CN108780275B

CN108780275B - Photosensitive film

Info

Publication number: CN108780275B
Application number: CN201780019777.4A
Authority: CN
Inventors: 池田芳史; 小山祐太朗
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2016-03-28
Filing date: 2017-03-22
Publication date: 2022-11-08
Anticipated expiration: 2037-03-22
Also published as: TWI728080B; JPWO2017170032A1; KR20180130099A; CN108780275A; SG11201807876SA; KR102314567B1; TW201802597A; JP6982786B2; WO2017170032A1

Abstract

Provided is a photosensitive film which can obtain a cured film having high heat resistance, has good pattern processability (high sensitivity), and has good adhesion to a substrate, that is, lamination properties. A photosensitive film comprising: (A1) An alkali-soluble resin having a structural unit represented by general formula (1); (A2) An alkali-soluble resin containing one or more selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof; (B) a photoacid generator; and (C) a thermal crosslinking agent. In the general formula (1), R ¹ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents an integer in the range of 0 to 4, b represents an integer in the range of 1 to 3, R ² Is any of a hydrogen atom, a methyl group, an ethyl group and a propyl group.

Description

Photosensitive film

Technical Field

The present invention relates to a photosensitive film. More specifically, the present invention relates to a photosensitive film suitable for a surface protective film on a semiconductor device surface, an interlayer insulating film, and an insulating layer of an organic electroluminescent device.

Background

Resins typified by polyimide and polybenzoxazole have excellent heat resistance and electrical insulation properties, and thus have been used for surface protection films of semiconductor elements, interlayer insulation films, insulation layers of organic electroluminescent elements, and the like. In recent years, with the miniaturization of semiconductor devices, resolution on the order of several μm is also required for surface protective films, interlayer insulating films, and the like. Therefore, in such applications, a positive photosensitive polyimide resin composition and a positive photosensitive polybenzoxazole resin composition which can be finely processed are often used.

In a general process for manufacturing a semiconductor device, a semiconductor element is formed on a substrate, a passivation film typified by Si or SiN is formed on the substrate, a photosensitive layer is formed on the passivation film, and then, the passivation film is heated and dried by using a hot plate or the like, and a pattern is formed by exposure and development. After the patterning, heat treatment at a high temperature is performed to cure the pattern, thereby forming an insulating layer.

In the past, a circular substrate has been used for forming a semiconductor element, but in recent years, a rectangular substrate has been used in accordance with the increase in size of the substrate.

The method for forming a photosensitive layer on a substrate includes: a method of coating a resin composition by a spin coating method; and a method of laminating the photosensitive film by applying heat to the substrate to press the photosensitive film. When an insulating layer is formed on a large-sized square substrate, a method of laminating the insulating layer using a photosensitive film is generally used in order to improve the uniformity of the film thickness after the formation.

As positive photosensitive polyimides used in resin compositions and photosensitive films, polyimide-based materials (for example, patent document 1), polyhydroxystyrene-based materials (for example, patent document 2), and materials obtained by mixing polyimide and polyhydroxystyrene (for example, patent document 3) are known.

Further, as photosensitive films, a technique using a phenol resin (for example, patent document 4) and a technique using a polyimide having a low glass transition temperature (for example, patent document 5) have been proposed.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2014-71374

Patent document 2: japanese patent laid-open publication No. 2006-154779

Patent document 3: japanese laid-open patent publication No. 2014-137523

Patent document 4: japanese laid-open patent publication No. 2015-19006

Patent document 5: international publication No. 2011/059089

Disclosure of Invention

Problems to be solved by the invention

As described above, when an insulating layer is formed on a square substrate, a method of laminating the insulating layer using a photosensitive film is generally used in order to improve the uniformity of the film thickness after the formation. Photosensitive films are required to have good pattern processability (high sensitivity) and good adhesion to substrates, i.e., lamination properties, in addition to mechanical properties such as high elongation and heat resistance which can be imparted to cured films.

However, films obtained using polyimide-based resin compositions as disclosed in patent documents 1 to 3 have insufficient flexibility, and have insufficient lamination properties, for example, when the films are laminated by applying heat to substrates to pressure-bond the films, cracks may occur. Patent document 4 discloses a technique of using a phenol resin for the purpose of improving fluidity, but has a problem that the heat resistance of the cured film is low. Patent document 5 discloses a technique using a polyimide having a low softening point, but has a problem that high heat resistance cannot be obtained.

Accordingly, the present invention provides a photosensitive film which can provide a cured film having high heat resistance, has good pattern processability (high sensitivity), and has good adhesion to a substrate, that is, lamination properties.

Means for solving the problems

In order to solve the above problems, the photosensitive film of the present invention has the following configuration. Namely, a photosensitive film comprising: (A1) An alkali-soluble resin having a structural unit represented by general formula (1); (A2) An alkali-soluble resin comprising one or more selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof; (B) a photoacid generator; and (C) a thermal crosslinking agent.

[ chemical formula 1]

(in the general formula (1), R ¹ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents an integer in the range of 0 to 4, b represents an integer in the range of 1 to 3, R ² Is any of a hydrogen atom, a methyl group, an ethyl group and a propyl group. )

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a photosensitive film having good pattern processability (high sensitivity) and good adhesion to a substrate, that is, lamination properties can be obtained. In addition, according to the photosensitive film of the present invention, a cured film having high elongation and high heat resistance can be obtained.

Drawings

FIG. 1 is an example of a schematic cross-sectional view of a semiconductor device using a photosensitive film of the present invention.

FIG. 2 is an example of a cross-sectional view of a coil portion of an inductor device using the photosensitive film of the present invention.

FIG. 3 is an example of a cross-sectional view of a hollow portion of an elastic wave device using the photosensitive film of the present invention.

FIG. 4 is an example of a cross-sectional view of a semiconductor device having a step on a substrate, using the photosensitive film of the present invention.

Detailed Description

The present invention is a photosensitive film, which contains: the above (A1) alkali-soluble resin having a structural unit represented by the general formula (1); (A2) An alkali-soluble resin containing one or more selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof; (B) a photoacid generator; and (C) a thermal crosslinking agent. Hereinafter, the resin (A1), the resin (A2), the component (B), and the component (C) may be omitted.

The photosensitive film of the present invention contains the above (A1) alkali-soluble resin having a structural unit represented by general formula (1). R in the above general formula (1) ¹ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents an integer in the range of 0 to 4, b represents an integer in the range of 1 to 3, R ² Represents any of a hydrogen atom, a methyl group, an ethyl group and a propyl group. By containing the resin (A1), the sensitivity of the photosensitive film can be improved.

The structural unit represented by the above general formula (1) can be obtained, for example, by subjecting an alkoxy group to an addition reaction with a part of a polymer obtained by polymerizing an aromatic vinyl compound having a phenolic hydroxyl group such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, or o-isopropenylphenol, and an aromatic vinyl compound such as styrene, o-methylstyrene, m-methylstyrene, or p-methylstyrene, alone or in combination of two or more of the above, by a known method (for example, the method described in japanese patent No. 5659259).

As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene and/or m-hydroxystyrene can be preferably used, and as the aromatic vinyl compound, styrene can be preferably used.

The alkali-soluble resin (A1) having a structural unit represented by the general formula (1) preferably further has at least one of the structural units represented by the general formulae (2) and (3) from the viewpoint of further improving sensitivity and the convenience of being able to adjust solubility in an alkaline developer. From the viewpoint of solubility in an alkaline developer, the structural unit of the general formula (3) is preferably 50mol% or less.

[ chemical formula 2]

(in the general formula (2), R ³ Represents a hydrogen atom or carbonAn alkyl group having 1 to 5 atoms, and e represents an integer in the range of 1 to 5. )

[ chemical formula 3]

(in the general formula (3), R ⁴ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )

For the alkoxyalkyl (CH) in the above-mentioned (A1) resin ₂ OR ² ) The introduction rate of the group is preferably 10mol% or more, more preferably 20mol% or more per 1mol of hydroxystyrene, from the viewpoint of heat resistance after curing. From the viewpoint of improving the resolution, it is preferably 70mol% or less, and more preferably 50mol% or less.

From the viewpoint of forming a pattern of unexposed portions without elution, the weight average molecular weight (Mw) of the resin (A1) in terms of polystyrene is preferably 3,000 or more. In addition, from the viewpoint of maintaining the alkali solubility that can reduce the residue at the exposed portion, it is preferably 60,000 or less, more preferably 25,000 or less.

The polystyrene-equivalent weight average molecular weight (Mw) is a value calculated by GPC (gel permeation chromatography) measurement based on polystyrene.

The photosensitive film of the present invention contains (A2) an alkali-soluble resin containing one or more selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.

The resin (A2) may contain any two or more of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof, and may also contain a copolymer having a repeating unit of two or more of these. In addition, the (A2) resin preferably has a substituent that reacts with the alkoxyalkyl group of the (Al) resin. The alkoxyalkyl group of (Al) means especially an alkoxymethyl group. (A2) The structure of the resin is not particularly limited as long as it has a substituent reactive with an alkoxyalkyl group, and preferably has one or more groups selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group in the main chain or at the end.

The alkoxyalkyl group of the (Al) resin reacts with the (A2) resin at the time of thermal curing, and thus heat resistance and mechanical properties can be sufficiently maintained, so that good pattern processability of the (A1) resin and high heat resistance and high mechanical properties of the (A2) resin can be simultaneously achieved. From the viewpoint of pattern processability, the content of the resin (A2) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the resin (A1) and the resin (A2). From the viewpoint of heat resistance and mechanical properties, it is preferably 90 parts by mass or less, and more preferably 70 parts by mass or less.

The resin (A2) preferably has at least one of the structural units represented by the general formulae (4) and (5).

[ chemical formula 4]

(in the general formula (4), R ⁵ Represents a C4-40 di-or tetravalent organic group. R ⁶ Represents a divalent organic group having 20 to 100 carbon atoms. n is ₁ Represents an integer in the range of 10 to 100,000. )

[ chemical formula 5]

(in the general formula (5), R ⁵ Represents a C4-40 di-or tetravalent organic group. R ⁶ Represents a divalent organic group having 20 to 100 carbon atoms. R ⁷ Represents hydrogen or an organic group having 1 to 20 carbon atoms. n is ₂ Represents an integer in the range of 10 to 100,000, and p and q represent integers satisfying 0. Ltoreq. P + q. Ltoreq.2. )

In the general formulae (4) and (5), R ⁵ Represents a di-to tetravalent organic group having 4 to 40 carbon atoms and having a monocyclic or fused polycyclic alicyclic structure. R ⁵ In (1), as monocyclic or condensed polycyclic estersThe ring structure preferably contains 1 or more organic groups selected from the following general formulae (6) to (9).

[ chemical formula 6]

(in the general formulae (6) to (9), R ⁸ ～R ⁵³ Each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms. In the case of a monovalent organic group having 1 to 3 carbon atoms, a hydrogen atom contained in the organic group may be substituted with a halogen atom. )

R in the general formulae (4) and (5) ⁵ Is an organic group derived from an acid dianhydride used as a raw material of a resin.

Specific examples of the acid dianhydride comprising a C4-40 bi-or tetravalent organic group having a monocyclic or fused polycyclic alicyclic structure used in the present invention include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

In the general formulae (4) and (5), as R ⁵ Preferred examples of the di-to tetravalent organic groups having 4 to 40 carbon atoms and having 1 to 4 aromatic rings include aromatic dicarboxylic acids selected from the group consisting of pyromellitic acid, 3,3',4,4' -biphenyltetracarboxylic acid, 2,3,3',4' -biphenyltetracarboxylic acid, 2,2',3,3' -biphenyltetracarboxylic acid, 3,3',4,4' -benzophenonetetracarboxylic acid, 2,2',3,3' -benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (8624-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3235-dicarboxyphenyl) ethane, 3292 zxft 3226-bis (34zzft) 3526-dicarboxyphenyl) ethane, 3527-bis (dicarboxyphenyl) naphthalene-4235-dicarboxyphenyl) pyridine, and the aromatic naphthalene-bis (34zzft) 4235-bis (dicarboxyphenyl) naphthalene-4258-bis (dicarboxyphenyl) pyridine), such as-4235-bis (3419) naphthalene-bis (dicarboxyphenyl) pyridine, 3458-bis (dicarboxyphenyl) naphthalene-4235-bis (dicarboxyphenyl) pyridine, and the likeA structure obtained by removing a carboxyl group from an acid, a structure obtained by substituting a part of hydrogen atoms thereof with an alkyl group having 1 to 4 carbon atoms and 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group, a fluorine atom, a chlorine atom, or the like.

From the viewpoint of increasing the elongation and improving the lamination property between the film and the substrate, R in the general formulae (4) and (5) ⁵ When set to 100mol%, R ⁵ The alicyclic structure of the monocyclic or condensed polycyclic ring in (1) is preferably 10mol% or more, more preferably 30mol% or more. From the viewpoint of obtaining an appropriate dissolution rate in the developer, it is preferably 80mol% or less, and more preferably 60mol% or less.

For example, R is relative to 100mol% of the total amount of the recurring units of the formulae (4) and (5) ⁵ When the resin composition has 70mol% of monocyclic or condensed polycyclic alicyclic structure and 30mol% of tetravalent organic group having an aromatic ring, the resin composition has 70mol% of monocyclic or condensed polycyclic alicyclic structure. At this time, R ⁵ When two or more alicyclic structures of monocyclic type or condensed polycyclic type are present in the resin composition, the amount is 70mol%.

R in the general formulae (4) and (5) ⁶ It is preferable that the organic group has a polyether structure represented by the following general formula (10).

[ chemical formula 7]

(in the formula, R ⁵⁴ ～R ⁵⁷ Each independently represents an alkylene group having 1 to 6 carbon atoms. R ⁵⁸ ～R ⁶⁵ Each independently represents hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms. The structure indicated in parentheses of the repeating unit x is different from the structure indicated in parentheses of the repeating unit y. The structure shown in parentheses in the repeating unit z is different from the structure shown in parentheses in the repeating unit y. x, y and z each independently represent an integer of 0 to 35. ) R in the general formulae (4) and (5) ⁶ Is an organic group derived from a diamine used as a raw material of a resin.

Specific examples of the diamine containing an organic group having a polyether structure used in the present invention include aliphatic diamines such as "JEFFAMINE" (registered trademark) HK-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000, "ELASTAMINE" (registered trademark) RP-409, RP-2009, RT-1000, HT-1100, HE-1000, and HT-1700 (trade name, manufactured by HUNTSMAN Co., ltd.). The polyether structure is preferably used because hydrophilicity and meltability at high temperature are imparted to the wafer, so that the substrate has improved laminatability, flexibility is imparted to the wafer, so that the elongation is improved, and the elastic modulus is reduced, so that warpage of the wafer is suppressed. These characteristics are effective for a multilayer, thick film. R in the general formulae (4) and (5) ⁶ When the polyether structure represented by the general formula (1O) is 1Omol% or more, the resin is preferably flexible, low in stress, and capable of being laminated on a substrate, in the case of 100mol%. In addition, from the viewpoint of obtaining an appropriate dissolution rate in the developer, a concentration of 80mol% or less is preferable. More preferably, it is contained in an amount of 20 to 50mol%.

For example, R is relative to 100mol% of the total amount of the repeating units of the general formulae (4) and (5) ⁶ When 70mol% of the organic group derived from diamine (the diamine contains an organic group having a polyether structure) and 30mol% of the divalent organic group having an aromatic ring is present, the organic group derived from diamine (the diamine contains an organic group having a polyether structure) is calculated to be 70mol%. At this time, R ⁶ When two or more organic groups derived from diamine (the diamine contains an organic group having a polyether structure) were present in the composition, the amount was 70mol%.

Further, the fluorine atom-containing organic group is contained as R in the general formulae (4) and (5) ⁵ This is preferable because water repellency can be imparted to the resin and bleeding from the film surface during alkali development can be suppressed. By suppressing bleeding from the film surface, a resin film having no tackiness in an unexposed portion and no development residue on a processed pattern and having a high residual film ratio can be obtained. These characteristics are important characteristics for realizing thick film processing. R is to be ⁵ When the total amount of (B) is 100mol%When the content of the organic group having a fluorine atom is 20mol% or more, an effect of preventing the interface from bleeding can be obtained, and when the content is 90mol% or less, an appropriate dissolution rate in the developer can be obtained, which is preferable from the viewpoint of containing 40mol% to 60mol%.

Specific examples of the compound having a fluorine atom include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, a compound obtained by substituting an aromatic ring thereof with an alkyl group or a halogen atom, and an aromatic acid dianhydride such as an acid dianhydride having an amide group. (A2) The resin is preferably a resin containing a structure derived from these compounds.

By using the acid dianhydride having an alicyclic structure having 4 to 40 carbon atoms, the diamine having a polyether structure having 20 to 100 carbon atoms, and the compound having a fluorine atom in the above ranges, a highly sensitive photosensitive film having high elongation and low stress, and having no tackiness during development and a high residual film ratio without development residue can be obtained.

These characteristics are particularly useful for rewiring of semiconductor devices used by stacking a plurality of layers as interlayer insulating films between metal wirings, noise filters of inductor devices, and the like. The photosensitive film of the present invention may contain a structure derived from an acid dianhydride or a diamine other than the acid dianhydride or the diamine described above within a range in which the above properties are not degraded.

Specific examples of the other acid dianhydrides include pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 2,2',3,3' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 2,2',3,3' -benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 58 zxft 6258-bis (2,3-dicarboxyphenyl) ethane dianhydride, 2,3-bis (58-dicarboxyphenyl) ethane dianhydride, 2,3-bis (2,3-dicarboxyphenyl) ethane dianhydride, 2,3-bis (6258) dicarboxyphenyl) naphthalene-bis (6258) pyridine dianhydride, 58 zxft 6258) dianhydride, aromatic tetracarboxylic acid dianhydrides such as 10-perylenetetracarboxylic acid dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 2,3 ' -diphenylether tetracarboxylic acid dianhydride, or compounds obtained by substituting hydrogen atoms of these compounds with alkyl groups or halogen atoms, 5- (2,3-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-2,3-dicarboxylic acid dianhydride, 2,3-tricarboxy-2-cyclopentaneacetic acid dianhydride, alicyclic and semi-alicyclic tetracarboxylic dianhydrides such as bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5,6-tricarboxyl-2-norbornaneacetic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, compounds obtained by substituting a hydrogen atom of these compounds with an alkyl group or a halogen atom, and acid dianhydrides having an amide group. These can be used in combination with two or more kinds of acid dianhydrides containing an alicyclic structure having 4 to 40 carbon atoms.

As the other diamine, specifically, examples thereof include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene and other hydroxyl group-containing diamines, 3-sulfonic acid-4,4 '-diaminodiphenyl ether and other sulfonic acid-containing diamines, dimercapto-diamine and other thiol group-containing diamines, 3,4' -diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl methane, 4,4 '-diaminodiphenyl methane, 3,4' -diaminodiphenyl sulfone, 5283 '-diaminodiphenyl sulfone, 5329' -diaminodiphenyl sulfide, 3729 '-diaminodiphenyl sulfide, 3735 zxft 3757, 3264' -diaminodiphenyl sulfone, 3282-bis (3-amino-4-hydroxyphenyl) diamine, bis (3-amino-4-hydroxyphenyl) biphenyl, bis (3-amino-4-hydroxyphenyl) sulfone, 3234-diaminodiphenyl ether, 3282-diaminodiphenyl ether, 3579-3282-diaminodiphenyl ether, 3532-m-3-amino-3-4-hydroxyphenyl diamine, etc, aromatic diamines such as 1,4-bis (4-aminophenoxy) benzene, 2,2 '-dimethyl-4,4' -diaminobiphenyl, 2,2 '-diethyl-4,4' -diaminobiphenyl, 3,3 '-dimethyl-4,4' -diaminobiphenyl, 3,3 '-diethyl-4,4' -diaminobiphenyl, 2,2',3,3' -tetramethyl-4,4 '-diaminobiphenyl, 3,3',4,4 '-tetramethyl-4,4' -diaminobiphenyl, 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, aromatic diamines in which a part of hydrogen atoms in these rings is substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, a cyclohexane diamine, and a bicyclic diamine. These diamines may be used as they are or in the form of the corresponding diisocyanate compounds, trimethylsilylated diamines. Two or more of these diamine components may be used in combination.

Among these, 3,4 '-diaminodiphenyl ether, 4,4' -diaminodiphenyl ether, 3,4 '-diaminodiphenyl sulfone, 4,4' -diaminodiphenyl sulfone, 3,4 '-diaminodiphenyl sulfide, 4,4' -diaminodiphenyl sulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl ] propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, aromatic diamines obtained by substituting alkyl rings thereof, and amides thereof are preferable. These may be used alone or in combination of two or more.

Further, an aliphatic group having a siloxane structure can be introduced within a range in which heat resistance is not lowered, and adhesiveness to a substrate can be improved. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane and the like in an amount such that 100mol% of R in the general formulae (4) and (5) is contained ⁶ And 1 to 15mol% of a copolymer.

In applications where heat resistance is required, the aromatic diamine is preferably used in an amount of 50mol% or more of the total diamine.

In addition, the resin (A2) preferably has a phenolic hydroxyl component. In the general formulae (4) and (5), R is preferably ⁵ 、R ⁶ At least one of which is an organic group having a phenolic hydroxyl group. The presence of the phenolic hydroxyl group can provide a suitable solubility in an alkaline developer, and also can inhibit the solubility of an unexposed portion by interacting with a photosensitizer, thereby improving the residual film ratio and realizing high sensitivity. In addition, the phenolic hydroxyl group also contributes to the reaction with the crosslinking agent, so from the viewpoint of obtaining high mechanical properties, chemical resistance is also preferred.

Specific examples of the compound having a phenolic hydroxyl group include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, a compound obtained by substituting an aromatic ring thereof with an alkyl group or a halogen atom, an aromatic acid dianhydride such as an acid dianhydride having an amide group, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, and the like hydroxyl group-containing diamines obtained by substituting a part of hydrogen atoms of the aromatic ring thereof with an alkyl group, fluoroalkyl group, halogen atom, or the like having 1 to 10 carbon atoms. (A2) The resin is preferably a resin containing a structure derived from these compounds.

In the general formulae (4) and (5), n ₁ And n ₂ Indicates the degree of polymerization. When the molecular weight per unit of the general formulae (4) and (5) is M and the weight average molecular weight of the alkali-soluble resin is Mw, the polymerization degree n is obtained by the formula of n = Mw/M. The weight average molecular weight of the alkali-soluble resin was determined by GPC (gel permeation chromatography) as described in examples. n is ₁ And n ₂ The weight average molecular weight (Mw) can be easily calculated by measuring it using a Gel Permeation Chromatography (GPC), a light scattering method, an X-ray small angle scattering method, or the like. When the molecular weight of the repeating unit is M and the weight average molecular weight of the polymer is Mw, n = Mw/M. The number of repetitions n in the present invention is a value calculated by GPC (gel permeation chromatography) measurement based on polystyrene conversion, which is the simplest measurement.

The weight average molecular weight of the (A2) resin is preferably in the range of 3,000 to 80,000, more preferably in the range of 8,000 to 50,000 in terms of polystyrene by gel permeation chromatography. When the amount is within this range, a thick film can be easily formed.

The resin (A2) may be end-capped with an end-capping agent such as a monoamine, an acid anhydride, an acid chloride, or a monocarboxylic acid. The rate of dissolution of the resin in an alkaline aqueous solution can be easily adjusted to a preferred range by capping the terminal of the resin with a capping agent having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group. The blocking agent is preferably used in an amount of 0.1 to 60mol%, more preferably 5 to 50mol%, based on the entire amine component of the resin.

Specific examples of the end-capping agent include end-capping agents having an unsaturated bond such as monoamines such as 3-aminophenylacetylene, 4-aminophenylacetylene, 3,5-diacetylanilide, monocarboxylic acids such as 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diacetylbenzoic acid, 3,5-diacetylbenzoic acid, anhydrides such as maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, compounds obtained by acid-chlorinating carboxyl groups of the monocarboxylic acids, compounds obtained by acid-chlorinating one carboxyl group of dicarboxylic acids such as maleic acid, and active ester compounds obtained by the reaction of a monoacid chloride compound with N-hydroxy-5-norbornene-2,3-dicarboxyimide, further, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 2-aminonaphthalene, and the like, monobasic carboxylic acid compounds such as 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, monoamines such as 4-aminothiophenol, phthalic anhydride such as phthalic anhydride, cyclohexane dicarboxylic anhydride, 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and their carboxyl groups, which are chloridized to obtain monocarboxylic acids and their carboxyl groups, and which are esterified with only 3245, 433224, 3562, 3724, 4332, 43xzft, and 3732, and so as a carboxyl-terminated unsaturated naphthalene chloride. Further, the hydrogen bond of the blocking agent having no unsaturated bond may be substituted with a vinyl group and used as a blocking agent having an unsaturated bond.

The resin having at least one of the structural units represented by the general formulae (4) and (5) can be produced by a known method for producing a polyimide or a polyimide precursor. Examples thereof include: (I) Will have R ⁵ Tetracarboxylic dianhydrides of (IV) and compounds having R ⁶ A method in which a diamine compound having a group and a monoamino compound as an end-capping agent are reacted at low temperature; (II) by having R ⁵ Reacting tetracarboxylic dianhydride of the group with an alcohol to give a diester, and reacting with a compound having R ⁶ A method in which a diamine compound having a group and a monoamino compound as an end-capping agent are reacted in the presence of a condensing agent; (III) by having R ⁵ Reacting tetracarboxylic dianhydride of the group with an alcohol to give a diester, then subjecting the remaining two carboxyl groups to acid chlorination with a compound having R ⁶ A method of reacting a diamine compound having a group with a monoamino compound as a terminal-blocking agent; and so on.

The resin polymerized by the above method is preferably isolated by being put into a large amount of water, a methanol/water mixture, or the like, precipitating the resin, filtering the precipitate, and drying the precipitate. By this precipitation operation, the unreacted oligomer components such as monomers, dimers, trimers, etc. are removed, and the film characteristics after thermal curing are improved. The polyimide obtained by imidizing and ring-closing the polyimide precursor can be synthesized by a known imidization reaction method after the polyimide precursor is obtained.

Hereinafter, an example of a method for producing a polyimide precursor will be described as a preferred example of (I). First, will have R ⁶ The diamine compound of the radical is dissolved in a polymerization solvent. To the solution is slowly added an amount of a compound having R substantially equimolar to the diamine compound ⁵ Tetracarboxylic dianhydrides of the group. The mixture is stirred at-20 to 100 ℃ and preferably at 10 to 50 ℃ for O.5 to 100 hours, more preferably for 2 to 24 hours using a mechanical stirrer. When the end-capping agent is used, the reaction mixture is stirred at-20 to 100 ℃ and preferably 10 to 50 ℃ for 0.1 to 24 hours after the tetracarboxylic dianhydride is added, and then the end-capping agent may be added gradually or may be added all at once to cause the reaction.

The polymerization solvent is not particularly limited as long as it can dissolve tetracarboxylic acid dianhydrides and diamines as raw material monomers. Examples thereof include amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone, cyclic esters such as γ -butyrolactone, γ -valerolactone, δ -valerolactone, γ -caprolactone, e-caprolactone and α -methyl- γ -butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane and dimethyl sulfoxide.

The polymerization solvent is preferably 150 to 950 parts by mass because 100 parts by mass or more based on 100 parts by mass of the total of the tetracarboxylic dianhydride, the diamine compound, and the monoamino compound as the end-capping agent used in the polymerization reaction allows the reaction to proceed without precipitation of the raw material or the resin, and the reaction proceeds rapidly when 1900 parts by mass or less.

Next, the photosensitive film of the present invention will be described. The photosensitive film of the present invention has photosensitivity by containing (B) a photoacid generator. That is, the photoacid generator (B) has a property of generating an acid by light irradiation to increase the solubility of the light-irradiated portion in an alkaline aqueous solution. Examples of the photoacid generator (B) include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among these, a quinone diazide compound can be preferably used from the viewpoint of exhibiting an excellent dissolution-inhibiting effect by using in combination (A1) an alkali-soluble resin having a structural unit represented by general formula (1) and (A2) an alkali-soluble resin containing at least one selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.

Examples of the quinonediazide compound include: a compound in which a sulfonic acid of a diazido quinone is bonded to a polyhydroxy compound through an ester bond; a compound in which a sulfonic acid of diazido quinone is bonded to a polyamino compound through a sulfonamide bond; a compound obtained by bonding a sulfonic acid of diazido quinone with a polyhydroxy polyamino compound through an ester bond or a sulfonamide bond; and compounds obtained by bonding a sulfonic acid of diazido quinone to a polyhydroxy polyamino compound through an ester bond and a sulfonamide bond.

The functional groups of these polyhydroxy compounds and polyamino compounds may not be completely substituted with a quinonediazido group, and preferably 50mol% or more of the total functional groups are substituted with a quinonediazido group. When the substitution with the quinonediazido group is 50mol% or more, the solubility in an alkaline developer is not excessively high, and a contrast with an unexposed portion can be obtained, and a desired pattern can be obtained. By using such a quinonediazide compound, a positive photosensitive film having photosensitivity to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a common ultraviolet lamp, can be obtained. These compounds may be used alone or in combination of two or more. In addition, by using two types of photoacid generators, a greater ratio of the dissolution rates of the exposed portions and the unexposed portions can be obtained, and as a result, a photosensitive film with high sensitivity can be obtained.

Examples of the polyol include Bis-Z, bisP-EZ, tekP-4HBPA, trisP-HAP, trisP-PA, trisP-SA, trisOCR-PA, bisOCHP-Z, bisP-MZ, bisP-PZ, bisP-IPZ, bisOCP-IPZ, bisP-CP, bisRS-2P, bisRS-3P, bisP-OCHP, methyl lens tris-FR-CR, bisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, triML-P, triML-35XL, TML-B P, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, manufactured by national chemical industry Co., ltd.), BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi organic materials industry Co., ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, bisP-AP (trade name, manufactured by national chemical industry Co., ltd.), etc., but is not limited thereto.

The polyamino compound includes, but is not limited to, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4 '-diaminodiphenyl ether, 4,4' -diaminodiphenyl methane, 4,4 '-diaminodiphenyl sulfone, 4,4' -diaminodiphenyl sulfide, and the like.

Examples of the polyhydroxylated polyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3' -dihydroxybenzidine.

In the present invention, as the quinonediazide, either of the naphthoquinone diazide-5-sulfonyl group and the naphthoquinone diazide-4-sulfonyl group can be preferably used. The diazidonaphthoquinone-4-sulfonyl ester compound has absorption in the i-line region of a mercury lamp, and is suitable for i-line exposure. The absorption of the diazidonaphthoquinone-5-sulfonyl ester compound extended to the g-line region of the mercury lamp, which is suitable for g-line exposure.

In the present invention, it is preferable to select the naphthoquinone diazide-4-sulfonyl ester and naphthoquinone diazide-5-sulfonyl ester compounds depending on the wavelength of exposure. In addition, a diazidonaphthoquinone sulfonyl ester compound in which a diazidonaphthoquinone-4-sulfonyl group and a diazidonaphthoquinone-5-sulfonyl group are used in combination in the same molecule can be obtained, or a diazidonaphthoquinone-4-sulfonyl ester compound and a diazidonaphthoquinone-5-sulfonyl ester compound can be used in combination.

The molecular weight of the quinonediazide compound of the present invention is preferably in the range of 300 to 3,000. When the molecular weight of the quinonediazide compound is more than 5,000, the quinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, and therefore, there is a possibility that the heat resistance of the obtained film is lowered, the mechanical properties are lowered, and the adhesiveness is lowered.

The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting a naphthoquinonediazide-5-sulfonyl chloride with a phenol compound in the presence of triethylamine is exemplified. Examples of the method for synthesizing the phenol compound include a method in which an α - (hydroxyphenyl) styrene derivative is reacted with a polyphenol compound in the presence of an acid catalyst.

Among the photoacid generators (B) used in the present invention, sulfonium salts, phosphonium salts, and diazonium salts are preferable as the substance that appropriately stabilizes the acid component generated by exposure. Since the photosensitive film of the present invention is used as a permanent film, it is not preferable for the environment if phosphorus or the like remains, and further, it is necessary to consider the color tone of the film, and thus, among these, sulfonium salts can be preferably used. Particularly preferred examples thereof include triarylsulfonium salts which can suppress the change in color tone of the film.

The content of the photoacid generator (B) is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the total amount of the resin (A1) and the resin (A2). Among them, the quinone diazide compound is preferably in the range of 3 to 40 parts by mass. The amount of the compound selected from the group consisting of sulfonium salts, phosphonium salts and diazonium salts is preferably 0.05 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, based on the whole. When the content of the photoacid generator (B) is in this range, high sensitivity can be achieved. If necessary, a sensitizer or the like may be further contained.

The photosensitive film of the present invention contains (C) a thermal crosslinking agent. The thermal crosslinking agent (C) is preferably a compound having an alkoxymethyl group, and particularly preferably a compound represented by the general formula (11).

[ chemical formula 8]

(in the general formula (11), R ⁶⁶ Represents a mono-to decavalent organic group. Plural R ⁶⁷ Each of which may be the same or different and represents an alkyl group having 1 to 4 carbon atoms. r meterAn integer of 1 to 5. s represents an integer of 1 to 1O. )

The alkoxymethyl group undergoes a thermal crosslinking reaction at 160 ℃ or higher. Therefore, a crosslinking reaction occurs in the step of thermally curing the photosensitive film, and a favorable pattern shape can be obtained.

The number of alkoxymethyl groups is preferably 2 or more for increasing the crosslinking density, and more preferably 4 or more for increasing the chemical resistance. In order to reduce the dimensional unevenness of the pattern after heat curing, it is preferable to use at least one compound having 6 or more alkoxymethyl groups as the (C) thermal crosslinking agent.

The compound represented by the general formula (11) functions as a thermal plasticizer at a temperature of less than 160 ℃ (thermal crosslinking reaction occurs at this temperature). The lamination is preferably performed at a temperature of 150 ℃ or lower, and it is estimated that the photosensitive layer is heated and melted at this time, and the contact area with the substrate increases, and therefore, the adhesion between the both is improved.

Specific examples of the thermal crosslinking agent (C) include the following compounds, but are not limited thereto. In addition, two or more of these compounds may be contained.

[ chemical formula 9]

[ chemical formula 10]

In order to improve the crosslinking density, chemical resistance, and adhesion to the substrate in the cured film obtained, the content of the (C) thermal crosslinking agent is preferably 1 part by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the total amount of the (A1) resin and the (A2) resin. In order to improve mechanical properties, the amount is preferably 70 parts by mass or less, and more preferably 50 parts by mass or less.

In order to improve the mechanical properties of the cured film after the heat treatment, the weight average molecular weight (Mw) of the (C) thermal crosslinking agent is preferably 100 or more, more preferably 300 or more. In order to improve the laminatability, it is preferably 2 to 500, and more preferably 2,000.

The photosensitive film of the present invention preferably contains a thermal crosslinking agent having a structural unit represented by the following general formula (12). By containing the crosslinking agent, the elongation can be further improved while maintaining the heat resistance and the lamination property.

[ chemical formula 11]

(in the general formula (12), R ⁶⁹ And R ⁷⁰ Each independently represents a hydrogen atom or a methyl group. R is ⁶⁸ Is a divalent organic group having an alkylene group having 2 or more carbon atoms, and may be linear, branched, or cyclic. As R ⁶⁸ Examples thereof include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, a group obtained by combining these groups, and the like, and may further have a substituent. )

The thermal crosslinking agent itself has a soft alkylene group and a rigid aromatic group, and thus has heat resistance and laminatability and can improve elongation. Examples of the crosslinking group include an acrylic group, a methylol group, an alkoxymethyl group, and an epoxy group, but are not limited thereto. Among them, an epoxy group is preferable from the viewpoint of reacting with the phenolic hydroxyl group of the resin (A1) and the resin (A2) to improve the heat resistance of the cured film and from the viewpoint of reacting without dehydration.

Examples of the compound represented by the general formula (12) include the following compounds, but are not limited to the following structures.

[ chemical formula 12]

(wherein n is an integer of 1 to 5, and m is 1 to 20.)

In the above structure, n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of improving both heat resistance and elongation.

The amount of the compound represented by the general formula (12) is preferably 2 to 35 parts by mass, and more preferably 5 to 25 parts by mass, based on 100 parts by mass of the total amount of the resin (A1) and the resin (A2). When the amount is2 parts by mass or more, the effect of improving the elongation can be sufficiently obtained, and when the amount is 35 parts by mass or less, the sensitivity of the photosensitive film before curing can be suppressed from decreasing.

The photosensitive film of the present invention may contain (D) an acrylate compound as required. In the present invention, the (D) acrylate compound means a compound having an acryloyl group or a methacryloyl group. (D) The acrylate compound includes a monofunctional acrylate and a polyfunctional acrylate. The monofunctional acrylate is a compound having at least one of an acryloyl group and a methacryloyl group. Examples thereof include acrylic acid esters, methacrylic acid esters, acrylamides, and methacrylamides. The polyfunctional acrylate compound is a compound having at least one of two or more acryloyl groups and methacryloyl groups.

The photosensitive film of the present invention is heat-treated after pattern processing. When the acrylic ester compound is used as a positive photosensitive film, the acrylic ester compound is thermally polymerized with each other or reacted with an alkali-soluble resin to crosslink the acrylic ester compound, thereby increasing the elongation of the cured film. When used as a negative photosensitive resin film, acrylates are photopolymerized with each other by exposure during patterning, thereby forming a lattice structure with an alkali-soluble resin.

In the case of the monofunctional acrylate compound, the film is not sufficiently cured by the crosslinking reaction, and the effect of improving the elongation is low, and therefore, a polyfunctional acrylate is preferable.

Preferred examples of the acrylate compound (D) include NK Ester series 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, BPE-100, BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, TMPT, A-TMM-3-L, A-TMMT, A-9300, ATM-4E, ATM-35E, ATM-4 3245 zxft-TMP, AD-3232 zTMP-3732 ztmp 3732-DPH, and the like, all manufactured by Xinzhongmu chemical industry Co., ltd. Further, light Ester series P-1M, P-2M, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, NP, 1.6HX, 1.9ND, 1.10DC, G-101P, G-201P, DCP-M, BP-2EM, BP-4EM, BP-6EM, TMP, and the like, available from Kyoeisha chemical Co., ltd. Ext>ext>ext> furtherext>ext>ext>,ext>ext>ext> Lightext>ext>ext> Acrylateext>ext>ext> (ext>ext>ext> registeredext>ext>ext> trademarkext>ext>ext>)ext>ext>ext> seriesext>ext>ext> 3ext>ext>ext> EGext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> 4ext>ext>ext> EGext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> 9ext>ext>ext> EGext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> 14ext>ext>ext> EGext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> TMGAext>ext>ext> -ext>ext>ext> 250ext>ext>ext>,ext>ext>ext> NPext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> MPDext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> 1.6ext>ext>ext> HXext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> BEPGext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> 1.9ext>ext>ext> NDext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> MODext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> DCPext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> BPext>ext>ext> -ext>ext>ext> 4ext>ext>ext> EAext>ext>ext>,ext>ext>ext> BPext>ext>ext> -ext>ext>ext> 4ext>ext>ext> PAext>ext>ext>,ext>ext>ext> BAext>ext>ext> -ext>ext>ext> 134ext>ext>ext>,ext>ext>ext> BPext>ext>ext> -ext>ext>ext> 10ext>ext>ext> EAext>ext>ext>,ext>ext>ext> HPPext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> TMPext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> TMPext>ext>ext> -ext>ext>ext> 3ext>ext>ext> EOext>ext>ext> -ext>ext>ext> Aext>ext>ext>,ext>ext>ext> TMPext>ext>ext> -ext>ext>ext> 6ext>ext>ext> EOext>ext>ext> -ext>ext>ext> 3ext>ext>ext> Aext>ext>ext>,ext>ext>ext> PEext>ext>ext> -ext>ext>ext> 3ext>ext>ext> Aext>ext>ext>,ext>ext>ext> PEext>ext>ext> -ext>ext>ext> 4ext>ext>ext> Aext>ext>ext>,ext>ext>ext> DPEext>ext>ext> -ext>ext>ext> 6ext>ext>ext> Aext>ext>ext>,ext>ext>ext> andext>ext>ext> theext>ext>ext> likeext>ext>ext>,ext>ext>ext> manufacturedext>ext>ext> byext>ext>ext> Kyowaext>ext>ext> Kagakuext>ext>ext> Kext>ext>ext>.ext>ext>ext> Examples thereof include Epoxy Ester series 40EM, 70PA, 200PA, 80MFA, 3002M, 3002A, 3000M, and 3000A manufactured by Kyoeisha chemical Co. Further, examples thereof include "ARONIX" (registered trademark) series M-203, M-208, M-210, M-211B, M-215, M-220, M-225, M-240, M-243, M-245, M-260, M-270, M-305, M-309, M-310, M-313, M-315, M-320, M-325, M-350, M-360, M-402, M-408, and M-450 manufactured by Toyo Seiya. Further, KAYARAD (registered trademark) series R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, T-1420 (T), RP-1040, and THE like, available from KaYARAD, japan chemical Co., ltd. Further, GMR-H, GAM, PDE-50, PDE-100, PDE-150, PDE-200, PDE-400, PDE-600, PDE-1000, ADE-200, ADE-400, PDP-400, ADP-200, ADP-400, PDT-650, ADT-250, PDBE-200, PDBE-250, PDBE-450, PDBE-1300, ADBE-200, ADBE-250, ADBE-450 and the like which are "BLEMMER" (registered trademark) series manufactured by Nippon fat and oil Co., ltd. Further, MBAA manufactured by MRC Unitec corporation, and the like can be mentioned. Two or more of these compounds may be contained.

Among the above (D) acrylate compounds, acrylate compounds having a molecular weight of 100 or more and 2,000 or less are preferable. When the molecular weight is 100 or more, a cured film having a high elongation can be obtained, and when the molecular weight is2,000 or less, a resin composition having appropriate alkali solubility and high compatibility with an alkali-soluble resin can be obtained.

In the present invention, an alkali-soluble resin other than the (A2) resin may be contained within a range not to impair the heat resistance of the cured film obtained by the heat treatment. Specifically, there may be mentioned acrylic polymers obtained by copolymerizing acrylic acid, phenolic resins such as silicone resins, novolac resins, resol resins and polyhydroxystyrene resins, resins obtained by introducing a crosslinking group such as a methylol group, an alkoxymethyl group or an epoxy group into these resins, and copolymers thereof. Such a resin is dissolved in an aqueous solution of a base such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, or sodium carbonate. By containing these alkali-soluble resins, the properties of each alkali-soluble resin can be imparted while maintaining the adhesion and excellent sensitivity of the heat-resistant resin film.

As the other alkali-soluble resin, a phenol resin is preferable from the viewpoint of sensitivity. The phenol resin can be obtained by polycondensation of a phenol and an aldehyde by a known method. Two or more resins having a phenolic hydroxyl group may be contained in combination.

Preferred examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, and 3,4,5-trimethylphenol. Particularly preferred are phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, or 2,3,5-trimethylphenol. Two or more of these phenols may be used in combination. From the viewpoint of solubility in an alkaline developer, m-cresol is preferable, and a combination of m-cresol and p-cresol is further preferable. That is, as the resin having a phenolic hydroxyl group, a cresol Novolac resin containing a m-cresol residue, or a m-cresol residue and a p-cresol residue is preferably contained. In this case, the molar ratio of m-cresol residues to p-cresol residues (m/p/m/p) in the cresol Novolac resin is preferably 1.8 or more. Within this range, the solubility in an alkaline developer is appropriate, and good sensitivity can be obtained. More preferably 4 or more.

Preferred examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, salicylaldehyde, and the like. Among these, formaldehyde is particularly preferable. Two or more of these aldehydes may be used in combination. The amount of the aldehyde used is preferably 0.6mol or more, more preferably 0.7mol or more, based on 1mol of the phenol. Further, it is preferably 3mol or less, more preferably 1.5mol or less.

An acidic catalyst is generally used for the polycondensation reaction of phenols and aldehydes. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid, and the like. The amount of these acidic catalysts used is usually 1X 10 relative to 1mol of phenols ^-5 ～5×10 ^-1 And (mol). In the polycondensation reaction, water is generally used as a reaction medium, but in the case of forming a heterogeneous system from the initial stage of the reaction, a hydrophilic solvent or a lipophilic solvent is used as a reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; cyclic ethers such as tetrahydrofuran and dioxane. Examples of the lipophilic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These reaction media are usually used in an amount of 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw materials.

The reaction temperature of the polycondensation is suitably adjusted depending on the reactivity of the raw material, and is usually 10 to 200 ℃. As the reaction method of the polycondensation, the following method can be suitably employed: a method of adding phenols, aldehydes, an acidic catalyst and the like together and reacting them; or a method in which phenols, aldehydes and the like are added in the presence of an acidic catalyst while the reaction is proceeding; and so on. After the polycondensation reaction is completed, in order to remove unreacted raw materials, an acidic catalyst, a reaction medium, and the like present in the system, the reaction temperature is generally increased to 130 to 230 ℃ and volatile components are removed under reduced pressure to recover a resin having a phenolic hydroxyl group.

In the present invention, the weight average molecular weight (hereinafter referred to as "Mw") of the phenol resin in terms of polystyrene is preferably 1,000 or more, and more preferably 2,000 or more. Further, it is preferably 20,000 or less, and more preferably 10,000 or less. When the amount is within this range, the positive photosensitive resin composition of the present invention is excellent in workability and sensitivity when applied to a substrate.

The content of the other alkali-soluble resin is preferably 1 part by mass or more, and more preferably 5 parts by mass or more, with respect to 100 parts by mass of the total amount of the (A1) resin and the (A2) resin, from the viewpoint of sensitivity. From the viewpoint of mechanical properties and heat resistance, it is preferably 70 parts by mass or less, and more preferably 50 parts by mass or less.

In the resin contained in the photosensitive film of the present invention, the resin having the structure represented by the general formulae (4) and (5) is preferably 30% by mass or more.

For the purpose of improving the sensitivity of the photosensitive film, if necessary, (E) a compound having a phenolic hydroxyl group may be contained in a range in which the shrinkage rate after curing is not reduced.

(E) Examples of the compound having a phenolic hydroxyl group include Bis-Z, bisOC-Z, bisOPP-Z, bisP-CP, bis26X-Z, bisOTBP-Z, bisOCHP-Z, bisOCR-CP, bisP-MZ, bisP-EZ, bis26X-CP, bisP-PZ, bisP-IPZ, bisCR-IPZ, bisOCP-IPZ, bisOIPP-CP, bis26X-IPZ, bisOTBP-CP, tekP-4HBPA (TetrakisP-DO-BPA), trisP-HAP, trisP-PA, trisP-SA, trisOCR-PA, bisOFP-Z, bisRS-2P, bisPG-26 zxft 3257 zxft-5657, bisOCHP-3282, bisOCHP-32HP-3226 zHP-OCHP-3282, bisOCHP-OCHP-CP, bisHP-32HP-OCHP-26, bisHP-OCHP-3282, bisHP-OCHP-3282, bisHP, manufactured by Wako chemical industries, ltd.), BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi organic materials industries, ltd.).

Preferred examples of (E) the compound having a phenolic hydroxyl group include Bis-Z, bisP-EZ, tekP-4HBPA, trisP-HAP, trisP-PA, bisOCHP-Z, bisP-MZ, bisP-PZ, bisP-IPZ, bisOCP-IPZ, bisP-CP, bisRS-2P, bisRS-3P, bisP-OCHP, methyl tris-FR-CR, bisRS-26X, BIP-PC, BIR-PTBP, BIR-BIPC-F and the like.

Particularly preferred (E) compounds having phenolic hydroxyl groups are Bis-Z, tekP-4HBPA, trisP-HAP, trisP-PA, bisRS-2P, bisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F. By containing (E) a compound having a phenolic hydroxyl group, the following photosensitive film can be obtained: since the composition is hardly soluble in an alkaline developer before exposure and easily soluble in an alkaline developer during exposure, the film can be developed in a short time with less film loss due to development. The content of the compound having a phenolic hydroxyl group (E) is preferably 1 to 50 parts by mass, and more preferably 3 to 40 parts by mass, based on 100 parts by mass of the total amount of the resin (A1) and the resin (A2).

The photosensitive film of the present invention may contain (F) a solvent. As the (F) solvent, the following solvents may be used alone or in combination: polar aprotic solvents such as γ -butyrolactone, ethers such as tetrahydrofuran, dioxane, and propylene glycol monomethyl ether, dialkylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, N-dimethylformamide, and N, N-dimethylacetamide, acetic acid esters such as 3-methoxybutyl acetate and ethylene glycol monoethyl ether acetate, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene. The content of the (F) solvent is preferably 0.0001 parts by mass or more, and preferably 50 parts by mass or less, relative to 100 parts by mass of the total amount of the (A1) resin and the (A2) resin.

The photosensitive film of the present invention may contain (G) a silane compound, and the silane compound (G) can be used as an adhesion promoter for improving adhesion to a base substrate. Specific examples of the silane compound (G) include, but are not limited to, N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β -methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and silane compounds having the following structures. Two or more of them may be contained.

[ chemical formula 13]

The content of the (G) silane compound is preferably 0.01 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total amount of the (A1) resin and the (A2) resin. When the amount is within this range, a sufficient effect as an adhesion promoter can be obtained while maintaining the heat resistance of the positive photosensitive film.

For the purpose of improving the wettability of the photosensitive film and the substrate, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be contained. Further, inorganic particles such as silica and titania, polyimide powder, or the like may be contained.

The photosensitive film of the present invention preferably contains (H) a compound represented by the following general formula (13) (hereinafter referred to as component (H)). By containing the component (H), the adhesion between the laminated film and a metal material (particularly, copper) is significantly improved. The reason for this is that the S atom and N atom of the compound represented by the general formula (13) interact with the metal surface, and further, the compound forms a steric structure which easily interacts with the metal surface. Based on these effects, photosensitivity can be imparted to the resin composition, and a resin cured film having excellent adhesion to a metal material can be obtained even in a composition having an additive. In the general formula (13), R ⁷¹ ～R ⁷³ Represents O atom or S atom, N atom, and R ⁷¹ ～R ⁷³ At least one table ofShowing an S atom. 1 represents 0 or 1,1 is 0R ⁷¹ R represents an oxygen atom or a sulfur atom, 1 is 1 ⁷¹ Represents a nitrogen atom. m and n represent 1 or 2.R ⁷⁴ ～R ⁷⁶ Each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. As R ⁷⁴ ～R ⁷⁶ Examples thereof include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, a group obtained by combining these groups, and the like, and may further have a substituent.

[ chemical formula 14]

The amount of the component (H) added is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the resin (A1) and the resin (A2). When the amount is 0.1 part by mass or more, the effect of improving adhesion after lamination with a metal material can be sufficiently obtained, and when the amount is 10 parts by mass or less, a decrease in sensitivity of the photosensitive film due to interaction with a photosensitive agent can be suppressed when the photosensitive film used in the present invention is a positive type, which is preferable.

In the compound represented by the general formula (13) used in the present invention, R is preferably ⁷¹ ～R ⁷³ Represents O atom or S atom, N atom, and R ⁷¹ ～R ⁷³ Is an S atom. In general, when a compound containing an N atom is added, the sensitivity may be impaired by the interaction between the sensitizer and the compound containing an N atom, but the effect of interaction can be appropriately maintained by the inclusion of an S atom, and the effect of improving the adhesion can be obtained without lowering the sensitivity. In addition, from the viewpoint of adhesion after lamination to a substrate other than a metal such as silicon, a trialkoxymethyl group is more preferably contained.

The compound represented by the general formula (13) includes the following compounds as examples, but is not limited to the following structures.

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

The method for producing the photosensitive film of the present invention is illustrated. Examples thereof include: the alkali-soluble resin (A1) having a structural unit represented by general formula (1), the alkali-soluble resin (A2) having at least one member selected from the group consisting of polyimides, polybenzoxazoles, polyamideimides, precursors thereof, and copolymers thereof, which have a substituent reactive with the alkali-soluble resin (A1), the photoacid generator (B), the thermal crosslinking agent (C), the solvent (F), and optionally other components, are added to a glass flask or a stainless steel vessel and dissolved by stirring with a mechanical stirrer or the like, the solvent is dissolved by ultrasonic waves, and the solvent is dissolved by stirring with a planetary stirring defoaming device. The viscosity of the composition containing the resin (A1), the resin (A2), the photoacid generator (B), the thermal crosslinking agent (C), the solvent (F), and the like is preferably 200 to 10,000mpa · s. In addition, in order to remove impurities, filtration can be performed using a filter having a pore size of 0.1 to 5 μm.

The photosensitive film of the present invention preferably has a support film. A photosensitive film having a photosensitive layer on a support film can be obtained by applying a composition containing a resin (A1), a resin (A2), a photoacid generator (B), a thermal crosslinking agent (C), a solvent (F), and the like to the support film and then drying the composition.

The support film is not particularly limited, and various films generally commercially available such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used. In order to improve the adhesion and release properties of the bonding surface between the support film and the photosensitive film, surface treatment of silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like may be performed. The thickness of the support film is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability.

The photosensitive film of the present invention may have a protective film on the film for protecting the surface. This can protect the surface of the photosensitive film from contaminants such as dust and dirt in the atmosphere.

Examples of the protective film include a polyolefin film and a polyester film. The protective film is preferably a film having a low adhesion to the photosensitive film.

Examples of the method for forming a photosensitive layer by applying a composition containing (A1) a resin, (A2) a resin, (B) a photoacid generator, (C) a thermal crosslinking agent, and (F) a solvent to a support film include methods using a spray coater, a roll coater, screen printing, a knife coater, a die coater, a calendar coater, a meniscus coater, a bar coater, a roll coater, a comma coater, a gravure coater, a screen coater, and a slot die coater. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, and in general, the film thickness of the photosensitive layer obtained after drying is preferably 0.5 μm or more and 100 μm or less. More preferably, the thickness is 3 μm or more and 40 μm or less.

For drying, an oven, a hot plate, infrared rays, or the like can be used. The drying temperature and the drying time may be set within a range in which the solvent can be volatilized, and are preferably set within a range in which the resin film material for a semiconductor is in an uncured or semi-cured state. Specifically, it is preferably carried out in the range of from 40 ℃ to 120 ℃ for 1 minute to several tens of minutes. Further, the temperature may be raised in stages in combination of these temperatures, and the heat treatment may be performed at 50 ℃, 60 ℃ and 70 ℃ for 1 minute, for example.

Next, a method for manufacturing a semiconductor device using the photosensitive film will be described. When the photosensitive film has a protective film, the protective film is first peeled off. The photosensitive film and the substrate are opposed to each other, and the photosensitive film is bonded by thermal pressure bonding, transferred to the substrate, and laminated. Subsequently, the support film is peeled off to obtain a photosensitive film. The heat crimping can be performed by a heat pressing treatment, a heat laminating treatment, a heat vacuum laminating treatment, or the like. The temperature at which the layers are laminated by heat-pressure bonding is preferably 40 ℃ or higher, and more preferably 50 ℃ or higher, from the viewpoint of adhesion to the substrate and embeddability. In order to prevent the photosensitive film from being cured during thermocompression bonding and thereby to prevent the resolution of pattern formation in the exposure/development step from being deteriorated, the temperature of thermocompression bonding is preferably 150 ℃ or lower, and more preferably 120 ℃ or lower. In the thermocompression bonding, for the purpose of removing air bubbles, the pressure may be reduced.

After the photosensitive film is laminated on the substrate, the support film is peeled from the photosensitive film at a temperature ranging from 0 ℃ to 100 ℃.

Examples of the substrate used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and materials obtained by disposing circuit components on these boards.

Examples of the organic circuit board include flexible boards such as glass base copper clad laminates such as glass cloth and epoxy copper clad laminates, composite copper clad laminates such as glass nonwoven fabrics and epoxy copper clad laminates, heat-resistant and thermoplastic boards such as polyetherimide resin boards, polyether ketone resin boards, polysulfone resin boards, polyester copper clad boards, and polyimide copper clad boards. Examples of the inorganic circuit board include ceramic substrates such as an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate, and metal substrates such as an aluminum base substrate and an iron base substrate. Examples of the material constituting the circuit include a conductor containing a metal such as gold, silver, or copper, a resistor containing an inorganic oxide or the like, a low dielectric containing a glass material or a resin, a high dielectric containing a resin or a high dielectric constant inorganic particle, and an insulator containing a glass material or the like.

Next, the photosensitive film formed by the above method is exposed to actinic rays through a mask having a desired pattern. The actinic ray used for the exposure includes ultraviolet rays, visible rays, electron beams, X-rays, and the like, but in the present invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of a mercury lamp are preferably used. In the case where the support film is made of a material transparent to these light rays, the support film may be peeled from the photosensitive film and then exposed, or may be exposed without being peeled. In the case of exposure without peeling, the support film is peeled off after exposure and before development treatment.

To form a pattern, an unexposed portion is removed using a developer after exposure. As the developer, an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of compounds exhibiting basicity such as diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferable. In addition, these aqueous alkaline solutions may contain, as the case may be, either alone or in combination of plural kinds: polar solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, γ -butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone.

The development may be carried out by the following method: spraying the developing solution on a surface having a photosensitive film; dipping in a developing solution; applying ultrasonic waves while dipping; or spraying the developing solution while rotating the substrate; and so on. The conditions for development, such as the development time and the temperature of the developer in the development step, are only required to be conditions under which the unexposed portions are removed, and it is preferable to perform further development after removing the unexposed portions in order to process fine patterns and remove residues between patterns.

After development, rinsing treatment may be performed with water. Here, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and the like may be added to water to carry out rinsing treatment. When the resolution of the pattern is improved during development and the allowable range of the development conditions is increased, a step of performing baking treatment may be introduced before development. The temperature is preferably in the range of 50 to 180 ℃ and particularly preferably in the range of 60 to 120 ℃. The time is preferably 5 seconds to several hours.

After the patterning, a temperature of from 120 ℃ to 400 ℃ is applied to obtain a cured film. The heating treatment comprises the following steps: selecting temperature, and raising the temperature in stages; alternatively, a temperature range is selected and the reaction is carried out for 5 minutes to 5 hours while continuously raising the temperature. As an example, the heat treatment is carried out at 130 ℃ and 200 ℃ for 30 minutes, respectively. Alternatively, the temperature may be raised linearly from room temperature to 250 ℃ over 2 hours. In this case, the heating temperature is preferably 150 ℃ to 300 ℃, and more preferably 180 ℃ to 250 ℃.

The thickness of the cured film is preferably 0.5 μm or more, more preferably 2 μm or more, for the purpose of improving the insulation property. In addition, from the viewpoint of reducing warpage of the substrate due to residual stress, it is preferably 100 μm or less, and more preferably 40 μm or less.

The cured film obtained by curing the photosensitive film of the present invention can be suitably used for applications such as a passivation film for a semiconductor, a protective film for a semiconductor, an interlayer insulating film for a multilayer wiring for high-density mounting, and an insulating layer for an organic electroluminescent element. The cured film obtained by curing the photosensitive film of the present invention can be used for a semiconductor device in a state where the relief pattern layer of the cured film is formed.

Further, the cured film may be disposed on the substrate with a film thickness of 2 to 40 μm as described above, and the copper wiring may be disposed thereon, and then, the cured film may be further formed with a film thickness of 2 to 40 μm as an insulating film between the copper wirings, thereby manufacturing the semiconductor device.

A preferred structure of a semiconductor device provided with a cured film obtained by curing the photosensitive film of the present invention is illustrated in fig. 1 below. A passivation film 2 is formed on the semiconductor element 1. The photosensitive film of the present invention is laminated on the passivation film 2 by thermocompression bonding, and is dried by heating using a hot plate or the like, and is exposed and developed to form a pattern of the photosensitive film. After the photosensitive film is patterned, the cured film 3 is formed by curing in a high-temperature treatment process. Metal wiring is formed on the cured film 3 by a method such as sputtering, vapor deposition, electroless plating, electrolytic plating, or the like. In order to protect the metal wiring, the photosensitive film of the present invention is laminated by thermocompression, dried by heating using a hot plate or the like, and exposed and developed to form a pattern. After the photosensitive film is patterned, the cured film 5 is formed by curing in a high-temperature treatment process. By forming the cured film by the above method, a semiconductor device having high flatness and high adhesion between the cured films and between the cured film and the metal wiring can be provided.

Next, an application example of a coil component of an inductor device in which a cured film obtained by curing the photosensitive film of the present invention is disposed will be described with reference to the drawings. Fig. 2 is a sectional view of a coil component having a cured film of the present invention. As shown in fig. 2, an insulating film 7 is formed on a substrate 6, and a cured film 8 is formed in a pattern on the insulating film 7. Ferrite or the like is used as the substrate 6. The photosensitive film of the present invention can be used for any of the cured films 7 and 8. A metal film 9 (Cr, ti, etc.) is formed in the opening of the pattern, and a metal wiring 10 (Ag, cu, etc.) is formed on the metal film 9 by plating. The metal wiring 10 (Ag, cu, etc.) is formed in a spiral shape. The lamination process is repeated 7 to 10 times, whereby the laminated coil can function as a coil. Finally, the metal wiring 10 (Ag, cu, etc.) is connected to the electrode 12 via the metal wiring 11 (Ag, cu, etc.), and is sealed with the sealing resin 13.

Next, an application example of an electronic component or a semiconductor device having a hollow portion, in which a cured film obtained by curing the photosensitive film of the present invention is disposed, will be described with reference to the drawings. FIG. 3 is an example of a cross-sectional view of a hollow portion of an elastic wave device using the photosensitive film of the present invention. As shown in fig. 3, formed in the substrate 14 are: an IDT (Inter Digital Transducer) electrode 15 formed of a pair of comb-shaped electrodes having a plurality of electrode fingers inserted into each other; and a bonding pad 16 for achieving electrical conduction. Examples of the substrate 14 include lithium niobate, potassium niobate, lithium tantalate, crystal, langasite (1 angasite), znO, PZT, and lithium tetraborate. Examples of the material of the electrode 15 and the bonding pad include metals such as A1, pt, cu, au, ti, ni, cr, W, pd, co, and Mn. In addition, an embossed pattern layer of a cured film of a photosensitive resin composition is formed as a support 18 in order to secure the hollow portion 17 on the piezoelectric substrate 14. Examples of the photosensitive resin composition include polyimide resins, epoxy resins, acrylic resins, and phenol resins. A coating material 19 is provided on the substrate 15 via the supporting material 17 so as to cover the electrode 15. Here, the photosensitive film of the present invention is used for the coating material 19 and may be used for the supporting material 17. The thickness of the covering material 19 is, for example, 20 μm. The protective member 20 is provided so as to cover the substrate 14, the support member 18, and the covering member 19. The thickness of the protective member 20 on the covering material 19 is, for example, 30 μm. The protective member is an insulating material, and examples thereof include an epoxy resin, a benzocyclobutene resin, a silicon resin, and SOG (Spin On glass). A via conductor 21 may be provided so as to penetrate through the support member 17 and the covering member 19 in the thickness direction. A solder bump 22 is formed on the via conductor 21.

Next, an application example of the photosensitive film of the present invention to a semiconductor device including a substrate having a step will be described with reference to the drawings. Fig. 4 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a cured film of the present invention, a structure referred to as a fan-out wafer level package (fan-out WLP). The silicon wafer 23 on which the A1 pads 24 and the passivation film 25 are formed is cut into individual chips by dicing, and then sealed with a resin 26. When sealing is performed, heat treatment is performed, and a (T-1) level difference is generated between the chip 23 and the resin 26 due to shrinkage of the resin 26. In this case, the difference in the (T-1) level between the (S-1) upper layer portion of the surface of the chip 23 and the (S-2) lower layer portion of the surface of the resin 26 is2 to 40 μm. The cured film 27 is formed in the form of the pattern of the photosensitive film of the present invention over the entire upper layer portion and the lower layer portion (S-2) of each of (S-1), and the difference in the (T-2) layer between the cured film disposed over the upper layer portion (S-1) and the cured film disposed over the lower layer portion (S-2) is 5 μm or less.

Further, a metal (Cr, ti, etc.) film 28 and a metal wiring 29 are formed. Then, a barrier metal 31 and a solder bump 32 are formed in an opening of an insulating film 30 formed on the sealing resin outside the chip. The fan-out WLP is the following semiconductor package: by using a sealing resin such as epoxy resin, an extension portion is provided around the semiconductor chip, rewiring is performed from an electrode on the semiconductor chip to the extension portion, and solder balls are mounted on the extension portion to secure a necessary number of terminals. In the fan-out WLP, wirings are provided so as to cross a boundary line formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a base material including two or more materials, i.e., a semiconductor chip on which metal wiring is formed and a sealing resin, and wiring is formed on the interlayer insulating film. In addition, in a semiconductor package of a type in which a semiconductor chip is embedded in a recess formed in a glass epoxy substrate, a wiring is provided so as to cross a boundary line between a main surface of the semiconductor chip and a main surface of a printed circuit board. In this embodiment mode, an interlayer insulating film is formed over a base material including two or more kinds of materials, and a wiring is formed over the interlayer insulating film. When the cured film obtained by curing the photosensitive film of the present invention is disposed on a substrate made of two or more materials, the cured film can be suitably used as an interlayer insulating film provided on a substrate made of two or more materials because the cured film can maintain the flatness of the cured film by reducing the level difference existing on the substrate.

Examples

The present invention will be described below by way of examples and comparative examples, but the present invention is not limited to these examples. Evaluation of the esterification rate of the synthesized quinonediazide compound and evaluation of the photosensitive film were carried out by the following methods.

< method for measuring film thickness >

The film after the pre-baking and the film after the development were measured with a refractive index of 1.629 using polyimide as a reference, using Lambda STM-602 manufactured by Dainippon Screen, inc.

< measurement of imidization ratio of polyimide >

The imidization ratio of the alkali-soluble resin (A2) was determined by coating a 6-inch silicon wafer with a solution of N-methylpyrrolidone (hereinafter referred to as NMP) having a solid content concentration of 50% by mass of a polyimide resin by a spin coating method, and then baking the coated substrate for 3 minutes using a hot plate (SKW-636, manufactured by Dainippon Screen Co., ltd.) at 120 ℃ to form a prebaked film having a thickness of 10 μm. + -. 1 μm. The film was divided into two halves, and one half of the film was put into an inert gas oven (INH-21 CD manufactured by Koyo Thermo Systems), raised to a curing temperature of 350 ℃ for 30 minutes, and subjected to heat treatment at 350 ℃ for 60 minutes. Then, the resultant was slowly cooled to 50 ℃ or lower in an oven to obtain a cured film. The obtained cured film (A) and the film (B) before curing were measured for infrared absorption spectrum by Fourier transform infrared spectrophotometer FT-720 (manufactured by horiba Ltd.). 1377cm of C-N stretching vibration derived from imide ring ^-1 The value of "peak intensity of film (B) before curing/peak intensity of cured film (A)" is the imidization ratio.

< evaluation of laminating Property >

The protective film of the photosensitive film produced in each of the examples and comparative examples described later was peeled off. Next, the release layer is laminated on the silicon wafer or the copper substrate. As the copper substrate, a substrate (copper-plated substrate) having a metal material layer obtained by sputtering 100nm of titanium and copper on a silicon wafer and then forming a copper plating film in a thickness of 2 μm by electrolytic plating was used. The lamination was carried out using a laminator (VTM-200M manufactured by Takatori, ltd.) under conditions of a table temperature of 80 ℃, a roll temperature of 80 ℃, a vacuum degree of 150Pa, an adhesion speed of 5 mm/sec and an adhesion pressure of 0.2 MPa. After lamination, the photosensitive film was scored in a checkered pattern so as to form 100 squares at intervals of 2mm × 2mm using a dicing guide at the center of the film on the substrate. After the transparent adhesive tape was adhered to the checkered portion, the substrate was stretched at an angle of 90 ° to be peeled off. After peeling, the number of photosensitive films peeled off among 100 photosensitive films was counted. When the number of peeling is small, the adhesion is high, and when it is large, the adhesion is low. Preferably 50 or less, more preferably 20 or less, and still more preferably 10 or less. The case where the evaluation of the laminatability was performed on a silicon wafer was defined as condition 1, and the case where the evaluation of the laminatability was performed on a copper substrate was defined as condition 2.

< evaluation of Pattern processability (high sensitivity) >

The protective films of the photosensitive films prepared in the examples and comparative examples were peeled off, and the peeled surface was laminated on an 8-inch silicon wafer using a laminating apparatus (VTM-200M manufactured by Takatori Co., ltd.) under conditions of a table temperature of 80 ℃, a roll temperature of 120 ℃, a vacuum degree of 150Pa, a bonding speed of 5 mm/sec, and a bonding pressure of 0.2 MPa. Next, the film was baked for 3 minutes using a hot plate at 120 ℃ (ACT-8 was used) to prepare a prebaked film having a thickness of 10 μm. Using an i-line stepper (NIKON NSRi 9) at 0-1000 mJ/cm ² The exposure amount of (2) is 10mJ/cm ² The film is exposed to light. After the exposure, development was carried out for 90 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) (manufactured by Mitsubishi Gas Chemical Co., ltd., ELM-D), followed by rinsing with pure water to obtain a developed film A having an isolated gap of 5 μm.

The developed film a was sensitive to an exposure amount (referred to as a minimum exposure amount Eth) at which the exposed portion of the isolated gap of 5 μm after exposure and development was completely dissolved and disappeared. Eth 400mJ/cm ² Hereinafter, the sensitivity is judged to be high. More preferably 300mJ/cm ² Hereinafter, more preferably 250mJ/cm ² The following.

< evaluation of high elongation >

The protective films of the photosensitive films prepared in the examples and comparative examples were peeled off, and laminated on a silicon wafer so that the film thickness T1=11 μ M under conditions of a stage temperature of 80 ℃, a roll temperature of 120 ℃, a degree of vacuum of 150Pa, a bonding speed of 5 mm/sec, and a bonding pressure of 0.2Mpa using a laminating apparatus (VTM-200M, manufactured by Takatori corporation). The laminated substrates were prebaked with a hot plate at 120 ℃ for 3 minutes, and then heated to 220 ℃ under a nitrogen stream at an oxygen concentration of 20ppm or less at a heating rate of 3.5 ℃ per minute for 1 hour at 220 ℃ using an inert gas oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., ltd.). The cured film (heat-resistant resin film) was obtained by peeling with a 46 mass% hydrofluoric acid aqueous solution. The cured film obtained by this method was cut with a single blade to 7X 1cm, and stretched at 50 mm/min using a Tensilon Universal tester (manufactured by Orientec Corporation, RTM-100). The value obtained by dividing the amount of stretching at this time by the sample length was obtained. The measurement was performed for 10 samples, and the maximum value thereof was taken as the elongation. The elongation is preferably 10% or more, more preferably 20% or more, and further preferably 40% or more.

<5% weight loss temperature measurement (evaluation of Heat resistance) >

The cured film obtained by the same method as the above-mentioned < evaluation of high elongation > was heated at a rate of 10 ℃/min under a nitrogen flow and under a condition of 80mL/min using a thermogravimetric loss measuring instrument (TGA 50 manufactured by shimadzu corporation) to measure the elongation. The 5% weight loss temperature is preferably 260 ℃ or higher, more preferably 300 ℃ or higher, and still more preferably 340 ℃ or higher.

Abbreviations and names of the compounds used in the respective examples and comparative examples are as follows.

PMDA-HH:1S,2S,4R, 5R-Cyclohexanetetracarboxylic dianhydride

TDA-100:3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthylsuccinic dianhydride

CBDA: cyclobutanetetracarboxylic dianhydride

6FDA:4,4' -Hexafluoroisopropylidene diphthalic dianhydride

ODPA:3,3',4,4' -Diphenyl Ether tetracarboxylic dianhydride

SiDA:1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane

BAHF:2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane

And (3) DAE:4,4' -diaminodiphenyl ether

NMP: n-methyl-2-pyrrolidone

ED-600: JEFFAMINE ED-600 (trade name, manufactured by HUNTSMAN corporation)

MAP: meta-aminophenol

NA: 5-norbornene-2,3-dicarboxylic anhydride

KBM-403: 3-glycidoxypropyltrimethoxysilane (silane compound (a)).

The thermal crosslinking agent (C) and the compound (H) used in each of the examples and comparative examples are shown below.

[ chemical formula 20]

[ chemical formula 21]

Synthesis example 1 Synthesis of quinonediazide Compound (a)

21.22g (0.05 mol) of TrisP-PA (trade name, manufactured by chemical industry, japan), 26.86g (0.10 mol) of naphthoquinonediazide-5-sulfonyl chloride, and 13.43g (0.05 mol) of naphthoquinonediazide-4-sulfonyl chloride were dissolved in 50g of 1,4-dioxane under a dry nitrogen stream and the mixture was allowed to stand at room temperature. While confirming that the temperature in the system was not lower than 35 ℃, 15.18g of triethylamine mixed with 50g of 1,4-dioxane was added dropwise thereto. After the dropwise addition, the mixture was stirred at 30 ℃ for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Then, the precipitated precipitate was collected by filtration. The precipitate was dried by a vacuum dryer to obtain a quinonediazide compound (a) represented by the following formula.

[ chemical formula 22]

Synthesis example 2 Synthesis of polyhydroxystyrene resin (a 0-1)

To a mixed solution containing 500ml of tetrahydrofuran and 0.01mol of sec-butyllithium as an initiator was added 20g in total of p-tert-butoxystyrene and styrene in a molar ratio of 3: 1, and the mixture was polymerized while stirring for 3 hours. The polymerization termination reaction was carried out by adding 0.1mol of methanol to the reaction solution. Subsequently, in order to purify the polymer, the reaction mixture was poured into methanol, and the polymer after the precipitation was dried, whereby a white polymer was obtained. Further, the resulting copolymer was dissolved in 400ml of acetone, and a small amount of concentrated hydrochloric acid was added thereto at 60 ℃ and stirred for 7 hours, and then poured into water to precipitate a polymer, thereby deprotecting p-tert-butoxystyrene to convert it into hydroxystyrene, followed by washing and drying, to obtain a purified copolymer of p-hydroxystyrene and styrene (hereinafter referred to as (a 0-1)). Further, according to the analysis by GPC, the weight average molecular weight (Mw) was 3500 (in terms of GPC polystyrene) and the degree of dispersion (Mw/Mn) was 2.80.

Synthesis example 3 Synthesis of polyhydroxystyrene resin (a 0-2)

The same procedure was carried out except that m-tert-butoxystyrene was used in place of the p-tert-butoxystyrene of synthesis example 2. The obtained copolymer of m-hydroxystyrene and styrene (hereinafter referred to as (a 0-2)) had a weight average molecular weight (Mw) of 5000 (in terms of GPC polystyrene) and a dispersity (Mw/Mn) of 3.20 by GPC analysis.

Synthesis example 4 Synthesis of polyhydroxystyrene resin (a 0-3)

The same operation was carried out except that styrene as in Synthesis example 2 was not added. The obtained p-hydroxystyrene resin (hereinafter referred to as (a 0-3)) had a weight average molecular weight (Mw) of 3000 (in terms of GPC polystyrene) and a dispersity (Mw/Mn) of 1.60 by GPC analysis.

Synthesis example 5 Synthesis of alkali-soluble resin (a 1-1)

The polyhydroxystyrene resin (a 0-1) was dissolved in a solution prepared by dissolving 80g (2.0 mol) of sodium hydroxide in 800g of pure water. After completely dissolving the mixture, 686g of a 36 to 38 mass% aqueous formaldehyde solution was added dropwise thereto at 20 to 25 ℃ over 2 hours. Then stirred for 17 hours at 20-25 ℃.98g of sulfuric acid and 552g of water were added thereto, and neutralization was carried out, and the mixture was left to stand for 2 days while maintaining this state. The white solid produced in the solution after standing was washed with 100mL of water. The white solid was dried under vacuum at 50 ℃ for 48 hours.

Subsequently, the white solid obtained in the above manner was dissolved in 300mL of methanol, 2g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To the solution was added 15g of an anionic ion exchange resin (Amberlyst IRA96SB, manufactured by Rohmand Haas Co., ltd.), and the mixture was stirred for 1 hour to remove the ion exchange resin by filtration. Then, 500mL of GBL was added, and methanol was removed by a rotary evaporator to prepare a GBL solution. By using ¹³ It was analyzed by C-NMR (GX-270, manufactured by Nippon electronics Co., ltd.) and it was confirmed that an alkali-soluble resin (hereinafter referred to as (a 1-1)) was obtained as a polyhydroxystyrene resin which was partially alkoxylated. By the analysis by GPC, the weight average molecular weight (Mw) was 8000 (in terms of GPC polystyrene), and the introduction rate of the alkoxylated hydroxystyrene was 35mol% per 1mol of hydroxystyrene.

Synthesis example 6 Synthesis of alkali-soluble resin (a 1-2)

Synthesis was carried out by the same preparation method except that (a 0-2) was used in place of (aO-1) in Synthesis example 5. The alkali-soluble resin (hereinafter referred to as (a 1-2)) as an alkoxylated polyhydroxystyrene resin obtained had a weight average molecular weight (Mw) of 7500 (in terms of GPC polystyrene) by GPC analysis, and the introduction rate of an alkoxy group was 55mol% per 1mol of hydroxystyrene.

Synthesis example 7 Synthesis of alkali-soluble resin (a 1-3)

Synthesis was carried out by the same method except that (a 0-3) was used in place of (a 0-1) in Synthesis example 5. The alkali-soluble resin (hereinafter referred to as (a 1-3)) as an alkoxylated polyhydroxystyrene resin obtained had a weight average molecular weight (Mw) of 3500 (in terms of GPC polystyrene) by GPC analysis and an introduction rate of an alkoxy group of 69mol% per 1mol of hydroxystyrene.

Synthesis example 8 Synthesis of Novolac resin (e)

Under a dry nitrogen stream, 70.2g (0.65 mol) of m-cresol, 37.8g (0.35 mol) of p-cresol, 75.5g (0.93 mol) of a 37 mass% aqueous formaldehyde solution, 0.63g (0.005 mol) of oxalic acid dihydrate, and 264g of methyl isobutyl ketone were added, and then immersed in an oil bath, and polycondensation reaction was performed for 4 hours while refluxing the reaction solution. Then, the temperature of the oil bath was raised over 3 hours, and then the pressure in the flask was reduced to 40 to 67hPa, volatile components were removed, and the dissolved resin was cooled to room temperature to obtain an alkali-soluble polymer solid of the Novolac resin (e). By the analysis by GPC, it was confirmed that the weight average molecular weight (Mw) was 3, 500. To the obtained Novolac resin (e), γ -butyrolactone (GBL) was added to obtain a solution of the Novolac resin (e) having a solid content concentration of 43 mass%.

Synthesis example 9 Synthesis of Ring-closed polyimide resin (A)

PMDA-HH 4.48g (0.020 mol) and 6FDA 11.11g (0.025 mol) were dissolved in NMP 100g under a dry nitrogen stream. To this was added 1.09g (0.010 mol) of 3-aminophenol together with 20g of NMP. Further, 11.90g (0.033 mol) of BAHF, 1.00g (0.005 mol) of DAE, 0.010mol of ED-6006.00g (0.010 mol) and 0.62g (0.003 mol) of SiDA were added together with 20g of NMP, reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours. After stirring was complete, the solution was poured into 2L of water to give a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (A).

Synthesis example 10 Synthesis of Ring-closed polyimide resin (B)

1.12g (0.005 mol) of PMDA-HH, 6FDA 11.11g (0.025 mol) and ODPA 4.65g (0.015 mol) were dissolved in 100g of NMP under a dry nitrogen stream. To this was added 1.09g (0.010 mol) of 3-aminophenol together with 20g of NMP. Further, 11.90g (0.033 mol) of BAHF, 1.00g (0.005 mol) of DAE, 6.00g (0.010 mol) of ED6006, 0.62g (0.003 mol) of SiDA and 20g of NMP were added together, reacted at 60 ℃ for 1 hour, and then stirred at 180 ℃ for 4 hours. After stirring was complete, the solution was poured into 2L of water to give a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (B).

Synthesis example 11 Synthesis of Ring-closed polyimide resin (C)

3.92g (0.020 mol) of CBDA and 11.11g (0.025 mol) of 6FDA were dissolved in 100g of NMP under a stream of dry nitrogen. To this was added 1.09g (0.010 mol) of 3-aminophenol together with 20g of NMP. Further, 11.90g (0.033 mol) of BAHF, 1.00g (0.005 mol) of DAE, 6.00g (0.010 mol) of ED6006 and 0.62g (0.003 mol) of SiDA were added together with 20g of NMP, and the mixture was reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours. After completion of stirring, the solution was poured into 2L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried by a vacuum dryer at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (C).

Synthesis example 12 Synthesis of Ring-closed polyimide resin (D)

0.98g (0.005 mol) of CBDA, 11.11g (0.025 mol) of 6FDA, and 4.65g (0.015 mol) of ODPA were dissolved in 100g of NMP under a stream of dry nitrogen. 11.90g (0.033 mol) of BAHF, 0.50g (0.003 mol) of DAE, 7.50g (0.013 mol) of ED6007, 0.62g (0.003 mol) of SiDA were added thereto together with 20g of NMP, and reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours, and then 5-norbornene-2,3-dicarboxylic anhydride 1.64g (0.010 mol) was added together with 10g of NMP as a blocking agent and reacted at 60 ℃ for 1 hour. After completion of stirring, the solution was poured into 2L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (D).

Synthesis example 13 Synthesis of Ring-closed polyimide resin (E)

0.98g (0.005 mol) of CBDA, 11.11g (0.025 mol) of 6FDA, and 5363 g (0.015 mol) of TDA-1004.50 were dissolved in 100g of NMP under a stream of dry nitrogen. 11.90g (0.033 mol) of BAHF, 0.50g (0.003 mol) of DAE, 7.50g (0.013 mol) of ED6007, 0.62g (0.003 mol) of SiDA were added thereto together with 20g of NMP, and reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours, and then 5-norbornene-2,3-dicarboxylic anhydride 1.64g (0.010 mol) was added together with 10g of NMP as a blocking agent and reacted at 60 ℃ for 1 hour. After completion of stirring, the solution was poured into 2L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (E).

Synthesis example 14 Synthesis of Ring-closed polyimide resin (F)

10.09g (O.045mol) of PMDA-HH was dissolved in 100g of NMP under a stream of dry nitrogen. To this was added 1.09g (0.010 mol) of 3-aminophenol together with 20g of NMP. Further, 15.57g (0.043 mol) of BAHF, 1.00g (0.005 mol) of DAE and 0.62g (0.003 mol) of SiDA were added together with 20g of NMP, and the mixture was reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours. After completion of stirring, the solution was poured into 2L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (F).

Synthesis example 15 Synthesis of Ring-closed polyimide resin (G)

8.82g (0.045 mol) of CBDA was dissolved in 100g of NMP under a stream of dry nitrogen. To this was added 1.09g (0.010 mol) of 3-aminophenol together with 20g of NMP. Further, 15.57g (0.043 mol) of BAHF, 1.00g (0.005 mol) of DAE and 0.62g (0.003 mol) of SiDA were added together with 20g of NMP, and the mixture was reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours. After completion of stirring, the solution was poured into 2L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (G).

Synthesis example 16 Synthesis of Ring-closed polyimide resin (H)

13.96g (0.045 mol) of ODPA was dissolved in 100g of NMP under a stream of dry nitrogen. To this was added 1.09g (0.010 mol) of 3-aminophenol together with 20g of NMP. Further, 11.90g (0.033 mol) of BAHF, 1.00g (0.005 mol) of DAE, 6.0g (0.010 mol) of ED6006, and 0.62g (0.003 mol) of SiDA were added together with 20g of NMP, and the mixture was reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours. After completion of stirring, the solution was poured into 2L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (H).

Synthesis example 17 Synthesis of Ring-closed polyimide resin (I)

TDA-1006.01g (0.020 mol) and 6FDA 11.11g (0.025 mol) were dissolved in 100g of NMP under a stream of dry nitrogen. To this was added 1.09g (0.010 mol) of 3-aminophenol together with 20g of NMP. Further, 11.90g (O.033mol) of BAHF, 1.00g (O.005mol) of DAE, 6.Og (O.O10mol) of ED600and O.62g (O.003mol) of SiDA were added together with 20g of NMP, and the mixture was reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours. After completion of stirring, the solution was poured into 2L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (I).

Synthesis example 18 Synthesis of Ring-closed polyimide resin (J)

Under a stream of dry nitrogen, 6FDA 19.99g (O.045mol) was dissolved in 100g of NMP. To this was added 1.09g (O.O10mol) of 3-aminophenol together with 20g of NMP. Further, 11.90g (O.033mol) of BAHF, 1.00g (O.005mol) of DAE, 6.Og (O.010mol) of ED6006 and 0.62g (0.003 mol) of SiDA were added together with 20g of NMP, and the mixture was reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours. After stirring was complete, the solution was poured into 2L of water to give a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (J).

Synthesis example 19 Synthesis of polybenzoxazole precursor (K)

18.3g (0.05 mol) of BAHF was dissolved in 50g (NMP) and 26.4g (0.3 mol) of glycidyl methyl ether under a stream of dry nitrogen, and the temperature of the solution was cooled to-15 ℃. To this solution was added dropwise a solution obtained by dissolving 14.7g (0.050 mol, manufactured by Nippon pesticide Co., ltd.) of diphenyl ether diformyl chloride in 25g of GBL so that the internal temperature did not exceed 0 ℃. After the addition was complete, stirring was continued at-15 ℃ for 6 hours. After the reaction was completed, the solution was poured into 3L of water containing 10 mass% of methanol to precipitate a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried for 72 hours using a vacuum drier at 50 ℃ to obtain an alkali-soluble polybenzoxazole precursor (K).

Synthesis example 20 Synthesis of polyimide precursor resin (L)

In a stream of dry nitrogen, 7.51g (0.038 mol) of 4,4' -diaminophenyl ether (hereinafter referred to as DAE), 1.86g (0.007 mol) of SiDA1, and 1.09g (0.010 mol) of 3-aminophenol were dissolved in 100g of NMP. To this was added 13.96g (0.045 mol) of ODPA together with 20g of NMP, followed by reaction at 20 ℃ for 1 hour and then at 50 ℃ for 4 hours. Then, a solution obtained by diluting 9.25g (0.08 mol) of N, N-dimethylformamide dimethyl acetal with 5g of NMP was added dropwise over 10 minutes, and the reaction was carried out at 50 ℃ for 3 hours. After the reaction was completed, the solution was poured into 2L of water, and the precipitate of a polymer solid was collected by filtration. Further, the resin was washed with 2L of water 2 times and dried in a vacuum dryer at 80 ℃ for 20 hours to obtain a polyimide resin (K).

Synthesis example 21 Synthesis of polyimide resin (M)

8.11g (0.04 mol) of DAE and 1.09g (0.010 mol) of 3-aminophenol were dissolved in 100g of NMP under a stream of dry nitrogen. To this was added 13.96g (O.045mol) of ODPA together with 20g of NMP, followed by reaction at 20 ℃ for 1 hour and then at 50 ℃ for 4 hours. Further, the mixture was stirred at 180 ℃ for 5 hours. After stirring was complete, the solution was poured into 2L of water to give a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 80 ℃ for 20 hours to obtain a polyimide resin (M).

Synthesis example 22 Synthesis of Ring-closed polyimide resin (N)

CBDA 3.92g (O.020mol) and 6FDA 11.11g (O.025mol) were dissolved in NMP 100g under a stream of dry nitrogen. To this was added 1.09g (O.010mol) of 3-aminophenol together with 20g of NMP. Further, 10.07g (O.028mol) of BAHF, 1.00g (O.005mol) of DAE, 1.50g (O.O18mol) of ED6001O.50g and 4 hours of SiDA O.62g (O.003mol) were added together with 20g of NMP, and the mixture was reacted at 60 ℃ for 1 hour and then stirred at 180 ℃ for 4 hours. After completion of stirring, the solution was poured into 2L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (N).

Synthesis example 23 Synthesis of Ring-closed polyimide resin (O)

3.92g (0.020 mol) of CBDA and 11.11g (0.025 mol) of 6FDA were dissolved in 100g of NMP under a dry nitrogen stream. To this was added 1.09g (O.010mol) of 3-aminophenol together with 20g of NMP. Further, 7.33g (0.020 mol) of BAHF, 1.00g (0.005 mol) of DAE, 15.00g (0.025 mol) of ED60015 and 0.62g (0.003 mol) of SiDA were added together with 20g of NMP, and the mixture was reacted at 60 ℃ for 1 hour, followed by stirring at 180 ℃ for 4 hours. After completion of stirring, the solution was poured into 2L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum drier at 50 ℃ for 72 hours to obtain a powder of the ring-closed polyimide resin (O).

Synthesis example 24 Synthesis of Novolac resin (f)

To 1000ml of a nitrogen-substituted three-necked flask, 108.0g of m-cresol, 108.0g of methanol and 40.0g of sodium hydroxide were added, and the mixture was heated to 67 ℃ with stirring, followed by reflux reaction for 30 minutes. Then, the reaction solution was cooled to 40 ℃, and 65.2g of 92 mass% paraformaldehyde was added thereto, and after the temperature was raised to 67 ℃ again, the reflux reaction was carried out for 5 hours. After the reaction was completed, the reaction solution was cooled to 30 ℃ or lower, and 140.0g of 30 mass% sulfuric acid was added dropwise over 30 minutes so that the reaction solution did not reach 35 ℃ or higher. The pH of the resulting reaction solution was 4.9. 540.0g of ion-exchanged water was further added to the reaction mixture, and after stirring for 20 minutes and standing for 20 minutes, the separated aqueous layer was removed. After removing the water layer, 108.0g of dioxane was added, and the residual water was removed at 40 ℃ under a pressure of 0.08MPa to less than 3% by mass. To the reaction mixture were added 432.0g of methanol and 2.0g of 96 mass% sulfuric acid. The pH of the obtained reaction solution was 0.8. The reaction solution was heated to 60 ℃ to conduct an alkoxylation reaction at 60 ℃ for 3 hours. After the reaction was completed, the reaction solution was cooled to 30 ℃ or lower, and a 10 mass% aqueous solution of sodium hydroxide was added dropwise over 30 minutes so that the temperature of the reaction solution did not become 35 ℃ or higher until the pH of the reaction solution became 9.0. Methyl isobutyl ketone (MIBK) 216.0g as a separation solvent for washing and 324.0g of ion exchange water were added to the reaction solution, and the mixture was stirred at 30 ℃ for 20 minutes and allowed to stand for 20 minutes to remove the separated aqueous layer. 324.0g of ion-exchanged water was further added thereto, and the washing operation was repeated with the ion-exchanged water until the conductivity of the water removed became 100. Mu.Scm or less. After the completion of the washing, 300g of gamma-butyrolactone was added, and ion-exchanged water and MIBK were distilled off at 70 ℃ under a pressure of 0.08MPa to obtain a Novolac resin solution (f) having a solid content of 50 mass%.

The weight average molecular weight (Mw) of the obtained Novolac resin solution (f) was 7000 (in terms of GPA in polystyrene) and the degree of dispersion (Mw/Mn) was 7.5 by GPC analysis. Based on ¹³ CNMR, the number of moles of alkoxyalkyl groups per 1mol of phenol skeleton was 57mol%, and the alkoxylation rate was 100mol%.

Example 1

10.5g of the alkali-soluble resin (a 1-1), 1O.5g of the resin (A) obtained in Synthesis example 9, 3.0g of the quinonediazide compound (a) obtained in Synthesis example 1, MX-2707.2g of the crosslinking agent, and KBM-4031.Og were added to GBL 25g to obtain varnish A of a positive photosensitive resin composition.

The varnish thus obtained was coated on a 38 μm thick PET film using a comma coater, dried at 80 ℃ for 8 minutes, and then a 10 μm thick PP film was laminated as a protective film to obtain a photosensitive film. The thickness of the photosensitive film was adjusted to 10 μm.

Using the obtained photosensitive film, each evaluation of the lamination property with a silicon substrate, high elongation, 5% weight loss temperature (heat resistance), and pattern processability was performed.

Examples 2 to 33 and comparative examples 1 to 8

Varnishes were produced in the same manner as in example 1, except that the amounts of the alkali-soluble resin (A1), the alkali-soluble resin (A2), other additives, the photoacid generator (B), and the crosslinking agent (C) added were changed as shown in tables 1, 2-1, and 2-2. Using the obtained photosensitive film, each evaluation of the lamination property with a silicon substrate, high elongation, 5% weight loss temperature (heat resistance), and pattern processability was performed.

The molar ratio of the components of the alkali-soluble resin (A2) is shown in table 1.

The evaluation results are shown in tables 3-1 and 3-2.

[ Table 3-1]

[ tables 3-2]

Description of the reference numerals

1. Semiconductor device with a plurality of semiconductor chips

2. Passivation film

3. Cured film

4. Metal wiring

5. Cured film

6. Substrate board

7. Cured film

8. Cured film

9. Metal film

10. Metal wiring

11. Metal wiring

12. Electrode for electrochemical cell

13. Sealing resin

14. Substrate

15 IDT electrode

16. Bonding pad

17. Hollow part

18. Supporting material

19. Coating material

20. Protective member

21. Via conductor

22. Solder bump

23. Silicon wafer

24 A1 bonding pad

25. Passivation film

26. Resin composition

27. Cured film

28. Metal film

29. Metal wiring

30. Insulating film

31. Barrier metal

32. Solder bump

Claims

1. A photosensitive film comprising:

(A1) An alkali-soluble resin having a structural unit represented by general formula (1);

(A2) An alkali-soluble resin containing one or more selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof;

(B) A photoacid generator; and

(C) A thermal crosslinking agent represented by the following general formula (11) and a thermal crosslinking agent containing a structural unit represented by the general formula (12),

in the general formula (1), R ¹ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents an integer in the range of 0 to 4, b represents an integer in the range of 1 to 3, R ² Is a hydrogen atom, a methyl group, an ethyl group, or a propyl group,

in the general formula (11), R ⁶⁶ Represents an organic group having a valency of one to ten, a plurality of R ⁶⁷ Each of which may be the same or different and represents an alkyl group having 1 to 4 carbon atoms, r represents an integer of 1 to 5, s represents an integer of 1 to 10,

in the general formula (12), R ⁶⁹ And R ⁷⁰ Each independently represents a hydrogen atom or a methyl group; r ⁶⁸ Is a divalent organic group having an alkylene group having 2 or more carbon atoms, and may be linear, branched, or cyclic.

2. The photosensitive film according to claim 1, wherein the weight average molecular weight (Mw) of the alkali-soluble resin (A1) is in the range of 3,000 to 60,000.

3. The photosensitive film according to claim 1 or 2, wherein the alkali-soluble resin (A1) further has at least one of structural units represented by general formula (2) and general formula (3),

in the general formula (2), R ³ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, e represents an integer in the range of 1 to 5,

in the general formula (3), R ⁴ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

4. The photosensitive film according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the thermal crosslinking agent represented by the general formula (11) is 100 to 2,500.

5. The photosensitive film according to claim 1 or 2, wherein the (A2) alkali-soluble resin has one or more substituents selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group.

6. The photosensitive film according to claim 1 or 2, wherein the alkali-soluble resin (A2) has at least any one of structural units represented by general formulae (4) and (5),

in the general formula (4), R ⁵ A tetravalent organic group having 4 to 40 carbon atoms; r ⁶ A divalent organic group having 20 to 100 carbon atoms; n is ₁ Represents an integer in the range of 10 to 100,000,

in the general formula (5), R ⁵ Three to four valent organic groups having 4 to 40 carbon atoms; r ⁶ A divalent organic group having 20 to 100 carbon atoms; r ⁷ Represents hydrogen or an organic group having 1 to 20 carbon atoms; n is ₂ Represents an integer in the range of 10 to 100,000, and p and q represent integers satisfying 0 < p + q.ltoreq.2.

7. The photosensitive film according to claim 6, wherein R is the sum of the repeating units represented by the general formulae (4) and (5) at 100mol% ⁶ The content of the organic groups of the general formulae (4) and (5) having a polyether structure and 20 to 100 carbon atoms is 10 to 80mol%.

8. The photosensitive film according to claim 7, wherein the organic group having a polyether structure and 20 to 100 carbon atoms is an organic group represented by the general formula (10),

in the general formula (10), R ⁵⁴ ～R ⁵⁷ Each independently represents an alkylene group having 1 to 6 carbon atoms; r ⁵⁸ ～R ⁶⁵ Each independently represents hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms; wherein the structure shown in parentheses of the repeating unit x is different from the structure shown in parentheses of the repeating unit y; the structure indicated in parentheses of the repeating unit z is different from the structure indicated in parentheses of the repeating unit y; x, y and z each independently represent an integer of 0 to 35.

9. The photosensitive film according to claim 6, wherein R is the sum of the repeating units represented by the general formulae (4) and (5) at 100mol% ⁵ The content of the organic groups of the general formulae (4) and (5) having an alicyclic structure and 4 to 40 carbon atoms is 10 to 80mol%.

10. The photosensitive film according to claim 1 or 2, further comprising (H) a compound represented by the general formula (13),

in the general formula (13), R ⁷¹ ～R ⁷³ Represents O atom or S atom, N atom, and R ⁷¹ ～R ⁷³ Represents an S atom; l represents 0 or 1,l is 0, R ⁷¹ Represents an oxygen atom or a sulfur atom, and when l is 1, R ⁷¹ Represents a nitrogen atom; m and n represent 1 or 2; r ⁷⁴ ～R ⁷⁶ Each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.

11. The photosensitive film according to claim 1 or 2, which has a photosensitive layer having a film thickness of 3 to 45 μm.

12. The photosensitive film according to claim 11, wherein a protective film is provided on the photosensitive layer, and a support film is provided under the photosensitive layer.

13. A cured film obtained by curing the photosensitive film according to any one of claims 1 to 12.

14. An interlayer insulating film or a semiconductor protective film provided with the cured film according to claim 13.

15. An electronic component or a semiconductor device having an embossed pattern layer of the cured film according to claim 13.

16. An electronic component or a semiconductor device, wherein the cured film according to claim 13 is provided on a substrate in a thickness of 2 to 40 μm, and copper wiring is provided on the cured film, and the cured film according to claim 13 is further provided in a thickness of 2 to 40 μm as an insulating film between the copper wiring.

17. An electronic component or a semiconductor device, wherein a relief pattern layer having a cured film of a photosensitive resin composition is provided on a substrate as a support, the cured film according to claim 13 is provided on the support as a cover, the cover is disposed in an opening of the relief pattern layer of the support, and the cover has a hollow portion surrounded by the support, the cover and the substrate.

18. An electronic component or a semiconductor device, wherein a substrate has an (S-1) upper layer part and an (S-2) lower layer part having a (T-1) layer difference of 2 to 40 [ mu ] m,

the cured film according to claim 13 being disposed on each of the (S-1) upper layer part and the (S-2) lower layer part,

the cured film according to claim 13 disposed on the upper layer portion of (S-1) and the cured film according to claim 13 disposed on the lower layer portion of (S-2) have a difference in (T-2) layer of 5 μm or less.

19. A method for manufacturing an electronic component or a semiconductor device, using the photosensitive film according to any one of claims 1 to 12, the method comprising:

forming a photosensitive film by thermally pressing the photosensitive film onto a substrate at a temperature of 40 to 150 ℃;

exposing the photosensitive film through an exposure mask;

and a step of removing the exposed portion of the photosensitive film with an alkaline developer to develop the photosensitive film.