Composition comprising polyimide precursor, cured film and producing method of the same, laminate, and semiconductor device

Abstract

This invention relates to compositions comprising polyimide precursors, hardened films, methods for manufacturing the same, laminates, semiconductor devices, and uses in forming hardened films. The compositions comprise at least one resin and at least one acetylated germanium compound. Furthermore, the precursor is a heterocyclic polymer precursor, wherein the heterocyclic polymer precursor is selected from polyimide (PI) precursors comprising formula (1):

Description

Technical Field

[0001] This disclosure relates to a polyimide precursor resin comprising a formulation containing a acetogermanium compound, and related processes, films, dry film structures, and articles thereof. Prior Technology

[0002] Polyimide precursor resins, including formulations for redistribution layer applications in semiconductor packaging, are continuously evolving. Electronic packaging trends continue to favor faster processing speeds, increased complexity, and higher packaging densities while maintaining high levels of reliability. As electronic packaging technologies advance and wafer sizes continue to shrink, the demand for innovative and high-performance resin compositions is growing. Various proposals have been made for photosensitive polyimide precursor compositions to address high resolution requirements. In some cases, photoinitiators with high sensitivity at longer wavelengths may be beneficial when used in photosensitive compositions employing lamp or laser direct imaging (LDI) technologies. Summary of the Invention

[0003] This invention is based on an accidental discovery that certain acetylated germanium compounds can be used as photoinitiators or photosensitizers in photosensitive polyimide precursors comprising formulations or compositions, allowing the compositions to be developed at relatively long ultraviolet wavelengths to form thin films. Long ultraviolet wavelengths include, but are not limited to: 375 nm lasers, 405 nm lasers, and the output spectra of mercury vapor lamps: 365 nm (I line), 405 nm (H line), and 435 nm (G line). The term "polyimide precursor containing formulations (compositions)" in this application refers to formulations comprising incompletely acetylated polyimide resins. Acetylated germanium compounds are non-toxic and can significantly improve the resolution of the films thus formed. This improved resolution directly improves the overall exposure latitude (EL) of the material. Furthermore, the high efficiency of acetylated germanium compounds increases the improved sensitivity. Therefore, the films thus formed can have excellent pattern shape and film hardness.

[0004] According to one aspect of the present invention, a polyimide precursor is provided comprising a composition including at least one resin and at least one acetylated germanium compound. Furthermore, the at least one resin in the polyimide precursor comprising the composition is the polyimide precursor itself.

[0005] The polyimide precursor comprising a composition is preferably a film-forming composition. As used herein, the terms "film-forming composition" and "polyimide precursor comprising a composition" are used interchangeably.

[0006] Advantageously, the aforementioned polyimide precursors may include polyimide precursors selected from one or more compounds of formula (1).

[0007] Equation (1)

[0008] In this context, 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.

[0009] Advantageously, the polyimide precursor used as a polymer precursor that is essentially a heterocyclic polymer precursor may include compounds of formula (1).

[0010] In some embodiments, the polyimide precursor is a heterocyclic polymer precursor, wherein the heterocyclic polymer precursor is selected from polyimide (PI) precursors including compounds of formula (1) ().

[0011] Equation (1)

[0012] In this context, 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.

[0013] Preferably, in formula (1), the divalent organic group R111 is a straight-chain 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 groups having 6 to 20 carbon atoms, or 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). Furthermore, in some embodiments, R115 in formula (1) may be selected from (X-1), (X-2), and (X-3), and R111 may be selected from (Y-1) and (Y-3).

[0014] In some embodiments, the polyimide precursor is a heterocyclic forming precursor, wherein the heterocyclic forming precursor is a heterocyclic forming polyimide precursor comprising a compound of formula (1).

[0015] In some embodiments, the polyimide precursor of formula (1) includes at least one methacrylic alkyl group as a side chain.

[0016] Advantageously, the acetylated germanium compound in the above-described composition comprising polyimide may include a compound of structure (I):

[0017]

[0018] Structure (I)

[0019] in

[0020] R1 is a C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, or C6-C22 heteroaryl;

[0021] R2, R3, and R4 are each independently C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, C6-C22 heteroaryl, or -C(O)R, wherein R is C1-C4 alkyl, C5-C12 cycloalkyl, C6-C18 aryl, or C6-C18 heteroaryl; and each alkyl, alkenyl, cycloalkyl, aryl, or heteroaryl is optionally independently substituted by at least one C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR5, -OC(O)R5, or -COOR5, wherein R5 is H, C1-C4 alkyl, C5-C12 cycloalkyl, C6-C18 aryl, or C6-C18 heteroaryl.

[0022] In some embodiments, at least one acetylgeral compound is a diacetylgeral compound.

[0023] According to another aspect of the invention, a curing film is provided, which is obtained by curing a polyimide precursor composition comprising at least one resin (polyimide precursor) and at least one acetogermanium compound.

[0024] According to another aspect, the present invention provides the use of the polyimide precursor composition described above or in any of the embodiments herein in the formation of a hardened film.

[0025] According to another aspect of the invention, a laminate is provided, comprising: two or more layers consisting of a hardened film obtained as described above; and

[0026] Metal layers between any layers consisting of a hardened film.

[0027] According to another aspect of the present invention, a method for manufacturing a hardened film is provided, comprising: The thin film forming step involves coating a polyimide precursor composition comprising at least one resin and at least one amide germanium compound onto a substrate to form a thin film; Exposure steps, selectively exposing the thin film; and The developing step involves using a developer to develop the film exposed in the exposure step to form a pattern.

[0028] In some embodiments, the method for manufacturing the above-described hardened film further includes a heating step of heating the film at a temperature of 50 degrees Celsius to 450 degrees Celsius.

[0029] In another aspect of the invention, a semiconductor device is described comprising a hardened film obtained by hardening a polyimide precursor composition, the polyimide precursor composition comprising: at least one resin (polyimide precursor) and at least one acetogermanium compound, or a laminate comprising: two or more layers consisting of the hardened film obtained as described above; and a metal layer between any of the layers consisting of the hardened film.

[0030] In another aspect, the present invention describes the use of a polyimide precursor composition comprising at least one resin and at least one acetogermanium compound for forming a hardened film. Simple Explanation of the Diagram

[0031] Figure 1 illustrates one aspect of the subject matter according to one embodiment. Figure 1 illustrates a semiconductor device 100. Implementation

[0032] Generally, the present invention relates to thin-film forming photosensitive polyimide precursor compositions, also known as polyimide precursor comprising compositions. The thin-film forming compositions described herein are sensitive to electromagnetic or photochemical radiation, electron beams, or X-rays in the wavelength range from about 150 nanometers to 450 nanometers (e.g., 355 nanometers, 365 nanometers, 375 nanometers, 405 nanometers, 435 nanometers), thereby producing solubility changes (e.g., increases or decreases in solubility) in a suitable developer (e.g., cyclopentanone).

[0033] The film forming composition (i.e., the polyimide precursor composition) includes the polyimide precursor itself as a resin compound and at least one acetylated germanium compound.

[0034] Furthermore, the polyimide precursor is preferably a polymer precursor formed from heterocyclic rings that can undergo cyclization reactions to form a fully acetylated polyimide structure.

[0035] In some embodiments, the present invention provides a thin film forming composition 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) acetylated germanium compound according to structure (I).

[0036] (I)

[0037] Wherein R1 is C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, or C6-C22 heteroaryl; R2, R3, and R4 are each independently C1-C12 alkyl, C2-C12 alkenyl, C4-C18 cycloalkyl, C6-C22 aryl, C6-C22 heteroaryl, or -C(O)R, where R is C1-C4 alkyl, C5-C12 cycloalkyl, C6-C18 aryl or C6-C18 heteroaryl; each alkyl, alkenyl, cycloalkyl, aryl, or heteroaryl group is independently and optionally substituted by at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR5, -OC(O)R5, or -COOR5, wherein R5 is H, C1-C4 alkyl, C5-C12 cycloalkyl, C6-C18 aryl, or C6-C18 heteroaryl. In some embodiments, the acetylgeralon compounds described herein may comprise one acetylgeralon group (i.e., monoacetylgeralon compound), two acetylgeralon groups (i.e., diacetylgeralon compound), three acetylgeralon groups (i.e., triacetylgeralon compound), or four acetylgeralon groups (i.e., tetraacetylgeralon compound). In some embodiments, the acetylgeralon compound according to structure (I) may comprise different acetylgeralon groups. In a preferred embodiment, the germanium compound is a diacetylgeralon compound, wherein R2 = R1-C(O).

[0038] 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, pyrene, anthracene, and phenanthryl. Examples of heteroaryl groups described herein include furanyl, furandiyl, fluorenyl, pyrroleyl, thiopheneyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinazolinyl, quinolinyl, isoquinolinyl, and indoleyl.

[0039] Suitable examples of structural (I) acetylated germanium compounds include, but are not limited to, (2,4,6-trimethylbenzoyl)triethyl germanium, (2,4,6-trimethylbenzoyl)tripropyl germanium, (2,4,6-trimethylbenzoyl)tributyl germanium, (2,6-dimethoxybenzoyl)triethyl germanium, (2,6-dimethoxybenzoyl)tripropyl germanium, (2,6-dimethoxybenzoyl)tributyl germanium, bis(4-methoxybenzoyl)diethyl germanium, bis(2,4,6-trimethylbenzoyl)diethyl germanium, triphenylbenzoylethyl germanium, tri(2,4,6-trimethylbenzoyl)ethyl germanium, etc. A commercial example of acetylated germanium compounds is Ivocerin (i.e., bis(4-methoxybenzoyl)diethylgermanium). Commercial examples of these compounds are available from Synthon (e.g., Ivocerin). Other examples of such acetylated germanium compounds are disclosed, for example, in U.S. Patent Nos. 7,605,190 and 9,532,930, the entire contents of which are incorporated herein by reference.

[0040] In some embodiments, the polyimide precursor comprises a composition including at least one acetylgeralon compound selected from (2,4,6-trimethylbenzoyl)triethylgermanium, (2,4,6-trimethylbenzoyl)tripropylgermanium, (2,4,6-trimethylbenzoyl)tributylgermanium, (2,6-dimethoxybenzoyl)triethylgermanium, and (2,6-dimethoxybenzoyl)triethylgermanium. One or more of the following: tripropylgermanium, (2,6-dimethoxybenzoyl)tributylgermanium, bisbenzoyldiethylgermanium, benzoyltrimethylgermanium, bisbenzoyldipropylgermanium, bis(4-methoxybenzoyl)diethylgermanium, bis(2,4,6-trimethylbenzoyl)diethylgermanium, tribenzoylethylgermanium, and tri(2,4,6-trimethylbenzoyl)ethylgermanium.

[0041] In some embodiments, the amount of acetylgeralic compound is at least about 0.05% by weight (e.g., at least about 0.1% by weight, at least about 0.2% by weight, at least about 0.4% by weight, at least about 0.5% by weight, at least about 0.6% by weight, at least about 0.8% by weight, at least about 1% by weight, at least about 1.5% by weight, or at least about 2% by weight) to at most about 20% by weight (e.g., at most about 18% by weight, at most about 16% by weight, at most about 15% by weight, at most about 14% by weight, at most about 12% by weight, at most about 10% by weight, at most about 8% by weight, at most about 6% by weight, at most about 5% by weight, at most about 4% by weight, at most about 2% by weight, or at most about 1% by weight) based on the solid weight of the polyimide precursor comprising the composition described herein. In the preferred embodiment, the acetylgeralic compound ranges from 0.05% by weight to 5% by weight based on the solid weight of the polyimide precursor comprising the composition described herein. As used herein, the solid weight of a thin film forming composition refers to the total weight of solids in such composition (i.e., excluding any solvents).

[0042] In some embodiments, the film-forming composition described herein (i.e., the polyimide precursor comprising composition) may selectively contain at least one (e.g., two, three, or four) radical initiators different from the acetogermanium 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 in a specific wavelength range (e.g., from about 150 nanometers (e.g., about 157 nanometers) or about 600 nanometers). In some embodiments, the wavelength range is selected such that the radical initiator has absorption while the radical polymerizable monomer does not have substantial absorption. Photoradical initiators (also referred to herein as photoinitiators) and thermal radical initiators (also referred to herein as thermal initiators) are examples of radical initiators. In some embodiments, photoradical initiators are preferred.

[0043] In some embodiments, the amount of free radical initiator (e.g., photoinitiator) is at least about 0.1% by weight (e.g., at least about 0.2% by weight, at least about 0.5% by weight, at least about 0.8% by weight, at least about 1% by weight, at least about 1.5% by weight, at least about 2% by weight, at least about 3% by weight, at least about 4% by weight, or at least about 5% by weight) to at most about 10% by weight (e.g., at most about 9% by weight, at most about 8% by weight, at most about 7% by weight, at most about 6% by weight, at most about 5% by weight, at most about 4% by weight, at most about 3% by weight, at most about 2% by weight, or at most about 1% by weight), based on the solid weight of the composition formed by the dielectric film described herein.

[0044] In some embodiments, the photoinitiator is photosensitive to radiation ranging from the ultraviolet region to the visible light region. In some embodiments, the photoinitiator may be an activator that generates free radicals through certain interactions with the photosensitive agent.

[0045] An example of a photoinitiator is an oxime ester of structure (II).

[0046]

[0047] (II),

[0048] R11 and R12 are each independently a substituted or unsubstituted C1-C12 alkyl, a substituted or unsubstituted C4-C18 cycloalkyl, a substituted or unsubstituted C6-C22 aryl, or a substituted or unsubstituted C6-C22 heteroaryl; and R13 is an ultraviolet-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 groups may be selectively substituted by at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR', -OC(O)R', or -COOR', wherein R' is H, C1-C4 alkyl, C5-C12 cycloalkyl, C6-C18 aryl, or C6-C18 heteroaryl.

[0049] Examples of formula (II) oxime esters include, but are not limited to: (OXE 1) (OXE 2) (OXE 3) (OXE 4) (OXE 5)

[0050] 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; and ADEKA OPTOMER N-1919, ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930, available from ADEKA Corporation. Examples of other photoinitiators are disclosed, for example, in EP Patent No. 3,492,982, the entire contents of which are incorporated herein by reference.

[0051] Examples of thermal initiators include, but are not limited to, benzoyl peroxide, cyclohexanone peroxide, lauryl peroxide, pentyl benzoate peroxide, butyl hydroperoxide, di(tertyl) peroxide, dicumylbenzene peroxide, cumyl hydroperoxide, succinate peroxide, di(n-propyl) peroxydicarbonate, 2,2-azobis(isobutyronitrile), 2,2-azobis(2,4-dimethylpentanitrile), dimethyl 2,2-azobisisobutyrate, 4,4-azobis(4-cyanopentanoic acid), azobiscyclohexaneformitrile, and 2,2-azobis(2-methylbutyronitrile).

[0052] Other examples of photoradical polymerization initiators include benzophenone derivatives, such as benzophenone, methyl o-benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives, such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives, such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives, such as benzyl, benzyl dimethyl ketal, and benzyl-β-methoxyethyl acetal; and benzoin derivatives, such as benzoin and benzoin methyl ether. Fragrance derivatives, such as benzoin and benzoin methyl ether; 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-diphenyltrione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxytrione-2-(o-benzoyl) oxime; N-aryl glycine, such as N-phenylglycine; peroxides, such as benzoyl peroxide, aromatic diimidazoles, etc. Furthermore, these can be used alone or as mixtures of two or more types.

[0053] In some embodiments, the film-forming composition described herein may include at least one (e.g., two, three, or four) photosensitizers different from acetylenium compounds, wherein the photosensitizers absorb light in the wavelength range of about 150 nanometers to about 600 nanometers (e.g., at about 405 nanometers). Examples of suitable photosensitizers that can be used in dielectric film-forming compositions include benzophenone compounds, thioxanthone compounds, anthraquinone compounds, anthracene compounds, coumarin compounds, and mixtures thereof. Specific examples of photosensitizers include, but are not limited to, 9-methylanthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, anthracene methanol, acenaphthene, thioxanthone, methyl-2-naphthyl ketone, 4-acetylbenylbenzene, and 1,2-benzofluorene. Examples of other photosensitizers are disclosed, for example, in U.S. Application Publication No. 2022 / 0171285, the entire contents of which are incorporated herein by reference. In some embodiments, the acetylenium compounds described herein may be used as photosensitizers.

[0054] In some embodiments, the amount of photosensitizer other than the acetylgera compound is 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%), based on the solid weight of the dielectric film composition described herein.

[0055] Polyimide precursors may preferably include at least one compound of formula (1): Equation (1)

[0056] In this context, 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.

[0057] In some embodiments, the polyimide precursor of the present invention is a heterocyclic polymer precursor, wherein the heterocyclic polymer precursor is selected from polyimide (PI) precursors comprising formula (1): Equation (1) In this context, 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.

[0058] The aforementioned polyimide precursor (PI) should be understood as the compound represented by formula (1). The terms "heterocycle-forming polymer precursor" or "heterocyclic ring-forming polymer precursor" as used herein should be understood specifically to refer to polyimide precursors that are not fully amide-iminated (partially amide-iminated) and form amide heterocycles upon further reaction (or, in other words, polymers containing amide-forming units but not fully cyclized in their initial form). The terms "heterocycle-forming polymer precursor" and "heterocyclic ring-forming polymer precursor" are used interchangeably herein.

[0059] In formula (1), A1 and A2 are preferably oxygen atoms or NH, and more preferably oxygen atoms.

[0060] In formula (1), preferably R113 and R114 each independently represent polymerizable groups, preferably A1 and / or A2 represent oxygen, wherein A1 and / or A2 are preferably linked to a methacrylic alkyl group, and more preferably both A1 and A2 are linked to a methacrylic alkyl group. In the preferred embodiment, R113 and R114 are given by the following structure (IV). Structure (IV)

[0061] In formula (1), R111 represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and groups containing aryl groups. The divalent organic group is preferably a straight-chain 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 groups having 6 to 20 carbon atoms, or a combination thereof, more preferably a group composed of aromatic groups having 6 to 20 carbon atoms.

[0062] R111 is preferably derived from diamines. Diamines used to generate polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. For diamines, only one type may be used, or two or more types may be used.

[0063] Specifically, diamines containing a straight-chain 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 combination thereof are preferred, and diamines containing a group composed of an aromatic group having 6 to 20 carbon atoms are even more preferred. Examples of aromatic diamines include the following.

[0064] R111 is preferably at least one structure represented by any one of the following formulas (Y-1) and (Y-3).

[0065] In the formula, A is preferably a single bond, or a group selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms that can be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -S(=O)2-, -NHCO-, and combinations thereof, more preferably a single bond, or a group selected from alkyl groups having 1 to 3 carbon atoms that can be substituted with fluorine atoms, -O-, -C(=O)-, -S-, and -SO2-, even more preferably a divalent group selected from groups composed of -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, and -C(CH3)2-.

[0066] As a diamine, specifically, it refers to 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. diamine); meta- and p-phenylenediamine, 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 sulfide, 4,4'- and 3,3'-diaminodibenzophenone, 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) arsenide, bis(4-amino-3-hydroxyphenyl) arsenide, 4,4'-diamino-p-terphenyl, 4,4-bis[ [4-aminophenoxy]biphenyl, bis[4-(4-aminophenoxy)phenyl]phenoxide, bis[4-(3-aminophenoxy)phenyl]phenoxide, bis[4-(2-aminophenoxy)phenyl]phenoxide, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenoxy)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylphenoxide, 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'-di Methyl-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-hydroxyanthracene, 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'-Diaminodiphenylene, 3,3',5,5'-Tetramethyl-4,4'-Diaminodiphenylmethane, 2,4- and 2,5-Diaminoisocumene, 2,5-Dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-Diaminofluorene, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline Esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzene trifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenyl)]hexafluoropropane, [4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl benzoylene, 4,4'-bis(3-amino-5-difluoromethylphenoxy)diphenyl benzoylene, p-bis(4-amino-5-difluoromethylphenoxy)diphenyl benzoylene, p-bis(4-amino-2-tri ...2-trifluoromethylphenoxy)diphenyl benzoylene, p-bis(4-amino-2-trifluoromethylphenoxy)diphenyl benzoylene, p-bis(4-amino-2 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'-hexafluorobitoluidine, 4-(4-{2-[4-(4-aminophenoxy)phenyl]propane-2-yl}phenoxy)aniline, and 4,4'-diaminotetraphenyl.

[0067] In addition, diamines (DA-1) to (DA-18) as shown below are also preferred.

[0068] Furthermore, as preferred examples of diamines, diamines having at least two alkyl glycol units in the main chain are also mentioned. Diamines containing a total of two or more ethylene glycol chains and propylene glycol chains in a molecule are preferred, and diamines without aromatic rings are even more preferred. As specific examples, 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-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amino, and 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine are mentioned, but not limited to these.

[0069] The structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176 are shown below.

[0070] In the above, x, y, and z are average values.

[0071] From the viewpoint of the resulting hardened film's flexibility, R111 is preferably represented by -Ar-L-Ar-, where each Ar independently represents an aromatic group, and L represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be substituted with a fluorine atom, or a group consisting of -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of these groups. Ar is preferably phenyl, and L is more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that can be substituted with a fluorine atom, or a group consisting of -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably alkyl.

[0072] From the viewpoint of i-ray transmittance, R111 is preferably a divalent organic group represented by formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, the divalent organic group represented by formula (61) is more preferred.

[0073] 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.

[0074] As a monovalent organic group in R10 to R17, unsubstituted alkyl groups having 1 to 10 (preferably 1 to 6) carbon atoms, fluorinated alkyl groups having 1 to 10 (preferably 1 to 6) carbon atoms, etc. are mentioned.

[0075] In formula (61), R18 and R19 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

[0076] As diamine compounds forming the structure of formula (51) or (61), dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. may be used. One of these types may be used, or two or more of these types may be used in combination.

[0077] In formula (1), R115 represents a tetravalent organic group. As a tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) is even more preferred.

[0078] In formula (5), R112 is preferably a single bond, or a group selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms that can be substituted with fluorine atoms, -O-, -CO-, -S-, -SO2-, -NHCO-, and combinations thereof, more preferably a single bond, or a group selected from alkyl groups having 1 to 3 carbon atoms that can be substituted with fluorine atoms, -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-.

[0079] In formula (1), R115 represents a tetravalent organic group. Preferably, the tetravalent organic group contains a structure represented by any one of formulas (X-1) to (X-3).

[0080] As the tetravalent organic group represented by R115 in formula (1), specifically, refers to the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. For the tetracarboxylic dianhydride, only one type may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by formula (O).

[0081] In formula (O), R115 represents a tetravalent organic group. R115 has the same meaning as R115 in formula (1).

[0082] As specific examples of tetracarboxylic dianhydrides, examples are given from pyromellitic dianhydride, pyromellitic dianhydride (PMDA), 3,3,4,4'-biphenyltetracarboxylic dianhydride, 3,3,4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3,4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3,4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, etc. Alkanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxophthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride Hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl) At least one of the following: ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 5-[4-(2-{4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl}propane-2-yl)phenoxy]-2-benzofuran-1,3-dione, 1,2,3,4-benzenetetracarboxylic acid dianhydride, or an alkyl derivative thereof having 1 to 6 carbon atoms and / or an alkoxy derivative thereof having 1 to 6 carbon atoms.

[0083] In addition, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) as shown below are also mentioned as preferred examples.

[0084] R113 and R114 each independently represent a hydrogen atom or a monovalent organic group. Preferably, at least one of R113 or R114 contains a free radical polymerizable group, and more preferably, both R113 and R114 contain free radical polymerizable groups. The free radical polymerizable group is a group capable of undergoing cross-linking reactions through free radical action, and preferred examples include groups having olefinic unsaturated bonds.

[0085] As groups having olefinic unsaturated bonds, vinyl, (methyl)allyl, and groups represented by formula (III) are mentioned.

[0086] In formula (III), R200 represents a hydrogen atom or a methyl group, with methyl being preferred.

[0087] 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.

[0088] Suitable examples of R201 include vinyl, propenyl, trimethyl, tetramethyl, 1,2-butadiyl, 1,3-butadiyl, pentamethyl, hexamethyl, octamethyl, dodecanmethyl, and -CH2CH(OH)CH2-, with vinyl, propenyl, trimethyl, and -CH2CH(OH)CH2- being more preferred.

[0089] Preferably, R200 is methyl and R201 is vinyl.

[0090] As a monovalent organic group represented by R113 or R114, it is preferable to use a substituent that improves the solubility of the developer.

[0091] From the viewpoint of solubility in aqueous developers, R113 or R114 can be a hydrogen atom or a monovalent organic group. As a monovalent organic group, references include one, two, or three acidic groups bonded to the carbon atoms constituting the aryl group, preferably aromatic groups or aralkyl groups with one acidic group. Specifically, references include aromatic groups having an acidic group and 6 to 20 carbon atoms, and aralkyl groups having an acidic group and 7 to 25 carbon atoms. More specifically, references include phenyl groups and benzyl groups having an acidic group. The acidic group is preferably an OH group.

[0092] From the viewpoint of solubility in aqueous developers, R113 or R114 is preferably hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl.

[0093] From the viewpoint of solubility in organic solvents, R113 or R114 is preferably a monovalent organic group. The monovalent organic group preferably contains a straight-chain or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

[0094] The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group can be straight-chain, branched, or cyclic. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, dibutyl, tributyl, 1-ethylpentyl, and 2-ethylhexyl. Cyclic alkyl groups can be monocyclic or polycyclic. Examples of monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alkyl groups include adamantyl, norbornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphoryl, dicyclohexyl, and pinenyl. Among these, cyclohexyl is most preferred from the viewpoint of high sensitivity compatibility. Furthermore, the aromatic-substituted alkyl group is preferably a straight-chain alkyl group as described below.

[0095] As an aromatic group, specifically, it refers to substituted or unsubstituted benzene rings, naphthyl rings, pentanene rings, indene rings, azulene rings, heptanene rings, indene rings, perylene rings, pentabenzene rings, acenaphthyl rings, phenanthrene rings, anthracene rings, tetrabenzene rings, cyclobenzene rings, tribenzene rings, fluorene rings, biphenyl rings, pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, thiazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, indoleazine rings, indole rings, benzofuran rings, benzothiophene rings, isobenzofuran rings, quinazine rings, quinoline rings, phthalazine rings, naphthidine rings, quinoxaline rings, quinoxazoline rings, isoquinoline rings, carbazole rings, phenanthridine rings, acridine rings, phenanthrene-rhein rings, thiamethoxam rings, benzopyran rings, xanthan rings, phenothiazine rings, phenothiazine rings, or pherazine rings. Benzene rings are preferred.

[0096] In formula (1), when R113 is a hydrogen atom or when R114 is a hydrogen atom, the polyimide precursor can form a countersalt with a tertiary amine compound having an olefinically unsaturated bond. As an example of such a tertiary amine compound having an olefinically unsaturated bond, N,N-dimethylaminopropyl methacrylate is mentioned.

[0097] Furthermore, it is preferable that the polyimide precursor contains fluorine atoms in its structural units. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0098] Furthermore, to improve adhesion to the substrate, aliphatic groups with siloxane structures can be copolymerized. Specifically, bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane are mentioned as diamine components.

[0099] The polyimide precursor may have one repeating structural unit represented by formula (1), or it may have two or more repeating structural units. In addition, the polyimide precursor may contain structural isomers of the repeating unit represented by formula (1). Furthermore, in addition to the repeating unit of formula (1), the polyimide precursor may also contain other types of repeating structural units.

[0100] As an example of the polyimide precursor in this invention, a polyimide precursor in which the repeating unit represented by formula (1) accounts for more than 50 mol%, or even more than 70 mol%, and particularly more than 90 mol% of the total repeating unit is exemplified.

[0101] The weight-average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000. Furthermore, its number-average molecular weight (Mn) is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, and even more preferably from 4,000 to 25,000.

[0102] The preferred dispersion of the polyimide precursor is 1.5 to 2.5.

[0103] Polyimide precursors are obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, polyimide precursors are obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent, followed by reacting the result with a diamine.

[0104] In the process of producing polyimide precursors, it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used.

[0105] The organic solvent can be appropriately determined according to the raw materials, for example pyridine, diethylene glycol dimethyl ether, N-methylpyrrolidone and N-ethylpyrrolidone.

[0106] In the manufacture of polyimide precursors, to further improve storage stability, end-capping agents such as acid dianhydrides, monocarboxylic acids, monocarboxylic acid chlorides, and monoactive ester compounds are preferably used for end-capping. Among these, monoamines are even more preferred. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-5-aminonaphthalene. 2-Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, or various different end groups can be introduced by reacting with multiple end-capping agents.

[0107] The production of polyimide precursors may include a step of precipitating solids. Specifically, solids can be precipitated by precipitating the polyimide precursor in the reaction solution in water and dissolving the precipitated polyimide precursor in a solvent such as tetrahydrofuran, in which the polyimide precursor is soluble.

[0108] Subsequently, the polyimide precursor can be dried to obtain powdered polyimide precursor.

[0109] The composition of this invention may contain a thermal alkali generating agent. By using a thermal alkali generating agent, exposure energy consumption can be suppressed and exposure latitude expanded, and an alkali substance that promotes the ring-closure reaction of polymer precursors during the heating step of the ring-closure reaction can also be generated. Therefore, the ring-closure rate tends to be further improved.

[0110] The type of hot alkali generating agent is not particularly limited, but it preferably includes at least one acidic compound selected from those that produce alkali when heated to 40 degrees Celsius or higher, or an ammonium salt having an anion and an ammonium cation with a pKa1 of 0 to 4. Here, pKa1 represents the logarithm (-Log10Ka) of the reciprocal of the dissociation constant (Ka) of the first proton of the acid, which will be described in detail later.

[0111] Acidic compounds (AC1) and ammonium salts (AM2) produce bases upon heating. Therefore, the bases generated from these compounds enable the cyclization reaction of heterocyclic polymer precursors, allowing the cyclization of heterocyclic polymer precursors to occur at low temperatures. Furthermore, even when these compounds coexist with polyimide precursors that have been cyclized and hardened by bases, the cyclization of heterocyclic polymer precursors hardly occurs unless heated, thus enabling the preparation of compositions with excellent storage stability.

[0112] In this specification, an acidic compound is defined as a compound whose pH value is less than 7 when measured with a pH (hydrogen ion concentration index) meter at 20 degrees Celsius for a solution obtained in the following manner: 1 g of the compound is collected in a container, 50 mL of a mixture of ion-exchanged water and tetrahydrofuran (mass ratio of water / tetrahydrofuran = 1 / 4) is added to it, and the mixture is stirred at room temperature for 1 hour.

[0113] In this embodiment, the alkali formation temperature of the acidic compound (AC1) and the ammonium salt (AM2) is preferably 40 degrees Celsius or higher, more preferably 120 to 200 degrees Celsius. The upper limit of the alkali formation temperature is preferably 190 degrees Celsius or lower, more preferably 180 degrees Celsius or lower, and even more preferably 165 degrees Celsius or lower. The lower limit of the alkali formation temperature is preferably 130 degrees Celsius or higher, more preferably 135 degrees Celsius or higher.

[0114] When the alkali formation temperature of the acidic compound (AC1) and ammonium salt (AM2) is 120°C or higher, almost no alkali is formed during storage, thus allowing for the preparation of compositions with excellent stability. When the alkali formation temperature of the acidic compound (AC1) and ammonium salt (AM2) is 200°C or lower, the cyclization temperature of the heterocyclic polymer precursor can be reduced. For example, the alkali formation temperature can be measured using differential scanning calorimetry, such as heating the compound to 250°C at a rate of 5°C per minute in a pressure-resistant capsule, reading the peak temperature of the exothermic peak with the lowest temperature, and using this peak temperature as the alkali formation temperature.

[0115] In this embodiment, the alkali generated by the hot alkali generating agent is preferably a secondary or tertiary amine, more preferably a tertiary amine. Because tertiary amines are highly basic, they can further reduce the cyclization temperature of the polyimide precursor. Furthermore, the boiling point of the alkali generated by the hot alkali generating agent is preferably 80 degrees Celsius or higher, more preferably 100 degrees Celsius or higher, and even more preferably 140 degrees Celsius or higher. Additionally, the molecular weight of the generated alkali is preferably between 80 and 2,000. The lower limit is more preferably 100 or higher, and the upper limit is more preferably 500 or lower. The molecular weight values ​​are theoretical values ​​obtained from the structural formula.

[0116] In this embodiment, the acidic compound (AC1) preferably contains at least one selected from ammonium salts or compounds having an ammonium structure represented by formula (101) or (102).

[0117] In this embodiment, the ammonium salt (AM2) is preferably an acidic compound. The ammonium salt (AM2) may be a compound containing an acidic compound that produces a base when heated to 40 degrees Celsius or higher (preferably 120 to 200 degrees Celsius), or may be a compound other than an acidic compound that produces a base when heated to 40 degrees Celsius or higher (preferably 120 to 200 degrees Celsius).

[0118] In this embodiment, ammonium salt refers to a salt of ammonium cation and anion represented by formula (101) or formula (102). The anion may be covalently bonded to any part of the ammonium cation, or it may exist outside the ammonium cation molecule. Preferably, the anion exists outside the ammonium cation molecule. The statement that the anion exists outside the ammonium cation molecule means that the ammonium cation and anion are not covalently bonded. Hereinafter, the anion outside the cation molecule is also referred to as a counter anion.

[0119] 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) can be bonded to each other to form a ring.

[0120] The ammonium cation is preferably represented by any one of formulas (Y1-1) to (Y1-5).

[0121] In formulas (Y1-1) to (Y1-5), R101 represents an n-valent organic group, and R1 and R7 have the same meaning as R1 and R7 in formula (101) or formula (102).

[0122] In equations (Y1-1) to (Y1-4), Ar101 and Ar102 each independently represent aryl groups, n represents an integer of 1 or higher, and m represents an integer from 0 to 5.

[0123] In this embodiment, the ammonium salt preferably has an anion and an ammonium cation with a pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is preferably 3.5 or lower, even more preferably 3.2 or lower. The lower limit is preferably 0.5 or higher, more preferably 1.0 or higher. When the pKa1 of the anion is within the above range, heterocyclic polymer precursors (e.g., polyimide precursors) can cyclize at lower temperatures, and the stability of the composition can be improved. When pKa1 is 4 or lower, the hot alkali generator exhibits good stability and can suppress alkali generation without heating, resulting in good stability of the composition. When pKa1 is 0 or higher, the generated alkali is difficult to neutralize, and the cyclization efficiency of heterocyclic polymer precursors, etc., is good.

[0124] The type of anion is preferably selected from carboxylate anions, phenolic anions, phosphate anions, and sulfate anions, with carboxylate anions being even more preferred because they can simultaneously achieve salt stability and thermal decomposability. In other words, the ammonium salt is preferably a salt of an ammonium cation and a carboxylate anion.

[0125] The carboxylic acid ester anion is preferably an anion of a divalent or higher-valent carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this embodiment, a hot alkali generating agent capable of further improving the stability, curing, and developability of the composition can be used. In particular, by using an anion of a divalent carboxylic acid, the stability, curing, and developability of the composition can be further improved.

[0126] In this embodiment, the carboxylic acid ester anion is preferably an anion of a carboxylic acid with a pKa1 of 4 or lower. More preferably, the pKa1 is 3.5 or lower, and even more preferably 3.2 or lower. According to this embodiment, the stability of the composition can be further improved.

[0127] Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and can be found in the values ​​described in *Determination of Organic Structures by Physical Methods* (authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; editors: Braude, EA, Nachod, FC; Academic Press, New York, 1955) or *Data for Biochemical Research* (authors: Dawson, RMC, et al.; Oxford Clarendon Press, 1959). For compounds not described in these literatures, values ​​were calculated from the structural formula using the software ACD / pKa (manufactured by ACD / Labs).

[0128] The preferred carboxylic acid ester anion is represented by formula (XI). Formula (XI)

[0129] In equation (XI), EWG represents an electron-withdrawing group.

[0130] In this embodiment, electron-withdrawing groups refer to groups whose Hammett substituent constant σm is positive. Here, σm is described in detail in the literature review by TSUNO Yuho in the Journal of the Society of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), pp. 631-642. The electron-withdrawing groups in this embodiment are not limited to the substituents described in the aforementioned literature.

[0131] Examples of substituents with positive σm values ​​include the CF3 group (σm = 0.43), CF3CO group (σm = 0.63), HC≡C group (σm = 0.21), CH2=CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCH group (σm = 0.21), PhCO group (σm = 0.34), and H2NCOCH2 group (σm = 0.06). Me represents methyl, Ac represents acetyl, and Ph represents phenyl (the same applies below).

[0132] EWG is preferably a basis represented by equations (EWG-1) to (EWG-6).

[0133] In formulas (EWG-1) to (EWG-6), Rx1 to Rx3 each independently represent a hydrogen atom, alkyl, alkenyl, aryl, hydroxyl, or carboxyl group, and Ar represents an aromatic group.

[0134] In this embodiment, the carboxylic acid ester anion is preferably represented by formula (XA).

[0135] In formula (XA), L10 represents a single bond, or a divalent linker selected from alkyl, alkenyl, aromatic, -NRX- and combinations thereof, and RX represents a hydrogen atom, alkyl, alkenyl or aryl.

[0136] As specific examples of carboxylic acid ester anions, maleate anion, phthalate anion, N-phenyliminodiacetate anion and oxalate anion are mentioned.

[0137] The following compounds can be mentioned as specific examples of thermal alkali generating agents.

[0138] When the composition of the present invention contains a hot alkali generating agent, the content of the hot alkali generating agent, based on the total solids content of the composition of the present invention, is preferably from 0.1% by mass to 50% by mass. The lower limit is more preferably 0.5% by mass or more, more preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. The upper limit may be 5% by mass or less, or 4% by mass or less.

[0139] For hot alkali generating agents, one or more types may be used. When using two or more types, the total amount is preferably within the range mentioned above.

[0140] The composition of this invention may contain organic compounds containing Group 4 elements (hereinafter sometimes referred to as "organo-titanium compounds, etc.").

[0141] Organic compounds containing Group 4 elements are preferably organic compounds containing at least one selected from titanium, zirconium, or hafnium atoms, and more preferably organic compounds containing at least one selected from titanium or zirconium atoms. Furthermore, organic compounds containing at least one selected from titanium or zirconium atoms are preferably compounds containing an organic group and titanium or zirconium atoms, with the total number of titanium and zirconium atoms in a molecule preferably being one. The organic group is not particularly limited, but is preferably alkyl, or a group composed of an alkyl group and a heteroatom. The heteroatom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom.

[0142] In this invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two of them are cyclic groups. The cyclic groups are preferably selected from 5-membered and 6-membered cyclic groups, and more preferably from 5-membered cyclic groups. As a 5-membered cyclic group, cyclopentadienyl is preferred. Furthermore, the organotitanium compounds used in this invention preferably contain 2 to 4 cyclic groups in one molecule.

[0143] In this invention, organotitanium compounds are preferably represented by formula (P).

[0144] In formula (P), M is a group 4 element, and R are each an independent substituent.

[0145] The substituents are preferably selected from aryl, alkyl, halogen atoms and alkylsulfonyloxy groups.

[0146] As a Group 4 element represented by M, titanium, zirconium, and hafnium atoms are preferred, with titanium and zirconium atoms being even more preferred.

[0147] As aryl, phenyl, 1-naphthyl, 2-naphthyl, etc. can be mentioned. As alkyl, methyl, ethyl, propyl, octyl, isopropyl, t-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. can be mentioned.

[0148] As halogen atoms, F, Cl, Br and I can be mentioned.

[0149] Alkyl chains constituting alkylsulfonyloxy groups may include methyl chains, ethyl chains, propyl chains, octyl chains, isopropyl chains, t-butyl chains, isopentyl chains, 2-ethylhexyl chains, 2-methylhexyl chains, cyclopentyl chains, etc.

[0150] The above-mentioned substituents may further have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acetyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acetyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, diarylamino groups, etc.

[0151] The organic compounds containing Group 4 elements used in this invention are preferably selected from titanium diacetic compounds, tetraalkoxytitanium compounds, titanium acetate compounds, titanium chelate compounds, zirconium diacetic compounds, and hafnium diacetic compounds, more preferably from titanium diacetic compounds, zirconium diacetic compounds, and hafnium diacetic compounds, and even more preferably from titanium diacetic compounds and zirconium diacetic compounds.

[0152] The molecular weight of organotitanium compounds, etc., is preferably from 50 to 2,000, and more preferably from 100 to 1,000.

[0153] Specific examples of organotitanium compounds include tetraisopropoxytitanium, tetra(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetate)titanium, diisopropoxybis(acetyl pyruvate)titanium, and the following compounds.

[0154] In addition, among organotitanium compounds, the following compounds can be used as organic compounds containing titanium atoms: Dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-bisphenyl, dicyclopentadienyl-titanium-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-titanium-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-titanium-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl-titanium-2,6-difluorophenyl-1-yl, dicyclopentadienyl-titanium-bis-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-titanium-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-titanium- Bis-2,3,5,6-tetrafluorophenyl-1-yl, dimethylcyclopentadienyl-titanium-bis-2,4-difluorophenyl-1-yl, bis(cyclopentadienyl)bis(2,6-difluoro-3-(pyrrolo-1-yl)phenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(methylsulfonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbisarylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylacetamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-( [N-methylacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylpropionic acid)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(2,2-dimethylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2-dimethylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-pentyl-(2,2-dimethylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-pentyl-(2,2-dimethylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(N-hexyl)-(2,2-dimethylbutyryl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methylbutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methylpentadienylamino)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-azapyrrolidin-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(octylsulfonyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-tolylsulfonyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-dodecylphenylsulfonyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-(1-pentylheptyl)phenylsulfonyl)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-Difluoro-3-((4-bromophenyl)-sulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-naphthylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(hexadecylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methyl-(4-dodecylphenyl)sulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methyl-4-(1-pentylheptyl)phenyl)sulfonamido)]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-tolyl)-sulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-tolyl)-sulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro] -3-(pyrrolidone-2,5-dione-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,4-dimethyl-3-pyrrolidone-2,5-dione-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis(2,6-difluoro-3-(phthalimino)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 Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylthiourea)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-butylthiourea)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylurea)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-butylurea)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N,N-diacetaminophen)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,3-dimethylurea)phenyl]titanium, bis(cyclopentadienyl)bis[2,[6-Difluoro-3-(butyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis2,6-difluoro-3-(decyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(octadecanoylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(isobutylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethylhexylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-methylbutylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(tertapeptylamino)phenyl]titanium )phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethylbutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethyl-2-methylheptadiamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(cyclohexylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3-chloropropadiamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylpropadiamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-chloromethyl-2-methyl-3-chloropropadiamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6- [Difluoro-3-(3,4-dimethylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-ethylphenylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,4,6-trimethylylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phenylamino)phenyl]titanium bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl)benzoamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-ethylheptyl)-2,2-dimethylpentadienyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-tolyl)amino]titanium )phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutylbenzoamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethylpentafenamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxacyclopentan-2-ylmethyl)benzoamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-ethylhepyl)-2,2-dimethylbutyrylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl-(4-tolyl)amino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxacyclohexane-2 [2,6-difluoro-3-(N-(4-tolylmethyl)benzoamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-tolylmethyl)benzoamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-tolylmethyl)-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,[6-Difluoro-3-(N-Butylphenylamino)phenyl]titanium, , Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-tolyl)amino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-tolyl)amino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2,4-dimethylpentyl)-2,2-dimethylbutane]titanium [Bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,4-dimethylpentyl)-2,2-dimethylpentadienyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-((4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethylpentadienyl)phenyl]titanium [Phenylacetyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3-ethoxypropionic)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3-allyloxypropionic)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-allylethoxypropionic)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethylbutyramine)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethylphenylamine)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(4-tolyl)amine)phenyl]titanium, bis(cyclopentadienyl) Bis[2,6-difluoro-3-(N-(2-ethylhexyl)benzoamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isopropylbenzoamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl)-2,2-dimethylpentafenyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(N-hexylbenzoamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-2,2-dimethylpentadienyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbenzoamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-( N-(2-ethylhexyl)-2,2-dimethylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-2,2-dimethylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isopropyl-2,2-dimethylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2 ,6-Difluoro-3-(N-(3-phenylpropyl)pentafenamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-2,2-dimethylpentafenamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)benzofenamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-Difluoro-3-(N-benzylphenylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-(4-tolyl)amino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-methylphenylmethyl)-2,2-dimethylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-2,2-dimethylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2-ethyl-2-methylheptyl)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-hexyl-(2-ethyl-2-methylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexyl-2,2-dimethylpentyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxacyclopentan-2-ylmethyl)-2,2-dimethylpentyl) [amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexyl-(4-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexyl-(2-chlorobenzoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,3-dimethyl-2-azacyclobutanone] -1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-isocyanate phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(4-toluenesulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-toluenesulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-toluenesulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-toluenesulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2-dimethyl-3-chloropropionic acid)amino)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropionyl)-2,2-dimethyl-3-chloropropionyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2,2-dimethyl-3-chloropropionyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3] -(N-isobutyl-(2,2-dimethyl-3-chloropropionic)phenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2-chloromethyl-2-methyl-3-chloropropionic)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-isocyanate phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(4-toluenesulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-toluenesulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-toluenesulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-toluenesulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-toluenesulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2-di-difluoro-3-(N-butyl-(2,2-di-difluoro-3-(N-butyl-(2,2-di-difluoro-3-(N-butyl-(2,2-difluoro-3-(N-ethyl ... [Methyl-3-chloropropionic acid)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropionic acid)-2,2-dimethyl-3-chloropropionic acid)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2,2-dimethyl-3-chloropropionic acid)amino)phenyl]titanium, bis( bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(2,2-dimethyl-3-chloropropionic)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2-chloromethyl-2-methyl-3-chloropropionic)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-dimethylbutyramine)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-2,2-dimethylpentylamino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-ethylacetylaminyl)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-ethylpropionic acid)phenyl]titanium, bis(trimethylcyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-2,2-dimethylpropionic acid)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-trimethylsilamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylhexyldimethylsilamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(1,1,2-trimethylpropyl)dimethylsilamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-ethoxymethyl-3-methyl-2-azathionone-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-allyloxymethyl-3-methyl-2-azathionone-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-Difluoro-3-(3-chloromethyl-3-methyl-2-azacyclobutanone-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-2,2-dimethylpropionic acid)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(5,5-dimethyl-2-pyrrolidone-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(6,6-diphenyl-2-piperidinone-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2,3-dihydro-1,2-benzothiazol-3-one(1,1-dioxide)-2 ... 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-(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-(4-methylphenylmethyl)-(2-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-dimethylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-ethylhexyl)-4-tolyl-sulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-oxaheptyl)benzoyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,6-dioxadecyl)benzoyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,6-dioxadecyl)benzoyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(trifluoromethylsulfonyl)amino ... Bis(cyclopentadienyl)bis[2,6-difluoro-3-(trifluoroacetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-chlorophenyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,6-dioxadecyl)-2,2-dimethylpentamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,7-dimethyl-7-methoxyoctyl)phenyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,7-dimethyl-7-methoxyoctyl)phenyl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylphenyl)phenyl]titanium, etc.

[0155] In addition, among organotitanium compounds, the following compounds can also be used as organic compounds containing zirconium atoms or compounds containing hafnium atoms: (cyclopentadienyl)trimethylzirconium, (cyclopentadienyl)triphenylzirconium, (cyclopentadienyl)tribenzylzirconium, (cyclopentadienyl)trichlorozirconium, (cyclopentadienyl)trimethoxyzirconium, (cyclopentadienyl)dimethyl(methoxy)zirconium, (cyclopentadienyl)methyldichlorozirconium, (methylcyclopentadienyl)trimethylzirconium, (methylcyclopentadienyl)triphenylzirconium, (methylcyclopentadienyl)tribenzylzirconium, (methylcyclopentadienyl)trichlorozirconium, (methylcyclopentadienyl)dimethyl(methoxy)zirconium, (dimethylcyclopentadienyl)trimethylzirconium, (trimethylcyclopentadienyl)trimethylzirconium, (trimethylsilylcyclopentadienyl) (Cyclopentadienyl)trimethylzirconium, (tetramethylcyclopentadienyl)trimethylzirconium, (pentamethylcyclopentadienyl)triphenylzirconium, (pentamethylcyclopentadienyl)tribenzylzirconium, (pentamethylcyclopentadienyl)trichlorozirconium, (pentamethylcyclopentadienyl)trimethoxyzirconium, (pentamethylcyclopentadienyl)dimethyl(methoxy)zirconium, (cyclopentadienyl)triethylzirconium, (cyclopentadienyl)tripropylzirconium, (cyclopentadienyl)trinepentylzirconium, (cyclopentadienyl)tri(diphenylmethyl)zirconium, (cyclopentadienyl)dimethylzirconium hydride, (cyclopentadienyl)triethoxyzirconium, (cyclopentadienyl)triisopropoxyzirconium, (cyclopentadienyl)triphenoxyzirconium, (cyclopentadienyl)dimethylisopropoxyzirconium, (cyclopentadienyl) Diphenylisopropoxyzirconium, (cyclopentadienyl)dimethoxyzirconium chloride, (cyclopentadienyl)methoxyzirconium dichloro, (cyclopentadienyl)diphenoxyzirconium chloride, (cyclopentadienyl)phenoxyzirconium dichloro, (cyclopentadienyl)tris(phenyldimethylsilyl)zirconium, (n-butylcyclopentadienyl)dimethyln-n-butoxyzirconium, (benzylcyclopentadienyl)di-m-tolylmethylzirconium, (trifluoromethylcyclopentadienyl)tribenzylzirconium, (diphenylcyclopentadienyl)dinorbornelmethylzirconium, (tetraethylcyclopentadienyl)tribenzylzirconium, (pentamethylsilylcyclopentadienyl)tribenzylzirconium, (pentamethylcyclopentadienyl)trinepentylzirconium, (pentamethylcyclopentadienyl)methyldichlorozirconium, (pentamethylcyclopentadienyl)triethoxyzirconium, (pentamethylcyclopentadienyl)triphenyl Zirconium oxide, (pentamethylcyclopentadienyl)methoxyzirconium dichloro, (pentamethylcyclopentadienyl)diphenoxyzirconium chloride, (pentamethylcyclopentadienyl)phenoxyzirconium dichloro, (indenyl)trimethylzirconium, (indenyl)tribenzylzirconium, (indenyl)trichlorozirconium, (indenyl)trimethoxyzirconium, (indenyl)triethoxyzirconium, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)diethylzirconium, bis(cyclopentadienyl)dibenzylzirconium, bis(cyclopentadienyl)dimethoxyzirconium, bis(cyclopentadienyl)dichlorozirconium, bis(cyclopentadienyl)zirconium dihydrogenide, bis(cyclopentadienyl)zirconium hydrochloride, bis(methylcyclopentadienyl)dimethylzirconium, bis(methylcyclopentadienyl)dibenzylzirconium, bis(methylcyclopentadienyl)dichlorozirconium,bis(pentamethylcyclopentadienyl)dimethylzirconium, bis(pentamethylcyclopentadienyl)dibenzylzirconium, bis(pentamethylcyclopentadienyl)dichlorozirconium, bis(pentamethylcyclopentadienyl)chloromethylzirconium, bis(pentamethylcyclopentadienyl)hydromethylzirconium, (cyclopentadienyl)(pentamethylcyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)dineopentylzirconium, bis(cyclopentadienyl)di-m-tolylzirconium, bis(cyclopentadienyl)di-p-tolylzirconium, bis(cyclopentadienyl)bis(diphenylmethyl)zirconium, bis(cyclopentadienyl)dibromozirconium, bis(cyclopentadienyl)methylzirconium chloride, bis(cyclopentadienyl)ethylzirconium chloride, bis(cyclopentadienyl)cyclohexylzirconium chloride, bis(cyclopentadienyl)phenylzirconium chloride, bis(cyclopentadienyl)benzylzirconium chloride, bis(cyclopentadienyl)dimethyl ... (By)hydrogenated methylzirconium, bis(cyclopentadienyl)methoxyzirconium chloride, bis(cyclopentadienyl)ethoxyzirconium chloride, bis(cyclopentadienyl)(trimethylsilyl)methylzirconium, bis(cyclopentadienyl)bis(trimethylsilyl)zirconium, bis(cyclopentadienyl)(triphenylsilyl)methylzirconium, bis(cyclopentadienyl)(tri(dimethylsilyl)silyl)methylzirconium, bis(cyclopentadienyl)(trimethylsilyl)(trimethylsilylmethyl)zirconium, bis(methylcyclopentadienyl)diphenylzirconium, bis(ethylcyclopentadienyl)dimethylzirconium, bis(ethylcyclopentadienyl)dichlorozirconium, bis(propylcyclopentadienyl)dimethylzirconium, bis(propylcyclopentadienyl)dichlorozirconium, bis(n-butylcyclopentadienyl)dichlorozirconium, bis(tert-butylcyclopentadienyl)bis(trimethylsilyl) Zirconium, bis(hexylcyclopentadienyl)zirconium dichloro, bis(cyclohexylcyclopentadienyl)dimethylzirconium, bis(dimethylcyclopentadienyl)dimethylzirconium, bis(dimethylcyclopentadienyl)zirconium dichloro, bis(dimethylcyclopentadienyl)ethoxyzirconium chloride, bis(ethylmethylcyclopentadienyl)zirconium dichloro, bis(propylmethylcyclopentadienyl)zirconium dichloro, bis(butylmethylcyclopentadienyl)zirconium dichloro, bis(trimethylcyclopentadienyl)zirconium dichloro, bis(tetramethylcyclopentadienyl)zirconium dichloro, bis(cyclohexylmethylcyclopentadienyl)dibenzylzirconium, bis(trimethylsilylcyclopentadienyl)dimethylzirconium, bis(trimethylsilylcyclopentadienyl)zirconium dichloro, bis(trimethylgermaniumylcyclopentadienyl)dimethylzirconium, bis(trimethylgermaniumylcyclopentadienyl)diphenylzirconium, bis (Trimethyltinylcyclopentadienyl)dimethylzirconium, bis(trimethyltinylcyclopentadienyl)dibenzylzirconium, bis(trifluoromethylcyclopentadienyl)dimethylzirconium, bis(trifluoromethylcyclopentadienyl)dinorbornelzirconium, bis(indenyl)dibenzylzirconium, bis(indenyl)dichlorozirconium, bis(indenyl)dibromozirconium, bis(tetrahydroindenyl)dichlorozirconium, bis(fluorenyl)dichlorozirconium, (propylcyclopentadienyl)zirconium Dienyl(cyclopentadienyl)dimethylzirconium, (cyclohexylmethylcyclopentadienyl(cyclopentadienyl)dibenzylzirconium, (pentatrimethylsilylcyclopentadienyl(cyclopentadienyl)dimethylzirconium, (trifluoromethylcyclopentadienyl(cyclopentadienyl)dimethylzirconium, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)dichlorozirconium, ethylenebis(tetrahydroindenyl)dimethylzirconiumEthylenebis(tetrahydroindenyl)zirconium dichloro, dimethylsilenebis(cyclopentadienyl)zirconium, dimethylsilenebis(cyclopentadienyl)zirconium dichloro, isopropylidene (cyclopentadienyl)(9-fluorenyl)dimethyl zirconium, isopropylidene (cyclopentadienyl)(9-fluorenyl)dichloro zirconium, [phenyl(methyl)phenoxy](9-fluorenyl)(cyclopentadienyl)dimethyl zirconium, diphenylphenoxy (cyclopentadienyl)(9-fluorenyl)dimethyl zirconium, ethylene(9-fluorenyl)(cyclopentadienyl)dimethyl zirconium, cyclohexyl(9-fluorenyl)(cyclopentadienyl)dimethyl zirconium (cyclopentadienyl)dimethyl zirconium, cyclopentylidene (9-fluorenyl)(cyclopentadienyl)dimethyl zirconium, cyclobutylidene (9-fluorenyl)(cyclopentadienyl)dimethyl Zirconium, dimethylsilene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium, dimethylsilenebis(2,3,5-trimethylcyclopentadienyl)dimethylzirconium, dimethylsilenebis(2,3,5-trimethylcyclopentadienyl)dichlorozirconium, dimethylsilenebis(indenyl)dichlorozirconium, methylbis(cyclopentadienyl)dimethylzirconium, methylbis(cyclopentadienyl)bis(trimethylsilyl)zirconium, methyl(cyclopentadienyl)(tetramethylcyclopentadienyl)dimethylzirconium, methyl(cyclopentadienyl)(fluorenyl) Dimethylzirconium, ethylenebis(cyclopentadienyl)dimethylzirconium, ethylenebis(cyclopentadienyl)dibenzylzirconium, ethylenebis(cyclopentadienyl)dihydrozirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)methylzirconium chloride, ethylenebis(tetrahydroindenyl)dibenzylzirconium, isopropylidene(cyclopentadienyl)(methylcyclopentadienyl)dichlorozirconium,Isopropylidene (cyclopentadienyl)(octahydrofluorenyl) dihydrido zirconium, dimethylsilenebis(cyclopentadienyl) dineopentyl zirconium, dimethylsilenebis(cyclopentadienyl) dihydrido zirconium, dimethylsilenebis(methylcyclopentadienyl) dichlorozirconium, dimethylsilenebis(dimethylcyclopentadienyl) dichlorozirconium, dimethylsilenebis(tetrahydroindyl) dichlorozirconium, dimethylsilene(cyclopentadienyl)(fluorenyl) dichlorozirconium, dimethylsilene(cyclopentadi ... Dienyl(fluorenyl)zirconium dihydrogenide, dimethylsilene(methylcyclopentadienyl)zirconium dihydrogenide, dimethylsilene bis(3-trimethylsilylcyclopentadienyl)zirconium dihydrogenide, dimethylsilene bis(indenyl)zirconium dihydrogenide, diphenylsilene bis(indenyl)zirconium dichlorogenide, phenylmethylsilene bis(indenyl)zirconium dichlorogenide, and compounds obtained by replacing zirconium atoms with hafnium atoms in these compounds, etc.

[0156] Based on the total solids content of the composition of the present invention, the content of organotitanium compounds, etc., is preferably from 0.1% to 30% by mass. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.

[0157] For organotitanium compounds, one or more types may be used. When using two or more types, the total amount is preferably within the range mentioned above.

[0158] Furthermore, in the composition of the present invention, the mass ratio of the content of organotitanium compounds, etc., to the content of the hot alkali generating agent 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 within this range, higher ring-closure rates and higher glass transition temperatures of heterocyclic polymer precursors at low temperatures can be achieved.

[0159] The composition of this invention preferably contains a solvent. Any known solvent may be used as the solvent. The solvent is preferably an organic solvent. Examples of organic solvents include esters, ethers, ketones, aromatic hydrocarbons, sulfides, and amides.

[0160] As 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, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, and butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate)), alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid and ethyl 3-alkoxypropionic acid (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, ethyl 3-propionic acid)), alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid and ethyl 3-alkoxypropionic acid (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, ethyl 3-propionic acid)). Methyl ethoxypropionate and ethyl 3-ethoxypropionate), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate and propyl 2-alkoxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate and ethyl 2-oxobutyrate.

[0161] As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl acetate cellosolve, ethyl acetate cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, cyclopentanone, 2-heptanone and 3-heptanone may be appropriately mentioned.

[0162] As aromatic hydrocarbons, for example, toluene, xylene, anisole and limonene may be appropriately mentioned.

[0163] As a subclass, for example, dimethyl subclass may be appropriately mentioned.

[0164] As acetamides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylmethamide may be appropriately mentioned.

[0165] From the viewpoint of improving the properties of the coated surface, mixing two or more types of solvents is preferable. Among these, a mixed solution composed of two or more solvents selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

[0166] From the viewpoint of the coatability of the composition of the present invention, the solvent content is preferably 5% to 80% by mass, more preferably 5% to 70% by mass, and particularly preferably 10% to 60% by mass. The solvent content can be adjusted according to the desired thickness and coating method. For example, when the coating method is spin coating or slot coating, a solvent content within the above-mentioned range is preferred. In the case of spray coating, the solvent has a preferred amount of 0.1% to 50% by mass, more preferably 1.0% to 25% by mass. By adjusting the amount of solvent according to the coating method, a photosensitive resin composition layer with the desired thickness can be uniformly formed.

[0167] The solvent may contain one type, or two or more types. When two or more types of solvent are contained, their total amount is preferably within the range described above.

[0168] The composition of this invention preferably contains a free radical polymerizable compound (hereinafter also referred to as a "polymerizable monomer"). By adopting this composition, a hardened film with excellent heat resistance can be formed.

[0169] As a polymerizable monomer, a compound having a free radical polymerizable group can be used. As a free radical polymerizable group, groups having an olefinic unsaturated bond can be mentioned, such as styryl, vinyl, (meth)acryl, and allyl. The (meth)acryl group is preferred as the free radical polymerizable group.

[0170] The polymerizable monomer may have one or two or more free radical polymerizable groups. Preferably, the polymerizable monomer has two or more free radical polymerizable groups, more preferably three or more free radical polymerizable groups. The upper limit is preferably 15 or lower, more preferably 10 or lower, and even more preferably 8 or lower.

[0171] The 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. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or higher.

[0172] From a reproducibility viewpoint, the composition of the present invention preferably contains at least one bifunctional or higher-functional polymerizable monomer containing two or more polymerizable groups, and more preferably contains at least one trifunctional or higher-functional polymerizable monomer. Furthermore, the polymerizable monomer may be a mixture of bifunctional and trifunctional or higher-functional polymerizable monomers. The number of functional groups in a polymerizable monomer refers to the number of free radical polymerizable groups in a molecule.

[0173] Specific examples of polymerizable monomers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), and their esters and amides, preferably esters of saturated carboxylic acids and polyols, and amides of unsaturated carboxylic acids and polyamines. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents (e.g., hydroxyl, amino, and thiol groups) with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitable. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents (e.g., isocyanate groups and epoxy groups) and monofunctional or polyfunctional alcohols, amines, or thiols, as well as substitution reaction products of unsaturated carboxylic acid esters or amides with leaving substituents (e.g., halogen groups and toluenesulfonyloxy groups) and monofunctional or polyfunctional alcohols, amines, or thiols, are also suitable. Additionally, as another example, compounds in which the unsaturated carboxylic acid is substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc., can also be used. For specific examples, see paragraphs 0113 to 0122 of JP2016-027357A.

[0174] Furthermore, the polymerizable monomer is preferably a compound having a boiling point of 100 degrees Celsius or higher at atmospheric pressure. As an example, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol (e.g., 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, glycerol, and trimethylolethane) followed by (meth)acrylation is mentioned, JP1973-041708B (JP-S48-04). The following are suitable: urethane (meth)acrylates described in JP1708B, JP1975-6034B (JP-S50-6034B), and JP1976-037193A (JP-S51-037193A); polyester acrylates described in JP1973-064183A (JP-S48-064183A), JP1974-043191B (JP-S49-043191B), and JP1977-030490B (JP-S52-030490B); multifunctional acrylates or methacrylates such as epoxy acrylates as products of the reaction of epoxy resin and (meth)acrylic acid; and mixtures thereof. Furthermore, 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 cyclic ether groups (e.g., glycidyl (meth)acrylates) and olefinic unsaturated groups may be mentioned.

[0175] In addition, as other preferred polymerizable monomers, compounds having two or more fluorene rings and olefinic unsaturated groups as described in JP2010-160418A, JP2010-129825A and Japanese Patent No. 4364216, as well as caloric resins, can also be used.

[0176] In addition, as other examples, specific unsaturated compounds described in JP1971-043946B (JP-S46-043946B), JP1989-040337B (JP-H1-040337B), and JP1989-040336B (JP-H1-040336B), as well as vinylphosphonic acid compounds described in JP1990-025493A (JP-H2-025493A), may also be mentioned. Furthermore, compounds containing perfluoroalkyl groups described in JP1986-022048A (JP-S61-022048A) may also be used. Additionally, compounds described as photopolymerizable monomers and oligomers in the Journal of the Japanese Society for Reproductive Technology, Vol. 20, No. 7, pp. 300-308 (1984) may also be used.

[0177] In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP2015-034964A may also be preferred.

[0178] In addition, the compounds described in JP1998-062986A (JP-H10-062986A) as formulas (1) and (2), as well as specific examples thereof, and compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then performing (meth)acrylation, can be used as polymerizable monomers.

[0179] In addition, the compounds described in paragraphs 0104 to 0131 of JP2015-187211A can also be used as polymerizable monomers.

[0180] Preferred polymerizable monomers are dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shimonakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shimonakamura Chemical Co., Ltd.), and structures in which the (meth)acrylic group is bonded through ethylene glycol or propylene glycol residues. Oligomeric forms of these monomers may also be used.

[0181] Commercially available polymerizable monomers include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups manufactured by Sartomer; SR-209, a difunctional methacrylate with four ethoxy groups manufactured by Sartomer; DPCA-60, a hexafunctional acrylate with six pentenoxy groups manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutyleneoxy groups; carbamate oligomers UAS-10 and UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.); NK Ester M-40G; NK Ester 4G; NK Ester M-9300; and NK Ester... A-9300, UA-7200 (manufactured by Shichinakamura 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.), Bre Nanoer PME400 (manufactured by NOF Co., Ltd.), etc.

[0182] As polymerizable monomers, the urethane acrylates described in JP1973-041708B (JP-S48-041708B), JP1976-037193A (JP-S51-037193A), JP1990-032293B (JP-H2-032293B) and JP1990-016765B (JP-H2-016765B), and JP1 The urethane ester compounds with an ethylene oxide skeleton described in JP1981-049860B (JP-S58-049860B), JP1987-039417B (JP-S62-039417B), and JP1987-039418B (JP-S62-039418B) are also suitable. Furthermore, compounds with an amine or sulfide structure in their molecules, as described in JP1988-277653A (JP-S63-277653A), JP1988-260909A (JP-S63-260909A), and JP1989-105238A (JP-H1-105238A), can also be used as polymerizable monomers.

[0183] The polymerizable monomer can be a polymerizable monomer with an acid group, such as a carboxyl group, a sulfonyl group, or a phosphate group. Preferably, the polymerizable monomer with an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a polymerizable monomer obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to obtain an acid group. Particularly preferred is a polymerizable monomer with an acid group obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to obtain an acid group, wherein the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available examples include, for instance, the polyacid-modified acrylic oligomers M-510 and M-520 manufactured by Toa Synthetic Co., Ltd.

[0184] For polymerizable monomers containing acid groups, one type can be used alone, or two or more types can be used in combination. Furthermore, if necessary, polymerizable monomers without acid groups and polymerizable monomers with acid groups can be used in combination.

[0185] The acid value of the polymerizable monomer with acid groups is preferably 0.1 to 40 mg KOH / g, and particularly preferably 5 to 30 mg KOH / g. When the acid value of the polymerizable monomer is within the above range, it exhibits excellent production and processing performance, as well as excellent developability. Furthermore, it exhibits good polymerization performance.

[0186] From the viewpoint of good polymerization performance and heat resistance, the content of polymerizable monomers, based on the total solids content of the composition of this invention, is preferably from 1% to 50% by mass. The lower limit is more preferably 5% by mass or greater than 5% by mass. The upper limit is more preferably 30% by mass or less than 30% by mass. For polymerizable monomers, one type may be used alone, or two or more types may be used in combination.

[0187] Furthermore, the mass ratio of the heterocyclic polymer precursor (i.e., polyimide precursor) to the polymerizable monomer (heterocyclic polymer precursor (i.e., polyimide precursor) / polymerizable monomer) is preferably 98 / 2 to 10 / 90, more preferably 95 / 5 to 30 / 70, and most preferably 90 / 10 to 50 / 50. When the mass ratio of the heterocyclic polymer precursor to the polymerizable monomer is within the above range, a hardened film with excellent polymerization performance and heat resistance can be formed.

[0188] In the composition of this invention, from the viewpoint of suppressing warping by controlling the elastic modulus of the hardened film, monofunctional polymerizable monomers are preferably used. Preferred monofunctional polymerizable monomers are (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-hydroxymethyl (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-vinylcaprolactone; and allyl compounds, such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate. As a monofunctional polymerizable monomer, compounds with a boiling point of 100 degrees Celsius or higher at atmospheric pressure are preferred to suppress pre-exposure volatilization. The photosensitive resin composition preferably further contains a migration suppressing agent. By containing a migration suppressing agent, the migration of metal ions from the metal layer (metal wiring) to the photosensitive resin composition layer can be effectively prevented.

[0189] As migration inhibitors, there are no particular limitations, and compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thiourea and thiol groups, hindered phenolic compounds, salicylic acid derivatives, and acehydrazine derivatives are preferred. Triazole compounds, such as triazoles and benzotriazoles, and tetraazole compounds, such as tetraazoles and benzotetrazoles, are particularly preferred.

[0190] In addition, ion scavengers that capture anions such as halide ions can also be used.

[0191] Other migration inhibitors may be used, such as 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.

[0192] Specific examples of migration inhibitors include 1H-1,2,3-triazole, 1H-tetrazole, and 5-aminotetrazole.

[0193] When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably from 0.01% to 5.0% by mass, more preferably from 0.05% to 2.0% by mass, and even more preferably from 0.1% to 1.0% by mass, based on the total solids content of the photosensitive resin composition.

[0194] Migration inhibitors may be used in single-type or multi-type combinations. When using two or more types of migration inhibitors, the total amount is preferably within the range described above.

[0195] The polyimide precursor of the present invention preferably includes a polymerization inhibitor as a constituent. In some embodiments, the polyimide precursor includes at least one polymerization inhibitor and / or solvent and / or free radical polymerizable compound.

[0196] Examples of polymerization inhibitors include 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'-epoxybis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, and 1 2-Cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthylcarboxylate, 2-nitroso-1-naphthylcarboxylate, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc., may also be used appropriately. In addition, polymerization inhibitors described in paragraph 0060 of JP2015-127817A and compounds described in paragraphs 0031 to 0046 of WO2015 / 125469A may also be used.

[0197] In addition, the following compounds (Me is methyl) can be used.

[0198] In addition, stereohindering amine oxy compounds without α-hydrogen atoms can also be used as polymerization inhibitors. For example, (2,2,6,6-tetramethylpiperidin-1-yl)oxy, (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxy, etc., may be used.

[0199] When the composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% to 5% by mass, based on the total solids content of the composition of the present invention.

[0200] In some embodiments, the polymerization inhibitor is selected from one or more of 1,4-benzoquinone and p-methoxyphenol.

[0201] For polymerization inhibitors, only one type may be used, or two or more types may be used. When using two or more types of polymerization inhibitors, the total amount is preferably within the range mentioned above.

[0202] In some embodiments, the free radical polymerizable compound is selected from one or more of tetraethylene glycol dimethacrylate (TEGDMA) and pentaerythritol tri(meth)acrylate.

[0203] In some embodiments, the solvent that can be used in the polyimide precursor, including the composition, may be selected from one or more of dimethyl sulfoxide, γ-butyrolactone, and N-methyl-2-pyrrolidone.

[0204] The composition of this invention preferably contains a metal adhesion modifier to improve adhesion to metal materials used in electrodes, wiring, etc. Silicon coupling agents are mentioned as metal adhesion modifiers.

[0205] Examples of silane coupling agents include compounds described in paragraphs 0062 to 0073 of JP2014-191002A, compounds described in paragraphs 0063 to 0071 of WO2011 / 080992A1, compounds described in paragraphs 0060 to 0061 of JP2014-191252A, compounds described in paragraphs 0045 to 0052 of JP2014-041264A, and compounds described in paragraph 0055 of WO2014 / 097594A. Furthermore, as described in paragraphs 0050 to 0058 of JP2011-128358A, it is preferable to use two or more different types of silane coupling agents. Additionally, the following compounds are also preferred as silane coupling agents. In the formula, Et represents ethyl.

[0206] In addition, as a metal adhesion modifier, compounds described in paragraphs 0046 to 0049 of JP2014-186186A and sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935A may also be used.

[0207] The content of the metal adhesion modifier relative to 100 parts by weight of the heterocyclic polymer precursor is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight. When the content is 0.1 parts by weight or higher, the cured film after the curing step exhibits good adhesion to the metal layer. When the content is 30 parts by weight or lower, the cured film after the curing step exhibits good heat resistance and mechanical properties. Only one type of metal adhesion modifier may be used, or two or more types may be used. When two or more types are used, their total amount is preferably within the above range.

[0208] If necessary, various additives, such as chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, and aggregation inhibitors, may be mixed with the composition of the present invention, provided that the effects of the present invention are not impaired. When these additives are mixed, the total amount mixed is preferably 3% by mass or less of the solids content of the composition.

[0209] For reference, a detailed description of these other additives can be found in the applicant's EP3492982.

[0210] From the viewpoint of coating surface properties, the water content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass.

[0211] From the viewpoint of insulation properties, the metal content of the composition of the present invention is preferably less than 5 ppm (parts per million) by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. Metals mentioned include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When multiple metals are contained, the total amount of these metals is preferably within the above-mentioned range.

[0212] Furthermore, as a method to reduce unintentionally contained metallic impurities in the composition of the present invention, methods such as selecting raw materials with low metal content as raw materials constituting the composition of the present invention, filtering the raw materials constituting the composition of the present invention using a filter, and distilling under conditions that suppress contamination as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0213] In the composition of this invention, from the viewpoint of wiring corrosion resistance, the 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. Wherein, when present in the form of halide ions, 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. Chlorine atoms and bromine atoms are mentioned as halogen atoms. Preferably, each chlorine atom and bromine atom, or the total amount of chloride ions and bromide ions, is within the above-mentioned range.

[0214] As a storage container for the components of this invention, storage containers known in the related art can be used. Furthermore, as a storage container, for the purpose of suppressing the contamination of raw materials and components, it is preferable to use a multi-layer bottle with an inner wall composed of six types of six-layer resins, or a bottle with a seven-layer structure made of six types of resins. Such containers include, for example, the container described in JP2015-123351A.

[0215] The composition of this invention can be prepared by mixing the above-mentioned components. There are no particular limitations on the mixing method; mixing can be performed using methods known in the related art.

[0216] Furthermore, to remove foreign matter such as dust and particles from the composition, filtration is preferably performed using a filter. The filter pore size is preferably less than 1 micrometer, more preferably less than 0.5 micrometers, and even more preferably less than 0.1 micrometers. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. Filters pre-cleaned with organic solvents can be used. In the filtration process using a filter, multiple types of filters can be connected in series or parallel. When using multiple types of filters, filters with different pore sizes and / or different materials can be combined. Furthermore, various materials can be filtered multiple times. In the case of multiple filtrations, circulating filtration can be used. Additionally, filtration can be performed under pressure. When filtration is performed under pressure, the pressure is preferably from 0.05 MPa to 0.3 MPa.

[0217] In addition to filtration using a filter, impurity removal can be performed using an adsorbent material. Filtration using a filter and impurity removal using an adsorbent material can be combined. Known adsorbent materials can be used. For example, inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon are mentioned.

[0218] Next, the curing film, the laminate, the semiconductor device, the method for manufacturing the curing film, the method for manufacturing the laminate, and the method for manufacturing the semiconductor device of the present invention will be described.

[0219] The hardened film of the present invention is obtained by hardening the components of the present invention. The thickness of the hardened film of the present invention can be, for example, 1 micrometer or more, or 5 micrometers or more. Furthermore, its upper limit can be 100 micrometers or less, or 30 micrometers or less.

[0220] The glass transition temperature (Tg) of the curing film of the present invention is preferably 240 degrees Celsius or higher, more preferably 250 degrees Celsius or higher, further preferably 260 degrees Celsius or higher, and even more preferably 270 degrees Celsius or higher. There is no particular upper limit specified for the Tg of the curing film of the present invention; for example, a Tg below 600 degrees Celsius, or even below 450 degrees Celsius, is a sufficiently practical level. In particular, the present invention is of great value in providing photosensitive resin compositions that can achieve the above-mentioned Tg. The Tg in the present invention is measured according to the description of the examples described later.

[0221] In some embodiments, the glass transition temperature (Tg) of the hardened film is in the range of 240 degrees Celsius to 600 degrees Celsius, preferably in the range of 240 degrees Celsius to 400 degrees Celsius.

[0222] Two or more layers of the hardened film of the present invention can be laminated to form a laminate. Preferably, a metal layer is present between the hardened films in the laminate having two or more layers of the hardened film of the present invention. This metal layer is preferably used as a redistribution layer or other metal wiring. The metal layer preferably contains copper.

[0223] As for the applications of the hardened film of this invention, insulating films for semiconductor devices and interlayer insulating films for redistribution layers are mentioned. In particular, due to its excellent resolution characteristics, the hardened film of this invention can be preferably used as an interlayer insulating film for redistribution layers in three-dimensional packaging devices.

[0224] Furthermore, the hardened film in this invention can also be used as photoresist for electronics, electroplating resist, etching resist, solder top resist, etc.

[0225] Furthermore, the hardened film in this invention can also be used for the fabrication of offset printing plates or screen printing plates, the etching of molded parts, and the fabrication of protective varnishes and dielectric layers in electronics, especially microelectronics.

[0226] The method for manufacturing a hardened film according to the present invention includes using the composition of the present invention. Preferably, the method for manufacturing a hardened film includes a photosensitive resin composition layer formation step, an exposure step, and a development step, wherein the photosensitive resin composition layer formation step involves coating the photosensitive resin composition of the present invention onto a substrate to form a layered shape, the exposure step involves exposing the photosensitive resin composition layer, and the development step involves developing the exposed photosensitive resin composition layer (resin layer). More preferably, the photosensitive resin composition of the present invention is used in cases where the development is a negative tone development process. Furthermore, in the manufacturing method of the present invention, after the development step, the developed photosensitive resin composition layer is preferably heated to a temperature of 50 degrees Celsius or higher, more preferably 80 degrees Celsius or higher, further preferably 100 degrees Celsius or higher, even more preferably 150 degrees Celsius or higher, and even more preferably 180 degrees Celsius or higher. The upper limit of the heating temperature is preferably below 450 degrees Celsius, more preferably below 400 degrees Celsius, further preferably below 380 degrees Celsius, even more preferably below 300 degrees Celsius, even more preferably below 280 degrees Celsius, even more preferably below 250 degrees Celsius, even more preferably below 240 degrees Celsius, even more preferably below 230 degrees Celsius, even more preferably below 220 degrees Celsius, even more preferably below 210 degrees Celsius, even more preferably below 205 degrees Celsius, and even more preferably below 200 degrees Celsius.

[0227] In some embodiments, the method of manufacturing a hardened film includes a heating step after the developing process, wherein the film is heated at a temperature in the range of 50 to 450 degrees Celsius.

[0228] Since the curing film of the present invention can achieve a high closed-loop rate even at low temperatures, the heating temperature can be reduced, and damage to semiconductor devices and the like can be minimized. In particular, in the present invention, a photosensitive resin composition that can achieve a closed-loop rate of 80% or more, and more than 90%, when heated within the above-mentioned temperature range (e.g., at 200 degrees Celsius) can be obtained.

[0229] The method for manufacturing a laminate of the present invention includes the method for manufacturing a hardened film of the present invention. Preferably, the method for manufacturing a laminate includes forming a hardened film according to the method for manufacturing a hardened film of the present invention, and then further sequentially performing a photosensitive resin composition layer formation step, an exposure step, and a development step. Specifically, it is preferred to further sequentially perform the photosensitive resin composition layer formation step, the exposure step, and the development step 2 to 5 times (i.e., a total of 3 to 6 times). By laminating the hardened film in this manner, a laminate can be obtained. In the present invention, it is particularly preferred that after providing the hardened film and developing, a metal layer is provided on the developed and removed portion.

[0230] The present invention also discloses semiconductor devices comprising the hardened film or laminate of the present invention. Embodiments of semiconductor devices in which the components of the present invention are used as interlayer insulating films in redistribution layers will be described below.

[0231] The semiconductor device 100 shown in Figure 1 is a so-called three-dimensional mounting device, in which a multilayer stack 101 of multiple semiconductor elements (semiconductor wafers) 101a to 101d is disposed on a wiring substrate 120. In this embodiment, the case where the number of laminated semiconductor elements (semiconductor wafers) is 4 layers will be mainly described. However, the number of laminated semiconductor elements (semiconductor wafers) is not particularly limited, and for example, it can be 2 layers, 8 layers, 16 layers, 32 layers, etc. In addition, the number can be 1 layer.

[0232] Each of the plurality of semiconductor elements 101a to 101d is made of a semiconductor wafer such as a silicon substrate. The uppermost semiconductor element 101a does not have a through electrode and has an electrode pad (not shown) formed on one of its surfaces. Semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) integrally provided with the through electrodes are disposed on both surfaces of each semiconductor element.

[0233] The multilayer assembly 101 has a structure in which a semiconductor element 101a without a through electrode and semiconductor elements 101b to 101d with through electrodes 102b to 102d are flip-chip connected. Specifically, the electrode pads of the semiconductor element 101a without a through electrode and the connection pads of the semiconductor element 101b with a through electrode 102b adjacent to the semiconductor element 101a on the semiconductor element 101a side are connected by metal bumps 103a, such as solder bumps. The connection pads on the other side of the semiconductor element 101b with a through electrode 102b and the connection pads of the semiconductor element 101c with a through electrode 102c adjacent to the semiconductor element 101b on the semiconductor element 101b side are connected by metal bumps 103b, such as solder bumps. Similarly, the bonding pads on the other side of the semiconductor element 101c having through electrode 102c and the bonding pads on the semiconductor element 101d having through electrode 102d adjacent to the semiconductor element 101c on the semiconductor element 101c side are connected by metal bumps 103c such as solder bumps.

[0234] An adhesive layer 110 is formed in each gap between semiconductor elements 101a to 101d, and each semiconductor element 101a to 101d is laminated by the adhesive layer 110 inserted therebetween.

[0235] The laminate 101 is laminated onto the wiring substrate 120. The wiring substrate 120 may be a multilayer wiring substrate, for example, obtained by using an insulating substrate such as a resin substrate, ceramic substrate, or glass substrate as the base material. As a wiring substrate 120 using a resin substrate, multilayer copper foil laminates (multilayer printed wiring boards) are mentioned.

[0236] A surface electrode 120a is disposed on one surface of the wiring substrate 120.

[0237] An insulating film 115, on which a redistribution layer 105 is formed, is disposed between a wiring substrate 120 and a laminate 101, and the wiring substrate 120 and the laminate 101 are electrically connected through the redistribution layer 105. The insulating film 115 is formed using the components of the present invention.

[0238] That is, one end of the redistribution layer 105 is connected to an electrode pad formed on the side surface of the semiconductor element 101d on the redistribution layer 105 via a metal bump 103d, such as a solder bump. In addition, the other end of the redistribution layer 105 is connected to the surface electrode 120a of the wiring substrate via a metal bump 103e, such as a solder bump.

[0239] An adhesive layer 110a is formed between the insulating film 115 and the laminate 101. Furthermore, an adhesive layer 110b is formed between the insulating film 115 and the wiring substrate 120.

[0240] In addition to the above, the hardened film of the present invention can be widely used in various applications using polyimide.

[0241] Furthermore, since polyimide is heat-resistant, the hardened film and the like of the present invention can be appropriately used in plastic substrates of display devices such as liquid crystal displays, organic EL displays and electronic paper, as well as in applications such as interlayer insulating films, automotive parts, heat-resistant coatings, coating agents and films.

[0242] In some embodiments, this disclosure is characterized by an article comprising at least one patterned dielectric film formed from a formulation containing a polyimide precursor as described herein. Examples of such articles include semiconductor substrates, flexible films for electronics, wire insulation, wire coatings, wire enamel, and ink substrates. In some embodiments, this disclosure is characterized by a semiconductor device comprising one or more of these articles. Examples of semiconductor devices that can be made from such articles include integrated circuits, light-emitting diodes, solar cells, and transistors.

[0243] All publications cited in this article (e.g., patents, patent application publications, and articles) are incorporated herein by reference in their entirety.

[0244] This disclosure is further illustrated by reference to the following examples, which are for illustrative purposes and should not be construed as limiting the scope of this disclosure.

[0245] [Example] [ ]

[0246] [Synthesis Example] [PI] [Precursor] [A1]

[0247] 20.0 g (64.5 mmol) of 4,4'-oxophthalic dianhydride (ODPA) (dried at 140°C for 12 h) and 17.12 g (131.58 mmol) of 2-hydroxyethyl methacrylate (HEMA) were suspended in 50 mL of N-methylpyrrolidone and dried over a molecular sieve. The suspension was heated at 100°C for 3 h. A clear 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) of pyridine and 90 mL of N-methylpyrrolidone were added to it. The reaction mixture was then cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl2 was added to it over 10 min while maintaining the temperature at -10°C ± 4°C. The viscosity increased upon the addition of SOCl2. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 h. 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 added dropwise to the reaction mixture over 20 minutes at 20°C to 23°C. 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 at 5,000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added back to 4 L of water, stirred for 30 minutes, and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45°C for 3 days to obtain polymer PA-2. The molecular weight of polymer PA-2 was determined by gel permeation chromatography (in standard polystyrene equivalents), and the weight-average molecular weight (Mw) was 20,000.

[0248] [Synthesis Example] [PI] [Precursor] [A2]

[0249] Except that 18.98 g of 3,3,4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 20.0 g of 4,4'-oxophthalic dianhydride (ODPA) in Synthesis Example 1, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer A2. The molecular weight of polymer A2, measured by gel permeation chromatography (in standard polystyrene equivalents), was 22,000 by weight-average molecular weight (Mw).

[0250] [Synthesis Example] [PI] [Precursor] [A3]

[0251] Except that 18.98 g of 3,3,4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 20.0 g of 4,4'-oxophthalic 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, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer A3.

[0252] [Synthesis Example] [PI] [Precursor] [A4]

[0253] Except that 14.07 g of pyromellitic dianhydride (PMDA) was used instead of 20.0 g of 4,4'-oxophthalic 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, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer A4.

[0254] [Synthesis Example] [PI] [Precursor] [A5]

[0255] Except that 14.07 g of pyromellitic dianhydride (PMDA) was used instead of 20.0 g of 4,4'-oxophthalic 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, and except that 15.55 g of 2-isobutoxyethanol was used instead of 17.12 g of 2-hydroxyethyl methacrylate (HEMA), the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer A4.

[0256] [Fabrication and Testing of Photosensitive Dielectric Thin Films] [ ]

[0257] Example 1: A photosensitive dielectric film forming composition was prepared by using 32.5 parts of polyimide precursor polymer A1 in 48.19 parts of organic solvent J1 and 12.05 parts of another organic solvent J2.

[0258] All other examples were prepared according to the components described in Example Table (I). PI precursors A2, A3, A4, A5; radical polymerizable compounds B1, B2; photoradical polymerization initiators C1, C2, C3, C4; polymerization inhibitors D1, D2; and solvents E1, E2, E3 were used. Actual concentrations can be found in the table.

[0259] All formulations were rolled and mixed for 24 hours, filtered through a 0.8 mm pore size filter at 0.3 MPa pressure, and then deep-frozen for 24 hours. After thawing for 4 hours, syringes were filled with the formulations and placed in a dark space to allow entrained air to rise to the surface. The substrate (silicon wafer) for spin coating was then prepared. Six-inch diameter silicon wafers underwent a 30-second O2 plasma pretreatment using a Trymax NEO 20 3 A etching tool. Next, the formulations were spin-coated onto the pretreated wafers using an Amcoss AMC2000 spin coater. Following coating, a 4-minute hot bake step at 110°C (also in the spin coater) was applied, achieving a soft-bake thickness of 10.0 micrometers. Film thickness was measured using a Foothill benchtop film thickness gauge (KF-10). Film thickness was determined by utilizing the n and k values ​​of the film material, as well as by measuring the absolute reflectance. The necessary n and k values ​​were determined for the photoresist using elliptic polarization on a JA Woollam VASE tool. This was performed on a Si wafer with a very thin photoresist film (<500 nm). Furthermore, the wafer was exposed on a Nikon stepper (Nikon 1755i7 model) with a numerical aperture of 0.5 and a 365 nm Hg lamp intensity of 500 mW / cm². A focus exposure matrix was used, where the focus varied in 2 μm steps and the energy varied from 40 mJ / cm² to 880 mJ / cm² in 60 mJ / cm² steps. After exposure, the substrate was held in the dark for 30 minutes, followed by negative toner development with cyclopentanone for 30 seconds on an Amcoss AMC2000 spin coater to obtain a resin layer. Next, the developed substrate was baked at 100°C for 30 seconds on a spin coater to evaporate any residual solvent. Subsequently, the substrate was oven-cured for 3 hours at 230°C in a YES brand convection oven under a controlled nitrogen atmosphere (oxygen-free) at 380 bar. Furthermore, the cured samples were descaled for 1 minute using O2 plasma on a NEO 20 3 A etching tool to remove residual slag. Then, the cross-section of the film with a 2-micron focal length energy matrix (in 60 mJ / cm² steps) was examined using JEOL SEM (secondary electron microscopy). Critical dimensions (CD values) were measured at the bottom of the via structure on secondary electron images (SEI images).

[0260] Key dimension illustration: Key dimensions (CD value) at the bottom of the through-hole after secondary electronic imaging inspection: A: CD value <= 5.5 micrometers B: 5.5 micrometers < CD value <= 7.0 micrometers C: 7.0 micrometers < CD value <= 8.5 micrometers D: 8.5 micrometers < CD value <= 10.0 micrometers E: 10.0 micrometers <= CD value

[0261] The exposure latitude (EL) score is based on the overall CD value's performance across the entire energy range. The sensitivity score is based only on the overall CD value within a lower energy range. [Components] [name] [supplier] A1 Polymer – Synthesis Example 1 - A2 Polymer – Synthesis Example 2 - A3 Polymer – Synthesis Example 3 - A4 Polymer – Synthesis Example 4 - A5 Polymer – Synthesis Example 5 - B1 Tetraethylene glycol dimethacrylate Sartomer B2 Pentaerythritol tri(meth)acrylate Sigma-Aldrich C1 Benzotrimethylgermanane Synthon C2 Dibenzo-diethylgermanium Hinton C3 bis(4-methoxybenzoyl)diethylgermanium Hinton C4 Irgacure OXE-01 BASF D1 1,4-Benzoquinone Tokyo Chemical Industry C., Ltd. D2 p-Methoxyphenol Tishiai Chemical Industry Development Co., Ltd. E1 γ-Butyrolactone SANWAYUKA INDUSTRY CORPORATION E2 dimethyl monoxide Wako Pure Pharmaceutical Co., Ltd. E3 N-Methyl-2-pyrrolidone Ashland

[0262] Components used in the examples section: A1 A2 A3 A4 A5 B1 B2 C1 C2 C3 C4 D1 D2 E1 E2 E3

[0263] Table (I): Experimental Examples with Effective Results Example (A) PI precursor resin (B) free radical polymeric compounds (C) Photoradical polymerization initiator (D) Polymerization inhibitor (E) Solvent type weight type weight type weight type weight type weight type weight 1 A1 32.5 B1 4.88 C3 0.65 D1 0.07 E1 48.19 E2 12.05 2 A1 32.5 B1 4.88 C2 0.65 D1 0.07 E1 48.19 E2 12.05 3 A1 32.5 B1 4.88 C1 0.65 D1 0.07 E1 48.19 E2 12.05 4 (Comparative Example) A1 32.5 B1 4.88 C4 1.1375 D1 0.07 E1 47.80 E2 11.95 5 A2 32.5 B1 4.88 C3 0.65 D1 0.07 E1 48.19 E2 12.05 6 A3 32.5 B1 4.88 C3 0.65 D1 0.07 E1 48.19 E2 12.05 7 A4 32.5 B1 4.88 C3 0.65 D1 0.07 E1 48.19 E2 12.05 8 A5 32.5 B1 4.88 C3 0.65 D1 0.07 E1 48.19 E2 12.05 9 A1 32.5 B2 3.61 C3 0.65 D1 0.07 E1 49.20 E2 12.30 10 A1 32.5 B2 4.88 C3 0.65 D1 0.07 E1 48.19 E2 12.05 11 A1 32.5 B2 6.5 C3 0.65 D1 0.07 E1 46.89 E2 11.72 12 A1 32.5 B1 4.88 C3 0.05 D1 0.07 E1 48.19 E2 12.05 13 A1 32.5 B1 4.88 C3 0.163 D1 0.07 E1 48.58 E2 12.14 14 A1 32.5 B1 4.88 C3 1.463 D1 0.07 E1 47.54 E2 11.88 15 A1 32.5 B1 4.88 C3 0.65 D1 0.07 E3 60.23 - - 16 A1 32.5 B1 4.88 C3 0.65 D1 0.07 E1 42.16 E2 18.07 17 A1 32.5 B1 4.88 C3 0.65 D1 0.07 E1 36.14 E2 24.09 18 A2 32.5 B2 3.61 C3 0.65 D1 0.07 E1 49.20 E2 12.30 19 A2 32.5 B2 4.88 C3 0.65 D1 0.07 E1 48.19 E2 12.05 20 A2 32.5 B2 6.5 C3 0.65 D1 0.07 E1 46.89 E2 11.72 twenty one A1 32.5 B1 4.88 C3 0.65 D2 0.07 E1 48.19 E2 12.05 twenty two A1 32.5 B1 4.88 C3 0.65 D2 0.14 E1 48.13 E2 12.03 twenty three A1 32.5 B1 4.88 C3 0.65 D2 0.21 E1 48.07 E2 12.02 (Continued from Table (I)) Example Critical dimension (mJ / cm²) Score EL Score Sensitivity 100 200 300 400 500 600 700 800 900 1 E A A A A B B B C A A 2 E A B B B B B C C B B 3 E B B B C C C D D C C 4 (Comparative Example) E C C C C D D D D D D[[ID=9th]] 5 E ]> B A A B B B C C A A 6 E A A A B B B B D A A 7 E B A A A B B B D A A 8 E C C B B A A A B A B 9 E D D B A A A A B B C 10 E A A A A B B B C A A 11 A A B B B C C D D B A 12 E E E D D C C C C C C 13 E C C C C B B B C C C 14 A B B C C C C D D C B 15 E A A A A B B B C A A 16 E A A A A B B B C A A 17 E A A A A B B B C A A 18 E C C C B A A A A B C 19 E B A A B B B C C B B 20 A A B B C C C D D B A 21 E A A A A B B B C A A 22 E B B A A A A B C A B 23 E C B B A A A A C A B

[0264] 100: Semiconductor devices 101: Laminated body 101a, 101b, 101c, 101d: Semiconductor components / semiconductor wafers 102b, 102c, 102d: Electrodes 103a, 103b, 103c, 103d, 103e: Metal bumps 105: Redistribution layer 110, 110a, 110b: Base coat 115: Insulating film 120: Wiring substrate 120a: Surface electrode

Claims

1. A composition comprising a polyimide precursor, comprising: At least one resin comprising a polyimide precursor selected from one or more compounds of 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; and at least one acetogermanium compound comprising a compound of structure (I): Structure (I) wherein R1 is a C1-C12 alkyl, C4-C18 cycloalkyl, C6-C22 aryl, or C6-C22 heteroaryl; Each of R2, R3, and R4 is independently C1-C12 alkyl, C4-C18 cycloalkyl, C6-C22 aryl, C6-C22 heteroaryl, or -C(O)R, wherein R is C1-C4 alkyl, C5-C12 cycloalkyl, C6-C18 aryl, or C6-C18 heteroaryl; and each of the alkyl, cycloalkyl, aryl, or heteroaryl groups is optionally independently substituted with at least one C1-C4 alkyl or -OR5, wherein R5 is H, C1-C4 alkyl, C5-C12 cycloalkyl, C6-C18 aryl, or C6-C18 heteroaryl, wherein i) at least one of R113 or R114 comprises a radical polymerizable group having an olefinically unsaturated bond; or ii) the composition comprises at least one radical polymerizable compound having an olefinically unsaturated group.

2. The composition as claimed in claim 1, wherein the divalent organic group is a divalent straight-chain aliphatic group having 2 to 20 carbon atoms, a divalent branched aliphatic group having 3 to 20 carbon atoms, a divalent cyclic aliphatic group having 3 to 20 carbon atoms, one or more divalent aromatic groups having 6 to 20 carbon atoms, or a group consisting of combinations thereof.

3. The composition as described in claim 1 or 2, wherein R115 is selected from (X-1), (X-2) and (X-3), R111 is selected from (Y-1) and (Y-3), and "*" is a connection point.

4. The composition as claimed in claim 1, wherein the at least one acetylgeral compound is a diacetylgeral compound.

5. The composition as claimed in claim 1, wherein the at least one acetylgeralon compound comprises a compound given by a diacetylgeralon compound, wherein R2 = R1-C(O).

6. The composition as claimed in claim 1, wherein the at least one acetylgebra compound is selected from (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, bis(4-methoxybenzoyl)diethylgermanium, bis(2,4,6-trimethylbenzoyl)diethylgermanium, triphenylethylgermanium, and tri(2,4,6-trimethylbenzoyl)ethylgermanium.

7. The composition as claimed in claim 1, wherein the amount of the at least one acetylgera compound is from about 0.05% to 5% by weight, based on the solid weight of the composition.

8. The composition as claimed in claim 1, wherein the polyimide precursor of formula (1) comprises at least one methacrylic alkyl group as a side chain.

9. The composition as claimed in claim 1, further comprising at least one polymerization inhibitor and / or solvent and / or free radical polymerizable compound.

10. The composition as claimed in claim 1, wherein the polyimide precursor is a heterocyclic polymer precursor.

11. A curing membrane obtained by curing a composition comprising a polyimide precursor as described in any one of claims 1 to 10.

12. A laminate, comprising: Two or more layers consisting of a hardened film as described in claim 11; And the metal layer between any layers composed of the hardened film.

13. A method for manufacturing a hardened film, comprising: The thin film forming step involves coating a composition comprising a polyimide precursor, as described in any one of claims 1 to 10, onto a substrate to form a thin film; The exposure step selectively exposes the film; and the development step develops the film exposed in the exposure step using a developer to form a pattern.

14. The method of manufacturing a hardened film as claimed in claim 13 further includes a heating step of heating the film at 50°C to 450°C.

15. A semiconductor device comprising a hardened film as claimed in claim 11, or a laminate as claimed in claim 12.

16. Use of a composition comprising a polyimide precursor as claimed in any one of claims 1 to 10 for forming a hardened film.

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