TW202234157A - Photosensitive resin composition, cured product, interlayer insulating film, cover coat layer, surface protective film and electronic component - Google Patents

Abstract

A photosensitive resin composition includes a polyimide precursor having a polymerizable unsaturated bond, a photopolymerization initiator, and a solvent, and the solvent includes at least one selected from the group consisting of N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and tetramethylurea.

Description

Photosensitive resin composition, cured product, interlayer insulating film, cover coat, surface protection film and electronic parts

The present disclosure relates to a photosensitive resin composition, a cured product, an interlayer insulating film, a cover coat, a surface protection film, and an electronic component.

In recent years, organic materials having high heat resistance such as polyimide resins have been widely used as protective film materials for semiconductor integrated circuits (large scale integration (LSI)). The protective film of the cured film using such a polyimide resin can be obtained by coating a polyimide precursor or a resin composition containing a polyimide precursor on a substrate and adding The resin film formed by drying is heat-hardened.

The polyimide precursor has high resistance to organic solvents, but has low solubility in organic solvents. Therefore, the kinds of organic solvents that can be used to prepare the resin composition containing the polyimide precursor are limited. In addition, in order to increase the concentration of the polyimide precursor in the resin composition, an organic solvent capable of dissolving the polyimide precursor at a high concentration is required. In general, as an organic solvent for dissolving a precursor of a heat-resistant resin such as a polyimide precursor, N-methyl-2- Pyrrolidone (N-methyl-2-pyrrolidone, NMP) (for example, refer to Japanese Patent Laid-Open No. 2013-40249).

[The problem to be solved by the invention] As the application of resin compositions containing polyimide precursors has expanded, resin compositions using organic solvents other than NMP have been demanded. Therefore, for the purpose of increasing the options of organic solvents, it is necessary to study solvents other than NMP. However, especially when the polyimide precursor exhibits photosensitivity, the change of the organic solvent also affects the photosensitivity of the polyimide precursor. Therefore, in order to obtain the appropriate photosensitivity of the polyimide precursor , it is necessary to reconsider the composition of various additives contained in the resin composition, and it is sometimes difficult to switch to an alternative solvent. The present disclosure is made in view of the foregoing circumstances, and an aspect of the present disclosure has an object to provide a photosensitive resin composition containing an organic solvent other than NMP and having excellent photosensitivity properties, and a photosensitive resin composition using the photosensitive resin composition. Cured products, interlayer insulating films, cover coats, surface protection films and electronic parts. [Means of Solving Problems]

Specific means for achieving the above-mentioned problems are as follows. <1> A photosensitive resin composition comprising a polyimide precursor having a polymerizable unsaturated bond, a photopolymerization initiator, and a solvent, The solvent contains at least one selected from the group consisting of N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea. <2> The photosensitive resin composition according to <1>, wherein the sum of N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea is The proportion of the solvent is 50% by mass or more. <3> The photosensitive resin composition according to <1>, wherein the ratio of N-ethyl-2-pyrrolidone in the solvent is 50% by mass or more. <4> The photosensitive resin composition according to <1>, wherein the ratio of 1,3-dimethyl-2-imidazolidinone to the solvent is 50% by mass or more. <5> The photosensitive resin composition as described in <1> in which the ratio of tetramethylurea in the said solvent is 50 mass % or more. <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the polyimide precursor has a structural unit represented by the following general formula (6).

[hua 1]

(In the general formula (6), X represents a tetravalent organic group, and Y represents a divalent organic group. R ⁶ and R ⁷ are each independently a hydrogen atom, a group represented by the following general formula (7), or a carbon number of 1 The aliphatic hydrocarbon group of to 4, at least one of R ⁶ and R ⁷ is a group represented by the following general formula (7).)

[hua 2]

(In the general formula (7), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10.) <7> Photosensitive according to <6> resin composition, wherein the proportion of 1,3-dimethyl-2-imidazolidinone in the solvent is 50% by mass or more, and the dimethicone represented by Y in the general formula (6) The ratio of the group represented by the following general formula (G1) in the valent organic group is less than 100 mol %.

[hua 3]

(In the general formula (G1), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a carboxyl group or a phenyl group, and n each independently represents an integer of 0 to 4.) <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the photopolymerization initiator contains an oxime derivative. <9> A cured product obtained by curing the photosensitive resin composition according to any one of <1> to <8>. <10> The cured product according to <9>, which is a patterned cured product. <11> The cured product according to <9> or <10>, which is used as an interlayer insulating film, a cover coat, or a surface protection film. <12> An interlayer insulating film comprising the cured product according to <9>. <13> A cover coat comprising the hardened product as described in <9>. <14> A surface protection film comprising the cured product according to <9>. <15> An electronic component comprising the hardened product according to any one of <9> to <11>. [Effect of invention]

According to one aspect of the present disclosure, a photosensitive resin composition containing an organic solvent other than NMP and having excellent photosensitivity properties, and a cured product, interlayer insulating film, cover coat, and surface protection using the photosensitive resin composition can be provided Films and electronic parts.

Hereinafter, a form for implementing the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same also applies to numerical values and their ranges, and does not limit the present disclosure.

In the present disclosure, the term "step" includes not only a step that is independent from other steps, but also includes the step as long as the purpose of the step is achieved even if it cannot be clearly distinguished from the other steps. In the present disclosure, in the numerical range represented by "-", the numerical values described before and after the "-" are included as the minimum value and the maximum value, respectively. In the numerical ranges described in stages in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be substituted for the upper limit value or the lower limit value described in another stage value range. In addition, in the numerical range described in the present disclosure, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. In the present disclosure, each component may also contain a plurality of corresponding substances. When there are multiple substances corresponding to each component in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the multiple substances present in the composition. In the present disclosure, when the term "layer" or "film" is used, when the region in which the layer or film is present is observed, in addition to the case where the layer or film is formed in the entire region, it also includes only a part of the region. in the situation.

<Photosensitive resin composition> The photosensitive resin composition of the present disclosure contains a polyimide precursor having a polymerizable unsaturated bond (hereinafter, sometimes referred to as an unsaturated polyimide precursor), a photopolymerization initiator, and a solvent, the The solvent contains a substance selected from the group consisting of N-ethyl-2-pyrrolidone (hereinafter, sometimes referred to as NEP.), 1,3-dimethyl-2-imidazolidinone (hereinafter, sometimes referred to as DMI.), and four At least one of the group consisting of methyl urea (hereinafter, sometimes referred to as TMU.) (hereinafter, these solvents may be referred to as "specific solvent".). As a result of diligent studies, the present inventors found that a photosensitive resin composition excellent in photosensitive properties can be obtained by using a specific solvent, and completed the present invention. In addition, since the unsaturated polyimide precursor exhibits solubility in a specific solvent equivalent to that of NMP, even if a specific solvent is used, the unsaturation in the photosensitive resin composition can be secured to the same extent as in the case of using NMP. Polyimide precursor concentration.

The photosensitive resin composition of the present disclosure is preferably a negative-type photosensitive resin composition. Hereinafter, each component contained in the photosensitive resin composition of this disclosure is demonstrated.

(Unsaturated polyimide precursor) The photosensitive resin composition of the present disclosure contains an unsaturated polyimide precursor. As a polymerizable unsaturated bond, a carbon-carbon double bond etc. are mentioned. The unsaturated polyimide precursor may be, for example, a polyimide precursor having a structural unit represented by the following general formula (6). Since the unsaturated polyimide precursor has a structural unit represented by the general formula (6), it has a high i-ray transmittance and tends to form a good cured product even when cured at 380° C. or lower. With respect to all the structural units contained in the unsaturated polyimide precursor, the content of the structural unit represented by the following general formula (6) in the unsaturated polyimide precursor is preferably 50 mol. % or more, more preferably 80 mol% or more, further preferably 90 mol% or more. The upper limit is not particularly limited, and may be 100 mol %.

The unsaturated polyimide precursor may be synthesized using tetracarboxylic dianhydride and diamine compound. In this case, X corresponds to a residue derived from a tetracarboxylic dianhydride, and Y corresponds to a residue derived from a diamine compound. Furthermore, the unsaturated polyimide precursor can also be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.

[hua 4]

In the general formula (6), X represents a tetravalent organic group, and Y represents a divalent organic group. R ⁶ and R ⁷ are each independently a hydrogen atom, a group represented by the following general formula (7), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R ⁶ and R ⁷ is the following general formula (7) represents the basis.

[hua 5]

In the general formula (7), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10.

In the general formula (6), the carbon number of the tetravalent organic group represented by X is preferably 3-20, more preferably 5-15, still more preferably 7-13. The tetravalent organic group represented by X may contain an aromatic ring. When the tetravalent organic group represented by X includes an aromatic ring, examples of the aromatic ring include a benzene ring, a naphthalene ring, a phenanthrene ring, and the like. Among these, a benzene ring is preferable from the viewpoint of improving the light transmittance of the unsaturated polyimide precursor in the ultraviolet region. When the tetravalent organic group represented by X includes an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. As a substituent of an aromatic ring, an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, an amine group, etc. are mentioned. When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains one to four benzene rings, more preferably contains one to three benzene rings, and more preferably contains One or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, each benzene ring may be linked by a single bond, or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, and an ether bond. (-O-), sulfide bond (-S-), silylene bond (-Si(RA ) ₂ -; R ^A independently represents ^a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (- O-(Si(R ^B ) ₂ -O-) _n ; R ^B each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more. A composite linking group or the like formed by combining the two is bonded. In addition, two benzene rings may be bonded at two positions through at least one of a single bond and a linking group, and a 5-membered ring or a 6-membered ring including a linking group may be formed between the two benzene rings.

In the general formula (6), when the tetravalent organic group represented by X includes an aromatic ring, it is preferable that the -COOR ⁶ group and the -CONH- group are in ortho positions with each other, and the -COOR ⁷ group and -CO- The bases are adjacent to each other.

Specific examples of the tetravalent organic group represented by X include groups represented by the following general formula (A) to the following general formula (E), but the present disclosure is not limited to the following specific examples.

[hua 6]

In the general formula (D), A and B each independently represent a single bond, a methylene group, a halogenated methylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-) or Silene bond (-Si( ^RA ) _2- ; ^RA independently represents a hydrogen atom, an alkyl group or a phenyl group), and both A and B do not become a single bond.

In the general formula (E), C represents a single bond or an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), a silylene bond (- Si(R ^A ) ₂ -; R ^A independently represents a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (-O-(Si(R ^B ) ₂ -O-) _n ; R ^B each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more) or a divalent group formed by combining at least two of these. In addition, C may be a structure represented by the following formula (C1).

[hua 7]

The alkylene group represented by C in the general formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably an alkylene group having 1 or 2 carbon atoms. of alkylene. Specific examples of the alkylene group represented by C in the general formula (E) include straight methylene groups, ethylidene groups, trimethylene groups, tetramethylene groups, pentamethylene groups, and hexamethylene groups. Chain alkylene; methylmethylene, methylethylidene, ethylmethylene, dimethylmethylene (isopropylidene), 1,1-dimethylethylidene, 1- Methyltrimethylene, 2-methyltrimethylene, ethylidene, 1-methyltetramethylene, 2-methyltetramethylene, 1-ethyltrimethylene, 2-ethyltrimethylene Methyl, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene Methylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyl tetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, 1,4-dimethyltetramethylene Branched chain alkylene such as methyl. Among these, a methylene group, an ethylidene group, and the like are preferable.

The halogenated alkylene group represented by C in the general formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and still more preferably a halogenated alkylene group having a carbon number of 1 to 5. 1-3 halogenated alkylene groups. Specific examples of the halogenated alkylene group represented by C in the general formula (E) include at least one hydrogen atom contained in the alkylene group represented by C in the above-mentioned general formula (E) via a fluorine atom, An alkylene group substituted with a halogen atom such as a chlorine atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, and the like are preferable.

The alkyl group represented by R ^A or R ^B contained in the silylene bond or the siloxane bond is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, Further preferred is an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by ^RA or ^RB include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.

The combination of A and B in the general formula (D) is not particularly limited, but is preferably a combination of a methylene group and an ether bond, a combination of a methylene group and a thioether bond, a combination of a carbonyl group and an ether bond, and the like. As C in the general formula (E), a single bond, an ether bond, a carbonyl group and the like are preferable.

The carbon number of the aliphatic hydrocarbon group represented by R ⁶ and R ⁷ in the general formula (6) is 1 to 4, preferably 1 or 2. Specific examples of the aliphatic hydrocarbon groups represented by R ⁶ and R ⁷ include methyl, ethyl, n-propyl, isopropyl, n-butyl and the like.

The carbon number of the aliphatic hydrocarbon group represented by R ⁸ to R ¹⁰ in the general formula (7) is 1 to 3, preferably 1 or 2. Specific examples of the aliphatic hydrocarbon groups represented by R ⁸ to R ¹⁰ include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, and the like, and methyl groups are preferred.

As a combination of R ⁸ to R ¹⁰ in the general formula (7), a combination in which R ⁸ and R ⁹ are a hydrogen atom and R ¹⁰ is a hydrogen atom or a methyl group is preferable.

q in the general formula (7) is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, still more preferably 2 or 3.

In the general formula (6), preferably at least one of R ⁶ and R ⁷ is a group represented by the general formula (7), more preferably R ⁶ and R ⁷ both of which are the general formula (7) represents the basis.

When X corresponds to a residue derived from a tetracarboxylic dianhydride, specific examples of the tetracarboxylic dianhydride used as a source of the residue include pyromellitic dianhydride, 2,3,6 ,7-Naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 1 ,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9, 10-Perylenetetracarboxylic dianhydride, m-triphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-triphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2 ,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxybenzene) base) propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxybenzene Oxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propanedi Anhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxygen diphthalic dianhydride, 4,4'-sulfonyl diphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.

In the general formula (6), the number of carbon atoms of the divalent organic group represented by Y is preferably 1-30, more preferably 5-25, still more preferably 10-20. The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group.

Specific examples of the divalent aromatic group represented by Y include groups represented by the following general formula (F) and the following general formula (G).

[hua 8]

In general formula (F) or general formula (G), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a carboxyl group or a phenyl group, and n each independently represents an integer of 0 to 4. In the general formula (G), D represents a single bond or an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), a silylene bond (- Si(R ^A ) ₂ -; R ^A independently represents a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (-O-(Si(R ^B ) ₂ -O-) _n ; R ^B each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more) or a divalent group formed by combining at least two of these. Moreover, D may be the structure represented by the said formula (C1).

The alkyl group represented by R in the general formula (F) or the general formula (G) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having a carbon number of 1 to 5. 1 or 4 alkyl groups. Specific examples of the alkyl group represented by R in the general formula (F) or the general formula (G) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second Butyl, tertiary butyl, etc.

The alkoxy group represented by R in the general formula (F) or the general formula (G) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and still more preferably is an alkoxy group having 1 or 4 carbon atoms. Specific examples of the alkoxy group represented by R in general formula (F) or general formula (G) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, Isobutoxy, second butoxy, third butoxy, etc.

The halogenated alkyl group represented by R in the general formula (F) or the general formula (G) is preferably a halogenated alkyl group having 1 to 10 carbon atoms, more preferably a halogenated alkyl group having 1 to 5 carbon atoms, and more preferably is a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in the general formula (F) or the general formula (G) include those contained in the alkyl group represented by R in the general formula (F) or the general formula (G). An alkyl group in which at least one hydrogen atom is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and the like are preferable.

In general formula (F) or general formula (G), n is each independently preferably 0 to 2, more preferably 0 or 1, still more preferably 0.

Furthermore, D may be a divalent group represented by the following formula (D1) or formula (D2). -Q-Ar-Q- (D1) -Q-Ar-Q-Ar-Q- (D2) In formula (D1) or formula (D2), Ar represents an optionally substituted phenylene or naphthylene . Q independently represents a single bond or an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), a silylene bond (-Si( ^RA ) _2- ; R ^A independently represents a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (-O-(Si(R ^B ) ₂ -O-) _n ; R ^B independently represents a hydrogen atom, an alkane group or phenyl group, n represents an integer of 1 or 2 or more) or a divalent group formed by combining at least two of these. In the formula (D1) and the formula (D2), the positional relationship of the two Qs bonded to each Ar may be an ortho position, a meta position, or a para position. Specific examples of the substituent which the phenylene group or naphthylene group represented by Ar may have are the same as those represented by R in the general formula (F) or the general formula (G). The number of substituents that the phenylene group or naphthylene group represented by Ar may have is not particularly limited.

Specific examples of D in general formula (G) other than formula (D1) and formula (D2), specific examples of Q in formula (D1) and formula (D2), and specific examples of C in general formula (E) Example is the same. As D in the general formula (G), a single bond or an ether bond is preferable.

Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, a divalent group having a polyalkylene oxide structure, and a polysiloxane structure. the bivalent base, etc.

The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 10 carbon atoms. 3 alkylene groups. Specific examples of the alkylene group represented by Y include tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, and undecamethylene , dodeca methylene, 2-methyl pentamethylene, 2-methyl hexamethylene, 2-methyl heptamethylene, 2-methyl octamethylene, 2-methyl nonamethylene group, 2-methyldecamethylene, etc.

The cycloextended alkyl group represented by Y is preferably a cycloextended alkyl group having 3 to 20 carbon atoms, more preferably a cycloextended alkyl group having 3 to 10 carbon atoms, and still more preferably a cycloextended alkyl group having 3 to 6 carbon atoms base. As a specific example of the cycloextended alkyl group represented by Y, a cycloextended propyl group, a cyclohexylene group, etc. are mentioned.

The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, Furthermore, it is preferably an alkylene oxide structure having 1 to 4 carbon atoms. Among them, as the polyalkylene oxide structure, a polyethylene oxide structure or a polypropylene oxide structure is preferable. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be one type or two or more types.

Examples of the divalent group having a polysiloxane structure represented by Y include a bond between a silicon atom and a hydrogen atom in the polysiloxane structure, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. The junction has a divalent group with a polysiloxane structure. Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and tert-butyl group. , n-octyl, 2-ethylhexyl, n-dodecyl, etc. Among these, a methyl group is preferable. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. As a specific example of the substituent when an aryl group has a substituent, a halogen atom, an alkoxy group, a hydroxyl group, etc. are mentioned. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, a benzyl group, and the like. Among these, a phenyl group is preferable. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be one type or two or more types. The silicon atom constituting the divalent group having the polysiloxane structure represented by Y can be connected to the NH group in the general formula (6) through an alkylene group such as a methylene group, an ethylidene group, an aryl group such as a phenylene group, and the like. bond.

When Y corresponds to a residue derived from a diamine compound, specific examples of the diamine compound to be the source of the residue include 2,2′-bis(trifluoromethyl)-4,4 '-Diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,5-diaminobenzoic acid, p-phenylenediamine, m-phenylenediamine, terephthalic acid Methyldiamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether , 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl base, 3,4'-diaminodiphenyl, 3,3'-diaminodiphenyl, 2,4'-diaminodiphenyl, 2,2'-diamino Diphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4 '-Diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine, 4,4'-methylenebis(2,6- Diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diamino-mesitylene, 4,4'-benzophenonediamine, Bis-{4-(4'-aminophenoxy)phenyl}propane, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 2,2-bis{4 -(4'-Aminophenoxy)phenyl}hexafluoropropane, 4,4'-(m-phenylene diisopropylidene) bisaniline, 4,4'-(p-phenylene diisopropylidene Propyl)dianiline, 1,7-bis(4-aminophenoxy)naphthalene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis(4-aminophenoxy) phenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5 ,5'-Tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}benzene, 2,2-bis(4-amino) Phenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 2,2'-dimethyl-4,4' -Diaminobiphenyl, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9 -Diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diamine pentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2 -Methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diamine Amine polysiloxane, etc. A diamine compound may be used individually by 1 type, and may use 2 or more types together.

The combination of the tetravalent organic group represented by X in the general formula (6) and the divalent organic group represented by Y is not particularly limited. In a certain aspect, in order to carry out the cyclization reaction of polyimide at low temperature, from the viewpoint of low temperature sclerosis, the tetravalent organic group represented by X in the general formula (6) and the tetravalent organic group represented by Y A combination of divalent organic groups, preferably X is a group represented by the general formula (E) and C in the general formula (E) is a group represented by a single bond or an ether bond, and Y is a group represented by the general formula (G) and the general formula A combination of groups in which D in (G) is represented by a single bond or an ether bond. In addition, in a certain aspect, in order to make the irradiation light reach the bottom of the film at the time of exposure, from the viewpoint of transmittance, the tetravalent organic group represented by X in the general formula (6) and the divalent organic group represented by Y A combination of organic groups, preferably X is a group represented by the general formula (E) and C in the general formula (E) is a group represented by an ether bond, and Y is a group represented by the general formula (G) and in the general formula (G) D is a combination of groups represented by ether bonds. In this case, Y may contain a group represented by the general formula (F). When Y is represented by the general formula (G) and D in the general formula (G) is represented by an ether bond, and the group represented by the general formula (F) is used together, the amount represented by the general formula (F) is based on the proportion of Y in the general formula (F). The ratio of mol% is preferably 5 mol% to 30 mol%, more preferably 6 mol% to 15 mol%. Moreover, in a certain aspect, as a combination of the tetravalent organic group represented by X in General formula (6), and the divalent organic group represented by Y, from the viewpoint of the toughness of the cured film, X can be mentioned. At least a part of is a group represented by the general formula (A), Y is a combination of arbitrary divalent organic groups, and the like. From the viewpoints of low temperature sclerosis, transmittance, and toughness, X may be a combination of a group represented by general formula (A) and a group represented by general formula (E). When X is a combination of a group represented by the general formula (A) and a group represented by the general formula (E), the ratio of the general formula (A) in X is preferably 10 mol % to 80 mol % , more preferably 30 mol% to 70 mol%. Moreover, in a certain aspect, when the ratio of 1,3-dimethyl-2-imidazolidinone in the solvent is 50 mass % or more, 70 mass % or more, 90 mass % or more, or 100 mass % Next, from the viewpoint of the uniformity of the film thickness, the ratio of the group represented by the following general formula (G1) in the divalent organic group represented by Y in the general formula (6) is preferably less than 100 mol %, more preferably 95 mol % or less, further preferably 80 mol % or less, and particularly preferably 50 mol % or less. When the ratio of the group represented by the following general formula (G1) in the divalent organic group represented by Y in the general formula (6) is less than 100 mol %, the group represented by Y in the general formula (6) The divalent organic group may contain at least one selected from the group consisting of a group represented by the general formula (F) and a group represented by the following general formula (G2). In this case, in the divalent organic group represented by Y in the general formula (6), the ratio of the total of the group represented by the general formula (F) and the group represented by the following general formula (G2) is relatively It is preferably more than 0 mol%, more preferably 5 mol% or more, more preferably 20 mol%, particularly preferably 50 mol% or more, and most preferably 100 mol%.

[Chemical 9]

In general formula (G1) or general formula (G2), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a carboxyl group or a phenyl group, and n each independently represents an integer of 0 to 4. Specific examples and preferred examples of R and n are the same as those of the general formula (G).

The unsaturated polyimide precursor may have other structural units than the structural unit represented by the general formula (6). Other structural units other than the structural unit represented by the general formula (6) include structural units in which R ⁶ and R ⁷ in the general formula (6) are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. That is, neither R ⁶ nor R ⁷ in the general formula (6) is a structural unit of the group represented by the general formula (7).

The unsaturated polyimide precursor can be obtained by mixing the tetracarboxylic dianhydride represented by the following general formula (8) and the compound represented by R-OH in N-methyl-2-pyrrole A diester derivative is prepared by reacting in an organic solvent such as pyridone, and then the diester derivative is subjected to a condensation reaction with a diamine compound represented by H ₂ NY-NH ₂ . In addition, the unsaturated polyimide precursor can be obtained by mixing a tetracarboxylic dianhydride represented by the following general formula (8) and a diamine compound represented by H ₂ NY-NH ₂ in an organic A polyamide acid is obtained by reacting in a solvent, a compound represented by R-OH is added, and an ester group is introduced by reacting in an organic solvent. Here, Y in the diamine compound represented by H ₂ NY-NH ₂ is the same as Y in the general formula (6), and specific examples and preferred examples are also the same. In addition, R in the compound represented by R—OH represents a group represented by the general formula (7) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and specific examples and preferred examples are the same as R ⁶ in the general formula (6). The same is true for R ⁷ . The tetracarboxylic dianhydride represented by general formula (8), the diamine compound represented by H ₂ NY-NH ₂ , and the compound represented by R—OH may be used alone or in combination of two or more. In addition, the unsaturated polyimide precursor can be obtained by reacting a compound represented by R—OH with a tetracarboxylic dianhydride represented by the following general formula (8) to obtain a diester derivative After the compound, a chlorinating agent, such as thionite chloride, is made to act to convert it into acetyl chloride, and then the diamine compound represented by H ₂ NY-NH ₂ is reacted with the acetyl chloride. Furthermore, an unsaturated polyimide precursor can be obtained by reacting a compound represented by R—OH on a tetracarboxylic dianhydride represented by the following general formula (8) to obtain a diester derivative After the compound, a diamine compound represented by H ₂ NY-NH ₂ is reacted with a diester derivative in the presence of a carbodiimide compound. Furthermore, the unsaturated polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H ₂ NY-NH ₂ After the polyamic acid is prepared, the polyamic acid is isoimidized in the presence of trifluoroacetic anhydride, and then the compound represented by R—OH is made to function. In this case, the compound represented by R-OH may act on a part of the tetracarboxylic dianhydride in advance, and the partially esterified tetracarboxylic dianhydride and the diamine represented by H ₂ NY-NH ₂ may be used. The compound reacts to make polyamide acid. The unsaturated polyimide precursor obtained in this way can be purified according to conventional methods.

[Chemical 10]

In the general formula (8), X is the same as X in the general formula (6), and the specific examples and preferred examples are also the same.

Examples of the compound represented by R—OH used in the synthesis of the unsaturated polyimide precursor include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, Acrylate-2-hydroxyethyl ester, etc.

The molecular weight of the unsaturated polyimide precursor is not particularly limited, but is preferably 10,000 to 200,000 in terms of weight average molecular weight. The weight average molecular weight can be measured by, for example, gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.

(polymerizable monomer) The photosensitive resin composition of the present disclosure may contain a polymerizable monomer. The polymerizable monomer may be a compound containing at least one polymerizable unsaturated bond in the molecule, and preferably a compound containing two or more polymerizable unsaturated bonds in the molecule. As a group containing a polymerizable unsaturated bond, an allyl group, an acryloxy group, a methacryloyloxy group, etc. are mentioned. Among these, acryloxy or methacryloyloxy is preferred.

The molecular weight of the polymerizable monomer is preferably 50 to 1000, more preferably 75 to 800, further preferably 100 to 500.

The polymerizable monomer is preferably a compound containing at least one of two acryloxy groups and methacryloyloxy groups in a molecule, more preferably two acryloxy groups contained in a molecule or A compound in which a methacryloyloxy group is linked by a linear divalent organic group, more preferably a compound represented by the following general formula (4) or the following general formula (5) (hereinafter, sometimes referred to as is a specific polymerizable monomer.).

[Chemical 11]

In general formula (4) or general formula (5), R ³ independently represents a hydrogen atom or a methyl group, R ⁴ represents an alkylene group having 1 to 8 carbon atoms, and R ⁵ represents an alkylene group having 1 to 8 carbon atoms. , p represents an integer from 2 to 5. A plurality of R ³ may be the same or different. A plurality of R ⁵ may be the same or different.

As R ³ in the general formula (4) or the general formula (5), a methyl group is preferable. Specific examples of the alkylene group having 1 to 8 carbon atoms represented by R ⁴ in the general formula (4) include a methylene group, an ethylidene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. , octamethylene, etc. Specific examples of the alkylene group having 1 to 8 carbon atoms represented by R ⁵ in the general formula (5) include a methylene group, an ethylidene group, a trimethylene group, a methylethylidene group, and a dimethylene group. Methylene, tetramethylene, hexamethylene, octamethylene, etc. As p in general formula (5), the integer of 3-4 is preferable.

Specific polymerizable monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol Glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethylacrylate Acrylate, 1,6-hexanediol dimethacrylate, etc. Among these, tetraethylene glycol dimethacrylate is preferable.

As the polymerizable monomer, other polymerizable monomers other than the specific polymerizable monomer can also be used. Specific examples of other polymerizable monomers include trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, and trimethylolpropane trimeth. base acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N- Vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-bis(acryloyloxy)-2-hydroxypropane, 1,3-bis(methacrylic acid) yloxy)-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, etc. A polymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

The content of the polymerizable monomer is not particularly limited, but for example, it is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the unsaturated polyimide precursor. From the viewpoint of improving the hydrophobicity of the cured product, it is more preferably 3 parts by mass to 50 parts by mass, and still more preferably 5 parts by mass to 35 parts by mass. When the content of the polymerizable monomer is within the above-described range, a practical relief pattern is easily obtained, and residues after development of an unexposed portion are easily suppressed.

When a specific polymerizable monomer and another polymerizable monomer are used in combination, the content of the other polymerizable monomer is not particularly limited, but for example, it is preferably 1 part by mass to 300 parts by mass relative to 100 parts by mass of the specific polymerizable monomer The mass part is more preferably 10 parts by mass to 200 parts by mass, and still more preferably 20 parts by mass to 150 parts by mass.

(photopolymerization initiator) The photosensitive resin composition of the present disclosure contains a photopolymerization initiator. By containing the photopolymerization initiator in the photosensitive resin composition, photosensitivity can be imparted to the resin composition containing the unsaturated polyimide precursor and the polymerizable monomer. The photopolymerization initiator is not particularly limited as long as it is a compound that can generate radicals when irradiated with actinic light. The active rays include ultraviolet rays such as i rays, visible rays, and radiation.

Specific examples of the photopolymerization initiator include: benzophenone; N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N' -Tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'- Dimethoxybenzophenone, 4,4'-diaminobenzophenone, methyl o-benzylbenzoate, 4-benzyl-4'-methylbenzophenone, dimethoxybenzyl Benzophenone derivatives such as benzyl ketone and fluorenone; Acetophenone; 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2- Acetophenone derivatives such as phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone; 2-methylthioxanthone, 2-isopropylthio Xanthone, 2-chlorothioxanthone, diethylthioxanthone and other thioxanthone derivatives; benzalkonium; benzalkonium dimethyl ketal, benzalkonium-β-methoxyethyl acetal, etc. Benzoin derivatives; benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, propyl benzoin and other benzoin derivatives; 1-phenyl-1,2-butane Diketo-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propane Diketo-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzyl)oxime, 1,3-diphenylpropanetrione -2-(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzyl) oxime, 1,2-octanedione, 1- [4-(Phenylthio)phenyl]-,2-(O-benzyl oxime), ethanone, 1-[9-ethyl-6(2-methylbenzyl)-9H- Oxime derivatives such as carbazol-3-yl]-,1-(O-acetoxime); N-arylglycines such as N-phenylglycine; peroxides such as benzyl peroxide; 2-(2-Chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2 -(2-Fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2- or 4-methoxyphenyl)-4,5-diphenylimidazole dimer and other aromatics Biimidazoles; 2,4,6-trimethylbenzyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide and other phosphonium phosphine oxide derivatives things etc. The photopolymerization initiator may be used alone or in combination of two or more. Among these, an oxime derivative is preferable from the viewpoint of no metal element, high reactivity, and high sensitivity.

With respect to 100 parts by mass of the unsaturated polyimide precursor, the content of the photopolymerization initiator is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 15 parts by mass, and more preferably 5 parts by mass to 12 parts by mass. When the content of the photopolymerization initiator is within the above-mentioned range, the photo-crosslinking tends to become uniform in the film thickness direction, and it becomes easy to obtain a practical relief pattern.

(coupling agent) The photosensitive resin composition of this disclosure may contain a coupling agent. The coupling agent preferably contains a functional group capable of interacting with the unsaturated polyimide precursor, the polyimide resin, or the substrate. As a functional group which a coupling agent may contain, a hydroxyl group, a glycidyl group, a phenyl group, a (meth)acrylic group, a carboxyl group, the group which has a urea bond, etc. are mentioned. In addition, the phenyl group may be substituted with a polar group such as a hydroxyl group, a carboxyl group, and an amine group. In the case where the coupling agent is a silane coupling agent, the functional group is included in the coupling agent, and in the heat treatment after development, the functional group part reacts with the unsaturated polyimide precursor, and the siloxane part reacts with the unsaturated polyimide precursor. The substrate reacts. Thereby, the adhesiveness of the obtained hardened|cured material and a board|substrate can be improved further.

Specific examples of the coupling agent are not particularly limited. As the coupling agent, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyl Trimethoxysilane, Dimethoxymethyl-3-piperidinylpropylsilane, Diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilane propyl) butanediimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N-[3 -Triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, Benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2 , 5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane and other silane coupling agents; tris(ethylacetate)aluminum, Aluminum-based adhering additives such as aluminum tris(acetoacetate) and aluminum ethyl acetate diisopropionate.

The coupling agent may be used alone or in combination of two or more.

When the photosensitive resin composition of the present disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass relative to 100 parts by mass of the unsaturated polyimide precursor parts to 10 parts by mass, more preferably 3 parts to 10 parts by mass.

(solvent) The photosensitive resin composition of this disclosure contains a specific solvent. In one aspect, the ratio of the sum of N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea in the solvent is preferably 50% by mass Above, more preferably 70 mass % or more, still more preferably 90 mass % or more. The upper limit is not particularly limited, and may be 100% by mass. In addition, in a certain aspect, the ratio of N-ethyl-2-pyrrolidone in the solvent is preferably 50 mass % or more, more preferably 70 mass % or more, from the viewpoint of film thickness uniformity , and more preferably 90% by mass or more. The upper limit is not particularly limited, and may be 100% by mass. Moreover, in a certain aspect, the ratio of 1,3-dimethyl-2-imidazolidinone in the solvent is preferably 50 mass % or more, more preferably 70 mass %, from the viewpoint of the dissolution contrast. above, more preferably 90 mass % or more. The upper limit is not particularly limited, and may be 100% by mass. Moreover, in a certain aspect, from the viewpoint of film thickness uniformity, the ratio of tetramethylurea to the solvent is preferably 50 mass % or more, more preferably 70 mass % or more, and still more preferably 90 mass % %above. The upper limit is not particularly limited, and may be 100% by mass.

The photosensitive resin composition of the present disclosure may contain other solvents than N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea. Examples of other solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxy propionate Ethyl ester, methyl 3-methoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphamide, tetramethylene Methyl ketone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, N-methylmorpholine, etc. When the content rate of the unsaturated polyimide precursor is kept constant, the solvent preferably contains NEP and TMU from the viewpoint of increasing the viscosity of the photosensitive resin composition and improving the thick film formability. at least one of them.

The solvent may be used alone or in combination of two or more. Although content of a solvent is not specifically limited, Generally, it is 50 mass parts - 1000 mass parts with respect to 100 mass parts of unsaturated polyimide precursors.

(thermal polymerization initiator) From the viewpoint of promoting the polymerization reaction, the photosensitive resin composition of the present disclosure may further contain a thermal polymerization initiator. The thermal polymerization initiator is preferably a compound that does not decompose under conditions of heating and drying to remove the solvent during film formation, but decomposes by heating during curing to generate radicals to promote A polymerization reaction between polymerizable monomers or an unsaturated polyimide precursor and a polymerizable monomer. The thermal polymerization initiator is preferably a compound having a decomposition point of 110°C to 200°C, and more preferably a compound having a decomposition point of 110°C to 175°C from the viewpoint of promoting the polymerization reaction at a lower temperature.

Specific examples of thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide; 1,1-bis(third hexyl peroxide)-3,3,5-trimethylcyclohexane, - Peroxyketals of bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, etc.; 1,1,3,3-tetramethylbutylperoxy Hydrogen peroxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide and other hydrogen peroxide; dicumyl peroxide, di-tert-butyl peroxide and other dialkyl peroxides Oxides; dilauryl peroxide, dibenzyl peroxide and other diacyl peroxides; bis(4-tert-butylcyclohexyl)peroxydicarbonate, bis(2-ethyl) Hexyl) peroxydicarbonate and other peroxydicarbonates; tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxybenzoic acid esters, peroxyesters such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; bis(1-phenyl-1-methylethyl) peroxide, etc.

When the photosensitive resin composition of the present disclosure contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor , in order to ensure good flux resistance, it is more preferably 0.2 to 20 parts by mass, and from the viewpoint of suppressing a decrease in solubility due to decomposition during drying, it is more preferably 0.3 to 10 parts by mass.

(sensitizer) The photosensitive resin composition of this disclosure may further contain a sensitizer. When the photosensitive resin composition contains a sensitizer, it is possible to achieve both the maintenance of the residual film rate and the favorable resolution under a wide range of exposure amounts.

As a sensitizer, Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-tert-butyl anthraquinone can be mentioned. , 1,2-benzo-9,10-anthraquinone, anthraquinone, methyl anthraquinone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, benzophenone , thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-[4-(methylthio) Phenyl]-2-morpholino-1-propanone, diacetylbenzyl, benzyl dimethyl ketal, benzil diethyl ketal, diphenyl disulfide, anthracene, phenanthrene Quinone (phenanthrenequinone), riboflavin tetrabutyrate, acridine orange, erythropolis, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl Alkyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenyl Cyclohexanone, aminostyryl ketone, 3-coumarin ketone compound, dicoumarin compound, N-phenylglycine, N-phenyldiethanolamine, 3,3',4,4'- Tetrakis(tert-butylperoxycarbonyl)benzophenone, etc.

A sensitizer may be used individually by 1 type, and may use 2 or more types together.

When the photosensitive resin composition of the present disclosure contains a sensitizer, the blending amount of the sensitizer is preferably 0.1 part by mass to 1.0 part by mass relative to 100 parts by mass of the unsaturated polyimide precursor, more preferably It is 0.2 mass part - 0.8 mass part.

(stabilizer) The photosensitive resin composition of this disclosure may contain a stabilizer. As a stabilizer, a radical scavenger etc. are mentioned. By containing the stabilizer in the photosensitive resin composition, the storage stability can be improved.

Examples of stabilizers include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitro Benzene, p-dinitrobenzene, m-dinitrobenzene, Phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-methylbenzoquinone (2,5- toluquinone), tannic acid, p-benzylaminophenol, nitrosoamines, etc.

A stabilizer may be used individually by 1 type, and may use 2 or more types together.

When the photosensitive resin composition of the present disclosure contains a stabilizer, the content of the stabilizer is preferably 0.05 parts by mass to 1.0 parts by mass, more preferably 0.1 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor parts to 0.8 parts by mass.

(surfactant and leveling agent) The photosensitive resin composition of this disclosure may contain at least one of a surfactant and a leveling agent. When the photosensitive resin composition contains at least one of a surfactant and a leveling agent, the developability can be improved, and further, the unevenness of the film thickness such as striation can be suppressed, and the applicability can be improved.

As a surfactant or a leveling agent, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc. are mentioned.

The surfactant and the leveling agent may be used alone or in combination of two or more.

When the photosensitive resin composition of the present disclosure contains at least one of a surfactant and a leveling agent, the total amount of the surfactant and the leveling agent is relative to 100 parts by mass of the unsaturated polyimide precursor. The content is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass, and still more preferably 0.05 parts by mass to 3 parts by mass.

(Rust inhibitor) The photosensitive resin composition of the present disclosure may contain a rust inhibitor. By containing a rust inhibitor in the photosensitive resin composition, corrosion of copper and copper alloys can be suppressed and discoloration of copper and copper alloys can be prevented. As a rust inhibitor, triazole derivatives, such as benzotriazole, a tetrazole derivative, etc. are mentioned. The rust inhibitor may be used alone or in combination of two or more.

In the case where the photosensitive resin composition of the present disclosure contains a rust inhibitor, the content of the rust inhibitor is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, more preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass.

The photosensitive resin composition of the present disclosure contains an unsaturated polyimide precursor, a photopolymerization initiator and a solvent, and as optional components, a polymerizable monomer, a coupling agent, a thermal polymerization initiator, a sensitizer, a stabilizer Agents, surfactants, leveling agents, and rust inhibitors, other components and inevitable impurities may also be included within a range that does not impair the effects of the present disclosure. For example, 80 mass % or more, 90 mass % or more, 95 mass % or more, 98 mass % or more, or 100 mass % of the photosensitive resin composition of the present disclosure may contain: Unsaturated polyimide precursor, photopolymerization initiator and solvent, Unsaturated polyimide precursor, polymerizable monomer, coupling agent, photopolymerization initiator and solvent, Unsaturated polyimide precursor, polymerizable monomer, coupling agent, photopolymerization initiator, solvent and thermal polymerization initiator, or, Unsaturated polyimide precursors, polymerizable monomers, coupling agents, photopolymerization initiators and solvents, as well as any thermal polymerization initiators, sensitizers, stabilizers, surfactants, leveling agents and inhibitors Rust agent.

<A cured product, an interlayer insulating film, a cover coat, a surface protection film, a method for producing the same, and an electronic component> The cured product of the present disclosure can be obtained by curing the photosensitive resin composition of the present disclosure. The cured product of the present disclosure may be a patterned cured product with a predetermined pattern, or a non-patterned cured product. The cured product of the present disclosure obtained by curing the photosensitive resin composition containing NEP or TMU as a solvent among the photosensitive resin compositions of the present disclosure tends to be excellent in film thickness uniformity. On the other hand, the photosensitive resin film before hardening formed using the photosensitive resin composition containing DMI as a solvent among the photosensitive resin compositions of the present disclosure tends to have a high residual film rate. As a result, the cured product obtained by curing the photosensitive resin composition containing DMI as a solvent tends to be a thick film. The average thickness of the cured product of the present disclosure is preferably 5 μm to 20 μm. The interlayer insulating film of the present disclosure may include the hardened material of the present disclosure. The covercoat of the present disclosure may include the hardener of the present disclosure. The surface protection film of the present disclosure may include the hardened product of the present disclosure.

The method for producing a patterned cured product of the present disclosure includes the steps of applying the photosensitive resin composition of the present disclosure on a substrate and drying to form a photosensitive resin film, and exposing the photosensitive resin film to pattern exposure to obtain a resin film. step, a step of developing the patterned resin film with a developer to obtain a patterned resin film, and a step of heat-treating the patterned resin film. Thereby, a pattern hardened material can be obtained.

The method of producing a patternless cured product includes, for example, the step of forming the photosensitive resin film of the present disclosure and the step of performing heat treatment. It can also further include the step of exposing.

Examples of the substrate include semiconductor substrates such as glass substrates and Si substrates (silicon wafers), metal oxide insulator substrates such as TiO ₂ substrates and SiO ₂ substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

There is no restriction|limiting in particular in the coating method of the photosensitive resin composition of this disclosure, A spinner etc. can be used for it.

Drying can be performed using a hot plate, an oven, or the like. The drying temperature is preferably 80°C to 150°C, and more preferably 90°C to 135°C from the viewpoint of securing the dissolution contrast. The drying time is preferably 30 seconds to 5 minutes. Drying can be performed more than twice. When drying is performed twice or more, it is preferable that the drying time per time is in the above-mentioned range. When drying is performed twice or more, the drying time may be the same or different. In addition, the drying temperature may be the same or different. Thereby, the photosensitive resin film which formed the photosensitive resin composition of this invention into a film shape can be obtained.

The average thickness of the photosensitive resin film is preferably 3 μm to 30 μm, more preferably 5 μm to 20 μm, and still more preferably 5 μm to 15 μm.

Regarding pattern exposure, for example, exposure is performed in a predetermined pattern through a photomask. Examples of actinic rays to be irradiated include ultraviolet rays such as i-rays, visible rays, and radiation, and i-rays are preferred. As an exposure apparatus, a parallel exposure machine, an aligner, a projection exposure machine, a stepper, a scanning exposure machine, etc. can be used.

By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, the unexposed part is removed by a developer. As the developer, a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be appropriately mixed and used. As a good solvent, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide can be mentioned. Amine, dimethylsulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, cyclohexanone, etc. As a poor solvent, toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water, etc. are mentioned.

A surfactant can also be added to the developer. As an addition amount, 0.01-10 mass parts is preferable with respect to 100 mass parts of developers, and 0.1-5 mass parts is more preferable.

The development time can be, for example, twice as long as the time until the photosensitive resin film is immersed and completely dissolved. The development time may vary depending on the unsaturated polyimide precursor to be used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and more preferably 10 seconds to 5 minutes from the viewpoint of productivity. 20 seconds to 5 minutes.

It can also be cleaned by rinse solution after developing. As the eluent, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used alone or in a suitable mixture, and can also be used in combination in stages .

By subjecting the patterned resin film to heat treatment, a patterned cured product can be obtained. The unsaturated polyimide precursor undergoes a dehydration and ring-closure reaction through the heat treatment step to become the corresponding polyimide resin.

The temperature of the heat treatment is preferably 380°C or lower, more preferably 250°C to 350°C, and still more preferably 270°C to 320°C. When the temperature of the heat treatment is within the range, the damage to the substrate or the device can be suppressed to a small extent, the device can be produced with good yield, and the energy saving of the process can be realized.

The time for the heat treatment is preferably 5 hours or less, more preferably 30 minutes to 3 hours. When the time of the heat treatment is within the above range, the crosslinking reaction or the dehydration ring-closure reaction can be sufficiently advanced. The environment for the heat treatment may be in the air or in an inert environment such as nitrogen gas, but from the viewpoint of preventing oxidation of the patterned resin film, it is preferably a nitrogen gas environment.

As an apparatus used for heat processing, a quartz tube furnace, a hot plate, a rapid annealing furnace, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, etc. are mentioned.

The cured product of the present disclosure can be used as an interlayer insulating film, a cover coat, or a surface protection film. Furthermore, the cured product of the present disclosure can be used as a passivation film, a buffer coating film, or the like. By using one or more selected from the group consisting of the passivation film, buffer coating film, interlayer insulating film, cover coat, surface protection film, etc., highly reliable semiconductor devices, multilayer wiring boards, various electronic devices can be produced , Multi-die Fan out Wafer Level Packaging (Multi-die Fan out Wafer Level Packaging) and other multi-layer devices and other electronic components. Here, the interlayer insulating film of the present disclosure includes the cured product of the present disclosure. The interlayer insulating film of the present disclosure, which includes a cured product of the present disclosure obtained by curing a photosensitive resin composition containing NEP or TMU as a solvent, tends to be excellent in film thickness uniformity. The interlayer insulating film of the present disclosure, which includes a cured product obtained by curing a photosensitive resin composition containing DMI as a solvent, tends to be a thick film. In addition, the covercoat of the present disclosure includes the hardened product of the present disclosure. The covercoat layer of the present disclosure including the cured product of the present disclosure obtained by curing a photosensitive resin composition containing NEP or TMU as a solvent tends to be excellent in film thickness uniformity. The overcoat layer of the present disclosure, which includes a cured product obtained by curing a photosensitive resin composition containing DMI as a solvent, tends to be a thick film. Moreover, the surface protection film of this disclosure includes the hardened|cured material of this disclosure. The surface protective film of the present disclosure including the cured product of the present disclosure obtained by curing a photosensitive resin composition containing NEP or TMU as a solvent tends to be excellent in uniformity of film thickness. The surface protective film of the present disclosure including a cured product obtained by curing a photosensitive resin composition containing DMI as a solvent tends to be a thick film.

An example of the manufacturing steps of the semiconductor device as the electronic component of the present disclosure will be described with reference to the drawings. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure as an electronic component according to an embodiment of the present disclosure. In FIG. 1 , a semiconductor substrate 1 such as a Si substrate having circuit elements is covered with a protective film 2 such as a silicon oxide film or the like except for predetermined portions of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. After that, the interlayer insulating film 4 is formed on the semiconductor substrate 1 .

Next, a photosensitive resin layer 5 such as a chlorinated rubber type or a phenol novolak type is formed on the interlayer insulating film 4, and a window is provided so as to expose a predetermined portion of the interlayer insulating film 4 by a known photolithography technique. 6A.

The interlayer insulating film 4 exposed from the window 6A is selectively etched, thereby providing the window 6B. Next, the photosensitive resin layer 5 is removed using an etching solution that does not etch the photosensitive resin layer 5 without etching the first conductor layer 3 exposed from the window 6B.

Furthermore, the second conductor layer 7 is formed using a known photo-etching technique, and is electrically connected to the first conductor layer 3 . In the case of forming a multilayer wiring structure of three or more layers, the steps described above can be repeated to form each layer.

Next, using the photosensitive resin composition of the present disclosure, the window 6C is opened by pattern exposure, and the surface protective film 8 is formed. The surface protection film 8 protects the second conductor layer 7 from external stress, α rays, and the like, and the obtained semiconductor device is excellent in reliability. In addition, in the above-described example, the interlayer insulating film 4 can also be formed using the photosensitive resin composition of the present disclosure. [Example]

Hereinafter, the present disclosure will be described more specifically based on examples. Furthermore, the present disclosure is not limited to the following examples.

[Details of materials] Details of the various materials used in the examples are as follows. ·Polymerizable monomer: Tetraethylene glycol dimethacrylate Photopolymerization initiator: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime (PDO, Lambson) Rust inhibitor: benzotriazole (BTA) · Unsaturated polyimide precursor A1 synthesized by the following method · Unsaturated polyimide precursor A2 synthesized by the following method · Unsaturated polyimide precursor A3 synthesized by the following method

(Synthesis of unsaturated polyimide precursor A1) 7.07 g of 4,4'-oxydiphthalic dianhydride (ODPA), 3.6 g of 4,4'-diaminodiphenyl ether (ODA) and 0.2 g of m-phenylenediamine were dissolved in N-methyl In 30 g of yl-2-pyrrolidone (NMP), the mixture was stirred at 30° C. for 4 hours, and then stirred at room temperature overnight to obtain a polyamic acid. Under water cooling, 9.45 g of trifluoroacetic anhydride was added thereto, and the mixture was stirred at 45° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added, followed by stirring. The reaction was added dropwise to distilled water, and the precipitate was filtered, separated and collected, and dried under reduced pressure to obtain unsaturated polyimide precursor A1. The number-average molecular weight of the unsaturated polyimide precursor A1 was determined in terms of standard polystyrene using a gel permeation chromatography (GPC) method under the following conditions. The number average molecular weight of the unsaturated polyimide precursor A1 was 25,000. Residue derived from diamine compound (divalent organic group represented by general formula (6)) in unsaturated polyimide precursor A1 group represented by general formula (G1) (residue derived from ODA) ) accounted for 90.6 mol%.

A measurement sample was prepared by dissolving 0.5 mg of the unsaturated polyimide precursor A1 in 1 mL of a solvent [tetrahydrofuran (THF)/dimethylformamide (DMF)=1/1 (volume ratio)].

Measuring device: detector Prominence SPD-M20A manufactured by Shimadzu Corporation Pump: Prominence LC-20AD manufactured by Shimadzu Corporation Standard monodisperse polystyrene: Tosoh TSKgel standard polystyrene manufactured by Co., Ltd. Mw=2350, 10200, 37900, 190000, 706000 Measurement conditions: Column: Gelpack GL-8300 MDT-5 Two in series (Showa Denko Materials Technical Service (Showa Denko Materials Techno Service Co., Ltd.) Eluent: THF/DMF=1/1 (volume ratio) LiBr (0.03 mol/L), H ₃ PO ₄ (0.06 mol/L) Flow rate: 1.0 mL/min Detection wavelength : 270 nm Injection volume: 5 μL Measurement temperature: 40°C

(Synthesis of unsaturated polyimide precursor A2) 7.07 g of ODPA and 4.12 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (DMAP) were dissolved in 30 g of NMP, stirred at 30°C for 4 hours, and then at room temperature The mixture was stirred overnight to obtain polyamide. Under water cooling, 9.45 g of trifluoroacetic anhydride was added thereto, and the mixture was stirred at 45° C. for 3 hours, and 7.08 g of HEMA was added, followed by stirring. The reaction was added dropwise to distilled water, and the precipitate was filtered, separated and collected, and dried under reduced pressure to obtain the unsaturated polyimide precursor A2. In the same manner as the unsaturated polyimide precursor A1, the number average molecular weight of the unsaturated polyimide precursor A2 was determined and found to be 30,000. Among the residues derived from diamine compounds (divalent organic groups represented by general formula (6)) in unsaturated polyimide precursor A2, groups represented by general formula (G1) (residues derived from ODA) ) is 0 mol%.

(Synthesis of unsaturated polyimide precursor A3) 31.02 g of ODPA and 26.24 g of HEMA were dissolved in 80 mL of γ-butyrolactone, and 16.30 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. The reaction mixture was left to cool to room temperature after the end of heat generation based on the reaction, and was further left to stand for 16 hours. Next, under ice cooling, a solution obtained by dissolving 41.26 g of dicyclohexylcarbodiimide (DCC) in 36 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Then, the suspension obtained by suspending 18.60 g of ODA in 70 mL of γ-butyrolactone was added over 60 minutes while stirring. The mixture was further stirred at room temperature for 2 hours, 6 mL of ethanol was added, and 80 mL of γ-butyrolactone was added after stirring for 1 hour. A reaction liquid was obtained by removing the precipitate produced in the reaction mixture by filtration. The obtained reaction liquid was thrown into 3 liters of ethanol, and the precipitate containing a crude polymer was produced|generated. The produced crude polymer was collected by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and dried under reduced pressure to obtain an unsaturated polyimide precursor A3. In the same manner as the unsaturated polyimide precursor A1, the number average molecular weight of the unsaturated polyimide precursor A3 was determined and found to be 40,000. The residue (divalent organic group represented by the general formula (6)) derived from the diamine compound in the unsaturated polyimide precursor A3 is the group represented by the general formula (G1) (the residue derived from ODA) ) is 100 mol %.

[Solubility] The solubility of the unsaturated polyimide precursor A1 to the unsaturated polyimide precursor A3 with respect to a specific solvent was evaluated by the following method. For comparison with specific solvents, NMP was also evaluated. 10 g of the unsaturated polyimide precursor A1 to the unsaturated polyimide precursor A3 were put into a predetermined amount of the solvent and stirred at 23°C. From the start of stirring to the elapse of 30 minutes, it was visually confirmed whether or not the unsaturated polyimide precursors A1 to A3 were dissolved. The above operation was repeated while increasing the amount of the solvent by 0.5 g, and the minimum amount of solvent required to dissolve the unsaturated polyimide precursor A1 to the unsaturated polyimide precursor A3 was obtained. The obtained results are shown in Table 1. At the same time, using an E-type viscometer (DV-2+Pro, manufactured by BROOKFIELD), it was determined that the unsaturated polyimide precursor A1 to the unsaturated polyimide precursor A3 were dissolved in the required minimum amount of solvent. The viscosity of the solution at 25°C. Based on the viscosity of Reference Example 1 or Reference Example 2 using NMP as a solvent, the viscosity of each Example was evaluated according to the following criteria. In addition, about Example 1 - Example 3, the viscosity (standard 1) of Reference Example 1 was used as a reference|standard. Regarding Example 4, the viscosity (standard 2) of Reference Example 2 was used as a reference. Regarding Example 5, no viscosity evaluation was performed. A: Compared with the viscosity of Reference Example 1 or Reference Example 2, the viscosity increased by more than 20%. B: Compared with the viscosity of Reference Example 1 or Reference Example 2, the viscosity change is within ±20%.

[Film thickness uniformity] The solution obtained by dissolving the unsaturated polyimide precursor A1 to the unsaturated polyimide precursor A3 in the required minimum amount of solvent was used as a coating liquid for film thickness uniformity evaluation. After spin-coating the obtained coating liquid on a 6-inch silicon wafer, the solvent was removed by heating at 100° C. for 5 minutes, whereby a coating film having the average film thickness described in Table 1 was formed. Next, the film thickness of the coating film was measured at 41 points selected from the wafer on the basis of the following criteria. The film thickness measurement was performed using a light interference type film thickness measuring apparatus (VM-2200, manufactured by SCREEN). The film thickness uniformity of the unsaturated polyimide precursor A1 to the unsaturated polyimide precursor A3 was estimated by the following formula. Film thickness uniformity [%] = (maximum film thickness of 41 points of film thickness after coating - minimum film thickness of 41 points of film thickness after coating)/average film thickness of 41 points x 100 Criteria for selecting measurement points: 41 points were set as measurement points in the shape of concentric circles at equal intervals in all the remaining areas, excluding an area of 10 mm from the outer peripheral edge of the wafer. The average film thickness was defined as the average value of each film thickness measured at 41 measurement points.

[Table 1] unit Reference Example 1 Example 1 Example 2 Example 3 Reference example 2 Example 4 Example 5 Unsaturated polyimide precursor A1 g 10 10 10 10 - - - Unsaturated polyimide precursor A2 g - - - - 10 10 - Unsaturated polyimide precursor A3 g - - - - - - 10 NMP g 13 - - - 13 - - NEP g - 13 - - - - - DMI g - - 14.5 - - 14.5 14.5 TMU g - - - 13 - - - viscosity Benchmark 1 A B A Benchmark 2 A - Average film thickness μm 20.0 19.6 17.8 18.7 19.3 18.8 17.9 Film thickness uniformity % 8.1 6.1 8.0 3.4 10.1 12.1 21.3

As is clear from Reference Example 1 and Examples 1 to 3 in Table 1, it can be seen that the unsaturated polyimide precursor A1 exhibits solubility equivalent to that of NMP with respect to a specific solvent. In addition, when a specific solvent is used instead of NMP, the uniformity of the film thickness is improved. As is clear from Reference Example 2 and Example 4 in Table 1, it was found that the unsaturated polyimide precursor A2 exhibited solubility and film thickness uniformity equivalent to those of NMP with respect to a specific solvent. The high-viscosity coating liquid is excellent in thick film formation. The higher viscosity of the coating liquid adjusted with the minimum required amount of solvent means that a thicker film can be formed during film formation. Thin film formation can be achieved by adding a solvent to reduce the viscosity of the coating liquid. The high viscosity of the coating liquid can be said to be excellent as a "material with a wide film thickness and film formation limit". Furthermore, since the solvent can be removed by heating during film formation and curing, this method of increasing the viscosity by a special combination of the solvent and the unsaturated polyimide precursor and the use of additives such as thickeners can improve the viscosity of the film. The viscosity of the coating solution varies according to the method, and there are advantages that additives are not easily left in the polyimide film, and the properties of the polyimide film are not hindered. If the spin coating during film formation can be performed at high rotation, the uniformity of film thickness can be improved, but when the viscosity of the coating liquid is low, it may be difficult to ensure the minimum required coating film thickness when spin coating is performed at high rotation. film thickness. In the examples of the present application, since the viscosity of the coating liquid is increased, even if spin coating is performed at a high rotation rate, the film thickness is not easily reduced. Therefore, it is presumed that the spin coating at the time of film formation can be performed at a high rotation rate, and the uniformity of the film thickness is improved.

[Composition properties] The properties regarding the photosensitive resin composition were evaluated as follows. In addition, the photosensitive resin composition was obtained by compounding each component described in Table 2 in the compounding amount described in Table 2. The compounding quantity of each component in Table 2 is based on a mass part.

(Dissolution contrast) The obtained photosensitive resin composition was spin-coated on a 6-inch silicon wafer using a coating apparatus Act8 (manufactured by Tokyo Electronics Co., Ltd.), dried at 90°C for 200 seconds, and then dried at 100°C. The photosensitive resin film was formed by drying for 200 seconds (prebaking). Regarding the spinning conditions of the spin coating, the spinning time was fixed to 30 seconds, and the rotational speed was adjusted so that the dry film thickness was about 15 μm. In this evaluation, it was set as the range of 2000 revolutions/min - 2500 revolutions/min. Table 2 shows the measured value (film thickness) of the dry film thickness. The obtained photosensitive resin film was immersed in cyclopentanone, and the time (development time) until the photosensitive resin film was completely melt|dissolved was measured, and the dissolution rate (DR1) of the unexposed part was computed by it. DR1=(film thickness after pre-baking)/development time In addition, a photosensitive resin film was produced in the same manner as described above, and an i-ray stepper FPA-3000iW (Canon) was used for the entire surface of the obtained photosensitive resin film. (manufactured by Canon Co., Ltd.), and exposure was performed by irradiating i-rays at 700 mJ/cm ² . Using Act8, the exposed photosensitive resin film was subjected to liquid development at the above-mentioned development time by cyclopentanone, and then rinsed and washed with propylene glycol monomethyl ether acetate (PGMEA). The dissolution rate (DR2) of the exposure part was calculated using the following formula. DR2=(film thickness after prebaking−film thickness after development)/development time based on the dissolution rate DR1 of the unexposed part of the photosensitive resin film and the dissolution of the exposed part of the photosensitive resin film obtained as described above Speed DR2, and calculate the dissolution contrast (DR1/DR2). The obtained results are shown in Table 2.

(Remaining film ratio) The obtained photosensitive resin composition was spin-coated on a 6-inch silicon wafer using a coating apparatus Act8 (manufactured by Tokyo Electronics Co., Ltd.), dried at 90°C for 200 seconds, and then heated at 100°C. The photosensitive resin film was formed by drying for 200 seconds (pre-baking). Regarding the spinning conditions of the spin coating, the spinning time was fixed to 30 seconds, and the rotational speed was adjusted so that the dry film thickness was about 15 μm. In this evaluation, it was set as the range of 2000 revolutions/min - 2500 revolutions/min. The obtained photosensitive resin film was immersed in cyclopentanone, and twice the time until the photosensitive resin film was completely dissolved was set as the development time. In addition, a photosensitive resin film was produced in the same manner as described above, and the obtained photosensitive resin film was subjected to 100 mJ/cm ² using an i-ray stepper FPA-3000iW (manufactured by Canon Co., Ltd.). Exposure is performed by irradiating i-rays of 100 mJ/cm ² to 1100 mJ/cm ² in a predetermined pattern at a unit exposure amount. Using Act8, the exposed photosensitive resin film was developed with cyclopentanone for the above-mentioned development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a predetermined patterned resin film. The residual film ratio when the exposure amount was 300 mJ/cm ² or 700 mJ/cm ² was calculated using the following formula. The obtained results are shown in Table 2. Residual film rate (%)=100×(film thickness after development)/(film thickness after pre-baking)

(Resolution) The obtained photosensitive resin composition was spin-coated on a 6-inch silicon wafer using a coating apparatus Act8 (manufactured by Tokyo Electronics Co., Ltd.), dried at 90°C for 200 seconds, and then dried at 100°C. The photosensitive resin film was formed by drying for 200 seconds (prebaking). Regarding the spinning conditions of the spin coating, the spinning time was fixed to 30 seconds, and the rotational speed was adjusted so that the dry film thickness was about 15 μm. In this evaluation, it was set as the range of 2000 revolutions/min - 2500 revolutions/min. The obtained photosensitive resin film was immersed in cyclopentanone, and twice the time until the photosensitive resin film was completely dissolved was set as the development time. In addition, a photosensitive resin film was produced in the same manner as described above, and the obtained photosensitive resin film was irradiated with an i-ray stepper FPA-3000iW (manufactured by Canon Co., Ltd.) at 700 mJ/ cm ² of i-rays (800 mJ/cm ² in Example 3). Using Act8, the exposed photosensitive resin film was developed with cyclopentanone for the above-mentioned development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a predetermined patterned resin film. The predetermined pattern was a hole pattern and a line and space pattern with a line width ratio of 1:1. The diameter of the smallest hole that can be patterned without peeling and residue, and the line width of the line were used as the resolution, and the evaluation was performed according to the following criteria. In Table 2, "resolution (L/S)" represents the resolution of the line and space pattern, and "resolution (hole)" represents the resolution of the hole pattern. A: The diameter of the smallest hole or the line width of the line is in the range of 20 μm or less. B: The diameter of the smallest hole or the line width of the line is in the range of more than 20 μm and 50 μm or less. C: The diameter of the smallest hole or the line width of the line is in the range of more than 50 μm.

[Table 2] project Reference Example 1 Example 1 Example 2 Example 3 Reference example 2 Example 4 Example 5 Unsaturated polyimide precursor A1 100 100 100 100 - - - Unsaturated polyimide precursor A2 - - - - 100 100 - Unsaturated polyimide precursor A3 - - - - - - 100 NMP 130 - - - 130 - - NEP - 130 - - - - - DMI - - 145 - - 145 145 TMU - - - 130 - - - polymerizable monomer 20 20 20 20 20 20 20 photopolymerization initiator 10 10 10 10 10 10 10 Rust inhibitor 2 2 2 2 2 2 2 DR2 (μm/s) 0.07 0.07 0.05 0.07 0.06 0.04 0.04 DR1 (μm/s) 1.73 2.58 4.03 4.02 1.54 5.12 2.11 dissolve contrast twenty four 39 78 57 26 128 53 Film thickness (μm) 14.8 14.8 15.8 14.6 14.7 16.1 14.9 Residual film rate (%) @300 mJ/cm ² 77.8 81.7 89.6 79.8 79.2 90.5 90.3 Residual film rate (%) @700 mJ/cm ² 87.8 86.8 93.3 90.3 89.2 94.1 94.1 Development time (s) 20 20 20 20 20 20 20 Resolution (L/S) @700 mJ/cm ² A A B A (@800 mJ/cm ² ) A A B Resolution (hole) @700 mJ/cm ² A A B A (@800 mJ/cm ² ) A A C

As is clear from Reference Example 1 and Examples 1 to 3 in Table 2, it was found that the photosensitive resin composition containing the specific solvent exhibited photosensitive properties equal to or more excellent than the photosensitive resin composition containing NMP. As is clear from the comparison of Example 2, Example 4, and Example 5 in Table 2, when DMI is used as a solvent, it can be seen that the residue derived from the diamine compound in the unsaturated polyimide precursor is The ratio of the group (residue derived from ODA) represented by the general formula (G1) in the (divalent organic group represented by the general formula (6)) decreases, and the dissolution contrast increases accordingly.

The entire disclosure of International Application No. PCT/JP2020/047736, filed on December 21, 2020, is incorporated herein by reference. All documents, patent applications, and technical specifications described in this specification are incorporated into this specification by reference to the same extent as the case where each document, patent application, and technical specification are specifically and separately described to be incorporated by reference. .

1: Semiconductor substrate 2: Protective film 3: The first conductor layer 4: Interlayer insulating film 5: Photosensitive resin layer 6A, 6B, 6C: Windows 7: The second conductor layer 8: Surface protection film

FIG. 1 is a manufacturing process diagram of an electronic component according to an embodiment of the present disclosure.

none.

Claims (15)

A photosensitive resin composition comprising a polyimide precursor having a polymerizable unsaturated bond, a photopolymerization initiator and a solvent, The solvent contains at least one selected from the group consisting of N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea. The photosensitive resin composition according to claim 1, wherein the total of N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and tetramethylurea is used in the solvent The ratio of the content is 50% by mass or more. The photosensitive resin composition according to claim 1, wherein the ratio of N-ethyl-2-pyrrolidone in the solvent is 50% by mass or more. The photosensitive resin composition according to claim 1, wherein the ratio of 1,3-dimethyl-2-imidazolidinone to the solvent is 50% by mass or more. The photosensitive resin composition according to claim 1, wherein the ratio of tetramethylurea to the solvent is 50% by mass or more. The photosensitive resin composition according to any one of claim 1 to claim 5, wherein the polyimide precursor has a structural unit represented by the following general formula (6):

(In the general formula (6), X represents a tetravalent organic group, and Y represents a divalent organic group; R ⁶ and R ⁷ are each independently a hydrogen atom, a group represented by the following general formula (7), or a carbon number of 1 an aliphatic hydrocarbon group of to 4, at least one of R ⁶ and R ⁷ is a group represented by the following general formula (7)),

(In the general formula (7), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10). The photosensitive resin composition according to claim 6, wherein the ratio of 1,3-dimethyl-2-imidazolidinone in the solvent is 50% by mass or more, and is represented by the general formula (6 ) in the bivalent organic group represented by Y in the ratio of the group represented by the following general formula (G1) is less than 100 mol%,

(In general formula (G1), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a carboxyl group or a phenyl group, and n each independently represents an integer of 0 to 4). The photosensitive resin composition according to any one of Claims 1 to 7, wherein the photopolymerization initiator contains an oxime derivative. A cured product obtained by curing the photosensitive resin composition according to any one of Claims 1 to 8. The cured product according to claim 9 is a patterned cured product. The cured product according to claim 9 or claim 10 is used as an interlayer insulating film, a cover coat or a surface protection film. An interlayer insulating film comprising the hardened product as claimed in claim 9. A cover coating comprising the hardened product of claim 9. A surface protection film, comprising the hardened product as claimed in claim 9. An electronic part comprising the hardened product according to any one of claim 9 to claim 11.

Images