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; and the polyimide (A) comprises a structural unit (a1) represented by general formula (a1) and a structural unit (a2) represented by general formula (a2), while having a group represented by general formula (t) at least at one of both ends.

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. Patent Document 5 discloses a photosensitive composition containing a polyimide having a predetermined maleimide group at its terminus.

[0007] Patent Document 6 discloses an optical waveguide having a core portion containing a first compound having a functional group that can be dimerized by light irradiation, and as the first compound, a cyclic olefin resin having a predetermined maleimide group at its terminus is given as the dimerizable functional group. [Prior art documents] [Patent Documents]

[0008] [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 [Patent Document 5] International Publication No. 2020 / 181021 [Patent Document 6] Japanese Patent Publication No. 2019-028115 [Overview of the project] [Problems that the invention aims to solve]

[0009] However, in the conventional technologies described in Patent Documents 1 to 5, there was room for improvement in the mechanical strength, such as elongation, of the polyimide-containing films obtained from the photosensitive resin composition.

[0010] 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. Furthermore, Patent Document 6 does not describe the use of this product in combination with a specific polyimide. [Means for solving the problem]

[0011] 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.

[0012] [1] (A) Polyimide Includes, The aforementioned 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 a group, wherein at least one of both ends is a group represented by the following general formula (t). [ka] [ka] [ka] (In general formula (a1), Y is a divalent organic group.) In general formula (a2), R 1 ~R 4Each 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. 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 X 1 they may be the same or different. In the general formula (t), R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q 2 represents a divalent organic group. * represents a bond. ) [2] The negative photosensitive resin composition according to [1], 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. [3] The negative photosensitive resin composition according to [1] or [2], wherein Y in the general formula (a1) is a divalent organic group selected from the following general formula (a1-1), the following general formula (a1-2), and the following general formula (a1-3).

Chemical formula

[10] A negative-type photosensitive resin composition according to any one of [1] to [9], further comprising a crosslinking agent (B) having a substituted or unsubstituted maleimide group (excluding the polyimide (A)).

[11] The crosslinking agent (B) comprises a structural unit represented by the following general formula (b), as described in

[10] , the negative-type photosensitive resin composition. [ka] (In general formula (b), R 1 and R 2 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q 1 This indicates a single bond or a divalent organic group, G 1 , G 2 , and G 3 Each of these independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group with 1 to 30 carbon atoms, and m is 0, 1, or 2.

[12] Q 1 The negative-type photosensitive resin composition according to

[11] , wherein the divalent organic group is an alkylene group having 1 to 8 carbon atoms or a (poly)alkylene glycol chain.

[13] A negative-type photosensitive resin composition according to any one of [1] to

[12] , further comprising a photosensitizer (C).

[14] A negative-type photosensitive resin composition according to any one of [1] to

[13] , further comprising a silane coupling agent (D).

[15] 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 comprising a group such that at least one of its ends is a group represented by the following general formula (t). [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 (t), R 5 and R 6 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q 2 indicates a divalent organic group. * indicates a bond.

[16] The negative-type photosensitive polymer according to

[15] , 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.

[17] The negative-type photosensitive polymer according to

[15] or

[16] , 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 formula (a1-3), Z 1 This represents an alkylene group with 1 to 5 carbon atoms, or a divalent aromatic group. * indicates a bond.

[18] The negative-type photosensitive polymer according to

[15] or

[16] , wherein Y in the general formula (a1) is a divalent organic group represented by the following general formula (a1-4). [ka] (In general formula (a1-4), Z 2 indicates a divalent aromatic group. * indicates a bond.

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

[15] to

[18] , wherein both ends are groups represented by the general formula (t).

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

[15] to

[19] , further comprising a structural unit (a3) ​​represented by general formula (a3). [ka] (In general formula (a3), R 5 and R 6Each of these independently represents a hydrogen atom, a C1-C4 haloalkyl group, or a hydroxyl group, and there are multiple R groups. 5 R with other Rs and multiple Rs with different Rs. 6 The elements may be identical or different. X represents a single bond, an alkylene group with 1-4 carbon atoms, or a haloalkylene group with 1-4 carbon atoms. m and n independently represent 0 or 1.

[21] The Q of the general formula (t) 2 The negative-type photosensitive polymer according to

[20] , wherein the divalent organic group is a structural unit (a2) represented by general formula (a2) or a structural unit (a3) ​​represented by general formula (a3).

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

[15] to

[21] , 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).)

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

[20] to

[22] , comprising a structural unit represented by the following general formula (2). [ka] (In general formula (2), R 5 ~R 6 X, m, and n are equivalent to those in general formula (a3), and Y is equivalent to that in general formula (a1).

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

[15] to

[23] , wherein the rate of decrease in weight-average molecular weight measured under the following conditions is less than 50%. (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

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

[14] .

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

[14] .

[27] 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

[14] , The rewiring embedded in the aforementioned resin film, A semiconductor device characterized by comprising the following features. [Effects of the Invention]

[0013] 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 yields a cured product such as a film that exhibits excellent solubility in organic solvents and excellent mechanical strength such as elongation. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic cross-sectional view of the semiconductor device according to this embodiment. [Modes for carrying out the invention]

[0015] 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 contains (A) polyimide.

[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), wherein at least one of both ends is a group represented by the following general formula (t).

[0017] [ka]

[0018] In general formula (a1), Y is a divalent organic group. As the divalent organic group, any organic group known 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. It is even more preferable that Y in general formula (a1) is a divalent organic group selected from the following general formulas (a1-1), (a1-2), (a1-3), and (a1-4).

[0019] [ka]

[0020] 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. 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 9From 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, more preferably a hydrogen atom. * represents a bond.

[0021] In 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. When there are a plurality of Rs 10 among themselves or a plurality of Rs 11 among themselves may be the same or different.

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

[0023] In general formula (a1-3), Z 1 represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group. * represents a bond. In general formula (a1-4), Z 2 represents a divalent aromatic group, preferably a divalent benzene ring. * represents a bond.

[0024]

Chemical formula

[0025] In general formula (a2), R 1 ~R 4 Each of these independently represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and from the viewpoint of the effects of the present invention, an alkyl group having 1 to 3 carbon atoms is preferred. R 1 and R 2 These are different groups, R 3 and R 4 These are different groups. As a result, the structural unit represented by general formula (a2) has an asymmetric molecular structure, which causes twisting of the main chain of the polymer containing this structural unit. This is thought to be one of the reasons for the improved solvent solubility.

[0026] 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.

[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] Polyimide (A) includes polyimides in which at least one of the ends is a group t represented by the following general formula (t).

[0030] [ka]

[0031] In general formula (t), R 5 and R 6 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. From the viewpoint of the effects of the present invention, an alkyl group having 1 or 2 carbon atoms is preferred, and an alkyl group having 1 carbon atom (methyl group) is more preferred. * indicates a bond. R 5 and R 6 Because all of these are methyl groups, the hydrolysis of polyimide is further suppressed, resulting in even better mechanical strength such as elongation, as well as superior solubility in organic solvents.

[0032] Q 2 This indicates a divalent organic group. As the divalent organic group, any organic group known within the range that achieves the effects of the present invention can be used, but it is preferable, for example, to be the structural unit (a2) represented by the general formula (a2). Specifically, a divalent organic group represented by the following general formula (t-1) can be mentioned.

[0033] [ka]

[0034] In general formula (t-1), X 1 , R 1 ~R 4 This is equivalent to general formula (a2). * indicates a bond.

[0035] The polyimide (A) may further contain structural units (a3) ​​represented by the following general formula (a3).

[0036] [ka]

[0037] In general formula (a3), R 5 and R 6 Each of these independently represents a hydrogen atom, a C1-C4 haloalkyl group, or a hydroxyl group, preferably a hydrogen atom or a C1-C4 haloalkyl group. Multiple R groups exist. 5 They can be the same or different, and there can be multiple Rs. 6 They may be the same or different.

[0038] X represents a single bonded alkylene group having 1 to 4 carbon atoms, or a haloalkylene group having 1 to 4 carbon atoms, preferably a single bonded haloalkylene group having 1 to 4 carbon atoms. m and n each independently represent either 0 or 1.

[0039] In the above general formula (t), Q 2 The divalent organic group may be the structural unit (a3) ​​represented by the general formula (a3) ​​above. Specifically, the divalent organic group represented by the following general formula (t-2) can be given.

[0040] [ka]

[0041] In general formula (t-2), R 5 , R 6 X, m, and n are equivalent to those in the general formula (a3). * indicates a bond.

[0042] From the viewpoint of the effects of the present invention, it is preferable that polyimide (A) contains a polyimide in which at least one end, preferably both ends, is a group t represented by the general formula (t).

[0043] The polyimide (A) of this embodiment contains a polyimide having a group t represented by the general formula (t) at at least one of its ends, and therefore exhibits excellent mechanical strength. Furthermore, since photodimerization is possible without radical reactions, polyimide (A) can be photopolymerized with other polyimide (A) and with the crosslinking agent (B) described later, resulting in even greater mechanical strength. Furthermore, polyimide (A) may include polyimide whose terminal end has a group u represented by the following general formula (u).

[0044] [ka]

[0045] In general formula (u), X 1 , R 1 ~R 4 This is equivalent to general formula (a2).

[0046] When polyimide (A) contains a polyimide comprising the group u, the ratio of the number of moles of group b to the total number of moles of group t and group u (t / t+u) can be 0.5 or more, preferably 0.55 or more, and more preferably 0.6 or more. Within this range, the polyimide components that leach during development can be reduced.

[0047] The polyimide (A) of this embodiment may specifically include a structural unit 1 represented by the following general formula (1).

[0048] [ka]

[0049] 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).

[0050] Specifically, the polyimide (A) of this embodiment may further include structural unit 2, which is represented by the following general formula (2), along with structural unit 1.

[0051] [ka]

[0052] In general formula (2), R 5~R 6 X, m, and n are equivalent to those in general formula (a3), and Y is equivalent to those in general formula (a1).

[0053] The weight-average molecular weight of polyimide (A) in this embodiment is 5,000 to 200,000, preferably 10,000 to 100,000.

[0054] The polyimide (A) (negative-type photosensitive polymer) of this embodiment exhibits excellent hydrolysis resistance, with a weight-average molecular weight reduction rate of less than 50%, preferably 30% or less, more preferably 20% or less, more preferably 10% or less, and particularly preferably 7% 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

[0055] In this embodiment, polyimide (A) 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.

[0056] 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.

[0057] <Method for producing polyimide (A)> The method for producing polyimide (A) (negative photosensitive polymer) having a structural unit represented by general formula (1) of this embodiment, and having at least one of its ends as a group t represented by general formula (t), is: The process includes a step of reacting an acid anhydride (a1') represented by the following general formula (a1'), a diamine (a2') represented by the following general formula (a2'), and a maleic anhydride derivative (t') represented by the following general formula (t'). According to this embodiment, polyimide (A) with excellent solubility in organic solvents can be synthesized by a simple method.

[0058] [ka]

[0059] In general formula (a1'), Y is selected from the groups represented by general formula (a1-1), general formula (a1-2), general formula (a1-3), and general formula (a1-4).

[0060] [ka]

[0061] In general formula (a2'), R 1 ~R 4 , X 1 This is equivalent to the general formula (a2).

[0062] [ka]

[0063] In general formula (t'), R 5 , R 6 This is equivalent to the general formula (t) above.

[0064] The equivalent ratio of diamine (a2') to acid anhydride (a1') in this reaction 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 diamine (a2') to acid anhydride (a1') used, but it is preferable that the equivalent ratio of acid anhydride (a1') to diamine (a2') is in the range of 0.80 to 1.06. Below 0.80, the molecular weight is low and brittle, resulting in weak mechanical strength. Above 1.06, unreacted carboxylic acid may decarboxylate during heating, generating gas and causing foaming, which is undesirable.

[0065] In this embodiment, from the viewpoint of the effects of the present invention, it is also preferable to react the acid anhydride (a1'), the diamine (a2'), the maleic anhydride derivative (t'), and the diamine (a3') represented by the following general formula (a3').

[0066] [ka]

[0067] In general formula (a3'), R 5 , R 6 X, m, and n are equivalent to those in the general formula (a3).

[0068] 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 0.80 to 1.06. If the equivalent ratio is within this range, the polymer will have excellent mechanical strength and manufacturing stability.

[0069] The amount of maleic anhydride derivative (t') can be three times the molar amount of the amino group not used in the reaction with acid anhydride (a1').

[0070] This allows for the imparting of photosensitivity to polyimide through photodimerization, resulting in cured products such as films that are superior in terms of low dielectric loss tangent and mechanical properties. This reaction can be carried out in an organic solvent by known methods.

[0071] 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. 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.

[0072] 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.

[0073] The maleic anhydride derivative (t') may be present in the imidation reaction between the acid anhydride (a1') and the diamines (a2') and (a3'), but the maleic anhydride derivative (t'), dissolved in the above organic solvent, can be added and reacted during or after the reaction between the acid anhydride (a1') and the diamines (a2') and (a3') to encapsulate the polyimide ends.

[0074] When a maleic anhydride derivative (t') is added separately, it is preferable to react the mixture at a temperature of 100°C to 250°C, preferably 120°C to 200°C, for about 1 to 5 hours after addition.

[0075] By following the above steps, a reaction solution containing the polyimide (A) (end-capped polyimide) of this embodiment can be obtained. This solution can then 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 process can be used, and it may be the same organic solvent as in the reaction process, or a different organic solvent may be used.

[0076] Alternatively, this reaction solution can be added to a poor solvent to reprecipitate polyimide (A) to remove unreacted monomers, and the dried and solidified product can be dissolved again in an organic solvent and used as a purified 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. The concentration of polyimide (A) in the polymer solution (100% by weight) is not particularly limited, but is approximately 10 to 30% by weight.

[0077] Table A below shows preferred formulations of the negative-type photosensitive polymer in this embodiment.

[0078] [Table 1]

[0079] MED-J: 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane HFBAPP: 4,4'-(hexafluoroisopropylidene)bis[(4-aminophenoxy)benzene] • TFMB: 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl ·TMPBP-TME:4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate HQDA: 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride • DMMI: 2,3-dimethylmaleic anhydride

[0080] [Crosslinking agent (B)] The negative-type photosensitive resin composition of this embodiment may preferably further contain a crosslinking agent (B) (excluding the polyimide (A)) comprising substituted or unsubstituted maleimide groups. The crosslinking agent (B) includes 4,4'-diphenylmethanebis(dimethyl)maleimide, polyphenylmethane(dimethyl)maleimide, m-phenylenebis(dimethyl)maleimide, p-phenylenebis(dimethyl)maleimide, bisphenol A diphenyl etherbis(dimethyl)maleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebis(dimethyl)maleimide, 4-methyl-1,3-phenylenebis(dimethyl)maleimide, 1,6'-bis(dimethyl)maleimide-(2,2,4-trimethyl)hexane, 1,2-bis((dimethyl)maleimide)ethane, 1,4-bis((dimethyl)maleimide)butane, 1,6-bis((dimethyl)maleimide)hexane, and 1,12-bis((dimethyl)maleimide) Examples include decane, 1-(dimethyl)maleimide-3-(dimethyl)maleimidemethyl-3,5,5-trimethylcyclohexane, 1,1'-(cyclohexane-1,3-diylbis(methylene))bis((3,4-dimethyl)-1H-pyrrole-2,5-dione), 1,1'-(4,4'-methylenebis(cyclohexane-4,1-diyl))bis((3,4-dimethyl)-1H-pyrrole-2,5-dione), 1,1'-(3,3'-(piperazine-1,4-diyl)bis(propane-3,1-diyl))bis(1H-pyrrole-2,5-dione), 2,2'-(ethylenedioxy)bis(ethyl(dimethyl)maleimide), and polynorbornene having substituted or unsubstituted maleimide groups, with polynorbornene being preferred. The polynorbornene preferably has a structural unit (b) represented by the following general formula (b).

[0081] [ka]

[0082] In general formula (b), R 1 and R 2 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. From the viewpoint of the effects of the present invention, an alkyl group having 1 or 2 carbon atoms is preferred, and an alkyl group having 1 carbon atom is more preferred. Q1 This indicates a single bond or a divalent organic group.

[0083] Q 1 As the divalent organic group, any organic group known within the range that achieves the effects of the present invention can be used, but examples include an alkylene group having 1 to 8 carbon atoms or a (poly)alkylene glycol chain. The alkylene group having 1 to 8 carbon atoms is preferably an alkylene group having 2 to 6 carbon atoms.

[0084] Examples of alkylene groups having 1 to 8 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene groups.

[0085] The alkylene oxides constituting the (poly)alkylene glycol chain are not particularly limited, but are preferably composed of alkylene oxides having 1 to 18 carbon atoms, and more preferably alkylene oxides having 2 to 8 carbon atoms. Examples include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, octylene oxide, and the like.

[0086] G 1 , G 2 , and G 3 Each of these independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a hydrogen atom. Examples of hydrocarbon groups having 1 to 30 carbon atoms include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalil groups, or cycloalkyl groups.

[0087] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Examples of alkenyl groups include allyl, pentenyl, and vinyl groups. An example of an alkynyl group is the ethynyl group. Examples of alkylidene groups include the methylidene group and the ethylidene group.

[0088] Examples of aryl groups include phenyl, naphthyl, and anthracenyl groups. Examples of aralkyl groups include the benzyl group and the phenethyl group.

[0089] Examples of alkalyl groups include tolyl groups and xylyl groups. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. A hydrocarbon group having 1 to 30 carbon atoms may contain at least one atom selected from O, N, S, P, and Si in its structure.

[0090] In this embodiment, the hydrocarbon group having 1 to 30 carbon atoms is preferably a hydrocarbon group having 1 to 15 carbon atoms, and more preferably a hydrocarbon group having 1 to 10 carbon atoms. Furthermore, the hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.

[0091] Substituents for the substituted C1-C30 hydrocarbon group include hydroxyl groups, amino groups, cyano groups, ester groups, ether groups, amide groups, sulfonamide groups, etc., and may be substituted with at least one of these groups.

[0092] In this embodiment, G 1 , G 2 , and G 3 Preferably, one of them is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and the rest are hydrogen atoms; more preferably, all are hydrogen atoms. m is 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0093] The crosslinking agent (B) of this embodiment has a structure represented by general formula (b), and therefore exhibits excellent low dielectric loss tangent. Furthermore, since the crosslinking agent (B) has a predetermined maleimide group in its side chain, no radical reaction occurs and photodimerization is possible, allowing for photopolymerization of crosslinking agents (B) with each other and with polyimide (A), resulting in superior mechanical strength. The crosslinking agent (B) of this embodiment can be synthesized as follows.

[0094] First, the compound (b') represented by the following general formula (b') is subjected to addition polymerization, and if necessary, further addition polymerization is carried out with other norbornene compounds to obtain a polymer. For example, addition polymerization is performed by coordination polymerization.

[0095] [ka]

[0096] In general formula (b'), R 1 , R 2 Q 1 , G 1 , G 2 , G 3 And m is synonymous with general formula (b).

[0097] Other norbornene compounds include norbornenes having alkyl groups such as 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, and 5-cyclopentylnorbornene; norbornenes having alkenyl groups such as 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene, and 5-cyclopentenylnorbornene; and norbornenes having aromatic rings such as 5-phenylnorbornene, 5-phenylmethylnorbornene, 5-phenylethylnorbornene, and 5-phenylpropylnorbornene.

[0098] In this embodiment, solution polymerization can be carried out by dissolving the above compound and an organometallic catalyst in a solvent and then heating for a predetermined time. At this time, the heating temperature can be, for example, 30°C to 200°C, preferably 40°C to 150°C, and more preferably 50°C to 120°C. In this embodiment, the yield of the crosslinking agent (B) can be improved by using a higher heating temperature than in the conventional method.

[0099] Furthermore, the heating time can be, for example, 0.5 hours to 72 hours. It is more preferable to remove dissolved oxygen from the solvent by nitrogen bubbling before performing solution polymerization.

[0100] Furthermore, molecular weight modifiers and chain transfer agents can be used as needed. Examples of chain transfer agents include alkylsilane compounds such as trimethylsilane, triethylsilane, and tributylsilane. These chain transfer agents may be used individually or in combination of two or more.

[0101] As solvents used in the above polymerization reaction, one or more of the following can be used: methyl ethyl ketone (MEK), propylene glycol monomethyl ether, diethyl ether, cyclopentyl methyl ether, tetrahydrofuran (THF), 4-methyltetrahydropyran, toluene, cyclohexane, methylcyclohexane, ethyl acetate, butyl acetate, and other esters, as well as alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol.

[0102] The organometallic catalysts mentioned above are not particularly selected as long as addition polymerization proceeds. For example, ligands such as phosphine-based or diimine-based ligands may be coordinated to the palladium complex and nickel complex, and counteranions may also be used. One or more of these can be used.

[0103] Examples of the above palladium complexes include (acetato-κ0)(acetonitrile)bis[tris(1-methylethyl)phosphine]palladium(I)tetrakis(2,3,4,5,6-pentafluorophenyl)borate, π-allylpalladium chloride dimer, and other allylpalladium complexes. Palladium organic carboxylates such as palladium acetate, propionate, maleate, and naphthoate, Palladium organic carboxylic acid complexes such as palladium acetate triphenylphosphine complex, palladium acetate tri(m-tolyl)phosphine complex, and palladium acetate tricyclohexylphosphine complex. Palladium dibutyl phosphate, p-toluenesulfonate and other palladium organosulfonates, Palladium β-diketone compounds such as bis(acetylacetonate)palladium, bis(hexafluoroacetylacetonate)palladium, bis(ethylacetoacetate)palladium, and bis(phenylacetoacetate)palladium. Examples include palladium halide complexes such as dichlorobis(triphenylphosphine)palladium, bis[tri(m-tolylphosphine)]palladium, dibromobis[tri(m-tolylphosphine)]palladium, and acetonyltriphenylphosphine complexes.

[0104] Examples of the phosphine ligands mentioned above include triphenylphosphine, dicyclohexylphenylphosphine, cyclohexyldiphenylphosphine, and tricyclohexylphosphine.

[0105] Examples of the above counteranions include triphenylcarbenium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate, triphenylcarbenium tetrakis(2,4,6-trifluorophenyl) borate, triphenylcarbenium tetraphenyl borate, tributylammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diphenylanilinium tetrakis(pentafluorophenyl) borate, and lithium tetrakis(pentafluorophenyl) borate.

[0106] The amount of organometallic catalyst can be 300 ppm to 5000 ppm, preferably 1000 ppm to 3500 ppm, and more preferably 1500 ppm to 2500 ppm, relative to the norbornene monomer. This can improve the yield of the crosslinking agent (B).

[0107] The reaction solution containing the obtained crosslinking agent (B) is added to, for example, an alcohol such as hexane or methanol to precipitate the crosslinking agent (B). Then, the crosslinking agent (B) is filtered off, washed with, for example, an alcohol such as hexane or methanol, and then dried. In this embodiment, the crosslinking agent (B) can be synthesized, for example, in this manner. According to the manufacturing method of this embodiment, the crosslinking agent (B) can be obtained in a high yield of 70% or more.

[0108] The conversion rate with dialkyl maleic anhydride is preferably 70% or higher. More preferably 80%, and even more preferably 90% or higher. Within this range, the polyimide components that leach out during development can be reduced.

[0109] The crosslinking agent (B) of this embodiment may include structural units other than structural unit (b) to the extent that it achieves the effects of the present invention, and other structural units include structural units derived from the above-mentioned other norbornene compounds.

[0110] The weight-average molecular weight of the crosslinking agent (B) in this embodiment is 3,000 to 300,000, preferably 5,000 to 200,000.

[0111] In this embodiment, from the viewpoint of the effects of the present invention, the ratio (A:B) of polyimide (A) to crosslinking agent (B) can be 5:95 to 95:5, preferably 10:90 to 90:10, and more preferably 20:80 to 80:20.

[0112] [Photosensitizer (C)] The negative-type photosensitive resin composition of this embodiment may further contain a photosensitizer (C).

[0113] Examples of photosensitizers (C) include benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, benzyl-based photopolymerization initiators, and Michler-ketone-based photopolymerization initiators. Among these, benzophenone-based photopolymerization initiators or thioxanthone-based photopolymerization initiators are preferred.

[0114] Examples of benzophenone-based photopolymerization initiators include benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4'-methyl-diphenyl sulfide. These benzophenones and their derivatives can improve the curing rate by using tertiary amines as hydrogen donors.

[0115] Examples of commercially available benzophenone-based photopolymerization initiators include SPEEDCUREMBP (4-methylbenzophenone), SPEEDCUREMBB (methyl-2-benzoylbenzoate), SPPEDCUREBMS (4-benzoyl-4'methyldiphenyl sulfide), SPPEDCUREPBZ (4-phenylbenzophenone), and SPPEDCUREEMK (4,4'-bis(diethylamino)benzophenone) (all trade names, manufactured by DKSH Japan Co., Ltd.).

[0116] Examples of thioxanthone-based photopolymerization initiators include thioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone. 2,4-diethylthioxanthone is preferred as diethylthioxanthone, 2-isopropylthioxanthone as isopropylthioxanthone, and 2-chlorothioxanthone as chlorothioxanthone. Among these, thioxanthone-based photopolymerization initiators containing diethylthioxanthone are even more preferred.

[0117] Examples of commercially available thioxanthone-based photopolymerization initiators include SpeedcureDETX (2,4-diethylthioxanthone), SpeedcureITX (2-isopropylthioxanthone), SpeedcureCTX (2-chlorothioxanthone), SPEEDCURECPTX (1-chloro-4-propylthioxanthone) (all trade names, manufactured by DKSH Japan Co., Ltd.), KAYACUREDETX (2,4-diethylthioxanthone) (trade name, manufactured by Nippon Kayaku Co., Ltd.), and DAIDO UV-CURE DETX (manufactured by Daido Chemical Industries, Ltd.).

[0118] The amount of photosensitizer (C) added is not particularly limited, but is preferably about 0.05 to 15% by mass of the total solid content of the negative-type photosensitive resin composition, more preferably about 0.1 to 12.5% ​​by mass, and even more preferably about 0.2 to 10% by mass. By setting the amount of photosensitizer (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.

[0119] [Silane coupling agent (D)] The negative-type photosensitive resin composition of this embodiment may further contain a silane coupling agent (D). This improves the adhesion between the resin film or pattern formed from the negative-type photosensitive resin composition and the substrate.

[0120] The usable silane coupling agent (D) is not particularly limited. For example, silane coupling agents such as aminosilane, epoxysilane, acrylicsilane, mercaptosilane, vinylsilane, ureidosilane, acid anhydride-functionalized silane, and sulfidesilane can be used. One type of silane coupling agent (D) 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. The group on the opposite side of the silane coupling agent can bond to polymer A or polymer B or become more compatible with the polymer, thereby further improving the adhesion of the resin film or pattern formed from the negative-type photosensitive resin composition to the substrate.

[0121] 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.

[0122] Examples of epoxysilanes include γ-glycidoxypropyltrimethoxysilane, γ Examples include glycidoxypropylmethyldiethoxysilane, or β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane, etc.

[0123] Examples of acrylicsilanes include γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, or γ-(methacryloxypropyl)methyldiethoxysilane. Examples of mercaptosilanes include 3-mercaptopropyltrimethoxysilane.

[0124] Examples of vinylsilanes include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, or vinyltrimethoxysilane. Examples of ureidosilanes include 3-ureidopropyltriethoxysilane. Examples of acid anhydride-functionalized silanes include 3-trimethoxysilylpropyl succinic anhydride.

[0125] Examples of sulfidosilanes include bis(3-(triethoxysilyl)propyl) disulfide or bis(3-(triethoxysilyl)propyl) tetrasulfide. When using a silane coupling agent (D), one type may be used alone, or two or more types may be used in combination.

[0126] The content of the silane coupling agent (D) is typically 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, when the total solid content of the negative-type photosensitive resin composition is 100 parts by mass. It is believed that this range allows for sufficient adhesion, which is the effect of the silane coupling agent (D), while maintaining a balance with other performance characteristics.

[0127] (solvent) The negative-type photosensitive resin composition according to this embodiment may contain a urea compound or an acyclic amide compound as a solvent. Preferably, the solvent contains a urea compound. This improves the adhesion between the cured product of the negative-type photosensitive resin composition and metals such as Al and Cu.

[0128] In this specification, a urea compound refers to a compound containing a urea bond, i.e., a urea bond. An amide compound refers to a compound containing an amide bond, i.e., an amide. Specifically, amides include primary amides, secondary amides, and tertiary amides.

[0129] Furthermore, in this embodiment, an acyclic structure means that the compound does not contain cyclic structures such as carbocyclic rings, inorganic rings, or heterocyclic rings. Examples of compounds that do not contain cyclic structures include linear structures and branched structures.

[0130] For urea compounds and acyclic amide compounds, those with a large number of nitrogen atoms in their molecular structure are preferred. Specifically, it is preferable that the molecular structure contains two or more nitrogen atoms. This increases the number of lone pairs of electrons. Therefore, adhesion to metals such as Al and Cu can be improved.

[0131] Specific structural examples of urea compounds include cyclic and acyclic structures. Of the above examples, an acyclic structure is preferred for the urea compound. This improves the adhesion between the cured product of the negative-type photosensitive resin composition and metals such as Al and Cu. The reason for this is presumed to be as follows: Acyclic urea compounds are thought to form coordination bonds more easily than cyclic urea compounds. This is because acyclic urea compounds have fewer restrictions on molecular motion and a greater degree of freedom in molecular structure deformation compared to cyclic urea compounds. Therefore, when an acyclic urea compound is used, strong coordination bonds can be formed, improving adhesion.

[0132] Examples of urea compounds include tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, tetrabutylurea, N,N'-dimethylpropyleneurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, and O-benzyl-N,N'-diisopropylisourea. One or more of the above specific examples of urea compounds can be used in combination. As the urea compound, it is preferable to use one or more selected from the group consisting of tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, and O-benzyl-N,N'-diisopropylisourea, with tetramethylurea (TMU) being more preferable. This allows for the formation of strong coordination bonds and improves adhesion.

[0133] Examples of acyclic amide compounds include 3-methoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N,N-dimethylpropionamide, N,N-dimethylacetamide, N,N-diethylacetamide, 3-butoxy-N,N-dimethylpropanamide, and N,N-dibutylformamide. The negative-type photosensitive resin composition according to this embodiment may contain, as a solvent, a urea compound, an acyclic amide compound, or a solvent that does not contain a nitrogen atom.

[0134] Examples of solvents that do not contain nitrogen atoms include ether-based solvents, ester-based solvents, alcohol-based solvents, ketone-based solvents, lactone-based solvents, carbonate-based solvents, sulfone-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. One or more of the above specific examples of solvents that do not contain nitrogen atoms can be used in combination.

[0135] Examples of the above-mentioned ether-based solvents include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, and 1,3-butylene glycol-3-monomethyl ether.

[0136] Examples of the ester-based solvents mentioned above include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, and methyl-1,3-butylene glycol acetate.

[0137] Examples of the above-mentioned alcohol-based solvents include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropyl alcohol. Examples of the ketone solvents mentioned above include cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone. Examples of the lactone-based solvents mentioned above include γ-butyrolactone (GBL) and γ-valerolactone. Examples of the carbonate-based solvents mentioned above include ethylene carbonate and propylene carbonate. Examples of the above-mentioned sulfone-based solvents include dimethyl sulfoxide (DMSO) and sulfolane. Examples of the ester solvents mentioned above include methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate. Examples of the above-mentioned aromatic hydrocarbon solvents include mesitylene, toluene, and xylene.

[0138] The lower limit of the content of urea compounds and acyclic amide compounds in the solvent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, and especially preferably 70 parts by mass or more, when the solvent is 100 parts by mass. This further improves the adhesion between the cured product of the negative-type photosensitive resin composition and metals such as Al and Cu.

[0139] Furthermore, the lower limit of the content of urea compounds and acyclic amide compounds in the solvent can be, for example, 100 parts by mass or less, when the solvent is 100 parts by mass. From the viewpoint of improving adhesion, it is preferable that the solvent contains a high amount of urea compounds and acyclic amide compounds.

[0140] (Surfactants) The negative-type photosensitive resin composition according to this embodiment may further contain a surfactant.

[0141] 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.).

[0142] 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).

[0143] In addition, as the surfactant, silicone-based surfactants (such as polyether-modified dimethylsiloxane) can also be preferably used. Specifically, as silicone-based surfactants, SH series, SD series and ST series of Toray Dow Corning, BYK series of Big Chemie Japan, KP series of Shin-Etsu Chemical Co., Ltd., Disform (registered trademark) series of NOF Corporation, TSF series of Toshiba Silicone Co., Ltd., etc. can be mentioned.

[0144] The upper limit of the content of the surfactant in the negative 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 still more preferably 0.3% by mass (3,000 ppm) or less with respect to the whole of the negative photosensitive resin composition (including the solvent).

[0145] In addition, there is no particular lower limit for the content of the surfactant in the negative photosensitive resin composition, but from the viewpoint of sufficiently obtaining the effects of the surfactant, for example, it is 0.001% by mass (10 ppm) or more with respect to the whole of the negative photosensitive resin composition (including the solvent). By appropriately adjusting the amount of the surfactant, coating properties, film uniformity, etc. can be improved while maintaining other performances.

[0146] (Antioxidant) The negative photosensitive resin composition according to this embodiment may further contain an antioxidant. As the antioxidant, one or more selected from phenolic 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 photosensitive resin composition.

[0147] 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], triethylene glycol 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)sulfide, 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), styrenated phenol, 2,4-bis((octylthio)methyl)-5-methylphenol, etc.

[0148] 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.

[0149] 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.

[0150] (Filler) The negative-type photosensitive resin composition according to this embodiment may further contain a filler. As the filler, an appropriate filler can be selected according to the mechanical and thermal properties required for the resin film made of the negative-type photosensitive resin composition.

[0151] Examples of fillers include inorganic fillers and organic fillers. Examples of the inorganic fillers mentioned above include silica such as molten crushed silica, molten spherical silica, crystalline silica, secondary aggregated silica, and fine silica; metal compounds such as alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, and titanium white; talc; clay; mica; and glass fibers. One or more of the above specific examples of inorganic fillers can be used in combination.

[0152] Examples of the above-mentioned organic fillers include organosilicone powder and polyethylene powder. One or more of the above-mentioned organic fillers can be used in combination.

[0153] (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.

[0154] (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.

[0155] When producing the above permanent film, pre-baking conditions can include, for example, heat treatment at a temperature of 80°C to 150°C for 30 seconds to 1 hour. Alternatively, the heat treatment conditions can include, for example, heat treatment at a temperature of 150°C to 350°C for 2 minutes to 10 hours.

[0156] 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. When adjusting the viscosity, it is necessary to keep the content of the urea compound and the acyclic amide compound in the solvent constant.

[0157] The upper limit of the viscosity of the negative-type photosensitive resin composition according to this embodiment may be, for example, 2000 mPa·s or less, 1800 mPa·s or less, or 1500 mPa·s or less. The lower limit of the viscosity of the negative-type photosensitive resin composition according to this embodiment may be, for example, 10 mPa·s or more, or 50 mPa·s or more, depending on the desired thickness of the resin film.

[0158] 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 2 to 200%, preferably 5 to 150%, and an average value of 1 to 150%, preferably 2 to 120%. The film obtained from the negative-type photosensitive resin composition of this embodiment can have a tensile strength of 30 to 300 MPa, preferably 50 to 200 MPa.

[0159] Thus, the negative-type photosensitive resin composition of this embodiment can provide cured products such as films with excellent mechanical strength. The reason for this is not clear, but it is presumed that strong packing between polymer chains suppresses breakage due to slippage of polymer chains, improves elongation, and results in excellent flexibility.

[0160] (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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] The semiconductor device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package can be obtained by mounting the semiconductor device 100 on a wiring board via bumps 52.

[0166] The semiconductor device 100 includes a semiconductor substrate provided with semiconductor elements such as transistors, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. On the uppermost layer of the multilayer wiring layer, an interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided. The uppermost layer wiring 34 is made of, for example, aluminum Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and on the uppermost layer wiring 34. An opening is provided in a part of the passivation film 32 through which the uppermost layer wiring 34 is exposed.

[0167] A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 has an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and on the rewiring 46. An opening for connecting to the uppermost layer wiring 34 is formed in the insulating layer 42. The rewiring 46 is formed on the insulating layer 42 and in the opening provided in the insulating layer 42, and is connected to the uppermost layer wiring 34. An opening for connecting to the rewiring 46 is provided in the insulating layer 44.

[0168] In the opening provided in the insulating layer 44, bumps 52 are formed via, for example, an UBM (Under Bump Metallurgy) layer 50. The semiconductor device 100 is connected to a wiring board or the like via the bumps 52, for example. As described above, embodiments of the present invention have been described, but these are examples of the present invention, and various configurations other than those described above can be adopted as long as the effects of the present invention are not impaired.

Example

[0169] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. [[ID=

[0170] 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane (hereinafter also referred to as MED-J), represented by the following formula [ka]

[0171] The following formula represents 4,4'-(hexafluoroisopropylidene)bis[(4-aminophenoxy)benzene] (hereinafter also referred to as HFBAPP) [ka]

[0172] 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (hereinafter also referred to as TFMB), represented by the following formula [ka]

[0173] 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]

[0174] The following formula represents 1,4-bis(3,4-dicarboxyphenoxy)benzene acid dianhydride (hereinafter also referred to as HQDA) [ka]

[0175] 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (hereinafter also referred to as 6FDA), represented by the following formula [ka]

[0176] [Example 1] First, 43.99 g (155.8 mmol) of MED-J and 89.22 g (144.2 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and condenser. Then, 399.64 g of γ-butyrolactone (hereinafter also referred to as 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 carried out for 1 hour. Prior to this, a solution was prepared by dissolving 8.73 g (69.2 mmol) of dimethyl maleic anhydride in 26.19 g of gamma butyrolactone. This solution was added to the reaction vessel, and the reaction was carried out for another 30 minutes. The reaction was then carried out at 175°C for 3 hours to polymerize the diamine and acid anhydride, and a polymerization solution was prepared with sealed ends. The obtained polymerization solution was diluted with tetrahydrofuran to prepare a dilution, and then a white solid was precipitated by adding the dilution dropwise to a methanol solution. The obtained white solid was collected and vacuum-dried at 80°C to obtain 125.88 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 74,000, a polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of 2.62, and a end-capacitation rate of 65%. The resulting polymer contained repeating units represented by the following formula in part, and had dimethylmaleimide groups at its termini. [ka]

[0177] [Example 2] First, 5.92 g (21.0 mmol) of MED-J, 10.86 g (21.0 mmol) of HFBAPP, and 23.57 g (38.1 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and condenser. Then, 121.04 g of γ-butyrolactone (hereinafter also referred to as 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 carried out for 1 hour. Prior to this, a solution was prepared by dissolving 2.88 g (22.9 mmol) of dimethyl maleic anhydride in 8.65 g of gamma butyrolactone. This solution was added to the reaction vessel and the reaction was carried out for another 30 minutes. The reaction was then carried out at 175°C for 3 hours to polymerize the diamine and acid anhydride and to prepare a polymerization solution with sealed ends. The obtained polymerization solution was diluted with tetrahydrofuran to prepare a dilution, and then the dilution was added dropwise to a methanol solution to precipitate a white solid. The obtained white solid was collected and vacuum-dried at 80°C to obtain 35.42 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 55,600, a polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of 2.33, and a end-capacitation rate of 75%. The resulting polymer contained repeating units represented by the following formula in part, and had dimethylmaleimide groups at its termini. [ka]

[0178] [Example 3] First, 7.33 g (26.0 mmol) of MED-J, 8.31 g (26.0 mmol) of TFMB, and 29.74 g (48.1 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and condenser. Subsequently, 136.16 g of γ-butyrolactone (hereinafter also referred to as 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 carried out for 1 hour. Prior to this, a solution was prepared by dissolving 2.91 g (23.1 mmol) of dimethyl maleic anhydride in 8.73 g of gamma butyrolactone. This solution was added to the reaction vessel, and the reaction was carried out for another 30 minutes. The reaction was then carried out at 175°C for 3 hours to polymerize the diamine and acid anhydride, and a polymerization solution was prepared with sealed ends. The obtained polymerization solution was diluted with tetrahydrofuran to prepare a dilution, and then the dilution was added dropwise to a methanol solution to precipitate a white solid. The obtained white solid was collected and vacuum-dried at 80°C to obtain 35.44 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 69,500, a polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of 2.51, and a end-capacitation rate of 65%. The resulting polymer contained repeating units represented by the following formula in part, and had dimethylmaleimide groups at its termini. [ka]

[0179] [Example 4] First, 8.60 g (30.4 mmol) of MED-J and 11.89 g (29.6 mmol) of HQDA were placed in a reaction vessel of appropriate size equipped with a stirrer and a condenser. Then, 81.96 g of γ-butyrolactone (hereinafter also referred to as 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 carried out for 1 hour. Prior to this, a solution was prepared by dissolving 0.67 g (5.3 mmol) of dimethyl maleic anhydride in 2.68 g of gamma butyrolactone. This solution was added to the reaction vessel and the reaction was carried out for another 30 minutes. The reaction was then carried out at 175°C for 3 hours to polymerize the diamine and acid anhydride and to prepare a polymerization solution with sealed ends. The obtained polymerization solution was diluted with tetrahydrofuran to prepare a dilution, and then a white solid was precipitated by adding the dilution dropwise to a methanol solution. The obtained white solid was collected and vacuum-dried at 80°C to obtain 15.15 g of polymer. GPC analysis of the polymer revealed a weight-average molecular weight (Mw) of 63,400, a polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of 2.83, and a end-capacity of 79%. The resulting polymer contained repeating units represented by the following formula in part, and had dimethylmaleimide groups at its termini. [ka]

[0180] [Comparative Examples 1-2] For Comparative Examples 1 and 2, synthesis was carried out using the same method as in Example 1, except for the conditions listed in Table 1. The obtained Mw and Mw / Mn are listed in Table 1.

[0181] [Measurement of end-capacitation rate] The post-reaction solution was measured by gas chromatography, and assuming that all of the dimethyl maleic anhydride consumed in the reaction was bound to the polymer ends, the ratio of the actual consumption to the theoretical consumption of dimethyl maleic anhydride was defined as the polymer end sealing rate by dimethyl maleic anhydride.

[0182] [Solubility in organic solvents] The solubility of the negative-type photosensitive polymers obtained in Examples 1-3 and Comparative Examples 1 and 2 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.

[0183] [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

[0184] (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

[0185] [Growth rate] The polymer solutions (100 parts by mass of polymer) obtained in the examples and comparative examples were spin-coated onto the surface of a silicon wafer. After pre-baking at 120°C for 4 minutes, the films were prepared by heat treatment at 200°C for 120 minutes under nitrogen. 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). Five test specimens were measured, and the tensile elongation was calculated from the fracture distance and initial distance. The maximum and average values ​​of the elongation were determined. The results are shown in Table 1.

[0186] [Table 2]

[0187] 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.

[0188] The following compounds were used in the preparation of the negative-type photosensitive resin composition. • Photosensitive agent: 1-chloro-4-propoxythioxanthone (manufactured by Lambson, UK; brand name: SPEEDCURE CPTX) • Solvent: Cyclopentanone

[0189] [Synthesis Example 1] (Synthesis of maleic anhydride-modified norbornene monomer (DMMIBuNB, 1-[4-(5-2-norbornyl)butyl]-3,4-dimethylpyrrole-2,5-dione)) In a 500 mL round-bottom flask, dimethyl maleic anhydride (42.6 g, 0.34 mol) was dissolved in toluene (300 mL) at room temperature. To remove oxygen, the solution was placed under a nitrogen atmosphere. The reaction flask was placed in an ice bath to prevent excessive heating due to the exothermic reaction. Once the dimethyl maleic anhydride was dissolved, a dropping funnel containing 5-norbornene-2-butylamine (49.6 g, 0.30 mol) was attached, and the norbornene compound was added dropwise to the reaction flask over 3 hours. The dropping funnel was removed, and a Dean-Stark tube and reflux condenser were attached to the flask. The solution was heated and refluxed in an oil bath set to 125°C, and the reactants were stirred at that temperature for 18 hours. During this time, approximately 6 mL of water was collected in the Dean-Stark tube. The flask was removed from the oil bath and cooled to room temperature. The toluene solvent was removed using an evaporator to obtain a yellow oily substance. The crude product was placed on a flash chromatography column (250 g of silica gel) and eluted using a solvent mixture of 1.7 liters of cyclohexane / ethyl acetate (95 / 5 wt ratio). The eluent was removed using an evaporator, and then dried under vacuum at 45°C for 18 hours to obtain 80.4 g (yield 92.7%) of the target product. The reaction equation is shown below.

[0190] [ka]

[0191] (Synthesis of polymer (DMMI-PNB)) In a nitrogen-purged reaction vessel, 24.6 g of 1-[4-(5-2-norbornyl)butyl]-3,4-dimethylpyrrole-2,5-dione) obtained by the above method, 3.1 g of triethylsilane, 13.5 g of toluene, and 4.5 g of ethyl acetate were charged. Furthermore, a mixed solution was prepared by adding 0.065 g of 2.1 wt% [Pd(P(iPr)3)2(OCOCH3)(NCCH3)]tetrakis(pentafluorophenyl)borate, 0.043 g of N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, 3.8 g of toluene, and 1.3 g of ethyl acetate to the reaction vessel and reacting at 70°C for 3 hours to obtain a polymer solution. The conversion rate to polymer was 91%. The weight-average molecular weight of the obtained polymer was 6,700, and the molecular weight distribution was 1.89. The prepared polymer solution was diluted with tetrahydrofuran, reprecipitation with methanol, filtered, and then vacuum-dried at 50°C to obtain 18 g of the polymer (DMMI-PNB).

[0192] [Example 5] (Preparation of negative-type photosensitive resin composition) A photosensitive resin composition was prepared by mixing the polymer solution from Example 1 (12.0 parts by mass of polymer DMMI-PI), the polymer from Synthesis Example 1 (DMMI-PNB), and the components shown in Table 2 in the amounts shown in Table 2. 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 4 minutes, and then exposed to high-pressure mercury lamp light at 1500 mJ / cm². 2 The film was prepared by exposing it to light and then heat-treating it in a nitrogen atmosphere at 200°C for 120 minutes.

[0193] [Glass transition temperature (Tg)] A test piece measuring 8 mm × 40 mm was cut from the film obtained in Example 5. 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.

[0194] [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 5 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 5 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.

[0195] (Dielectric loss tangent Df) The photosensitive resin composition of Example 5 was applied to a substrate, the coating was dried at 120°C for 10 minutes, and then subjected to PLA exposure (540 mJ). The film was cured at 200°C for 2 hours under a nitrogen atmosphere to obtain a film with a thickness of 100 μm. The dielectric loss tangent of the obtained film at 10 GHz was measured using the cavity resonator method.

[0196] [Evaluation of patterning characteristics] The photosensitive resin composition of Example 5 was confirmed to be sufficiently patternable by exposure and development as follows. The photosensitive resin composition of Example 5 was applied onto an 8-inch silicon wafer using a spin coater. After application, it was pre-baked on a hot plate at 120°C for 4 minutes under atmospheric pressure to obtain a coating with a thickness of approximately 8.0 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, cyclopentanone was used as the developer, and the image was spray-developed for 120 seconds to dissolve and remove the unexposed areas, 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 5 exhibited good patternability.

[0197] [Table 3]

[0198] 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 low dielectric loss tangent and elongation, and furthermore, due to the inclusion of a negative-type photosensitive polymer with excellent hydrolysis resistance, it was found to have excellent mechanical strength even after HAST testing. In addition, it also exhibits good patternability, confirming its suitability as a negative-type photosensitive resin composition.

[0199] This application claims priority based on Japanese Patent Application No. 2021-105687, filed on 25 June 2021, and incorporates all of its disclosures herein. [Explanation of symbols]

[0200] 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 Includes, The aforementioned 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 a group such that at least one of both ends is a group represented by the following general formula (t). 【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 (t), R ５ and R ６ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q ２ ( indicates a divalent organic group. * indicates a bond.)

2. The negative-type photosensitive resin composition according to claim 1, 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.

3. The negative-type photosensitive resin composition according to claim 1 or 2, 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 4】 (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 general formula (a1-3), Z １ This represents an alkylene group with 1 to 5 carbon atoms, or a divalent aromatic group. * indicates a bonding position.

4. The negative-type photosensitive resin composition according to claim 1 or 2, wherein Y in the general formula (a1) is a divalent organic group represented by the following general formula (a1-4). 【Transformation 5】 (In general formula (a1-4), Z ２ ( indicates a divalent aromatic group. * indicates a bond.)

5. The negative-type photosensitive resin composition according to claim 1 or 2, wherein both ends of the polyimide (A) are groups represented by the general formula (t).

6. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the polyimide (A) further comprises a structural unit (a3) ​​represented by general formula (a3). 【Transformation 6】 (In general formula (a3), R ５ and R ６ Each of these independently represents a hydrogen atom, a C1-C4 haloalkyl group, or a hydroxyl group, and there are multiple R groups. ５ R with other Rs and multiple Rs with other Rs. ６ The elements may be identical or different. X represents a single bond, an alkylene group with 1 to 4 carbon atoms, or a haloalkylene group with 1 to 4 carbon atoms. m and n each independently represent 0 or 1.

7. The Q of the general formula (t) ２ The negative-type photosensitive resin composition according to claim 6, wherein the divalent organic group in is a structural unit (a2) represented by general formula (a2) or a structural unit (a3) ​​represented by general formula (a3).

8. 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 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).)

9. The negative-type photosensitive resin composition according to claim 6, wherein the polyimide (A) includes a structural unit represented by the following general formula (2). 【Transformation 8】 (In general formula (2), R ５ ~R ６ X, m, and n are equivalent to those in general formula (a3), and Y is equivalent to those in general formula (a1).

10. Furthermore, the negative-type photosensitive resin composition according to claim 1 or 2, comprising a crosslinking agent (B) having substituted or unsubstituted maleimide groups (excluding the polyimide (A)).

11. The negative-type photosensitive resin composition according to claim 10, wherein the crosslinking agent (B) comprises a structural unit represented by the following general formula (b). 【Chemistry 9】 (In general formula (b), R １ and R ２ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q １ This indicates a single bond or a divalent organic group, G １ G ２ , and G ３ Each of these independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and m is 0, 1, or 2.

12. Q １ The negative-type photosensitive resin composition according to claim 11, wherein the divalent organic group is an alkylene group having 1 to 8 carbon atoms or a (poly)alkylene glycol chain.

13. The negative-type photosensitive resin composition according to claim 1 or 2, further comprising a photosensitizer (C).

14. The negative-type photosensitive resin composition according to claim 1 or 2, further comprising a silane coupling agent (D).

15. 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 comprising a group such that at least one of its ends is a group represented by the following general formula (t). 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 (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 (t), R ５ and R ６ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q ２ ( indicates a divalent organic group. * indicates a bond.)

16. The negative-type photosensitive polymer according to claim 15, 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.

17. The negative-type photosensitive polymer according to claim 15 or 16, 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 13】 (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 general formula (a1-3), Z １ This represents an alkylene group with 1 to 5 carbon atoms, or a divalent aromatic group. * indicates a bonding position.

18. The negative-type photosensitive polymer according to claim 15 or 16, wherein Y in the general formula (a1) is a divalent organic group represented by the following general formula (a1-4). 【Chemistry 14】 (In general formula (a1-4), Z ２ ( indicates a divalent aromatic group. * indicates a bond.)

19. The negative-type photosensitive polymer according to claim 15 or 16, wherein both ends are groups represented by the general formula (t).

20. The negative-type photosensitive polymer according to claim 15 or 16, further comprising a structural unit (a3) ​​represented by general formula (a3). 【Chemistry 15】 (In general formula (a3), R ５ and R ６ Each of these independently represents a hydrogen atom, a C1-C4 haloalkyl group, or a hydroxyl group, and there are multiple R groups. ５ R with other Rs and multiple Rs with other Rs. ６ The elements may be identical or different. X represents a single bond, an alkylene group with 1 to 4 carbon atoms, or a haloalkylene group with 1 to 4 carbon atoms. m and n each independently represent 0 or 1.

21. The Q of the general formula (t) ２ The negative-type photosensitive polymer according to claim 20, wherein the divalent organic group in is a structural unit (a2) represented by general formula (a2) or a structural unit (a3) ​​represented by general formula (a3).

22. A negative-type photosensitive polymer according to claim 15 or 16, comprising a structural unit represented by the following general formula (1). 【Chemistry 16】 (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).)

23. The negative-type photosensitive polymer according to claim 20, comprising a structural unit represented by the following general formula (2). 【Chemistry 17】 (In general formula (2), R ５ ~R ６ X, m, and n are equivalent to those in general formula (a3), and Y is equivalent to those in general formula (a1).

24. The negative-type photosensitive polymer according to claim 15 or 16, wherein the rate of decrease in weight-average molecular weight measured under the following conditions is less than 50%. (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

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

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

27. 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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