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 comprises a polyimide (A), a polyfunctional (meth)acrylate-containing cross-linking agent (B), and a photopolymerization initiator (C), wherein the polyimide (A) includes a structural unit (a1) represented by general formula (a1), a structural unit (a2) represented by general formula (a2), and a structural unit (a3) represented by general formula (a3).

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 project] [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 structural unit (a3) ​​represented by the following general formula (a3), A negative-type photosensitive resin composition containing [the specified element]. [ka] [ka] [ka] (In general formula (a1), Y is a divalent organic group.) 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 X 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 there are multiple X groups. 1 They may be the same or different. In general formula (a3), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and a plurality of Qs may be the same or different. R 5 and R 6 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. m1 and m2 each independently represent an integer of 1 to 3. 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 Xs 2 may be the same or different.) [2] The negative photosensitive resin composition according to [1], wherein at least one of both ends of the polyimide (A) is a (meth) acrylate group. [3] (A) A polyimide, (B) A crosslinking agent containing a polyfunctional (meth) acrylate, (C) A photoinitiator, comprising, The 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 photosensitive resin composition comprising, wherein at least one of both ends of the polyimide (A) is a (meth) acrylate group. [Chemical formula] [Chemical formula] (In general formula (a1), Y is a divalent organic group. 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, and R 1 and R 2 are different groups, and R 3 and R 4 are different groups. X 1 X 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 there are multiple X groups. 1 They may be the same or different. [4] The negative-type photosensitive resin composition according to any one of [1] to [3], wherein Y in the general formula (a1) is a divalent group containing an alkylene group, or a divalent group containing at least one aromatic ring. [5] A negative-type photosensitive resin composition according to any one of [1] to [4], wherein Y in the general formula (a1) is a divalent organic group selected from the following general formulas (a1-1), (a1-2), and (a1-3). [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 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 The elements can be identical or different. * indicates a bonding action. In general formulas (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms, or a divalent aromatic group. * indicates a bond. [6] The polyimide (A) comprises a structural unit represented by the following general formula (1), a negative-type photosensitive resin composition according to any one of [1] to [5]. [ka] (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).) [7] The polyimide (A) comprises a structural unit represented by the following general formula (2), a negative-type photosensitive resin composition according to any one of [1], [2], and [4] to [6]. [ka] (In general formula (2), Q, R 5 , R 6 , m1, m2, and X 2 (This is equivalent to general formula (a3), and Y is equivalent to general formula (a1).) [8] A structural unit (a1) represented by the following general formula (a1), A structural unit (a2) represented by the following general formula (a2), A structural unit (a3) ​​represented by the following general formula (a3), A negative-type photosensitive polymer containing [a specific compound / component]. [ka] [ka] [ka] (In general formula (a1), Y is a divalent organic group.) 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 1X 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 there are multiple X groups. 1 They may be the same or different. In general formula (a3), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different. R 5 and R 6 Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 alkoxy group. m1 and m2 each independently represent integers between 1 and 3. X 2 X 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 there are multiple X groups. 2 They may be the same or different. [9] The negative-type photosensitive polymer according to [8], wherein at least one of both ends is a (meth)acrylate group.

[10] A structural unit (a1) represented by the following general formula (a1), A structural unit (a2) represented by the following general formula (a2), Includes, A negative-type photosensitive polymer in which at least one of both ends is a (meth)acrylate group. [ka] [ka] (In general formula (a1), Y is a divalent organic group.) 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 1X 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 there are multiple X groups. 1 They may be the same or different.

[11] The negative-type photosensitive polymer according to any one of [8] to

[10] , wherein Y in the general formula (a1) is a divalent group containing an alkylene group, or a divalent group containing at least one aromatic ring.

[12] A negative-type photosensitive polymer according to any one of [8] to

[11] , wherein Y in the general formula (a1) is a divalent organic group selected from the following general formulas (a1-1), (a1-2), and (a1-3). [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 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 The elements can be identical or different. * indicates a bonding action. In general formulas (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms, or a divalent aromatic group. * indicates a bond.

[13] A negative-type photosensitive polymer according to any of [8] to

[12] , comprising a structural unit represented by the following general formula (1). [ka] (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).)

[14] A negative-type photosensitive polymer according to any of [8], [9], and

[11] to

[13] , comprising a structural unit represented by the following general formula (2). [ka] (In general formula (2), Q, R 5 , R 6 , m1, m2, and X 2 (This is equivalent to general formula (a3), and Y is equivalent to general formula (a1).)

[15] A negative-type photosensitive polymer according to any of [8] to

[14] , wherein the rate of decrease in weight-average molecular weight measured under the following conditions is 15% 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 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

[16] A cured film comprising a cured product of a negative-type photosensitive resin composition described in any of [1] to [7].

[17] A semiconductor device comprising a resin film containing a cured product of a negative-type photosensitive resin composition described in any of [1] to [7].

[18] 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 [7], The rewiring embedded in the aforementioned resin film, The semiconductor device according to

[17] , characterized by comprising

[17] . [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic cross-sectional view of the semiconductor device according to this embodiment. [Modes for carrying out the invention]

[0013] 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". 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.

[0014] [Polyimide (A)] The polyimide (A) (negative photosensitive polymer) of this embodiment can be described by the first or second embodiment.

[0015] (First Embodiment) The polyimide (A) (negative photosensitive polymer) of this embodiment includes a structural unit (a1) represented by the following general formula (a1), a structural unit (a2) represented by the following general formula (a2), and a structural unit (a3) ​​represented by the following general formula (a3).

[0016] [ka]

[0017] In general formula (a1), Y is a divalent organic group. As the divalent organic group, any known organic group within the range that exhibits the effects of the present invention can be used, but from the viewpoint of the effects of the present invention, Y is preferably a divalent group containing an alkylene group, or a divalent group containing at least one aromatic ring. The alkylene group is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. Examples of aromatic rings include a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring, and a divalent biphenyl group, with a divalent benzene ring or a divalent biphenyl group being preferred. In general formula (a1), Y is preferably a divalent organic group selected from the following general formulas (a1-1), (a1-2), and (a1-3).

[0018] [ka]

[0019] 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. 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.

[0020] 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.

[0021] 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.

[0022] 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 R10 at least one of and R 11 at least one of is an alkyl group having 1 to 3 carbon atoms, and more preferably the three Rs 10 are an alkyl group having 1 to 3 carbon atoms, one R 10 is a hydrogen atom, and the three Rs 11 are an alkyl group having 1 to 3 carbon atoms, one R 11 is a hydrogen atom, and particularly preferably the three Rs 10 are a methyl group, one R 10 is a hydrogen atom, and the three Rs 11 are a methyl group, one R 11 is a hydrogen atom. * represents a bond.

[0023] In the general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group, and the divalent aromatic group is preferred. Examples of the divalent aromatic group include a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring, and a divalent biphenyl group, and the divalent benzene ring is preferred. * represents a bond.

[0024]

Chemical formula

[0025] 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, R 1 and R 2 are different groups, R 3 and R 4 are different groups. R 1 ~R 4 are preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of the effects of the present invention.

[0026] X 1X 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 there are multiple X groups. 1 They may be the same or different.

[0027] X 1 From the viewpoint of the effects of the present invention, it 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, 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.

[0028] The polyimide (A) of this embodiment contains a structural unit represented by general formula (a2), which suppresses the influence of the imide ring on electrons, inhibits hydrolysis of the polyimide, and exhibits excellent mechanical strength such as elongation, as well as excellent solubility in organic solvents. In other words, the polyimide (A) of this embodiment and the negative-type photosensitive resin composition containing polyimide (A) have an excellent balance of these properties.

[0029] [ka]

[0030] In general formula (a3), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different.

[0031] Examples of divalent to tetravalent organic groups having 1 to 10 carbon atoms include ester groups, divalent to tetravalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms, and divalent to tetravalent alicyclic hydrocarbon groups having 3 to 10 carbon atoms. These hydrocarbon groups may contain heteroatoms such as oxygen, nitrogen, and sulfur atoms, and may have ester bonds, thioester bonds, urethane bonds, thiourethane bonds, urea bonds, etc., in their structure.

[0032] R 5 and R 6Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 alkoxy group. m1 and m2 each independently represent integers between 1 and 3.

[0033] X 2 X 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 there are multiple X groups. 2 They may be the same or different.

[0034] X 2 From the viewpoint of the effects of the present invention, it is preferable that the group is 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.

[0035] The polyimide (A) of this embodiment may specifically include structural units represented by the following general formula (1).

[0036] [ka]

[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 specifically include structural units represented by the general formula (1) above, as well as structural units represented by the general formula (2) below.

[0039] [ka]

[0040] In general formula (2), Q, R 5 , R 6 , m1, m2, and X 2This is equivalent to general formula (a3), and Y is equivalent to general formula (a1).

[0041] The polyimide (A) of this embodiment may specifically include the structural unit represented by the general formula (3) described above.

[0042] [ka]

[0043] In general formula (3), Q, R 5 , R 6 , m1, m2, and X 2 is synonymous with general formula (a3), Y is synonymous with general formula (a1), and R 1 ~R 4 , X 1 This is equivalent to the general formula (a2).

[0044] The polyimide (A) of this embodiment includes the above-mentioned structural units and may further include the following structural units in part.

[0045] [ka]

[0046] In these general formulas, Q, R 5 , R 6 , m1, m2, and X 2 This is equivalent to general formula (a3), and Y is equivalent to general formula (a1). In this embodiment, it is preferable that polyimide (A) has at least one (meth)acrylate group at both ends. The inclusion of this group provides superior mechanical strength, such as elongation. Having a (meth)acrylate group is advantageous. 1 It can be analyzed by 1H-NMR.

[0047] Specifically, polyimide (A) preferably has at least one of the terminal structures (a4) to (a12) represented by the following general formulas (a4) to (a12) at at least one of its ends, and it is preferable that it has terminal structure (a4). [ka] TIFF0007882253000026.tif176153

[0048] In general formula (a4), Q is equivalent to general formula (a3), and Y is equivalent to general formula (a1). 7 This represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. m3 represents an integer between 1 and 3. * indicates a combination. In general formula (a5), Q is equivalent to general formula (a3), and X 1 , R 1 ~R 4 This is equivalent to general formula (a2). 7 m3 is equivalent to general formula (a4). * indicates a bond. In general formulas (a6) to (a12), Q, R 5 , R 6 , m1, m2, and X 2 This is equivalent to the general formula (a3). 7 m3 is equivalent to general formula (a4). * indicates a bond.

[0049] The weight-average molecular weight of polyimide (A) in this embodiment is 5,000 to 200,000, preferably 10,000 to 100,000.

[0050] The polyimide (A) in this embodiment has suppressed hydrolysis, and the polyimide (A) and the negative-type photosensitive resin composition containing polyimide (A) can be used to obtain cured products such as films with excellent mechanical strength, such as elongation. 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.

[0051] <Method for producing polyimide (A)> The method for producing polyimide (A) (negative-type photosensitive polymer) having structural units represented by general formula (1) and general formula (2) of this embodiment, or polyimide (A) (negative-type photosensitive polymer) having structural units represented by general formula (3), is as follows: Step 1 involves imidizing an acid anhydride (a1') represented by the following general formula (a1'), a diamine (a2') represented by the following general formula (a2'), and a bisaminophenol (a3') represented by the following general formula (a3') at a temperature of 100°C to 250°C. Step 2 involves reacting a compound having a (meth)acrylate group with the hydroxyl group of the bisaminophenol (a3') structural unit of the polymer obtained in Step 1 with the compound having a (meth)acrylate group, thereby introducing a group containing a (meth)acrylate group. Includes. According to this embodiment, polyimide (A) with excellent solubility in organic solvents can be synthesized by a simple method.

[0052] [ka]

[0053] In general formula (a1'), Y is synonymous with general formula (a1) and is preferably selected from the groups represented by general formulas (a1-1), (a1-2), or (a1-3).

[0054] [ka]

[0055] In general formula (a2'), R 1 ~R 4 , X 1This is equivalent to the general formula (a2).

[0056] [ka]

[0057] In general formula (a3'), X 2 This is equivalent to the general formula (a3).

[0058] To control the molecular weight of the resulting polyhydroxyimide, it is also possible to carry out the reaction by adding a small amount of acid anhydride or aromatic amine as an end-capping agent.

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

[0060] The equivalent ratio of the acid anhydride (a1'), diamine (a2'), and bisaminophenol (a3') in the imidation reaction of Step 1 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 the acid anhydride (a1'), diamine (a2'), and bisaminophenol (a3') used is not particularly limited, but it is preferable that the equivalent ratio of the diamine (a2') and bisaminophenol (a3') to the 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] Furthermore, from the viewpoint of improving mechanical properties, even if the equivalent ratio of diamine (a2') and bisaminophenol (a3') to acid anhydride (a1') falls outside the above range, the apparent molecular weight can be increased by cross-linking the resin's side chains. Step 1 (imidation reaction step) can be carried out in an organic solvent by a known method.

[0062] 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.

[0063] 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.

[0064] Step 1 yields a polyhydroxyimide having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2'), or a polyhydroxyimide containing a structural unit represented by the following general formula (3'). In Step 1, the polyhydroxyimide can be purified by known methods, but by improving the dehydration efficiency during polymerization, Steps 1 and 2 can be carried out continuously without purifying the obtained polyhydroxyimide.

[0065] [ka]

[0066] In these general formulas, R 1 ~R 4 , X 1 This is equivalent to the general formula (a2), and X 2 is synonymous with general formula (a3), and Y is synonymous with general formula (a1), preferably selected from the groups represented by the general formulas (a1-1), (a1-2), or (a1-3). Step 2 involves reacting the hydroxyl group of the polyhydroxyimide obtained in Step 1 with a compound containing a (meth)acrylate group to introduce a crosslinking group containing a (meth)acrylate group. The crosslinking groups introduced into the polyimide (A) react with the crosslinking agent (B), described later, during the exposure process, making the exposed area insoluble in organic solvents.

[0067] Examples of compounds containing a (meth)acrylate group include 2-isocyanatoethyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyl oxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.

[0068] To introduce a crosslinking group containing a (meth)acrylate group into polyhydroxyimide, the polyhydroxyimide and the compound containing the (meth)acrylate group are reacted in an organic solvent at 60°C to 150°C for about 2 to 10 hours while being mixed. The reaction is not particularly limited, but can be carried out at atmospheric pressure.

[0069] The compound containing the (meth)acrylate group can be appropriately selected in accordance with the amount of crosslinking group introduced to the polyhydroxyimide. For example, it can be added in an amount of 0.8 to 3.0 molars relative to the molar amount of hydroxyl groups in the polyhydroxyimide, and preferably 2.0 to 3.0 molars. If the polyhydroxyimide has a group that can introduce a crosslinking group, that group can be added to the molar amount.

[0070] 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. During the reaction, bases such as triethylamine and 1,1,3,3-tetramethylguanidine can also be added.

[0071] Step 2 makes it possible to obtain polyimide (A) having structural units represented by general formula (1) and structural units represented by general formula (2), or polyimide (A) having structural units represented by general formula (3).

[0072] In step 2, the reaction solution containing the polyhydroxyimide obtained in step 1 can be purified by reprecipitation or the like, and the resulting polyhydroxyimide can be used; however, the reaction solution from step 1 can be used directly in step 2.

[0073] By the manufacturing method of this embodiment described above, a reaction solution containing the polyimide (A) (negative-type 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 reaction step can be used, and it may be the same organic solvent as in the reaction step, or a different organic solvent may be used.

[0074] Alternatively, this reaction solution can be added to a poor solvent to reprecipitate the polyimide (A) resin to remove unreacted monomers, and the resulting 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 substances are a concern, it is preferable to dissolve it again in an organic solvent and filter and purify it to obtain a varnish.

[0075] (Second Embodiment) The polyimide (A) of this embodiment is The structural unit (a1) represented by the general formula (a1) above, The structural unit (a2) represented by the general formula (a2) above, It contains a (meth)acrylate group at least one of its ends.

[0076] In this embodiment, polyimide (A) has at least one (meth)acrylate group at both ends. The inclusion of this group provides excellent mechanical strength, such as elongation. Having a (meth)acrylate group means that 1 It can be analyzed by 1H-NMR. Specifically, polyimide (A) preferably has at least one of the terminal structures represented by the general formula (a4) (a4) or the terminal structure represented by the general formula (a5) (a5) at at least one of its ends, and it is preferable that it has terminal structure (a4).

[0077] The polyimide (A) of this embodiment preferably contains structural units represented by the following general formula (1).

[0078] [ka] 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).

[0079] The weight-average molecular weight of polyimide (A) in this embodiment is 5,000 to 200,000, preferably 10,000 to 100,000.

[0080] The polyimide (A) in this embodiment has suppressed hydrolysis, and the polyimide (A) and the negative-type photosensitive resin composition containing polyimide (A) can be used to obtain cured products such as films with excellent mechanical strength, such as elongation. 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.

[0081] <Method for producing polyimide (A)> The polyimide (A) of this embodiment can be produced in the same manner as in the first embodiment, except that the bisaminophenol (a3') represented by the general formula (a3') is not used.

[0082] In this embodiment, there are no particular restrictions on the equivalent ratio of the acid anhydride (a1') to the diamine (a2') used, however, it is preferable that the equivalent ratio of diamine (a2') to acid anhydride (a1') is in the range of 0.70 to 1.30. Below 0.70, the molecular weight is low and brittle, resulting in weak mechanical strength. Conversely, above 1.30, the molecular weight is low and brittle, resulting in weak mechanical strength. In other words, if the equivalent ratio is within the above range, it exhibits excellent mechanical strength and manufacturing stability.

[0083] The polyimide (A) (negative-type photosensitive polymer) of this embodiment exhibits excellent hydrolysis resistance, with a weight-average molecular weight reduction rate of 15% or less, preferably 12% 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 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

[0084] In this embodiment, the negative-type photosensitive polymer has a weight-average molecular weight reduction rate within the above range, which allows for the production of cured products such as films with excellent mechanical strength, including elongation.

[0085] Table A below shows preferred formulations of the negative-type photosensitive polymer in this embodiment.

[0086] [Table 1]

[0087] MED-J: 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane HFBAPP: 4,4'-(hexafluoroisopropylidene)bis[(4-aminophenoxy)benzene] BAPA: 2,2-bis(3-amino-4-hydroxyphenyl)propane BAFA: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane ·TMPBP-TME:4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate • TMHQ: p-phenylenebis(trimellitate anhydrous) • AOI: 2-Isocyanatoethyl acrylate • MOI: 2-Isocyanatoethyl methacrylate

[0088] [Crosslinking agent (B)] The crosslinking agent (B) includes a polyfunctional (meth)acrylate. The aforementioned polyfunctional (meth)acrylate is a compound having two or more (meth)acryloyl groups, and any conventionally known compound can be used as long as it can exhibit the effects of the present invention. In this embodiment, the (meth)acrylic group refers to an acrylic group or a methacrylic group.

[0089] Specific examples of polyfunctional (meth)acrylates include difunctional (meth)acrylates such as diethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, and polyethylene glycol #400 di(meth)acrylate; trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and ethoxylated isocyanuric acid triacrylate; tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate; octafunctional (meth)acrylates such as tripentaerythritol octa(meth)acrylate; and decafunctional (meth)acrylates such as tetrapentaerythritol deca(meth)acrylate. One or more of these may be used.

[0090] From the viewpoint of the effects of the present invention, the amount of crosslinking agent (B) per 100 parts by mass of polyimide (A) can be 1 part by mass or more and 30 parts by mass or less, preferably 2 parts by mass or more and 20 parts by mass or less, and preferably 3 parts by mass or more and 15 parts by mass or less. Within this range, the elongation is further improved.

[0091] [Photopolymerization initiator (C)] As the photopolymerization initiator (C), for example, a photoradical generator can be used. The photoradical generator contains a photoradical generator that generates radicals upon irradiation with active light such as ultraviolet light and functions as a photopolymerization initiator for the polyimide (A) described above.

[0092] Examples of the aforementioned photoradical generators include alkylphenone-type initiators, oxime ester-type initiators, and acylphosphine oxide-type initiators. For example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1[4-(methylthio)phenyl]-2-molifolinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimetho Examples include ethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), 2-(dimethylamino)-1-(4-(4-morpholino)phenyl)-2-(phenylmethyl)-1-butanone, Irgacure Oxe01 (BASF Japan Ltd.), Irgacure Oxe02 (BASF Japan Ltd.), Irgacure Oxe03 (BASF Japan Ltd.), Irgacure Oxe04 (BASF Japan Ltd.), N-1919T (ADEKA Corporation), NCI-730 (ADEKA Corporation), NCI-831E (ADEKA Corporation), NCI-930 (ADEKA Corporation), etc. You may use one or more of these. Among these, oxime ester type initiators are preferred from the viewpoint of the effects of the present invention, and further from the viewpoint of producing a resin film composed of a photosensitive resin composition with even better exposure sensitivity.

[0093] The amount of polymerization initiator (C) added is not particularly limited, but is preferably about 0.3 to 20% by mass of 100% by mass of the nonvolatile components of the negative-type photosensitive resin composition excluding the solvent, more preferably about 0.5 to 15% by mass, and even more preferably about 1 to 10% by mass. By setting the amount of polymerization initiator (C) added within the above range, the patternability of the photosensitive resin layer containing the negative-type photosensitive resin composition can be improved, and the long-term storage properties of the negative-type photosensitive resin composition can be improved.

[0094] (solvent) The negative-type photosensitive resin composition according to this embodiment may contain a solvent. This allows for the formation of a uniform photosensitive resin film on various substrate surfaces.

[0095] Organic solvents are preferred as solvents. Specifically, one or more of the following can be used: ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, etc.

[0096] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutylcarbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof. The amount of solvent used is not particularly limited. For example, it is used in an amount such that the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0097] (Surfactants) The negative-type photosensitive resin composition according to this embodiment may further contain a surfactant. The surfactants are not limited to, but specifically include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; F-Top EF301, F-Top EF303, F-Top EF352 (manufactured by Shin Akita Chemical Co., Ltd.), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Megafac F470, Examples include fluorinated surfactants commercially available under names such as Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Florard FC-430, Florard FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.); organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); and (meth)acrylic acid copolymer Polyflow No. 57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0098] Among these, it is preferable to use a fluorinated surfactant having a perfluoroalkyl group. As a fluorinated surfactant having a perfluoroalkyl group, it is preferable to use one or more selected from the above specific examples: Megafac F171, Megafac F173, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Surflon S-381, Surflon S-383, Surflon S-393 (manufactured by AGC Seimi Chemical Co., Ltd.), Novec FC4430, and Novec FC4432 (manufactured by 3M Japan).

[0099] Furthermore, silicone-based surfactants (such as polyether-modified dimethylsiloxane) can also be preferably used as surfactants. Specific examples of silicone-based surfactants include the SH series, SD series, and ST series from Toray Dow Corning, the BYK series from BIC Chemie Japan, the KP series from Shin-Etsu Chemical Co., Ltd., the Disform® series from NOF Corporation, and the TSF series from Toshiba Silicone Co., Ltd.

[0100] The upper limit of the surfactant content in the negative-type photosensitive resin composition is preferably 1% by mass (10,000 ppm) or less, more preferably 0.5% by mass (5,000 ppm) or less, and even more preferably 0.1% by mass (1,000 ppm) or less, relative to the total amount of the negative-type photosensitive resin composition (including the solvent).

[0101] Furthermore, there is no particular lower limit for the surfactant content in the negative-type photosensitive resin composition, but from the viewpoint of obtaining sufficient effects from the surfactant, for example, it should be 0.001% by mass (10 ppm) or more relative to the total (including solvent) of the negative-type photosensitive resin composition. By appropriately adjusting the amount of surfactant, it is possible to improve application properties and the uniformity of the coating film while maintaining other performance characteristics.

[0102] (Antioxidant) The negative-type photosensitive resin composition according to this embodiment may further contain an antioxidant. One or more antioxidants selected from phenol-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants can be used. The antioxidant can suppress the oxidation of the resin film formed by the negative-type photosensitive resin composition.

[0103] Examples of phenol-based antioxidants include pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}2,4,8,10-tetraoxaspiro[5,5]undecane, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate [(3,5-di-t-butyl-4-hydroxybenzyl)benzene], 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl(3,5-di-t-butyl-4-hydroxyphenyl)propionate, distearyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate 4,4'-thiobis(6-t-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-t-butyl-6-butylphenol), 2,-2'-methylenebis(4-ethyl-6-t-butylphenol), bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butyric acid] glycol ester, 4,4'-butylidenebis(6-t-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di- t-butylphenol), 2,2'-ethylidenebis(4-s-butyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-Tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2-t-butyl-4-methyl-6-(2-acryloyloxy-3-t-butyl-5-methylbenzyl)phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4-8,10-tetraoxaspiro[5,5] Undecane-bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], triethyleneglycol-bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(6-(1 -methylcyclohexyl)-4-methylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis(2-(3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy)1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-bis(3,5-di-t-butyl-4-hydroxybenzyl) Examples include ruphaide, 4,4'-thiobis(6-t-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-dimethyl-6-(1-methylcyclohexyl, styrenelated phenol, 2,4-bis((octylthio)methyl)-5-methylphenol, etc.

[0104] Examples of phosphorus-based antioxidants include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl phosphite), tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis-(2,6-dicumylphenyl)pentaerythritol diphosphite, and 2,2-methylenebi. Examples include s(4,6-di-t-butylphenyl)octyl phosphite, tris(mixed mono- and di-nonylphenyl phosphite), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methoxycarbonylethylphenyl)pentaerythritol diphosphite, and bis(2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl)pentaerythritol diphosphite.

[0105] Examples of thioethyl antioxidants include dilauryl-3,3'-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl) sulfide, distearyl-3,3'-thiodipropionate, and pentaerythritol-tetrakis(3-lauryl)thiopropionate.

[0106] (Adhesion enhancer) The negative-type photosensitive resin composition according to this embodiment may further contain an adhesion aid. As adhesion aids, silane coupling agents such as aminosilane, epoxysilane, (meth)acrylsilane, mercaptosilane, vinylsilane, ureidosilane, acid anhydride-functionalized silane, and sulfidesilane can be used. One type of silane coupling agent may be used alone, or two or more types may be used in combination. Among these, epoxysilane (i.e., a compound containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in one molecule) or acid anhydride-functionalized silane (i.e., a compound containing both an acid anhydride group and a group that generates a silanol group by hydrolysis in one molecule) is preferred.

[0107] Examples of aminosilanes 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, or N-phenyl-γ-aminopropyltrimethoxysilane.

[0108] Examples of epoxysilanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane, etc.

[0109] Examples of acrylicsilanes include γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, or γ-(methacryloxypropyl)methyldiethoxysilane. Examples of mercaptosilanes include 3-mercaptopropyltrimethoxysilane.

[0110] Examples of vinylsilanes include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, or vinyltrimethoxysilane. Examples of ureidosilanes include 3-ureidopropyltriethoxysilane.

[0111] Examples of acid anhydride-functionalized silanes include the product X-12-967C (compound name: 3-trimethoxysilylpropyl succinic anhydride), manufactured by Shin-Etsu Chemical Co., Ltd.

[0112] Examples of sulfidosilanes include bis(3-(triethoxysilyl)propyl) disulfide or bis(3-(triethoxysilyl)propyl) tetrasulfide. The amount of adhesion enhancer added is not particularly limited, but is 0.1 to 5% by mass, preferably 0.5 to 3% by mass, of the total solid content of the negative-type photosensitive resin composition.

[0113] (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.

[0114] (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.

[0115] 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.

[0116] 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%.

[0117] 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.

[0118] 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 20% or less, preferably 15% or less, and more preferably 12% or less. [(Growth rate before the exam - Growth rate after the exam) / Growth rate before the exam)] × 100

[0119] 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.

[0120] 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 more, preferably 2.5 GPa or more, and more preferably 3.0 GPa or more. Furthermore, the storage modulus E' at 200°C can have a storage modulus E' of 0.5 GPa or more, preferably 0.7 GPa or more, and more preferably 0.8 GPa or more.

[0121] 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.

[0122] 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 (%)}

[0123] 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.

[0124] 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. 2When 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

[0125] 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.

[0126] 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.

[0127] 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.

[0128] (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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] An example of a semiconductor device according to this embodiment is shown in Figure 1. 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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]

[0137] 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 synthesis of the polymer.

[0138] 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane (hereinafter also referred to as MED-J), represented by the following formula [ka]

[0139] 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter also referred to as BAPA), represented by the following formula [ka]

[0140] 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter also referred to as BAFA) represented by the following formula [Chemical formula]

[0141] 4,4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl (hereinafter also referred to as TFMB) represented by the following formula [Chemical formula]

[0142] 4,4'-(Hexafluoroisopropylidene)bis[(4-aminophenoxy)benzene] (hereinafter also referred to as HFBAPP) represented by the following formula [Chemical formula]

[0143] 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) represented by the following formula [Chemical formula]

[0144] p-Phenylenebis(trimesate anhydride) (hereinafter also referred to as TMHQ) represented by the following formula [Chemical formula]

[0145] [Example 1] First, 29.01 g (102.7 mmol) of MED-J, 26.53 g (102.7 mmol) of BAPA, and 151.29 g (244.6 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and condenser. Then, 620.49 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 bisaminophenol and acid anhydride, thereby preparing a polymerization solution. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 20,000 and a polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of 1.98. Next, 57.99 g (410.9 mmol) of 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by Showa Denko Corporation) and 177.84 g of γ-butyl lactone (GBL) were added to the entire volume of the obtained polyimide solution (205.4 mmol in terms of hydroxyl groups). The mixture was then stirred and the temperature was raised to 120°C for 6 hours. 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 40°C to obtain 212.35 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 26,100 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 2.30. Also, 1 ¹H-NMR measurements revealed peaks in the aromatic region (6.8 ppm to 8.8 ppm) with area ratios corresponding to the number of protons. Furthermore, based on the area ratio of the aromatic region (6.8 ppm to 8.8 ppm) and the alkene region (5.8 ppm to 6.3 ppm), the introduction rate of crosslinking groups was 83%. The polymer into which the crosslinking group was introduced contained, in part, repeating units represented by the following formula. [ka]

[0146] [Example 2] First, 9.67 g (34.2 mmol) of MED-J, 2.95 g (11.4 mmol) of BAPA, and 33.62 g (54.3 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and condenser. Then, 138.71 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 bisaminophenol and acid anhydride, thereby preparing a polymerization solution. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 21,500 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 2.02. Next, 6.44 g (45.6 mmol) of 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by Showa Denko Corporation) and 43.02 g of γ-butyl lactone (GBL) were added to the entire volume of the obtained polyimide solution (22.8 mmol in terms of hydroxyl groups). The mixture was then stirred and the temperature was raised to 120°C for 6 hours. 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 40°C to obtain 43.73 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 22,800 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 2.15. Also, 1 ¹H-NMR measurements revealed peaks in the aromatic region (6.8 ppm to 8.8 ppm) with area ratios corresponding to the number of protons. Furthermore, based on the area ratio of the aromatic region (6.8 ppm to 8.8 ppm) and the alkene region (5.8 ppm to 6.3 ppm), the introduction rate of crosslinking groups was 100%. The polymer into which the crosslinking group was introduced contained in part the repeating unit represented by the above formula.

[0147] [Example 3] First, 12.89 g (45.7 mmol) of MED-J and 33.62 g (54.3 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and a cooling tube. Then, 125.58 g of GBL was further added to the reaction vessel. After purging with nitrogen for 10 minutes, the temperature was raised to 60 °C with stirring and reacted for 1.5 hours. Then, by further reacting at 180 °C for 3 hours, bisaminophenol and an acid anhydride were polymerized to prepare a polymerization solution. When the polymer was measured by GPC, the weight-average molecular weight Mw was 23,600 and the polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) was 2.05. Next, 4.91 g (34.8 mmol) of 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by Showa Denko KK) and 44.06 g of γ-butyrolactone (GBL) were added to the total amount of the obtained polyimide solution (17.4 mmol in terms of terminal acid anhydride). Then, the temperature was raised to 120 °C with stirring and reacted for 6 hours. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution. Then, the diluted solution was dropped into methanol to precipitate a white solid. The obtained white solid was recovered and vacuum dried at 40 °C to obtain 41.73 g of a polymer. When the polymer was measured by GPC, the weight-average molecular weight Mw was 23,100 and the polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) was 2.09. Also, 1 When 1H-NMR measurement was performed, peaks were confirmed at an area ratio corresponding to the number of protons in the aromatic region (6.9 ppm to 8.9 ppm). Also, from the calculation based on the area ratio between the aromatic region (6.9 ppm to 8.9 ppm) and the alkene region (5.8 ppm to 6.5 ppm) and the degree of polymerization, the introduction rate of the crosslinking group to the terminal was 100%. The obtained polymer contained a repeating unit represented by the following formula in part and a crosslinking group was introduced at the terminal.

Chemical formula

[0148] [Examples 4-7, Comparative Examples 1-4] Examples 4-7 and Comparative Examples 1-4 were synthesized using the same method as in Example 1, 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 "×".

[0149] [Solubility in organic solvents] The solubility of the negative-type photosensitive polymers obtained in Examples 1-6 and Comparative Examples 3 and 4 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.

[0150] [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. (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. The results are shown in Table 1. 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 were 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. The results are shown in Table 1. Formula: [(Weight-average molecular weight before testing - Weight-average molecular weight after testing) / Weight-average molecular weight before testing] × 100

[0151] [Growth rate] A composition containing the polymer solution obtained in the Examples and Comparative Examples (100 parts by mass of polymer), 5 parts by mass of the thermal radical generator Percadox BC, 2 parts by mass of the adhesion aid KBM-503P, and 0.1 parts by mass of the surfactant FC4432 was spin-coated onto the surface of a silicon wafer. After pre-baking at 110°C for 3 minutes, a film was prepared by heat treatment at 170°C for 240 minutes under nitrogen. Details of each component are described below. Tensile tests (stretching speed: 5 mm / min) were performed on test specimens (6.5 mm × 60 mm × 10 μm thick) cut from the obtained film in a 23°C atmosphere. The tensile tests were performed using an Orientec tensile testing machine (Tensilon RTC-1210A). Ten test specimens were measured, and the tensile elongation was calculated from the fracture distance and initial distance, and the maximum elongation was determined. The results are shown in Table 1.

[0152] [Table 2]

[0153] As shown in Table 1, the negative-type photosensitive polymer of the present invention obtained in the examples exhibited excellent solubility and elongation in organic solvents, and it was inferred that hydrolysis was suppressed, resulting in less reduction in elongation and suppression of reduction in mechanical strength.

[0154] The following compounds were used in the preparation of the negative-type photosensitive resin composition. (Crosslinking agent) • Acrylate compound 1: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK Ester A-DPH)

[0155] (Polymerization initiator) • Photoradical generator: 2-(dimethylamino)-1-(4-(4-morpholino)phenyl)-2-(phenylmethyl)-1-butanone (Irgacure Oxe 01, manufactured by BASF Japan) • Thermal radical generator: Dicumyl peroxide (Parcadox BC, peroxide, manufactured by Kayaku Akzo)

[0156] (Adhesion enhancer) • Adhesion enhancer 1:3-methacryloxypropyltrimethoxysilane (KBM-503P, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0157] (Surfactants) • Surfactant 1: Surfactant containing a fluorocarbon chain (FC-4432, manufactured by Sumitomo 3M Co., Ltd.)

[0158] (solvent) • Solvent 1: γ-butyllactone (GBL)

[0159] [Example 8] (Preparation of negative-type photosensitive resin composition) A photosensitive resin composition was prepared by mixing the polymer from Example 5 (100 parts by mass of polymer) with the components shown in Table 2, which had been pre-dissolved to form a 22 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 glass transition temperature (Tg) and elongation of the obtained films were measured using the method described below, and the patterning properties were evaluated. The results are shown in Table 2.

[0160] [Glass transition temperature (Tg)] A test piece measuring 8 mm × 40 mm was cut from the film obtained in Example 8. Dynamic viscoelasticity measurements were performed on this test piece using a dynamic viscoelasticity analyzer (DMA device, TA Instruments, Q800) at a heating rate of 5°C / min and a frequency of 1 Hz. The temperature at which the loss tangent tanδ showed its maximum value was measured as the glass transition temperature.

[0161] [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 8 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 strength was defined as the average stress at the fracture point. The tensile elongation was calculated from the fracture distance and initial distance, and the average and maximum values ​​of the elongation were determined. Furthermore, the test pieces cut from the film obtained in Example 8 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.

[0162] [Evaluation of patterning characteristics] The photosensitive resin composition of Example 8 was confirmed to be sufficiently patternable by exposure and development as follows. The photosensitive resin composition of Example 8 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 under atmospheric pressure to obtain a coating with a thickness of approximately 5.0 μm. The coating was irradiated with i-rays through a mask on which a 20 μm wide via pattern was drawn. An i-ray stepper (Nikon NSR-4425i) was used for the irradiation. After exposure, the unexposed areas were dissolved and removed by spray development using cyclopentanone as the developer for 40 seconds, followed by spray development using PGMEA as the developer for 10 seconds, thereby obtaining a via pattern. The cross-section of the obtained via pattern was observed using a benchtop SEM. The width at the midpoint between the bottom surface and the opening of the via pattern was defined as the via width and evaluated according to the following criteria. Excellent patternability: 20μm via pattern opens. Poor patterning: 20μm via pattern does not open. The coating film obtained from the photosensitive resin composition of Example 8 exhibited good patternability.

[0163] [Table 3]

[0164] As shown in Table 2, the film obtained from the negative-type photosensitive resin composition containing the negative-type photosensitive polymer of the present invention exhibits excellent elongation and, due to the inclusion of a negative-type photosensitive polymer with excellent hydrolysis resistance, demonstrates superior mechanical strength even after HAST testing. Furthermore, it exhibits good patternability, confirming its suitability as a negative-type photosensitive resin composition.

[0165] This application claims priority based on Japanese Patent Application No. 2021-105682, filed on 25 June 2021, and incorporates all of its disclosures herein. [Explanation of Symbols]

[0166] 100 Semiconductor Equipment 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 structural unit (a3) ​​represented by the following general formula (a3), A negative-type photosensitive resin composition containing [the specified element]. 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 (In general formula (a1), Y is a divalent organic group.) 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 is a single bond, -SO ２ -, -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 １ may be the same or different. In general formula (a3), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different. R ５ and R ６ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 alkoxy group. m1 and m2 each independently represent integers between 1 and 3. X 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.

2. The negative-type photosensitive resin composition according to claim 1, wherein the polyimide (A) has at least one of its ends being a (meth)acrylate group.

3. (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 comprising, wherein at least one of the ends of the polyimide (A) is a (meth)acrylate group. 【Chemistry 4】 【Transformation 5】 (In general formula (a1), Y is a divalent organic group.) 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.

4. The negative-type photosensitive resin composition according to claim 1 or 3, wherein Y in the general formula (a1) is a divalent group containing an alkylene group, or a divalent group containing at least one aromatic ring.

5. The negative-type photosensitive resin composition according to claim 1 or 3, wherein Y in the general formula (a1) is a divalent organic group selected from the following general formulas (a1-1), (a1-2), and (a1-3). 【Transformation 6】 (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.

6. The negative-type photosensitive resin composition according to claim 1 or 3, wherein the polyimide (A) comprises a structural unit represented by the following general formula (1). 【Transformation 7】 (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).)

7. The negative-type photosensitive resin composition according to claim 1, wherein the polyimide (A) includes a structural unit represented by the following general formula (2). 【Transformation 8】 (In general formula (2), Q, R ５ , R ６ , m1, m2, and X ２ (This is equivalent to general formula (a3), and Y is equivalent to general formula (a1).)

8. A structural unit (a1) represented by the following general formula (a1), A structural unit (a2) represented by the following general formula (a2), A structural unit (a3) ​​represented by the following general formula (a3), A negative-type photosensitive polymer containing [a specific compound / component]. 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 (In general formula (a1), Y is a divalent organic group.) 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. In general formula (a3), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different. R ５ and R ６ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 alkoxy group. m1 and m2 each independently represent integers between 1 and 3. X 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.

9. The negative-type photosensitive polymer according to claim 8, wherein at least one of both ends is a (meth)acrylate group.

10. A structural unit (a1) represented by the following general formula (a1), A structural unit (a2) represented by the following general formula (a2), Includes, A negative-type photosensitive polymer in which at least one of both ends is a (meth)acrylate group. 【Chemistry 12】 【Chemistry 13】 (In general formula (a1), Y is a divalent organic group.) 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.

11. The negative-type photosensitive polymer according to claim 8 or 10, wherein Y in the general formula (a1) is a divalent group containing an alkylene group, or a divalent group containing at least one aromatic ring.

12. The negative-type photosensitive polymer according to claim 8 or 10, wherein Y in the general formula (a1) is a divalent organic group selected from the following general formulas (a1-1), (a1-2), and (a1-3). 【Chemistry 14】 (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.

13. A negative-type photosensitive polymer according to claim 8 or 10, comprising a structural unit represented by the following general formula (1). 【Chemistry 15】 (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).)

14. The negative-type photosensitive polymer according to claim 8, comprising a structural unit represented by the following general formula (2). 【Chemistry 16】 (In general formula (2), Q, R ５ , R ６ , m1, m2, and X ２ (This is equivalent to general formula (a3), and Y is equivalent to general formula (a1).)

15. The negative-type photosensitive polymer according to claim 8 or 10, wherein the decrease rate of the weight-average molecular weight measured under the following conditions is 15% 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

16. A cured film comprising a cured product of the negative-type photosensitive resin composition according to claim 1 or 3.

17. A semiconductor device comprising a resin film containing a cured product of the negative-type photosensitive resin composition according to claim 1 or 3.

18. 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 3, The rewiring embedded in the aforementioned resin film, A semiconductor device characterized by comprising the following features.

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