with a photo-excited sensitizer.

[0037] One example of a photoinitiator is an oxime ester of structure (II),

[0038] (II), wherein each of R11 and R12, independently, is substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C4-C18 cycloalkyl, substituted or unsubstituted C6-C22 aryl, or substituted or unsubstituted C6-C22 heteroaryl; and R13 is a UV absorbing functional group (e.g., a substituted or unsubstituted C6-C22 aryl or a substituted or unsubstituted C6-C22 heteroaryl). In some embodiments, the alkyl, cycloalkyl, aryl, or heteroaryl described above is optionally substituted by at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR’, -OC(O)R’, or -COOR’, where R’ is H, C1-C4 alkyl, C5-C12 cycloalkyl, C6-C18 aryl, or C6- C18 heteroaryl.

[0039] Examples of oxime esters of formula (II) include, but are not limited to:

[0040] Commercial examples of photoinitiators include, but are not limited to, IRGACURE-784, IRGACURE OXE 01 , IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, and IRGACURE OXE 05 available from BASF; ADEKA OPTOMER N-1919, ADEKA ARKLS NCI- 831, and ADEKA ARKLS NCI-930 available from ADEKA Corporation. Examples of other photoinitiators are disclosed in, e.g., EP patent numbers 3,492, 982, the entire contents of which are hereby incorporated by reference.

[0041] Examples of thermal initiators include, but are not limited to, benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, tert-amyl peroxy benzoate, tert-butyl hydroperoxide, di(tert-butyl)peroxide, dicumyl peroxide, cumene hydroperoxide, succinic acid peroxide, di(n- propyl)peroxydicarbonate, 2,2-azobis(isobutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobisisobutyrate, 4,4-azobis(4-cyanopentanoic acid), azobiscyclohexanecarbonitrile, 2,2-azobis(2-methylbutyronitrile) and the like. Other examples of radical photopolymerization initiators include benzophenone derivatives such as benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyl diphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'- diethoxyacetophenone, 2-hydroxy-2-methyl propiophenone, 1 -hydroxy cyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2- isopropylthioxanthone, diethylthioxanthone, and the like; benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-beta-methoxyethyl acetal and the like; benzoin derivatives such as benzoin, benzoin methyl ether and the like; benzoin derivatives such as benzoin, benzoin methyl ether and the like; 1 -phenyl- 1,2-butanedione-2-(o-methoxycarbonyl) oxime, 1-phenyl- 1 ,2-propanedione-2-(o-methoxycarbonyl) oxime, 1-phenyl-1 ,2-propanedione-2-(o- ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl) oxime, oximes such as 3- diphenylpropanetrione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2-(o- benzoyl) oxime; N-arylglycines such as N-phenylglycine, peroxides such as benzoyl peroxide, aromatic biimidazoles, and the like. Furthermore, these may be used alone or as a mixture of 2 or more types.

[0042] In some embodiments, the film forming compositions described herein can include at least one (e.g., two, three, or four) photosensitizer different from the acyl germanium compound, where the photosensitizer can absorb light in the wavelength range of from about 150 nm to about 600 nm (e.g., at about 405 nm). Examples of suitable photosensitizers that can be used in the dielectric film forming composition include benzophenone compounds, thioxanthone compounds, anthraquinone compounds, anthracene compounds, coumarine compounds, and mixtures thereof. Specific examples of photosensitizers include, but are not limited to, 9- methylanthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, anthracenemethanol, acenaphthylene, thioxanthone, methyl-2-naphthyl ketone, 4-acetylbiphenyl, and 1,2- benzofluorene. Examples of other photosensitizers are disclosed in, e.g., U.S. Application Publication No. 2022 / 0171285, the entire contents of which are hereby incorporated by reference. In some embodiments, the acyl germanium compounds described herein can serve as a photosensitizer.

[0043] In some embodiments, the amount of a photosensitizer other than an acyl germanium compound is from at least about 0.01 wt% (e.g., at least about 0.05 wt%, at least about 0.1 wt%, or at least about 0.5 wt%) to at most about 1 wt% (e.g., at most about 0.8 wt%, at most about 0.6 wt%, at most about 0.5 wt%, at most about 0.4 wt%, at most about 0.2 wt%, or at most about 0.1 wt%) of the solid weight of a dielectric film forming composition described herein. The polyimide precursor may preferably comprise at least one compound of Formula (1):

[0044] , Formula (1) wherein A1 and A2 each independently represent an oxygen atom or NH, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 each independently represent a hydrogen atom or a monovalent organic group.

[0045] In some embodiments, the polyimide precursor of the present invention is a heterocycleforming polymer precursor wherein the heterocycle-forming polymer precursor is selected from a polyimide (PI) precursor comprising Formula (1):

[0046] Formula (1) wherein A1 and A2 each independently represent an oxygen atom or NH, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 each independently represent a hydrogen atom or a monovalent organic group. The polyimide precursor (PI) described above is to be understood as the compound represented by Formula (1), The terms 'heterocycle-forming polymer precursor' or “heterocyclic ring-forming polymer precursor” as used herein is to be understood as referring specifically to the polyimide precursor, that is not fully imidized (partially imidized form) and forms imide heterocyclic rings upon further reaction (or in other words a polymer containing imide-forming units but not fully cyclized in its initial form). The terms “heterocycle-forming polymer precursor” and “heterocyclic ring-forming polymer precursor” are used herein interchangeably.

[0047] In Formula (1), A1 and A2 are preferably an oxygen atom or NH, and more preferably an oxygen atom.

[0048] In formula (1) preferably R113 and R114 each independently represent a polymerizable group and preferably A1 and / or A2 represent oxygen where A1 and / or A2 are attached to preferably a methacryloyl alkyl group and even more preferred both A1 and A2 are attached to a methacryloyl alkyl group. In the most preferred embodiment R113 and R114 are given by the following structure (IV).

[0049] Structure (IV)

[0050] R111 in Formula (1) represents a divalent organic group. As the divalent organic group, a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group are exemplified. The divalent organic group is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, one or more aromatic group(s) having 6 to 20 carbon atoms, or a group composed of a combination thereof, and is more preferably a group composed of an aromatic group having 6 to 20 carbon atoms.

[0051] R 111 is preferably derived from diamine. As the diamine used for producing the polyimide precursor, linear or branched aliphatic, cyclic aliphatic, or aromatic diamine, or the like is mentioned. For the diamine, only one type may be used, or two or more types may be used.

[0052] Specifically, diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and diamine containing a group composed of an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of the aromatic group include the following.

[0053]

[0054] R 111 is preferably at least one structure represented by any of the following formula (Y- 1) and formula (Y-3).

[0055] In the formulas, A is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHCO-, and a combination thereof, more preferably a single bond, or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, and -SO2-, and even more preferably a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, and - C(CH3)2-. As the diamine, specifically, at least one diamine selected from 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 isophorone diamine; meta- and paraphenylene diamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether,3,3-diaminodiphenyl ether, 4,4'- and 3,3'- diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 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, 3,3'-dimethoxy-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]sulfone, 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-aminophenoxy)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'- diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4- aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-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'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylene diamine, acetoguanamine, 2, 3,5,6- tetramethyl-paraphenylene diamine, 2,4,6-trimethyl-metaphenylene diamine, bis(3- aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1 ,2-bis(4- aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5- diaminonaphthalene, diaminobenzotrifluoride, 1 ,3-bis(4-aminophenyl)hexafluoropropane, 1,4- bis(4-aminophenyl)octafluorobutane, 1 ,5-bis(4-aminophenyl)decafluoropentane, 1 ,7-bis(4- aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5- dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-amino phenoxy)-3,5 -bis(trifluoromethyl)phenyl] hexafluoropropane, parabis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2- trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4- amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5- trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3- trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, 4-(4-{2-[4-(4- aminophenoxy)phenyl]propan-2-yl} phenoxy)aniline and 4,4'-diaminoquaterphenyl is mentioned.

[0056] In addition, diamines (DA-1) to (DA- 18) as shown below are also preferable.

[0057]

[0058] In addition, as preferable examples of the diamine, diamines having at least two alkylene glycol units in a main chain are also mentioned. Diamines containing two or more in total of either or both of ethylene glycol chain and propylene glycol chain in one molecule are preferable, and diamines containing no aromatic ring are more preferable. As specific examples thereof, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED- 600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, D- 200, D-400, D-2000, D-4000 (all trade names, manufactured by Huntsman Corporation), 1-(2-

[0059] (2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amino, and 1-(1-(1-(2-aminopropoxy)propan-2- yl)oxy)propane-2-amine are mentioned, but not limited thereto.

[0060] Structures of JEFFAMINE (registered trademark) KH-511 , JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176 are shown below.

[0061] In the above, x, y, z are average values.

[0062] From the viewpoint of flexibility of the resulting cured film, R111 is preferably represented by -Ar-L-Ar-, where Ar's each independently represent an aromatic group, and L represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of a combination of two or more thereof. Ar is preferably a phenylene group, and L is more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group herein is preferably an alkylene group.

[0063] From the viewpoint of i-ray transmittance, R 111 is preferably a divalent organic group represented by Formula (51) or Formula (61). Especially from the viewpoint of i-ray transmittance and ease of availability, a divalent organic group represented by Formula (61) is more preferable.

[0064] Formula (51 ) In Formula (51), R10 to R17 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R10, ..., or R17 represents a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

[0065] As the monovalent organic group in R10 to R17, an unsubstituted alkyl group having 1 to 10 (preferably 1 to 6) carbon atoms, a fluorinated alkyl group having 1 to 10 (preferably 1 to 6) carbon atoms, and the like are mentioned.

[0066] In Formula (61), R18 and R19 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group. As a diamine compound that forms a structure of Formula (51) or (61), dimethyl-4,41- diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'- diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like are mentioned. One type of these may be used, or two or more types thereof may be used in combination.

[0067] R115 in Formula (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by Formula (5) or Formula (6) is more preferable.

[0068] Formula (5)

[0069] In Formula (5), R112 is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, -NHCO-, and a combination thereof, more preferably a single bond, or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO2-, and even more preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0070] R115 in Formula (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing the structure represented by any one of the formula (X-1) to formula (X-3) is preferable:

[0071] As the tetravalent organic group represented by R115 in Formula (1), specifically, a tetracarboxylic acid residue that remains after removing an acid dianhydride group from tetracarboxylic acid dianhydride is mentioned. For the tetracarboxylic acid dianhydride, only one type may be used, or two or more types may be used. The tetracarboxylic acid dianhydride is preferably a compound represented by Formula (O).

[0072] Formula (())

[0073] In Formula (O), R115 represents a tetravalent organic group. R115 has the same meaning as R115 in Formula (1).

[0074] As specific examples of the tetracarboxylic acid dianhydride, at least one selected from pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic acid dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2, 3,3', 4'- benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2, 3,6,7- naphthalene tetracarboxylic acid dianhydride, 1 ,4,5,7-naphthalene tetracarboxylic acid 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 acid dianhydride, 1, 4,5,6- naphthalene tetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyl tetracarboxylic acid dianhydride, 3,4,9, 10-perylene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 1,8,9,10-phenanthrene tetracarboxylic acid dianhydride, 1,1 -bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4- dicarboxyphenyl)ethane dianhydride, 5-[4-(2-{4-[(1 ,3-dioxo-2-benzofuran-5- yl)oxy]phenyl}propan-2-yl)phenoxy]-2-benzofuran-1 ,3-dione, 1 ,2,3,4-benzene tetracarboxylic acid dianhydride, or alkyl derivatives having 1 to 6 carbon atoms and / or alkoxy derivatives having 1 to 6 carbon atoms thereof are exemplified.

[0075] In addition, tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) as shown below are also mentioned as preferable examples.

[0076] R113 and R114 each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R113 or R114 contains a radically polymerizable group, and it is more preferable that both of R113 and R114 contain a radically polymerizable group. The radically polymerizable group is a group capable of undergoing a crosslinking reaction by an action of a radical, and preferable examples thereof include a group having an ethylenically unsaturated bond.

[0077] As the group having an ethylenically unsaturated bond, a vinyl group, a (meth)allyl group, a group represented by Formula (III), and the like are mentioned.

[0078] In Formula (III), R200 represents a hydrogen atom or a methyl group, with a methyl group is more preferable.

[0079] In Formula (III), R201 represents an alkylene group having 2 to 12 carbon atoms, - CH2CH(OH)CH2-, or a polyoxyalkylene group having 4 to 30 carbon atoms.

[0080] Suitable examples of R201 include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, and -CH2CH(OH)CH2-, with an ethylene group, a propylene group, a trimethylene group, and -CH2CH(OH)CH2- being even more preferable. Particularly preferably, R200 is a methyl group, and R201 is an ethylene group.

[0081] As the monovalent organic group represented by R113 or R114, a substituent that improves solubility of a developer is preferably used.

[0082] From the viewpoint of solubility in an aqueous developer, R113 or R114 may be a hydrogen atom or a monovalent organic group. As the monovalent organic group, an aromatic group, an aralkyl group, and the like which have 1 , 2, or 3 acidic groups, preferably 1 acidic group, bonded to carbon atoms constituting an aryl group are mentioned. Specifically, an aromatic group having 6 to 20 carbon atoms which has an acidic group and an aralkyl group having 7 to 25 carbon atoms which has an acidic group are mentioned. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are mentioned. The acidic group is preferably an OH group.

[0083] R113 or R114 is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

[0084] From the viewpoint of solubility in an organic solvent, R113 or R114 is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

[0085] The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched, or cyclic. As the linear or branched alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 1 -ethylpentyl group, and a 2-ethylhexyl group are mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As the monocyclic cyclic alkyl group, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned. As the polycyclic cyclic alkyl group, for example, an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group are mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of compatibility with high sensitivity. In addition, the alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group as described later. As the aromatic group, specifically, a substituted or unsubstituted benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, or a phenazine ring is mentioned. A benzene ring is most preferable.

[0086] In Formula (1), in a case where R113 is a hydrogen atom, or in a case where R114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. As an example of such a tertiary amine compound having an ethylenically unsaturated bond, N,N-dimethylaminopropyl methacrylate is mentioned.

[0087] In addition, it is also preferable that the polyimide precursor has a fluorine atom in a structural unit. A content of fluorine atoms in the polyimide precursor is preferably 10% by mass or higher, and more preferably 20% by mass or lower.

[0088] In addition, for the purpose of improving adhesiveness to a substrate, an aliphatic group having a siloxane structure may be copolymerized. Specifically, as the diamine component, bis(3-aminopropyl) tetramethyldisiloxane, bis(paraaminophenyl)octamethyl pentasiloxane, and the like are mentioned.

[0089] The polyimide precursor may have one type of the repeating structural units represented by Formula (1) and may have two or more types thereof. In addition, the polyimide precursor may contain a structural isomer of the repeating unit represented by Formula (1). In addition, the polyimide precursor may also contain another type of repeating structural unit in addition to the repeating unit of Formula (1).

[0090] As one embodiment of the polyimide precursor in the present invention, polyimide precursors in which the repeating unit represented by Formula (1) accounts for 50% by mol or higher, even 70% by mol or higher, and especially 90% by mol or higher in an entirety of the repeating units are exemplified. A weight-average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. In addition, a number average molecular weight (Mn) thereof is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0091] A degree of dispersion of the polyimide precursor is preferably 1.5 to 2.5.

[0092] The polyimide precursor is obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. Preferably, the polyimide precursor is obtained by halogenating dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent, and then causing the resultant to be reacted with diamine.

[0093] In a method for producing the polyimide precursor, it is preferable to use an organic solvent at the time of reaction. For the organic solvent, one type may be used, or two or more types may be used.

[0094] The organic solvent can be appropriately determined according to raw materials, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone are exemplified.

[0095] At the time of producing the polyimide precursor, to further improve storage stability, it is preferable to perform sealing with a terminal sealing agent such as acid dianhydride, monocarboxylic acid, a mono-acid chloride compound, and a mono-active ester compound. Among these, it is even more preferable to use monoamine. As preferable compounds of the monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8- hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1 -hydroxy- 5- aminonaphthalene, 1 -hydro xy-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 -amino naphthalene, 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-aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like are mentioned. Two or more types of these may be used, or a plurality of different terminal groups may be introduced by applying a plurality of terminal sealing agents for reaction.

[0096] At the time of producing the polyimide precursor, a step of precipitating a solid may be included. Specifically, it is possible to precipitate a solid by causing the polyimide precursor in a reaction solution to be sedimented in water and causing the sedimented polyimide precursor to be dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble.

[0097] Thereafter, the polyimide precursor can be dried to obtain a powdery polyimide precursor.

[0098] The composition of the present invention may contain a thermal-base generator. By using the thermal-base generator, it is possible to suppress exposure energy consumption and to expand exposure latitude, and it is also possible to generate base species that promote a ring closure reaction of the heterocyclic ring-forming polymer precursor during a heating step of performing the ring closure reaction. Thus, a ring closure rate tends to be further improved.

[0099] As the thermal-base generator, a type and the like thereof are not particularly specified, and the thermal-base generator preferably includes a thermal-base generator that contains at least one selected from an acidic compound which generates a base in a case of being heated to 40°C or higher, or an ammonium salt which has an anion having pKa1 of 0 to 4 and an ammonium cation. Here, pKa1 represents logarithm (-LoglOKa) of a reciprocal of a dissociation constant (Ka) of a first proton of an acid, and details thereof will be described later.

[0100] The acidic compound (AC1) and the ammonium salt (AM2) generate a base in a case of being heated. Thus, the base generated from these compounds makes it possible to promote a cyclization reaction of the heterocyclic ring-forming polymer precursor and makes it possible to cause cyclization of the heterocyclic ring-forming polymer precursor to be carried out at a low temperature. In addition, even in a case where these compounds are caused to coexist with a polyimide precursor or the like which is cyclized by a base and cured, cyclization of the heterocyclic ring-forming polymer precursor hardly proceeds unless heated, so that a composition having excellent storage stability can be prepared.

[0101] In the present specification, the acidic compound means a compound having a pH value of less than 7 as measured at 20°C using a pH (power of hydrogen) meter for a solution obtained in such a manner that 1 g of the compound is collected in a container, 50 mL of a mixed liquid of ion-exchanged water and tetra hydrofuran (mass ratio is water / tetrahydrofuran = 1 / 4) is added thereto, and the mixture is stirred at room temperature for 1 hour.

[0102] In the present embodiment, a base generation temperature of the acidic compound (AC1) and the ammonium salt (AM2) is preferably 40°C or higher, and more preferably 120°C to 200°C. An 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. A lower limit of the base generation temperature is preferably 130°C or higher, and more preferably 135°C or higher.

[0103] In a case where the base generation temperature of the acidic compound (AC1) and the ammonium salt (AM2) is 120°C or higher, a base is hardly generated during storage, so that a composition which is excellent in stability can be prepared. In a case where the base generation temperature of the acidic compound (AC1) and the ammonium salt (AM2) is 200°C or lower, a cyclization temperature of the heterocyclic ring-forming polymer precursor can be decreased. For example, the base generation temperature may be measured, for example, using differential scanning calorimetry by heating a compound to 250°C at a rate of 5°C / minute in a pressure-resistant capsule, reading a peak temperature of an exothermic peak having the lowest temperature, and taking the peak temperature as a base generation temperature.

[0104] In the present embodiment, a 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 has high basicity, a cyclization temperature of the polyimide precursor can be further decreased. In addition, a 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. In addition, a molecular weight of the generated base is preferably 80 to 2,000. A lower limit thereof is more preferably 100 or higher. An upper limit thereof is more preferably 500 or lower. A value of the molecular weight is a theoretical value obtained from a structural formula.

[0105] In the present embodiment, the acidic compound (AC1) preferably contains at least one selected from an ammonium salt or a compound having an ammonium structure represented by Formula (101) or (102).

[0106] In the present embodiment, the ammonium salt (AM2) is preferably an acidic compound. The ammonium salt (AM2) may be a compound containing an acidic compound which generates a base in a case of being heated to 40°C or higher (preferably 120°C to 200°C) or may be a compound other than the acidic compound which generates a base in a case of being heated to 40°C or higher (preferably 120°C to 200°C).

[0107] In the present embodiment, the ammonium salt means a salt of an ammonium cation represented by Formula (101) or Formula (102) with an anion. The anion may be bonded via a covalent bond to any portion of the ammonium cation or may also be present outside a molecule of the ammonium cation. The anion is preferably present outside a molecule of the ammonium cation. The expression of the anion being present outside the molecule of the ammonium cation refers to a case where the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, an anion outside a molecule of a cation moiety is also referred to as a counter anion.

[0108] Formula (101) Formula ( 102)

[0109] In Formulas (101) and (102), R1 to R6 each independently represent a hydrogen atom or a hydrocarbon group, and R7 represents a hydrocarbon group. R1 and R2, R3 and R4, R5 and R6, or R5 and R7 in Formulas (101) and (102) may be bonded to each other to form a ring.

[0110] The ammonium cation is preferably represented by any one of Formulas (Y1-1) to (Y1- 5).

[0111]

[0112] In Formulas (Y1-1) to (Y1-5), R101 represents an n-valent organic group, and R1 and R7 have the same meanings as R1 and R7 in Formula (101) or Formula (102).

[0113] In Formulas (Y1-1) to (Y1-4), Ar101 and Ar102 each independently represent an aryl group, n represents an integer of 1 or higher, and m represents an integer of 0 to 5.

[0114] In the present embodiment, the ammonium salt preferably has an anion having pKa1 of 0 to 4 and an ammonium cation. An upper limit of the pKa1 of the anion is more preferably 3.5 or lower, and even more preferably 3.2 or lower. A lower limit thereof is preferably 0.5 or higher, and more preferably 1.0 or higher. In a case where the pKa1 of the anion is within the above- mentioned range, the heterocyclic ring-forming polymer precursor (e.g. polyimide precursor) can be cyclized at a lower temperature, and stability of the composition can also be improved. In a case where the pKa1 is 4 or lower, good stability of the thermal-base generator can be exhibited and generation of a base can be suppressed in the absence of heating, so that the composition exhibits good stability. In a case where the pKa1 is 0 or higher, the generated base is hardly neutralized, and cyclization efficiency of the heterocyclic ring-forming polymer precursor or the like is good.

[0115] A type of the anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is even more preferable for the reason that both salt stability and thermal decomposability are achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation with a carboxylate anion.

[0116] The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to the present embodiment, it is possible to use a thermal-base generator which can further improve stability, curability, and developability of the composition. Especially by using an anion of a divalent carboxylic acid, stability, curability, and developability of the composition can be further improved.

[0117] In the present embodiment, the carboxylate anion is preferably an anion of a carboxylic acid having pKa1 of 4 or lower. The pKa1 is more preferably 3.5 or lower, and even more preferably 3.2 or lower. According to this embodiment, stability of the composition can be further improved.

[0118] Here, the pKa1 represents logarithm of a reciprocal of a dissociation constant of a first proton of an acid and reference can be made to the values described in Determination of Organic Structures by Physical Methods (written by Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; edited by Braude, E. A., Nachod, F. C.; and Academic Press, New York, 1955), or Data for Biochemical Research (written by Dawson, R. M. C. et al.; and Oxford, Clarendon Press, 1959). For compounds which are not described in these documents, values calculated from structural formulas using a software ACD / pKa (manufactured by ACD / Labs) are used.

[0119] The carboxylate anion is preferably represented by Formula (XI).

[0120] Formula (XI)

[0121] In Formula (XI), EWG represents an electron withdrawing group.

[0122] In the present embodiment, the electron withdrawing group means a group in which a Hammett's substituent constant om shows a positive value. Here, the om is described in detail in the review by TSLINO Yuho, Journal of the Society of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), pp. 631 to 642. The electron withdrawing group in the present embodiment is not limited to the substituents described in the document.

[0123] As examples of a substituent having a positive value of om, a CF3 group (om = 0.43), a CF3CO group (om = 0.63), an HC=C group (om = 0.21), a CH2=CH group (om = 0.06), an Ac group (om = 0.38), a MeOCO group (om = 0.37), a MeCH group (om = 0.21), a PhCO group (om = 0.34), and H2NCOCH2 group (om = 0.06) are mentioned. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same applies).

[0124] EWG is preferably a group represented by Formulas (EWG-1) to (EWG-6). ) (E (EWG-5)

[0125] (EWG-1 WG-2) (EWG-4)

[0126] (EWG-3) (EWG-6)

[0127] In Formulas (EWG-1) to (EWG-6), Rx1 to Rx3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.

[0128] In the present embodiment, the carboxylate anion is preferably represented by Formula

[0129] (XA).

[0130] Formula ( A)

[0131] In Formula (XA), L10 represents a single bond, or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, -NRX-, and a combination thereof, and RX represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. As specific examples of the carboxylate anion, a maleate anion, a phthalate anion, an N- phenyliminodiacetate anion, and an oxalate anion are mentioned.

[0132] As specific examples of the thermal-base generator, the following compounds can be mentioned.

[0133]

[0134] In a case where the composition of the present invention contains the thermal-base generator, a content of the thermal-base generator is preferably 0.1% to 50% by mass with respect to a total solid content of the composition of the present invention. A lower limit thereof is more preferably 0.5% by mass or higher, more preferably 0.85% by mass or higher, and even more preferably 1% by mass or higher. An upper limit thereof is more preferably 30% by mass or lower, more preferably 20% by mass or lower, and even more preferably 10% by mass or lower. The upper limit may be 5% by mass or lower, or 4% by mass or lower. For the thermal-base generator, one type or two or more types may be used. In a case where two or more types are used, a total amount is preferably within the above-mentioned range.

[0135] The composition of the present invention may contain an organic compound (hereinafter referred to as "organotitanium compound or the like" in some cases) containing a Group 4 element.

[0136] The organic compound containing a Group 4 element is preferably an organic compound containing at least one selected from a titanium atom, a zirconium atom, or a hafnium atom, and more preferably an organic compound containing at least one selected from a titanium atom or a zirconium atom. In addition, the organic compound containing at least one selected from a titanium atom or a zirconium atom is preferably a compound containing an organic group and a titanium atom or a zirconium atom, with the number of the titanium atom and the zirconium atom in one molecule being preferably one in total. The organic group is not particularly specified, and is preferably a hydrocarbon group, or a group composed of a combination of a hydrocarbon group and a hetero atom. The hetero atom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom.

[0137] In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two thereof are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably selected from a 5-membered cyclic group. As the 5-membered cyclic group, a cyclopentadienyl group is preferable. In addition, the organotitanium compound or the like used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

[0138] The organotitanium compound or the like in the present invention is preferably represented by Formula (P). f i.r ni.i ( lJJ

[0139] In Formula (P), M is a Group 4 element, and R's are each independently a substituent. The substituent is preferably selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

[0140] As the Group 4 element represented by M, a titanium atom, a zirconium atom, and a hafnium atom are preferable, and a titanium atom and a zirconium atom are even more preferable.

[0141] As the aromatic group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like are mentioned. As the alkyl group, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2- methylhexyl group, a cyclopentyl group, and the like are mentioned.

[0142] As the halogen atom, F, Cl, Br, and I are mentioned.

[0143] As an alkyl chain constituting the alkylsulfonyloxy group, a methyl chain, an ethyl chain, a propyl chain, an octyl chain, an isopropyl chain, a t-butyl chain, an isopentyl chain, a 2- ethylhexyl chain, a 2-methylhexyl chain, a cyclopentyl chain, and the like are mentioned.

[0144] The above substituent may further have a substituent. As examples of the substituent, a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxylcarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, and the like are mentioned.

[0145] The organic compound containing a Group 4 element used in the present invention is preferably selected from a titanocene compound, a tetraalkoxytitanium compound, a titanium acylate compound, a titanium chelate compound, a zirconocene compound, and a hafhocene compound, more preferably selected from a titanocene compound, a zirconocene compound, and a hafnocene compound, and even more preferably selected from a titanocene compound and a zirconocene compound.

[0146] A molecular weight of the organotitanium compound or the like is preferably 50 to 2,000, and more preferably 100 to 1,000.

[0147] As specific examples of the organotitanium compound or the like, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, and the following compounds are exemplified.

[0148] In addition, among the organotitanium compounds or the like, the following compounds can be used as an organic compound containing a titanium atom: di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl- Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1 -yl, di-cyclopentadienyl-Ti-2,6-difluorophenyl-1- yl, di-cyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6- pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di- methylcyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, bis(cyclopentadienyl)bis(2,6-difluoro-3- (pyrr-1-yl)phenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (methylsulfoneamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbiaroyl- amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- ethylacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- methylacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- ethylpropionylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(2,2- dimethylbutanoyl)amino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2- dimethylbutanoyl)amino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-pentyl-(2,2- dimethylbutanoyl)amino)phenyl]titani urn, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl)-(2,2- dimethylbutanoyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- methylbutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- methylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- ethylcyclohexylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- ethylisobutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- ethylacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2,5,5-tetramethyl-1 ,2,5-azadipyrolidin-1- yl)phenyl] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(octylsulfoneamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-tolylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)[2,6-difluoro-3-(4-dodecylphenylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-(1-pentylheptyl)phenylsulfonylamido)phenyl]titani um, bis(cyclopentadienyl)bis[2,6-difluoro-3-(ethylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-((4-bromophenyl)-sulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-naphthylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(hexadecylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methyl-(4-dodecylphenyl)sulfonylamido)phenyl]tit anium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methyl-4-(1- pentylheptyl)phenyl)sulfonylamido)]ti tanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4- tolyl)-sulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(pyrrolidine-2,5-dion- 1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,4-dimethyl-3-pyrrolidine-2,5-dion- 1-yl)phenyl]titan ium, bis(cyclopentadienyl)bis(2,6-difluoro-3-(phthalimido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(isobutoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(ethoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-((2-chloroethoxy)-carbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phenoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylthioureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-butylthioureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-butylureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N,N-diacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,3-dimethylureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(acetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(butyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis2,6-difluoro-3-(decanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(octadecanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(isobutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethylhexanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-methylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(pivaloylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethyl-2-methylheptanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(cyclohexylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3-chloropropanoylamino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylpropanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-chloromethyl-2-methyl-3-chloropropanoylamino)p henyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,4-xyloylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-ethylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,4,6-mesitylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-ethylheptyl)-2,2-dimethylpentanoylamino)phen yl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethylpivaloylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxolan-2-ylmethyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-ethylheptyl)-2,2-dimethylbutanoylamino)pheny l]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl-(4- toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxoran-2-ylmethyl)-(4- toluyl)amino)phenyl]titani um, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4- toluylmethyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4- toluylmethyl)-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- butylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2,4-dimethylpentyl)-2,2-dimethylbutanoylamino) phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,4-dimethylpentyl)-2,2- dimethylpentanoylamino)ph enyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-((4- toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2- dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3- ethoxypropanoylamino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3- allyloxypropanoylamino)phenyl]titan ium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- allylacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2- ethylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- cyclohexylmethylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- cyclohexylmethyl-(4-toluyl)amino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2- ethylhexyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- isopropylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3- phenylpropyl)-2,2-dimethylpentanoyl)amino)ph enyl]titanium, bis(cyclopentadienyl)bis[2,6- difluoro-3-(N-hexylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- cyclohexylmethyl-2,2-dimethylpentanoyl)amino)p henyl]titanium, bis(cyclopentadienyl)bis[2,6- difluoro-3-(N-butylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2- ethylhexyl)-2,2-dimethylpentanoyl)amino)phen yl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(N-hexyl-2,2-dimethylpentanoylamino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3- (N-isopropyl-2,2-dimethylpentanoylamino)phenyl]tita nium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(N-(3-phenylpropyl)pivaloylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- butyl-2,2-dimethylpentanoylamino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- (2-methoxyethyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- benzylbenzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-(4- toluyl)amino)phenyl]titanium,

[0149] Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-(4-toluyl)amino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-methylphenylmethyl)-2,2-dimethylpentanoylam ino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-2,2- dimethylpentanoylamino)ph enyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- cyclohexylmethyl-(2-ethyl-2-methylheptanoyl)ami no)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(2-ethyl-2-methylbutanoyl)amino)phenyl]tit anium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexyl-2,2- dimethylpentanoyl)amino)phenyl]t itanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxoran-2- ylmethyl)-2,2-dimethylpentanoyl)amino )phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (N-cyclohexyl-(4-chlorobenzoyl)amino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3- (N-cyclohexyl-(2-chlorobenzoyl)amino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3- (3,3-dimethyl-2-azetidinon-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- isocyanatophenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(4- tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4- tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4- tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4- tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2- dimethyl-3-chloropropanoyl)amino)phe nyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- (3-phenylpropanoyl)-2,2-dimethyl-3-chloropropan oyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2,2-dimethyl-3-chloropropanoy l)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(2,2-dimethyl-3- chloropropanoyl)phenyl]t itanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2- chloromethyl-2-methyl-3-chloropropanoy l)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6- difluoro-3-(butylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (phenylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- isocyanatophenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(4- tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4- tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4- tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4- tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2- dimethyl-3-chloropropanoyl)amino)phe nyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropanoyl)-2,2-dimethyl-3- chloropropan oyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- cyclohexylmethyl-(2,2-dimethyl-3-chloropropanoy l)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(2,2-dimethyl-3-chloropropanoyl)phenyl]t itanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2-chloromethyl-2-methyl-3- chloropropanoy l)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (butylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (phenylthiocarbonylamino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N- hexyl-2,2-dimethylbutanoyl)amino)phenyl]t itanium, bis(methylcyclopentadienyl)bis[2,6-difluoro- 3-(N-hexyl-2,2-dimethylpentanoylamino)phenyl] titanium, bis(methylcyclopentadienyl)bis[2,6- difluoro-3-(N-ethylacetylamino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N- ethylpropionylamino)phenyl]titanium, bis(trimethylcyclopentadienyl)bis[2,6-difluoro-3-(N-butyl- 2,2-dimethylpropanoylamino)phen yl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2- methoxyethyl)-trimethylsilylamino)phenyl]titan ium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- butylhexyldimethylsilylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl- (1 , 1 ,2,-trimethylpropyl)dimethylsilylamino)p henyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(3-ethoxymethyl-3-methyl-2-azethiodinon-1-yl)pheny l]titanium, bis(cyclopentadienyl)bis[2,6- difluoro-3-(3-allyloxymethyl-3-methyl-2-azethidmon-1-yl)pheny l]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-chloromethyl-3-methyl-2-azetidmon-1-yl)phenyl]ti tanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-2,2- dimethylpropanoylamino)phenyl]titani urn, bis(cyclopentadienyl)bis[2,6-difluoro-3-(5,5-dimethyl- 2-pyrrolidinon-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(6,6-diphenyl-2- piperidinon-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2,3-dihydro-1 ,2- benzothiazol-3-on(1 ,1-dioxido)-2 -yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- hexyl-(4-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(2-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isopropyl-(4-chlorobenzoyl)amino)phenyl]titaniu m, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-methylphenylmethyl)-(4-chlorobenzoyl)amino) phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-methylphenylmethyl)-(2- chlorobenzoyl)amino) phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4- chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-2,2- dimethylpentanoylamino)phenyl]titani um, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2- ethylhexyl)-4-tolyl-sulfonyl)amino)phenyl]titan ium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3- oxaheptyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,6- dioxadecyl)benzoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (trifluoromethylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (trifluoroacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2- chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4- chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,6- dioxadecyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(N-(3,7-dimethyl-7-methoxyoctyl)benzoylamino)phen yl]titanium, bis(cyclopentadienyl)bis[2,6- difluoro-3-(N-cyclohexylbenzoylamino)phenyl]titanium, and the like.

[0150] In addition, among the organotitanium compounds or the like, the following compounds can also be used as the organic compound containing a zirconium atom or the compound containing a hafnium atom: (cyclopentadienyl)trimethyl zirconium, (cyclopentadienyl)triphenyl zirconium, (cyclopentadienyl)tribenzyl zirconium, (cyclopentadienyl)trichloro zirconium, (cyclopentadienyl)trimethoxy zirconium, (cyclopentadienyl)dimethyl(methoxy) zirconium, (cyclopentadienyl)methyldichloro zirconium, (methylcyclopentadienyl)trimethyl zirconium, (methylcyclopentadienyl)triphenyl zirconium, (methylcyclopentadienyl)tribenzyl zirconium, (methylcyclopentadienyl)trichloro zirconium, (methylcyclopentadienyl)dimethyl(methoxy) zirconium, (dimethylcyclopentadienyl)trimethyl zirconium, (trimethylcyclopentadienyl)trimethyl zirconium, (trimethylsilylcyclopentadienyl)trimethyl zirconium, (tetramethylcyclopentadiethyl)trimethyl zirconium, (pentamethylcyclopentadienyl)trimethyl zirconium, (pentamethylcyclopentadienyl)triphenyl zirconium, (pentamethylcyclopentadienyl)tribenzyl zirconium, (pentamethylcyclopentadienyl)trichloro zirconium, (pentamethylcyclopentadienyl)trimethoxy zirconium, (pentamethylcyclopentadienyl) dimethyl(methoxy) zirconium, (cyclopentadienyl)triethyl zirconium, (cyclopentadienyl)tripropyl zirconium, (cyclopentadienyl)trineopentyl zirconium, (cyclopentadienyl)tri(diphenylmethyl) zirconium, (cyclopentadienyl)dimethylhydrido zirconium, (cyclopentadienyl)triethoxy zirconium, (cyclopentadienyl)triisopropoxy zirconium, (cyclopentadienyl)triphenoxy zirconium, (cyclopentadienyl)dimethylisopropoxy zirconium, (cyclopentadienyl)diphenylisopropoxy zirconium, (cyclopentadienyl)dimethoxychloro zirconium, (cyclopentadienyl)methoxydichloro zirconium, (cyclopentadienyl)diphenoxychloro zirconium, (cyclopentadienyl)phenoxydichloro zirconium, (cyclopentadienyl)tri(phenyldimethylsilyl) zirconium, (n- butylcyclopentadienyl)dimethyl n-butoxy zirconium, (benzylcyclopentadienyl)di m-tolyl methyl zirconium, (trifluoromethylcyclopentadienyl)tribenzyl zirconium, (diphenylcyclopentadienyl)dinorbornylmethyl zirconium, (tetraethylcyclopentadienyl)tribenzyl zirconium, (pentamethylsilylcyclopentadienyl)tribenzyl zirconium, (pentamethylcyclopentadienyl)trineopentyl zirconium, (pentamethylcyclopentadienyl)methyldichloro zirconium, (pentamethylcyclopentadienyl)triethoxy zirconium, (pentamethylcyclopentadienyl)triphenoxy zirconium, (pentamethylcyclopentadienyl)methoxydichloro zirconium, (pentamethylcyclopentadienyl)diphenoxychloro zirconium, (pentamethylcyclopentadienyl)phenoxydichloro zirconium, (indenyl)trimethyl zirconium, (indenyl)tribenzyl zirconium, (indenyl)trichloro zirconium, (indenyl)trimethoxy zirconium, (indenyl)triethoxy zirconium, bis(cyclopentadienyl)dimethyl zirconium, bis(cyclopentadienyl)diphenyl zirconium, bis(cyclopentadienyl)diethyl zirconium, bis(cyclopentadienyl)dibenzyl zirconium, bis(cyclopentadienyl)dimethoxy zirconium, bis(cyclopentadienyl)dichloro zirconium, bis(cyclopentadienyl)dihydrido zirconium, bis(cyclopentadienyl)chlorohydrido zirconium, bis(methylcyclopentadienyl)dimethyl zirconium, bis(methylcyclopentadienyl)dibenzyl zirconium, bis(methylcyclopentadienyl)dichloro zirconium, bis(pentamethylcyclopentadienyl)dimethyl zirconium, bis(pentamethylcyclopentadienyl)dibenzyl zirconium, bis(pentamethylcyclopentadienyl)dichloro zirconium, bis(pentamethylcyclopentadienyl)chloromethyl zirconium, bis(pentamethylcyclopentadienyl)hydridomethyl zirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl)dimethyl zirconium, bis(cyclopentadienyl)dineopentyl zirconium, bis(cyclopentadienyl)di m-tolyl zirconium, bis(cyclopentadienyl)di p-tolyl zirconium, bis(cyclopentadienyl)bis(diphenylmethyl) zirconium, bis(cyclopentadienyl)dibromo zirconium, bis(cyclopentadienyl)methylchloro zirconium, bis(cyclopentadienyl)ethylchloro zirconium, bis(cyclopentadienyl)cyclohexylchloro zirconium, bis(cyclopentadienyl)phenylchloro zirconium, bis(cyclopentadienyl)benzylchloro zirconium, bis(cyclopentadienyl)hydridomethyl zirconium, bis(cyclopentadienyl)methoxychloro zirconium, bis(cyclopentadienyl)ethoxychloro zirconium, bis(cyclopentadienyl)(trimethylsilyl)methyl zirconium, bis(cyclopentadienyl)bis(trimethylsilyl) zirconium, bis(cyclopentadienyl)(triphenylsilyl)methyl zirconium, bis(cyclopentadienyl)(tris(dimethylsilyl)silyl)methyl zirconium, bis(cyclopentadienyl) (trimethylsilyl)(trimethylsilylmethyl) zirconium, bis(methylcyclopentadienyl)diphenyl zirconium, bis(ethylcyclopentadienyl)dimethyl zirconium, bis(ethylcyclopentadienyl)dichloro zirconium, bis(propylcyclopentadienyl)dimethyl zirconium, bis(propylcyclopentadienyl)dichloro zirconium, bis(n-butylcyclopentadienyl)dichloro zirconium, bis(t-butylcyclopentadienyl)bis(trimethylsilyl) zirconium, bis(hexylcyclopentadienyl)dichloro zirconium, bis(cyclohexylcyclopentadienyl)dimethyl zirconium, bis(dimethylcyclopentadienyl)dimethyl zirconium, bis(dimethylcyclopentadienyl)dichloro zirconium, bis(dimethylcyclopentadienyl)ethoxychloro zirconium, bis(ethylmethylcyclopentadiethyl)dichloro zirconium, bis(propylmethylcyclopentadienyl)dichloro zirconium, bis(butylmethylcyclopentadienyl)dichloro zirconium, bis(trimethylcyclopentadienyl)dichloro zirconium, bis(tetramethylcyclopentadienyl)dichloro zirconium, bis(cyclohexylmethylcyclopentadienyl)dibenzyl zirconium, bis(trimethylsilylcyclopentadienyl)dimethyl zirconium, bis(trimethylsilylcyclopentadienyl) dichloro zirconium, bis(trimethylgermylcyclopentadienyl)dimethyl zirconium, bis(trimethylgermylcyclopentadienyl)diphenyl zirconium, bis(trimethylstannylcyclopentadienyl)dimethyl zirconium, bis(trimethylstannylcyclopentadienyl)dibenzyl zirconium, bis(trifluoromethylcyclopentadienyl)dimethyl zirconium, bis(trifluoromethylcyclopentadienyl)dinorbornyl zirconium, bis(indenyl)dibenzyl zirconium, bis(indenyl)dichloro zirconium, bis(indenyl)dibromo zirconium, bis(tetrahydroindenyl)dichloro zirconium, bis(fluorenyl)dichloro zirconium, (propylcyclopentadienyl)(cyclopentadienyl)dimethyl zirconium, (cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)dibenzyl zirconium, (pentatrimethylsilylcyclopentadienyl)(cyclopentadienyl)dimethyl zirconium, (trifluoromethylcyclopentadienyl)(cyclopentadienyl)dimethyl zirconium, ethylene bis(indenyl)dimethyl zirconium, ethylene bis(indenyl)dichloro zirconium, ethylene bis(tetrahydroindenyl)dimethyl zirconium, ethylene bis(tetrahydroindenyl)dichloro zirconium, dimethylsilylene bis(cyclopentadienyl)dimethyl zirconium, dimethylsilylene bis(cyclopentadienyl)dichloro zirconium, isopropylidene (cyclopentadienyl)(9-fluorenyl)dimethyl zirconium, isopropylidene (cyclopentadienyl)(9-fluorenyl)dichloro zirconium, [phenyl(methyl)methylene] (9- fluorenyl)(cyclopentadienyl)dimethyl zirconium, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)dimethyl zirconium, ethylene (9- fluorenyl)(cyclopentadienyl)dimethyl zirconium, cyclohexylidene(9-fluorenyl) (cyclopentadienyl)dimethyl zirconium, cyclopentylidene (9-fluorenyl)(cyclopentadienyl)dimethyl zirconium, cyclobutylidene (9-fluorenyl)(cyclopentadienyl)dimethyl zirconium, dimethylsilylene (9-fluorenyl)(cyclopentadienyl)dimethyl zirconium, dimethylsilylenebis(2,3,5- trimethylcyclopentadienyl)dimethyl zirconium, dimethylsilylenebis(2,3,5- trimethylcyclopentadienyl)dichloro zirconium, dimethylsilylenebis(indenyl)dichloro zirconium, methylenebis(cyclopentadienyl)dimethyl zirconium, methylenebis(cyclopentadienyl)di(trimethylsilyl) zirconium, methylene (cyclopentadienyl)(tetramethylcyclopentadienyl)dimethyl zirconium, methylene (cyclopentadienyl)(fluorenyl)dimethyl zirconium, ethylenebis(cyclopentadienyl)dimethyl zirconium, ethylenebis(cyclopentadienyl)dibenzyl zirconium, ethylenebis(cyclopentadienyl)dihydrido zirconium, ethylenebis(indenyl)diphenyl zirconium, ethylenebis(indenyl)methylchloro zirconium, ethylenebis(tetrahydroindenyl)dibenzyl zirconium, isopropylidene(cyclopentadienyl)(methylcyclopentadienyl)dichloro zirconium, isopropylidene (cyclopentadienyl)(octahydrofluorenyl)dihydrido zirconium, dimethylsilylenebis(cyclopentadienyl)dineopentyl zirconium, dimethylsilylenebis(cyclopentadienyl)dihydrido zirconium, dimethylsilylenebis(methylcyclopentadienyl)dichloro zirconium, dimethylsilylenebis(dimethylcyclopentadienyl)dichloro zirconium, dimethylsilylenebis(tetrahydroindenyl)dichloro zirconium, dimethylsilylene(cyclopentadienyl)(fluorenyl)dichloro zirconium, dimethylsilylene(cyclopentadienyl)(fluorenyl)dihydrido zirconium, dimethylsilylene(methylcyclopentadienyl)(fluorenyl)dihydrido zirconium, dimethylsilylenebis(3- trimethylsilylcyclopentadientyl)dihydrido zirconium, dimethylsilylenebis(indenyl)dimethyl zirconium, diphenylsilylenebis(indenyl)dichloro zirconium, phenylmethylsilylenebis(indenyl)dichloro zirconium, compounds obtained by substituting zirconium atoms in these compounds with hafnium atoms, and the like.

[0151] A content of the organotitanium compound or the like is preferably 0.1% to 30% by mass with respect to a total solid content of the composition of the present invention. A lower limit thereof is more preferably 1.0% by mass or higher, even more preferably 1.5% by mass or higher, and particularly preferably 3.0% by mass or higher. An upper limit thereof is more preferably 25% by mass or lower.

[0152] For the organotitanium compound or the like, one type or two or more types can be used. In a case where two or more types are used, a total amount is preferably within the above-mentioned range.

[0153] In addition, in the composition of the present invention, a mass ratio of a content of the organotitanium compound or the like to a content of the thermal-base generator is preferably 100:1 to 1:100, more preferably 90:10 to 10:90, and even more preferably 40:60 to 20:80. By setting the mass ratio to be within such a range, it is possible to achieve a higher ring closure rate at a low temperature and a higher glass transition temperature for the heterocyclic ringforming polymer precursor.

[0154] The composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be optionally used. The solvent is preferably an organic solvent. As the organic solvent, compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides are mentioned.

[0155] As the esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, isoamyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, y-butyrolactone, e-caprolactone, b-valerolactone, alkyl alkyloxyacetate (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, and butyl alkyloxyacetate (for example, methyl meth oxy acetate, ethyl methoxyacetate, butyl meth oxy acetate, methyl ethoxyacetate, and ethyl ethoxyacetate)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, and ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 2- alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate are suitably mentioned.

[0156] As the ethers, for example, 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, cyclopentanone, 2-heptanone, and 3-heptanone are suitably mentioned.

[0157] As the aromatic hydrocarbons, for example, toluene, xylene, anisole, and limonene are suitably mentioned.

[0158] As the sulfoxides, for example, dimethyl sulfoxide is suitably mentioned. As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and the like are suitably mentioned.

[0159] From the viewpoint of improving properties of a coated surface or the like, it is also preferable to mix two or more types of solvents. Among these, a mixed solution composed of two or more selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3- methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, y-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. A combination of dimethyl sulfoxide and y- butyrolactone is particularly preferable.

[0160] From the viewpoint of coatability of the composition of the invention, a content of the solvent is preferably such that a total concentration of solid contents of the composition of the present invention is 5% to 80% by mass, with 5% to 70% by mass is even more preferable, and 10% to 60% by mass being particularly preferable. The content of the solvent may be adjusted depending on a desired thickness and a coating method. For example, in a case where the coating method is a spin coating or slit coating, the content of the solvent which causes the concentration of solid contents within the above-mentioned range is preferable. In a case of spray coating, the solvent has an amount which causes preferably 0.1% by mass to 50% by mass, and more preferably 1.0% by mass to 25% by mass. By adjusting the amount of solvent depending on the coating method, it is possible to uniformly form a photosensitive resin composition layer having a desired thickness.

[0161] For the solvent, one type may be contained, or two or more types may be contained. In a case where two or more types of solvents are contained, a total thereof is preferably within the above-mentioned range.

[0162] The composition of the present invention preferably contains a radically polymerizable compound (hereinafter also referred to as "polymerizable monomer"). By adopting such a constitution, a cured film which is excellent in heat resistance can be formed.

[0163] As the polymerizable monomer, a compound having a radically polymerizable group can be used. As the radically polymerizable group, a group having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth)acryloyl group, and an allyl group is mentioned. The radically polymerizable group is preferably a (meth)acryloyl group. The polymerizable monomer may have one radically polymerizable group or two or more radically polymerizable groups. The polymerizable monomer preferably has two or more radically polymerizable groups, and more preferably three or more radically polymerizable groups. An upper limit thereof is preferably 15 or lower, more preferably 10 or lower, and even more preferably 8 or lower.

[0164] A molecular weight of the polymerizable monomer is preferably 2,000 or lower, more preferably 1 ,500 or lower, and even more preferably 900 or lower. A lower limit of the molecular weight of the polymerizable monomer is preferably 100 or higher.

[0165] From the viewpoint of developability, the composition of the present invention preferably contains at least one bi- or higher-functional polymerizable monomer containing two or more polymerizable groups, and more preferably contains at least one tri- or higher-functional polymerizable monomer. In addition, the polymerizable monomer may be a mixture of a bifunctional polymerizable monomer and a tri- or higher-functional polymerizable monomer. The number of functional groups in the polymerizable monomer means the number of radically polymerizable groups in one molecule.

[0166] Specific examples of the polymerizable monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), and esters and amides thereof, and are preferably esters of saturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amino group, and a mercapto group, with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products thereof with monofunctional or polyfunctional carboxylic acids, and the like are also suitably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group and an epoxy group, with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogen group and a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. In addition, as another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid is substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether, or the like. As specific examples, reference can be made to the description of paragraphs 0113 to 0122 of JP2016-027357A. In addition, the polymerizable monomer is also preferably a compound having a boiling point of 100°C or higher under atmospheric pressure. As examples thereof, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, and trimethylolethane, and then being subjected to (meth)acrylation, the urethane (meth)acrylates as described in JP1973-041708B (JP-S48-041708B), JP1975-6034B (JP-S50- 6034B), and J P1976-037193A (JP-S51-037193A), polyester acrylates described in JP1973- 064183A (JP-S48-064183A), JP1974-043191 B (JP-S49-043191 B), and JP1977-030490B (JP- S52-030490B), polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acids, and mixtures thereof can be mentioned. In addition, the compounds described in paragraphs 0254 to 0257 of JP2008- 292970A are also suitable. In addition, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated group can be mentioned.

[0167] In addition, as other preferable polymerizable monomers, compounds having two or more groups containing a fluorene ring and an ethylenically unsaturated bond which are described in JP2010-160418A, JP2010-129825A, and Japanese Patent No. 4364216, and cardo resins can also be used.

[0168] Furthermore, as other examples, the specific unsaturated compounds described in JP1971-043946B (JP-S46-043946B), JP1989-040337B (JP-H1-040337B), and JP1989- 040336B (JP-H1-040336B), the vinylphosphonic acid-based compounds described in JP1990- 025493A (JP-H2-025493A), and the like can also be mentioned. In addition, the compounds containing a perfluoroalkyl group described in JP1986-022048A (JP-S61-022048A) can also be used. Furthermore, the compounds introduced as photo-polymerizable monomers and oligomers in the Journal of Adhesion Society of Japan, Vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.

[0169] In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP2015-034964A can also be preferably used. In addition, the compounds which are described in JP1998-062986A (JP-H10-062986A) as Formulas (1) and (2) as well as specific examples thereof and are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then being subjected to (meth)acrylation can be used as the polymerizable monomer.

[0170] Furthermore, the compounds described in paragraphs 0104 to 0131 of JP2015-187211A can also be used as the polymerizable monomer.

[0171] As the polymerizable monomer, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth)acrylate (commercially available as KAYARAD DPHA; by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which (meth)acryloyl groups thereof are bonded via ethylene glycol or propylene glycol residues are preferable. Oligomer types thereof can also be used.

[0172] As commercially available products of the polymerizable monomer, for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209 which is a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer, DPCA-60 which is a hexafunctional acrylate having six pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd., TPA-330 which is a trifunctional acrylate having three isobutylene oxy chains, urethane oligomers UAS-10, UAB-140 (manufactured by 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 Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Brenmer PME400 (manufactured by NOF Corporation), and the like are mentioned.

[0173] As the polymerizable monomer, the urethane acrylates as described in JP1973-041708B (JP-S48-041708B), J P1976-037193A (JP-S51-037193A), JP1990-032293B (JP-H2-032293B), and JP1990-016765B (JP-H2-016765B), and the urethane compounds having an ethylene oxide-based skeleton described in JP1983-049860B (JP-S58-049860B), JP1981-049860B (JP- S56-017654B), J P1987-039417B (JP-S62-039417B), and J P1987-039418B (JP-S62-039418B) are also suitable. Furthermore, as the polymerizable monomer, the compounds having an amino structure or a sulfide structure in a molecule as described in JP1988-277653A (JP-S63- 277653A), JP1988-260909A (JP-S63-260909A), and JP1989-105238A (JP-H1-105238A) can also be used.

[0174] The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, and a phosphoric acid group. The polymerizable monomer having an acid group is preferably ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a polymerizable monomer obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride so as to have an acid group. Particularly preferably, the polymerizable monomer is a polymerizable monomer having an acid group obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride so as to have an acid group, in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. As commercially available products thereof, for example, M-510 and M-520 as polybasic acid-modified acrylic oligomers which are manufactured by Toagosei Co., Ltd are mentioned.

[0175] For the polymerizable monomer having an acid group, one type may be used alone, or two or more types may be used in admixture. In addition, if necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group may be used in combination.

[0176] An acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40 mg KOH / g, and particularly preferably 5 to 30 mg KOH / g. In a case where the acid value of the polymerizable monomer is within the above-mentioned range, excellent production and handling properties are exhibited, and furthermore, excellent developability is exhibited. In addition, good polymerization properties are exhibited.

[0177] From the viewpoints of good polymerization properties and heat resistance, a content of the polymerizable monomer is preferably 1% to 50% by mass with respect to a total solid content of the composition of the present invention. A lower limit thereof is more preferably 5% by mass or higher. An upper limit thereof is more preferably 30% by mass or lower. For the polymerizable monomer, one type may be used alone, or two or more types may be used in admixture. In addition, a mass ratio (heterocyclic ring-forming polymer precursor (i.e. the polyimide precursor) / polymerizable monomer) of the heterocyclic ring-forming polymer precursor (i.e the polyimide precursor) to the polymerizable monomer is preferably 98 / 2 to 10 / 90, more preferably 95 / 5 to 30 / 70, and most preferably 90 / 10 to 50 / 50. In a case where the mass ratio of the heterocyclic ring-forming polymer precursor to the polymerizable monomer is within the above- mentioned range, a cured film which is excellent in polymerization properties and heat resistance can be formed.

[0178] In the composition of the present invention, from the viewpoint of suppressing warping due to control of a modulus of elasticity of a cured film, a monofunctional polymerizable monomer can be preferably used. As the monofunctional polymerizable monomer, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, and polypropylene glycol mono (meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate, and the like are preferably used. As the monofunctional polymerizable monomer, a compound having a boiling point of 100°C or higher under atmospheric pressure is also preferable in order to suppress volatilization before exposure. The photosensitive resin composition preferably further contains a migration suppressing agent. By containing the migration suppressing agent, it is possible to effectively prevent metal ions derived from a metal layer (metal wiring) from being migrated into a photosensitive resin composition layer.

[0179] As the migration suppressing agent, there is no particular limitation, and compounds having a heterocyclic ring (a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring and a 6H-pyran ring, a triazine ring), compounds having thioureas and a mercapto group, hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds are mentioned. In particular triazole-based compounds such as triazole and benzotriazole, and tetrazole-based compounds such as tetrazole and benzotetrazole can be preferably used.

[0180] In addition, an ion trapping agent that captures an anion such as a halogen ion can also be used. As other migration suppressing agents, the rust inhibitors described in paragraph 0094 of JP2013-015701A, the compounds described in paragraphs 0073 to 0076 of JP2009- 283711A, the compounds described in paragraph 0052 of JP2011-059656A, and the compounds described in paragraphs 0114, 0116, and 0118 of JP2012-194520A, and the like can be used.

[0181] As specific examples of the migration suppressing agent, 1 H-1,2,3-triazole, 1 H-tetrazole and 5-aminotetrazole can be mentioned.

[0182] In a case where the photosensitive resin composition has the migration suppressing agent, a content of the migration suppressing agent is preferably 0.01% to 5.0% by mass, more preferably 0.05% to 2.0% by mass, and even more preferably 0.1% to 1.0% by mass, with respect to a total solid content of the photosensitive resin composition.

[0183] For the migration suppressing agent, only one type may be used, or two or more types may be used. In a case where two or more types of migration suppressing agents are used, a total thereof is preferably within the above-mentioned range.

[0184] The polyimide precursor comprising composition of the present invention preferably comprises a polymerization inhibitor. In some embodiments, the polyimide precursor comprising composition comprises at least one polymerization inhibitor and / or solvent and / or radically polymerizable compound.

[0185] As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert- butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p-benzoquinone, diphenyl-p-benzoquinone, 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-phenyl naphthylamine, ethylenediamine tetraacetic acid, 1 ,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methyl phenol, 5-nitroso-8- hydroxyquinoline, 1-nitroso-2-naphtoyl, 2-nitroso-1-naphtoyl, 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 suitably used. In addition, the polymerization inhibitors described in paragraph 0060 of JP2015-127817A and the compounds described in paragraphs 0031 to 0046 of WO2015 / 125469A can also be used.

[0186] In addition, the following compounds can be used (Me is a methyl group). In addition, a sterically hindered aminoxyl compound without alpha-hydrogens can also be used as the polymerization inhibitor. For example (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl, (4- Hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl and the like are likely to be used.

[0187] In a case where the composition of the present invention has a polymerization inhibitor, a content of the polymerization inhibitor is preferably 0.01% to 5% by mass with respect to a total solid content of the composition of the present invention.

[0188] In some embodiments, the polymerization inhibitor is selected from one or more of 1,4- Benzoquinone, and p-methoxyphenol.

[0189] For the polymerization inhibitor, only one type may be used, or two or more types may be used. In a case where two or more types of polymerization inhibitors are used, a total thereof is preferably within the above-mentioned range

[0190] In some embodiments, the radically polymerizable compound is selected from one or more of tetra ethylene glycol dimethacrylate (TEGDMA), and pentaerythritol tri(meth)acrylate.

[0191] In some embodiments, the solvent that may be used in the polyimide precursor comprising composition can be selected from one or more dimethyl sulfoxide, gamma- Butyrolactone, and N-Methyl-2-pyrrolidone.

[0192] The composition of the present invention preferably contains a metal adhesiveness improving agent for improving adhesiveness to a metal material used for electrodes, wirings, and the like. As the metal adhesiveness improving agent, a silane coupling agent and the like are mentioned.

[0193] As examples of the silane coupling agent, the compounds described in paragraphs 0062 to 0073 of JP2014-191002A, the compounds described in paragraphs 0063 to 0071 of W02011 / 080992A1, the compounds described in paragraphs 0060 to 0061 of JP2014- 191252A, the compounds described in paragraphs 0045 to 0052 of JP2014-041264A, and the compounds described in paragraph 0055 of WO2014 / 097594A are mentioned. In addition, it is also preferable to use two or more types of the different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. In addition, as the silane coupling agent, the following compounds are also preferably used. In the formulas, Et represents an ethyl group.

[0194] In addition, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A, and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP2013-072935A can also be used. A content of the metal adhesiveness improving agent 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 heterocyclic ring-forming polymer precursor. In a case where the content is 0.1 parts by mass or higher, good adhesiveness between a cured film and a metal layer after a curing step is exhibited. In a case where the content is 30 parts by mass or lower, the cured film after the curing step exhibits good heat resistance and mechanical properties. For the metal adhesiveness improving agent, only one type may be used, or two or more types may be used. In a case where two or more types are used, a total thereof is preferably within the above- mentioned range.

[0195] Various additives, for example, a chain transfer agent, a surfactant, a higher fatty acid derivative, an inorganic particle, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorbent, and an aggregation inhibitor can be blended, if necessary, with the composition of the present invention to the extent that an effect of the present invention is not impaired. In a case where these additives are blended, a total blending amount thereof is preferably 3% by mass or lower of the solid content of the composition.

[0196] For reference a detailed description of these other additives can be found in EP3492982 from applicant.

[0197] A 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 properties of a coated surface.

[0198] A metal content of the composition of the present invention is preferably less than 5 parts per million (ppm) by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass, from the viewpoint of insulating properties. As the metal, sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like are mentioned. In a case where a plurality of metals are contained, a total of these metals is preferably within the above-mentioned range.

[0199] In addition, as a method for decreasing metal impurities which are unintentionally contained in the composition of the present invention, a method of selecting raw materials having a small metal content as raw materials constituting the composition of the present invention, a method of carrying out filtration using a filter on raw materials constituting the composition of the present invention, a method of carrying out distillation under conditions where contamination is suppressed as much as possible by lining an inside of an apparatus with polytetrafluoroethylene or the like, and the like can be mentioned.

[0200] In the composition of the present invention, a content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass, from the viewpoint of wiring corrosiveness. Among these, in a case of being present in a halogen ion state, the content is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. As the halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that each of the chlorine atom and the bromine atom, or a total of the chlorine ion and the bromine ion is within the above-mentioned range.

[0201] As a storage container for the composition of the present invention, storage containers known in the related art can be used. In addition, as the storage container, for the purpose of suppressing incorporation of impurities into raw materials and the composition, a multilayer bottle in which an inner wall of a container is composed of six types of six layers of resin, and a bottle with 6 types of resin being made as a seven-layer structure are preferably used. As such a container, for example, the container described in JP2015-123351A is mentioned.

[0202] The composition of the present invention can be prepared by mixing the above- mentioned respective components. A mixing method is not particularly limited, and mixing can be carried out by methods known in the related art.

[0203] In addition, for the purpose of removing foreign substances such as dust and fine particles in the composition, it is preferable to carry out filtration using a filter. A filter pore size is preferably 1 pm or lower, more preferably 0.5 pm or lower, and even more preferably 0.1 pm or lower. A material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. As the filter, a filter which has been previously washed with an organic solvent may be used. In a filtration step using a filter, a plurality of type of filters may be connected in series or in parallel and used. In a case where a plurality of types of filters are used, filters having different pore sizes and / or different materials may be used in combination. In addition, various materials may be filtered a plurality of times. In a case of being filtered a plurality of times, circulation filtration may be used. In addition, filtration may be carried out under pressure. In a case of where filtration is carried out under pressure, the pressure is preferably 0.05 MPa to 0.3 MPa. In addition to filtration using a filter, impurity removal treatment using an adsorbing material may be carried out. The filtration using a filter and the impurity removal treatment using an adsorbing material may be combined. As the adsorbing material, a known adsorbing material can be used. For example, an inorganic adsorbing material such as silica gel and zeolite, and an organic adsorbing material such as activated carbon are mentioned.

[0204] Next, the cured film, the laminate, the semiconductor device, the method for producing a cured film, the method for producing a laminate, and the method for manufacturing a semiconductor device of the present invention will be described.

[0205] The cured film of the present invention is obtained by curing the composition of the present invention. A film thickness of the cured film of the present invention can be, for example, 1 pm or higher, and can be 5 pm or higher. In addition, an upper limit value thereof can be 100 pm or lower and can be 30 pm or lower.

[0206] A glass transition temperature ( Tg) of the cured film of the present invention is preferably 240°C or higher, more preferably 250°C or higher, even more preferably 260°C or higher, and still more preferably 270°C or higher. An upper limit value of the Tg of the cured film of the present invention is not particularly specified, and, for example, the Tg at 600°C or lower, or even 450°C or lower is a sufficiently practical level. In particular, the present invention is highly valuable in that it is possible to provide a photosensitive resin composition capable of achieving the above-mentioned Tg. The Tg in the present invention is measured in accordance with descriptions of examples as described later.

[0207] In some embodiment, the glass transition temperature (Tg) of the cured film is in the range of 240°C to 600 °C, preferably in the range of 240°C to 400°C.

[0208] Two or more layers of the cured film of the present invention may be laminated to form a laminate. A laminate having two or more layers of the cured film of the present invention preferably has a metal layer between the cured films. Such a metal layer is preferably used as a metal wiring such as a re-distribution layer. The metal layer preferably contains copper.

[0209] As a field to which the cured film of the present invention can be applied, an insulating film of a semiconductor device, an interlayer insulating film for a re-distribution layer, and the like are mentioned. In particular, due to good resolution properties, the cured film of the present invention can be preferably used for an interlayer insulating film for a re-distribution layer in a three-dimensional mounting device. In addition, the cured film in the present invention can also be used for photoresist for electronics, galvanic (electrolytic) resist, etching resist, solder top resist, and the like.

[0210] In addition, the cured film in the present invention can also be used for production of board surfaces such as an offset board surface or a screen board surface, for etching of molded parts, for production of protective lacquers and dielectric layers in electronics, in particular, microelectronics, and the like.

[0211] The method for producing a cured film of the present invention includes using the composition of the present invention. Preferably, a method for producing a cured film which has a photosensitive resin composition layer forming step of applying the photosensitive resin composition of the present invention to a substrate to form a layered shape, an exposing step of exposing the photosensitive resin composition layer, and a step of subjecting the exposed photosensitive resin composition layer (resin layer) to a development treatment is mentioned. More preferably, the photosensitive resin composition of the present invention is preferably used in a case where the development is a negative tone development treatment. In addition, in the production method of the present invention, after the development treatment step, the developed photosensitive resin composition layer is preferably heated to a temperature of 50°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and still more preferably 150°C or higher, and further still more preferably 180°C or higher. An upper limit of the heating temperature is preferably 450°C or lower, more preferably 400°C or lower, even more preferably 380°C or lower, still more preferably 300°C or lower, further still more preferably 280°C or lower, yet further still more preferably 250°C or lower, yet further still more preferably 240°C or lower, yet further still more preferably 230°C or lower, yet further still more preferably 220°C or lower, yet further still more preferably 210°C or lower, yet further still more preferably 205°C or lower, and yet further still more preferably 200°C or lower.

[0212] In some embodiments, the method of manufacturing a cured film comprises a heating step after the development treatment step, of heating the film at a temperature in the range of 50°C to 450°C.

[0213] Since the cured film of the present invention allows ring closure to be made with a high ring closure rate even at a low temperature, the heating temperature can be decreased, and damage to a semiconductor element or the like can be decreased. In particular, in the present invention, it is possible to obtain a photosensitive resin composition which is capable of achieving a ring closure rate of 80% or higher, and furthermore 90% or higher, in a case of being heated in the above-mentioned temperature range (for example, at 200°C). The method for producing a laminate of the present invention includes a method for producing a cured film of the present invention. The method of producing a laminate preferably includes forming a cured film in accordance with the method of producing a cured film of the present invention, and then further performing the photosensitive resin composition layer forming step, the exposure step, and the development treatment step, in this order. In particular, it is preferable that the photosensitive resin composition layer forming step, the exposure step, and the development treatment step are further carried out, in this order, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this manner, a laminate can be obtained. In the present invention, in particular, it is preferable to provide a metal layer on a portion which has been developed and removed, after the cured film is provided and developed.

[0214] The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. Hereinafter, an embodiment of a semiconductor device in which the composition of the present invention is used for an interlayer insulating film for a redistribution layer will be described.

[0215] A semiconductor device 100 shown in Fig. 1 is a so-called three-dimensional mounting device, and a laminate 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101 d are laminated is disposed on a wiring substrate 120. In this embodiment, a case where the number of laminated semiconductor elements (semiconductor chips) is 4-layer will be mainly described. However, the number of laminated semiconductor elements (semiconductor chips) is not particularly limited, and may be, for example, 2-layer, 8-layer, 16- layer, 32-layer, or the like. In addition, the number may be 1-layer.

[0216] Each of the plurality of semiconductor elements 101a to 101 d is made of a semiconductor wafer such as a silicon substrate. An 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 101 b to 101 d have through electrodes 102b to 102d, and connection pads (not shown) which are integrally provided on the through electrodes are provided on both surfaces of each semiconductor element.

[0217] The laminate 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101 b to 101 d having through electrodes 102b to 102d are flip-chip connected. That is, an electrode pad of the semiconductor element 101a having no through electrode, and a connection pad on a semiconductor element 101a side of the semiconductor element 101b having the through electrode 102b which is adjacent to the semiconductor element 101a are connected by a metal bump 103a such as solder bump. A connection pad on the other side of the semiconductor element 101b having the through electrode 102b, and a connection pad on a semiconductor element 101 b side of the semiconductor element 101c having the through electrode 102c which is adjacent to the semiconductor element 101b are connected by a metal bump 103b such as a solder bump. Similarly, a connection pad on the other side of the semiconductor element 101c having the through electrode 102c, and a connection pad on a semiconductor element 101c side of the semiconductor element 101 d having the through electrode 102d which is adjacent to the semiconductor element 101c are connected by a metal bump 103c such as a solder bump.

[0218] An underfill layer 110 is formed in each gap between the semiconductor elements 101a to 101 d, and the respective semiconductor elements 101a to 101 d are laminated via the underfill layer 110 interposed therebetween.

[0219] The laminate 101 is laminated on the wiring substrate 120. As the wiring substrate 120, for example, a multilayer wiring substrate obtained by using an insulating substrate such as a resin substrate, a ceramic substrate, and a glass substrate as a base material is used. As the wiring substrate 120 to which the resin substrate is applied, a multilayer copper-clad laminated board (multilayer printed wiring board) and the like are mentioned.

[0220] On one surface of the wiring substrate 120, a surface electrode 120a is provided.

[0221] An insulating film 115 on which a re-distribution layer 105 is formed is disposed between the wiring substrate 120 and the laminate 101 , and the wiring substrate 120 and the laminate 101 are electrically connected via the re-distribution layer 105. The insulating film 115 is formed using the composition of the present invention.

[0222] That is, one end of the re-distribution layer 105 is connected, via a metal bump 103d such as a solder bump, to an electrode pad formed on a surface of the semiconductor element 101 d on a re-distribution layer 105 side. In addition, the other end of the re-distribution layer 105 is connected, via a metal bump 103e such as a solder bump, to the surface electrode 120a of the wiring substrate.

[0223] An underfill layer 110a is formed between the insulating film 115 and the laminate 101. In addition, an underfill layer 110b is formed between the insulating film 115 and the wiring substrate 120. In addition to the above, the cured film of the present invention can be widely adopted for various applications using polyimide.

[0224] In addition, since polyimide is resistant to heat, the cured film and the like in the present invention can be suitably used in plastic substrates for display devices such as liquid crystal display, organic EL display, and electronic paper as well as in applications for interlayer insulating films, automobile parts, heat-resistant paints, coating agents, and films.

[0225] In some embodiments, this disclosure features an article containing at least one patterned dielectric film formed by a polyimide precursor containing formulation described herein. Examples of such articles include a semiconductor substrate, a flexible film for electronics, a wire isolation, a wire coating, a wire enamel, and an inked substrate. In some embodiments, this disclosure features semiconductor devices that include one or more of these articles. Examples of semiconductor devices that can be made from such articles include an integrated circuit, a light emitting diode, a solar cell, and a transistor.

[0226] The contents of all publications cited herein (e.g., patents, patent application publications, and articles) are hereby incorporated by reference in their entirety.

[0227] The present disclosure is illustrated in more detail with reference to the following examples, which are for illustrative purposes and should not be construed as limiting the scope of the present disclosure.

[0228] Examples

[0229] Synthesis example PI precursor A1

[0230] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (ODPA) (dried at 140°C for 12 hours) and 17.12 g (131.58 mmol) of 2-hydroxyethyl methacrylate (HEMA) were suspended in 50 mL of N-methylpyrrolidone and dried with a molecular sieve. The suspension was heated at 100°C for 3 hours. A transparent solution was obtained a few minutes after the start of heating. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) pyridine and 90 ml N-methylpyrrolidone were added thereto. Then, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCI2 was added thereto over 10 minutes while keeping the temperature at -10°C ± 4°C. Viscosity increased while adding SOCI2. 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 11.75 g (58.7 mmol) of 4,4 -diaminodiphenyl ether (ODA) in 100 ml of N-methylpyrrolidone was dropwise added to the reaction mixture at 20°C to 23°C over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 L of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5,000 rpm. The polyimide precursor was collected by filtration, put into 4 liters of water again, stirred for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45°C for 3 days to obtain polymer PA-2. As a result of measuring the molecular weight of the polymer PA-2 by gel permeation chromatography (in terms of standard polystyrene equivalent value), the weightaverage molecular weight (Mw) was 20,000.

[0231] Synthesis example PI precursor A2

[0232] The reaction was carried out in the same manner as described in Synthesis Example 1 to obtain a polymer A2, except that 18.98 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 20.0 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in Synthesis Example 1. As a result of measuring the molecular weight of the polymer A2 by gel permeation chromatography (in terms of standard polystyrene equivalent value), the weight-average molecular weight (Mw) was 22,000.

[0233] Synthesis example PI precursor A3

[0234] The reaction was carried out in the same manner as described in Synthesis Example 1 to obtain a polymer A3, except that 18.98 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 20.0 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in Synthesis Example 1. And except that 6.348 g of p-phenylenediamine was used instead of 11.75 g of 4,4'- diaminodiphenyl ether (ODA) in Synthesis Example 1. Synthesis example PI precursor A4

[0235] The reaction was carried out in the same manner as described in Synthesis Example 1 to obtain a polymer A4, except that 14.07 g of pyromellitic acid dianhydride (PMDA) was used instead of 20.0 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in Synthesis Example 1. And except that 6.348 g of p-phenylenediamine was used instead of 11.75 g of 4,4'-diaminodiphenyl ether

[0236] (ODA) in Synthesis Example 1.

[0237] Synthesis example PI precursor A5

[0238] The reaction was carried out in the same manner as described in Synthesis Example 1 to obtain a polymer A4, except that 14.07 g of pyromellitic acid dianhydride (PMDA) was used instead of 20.0 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in Synthesis Example 1. And except that

[0239] 6.348 g of p-phenylenediamine was used instead of 11.75 g of 4,4'-diaminodiphenyl ether (ODA) in Synthesis Example 1. And except that 15.55g of 2-isobutoxyethanol was used instead of 17.12g of 2-hydroxyethyl methacrylate (HEMA).

[0240] Manufacturing and testing of photosensitive dielectric film forming composition

[0241] A photosensitive dielectric film forming composition example 1 was prepared by using 32.5 parts of a polyimide-precursor polymer A1 in 48.19 parts of an organic solvent J1 and 12.05 parts of another organic solvent J2.

[0242] All other examples have been made according to the components described in the example table (I). Using PI precursor A2, A3, A4, A5; radically polymerizable compound B1 , B2; photoradical polymerization initiator C1 , C2, C3, C4; polymerization inhibitor D1 , D2; solvent E1, E2, E3. The actual concentrations can be found in the table.

[0243] All formulations were mixed by rolling for 24 hours, filtered under a pressure of 0.3 MPa through a filter having a pore width of 0.8 mm and deep frozen afterwards for 24 hours. After four hours of defrosting, syringes were filled with the formulations and put in a dark space to let entrapped air rise to the surface. Then, the substrates for spin coating (silicon wafers) were prepared. The 6 inch-diameter sized silicon wafers received an 02-plasma pre-treatment of 30 seconds with a NEO 203A etching tool from the brand Trymax. Next, the formulations were spin coated on the pretreated wafers on an AMC2000 spin coater from the brand Amcoss. After coating, a hot bake step of 110°C for 4 minutes was applied (also in the spin coater) and a soft bake thickness was reached of 10.0 pm. The film thickness was measured on a tabletop film thickness tool from the brand Foothill (KF-10). By making use of the n, k values of the thin film material, and by measuring the absolute reflectivity, the film thickness can be determined. The necessary n, k values were determined for the resist by ellipsometry on the VASE tool of the brand J. A. Woollam. This was done with a Si wafer on which a very thin film of the resist (<500nm) was applied. Further, the wafers were exposed on a Nikon stepper (Nikon 1755i7 model) with an N.A. (=numerical aperture) of 0.5 and a Hg-lamp with a 365nm lamp-intensity of 500mW / cm2. A focus-exposure matrix was used where the focus varied in steps of 2pm and the energy was varied from 40mJ / cm2to 880mJ / cm2in steps of 60mJ / cm2. After exposure, the substrates were kept in the dark for 30 minutes after which negative tone development was further carried out with cyclopentanone for 30 seconds on the AMC2000 spin coater from Amcoss, to obtain a resin layer. Next, the developed substrate got a post-development bake of 100°C for 30 seconds to evaporate any residual solvent also on the spin coater. Afterwards, the substrates received a box oven cure at 230°C for 3 hours under a controlled nitrogen atmosphere of 380 bar (in absence of oxygen) in a convection oven from the brand YES. Further, the cured samples were descummed with an 02-plasma for 1 minute to remove residual scumming on the NEO 203A etching tool. Then, a JEOL SEM (=secondary electron microscope) was utilized to inspect the cross sections for the energy matrix (in steps of 60mJ / cm2) at a focus of 2pm within the film. Critical dimensions (=CD-values) were measured on the bottom of the via structures on the secondary electron images (=SEI-images). Critical dimension legend:

[0244] Critical dimension (=CD-value) of the bottom of the via after secondary electron imageinspection:

[0245] A: CD-value <= 5.5pm

[0246] B: 5.5pm < CD-value <= 7.0pm

[0247] C: 7.0pm < CD-value <= 8.5pm

[0248] D: 8.5pm < CD-value <= 10.0pm E: 10.0pm <= CD-value

[0249] The Exposure Latitude (EL) score was based on how well the overall CD-values performed over the total energy range. The Sensitivity score was based on the overall CD-values in the lower energy range only.

Claims

Claims:

1. A polyimide precursor comprising composition, comprising: at least one resin; and at least one acyl germanium compound.

2. The composition according to claim 1, wherein said polyimide precursor is selected from one or more compounds of Formula (1)Formula (1) wherein A1 and A2 each independently represent an oxygen atom or NH, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 each independently represent a hydrogen atom or a monovalent organic group.

3. The composition according to claim 2, wherein the divalent organic group is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, one or more aromatic group(s) having 6 to 20 carbon atoms, or a group composed of a combination thereof.

4. The composition according to claims 2 or 3, wherein R115 is selected from (X-1), (X-2) and (X-3), and R111 is selected from (Y-1) and (Y-3).(X-1 ) (X-2) (X-3)5. The composition according to any of the previous claims, wherein at least one acyl germanium compound comprises a compound of structure (I):structure (I) in whichR1is C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, or C6-C22 heteroaryl; each of R2, R3, and R4, independently, is C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, C6-C22 heteroaryl, or -C(O)R, in which R is C1-C4 alkyl, C5-C12 cycloalkyl, Ce-Cis aryl, or Ce- C18 heteroaryl; and each of alkyl, alkenyl, cycloalkyl, aryl, or heteroaryl, independently, is optionally substituted by at least one C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR5, -OC(O)R5, or -COOR5, where R5is H, Ci- 04 alkyl, C5-C12 cycloalkyl, Ce-Cis aryl, or Ce-Cis heteroaryl.

6. The composition according to any of the previous claims, wherein at least one acyl germanium compound is a diacylgermanium compound.

7. The composition according to any one of claims 5 or 6, wherein the at least one acyl germanium compound comprises a compound given by a diacylgermanium compound wherein R2 = R1-C(O).

8. The composition according to any of the previous claims, wherein the at least one acyl germanium compound is selected from one or more of (2,4,6- trimethylbenzoyl)triethylgermanium, (2,4,6-trimethylbenzoyl)tripropylgermanium, (2,4,6-trimethylbenzoyl)tributylgermanium, (2,6-dimethoxybenzoyl)triethylgermanium, (2.6- dimethoxybenzoyl)tripropylgermanium, (2,6-dimethoxybenzoyl)tributylgermanium, bisbenzoyldiethylgermanium, benzoyltrimethylgermanium, bisbenzoyldipropylgermanium, bis(4- methoxybenzoyl)diethylgermanium, bis(2,4,6-trimethylbenzoyl)diethylgermanium, trisbenzoylethylgermanium, and tris(2,4,6-trimethylbenzoyl)ethylgermanium.

9. The composition according to any of the previous claims, wherein the at least one acyl germanium compound is in an amount of from about 0.05% to 5% by weight based on the solid weight of the composition.

10. The composition according to claim 2, wherein the polyimide precursor of formula (1) comprises at least one methacryloyl alkyl group as side chain.

11. The composition according to any of the previous claims, comprising at least one polymerization inhibitor and / or solvent and / or radically polymerizable compound.

12. The composition according to any of the previous claims, wherein the polyimide precursor is a heterocycle-forming polymer precursor.

13. A cured film that is obtained by curing the polyimide precursor comprising composition according to any one of claims 1 to 12.

14. A laminate comprising: two or more layers consisting of the cured film according to claim 13; and a metal layer between any layers consisting of the cured film.

15. A manufacturing method for a cured film, comprising: a film forming step of applying the polyimide precursor comprising composition according to any one of claims 1 to 12 onto a substrate to form a film; an exposure step of selectively exposing the film; and a development step of developing, by using a developer, the film exposed in the exposure step to form a pattern.

16. The manufacturing method for a cured film according to claim 15, further comprising a heating step of heating the film at 50°C to 450°C.

17. The semiconductor device comprising the cured film according to claim 13, or the laminate according to claim 13.

18. Use of a polyimide precursor comprising composition according to any one of claims 1 to 12 for forming a cured film.

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