Negative-type photosensitive resin composition, negative-type photosensitive polymer, cured film, and semiconductor device

Abstract

A negative photosensitive resin composition according to the present invention contains (A) a polyimide, (B) a crosslinking agent that contains a multifunctional (meth)acrylate, and (C) a photopolymerization initiator; and the polyimide (A) comprises a structural unit (a1) represented by general formula (a1) and a structural unit (a2) represented by general formula (a2). (In general formula (a1), each Y represents a group that is selected from among groups represented by general formula (a1-1), general formula (a1-2) and general formula (a1-3); and the plurality of Y moieties may be the same as or different from each other.)

Description

[Technical Field]

[0001] The present invention relates to a negative-type photosensitive resin composition, a negative-type photosensitive polymer, a cured film, and a semiconductor device. [Background technology]

[0002] Polyimide resins possess high mechanical strength, heat resistance, insulation, and solvent resistance, making them widely used as thin films for electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display elements and semiconductors.

[0003] Patent Document 1 discloses a block copolyimide that is soluble in a bipolar aprotic solvent, and states that a block copolyimide can be obtained using a predetermined acid anhydride.

[0004] Patent Document 2 discloses a polyimide resin composed of structural units having a predetermined structure. This document describes an example of synthesizing a polyimide resin using 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane.

[0005] Patent Document 3 discloses a polyimide elastomer resin having a predetermined molecular weight, which is a ternary copolymer obtained from an aromatic tetracarboxylic dianhydride, 4,4′-diaminodiphenylmethane having at least one alkyl group on an aromatic ring containing an amino group, and a polyether oligomer having p-aminobenzoic acid ester groups at both ends. In this document, bis(4-amino-3-ethyl-5-methylphenyl)methane is given as 4,4′-diaminodiphenylmethane. The document states that this resin has excellent heat and moisture resistance.

[0006] Patent Document 4 discloses a block copolymer comprising polyimide structural units formed from aromatic tetracarboxylic dianhydride and a 4,4′-diaminodiphenylmethane derivative, and dimethylsiloxane structural units. In this document, bis(4-amino-3-ethyl-5-methylphenyl)methane is given as the 4,4′-diaminodiphenylmethane. The document states that this resin has excellent heat resistance and solvent solubility. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 015 / 091122 Australia [Patent Document 2] Japanese Patent Application Publication No. 16829 / 1983 [Patent Document 3] Japanese Patent Application Publication No. 8-217874 [Patent Document 4] Japanese Patent Application Publication No. 9-40777 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] However, in the conventional technologies described in Patent Documents 1 to 4, there was room for improvement in the mechanical strength, such as elongation, of the polyimide-containing films obtained from the photosensitive resin composition.

[0009] Conventionally, fluorine atoms have been introduced into the polyimide skeleton to improve the solubility of polyimides in organic solvents. However, the present inventors have found that when polyimides are synthesized using a diamine compound containing fluorine atoms, the strong electron-withdrawing properties of the fluorine atoms affect the electrons of the imide ring, making the resulting polyimide more susceptible to hydrolysis, which in turn reduces its mechanical strength, such as elongation. In other words, conventional polyimides had room for improvement in terms of the balance between solubility in organic solvents and mechanical strength such as elongation. [Means for solving the problem]

[0010] The inventors of the present invention have discovered that the above problems can be solved by using a polyimide having a specific structure, and have completed the present invention. In other words, the present invention can be described as follows.

[0011] [1] (A) Polyimide and (B) A crosslinking agent containing a polyfunctional (meth)acrylate, (C) Photopolymerization initiator and, Includes, Polyimide (A) is A structural unit (a1) represented by the following general formula (a1), A structural unit (a2) represented by the following general formula (a2), A negative-type photosensitive resin composition containing [the specified element]. [ka] [ka] (In general formula (a1), Y is selected from the bases represented by the following general formulas (a1-1), (a1-2), and (a1-3), and multiple Ys may be the same or different. [ka] (In general formula (a1-1), R 7 and R 8 Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 alkoxy group, and there are multiple R groups. 7 Multiple Rs exist. 8 They may be the same or different. 9 R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and there are multiple R groups. 9 The elements can be identical or different. * indicates a bonding action. In general formula (a1-2), R 10 and R 11Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. When there are a plurality of Rs 10 among themselves, when there are a plurality of Rs 11 they may be the same or different. * represents a bond. In the general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group. * represents a bond.) In the general formula (a2), R 1 ~R 4 each independently represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R 1 and R 2 are different groups, and R 3 and R 4 are different groups. X 1 represents a single bond, -SO2-, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. When there are a plurality of Xs 1 they may be the same or different.) [[ID=二十九]] [2] The negative-type photosensitive resin composition according to [1], wherein the polyimide (A) further contains a structural unit (a3) represented by the following general formula (a3). <00001九十5><00001九十6>

Chemical formula

Chemical formula

[10] A cured film comprising a cured product of a negative-type photosensitive resin composition described in any of [1] to [4].

[11] A semiconductor device comprising a resin film containing a cured product of a negative-type photosensitive resin composition described in any of [1] to [4].

[12] Interlayer insulating film and A resin film provided on the interlayer insulating film, comprising a cured product of a negative-type photosensitive resin composition according to any one of [1] to [4], The rewiring embedded in the aforementioned resin film, A semiconductor device characterized by comprising the following features. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a negative-type photosensitive polymer and a negative-type photosensitive resin composition containing the polymer that yield cured products such as films that have excellent solubility in organic solvents, suppress hydrolysis, and have excellent mechanical strength such as elongation. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic cross-sectional view of the semiconductor device according to this embodiment. [Modes for carrying out the invention]

[0014] Embodiments of the present invention will be described below with reference to the drawings. In all drawings, similar components are denoted by the same reference numerals, and their descriptions are omitted as appropriate. Unless otherwise specified, "A to B" represents "greater than or equal to A" to "less than or equal to B".

[0015] The negative-type photosensitive resin composition of this embodiment comprises (A) polyimide, (B) a crosslinking agent containing a polyfunctional (meth)acrylate, and (C) a photopolymerization initiator.

[0016] [Polyimide (A)] The polyimide (A) (negative photosensitive polymer) of this embodiment includes a structural unit (a1) represented by the following general formula (a1) and a structural unit (a2) represented by the following general formula (a2).

[0017] [ka]

[0018] In general formula (a1), Y is a divalent organic group. As the divalent organic group, any known organic group can be used within the range that achieves the effects of the present invention. However, from the viewpoint of the effects of the present invention, it is preferable to use a divalent organic group selected from the following general formulas (a1-1), (a1-2), and (a1-3).

[0019] [ka]

[0020] In general formula (a1-1), R 7 and R 8Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 alkoxy group, and there are multiple R groups. 7 Multiple Rs exist. 8 They may be the same or different. R 7 and R 8 From the viewpoint of the effects of the present invention, it is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0021] R 9 R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and there are multiple R groups. 9 They may be the same or different. R 9 From the viewpoint of the effects of the present invention, it is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. * indicates a bond.

[0022] In general formula (a1-2), R 10 and R 11 Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 alkoxy group, and there are multiple R groups. 10 Multiple Rs exist. 11 They may be the same or different.

[0023] R 10 and R 11 From the viewpoint of the effects of the present invention, it is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably R 10 at least one of and R 11 At least one of them is an alkyl group having 1 to 3 carbon atoms, and more preferably three R 10 is an alkyl group having 1 to 3 carbon atoms and one R 10 It is a hydrogen atom and has three R 11 is an alkyl group having 1 to 3 carbon atoms and one R 11 is a hydrogen atom, and particularly preferably three R 10 It is a methyl group and one R 10 It is a hydrogen atom and has three R11 is a methyl group and one R 11 is a hydrogen atom. * indicates a bond.

[0024] In general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group. * indicates a bond.

[0025]

Chemical formula

[0026] In general formula (a2), R 1 ~R 4 each independently represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R 1 and R 2 are different groups, and R 3 and R 4 are different groups. R 1 ~R 4 are preferably alkyl groups having 1 to 3 carbon atoms from the viewpoint of the effects of the present invention.

[0027] X 1 represents a single bond, -SO2-, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of X 1 may be the same or different.

[0028] X 1 is preferably a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms from the viewpoint of the effects of the present invention, and more preferably a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms.

[0029] Since the polyimide (A) of the present embodiment contains a structural unit represented by the general formula (a2), the influence on the electrons of the imide ring is suppressed, the hydrolysis of the polyimide is suppressed, and it has excellent mechanical strength such as elongation and excellent solubility in organic solvents. In other words, the polyimide (A) of the present embodiment and the negative photosensitive resin composition containing the polyimide (A) have an excellent balance of these properties.

[0030] The polyimide (A) may further contain a structural unit (a3) represented by the following general formula (a3). By including the structural unit (a3), the solvent solubility is further improved.

[0031]

Chemical formula

[0032] In the general formula (a3), Q 1 , Q 2 each independently represents a hydroxyl group or a carboxyl group, preferably a hydroxyl group.

[0033] X 2 represents a single bond, -SO2-, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, and a plurality of X 2 may be the same or different.

[0034] X 2 is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms from the viewpoint of the effects of the present invention.

[0035] Specifically, the polyimide (A) of the present embodiment may contain a structural unit represented by the following general formula (1).

[0036]

Chemical formula

[0037] In general formula (1), R 1 ~R 4 , X 1 This is equivalent to general formula (a2), and Y is equivalent to general formula (a1).

[0038] The polyimide (A) of this embodiment may further include structural units represented by the following general formula (2).

[0039] [ka]

[0040] In general formula (2), Q 1 Q 2 , and X 2 This is equivalent to general formula (a3), and Y is equivalent to general formula (a1).

[0041] In this embodiment, it is preferable that at least one of the ends of the polyimide (A) is a group represented by the following general formula (3). By including this group, hydrolysis is suppressed and mechanical strength such as elongation is improved.

[0042] [ka]

[0043] In general formula (3), Y is equivalent to that in general formula (a1). * indicates a bond.

[0044] The weight-average molecular weight of polyimide (A) in this embodiment is 5,000 to 200,000, preferably 10,000 to 100,000.

[0045] Furthermore, since the polyimide (A) of this embodiment has excellent solubility in solvents and does not need to be prepared as a varnish in its precursor state, a varnish containing polyimide (A) can be prepared, and a cured product such as a film can be obtained from this varnish.

[0046] <Method for producing polyimide (A)> The method for producing polyimide (A) (negative photosensitive polymer) having a structural unit represented by the general formula (1) of this embodiment is: The process includes imidizing an acid anhydride (a1') represented by the following general formula (a1') and a diamine (a2') represented by the following general formula (a2') at a temperature of 100°C to 250°C. According to this embodiment, polyimide (A) with excellent solubility in organic solvents can be synthesized by a simple method.

[0047] [ka]

[0048] In general formula (a1'), Y is selected from the groups represented by general formulas (a1-1), (a1-2), or (a1-3).

[0049] [ka]

[0050] In general formula (a2'), R 1 ~R 4 , X 1 This is equivalent to the general formula (a2).

[0051] The equivalent ratio of acid anhydride (a1') to diamine (a2') in the imidation reaction of this process is an important factor in determining the molecular weight of the resulting polyimide. Generally, it is well known that there is a correlation between the molecular weight of a polymer and its mechanical properties, with higher molecular weights resulting in superior mechanical properties. Therefore, to obtain a polyimide with practically excellent strength, a certain degree of high molecular weight is necessary. In this invention, there are no particular restrictions on the equivalent ratio of acid anhydride (a1') to diamine (a2') used, but it is preferable that the equivalent ratio of acid anhydride (a1') to diamine (a2') is in the range of 0.85 to 1.15. Below 0.85, the molecular weight is low and brittle, resulting in weak mechanical strength. Also, above 1.15, the molecular weight is low and brittle, resulting in weak mechanical strength. In other words, if the equivalent ratio is within the above range, the polyimide will have excellent mechanical strength and manufacturing stability.

[0052] This process preferably yields a polyimide (A) in which at least one of both ends is an acid anhydride group represented by the following general formula (3). The inclusion of this acid anhydride group further improves the mechanical strength, such as the elongation of the cured product. Specifically, the acid anhydride group reacts with the epoxy group of the epoxy group-containing compound. If there are two or more epoxy groups, polyimide (A) can be crosslinked with the compound.

[0053] [ka]

[0054] In general formula (3), Y is equivalent to that in general formula (a1). * indicates a bond.

[0055] Furthermore, in this process, from the viewpoint of the effects of the present invention, it is also preferable to use a diamine (a3') represented by the following general formula (a3') and imide the acid anhydride (a1'), the diamine (a2'), and the diamine (a3') at a temperature of 100°C to 250°C.

[0056] This makes it possible to obtain a polyimide (A) (negative-type photosensitive polymer) having both the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2).

[0057] [ka]

[0058] In general formula (a3'), Q 1 Q 2 , and X 2 This is equivalent to the general formula (a3). To control the molecular weight of the resulting polyimide, it is possible to add small amounts of acid anhydride or aromatic amine as an end capping agent and react them to form terminal groups that can react with epoxy groups to form bonds.

[0059] Examples of acid anhydrides used as end capping agents include phthalic anhydride, maleic anhydride, nadic anhydride, and trimellitic anhydride, while examples of aromatic amines include p-methylaniline, p-methoxyaniline, p-phenoxyaniline, and 4-carboxyaniline. The amount of these end capping agents, acid anhydrides or aromatic amines, added is preferably 5 mol% or less. If it exceeds 5 mol%, the molecular weight of the resulting polyimide (A) will decrease significantly, causing problems with heat resistance and mechanical properties.

[0060] The equivalent ratio of acid anhydride (a1') to diamine (a2') and diamine (a3') is an important factor in determining the molecular weight of the resulting polymer. Generally, it is well known that there is a correlation between the molecular weight of a polymer and its mechanical properties, with higher molecular weights resulting in superior mechanical properties. Therefore, to obtain a polymer with practically excellent strength, a certain degree of high molecular weight is necessary. In this invention, the equivalent ratio of acid anhydride (a1') to diamine (a2') and diamine (a3') used is not particularly limited, but it is preferable that the equivalent ratio of diamine (a2') and diamine (a3') to acid anhydride (a1') is in the range of 0.70 to 1.30. If the equivalent ratio is within this range, the polymer will have excellent mechanical strength and manufacturing stability.

[0061] This step (imidation reaction step) can be carried out in an organic solvent using a known method. Examples of organic solvents include aprotic polar solvents such as γ-butyllactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane, and one or more of these may be used in combination. In this case, a nonpolar solvent that is compatible with the above aprotic polar solvent may be mixed and used. Examples of nonpolar solvents include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene, and solvent naphtha, and ether-based solvents such as cyclopentyl methyl ether. The proportion of the nonpolar solvent in the mixed solvent can be arbitrarily set according to the stirring capacity and resin properties such as solution viscosity, as long as the solubility of the solvent does not decrease and the polyamic acid resin obtained by the reaction does not precipitate.

[0062] The reaction temperature is 0°C to 100°C, preferably 20°C to 80°C, for about 30 minutes to 2 hours, followed by a reaction at 100°C to 250°C, preferably 120°C to 200°C, for about 1 to 5 hours.

[0063] By the above manufacturing method, a reaction solution containing the polyimide (A) (negative photosensitive polymer) of this embodiment can be obtained, and can be further diluted with an organic solvent or the like as needed and used as a polymer solution (coating varnish). As the organic solvent, those exemplified in the above steps can be used, and it may be the same organic solvent as in those steps, or a different organic solvent may be used.

[0064] Alternatively, this reaction solution can be added to a poor solvent to reprecipitate the polyimide (A) resin to remove unreacted monomers, and the dried and solidified product can be dissolved again in an organic solvent and used as a refined product. In particular, for applications where impurities and foreign matter are a concern, it is preferable to dissolve it again in an organic solvent and filter and purify it to obtain a varnish.

[0065] The polyimide (A) (negative photosensitive polymer) of this embodiment exhibits excellent hydrolysis resistance, with a weight-average molecular weight reduction rate of 9% or less, preferably 8% or less, as measured under the following conditions. (conditions) When 100 parts by mass of the negative-type photosensitive polymer is added to 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water, and stirred at 100°C for 6 hours, the following formula is used to calculate the result. Formula: [(Weight-average molecular weight before testing - Weight-average molecular weight after testing) / Weight-average molecular weight before testing] × 100

[0066] In this embodiment, the negative-type photosensitive polymer has a weight-average molecular weight reduction rate within the above range, which suppresses hydrolysis and allows for the production of cured products such as films with excellent mechanical strength, including elongation.

[0067] Table A below shows preferred formulations of the negative-type photosensitive polymer in this embodiment.

[0068] [Table 1]

[0069] MED-J: 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane BAFA: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BAPA: 2,2-bis(3-amino-4-hydroxyphenyl)propane ·TMPBP-TME:4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate ·BPZ-TME:4-{[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)phenyl]cyclohexyl}phenyl 1,3-dioxoisobenzofuran-5-carboxylate • TMHQ: p-phenylenebis(trimellitate anhydrous)

[0070] [Crosslinking agent (B)] In this embodiment, the crosslinking agent (B) may include a polyfunctional (meth)acrylate. Here, a polyfunctional (meth)acrylate is a compound having two or more (meth)acryloyl groups. In this embodiment, the (meth)acryloyl group refers to either an acryloyl group or a methacryloyl group.

[0071] From the viewpoint of the effects of the present invention, it is preferable that the polyfunctional (meth)acrylate has three or more functional groups. There is no particular upper limit to the number of functional groups in the polyfunctional (meth)acrylate compound, but considering the ease of obtaining raw materials, the upper limit is, for example, 11 functional groups. As a general trend, when polyfunctional (meth)acrylate compounds with a large number of functional groups ((meth)acryloyl groups) are used, the chemical resistance of the cured film tends to improve. On the other hand, when polyfunctional (meth)acrylate compounds with a small number of functional groups ((meth)acryloyl groups) are used, the mechanical properties of the cured film, such as tensile elongation, tend to be good.

[0072] As an example, the polyfunctional (meth)acrylate compound preferably contains a (meth)acrylate compound (B1) with seven or more functions.

[0073] As an example, the polyfunctional (meth)acrylate compound preferably contains a 5-6 functional (meth)acrylate compound (B2).

[0074] As an example, the polyfunctional (meth)acrylate compound preferably includes a 3- to 4-functional (meth)acrylate compound (B3).

[0075] As an example, polyfunctional (meth)acrylate compounds may include compounds represented by the following general formula. In the following general formula, R' is a hydrogen atom or a methyl group, n is 0 to 3, and R is a hydrogen atom or a (meth)acryloyl group.

[0076] [ka]

[0077] Specific examples of polyfunctional (meth)acrylate compounds include the following. Of course, polyfunctional (meth)acrylate compounds are not limited to these.

[0078] Polyol polyacrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy acrylates such as bisphenol A diglycidyl ether di(meth)acrylate and hexanediol diglycidyl ether di(meth)acrylate; and urethane(meth)acrylates obtained by the reaction of polyisocinate with hydroxyl group-containing(meth)acrylates such as hydroxyethyl(meth)acrylate.

[0079] Commercially available products such as Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, Aronix M-520 (manufactured by Toagosei Co., Ltd.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat #230, Viscoat #300, Viscoat #802, Viscoat #2500, Viscoat #1000, Viscoat #1080 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-BPE-10, NK Ester A-GLY-9E, NK Ester A-9550, NK Ester A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0080] The photosensitive resin composition may contain only one polyfunctional (meth)acrylate compound, or it may contain two or more polyfunctional (meth)acrylate compounds. In the latter case, it is preferable to use polyfunctional (meth)acrylate compounds with different numbers of functional groups in combination. By using polyfunctional (meth)acrylate compounds with different numbers of functional groups in combination, a more complex "intertwined structure of cyclic polyimide and polyfunctional (meth)acrylate" can be formed, which is thought to result in better heat resistance and mechanical properties. Incidentally, some commercially available polyfunctional (meth)acrylate compounds are mixtures of (meth)acrylates with different numbers of functional groups.

[0081] The amount of the polyfunctional (meth)acrylate compound per 100 parts by mass of polyimide (A) is, for example, 50 to 200 parts by mass, preferably 60 to 150 parts by mass, and more preferably 70 to 120 parts by mass. The amount of polyfunctional (meth)acrylate compound used is not particularly limited, but as described above, by appropriately adjusting the amount used, one or more of the various performance characteristics can be further improved. As mentioned above, in the photosensitive resin composition of this embodiment, it is thought that an "entangled structure of cyclic polyimide and polyfunctional (meth)acrylate" is formed upon curing. By appropriately adjusting the amount of polyfunctional (meth)acrylate compound used relative to polyimide (A), the polyimide (A) and the polyfunctional (meth)acrylate compound become sufficiently entangled, and the amount of excess components that do not participate in the entanglement is reduced, resulting in further improved performance.

[0082] In this embodiment, if at least one of the ends of the polyimide (A) is an acid anhydride group represented by the general formula (3), the crosslinking agent (B) can include an epoxy resin. This further improves the mechanical strength, such as the elongation of the cured product.

[0083] As the epoxy resin, any compound having two or more epoxy groups in one molecule can be used as appropriate. Specific examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), and bisphenol Z type epoxy resin (4,4'-cyclohexydiene bisphenol type epoxy resin). Bisphenol-type epoxy resins such as xylylene-type epoxy resins, tetramethylbisphenol F-type epoxy resins; phenol novolac-type epoxy resins, brominated phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, tetraphenol group ethane-type novolac-type epoxy resins, novolac-type epoxy resins having a condensed ring aromatic hydrocarbon structure, and other novolac-type epoxy resins; biphenyl-type epoxy resins; xylylene-type epoxy resins, biphenyl aralkyl-type epoxy resins, and other aralkyl-type epoxy resins; naphthylene ether-type epoxy resins, Epoxy resins containing a naphthalene skeleton, such as tall-type epoxy resins, naphthalene-type epoxy resins, naphthalenediol-type epoxy resins, 2-4 functional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, and naphthalene aralkyl-type epoxy resins; anthracene-type epoxy resins; phenoxy-type epoxy resins; dicyclopentadiene-type epoxy resins; norbornene-type epoxy resins; adamantane-type epoxy resins; fluorene-type epoxy resins, phosphorus-containing epoxy resins, alicyclic epoxy resins, aliphatic chain epoxy resins, and bisphenol A novolac-type epoxy resins. Heterocyclic epoxy resins such as bixylenol-type epoxy resins, trihydroxyphenylmethane-type epoxy resins, stilbene-type epoxy resins, tetraphenyloleethane-type epoxy resins, and triglycidyl isocyanurates; glycidylamines such as N,N,N',N'-tetraglycidylmetoxylendiamine, N,N,N',N'-tetraglycidylbisaminomethylcyclohexane, and N,N-diglycidylaniline, and copolymers of glycidyl (meth)acrylate and compounds having ethylenically unsaturated double bonds; epoxy resins having a butadiene structure;Examples include diglycidyl ethers of bisphenols; diglycidyl ethers of naphthalenediols; and glycidyl ethers of phenols. Furthermore, epoxy resins include n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ethers such as bisphenol A (or F) glycidyl ether, glycidyl esters such as adipic acid diglycidyl ester and o-phthalate diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, and 3,4-epoxy-6-methylcyclohexylmethyl (3 ,4-epoxy-6-methylcyclohexane)carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis(2,3-epoxycyclopentyl) ether, and alicyclic epoxy resins such as Daicel's Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, Epolid GT401, 2,2'-(((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxiran)) (for example, Techmore from Printec Other examples include aliphatic polyglycidyl ethers such as VG3101L, Epolite 100MF (manufactured by Kyoeisha Chemical Industry Co., Ltd.), and Epiol TMP (manufactured by NOF Corporation), as well as 1,1,3,3,5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)trisiloxane (e.g., DMS-E09 (manufactured by Gellet)).

[0084] Preferably, the epoxy resin has 2 to 4 epoxy groups per molecule, and more preferably, 2 to 3 epoxy groups per molecule. By adjusting the number of functional groups in the epoxy resin, it is easy to improve, for example, the heat resistance and mechanical properties of the cured film in a balanced manner. From another perspective, epoxy resins having an aromatic ring structure and / or an alicyclic structure are preferred. Using such epoxy resins is particularly preferable from the viewpoint of heat resistance.

[0085] When using epoxy resin, you may use only epoxy resin 1, or you may use epoxy resins 2 or more in combination. When epoxy resin is used, the amount is, for example, 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass, per 100 parts by mass of polyimide (A).

[0086] [Photopolymerization initiator (C)] As the photopolymerization initiator (C), for example, a photoradical generator can be used. Photoradical generators are particularly effective in polymerizing polyfunctional (meth)acrylate compounds.

[0087] The photoradical generators that can be used are not particularly limited, and known ones can be used as appropriate. For example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl Alkylphenone compounds such as (L)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzophenone, 4,4′-bis(dimethylamino)benzophenone, 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin compounds such as benzoin ether and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis( Halomethylated triazine compounds such as lichloromethyl)-s-triazine and 2-(4-ethoxycarbokynylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, and 2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, Examples include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. Among these, oxime ester compounds are particularly preferred.

[0088] The negative-type photosensitive resin composition of this embodiment may contain only one type of photopolymerization initiator (C), or it may contain two or more types. The amount of photopolymerization initiator (C) used is, for example, 1 to 30 parts by mass, preferably 5 to 20 parts by mass, per 100 parts by mass of the polyfunctional (meth)acrylate compound.

[0089] (Thermal radical initiator (D)) The negative-type photosensitive resin composition of this embodiment preferably contains a thermal radical initiator (D). By using a thermal radical initiator (D), for example, the heat resistance of the cured film can be further enhanced, and / or the chemical resistance (resistance to organic solvents, etc.) of the cured film can be improved. This is thought to be because the polymerization reaction of the polyfunctional (meth)acrylate compound is further promoted by using a thermal radical initiator (D).

[0090] The thermal radical initiator (D) preferably includes an organic peroxide. Examples of organic peroxides include octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, oxalic acid peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy 2-ethylhexanoate, t-hexyl peroxy 2-ethylhexanoate, t-butyl peroxy 2-ethylhexanoate, m-toluyl peroxide, benzoyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, parachlorobenzoyl peroxide, and cyclohexanone peroxide.

[0091] When using a thermal radical initiator (D), one thermal radical initiator (D) may be used, or two or more thermal radical initiators (D) may be used. When a thermal radical initiator (D) is used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the polyfunctional (meth)acrylate compound.

[0092] (Adhesion enhancer) The negative-type photosensitive resin composition according to this embodiment may further contain an adhesion aid. A silane coupling agent can be preferably used as an adhesion enhancer. By using a silane coupling agent, for example, the adhesion between the substrate and the cured film can be further improved.

[0093] Examples of silane coupling agents that can be used include amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, (meth)acryloyl group-containing silane coupling agents, mercapto group-containing silane coupling agents, vinyl group-containing silane coupling agents, ureido group-containing silane coupling agents, sulfide group-containing silane coupling agents, and silane coupling agents having a cyclic anhydride structure.

[0094] Examples of amino group-containing silane coupling agents include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane. Examples of epoxy group-containing silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidylpropyltrimethoxysilane. Examples of silane coupling agents containing a (meth)acryloyl group include γ-((meth)acryloyloxypropyl)trimethoxysilane, γ-((meth)acryloyloxypropyl)methyldimethoxysilane, and γ-((meth)acryloyloxypropyl)methyldiethoxysilane. Examples of mercapto group-containing silane coupling agents include 3-mercaptopropyltrimethoxysilane. Examples of vinyl group-containing silane coupling agents include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane. Examples of ureido group-containing silane coupling agents include 3-ureidopropyltriethoxysilane. Examples of sulfide group-containing silane coupling agents include bis(3-(triethoxysilyl)propyl) disulfide and bis(3-(triethoxysilyl)propyl) tetrasulfide. Examples of silane coupling agents having a cyclic anhydride structure include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and 3-dimethylmethoxysilylpropyl succinic anhydride.

[0095] In this embodiment, a silane coupling agent having a cyclic anhydride structure is particularly preferred. Although the details are unclear, it is presumed that the cyclic anhydride structure readily reacts with the main chain, side chains, and / or terminals of polyimide (A), thereby providing a particularly good adhesion improvement effect.

[0096] When a silane coupling agent is used, it may be used alone or in combination with two or more adhesion promoters. When a silane coupling agent is used, the amount used is, for example, 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, more preferably 0.4 to 12 parts by mass, and even more preferably 0.5 to 10 parts by mass, when the amount of polyimide (A) used is 100 parts by mass.

[0097] (Surfactants) The photosensitive resin composition of this embodiment preferably contains a surfactant. This can further improve the coatability of the photosensitive resin composition and the flatness of the film. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, and acrylic-based surfactants. From another perspective, it is preferable that the surfactant is nonionic. The use of a nonionic surfactant is preferable, for example, in that it suppresses unintentional reactions with other components in the composition and improves the storage stability of the composition.

[0098] The surfactant preferably contains at least one of a fluorine atom and a silicon atom. This contributes to obtaining a uniform resin film (improved coatability), improved developability, and improved adhesive strength. Such a surfactant is preferably a nonionic surfactant containing at least one of a fluorine atom and a silicon atom. Examples of commercially available surfactants that can be used include the "MegaFac" series from DIC Corporation: F-251, F-253, F-281, F-430, F-477, F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-56 Examples include fluorine-containing oligomer surfactants such as F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, and R-94; fluorine-containing nonionic surfactants such as Futergent 250 and Futergent 251 manufactured by Neos Co., Ltd.; and silicone-based surfactants such as the SILFOAM® series (e.g., SD 100 TS, SD 670, SD 850, SD 860, SD 882) manufactured by Wacker Chemie. Furthermore, FC4430 and FC4432 manufactured by 3M can also be cited as preferred surfactants.

[0099] If the photosensitive resin composition of this embodiment contains a surfactant, it may contain one or more surfactants. If the photosensitive resin composition of this embodiment contains a surfactant, the amount is, for example, 0.001 to 1 part by mass, preferably 0.005 to 0.5 parts by mass, when the polyimide (A) content is 100 parts by mass.

[0100] (water) The photosensitive resin composition of this embodiment may contain water. The presence of water tends to facilitate the hydrolysis reaction of the silane coupling agent, for example, and improve the adhesion between the substrate and the cured film.

[0101] If the photosensitive resin composition of this embodiment contains water, the amount is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the total solid content (non-volatile components) of the photosensitive resin composition.

[0102] The water content of the photosensitive resin composition can be quantified by the Karl Fischer method.

[0103] (solvent) The photosensitive resin composition of this embodiment preferably contains a solvent. This allows for easy formation of a photosensitive resin film on a substrate (especially a substrate with steps) by coating. The solvent typically includes organic solvents. The organic solvent is not particularly limited, as long as it is capable of dissolving or dispersing each of the above-mentioned components and does not substantially react with each component.

[0104] Examples of organic solvents include acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, butyl acetate, γ-butyrolactone, methyl lactate, ethyl lactate, and butyl lactate. These may be used individually or in combination.

[0105] When the photosensitive resin composition of this embodiment contains a solvent, the photosensitive resin composition of this embodiment is usually varnish-like. More specifically, the photosensitive resin composition of this embodiment is preferably a varnish-like composition in which at least polyimide (A) and a polyfunctional (meth)acrylate compound are dissolved in the solvent. Because the photosensitive resin composition of this embodiment is varnish-like, a uniform film can be formed by coating. Furthermore, because the polyimide (A) and the polyfunctional (meth)acrylate compound are "dissolved" in the solvent, a homogeneous cured film can be obtained.

[0106] When using a solvent, the concentration of total solids (non-volatile components) in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 to 45% by mass. This range allows for sufficient dissolution or dispersion of each component. Furthermore, it ensures good coatability, leading to improved flatness during spin coating. Additionally, the viscosity of the photosensitive resin composition can be appropriately controlled by adjusting the content of non-volatile components. From another perspective, the proportion of polyimide (A) and polyfunctional (meth)acrylate compound in the overall composition is preferably 20 to 50% by mass. Using a relatively large amount of polyimide (A) and polyfunctional (meth)acrylate compound makes it easier to form a film of appropriate thickness.

[0107] (Other ingredients) The photosensitive resin composition of this embodiment may, in addition to the above-mentioned components, optionally contain components other than those listed above. Examples of such components include antioxidants, fillers such as silica, sensitizers, and film-forming agents.

[0108] (Preparation of negative-type photosensitive resin composition) The method for preparing the negative-type photosensitive resin composition in this embodiment is not limited, and known methods can be used depending on the components contained in the negative-type photosensitive resin composition. For example, the above components can be prepared by mixing and dissolving them in a solvent.

[0109] (Negative-type photosensitive resin composition) The negative-type photosensitive resin composition according to this embodiment is used by coating the negative-type photosensitive resin composition onto a surface having a metal such as Al or Cu, then pre-baking and drying to form a resin film, then exposing and developing the resin film to a desired shape to pattern it, and then heat-treating the resin film to cure it and form a cured film.

[0110] When producing the above permanent film, pre-baking conditions can include, for example, heat treatment at a temperature of 90°C to 130°C for 30 seconds to 1 hour. The heat treatment conditions can also include, for example, heat treatment at a temperature of 150°C to 250°C for 30 minutes to 10 hours, preferably at around 170°C for 1 to 6 hours.

[0111] The film obtained from the negative-type photosensitive resin composition of this embodiment has an elongation rate measured by tensile testing using a Tensilon tester, with a maximum value of 15-200%, preferably 20-150%, and an average value of 10-150%, preferably 15-120%.

[0112] The film obtained from the negative-type photosensitive resin composition of this embodiment preferably has a tensile strength of 20 MPa or more, and more preferably 30 to 300 MPa, as measured by a tensile test using a Tensilon test machine.

[0113] Furthermore, since the negative-type photosensitive resin composition of this embodiment contains polyimide (A) (negative-type photosensitive polymer) which has excellent hydrolysis resistance, even after performing a HAST test (unsaturated pressurized steam test) for 96 hours under conditions of a temperature of 130°C and a relative humidity of 85%RH, the decrease rate of the elongation rate (maximum value, average value) expressed by the following formula is 40% or less, preferably 35% or less, and more preferably 33% or less. [(Growth rate before the exam - Growth rate after the exam) / Growth rate before the exam)] × 100

[0114] The negative-type photosensitive resin composition of this embodiment exhibits excellent low-temperature curing properties. For example, a cured product obtained by curing the negative-type photosensitive resin composition of this embodiment at 170°C for 4 hours can have a glass transition temperature (Tg) of 200°C or higher, preferably 210°C or higher, and more preferably 220°C or higher.

[0115] Furthermore, the cured product obtained by curing the negative-type photosensitive resin composition of this embodiment at 170°C for 4 hours can have a storage modulus E' at 30°C of 2.0 GPa or higher, preferably 2.2 GPa or higher, and more preferably 2.5 GPa or higher. Furthermore, the storage modulus E' at 200°C can have a storage modulus E' of 0.5 GPa or higher, preferably 0.8 Pa or higher, and more preferably 1.0 GPa or higher.

[0116] The viscosity of the negative-type photosensitive resin composition according to this embodiment can be appropriately set according to the desired thickness of the resin film. The viscosity of the negative-type photosensitive resin composition can be adjusted by adding a solvent.

[0117] Cured products such as films obtained from the negative-type photosensitive resin composition of this embodiment exhibit excellent chemical resistance. Specifically, the film is immersed in a solution of less than 99% by mass of dimethyl sulfoxide and less than 2% by mass of tetramethylammonium hydroxide at 40°C for 10 minutes, then thoroughly washed with isopropyl alcohol and air-dried, and the film thickness after treatment is measured. The rate of change in film thickness between the film thickness after treatment and the film thickness before treatment is calculated using the following formula and evaluated as the film reduction rate. Formula: Film reduction rate (%) { (Film thickness after immersion - Film thickness before immersion) / Film thickness before immersion × 100 (%)}

[0118] The rate of change in film thickness is preferably 40% or less, and more preferably 30% or less. This ensures that the film thickness hardly decreases even when the cured film is subjected to a process in which it is immersed in dimethyl sulfoxide. As a result, a cured film that can maintain its function even after being subjected to such a process is obtained.

[0119] The negative-type photosensitive resin composition of this embodiment has suppressed curing shrinkage. It is spin-coated onto the surface of a silicon wafer to a dry film thickness of 10 μm, pre-baked at 120°C for 3 minutes, and then exposed to high-pressure mercury lamp light at 600 mJ / cm². 2 When a film is prepared by exposure and then heat treatment at 170°C for 120 minutes in a nitrogen atmosphere, the film thickness after pre-baking is denoted as film thickness A, and the film thickness after heat treatment is denoted as film thickness B, the curing shrinkage rate calculated from the following formula can preferably be 12% or less, more preferably 10% or less. Formula: Curing shrinkage rate [%] = {(Film thickness A - Film thickness B) / Film thickness A} x 100

[0120] The negative-type photosensitive resin composition of this embodiment has high heat resistance, and the resulting film can have a weight loss temperature (Td5) of 200°C or higher, preferably 300°C or higher, as measured by simultaneous thermogravimetric differential thermal analysis.

[0121] The film made from the negative-type photosensitive resin composition of this embodiment has suppressed curing shrinkage, and its linear thermal expansion coefficient (CTE) can be 200 ppm / °C or less, preferably 100 ppm / °C or less.

[0122] The film made from the negative-type photosensitive resin composition of this embodiment has excellent mechanical strength, and its modulus of elasticity at 25°C can be 1.0 to 5.0 GPa, preferably 1.5 to 3.0 GPa.

[0123] (Application) The negative-type photosensitive resin composition of this embodiment is used to form resin films for semiconductor devices such as permanent films and resists. Among these, it is preferable to use it in applications where a permanent film is used, from the viewpoint of achieving a good balance between improving the adhesion between the negative-type photosensitive resin composition and the Al pad after pre-baking and suppressing the generation of residue of the negative-type photosensitive resin composition during development, from the viewpoint of improving the adhesion between the cured film of the negative-type photosensitive resin composition after heat treatment and the metal, and from the viewpoint of improving the chemical resistance of the negative-type photosensitive resin composition after heat treatment.

[0124] In this embodiment, the resin film includes a cured film of a negative-type photosensitive resin composition. That is, the resin film according to this embodiment is obtained by curing a negative-type photosensitive resin composition.

[0125] The above-mentioned permanent film is composed of a resin film obtained by pre-baking, exposing, and developing a negative-type photosensitive resin composition, patterning it into a desired shape, and then curing it by heat treatment. The permanent film can be used as a protective film, interlayer film, or dam material for semiconductor devices.

[0126] The above-mentioned resist is composed of a resin film obtained by, for example, applying a negative-type photosensitive resin composition to an object to be masked by the resist using methods such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, and then removing the solvent from the negative-type photosensitive resin composition. An example of a semiconductor device according to this embodiment is shown in Figure 1.

[0127] The semiconductor device 100 according to this embodiment may be a semiconductor device comprising the resin film described above. Specifically, one or more of the group consisting of the passivation film 32, insulating layer 42, and insulating layer 44 in the semiconductor device 100 may be a resin film containing the cured product of this embodiment. Here, it is preferable that the resin film is the permanent film described above.

[0128] The semiconductor device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package is obtained by mounting the semiconductor device 100 on a wiring board via bumps 52.

[0129] The semiconductor device 100 comprises a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. The uppermost layer of the multilayer wiring layer is provided with an interlayer insulating film 30 and an uppermost wiring 34 provided on the interlayer insulating film 30. The uppermost wiring 34 is made of, for example, aluminum Al. A passivation film 32 is also provided on the interlayer insulating film 30 and the uppermost wiring 34. An opening is provided in a part of the passivation film 32 that exposes the uppermost wiring 34.

[0130] A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46. The insulating layer 42 has openings formed therein that connect to the uppermost wiring 34. The rewiring 46 is formed on the insulating layer 42 and within the openings provided in the insulating layer 42 and is connected to the uppermost wiring 34. The insulating layer 44 has openings that connect to the rewiring 46.

[0131] Bumps 52 are formed within the openings provided in the insulating layer 44, for example, via a UBM (Under Bump Metallurgy) layer 50. The semiconductor device 100 is connected to a wiring board or the like via the bumps 52. Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted as long as they do not impair the effects of the present invention. [Examples]

[0132] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The following compounds were used in the examples.

[0133] 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane (hereinafter also referred to as MED-J), represented by the following formula [ka]

[0134] 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (hereinafter also referred to as TFMB), represented by the following formula [ka]

[0135] 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter also referred to as BAPA), represented by the following formula [ka]

[0136] 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter also referred to as BAFA), represented by the following formula [ka]

[0137] The following formula represents 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME) [ka]

[0138] The following formula represents 3,3',4,4'-benzophenonetetracarboxylic dianhydride (hereinafter also referred to as BTDA) [ka]

[0139] [Example 1] First, 10.83 g (38.3 mmol) of MED-J and 25.77 g (41.7 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and condenser. Then, 109.80 g of GBL was added to the reaction vessel. After aeration with nitrogen for 10 minutes, the temperature was raised to 60°C while stirring and the reaction was allowed to proceed for 1.5 hours. Subsequently, the reaction was further carried out at 180°C for 3 hours to polymerize the diamine and acid anhydride, thereby preparing a polymerization solution. The resulting reaction solution was diluted with tetrahydrofuran to prepare a dilution, and then a white solid was precipitated by adding the dilution dropwise to methanol. The obtained white solid was collected and vacuum-dried at 80°C to obtain 31.17 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 55,900 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 2.64. The resulting polymer contained repeating units represented by the following formula in part. [ka]

[0140] [Example 2] First, 3.87 g (13.7 mmol) of MED-J, 5.02 g (13.7 mmol) of BAFA, and 20.17 g (32.6 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and condenser. Then, 7.17 g of GBL was added to the reaction vessel. After aeration with nitrogen for 10 minutes, the temperature was raised to 60°C while stirring and the reaction was allowed to proceed for 1.5 hours. Subsequently, the reaction was further carried out at 180°C for 3 hours to polymerize the diamine, bisaminophenol, and acid anhydride, thereby preparing a polymerization solution. The resulting reaction solution was diluted with tetrahydrofuran to prepare a dilution, and then a white solid was precipitated by adding the dilution dropwise to methanol. The obtained white solid was collected and vacuum-dried at 80°C to obtain 24.70 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 18,500 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 1.81. The resulting polymer contained repeating units represented by the following formula in part. [ka]

[0141] [Example 3] First, 3.87 g (13.7 mmol) of MED-J, 3.54 g (13.7 mmol) of BAPA, and 20.17 g (32.6 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and condenser. Then, 82.73 g of GBL was added to the reaction vessel. After aeration with nitrogen for 10 minutes, the temperature was raised to 60°C while stirring and the reaction was allowed to proceed for 1.5 hours. Subsequently, the reaction was further carried out at 180°C for 3 hours to polymerize the diamine, bisaminophenol, and acid anhydride, thereby preparing a polymerization solution. The resulting reaction solution was diluted with tetrahydrofuran to prepare a dilution, and then a white solid was precipitated by adding the dilution dropwise to methanol. The obtained white solid was collected and vacuum-dried at 80°C to obtain 23.13 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 20,900 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 1.92. The resulting polymer contained repeating units represented by the following formula in part. [ka]

[0142] [Comparative Examples 1-3] For Comparative Examples 1 to 3, synthesis was carried out using the same method as in Example 2, except for the conditions listed in Table 1. For Comparative Examples 1 and 2, gelation occurred during the polymerization reaction, making it difficult to continue the reaction; therefore, solvent solubility in GBL was marked as "×".

[0143] [Comparative Example 4] First, 12.55 g (44.4 mmol) of MED-J and 17.90 g (55.6 mmol) of BTDA were placed in a reaction vessel of appropriate size equipped with a stirrer and a condenser. Then, 91.36 g of GBL was added to the reaction vessel. After aeration with nitrogen for 10 minutes, the temperature was raised to 60°C while stirring and the reaction was allowed to proceed for 1.5 hours. Subsequently, the reaction was further carried out at 180°C for 3 hours to polymerize the diamine and acid anhydride, thereby preparing a polymerization solution. The resulting reaction solution was diluted with tetrahydrofuran to prepare a dilution, and then a white solid was precipitated by adding the dilution dropwise to methanol. The obtained white solid was collected and vacuum-dried at 60°C to obtain 23.77 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 8,900 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 1.69.

[0144] [Comparative Example 5] First, 13.53 g (47.9 mmol) of MED-J and 16.78 g (52.1 mmol) of BTDA were placed in a reaction vessel of appropriate size equipped with a stirrer and a condenser. Then, 90.95 g of GBL was added to the reaction vessel. After aeration with nitrogen for 10 minutes, the temperature was raised to 60°C while stirring and the reaction was allowed to proceed for 1.5 hours. Subsequently, the reaction was further carried out at 180°C for 3 hours to polymerize the diamine and acid anhydride, thereby preparing a polymerization solution. The resulting reaction solution was diluted with tetrahydrofuran to prepare a dilution, and then a white solid was precipitated by adding the dilution dropwise to methanol. The obtained white solid was collected and vacuum-dried at 60°C to obtain 26.16 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 28,400 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 1.95.

[0145] [Solubility in organic solvents] The solubility of the negative-type photosensitive polymers obtained in Examples 1-3 and Comparative Examples 3-5 in γ-butyl lactone (GBL) was evaluated according to the following criteria. The results are shown in Table 1. (Evaluation criteria for solubility) ○: Polymer dissolved at 5% by mass or more △: Polymer dissolves at 1-5% by mass. ×: Polymer dissolution is less than 1% by mass.

[0146] [Hydrolysis resistance] The weight-average molecular weight reduction rate of the negative-type photosensitive polymers obtained in the examples and comparative examples was measured under the following conditions. The results are shown in Table 1. (Condition: No triethylamine added) When 100 parts by mass of negative-type photosensitive polymer were added to 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water, and stirred at 100°C for 6 hours, the following formula was used to calculate the result. Formula: [(Weight-average molecular weight before testing - Weight-average molecular weight after testing) / Weight-average molecular weight before testing] × 100 (Condition: Addition of triethylamine) When 100 parts by mass of negative-type photosensitive polymer was added to 10 parts by mass of triethylamine, 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water, and stirred at 100°C for 6 hours, the following formula was used to calculate the result. Formula: [(Weight-average molecular weight before testing - Weight-average molecular weight after testing) / Weight-average molecular weight before testing] × 100

[0147] [Polymer stability] Compositions were prepared by adding the adhesion aid KBM-503P (2 parts by mass) and the surfactant FC4432 (0.1 parts by mass) to the GBL solution of the polymer obtained in Example 1 and Comparative Example 5. When these compositions were stored at room temperature for one day, only the composition of Comparative Example 5 thickened and gelled, making it impossible to evaluate its elongation and other properties.

[0148] [Table 2]

[0149] As shown in Table 1, the negative photosensitive polymer of the present invention obtained in the examples is excellent in solubility in organic solvents, and further hydrolysis is suppressed, so it is presumed that the decrease in elongation is small and the decrease in mechanical strength is suppressed.

[0150] The following compounds were used in the preparation of the negative photosensitive resin composition. (Crosslinking agent) · Acrylate compound 1: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DPH) · Epoxy compound 1: Epoxy compound represented by the following chemical formula (manufactured by Printec Co., Ltd., VG3101L) [Chemical formula]

[0151] (Additive) · Additive 1: Phenol compound represented by the following formula (manufactured by Honshu Chemical Industry Co., Ltd., TrisP-PA) [Chemical formula]

[0152] (Polymerization initiator) · Photo radical generator: Oxime ester-based photo radical generator (manufactured by ADEKA Corporation, NCI-730) · Thermal radical generator: Dicumyl peroxide (Perkadox BC, peroxide, manufactured by Kayaku Akzo Corporation)

[0153] (Adhesion promoter) · Adhesion promoter 1: 3-Methacryloxypropyltrimethoxysilane (KBM-503P, manufactured by Shin-Etsu Chemical Co., Ltd.) · Adhesion promoter 2: 3-Trimethoxysilylpropyl succinic anhydride (X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0154] (Surfactant) • Surfactant 1: Surfactant containing a fluorocarbon chain (FC-4432, manufactured by Sumitomo 3M Co., Ltd.)

[0155] (solvent) • Solvent 1: Water • Solvent 2: γ-butyllactone (GBL)

[0156] [Example 4] (Preparation of negative-type photosensitive resin composition) A photosensitive resin composition was prepared by mixing the polymer from Example 1 (100 parts by mass of polymer) with the components shown in Table 2, which had been pre-dissolved to form a 26.5 wt% GBL solution. The obtained negative-type photosensitive resin composition was spin-coated onto the surface of a silicon wafer to a dry film thickness of 10 μm, pre-baked at 120°C for 3 minutes, and then exposed to high-pressure mercury lamp light at 600 mJ / cm². 2 The film was prepared by exposing it to light and then heat-treating it at 170°C for 120 minutes under a nitrogen atmosphere. The elongation of the obtained film was measured using the method described below, and its patterning characteristics were evaluated. The results are shown in Table 2.

[0157] [Growth rate] Tensile tests (stretching speed: 5 mm / min) were performed on test specimens (6.5 mm × 60 mm × 10 μm thick) cut from the film obtained in Example 4 in a 23°C atmosphere. The tensile tests were performed using an Orientec tensile testing machine (Tensilon RTC-1210A). Five test specimens were measured, and the tensile elongation was calculated from the fracture distance and initial distance. The average and maximum values ​​of the elongation were then determined. Furthermore, the test pieces cut from the film obtained in Example 4 were subjected to a HAST (Unsaturated Pressurized Steam Test) for 96 hours under conditions of a temperature of 130°C and a relative humidity of 85%RH, and the average and maximum values ​​of the elongation were determined in the same manner as described above.

[0158] [Evaluation of patterning characteristics] The photosensitive resin composition of Example 4 was confirmed to be sufficiently patternable by exposure and development as follows. The photosensitive resin composition of Example 4 was applied onto an 8-inch silicon wafer using a spin coater. After application, it was pre-baked on a hot plate at 110 °C for 3 minutes in the atmosphere to obtain a coating film with a film thickness of approximately 5.0 μm. This coating film was irradiated with i-line through a mask on which a via pattern with a width of 20 μm was drawn. For the irradiation, an i-line stepper (manufactured by Nikon Corporation, NSR-4425i) was used. After exposure, cyclopentanone was used as the developer, and spray development was performed for 30 seconds. Further, PGMEA was used as the developer, and spray development was performed for 10 seconds to dissolve and remove the unexposed portions, thereby obtaining a via pattern. The cross-section of the obtained via pattern was observed using a desktop SEM. The width at the height midway between the bottom surface and the opening of the via pattern was defined as the via width, and evaluation was performed based on the following criteria. Good patterning property: The 20-μm via pattern is open Poor patterning property: The 20-μm via pattern is not open The coating film obtained from the photosensitive resin composition of Example 4 had good patterning property.

[0159] [Table 3]

[0160] As described in Table 2, the film obtained from the negative photosensitive resin composition containing the negative photosensitive polymer of the present invention is excellent in elongation, and further contains a negative photosensitive polymer excellent in hydrolysis resistance. Therefore, it was clarified that the film is excellent in mechanical strength even after the HAST test. Also, the patterning property is good, and it was confirmed that it is suitably used as a negative photosensitive resin composition.

[0161] This application claims priority based on Japanese Patent Application No. 2,021-105,686 filed on June 25, 2021, and incorporates the entire disclosure thereof herein.

Explanation of Reference Signs

[0162] 100 Semiconductor device 30 Interlayer insulating film 32 Passivation membrane 34 Top layer wiring 40 Redistribution layer 42 Insulating layer 44 Insulating layer 46 Rewiring 50 UBM layers 52 Bump

Claims

1. (A) Polyimide and (B) A crosslinking agent containing a polyfunctional (meth)acrylate, (C) Photopolymerization initiator and Includes, Polyimide (A) is, A structural unit (a1) represented by the following general formula (a1), A structural unit (a2) represented by the following general formula (a2), A negative-type photosensitive resin composition containing [the specified element]. 【Chemistry 1】 【Chemistry 2】 (In general formula (a1), Y is selected from the bases represented by the following general formulas (a1-1), (a1-2), and (a1-3), and multiple Ys may be the same or different.) 【Transformation 3】 (In general formula (a1-1), R ７ and R ８ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and there are multiple R groups. ７ Multiple Rs exist ８ They may be the same or different. ９ R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and there are multiple R groups. ９ The elements can be identical or different. * indicates a combination. In the general formula (a1-2), R １０ and R １１ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and when there are a plurality of Rs １０ among themselves, and when there are a plurality of Rs １１ among themselves, they may be the same or different. * represents a bond. In the general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms, or a divalent aromatic group. * indicates a bonding position. In general formula (a2), R １ ~R ４ Each independently represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R １ and R ２ These are different groups, R ３ and R ４ These are different groups. X １ It is a single bond, -SO ２ X represents -, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, and there are multiple such X groups. １ They may be the same or different.

2. The negative-type photosensitive resin composition according to claim 1, wherein the polyimide (A) further comprises a structural unit (a3) ​​represented by the following general formula (a3). 【Chemistry 4】 (In general formula (a3), Q １ Q ２ These independently represent a hydroxyl group and a carboxyl group, respectively. ２ It is a single bond, -SO ２ X represents -, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, and there are multiple such X groups. ２ They may be the same or different.

3. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the polyimide (A) comprises a structural unit represented by the following general formula (1). 【Transformation 5】 (In general formula (1), R １ ~R ４ , X １ (This is equivalent to general formula (a2), and Y is equivalent to general formula (a1).)

4. The negative-type photosensitive resin composition according to claim 2, wherein the polyimide (A) comprises a structural unit represented by the following general formula (2). 【Transformation 6】 (In general formula (2), Q １ Q ２ , and X ２ (This is equivalent to general formula (a3), and Y is equivalent to general formula (a1).)

5. A structural unit (a1) represented by the following general formula (a1), A structural unit (a2) represented by the following general formula (a2), A negative-type photosensitive polymer containing [a specific compound / component]. 【Transformation 7】 【Transformation 8】 (In general formula (a1), Y is selected from the bases represented by the following general formulas (a1-1), (a1-2), and (a1-3), and multiple Ys may be the same or different.) 【Chemistry 9】 (In general formula (a1-1), R ７ and R ８ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and there are multiple R groups. ７ Multiple Rs exist ８ They may be the same or different. ９ R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and there are multiple R groups. ９ The elements can be identical or different. * indicates a combination. In general formula (a1-2), R １０ and R １１ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and there are multiple R groups. １０ Multiple Rs exist １１ The elements can be identical or different. * indicates a combination. In the general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms, or a divalent aromatic group. * indicates a bonding position. In general formula (a2), R １ ~R ４ Each independently represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R １ and R ２ These are different groups, R ３ and R ４ These are different groups. X １ It is a single bond, -SO ２ X represents -, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, and there are multiple such X groups. １ They may be the same or different.

6. The negative-type photosensitive polymer according to claim 5, further comprising a structural unit (a3) ​​represented by the following general formula (a3). 【Chemistry 10】 (In general formula (a3), Q １ Q ２ These independently represent a hydroxyl group and a carboxyl group, respectively. ２ It is a single bond, -SO ２ X represents -, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, and there are multiple such X groups. ２ They may be the same or different.

7. A negative-type photosensitive polymer according to claim 5 or 6, comprising a structural unit represented by the following general formula (1). 【Chemistry 11】 (In general formula (1), R １ ~R ４ , X １ (This is equivalent to general formula (a2), and Y is equivalent to general formula (a1).)

8. A negative-type photosensitive polymer according to claim 5 or 6, comprising a structural unit represented by the following general formula (2). 【Chemistry 12】 (In general formula (2), Q １ Q ２ , and X ２ (This is equivalent to general formula (a3), and Y is equivalent to general formula (a1).)

9. The negative-type photosensitive polymer according to claim 6, wherein the decrease rate of the weight-average molecular weight measured under the following conditions is 9% or less. (conditions) When 100 parts by mass of the negative-type photosensitive polymer is added to 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water, and the mixture is stirred at 100°C for 6 hours, the result is calculated using the following formula. Formula: [(Weight-average molecular weight before testing - Weight-average molecular weight after testing) / Weight-average molecular weight before testing] × 100

10. A cured film comprising a cured product of the negative-type photosensitive resin composition according to claim 1 or 2.

11. A semiconductor device comprising a resin film containing a cured product of the negative-type photosensitive resin composition according to claim 1 or 2.

12. Interlayer insulating film and A resin film provided on the interlayer insulating film, comprising a cured product of the negative-type photosensitive resin composition according to claim 1 or 2, The rewiring embedded in the aforementioned resin film, A semiconductor device characterized by comprising the following features.

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