WO2022270527A1

WO2022270527A1 - Negative photosensitive resin composition, negative photosensitive polmer, cured film and semiconductor device

Info

Publication number: WO2022270527A1
Application number: PCT/JP2022/024837
Authority: WO
Inventors: 啓太今井; 昭彦乙黒
Original assignee: 住友ベークライト株式会社
Priority date: 2021-06-25
Filing date: 2022-06-22
Publication date: 2022-12-29
Also published as: CN116848467A; TW202311368A; JPWO2022270527A1

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

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

The present invention relates to a negative photosensitive resin composition, a negative photosensitive polymer, a cured film and a semiconductor device.

Polyimide resin has high mechanical strength, heat resistance, insulation, and solvent resistance, so it is widely used as a protective material for liquid crystal display elements and semiconductors, as an insulating material, and as a thin film for electronic materials such as color filters. there is

Patent Document 1 discloses a block copolyimide that is soluble in a dipolar aprotic solvent, and states that a predetermined acid anhydride can be used to obtain the block copolyimide.

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.

Patent Document 3 discloses an aromatic tetracarboxylic dianhydride, 4,4'-diaminodiphenylmethane having at least one or more alkyl groups in an aromatic ring having an amino group, and p-aminobenzoic acid ester groups at both ends. A polyimide elastomer resin is disclosed which is a terpolymer obtained from a polyether oligomer having a specific molecular weight. The document mentions bis(4-amino-3-ethyl-5-methylphenyl)methane as 4,4'-diaminodiphenylmethane. The document describes that the resin has excellent heat and humidity resistance.

Patent Document 4 discloses a block copolymer comprising a polyimide structural unit formed from an aromatic tetracarboxylic dianhydride and a 4,4'-diaminodiphenylmethane derivative and a dimethylsiloxane structural unit. The document mentions bis(4-amino-3-ethyl-5-methylphenyl)methane as 4,4'-diaminodiphenylmethane. The literature describes that the resin is excellent in heat resistance and solvent solubility.
Patent Document 5 discloses a photosensitive composition containing a polyimide terminated with a predetermined maleimide group.

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. are exemplified by cyclic olefin resins terminated with maleimide groups of

International Publication No. 015/091122 Australia JP-A-64-16829 JP-A-8-217874 JP-A-9-40777 WO2020/181021 JP 2019-028115 A

However, in the conventional techniques described in Patent Documents 1 to 5, the film containing polyimide obtained from the photosensitive resin composition has room for improvement in mechanical strength such as elongation.

Conventionally, in order to improve the solubility of polyimide in organic solvents, fluorine atoms have been introduced into the skeleton of the polyimide. When synthesized, it was found that the strong electron-withdrawing property of fluorine atoms affects the electrons of the imide ring, making the resulting polyimide susceptible to hydrolysis, which reduces mechanical strength such as elongation.
That is, conventional polyimides have room for improvement in terms of the balance between solubility in organic solvents and mechanical strength such as elongation.
In addition, Patent Document 6 does not describe the combined use with a predetermined polyimide.

The present inventors have found that the above problems can be solved by using a polyimide having a specific structure, and completed the present invention.
That is, the present invention can be shown below.

[1] (A) contains polyimide,
The polyimide (A) is
a structural unit (a1) represented by the following general formula (a1);
a structural unit (a2) represented by the following general formula (a2);
At least one of both ends is a group represented by the following general formula (t), a negative photosensitive resin composition.

(In general formula (a1), Y is a divalent organic group.
In general formula (a2), R ¹ to R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R ¹ and R ² are different groups; R3 and ^R4 ^are different groups.
X ¹ represents 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; , a plurality of X ¹ may be the same or different.
In 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. * indicates 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] 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). The negative photosensitive resin composition according to [1] or [2].

(In general formula (a1-1), R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ⁷ and a plurality of R ⁸ may be the same or different, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to ³ carbon atoms; may be the same or different, and * indicates a bond.
In general formula (a1-2), each of R ¹⁰ and R ¹¹ independently represents a hydrogen atom, an alkyl group having ¹ to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R ¹¹ may be the same or different. * indicates a bond.
In general formula (a1-3), Z ¹ represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond. )
[4] The negative photosensitive resin composition according to [1] or [2], wherein Y in the general formula (a1) is a divalent organic group represented by the following general formula (a1-4): thing.

(In general formula (a1-4), Z2 represents a ^divalent aromatic group. * represents a bond.)
[5] The negative photosensitive resin composition according to any one of [1] to [4], wherein both ends of the polyimide (A) are groups represented by the general formula (t).
[6] The negative photosensitive resin composition according to any one of [1] to [5], wherein the polyimide (A) further contains a structural unit (a3) represented by general formula (a3).

(In general formula (a3), R ⁵ and R ⁶ each independently represent a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a hydroxyl group, and multiple R ⁵ and multiple R ⁶ are the same X represents a single bond, an alkylene group having 1 to 4 carbon atoms, or a haloalkylene group having 1 to 4 carbon atoms, and m and n each independently represent 0 or 1.)
[7] The ^divalent organic group in Q2 of the general formula (t) is a structural unit (a2) represented by the general formula (a2) or a structural unit (a3) represented by the general formula (a3) The negative photosensitive resin composition according to [6].
[8] The negative photosensitive resin composition according to any one of [1] to [7], wherein the polyimide (A) comprises a structural unit represented by the following general formula (1).

(In general formula (1), R ¹ to R ⁴ and X ¹ have the same meanings as in general formula (a2), and Y has the same meaning as in general formula (a1).)
[9] The negative photosensitive resin composition according to any one of [6] to [8], wherein the polyimide (A) contains a structural unit represented by the following general formula (2).

(In general formula (2), R ⁵ to R ⁶ , X, m, and n are synonymous with general formula (a3), and Y is synonymous with general formula (a1).)
[10] The negative photosensitive resin composition according to any one of [1] to [9], further comprising a cross-linking agent (B) having a substituted or unsubstituted maleimide group (excluding the polyimide (A)). thing.
[11] The negative photosensitive resin composition according to [10], wherein the cross-linking agent (B) contains a structural unit represented by the following general formula (b).

(In general formula (b), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q ¹ represents a single bond or a divalent organic group, G ¹ , G ² and G ³ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and m is 0, 1 or 2.)
[12] The negative photosensitive resin composition according to [11], wherein the divalent organic group of Q ¹ is an alkylene group having 1 to 8 carbon atoms or a (poly)alkylene glycol chain.
[13] The negative photosensitive resin composition according to any one of [1] to [12], further comprising a photosensitizer (C).
[14] The negative 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);
At least one of both ends is a group represented by the following general formula (t), a negative photosensitive polymer.

(In general formula (a1), Y is a divalent organic group. In general formula (a2), R ¹ to R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. is an alkoxy group, R ¹ and R ² are different groups, and R ³ and R ⁴ are different groups.
X ¹ represents 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; , a plurality of X ¹ may be the same or different.
In 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. * indicates a bond. )
[16] The negative 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] Y in the general formula (a1) is a divalent organic group selected from the following general formula (a1-1), general formula (a1-2) and general formula (a1-3) below. The negative photosensitive polymer according to [15] or [16].

(In general formula (a1-1), R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ⁷ and a plurality of R ⁸ may be the same or different, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to ³ carbon atoms; may be the same or different, and * indicates a bond.
In general formula (a1-2), each of R ¹⁰ and R ¹¹ independently represents a hydrogen atom, an alkyl group having ¹ to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R ¹¹ may be the same or different. * indicates a bond.
In general formula (a1-3), Z ¹ represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond. )
[18] The negative photosensitive polymer according to [15] or [16], wherein Y in general formula (a1) is a divalent organic group represented by general formula (a1-4) below.

(In general formula (a1-4), Z2 represents a ^divalent aromatic group. * represents a bond.)
[19] The negative photosensitive polymer according to any one of [15] to [18], wherein both terminals are groups represented by the general formula (t).
[20] The negative photosensitive polymer according to any one of [15] to [19], further comprising a structural unit (a3) represented by general formula (a3).

(In general formula (a3), R ⁵ and R ⁶ each independently represent a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a hydroxyl group, and multiple R ⁵ and multiple R ⁶ are the same X represents a single bond, an alkylene group having 1 to 4 carbon atoms, or a haloalkylene group having 1 to 4 carbon atoms, and m and n each independently represent 0 or 1.)
[21] The ^divalent organic group in Q2 of the general formula (t) is a structural unit (a2) represented by the general formula (a2) or a structural unit (a3) represented by the general formula (a3) The negative photosensitive polymer according to [20].
[22] The negative photosensitive polymer according to any one of [15] to [21], which contains a structural unit represented by the following general formula (1).

(In general formula (1), R ¹ to R ⁴ and X ¹ have the same meanings as in general formula (a2), and Y has the same meaning as in general formula (a1).)
[23] The negative photosensitive polymer according to any one of [20] to [22], which contains a structural unit represented by the following general formula (2).

(In general formula (2), R ⁵ to R ⁶ , X, m, and n are synonymous with general formula (a3), and Y is synonymous with general formula (a1).)
[24] The negative photosensitive polymer according to any one of [15] to [23], which has a weight-average molecular weight reduction rate of less than 50% as measured under the following conditions.
(conditions)
400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water are added to 100 parts by mass of the negative photosensitive polymer, and the mixture is stirred at 100°C for 6 hours. .
Formula: [(weight average molecular weight before test - weight average molecular weight after test) / weight average molecular weight before test] × 100
[25] A cured film comprising a cured product of the negative photosensitive resin composition according to any one of [1] to [14].
[26] A semiconductor device comprising a resin film containing a cured product of the negative photosensitive resin composition according to any one of [1] to [14].
[27] an interlayer insulating film;
a resin film containing a cured product of the negative photosensitive resin composition according to any one of [1] to [14] provided on the interlayer insulating film;
a rewiring embedded in the resin film;
A semiconductor device comprising:

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a negative photosensitive polymer capable of obtaining a cured product such as a film having excellent solubility in an organic solvent and excellent mechanical strength such as elongation, and a negative photosensitive resin composition containing the polymer. can be provided.

1 is a schematic cross-sectional view of a semiconductor device according to an embodiment; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the description thereof will be omitted as appropriate. In addition, "A to B" represents "above A" to "below B" unless otherwise specified.
The negative photosensitive resin composition of the present embodiment contains (A) polyimide.

[Polyimide (A)]
The polyimide (A) (negative photosensitive polymer) of the present 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). and at least one of both ends is a group represented by the following general formula (t).

In general formula (a1), Y is a divalent organic group.
As the divalent organic group, a known organic group can be used as long as the effect of the present invention is exhibited. From the viewpoint of the effect of the present invention, Y is a divalent group containing an alkylene group, or at least one A divalent group containing one aromatic ring is preferred.
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. The aromatic ring includes a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring, a divalent biphenyl group and the like, preferably a divalent benzene ring or a divalent biphenyl group.
Y in the general formula (a1) is a divalent selected from the following general formula (a1-1), the following general formula (a1-2), the following general formula (a1-3) and the following general formula (a1-4) is more preferably an organic group of

In general formula (a1-1), R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple R ⁷ , multiple R ⁸ may be the same or different.
From the viewpoint of the effects of the present invention, R ⁷ and R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
R ⁹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ⁹ may be the same or different.
From the viewpoint of the effects of the present invention, R ⁹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
* indicates a bond.

In general formula (a1-2), each of R ¹⁰ and R ¹¹ independently represents a hydrogen atom, an alkyl group having ¹ to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R ¹¹ may be the same or different.

From the viewpoint of the effect of the present invention, R ¹⁰ and R ¹¹ 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 an alkyl group having 1 to 3 carbon atoms, more preferably three R ¹⁰ are alkyl groups having 1 to 3 carbon atoms, one R ¹⁰ is a hydrogen atom, and three R ¹¹ are alkyl groups having 1 to 3 carbon atoms one R ¹¹ is a hydrogen atom, particularly preferably three R ¹⁰ are methyl groups and one R ¹⁰ is a hydrogen atom, and three R ¹¹ are methyl groups and one R ¹¹ is It is a hydrogen atom.
* indicates a bond.

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

In general formula (a2), R ¹ to R ⁴ each independently represent 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 effect of the present invention, preferably carbon It is an alkyl group of numbers 1 to 3.
R ¹ and R ² are different groups, and R ³ and R ⁴ are different groups. As a result, the structural unit represented by the general formula (a2) has an asymmetric molecular structure, so that the main chain of the polymer having the structural unit is twisted. This is considered to be one of the reasons for the improvement in solvent solubility.

X ¹ represents 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; , a plurality of X ¹ may be the same or different.

X ¹ is preferably a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, and more 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 is preferred.

By containing the structural unit represented by the general formula (a2), the polyimide (A) of the present embodiment suppresses the influence of the imide ring on the electrons, suppresses the hydrolysis of the polyimide, and improves mechanical properties such as elongation. Excellent strength and excellent solubility in organic solvents. In other words, the polyimide (A) of the present embodiment and the negative photosensitive resin composition containing the polyimide (A) have an excellent balance of these properties.

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

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 from the viewpoint of the effect of the present invention, an alkyl group having 1 or 2 carbon atoms is preferable, A C 1 alkyl group (methyl group) is more preferred. * indicates a bond.
When both R ⁵ and R ⁶ are methyl groups, hydrolysis of the polyimide is further suppressed, and mechanical strength such as elongation is further excellent, and solubility in organic solvents is also excellent.

^Q2 represents a divalent organic group.
As the divalent organic group, a known organic group can be used as long as the effect of the present invention is exhibited. For example, the structural unit (a2) represented by the general formula (a2) is preferable. . Specific examples include a divalent organic group represented by the following general formula (t-1).

In general formula (t-1), X ¹ and R ¹ to R ⁴ have the same meanings as in general formula (a2).
* indicates a bond.

The polyimide (A) can further contain a structural unit (a3) represented by the following general formula (a3).

In general formula (a3), R ⁵ and R ⁶ each independently represent a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a hydroxyl group, preferably a hydrogen atom or a haloalkyl group having 1 to 4 carbon atoms. A plurality of R ⁵ may be the same or different, and a plurality of R ⁶ may be the same or different.

X represents a single bond, an alkylene group having 1 to 4 carbon atoms, or a haloalkylene group having 1 to 4 carbon atoms, preferably a single bond or a haloalkylene group having 1 to 4 carbon atoms.
m and n each independently represent 0 or 1;

In the general formula (t), the divalent organic group Q ² may be the structural unit (a3) represented by the general formula (a3). Specific examples include a divalent organic group represented by the following general formula (t-2).

In general formula (t-2), R ⁵ , R ⁶ , X, m and n have the same meanings as in general formula (a3).
* indicates a bond.

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

The polyimide (A) of the present embodiment is excellent in mechanical strength because it contains a polyimide having a group t represented by general formula (t) at at least one end. Furthermore, since photodimerization is possible without causing a radical reaction, polyimide (A) can be photopolymerized with each other, polyimide (A) and a cross-linking agent (B) described later, and mechanical strength is excellent.
Moreover, the polyimide (A) may contain a polyimide having a group u represented by the following general formula (u) at its end.

In general formula (u), X ¹ and R ¹ to R ⁴ have the same meanings as in general formula (a2).

When the polyimide (A) contains a polyimide having the group u, the ratio of the number of moles of the group b to the total number of moles of the group t and the group u (t/t+u) is 0.5 or more, preferably 0.55. above, more preferably 0.6 or above. If it is this range, the polyimide component eluted by development can be reduced.

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

In general formula (1), R ¹ to R ⁴ and X ¹ have the same meanings as in general formula (a2), and Y has the same meaning as in general formula (a1).

Specifically, the polyimide (A) of the present embodiment may further contain a structural unit 2 represented by the following general formula (2) in addition to the structural unit 1.

In general formula (2), R ⁵ to R ⁶ , X, m and n have the same meanings as in general formula (a3), and Y has the same meaning as in general formula (a1).

The weight average molecular weight of the polyimide (A) of this embodiment is 5,000 to 200,000, preferably 10,000 to 100,000.

The polyimide (A) (negative photosensitive polymer) of the present embodiment is excellent in hydrolysis resistance, and has a weight average molecular weight reduction rate of less than 50%, preferably 30% or less, measured under the following conditions. More preferably 20% or less, more preferably 10% or less, particularly preferably 7% or less.
(conditions)
400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water are added to 100 parts by mass of the negative photosensitive polymer, and the mixture is stirred at 100°C for 6 hours. .
Formula: [(weight average molecular weight before test - weight average molecular weight after test) / weight average molecular weight before test] × 100

The polyimide (A) of the present embodiment has a weight average molecular weight reduction rate within the above range, so that hydrolysis is suppressed and a cured product such as a film having excellent mechanical strength such as elongation can be obtained. .

In addition, since the polyimide (A) of the present embodiment has excellent solubility in solvents and does not need to be varnished in a precursor state, a varnish containing the polyimide (A) can be prepared. A cured product such as a film can be obtained from the varnish.

<Method for producing polyimide (A)>
Polyimide (A) (negative photosensitive polymer) having a structural unit represented by the general formula (1) of the present embodiment and at least one of both ends being a group t represented by the general formula (t) The manufacturing method is
An acid anhydride (a1′) represented by the following general formula (a1′), a diamine (a2′) represented by the following general formula (a2′), and an anhydride represented by the following general formula (t′) A step of reacting with a maleic acid derivative (t') is included.
According to this embodiment, a polyimide (A) having excellent solubility in organic solvents can be synthesized by a simple method.

In general formula (a1′), Y is a group represented by general formula (a1-1), general formula (a1-2), general formula (a1-3) and general formula (a1-4). is selected from

In general formula (a2'), R ¹ to R ⁴ and X ¹ have the same meanings as in general formula (a2).

In general formula (t'), R ⁵ and R ⁶ have the same meanings as in general formula (t).

The equivalent ratio of diamine (a2') and acid anhydride (a1') in the reaction is an important factor that determines the molecular weight of the resulting polyimide. In general, it is well known that there is a correlation between the molecular weight and mechanical properties of polymers, the higher the molecular weight the better the mechanical properties. Therefore, in order to obtain a polyimide having practically excellent strength, it is necessary to have a certain degree of high molecular weight. In the present invention, the equivalent ratio of the diamine (a2′) and the acid anhydride (a1′) to be used is not particularly limited, but the equivalent ratio of the acid anhydride (a1′) to the diamine (a2′) is from 0.80 to It is preferably in the range of 1.06. If it is less than 0.80, the molecular weight is low and the material becomes brittle, resulting in low mechanical strength. On the other hand, if it exceeds 1.06, unreacted carboxylic acid may be decarboxylated during heating to cause gas generation and foaming, which is not preferable.

In the present embodiment, from the viewpoint of the effect of the present invention, an acid anhydride (a1′), a diamine (a2′), a maleic anhydride derivative (t′), and further represented by the following general formula (a3′) It is also preferred to react the diamine (a3′) to be formed.

In general formula (a3'), R ⁵ , R ⁶ , X, m and n are synonymous with general formula (a3).

The equivalent ratio of acid anhydride (a1'), diamine (a2') and diamine (a3') is an important factor that determines the molecular weight of the resulting polymer. In general, it is well known that there is a correlation between the molecular weight and mechanical properties of polymers, the higher the molecular weight the better the mechanical properties. Therefore, in order to obtain a polymer having practically excellent strength, it is necessary to have a high molecular weight to some extent. In the present invention, the equivalent ratio of the acid anhydride (a1′), the diamine (a2′) and the diamine (a3′) to be used is not particularly limited. The equivalent ratio of diamine (a3') is preferably in the range of 0.80 to 1.06. If the corresponding amount ratio is within the above range, the mechanical strength is excellent and the manufacturing stability is excellent.

The amount of the maleic anhydride derivative (t') can be 3 times the molar amount of amino groups that are not reacted with the acid anhydride (a1').

Thereby, photosensitivity by photodimerization can be imparted to the polyimide, and a cured product such as a film having excellent mechanical properties as well as excellent low dielectric loss tangent can be obtained.
The reaction can be carried out by a known method in an organic solvent.

Examples of organic solvents include aprotic polar solvents such as γ-butyl lactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane. , and one type or two or more types may be used in combination. At this time, a nonpolar solvent compatible with the aprotic polar solvent may be mixed and used. Nonpolar solvents include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene and solvent naphtha. The ratio of the non-polar solvent in the mixed solvent is set arbitrarily according to the resin properties such as the stirring device capacity and solution viscosity, as long as the solubility of the solvent decreases and the polyamic acid resin obtained by the reaction does not precipitate. can do.

The reaction temperature is 0° C. or higher and 100° C. or lower, preferably 20° C. or higher and 80° C. or lower, for about 30 minutes to 2 hours. React for some time.

Maleic anhydride derivative (t') may be present in the imidization reaction of acid anhydride (a1') with diamine (a2') and diamine (a3'), but acid anhydride (a1' ) and the diamines (a2′) and (a3′) during or after the reaction is completed, the maleic anhydride derivative (t′) dissolved in the above organic solvent is added and reacted to block the polyimide terminals. can be done.

When the maleic anhydride derivative (t') is added separately, it is preferable to react after the addition at 100°C or higher and 250°C or lower, preferably 120°C or higher and 200°C or lower for about 1 to 5 hours.

A reaction solution containing the polyimide (A) (terminal-blocked polyimide) of the present embodiment can be obtained by the above steps, further diluted with an organic solvent or the like as necessary, and used as a polymer solution (coating varnish). be able to. As the organic solvent, those exemplified in the reaction step can be used, and the same organic solvent as in the reaction step may be used, or a different organic solvent may be used.

In addition, this reaction solution can be put into a poor solvent to reprecipitate the polyimide (A) to remove unreacted monomers, dry and solidify, and dissolve again in an organic solvent for use as a purified product. Particularly in applications where impurities and foreign matters are a problem, it is preferable to redissolve the varnish in an organic solvent to obtain a filtration-purified varnish.
The polyimide (A) concentration in the polymer solution (100% by weight) is not particularly limited, but is about 10 to 30% by weight.

Table A below shows preferred formulation examples of the negative photosensitive polymer of the present embodiment.

・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)benzoic acid Dianhydride/DMMI: 2,3-dimethylmaleic anhydride

[Crosslinking agent (B)]
The negative photosensitive resin composition of the present embodiment can preferably further contain a cross-linking agent (B) having a substituted or unsubstituted maleimide group (excluding the polyimide (A)).
Examples of the cross-linking agent (B) include 4,4′-diphenylmethanebis(dimethyl)maleimide, polyphenylmethane(dimethyl)maleimide, m-phenylenebis(dimethyl)maleimide, p-phenylenebis(dimethyl)maleimide, bisphenol A diphenyl ether bis (dimethyl)maleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebis(dimethyl)maleimide, 4-methyl-1,3-phenylenebis(dimethyl)maleimide, 1,6′ -bis(dimethyl)maleimido-(2,2,4-trimethyl)hexane, 1,2-bis((dimethyl)maleimido)ethane, 1,4-bis((dimethyl)maleimido)butane, 1,6-bis( (dimethyl)maleimido)hexane, 1,12-bis((dimethyl)maleimido)dodecane, 1-(dimethyl)maleimido-3-(dimethyl)maleimidomethyl-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), polynorbornene with a substituted or unsubstituted maleimide group, etc. and preferably the polynorbornene.
The polynorbornene preferably has a structural unit (b) represented by the following general formula (b).

In the general formula (b), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and from the viewpoint of the effect of the present invention, an alkyl group having 1 or 2 carbon atoms is preferable, A C 1 alkyl group is more preferred.
^Q1 represents a single bond or a divalent organic group.

As the divalent organic group of Q ¹ , a known organic group can be used within the scope of the effects of the present invention, and examples thereof include an alkylene group having 1 to 8 carbon atoms or a (poly)alkylene glycol chain. can be done. The alkylene group having 1 to 8 carbon atoms is preferably an alkylene group having 2 to 6 carbon atoms.

Examples of the alkylene group having 1 to 8 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, and octylene group.

The alkylene oxide constituting the (poly)alkylene glycol chain is not particularly limited, but is preferably composed of an alkylene oxide having 1 to 18 carbon atoms, more preferably an alkylene oxide having 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monoxide, octylene oxide and the like.

G ¹ , G ² and G ³ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.
Examples of hydrocarbon groups having 1 to 30 carbon atoms include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, and the like.

Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, Octyl, nonyl, and decyl groups are included.
Alkenyl groups include, for example, allyl groups, pentenyl groups, and vinyl groups. Alkynyl groups include ethynyl groups.
The alkylidene group includes, for example, a methylidene group and an ethylidene group.

Aryl groups include, for example, phenyl, naphthyl, and anthracenyl groups.
Aralkyl groups include, for example, benzyl groups and phenethyl groups.

Examples of alkaryl groups include tolyl and xylyl groups.
Cycloalkyl groups include, for example, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
The 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.

In the present embodiment, the hydrocarbon group having 1 to 30 carbon atoms is preferably a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms. 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 an alkyl group having 1 to 10 carbon atoms. is even more preferred.

Examples of the substituted hydrocarbon group having 1 to 30 carbon atoms include a hydroxyl group, an amino group, a cyano group, an ester group, an ether group, an amide group, a sulfonamide group, and the like. may be substituted.

In the present embodiment, any one of G ¹ , G ² , and G ³ is preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and the rest are hydrogen atoms, and all are hydrogen atoms. It is more preferable to have
m is 0, 1 or 2, preferably 0 or 1, more preferably 0;

Since the cross-linking agent (B) of the present embodiment has the structure represented by the general formula (b), it is excellent in low dielectric loss tangent. Furthermore, the cross-linking agent (B) has a predetermined maleimide group in the side chain, and photodimerization is possible without causing a radical reaction. A) can be photopolymerized, and the mechanical strength is also superior.
The cross-linking agent (B) of the present embodiment can be synthesized as follows.

First, a compound (b') represented by the following general formula (b') is addition-polymerized, and if necessary, addition-polymerized with another norbornene-based compound to obtain a polymer. Addition polymerization is carried out, for example, by coordination polymerization.

In general formula (b'), R ¹ , R ² , Q ¹ , G ¹ , G ² , G ³ and m have the same meanings as in general formula (b).

Other norbornene compounds include norbornenes having an alkyl group such as 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, 5-cyclopentylnorbornene Norbornenes having an alkenyl group such as 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene, 5-cyclopentenylnorbornene; 5-phenylnorbornene, 5-phenylmethylnorbornene, 5-phenyl norbornenes having an aromatic ring such as ethyl norbornene and 5-phenylpropyl norbornene;

In the present embodiment, solution polymerization can be performed by dissolving the compound and the 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, more preferably 50°C to 120°C. In this embodiment, the yield of the cross-linking agent (B) can be improved by making the heating temperature higher than conventionally.

Also, the heating time can be, for example, 0.5 hours to 72 hours. In addition, after removing the dissolved oxygen in a solvent by nitrogen bubbling, it is more preferable to perform solution polymerization.

In addition, molecular weight modifiers and chain transfer agents can be used as necessary. Examples of chain transfer agents include alkylsilane compounds such as trimethylsilane, triethylsilane, and tributylsilane. These chain transfer agents may be used singly or in combination of two or more.

Solvents used in the polymerization reaction include, for example, methyl ethyl ketone (MEK), propylene glycol monomethyl ether, diethyl ether, cyclopentyl methyl ether, tetrahydrofuran (THF), 4-methyltetrahydropyran, toluene, cyclohexane, methylcyclohexane, ethyl acetate, One or more of esters such as butyl acetate and alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol can be used.

The organometallic catalyst is not particularly selected as long as the addition polymerization proceeds. good. One or more of these can be used.

Examples of the palladium complex include (acetato-κ0)(acetonitrile)bis[tris(1-methylethyl)phosphine]palladium(I) tetrakis(2,3,4,5,6-pentafluorophenyl)borate, π- allylpalladium complexes such as allylpalladium chloride dimer,
Organic carboxylates of palladium such as palladium acetate, propionate, maleate, naphthoate,
palladium complexes of organic carboxylic acids such as palladium acetate triphenylphosphine complexes, palladium acetate tri(m-tolyl)phosphine complexes, palladium acetate tricyclohexylphosphine complexes,
organic sulfonates of palladium such as palladium dibutyl phosphite, p-toluenesulfonate,
β-diketone compounds of palladium such as bis(acetylacetonate)palladium, bis(hexafluoroacetylacetonate)palladium, bis(ethylacetoacetate)palladium, bis(phenylacetoacetate)palladium,
Halide complexes of palladium such as dichlorobis(triphenylphosphine)palladium, bis[tri(m-tolylphosphine)]palladium, dibromobis[tri(m-tolylphosphine)]palladium, acetonyltriphenylphosphonium complexes, and the like. be done.

Examples of the phosphine ligands include triphenylphosphine, dicyclohexylphenylphosphine, cyclohexyldiphenylphosphine, and tricyclohexylphosphine.

Examples of the counter anion include triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis(2,4, 6-trifluorophenyl)borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis ( pentafluorophenyl)borate, N,N-diphenylanilinium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate and the like.

The amount of the organometallic catalyst can be 300 ppm to 5000 ppm, preferably 1000 ppm to 3500 ppm, more preferably 1500 ppm to 2500 ppm with respect to the norbornene-based monomer. Thereby, the yield of the cross-linking agent (B) can be improved.

The resulting reaction solution containing the cross-linking agent (B) is added to an alcohol such as hexane or methanol to precipitate the cross-linking agent (B). Next, the cross-linking agent (B) is collected by filtration, washed with alcohol such as hexane or methanol, and dried.
In this embodiment, for example, the cross-linking agent (B) can be synthesized in this manner.
According to the production method of the present embodiment, the cross-linking agent (B) can be obtained with a high yield of 70% or more.

The conversion rate with dialkyl maleic anhydride is preferably 70% or more. More preferably 80%, more preferably 90% or more. If it is this range, the polyimide component eluted by development can be reduced.

The cross-linking agent (B) of the present embodiment may contain other structural units other than the structural unit (b) within the scope of the effect of the present invention, and the other structural units include the other norbornene-based compounds Structural units derived from

The weight average molecular weight of the cross-linking agent (B) of the present embodiment is 3,000 to 300,000, preferably 5,000 to 200,000.

In the present embodiment, from the viewpoint of the effect of the present invention, the ratio (A:B) of the polyimide (A) and the cross-linking agent (B) is 5:95 to 95:5, preferably 10:90 to 90:10. , and more preferably 20:80 to 80:20.

[Photosensitizer (C)]
The negative photosensitive resin composition of this embodiment can further contain a photosensitizer (C).

Examples of the photosensitizer (C) include benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, benzyl-based photopolymerization initiators, and Michler's ketone-based photopolymerization initiators. Among these, benzophenone-based photopolymerization initiators and thioxanthone-based photopolymerization initiators are preferred.

Benzophenone-based photopolymerization initiators include benzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide and the like. These benzophenones and derivatives thereof can improve the curing speed by using a tertiary amine as a hydrogen donor.

Examples of commercially available benzophenone-based photopolymerization initiators include SPEEDCUREMBP (4-methylbenzophenone), SPEEDCUREMBB (methyl-2-benzoylbenzoate), SPPEDCUREBMS (4-benzoyl-4'methyldiphenyl sulfide), SPPEDCUREPBZ (4-phenyl benzophenone), SPPEDCUREEMK (4,4′-bis(diethylamino)benzophenone) (both trade names, manufactured by DKSH Japan Co., Ltd.), and the like.

Thioxanthone-based photopolymerization initiators include thioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone. Preferred diethylthioxanthone is 2,4-diethylthioxanthone, isopropylthioxanthone is 2-isopropylthioxanthone, and chlorothioxanthone is 2-chlorothioxanthone. Among them, a thioxanthone-based photopolymerization initiator containing diethylthioxanthone is more preferable.

Examples of commercially available thioxanthone-based photopolymerization initiators include SpeedcureDETX (2,4-diethylthioxanthone), SpeedcureITX (2-isopropylthioxanthone), SpeedcureCTX (2-chlorothioxanthone), and SPEEDCURECPTX (1-chloro-4-propylthioxanthone). (trade name, manufactured by DKSH Japan Co., Ltd.), KAYACUREDETX (2,4-diethylthioxanthone) (trade name, manufactured by Nippon Kayaku Co., Ltd.), DAIDO UV-CURE DETX (manufactured by Daido Kasei Kogyo Co., Ltd.), and the like. .

The amount of the photosensitizer (C) added is not particularly limited, but it is preferably about 0.05 to 15% by mass of the total solid content of the negative photosensitive resin composition, and 0.1 to 12.5%. It is more preferably about mass %, more preferably about 0.2 to 10 mass %. By setting the addition amount of the photosensitizer (C) within the above range, the patterning property of the photosensitive resin layer containing the negative photosensitive resin composition is enhanced, and the negative photosensitive resin composition is stored for a long period of time. can improve sexuality.

[Silane coupling agent (D)]
The negative photosensitive resin composition of this embodiment can further contain a silane coupling agent (D).
Thereby, the adhesiveness of the resin film or pattern formed of the negative photosensitive resin composition to the substrate can be enhanced.

The usable silane coupling agent (D) is not particularly limited. For example, silane coupling agents such as aminosilane, epoxysilane, acrylsilane, mercaptosilane, vinylsilane, ureidosilane, acid anhydride-functional silane, and sulfidesilane can be used. Silane coupling agents (D) may be used alone or in combination of two or more. Among these, epoxysilanes (i.e., compounds containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in one molecule) or anhydride-functional silanes (i.e., in one molecule, an anhydride and a group that generates a silanol group by hydrolysis) are preferred. The group of the silane coupling agent on the side opposite to the silane is bonded to the polymer A or the polymer B or has good compatibility with the polymer, so that the resin film or pattern formed with the negative photosensitive resin composition is Adhesion to the substrate can be further enhanced.

Examples of aminosilanes include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-amino propylmethyldimethoxysilane, N-β (aminoethyl)γ-aminopropyltrimethoxysilane, N-β (aminoethyl)γ-aminopropyltriethoxysilane, N-β (aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, and the like.

Examples of epoxysilanes include γ-glycidoxypropyltrimethoxysilane, γ
-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane, and the like.

Examples of acrylic silanes include γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, γ-(methacryloxypropyl)methyldiethoxysilane, and the like.
Mercaptosilanes include, for example, 3-mercaptopropyltrimethoxysilane.

Vinylsilanes include, for example, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like.
Ureidosilanes include, for example, 3-ureidopropyltriethoxysilane.
Anhydride-functional silanes include, for example, 3-trimethoxysilylpropylsuccinic anhydride.

Examples of sulfide silanes include bis(3-(triethoxysilyl)propyl)disulfide and bis(3-(triethoxysilyl)propyl)tetrasulfide.
When using a silane coupling agent (D), only 1 type may be used and 2 or more types may be used together.

The content of the silane coupling agent (D) is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass when the total solid content of the negative photosensitive resin composition is 100 parts by mass. be. It is considered that by setting the amount in this range, it is possible to obtain sufficient "adhesion", which is the effect of the silane coupling agent (D), while maintaining a balance with other performances.

(solvent)
The negative photosensitive resin composition according to the present embodiment can contain a urea compound or an amide compound having an acyclic structure as a solvent. The solvent preferably contains, for example, a urea compound. Thereby, the adhesiveness of the hardened|cured material of a negative photosensitive resin composition and metals, such as Al and Cu, can be improved more.

In this specification, a urea compound indicates a compound having a urea bond, that is, a urea bond. Moreover, an amide compound indicates a compound having an amide bond, that is, an amide. Note that amides specifically include primary amides, secondary amides, and tertiary amides.

In addition, in the present embodiment, an acyclic structure means that the structure of a compound does not have a cyclic structure such as a carbocyclic ring, an inorganic ring, or a heterocyclic ring. Examples of structures of compounds that do not have a cyclic structure include straight-chain structures and branched-chain structures.

As the urea compound and the amide compound having a non-cyclic structure, those having a large number of nitrogen atoms in the molecular structure are preferred. Specifically, the number of nitrogen atoms in the molecular structure is preferably two or more. Thereby, the number of lone electron pairs can be increased. Therefore, the adhesion to metals such as Al and Cu can be improved.

Specific examples of the structure of the urea compound include a cyclic structure and an acyclic structure. Of the above specific examples, the structure of the urea compound is preferably an acyclic structure. Thereby, the adhesiveness of the hardened|cured material of a negative photosensitive resin composition and metals, such as Al and Cu, can be improved. The reason for this is presumed as follows. It is presumed that a urea compound with a non-cyclic structure forms a coordinate bond more easily than a urea compound with a cyclic structure. This is probably because the urea compound having a non-cyclic structure is less constrained in molecular motion and has a greater degree of freedom in deformation of the molecular structure than the urea compound having a cyclic structure. Therefore, when a urea compound having a non-cyclic structure is used, a strong coordinate bond can be formed and adhesion can be improved.

Specific 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, O-benzyl-N,N'-diisopropylisourea and the like. As the urea compound, one or a combination of two or more of the above specific examples can be used. Among the above specific examples of the urea compound, for example, 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 It is preferable to use one or more selected from the group consisting of, more preferably tetramethylurea (TMU). Thereby, a strong coordinate bond can be formed and the adhesion can be improved.

Specific examples of the 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, N,N-dibutylformamide and the like.
The negative photosensitive resin composition according to the present embodiment may contain, as a solvent, a solvent having no nitrogen atom in addition to the urea compound and the amide compound having an acyclic structure.

Specific examples of solvents having no nitrogen atom 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 hydrocarbons. system solvents and the like. As the solvent having no nitrogen atom, one or a combination of two or more of the above specific examples can be used.

Specific examples of the ether solvent 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, and diethylene glycol diethyl ether. , diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol-3-monomethyl ether and the like.

Specific examples of the ester solvent include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, and methyl-1,3-butylene glycol acetate.

Specific examples of the alcohol solvent include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropyl alcohol.
Specific examples of the ketone solvent include cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone.
Specific examples of the lactone solvent include γ-butyrolactone (GBL) and γ-valerolactone.
Specific examples of the carbonate-based solvent include ethylene carbonate and propylene carbonate.
Specific examples of the sulfone-based solvent include dimethylsulfoxide (DMSO) and sulfolane.
Specific examples of the ester solvent include methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate.
Specific examples of the aromatic hydrocarbon solvent include mesitylene, toluene, and xylene.

The lower limit of the content of the urea compound and the amide compound having an acyclic structure in the solvent is, for example, preferably 10 parts by mass or more, preferably 20 parts by mass or more, when the solvent is 100 parts by mass. More preferably, it is 30 parts by mass or more, even more preferably 50 parts by mass or more, and even more preferably 70 parts by mass or more. Thereby, the adhesiveness of the hardened|cured material of a negative photosensitive resin composition and metals, such as Al and Cu, can be improved more.

In addition, the lower limit of the content of the urea compound and the amide compound with an acyclic structure 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 large amount of the urea compound and the amide compound having an acyclic structure.

(Surfactant)
The negative photosensitive resin composition according to this embodiment may further contain a surfactant.

The surfactant is not limited, and specifically polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Ftop EF301, Ftop EF303, Ftop EF352 (manufactured by Shin-Akita Kasei), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (DIC Corporation) manufactured), Florado 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, commercially available fluorine-based surfactants (manufactured by AGC Seimi Chemical Co., Ltd.); Combined KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid-based copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. Among the specific examples of the perfluoroalkyl group-containing fluorosurfactant, Megafac F171, Megafac F173, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, and Megafac One or more selected from F477 (manufactured by DIC), 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) is preferably used.

Also, as the surfactant, a silicone-based surfactant (eg, polyether-modified dimethylsiloxane, etc.) can be preferably used. Specific examples of silicone surfactants include SH series, SD series and ST series from Dow Corning Toray Co., Ltd., BYK series from BYK Chemie Japan, KP series from Shin-Etsu Chemical Co., Ltd., Disfoam from NOF CORPORATION ( (registered trademark) series, TSF series of Toshiba Silicone Co., Ltd., and the like.

The upper limit of the content of the surfactant in the negative photosensitive resin composition is 1% by mass (10,000 ppm) or less with respect to the entire negative photosensitive resin composition (including the solvent). It is preferably 0.5% by mass (5,000 ppm) or less, more preferably 0.3% by mass (3,000 ppm) or less.

In addition, although there is no particular lower limit for the content of the surfactant in the negative photosensitive resin composition, from the viewpoint of sufficiently obtaining the effect of the surfactant, for example, the negative photosensitive resin composition It is 0.001% by mass (10 ppm) or more with respect to the whole (including the solvent).
Applicability and uniformity of the coating film can be improved while maintaining other properties by appropriately adjusting the amount of the surfactant.

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

Phenolic 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, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 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- Lis[(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, styreneated phenol, 2,4-bis(( octylthio)methyl)-5-methylphenol, and the like.

Phosphorus antioxidants include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenylphosphite), 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, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, tris(mixed mono and di-nonylphenylphosphite), bis(2, 4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl)pentaerythritol diphosphite, bis(2,6-di-t -Butyl-4-octadecyloxycarbonylethylphenyl)pentaerythritol diphosphite and the like.

Thioether antioxidants include dilauryl-3,3′-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl)sulfide , distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis(3-lauryl)thiopropionate, and the like.

(filler)
The negative 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 properties and thermal properties required for the resin film made of the negative photosensitive resin composition.

Specific examples of fillers include inorganic fillers and organic fillers.
Specific examples of the inorganic filler include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely divided silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, and silicon carbide. , aluminum hydroxide, magnesium hydroxide, titanium white, and other metal compounds; talc; clay; mica; As the inorganic filler, one or a combination of two or more of the above specific examples can be used.

Specific examples of the organic filler include organosilicone powder and polyethylene powder. As the organic filler, one or a combination of two or more of the above specific examples can be used.

(Preparation of negative photosensitive resin composition)
A method for preparing the negative photosensitive resin composition in the present embodiment is not limited, and a known method can be used depending on the components contained in the negative photosensitive resin composition.
For example, it can be prepared by mixing and dissolving the above components in a solvent.

(Negative photosensitive resin composition)
The negative photosensitive resin composition according to the present embodiment is formed by applying the negative photosensitive resin composition to a surface comprising a metal such as Al or Cu, and then pre-baking to dry it to form a resin film. Then, the resin film is patterned into a desired shape by exposure and development, and then the resin film is cured by heat treatment to form a cured film.

When the permanent film is produced, the pre-baking conditions may be, for example, heat treatment at a temperature of 80° C. or higher and 150° C. or lower for 30 seconds or longer and 1 hour or shorter. Further, as the conditions of the heat treatment, for example, the heat treatment can be performed at a temperature of 150° C. or more and 350° C. or less for 2 minutes or more and 10 hours or less.

The viscosity of the negative 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 photosensitive resin composition can be adjusted by adding a solvent. During the adjustment, it is necessary to keep the contents of the urea compound and the non-cyclic amide compound in the solvent constant.

The upper limit of the viscosity of the negative 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. Also, the lower limit of the viscosity of the negative photosensitive resin composition according to the present 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.

The film obtained from the negative photosensitive resin composition of the present embodiment has a maximum elongation of 2 to 200%, preferably 5 to 150%, and an average elongation of 1 as measured by a tensile test using a Tensilon tester. ~150%, preferably 2-120%.
A film obtained from the negative photosensitive resin composition of the present embodiment can have a tensile strength of 30 to 300 MPa, preferably 50 to 200 MPa.

Thus, the negative photosensitive resin composition of this embodiment can provide a cured product such as a film having excellent mechanical strength. Although the reason for this is not clear, it is presumed that strong packing between polymer chains suppresses breakage due to sliding of the polymer chains, improves elongation, and provides excellent flexibility.

(Application)
The negative photosensitive resin composition of the present embodiment is used for forming resin films for semiconductor devices such as permanent films and resists. Among these, from the viewpoint of expressing in a well-balanced manner the improvement in adhesion between the negative photosensitive resin composition and the Al pad after prebaking and the suppression of the generation of residues of the negative photosensitive resin composition during development, Use of a permanent film from the viewpoint of improving the adhesion between the cured film of the negative photosensitive resin composition and the metal, and also from the viewpoint of improving the chemical resistance of the negative photosensitive resin composition after heat treatment. It is preferably used for

In addition, in the present embodiment, the resin film includes a cured film of a negative photosensitive resin composition. That is, the resin film according to this embodiment is obtained by curing a negative photosensitive resin composition.

The permanent film is composed of a resin film obtained by pre-baking, exposing, and developing a negative photosensitive resin composition, patterning it into a desired shape, and then curing it by heat treatment. Permanent films can be used as protective films, interlayer films, dam materials, and the like for semiconductor devices.

The above-mentioned resist can be obtained, for example, by applying a negative photosensitive resin composition to an object to be masked by the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, and negative photosensitive resin composition. It is composed of a resin film obtained by removing the solvent from a flexible resin composition.

An example of a semiconductor device according to this embodiment is shown in FIG.
The semiconductor device 100 according to this embodiment can be a semiconductor device including the resin film. Specifically, one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 in the semiconductor device 100 can be a resin film containing the cured product of the present embodiment. Here, the resin film is preferably the permanent film described above.

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

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. An interlayer insulating film 30 and a top layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layers. The uppermost layer wiring 34 is made of aluminum Al, for example. A passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34 . A portion of the passivation film 32 is provided with an opening through which the uppermost layer wiring 34 is exposed.

A rewiring layer 40 is provided on the passivation film 32 . The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, have An opening connected 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 openings provided in the insulating layer 42 and connected to the uppermost layer wiring 34 . The insulating layer 44 is provided with an opening connected to the rewiring 46 .

A bump 52 is formed in the opening provided in the insulating layer 44 via a UBM (Under Bump Metallurgy) layer 50, for example. Semiconductor device 100 is connected to a wiring substrate or the like via bumps 52, for example.
Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be employed within the scope that does not impair the effects of the present invention.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.
The following compounds were used in the examples.

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

4,4′-(hexafluoroisopropylidene)bis[(4-aminophenoxy)benzene] (hereinafter also referred to as HFBAPP) represented by the following formula

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

4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3 represented by the following formula -dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME)

1,4-bis(3,4-dicarboxyphenoxy)benzoic acid dianhydride (hereinafter also referred to as HQDA) represented by the following formula

4,4′-(Hexafluoroisopropylidene)diphthalic anhydride (hereinafter also referred to as 6FDA) represented by the following formula

[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 an appropriately sized reaction vessel equipped with a stirrer and condenser. After that, 399.64 g of γ-butyrolactone (hereinafter also referred to as GBL) was added to the reactor.
After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 1 hour. In advance, a solution was prepared by dissolving 8.73 g (69.2 mmol) of dimethylmaleic anhydride in 26.19 g of gamma-butyrolactone, and this solution was placed in a reaction vessel and reacted for an additional 30 minutes. Furthermore, by reacting at 175° C. for 3 hours, a polymerization solution was prepared in which the diamine and the acid anhydride were polymerized and the terminals were blocked.
The resulting polymerization solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to a methanol solution to precipitate a white solid. The resulting white solid was collected and vacuum dried at 80° C. to obtain 125.88 g of polymer.
GPC measurement 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 terminal blocking rate of 65%.
The obtained polymer partially contained repeating units represented by the following formula and had a dimethylmaleimide group at the terminal.

[Example 2]
First, 5.92 g (21.0 mmol) of MED-J, 10.86 g (21.0 mmol) of HFBAPP and 23.57 g of TMPBP-TME (38 .1 mmol) was added. After that, 121.04 g of γ-butyrolactone (hereinafter also referred to as GBL) was added to the reactor.
After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 1 hour. In advance, a solution was prepared by dissolving 2.88 g (22.9 mmol) of dimethylmaleic anhydride in 8.65 g of gamma-butyrolactone, and this solution was placed in a reaction vessel and reacted for an additional 30 minutes. Furthermore, by reacting at 175° C. for 3 hours, a polymerization solution was prepared in which the diamine and the acid anhydride were polymerized and the terminals were blocked.
The resulting polymerization solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to a methanol solution to precipitate a white solid. The obtained white solid was collected and dried in vacuum at a temperature of 80° C. to obtain 35.42 g of polymer.
GPC measurement 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 terminal blocking rate of 75%.
The obtained polymer partially contained repeating units represented by the following formula and had a dimethylmaleimide group at the terminal.

[Example 3]
First, 7.33 g (26.0 mmol) of MED-J, 8.31 g (26.0 mmol) of TFMB, and 29.74 g of TMPBP-TME (48 .1 mmol) was added. After that, 136.16 g of γ-butyrolactone (hereinafter also referred to as GBL) was added to the reactor.
After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 1 hour. In advance, a solution was prepared by dissolving 2.91 g (23.1 mmol) of dimethylmaleic anhydride in 8.73 g of gamma-butyrolactone, and this solution was placed in a reaction vessel and reacted for an additional 30 minutes. Furthermore, by reacting at 175° C. for 3 hours, a polymerization solution was prepared in which the diamine and the acid anhydride were polymerized and the terminals were blocked.
The resulting polymerization solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to a methanol solution to precipitate a white solid. The resulting white solid was collected and vacuum dried at a temperature of 80° C. to obtain 35.44 g of polymer.
GPC measurement 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 terminal blocking rate of 65%.
The obtained polymer partially contained repeating units represented by the following formula and had a dimethylmaleimide group at the terminal.

[Example 4]
First, 8.60 g (30.4 mmol) of MED-J and 11.89 g (29.6 mmol) of HQDA were placed in an appropriately sized reaction vessel equipped with a stirrer and condenser. After that, 81.96 g of γ-butyrolactone (hereinafter also referred to as GBL) was added to the reactor.
After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 1 hour. In advance, a solution was prepared by dissolving 0.67 g (5.3 mmol) of dimethylmaleic anhydride in 2.68 g of gamma-butyrolactone, and this solution was placed in a reaction vessel and reacted for an additional 30 minutes. Furthermore, by reacting at 175° C. for 3 hours, a polymerization solution was prepared in which the diamine and the acid anhydride were polymerized and the terminals were blocked.
The resulting polymerization solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to a methanol solution to precipitate a white solid. The resulting white solid was collected and vacuum dried at a temperature of 80° C. to obtain 15.15 g of polymer.
GPC measurement 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 terminal blocking rate of 79%.
The obtained polymer partially contained repeating units represented by the following formula and had a dimethylmaleimide group at the terminal.

[Comparative Examples 1 and 2]
Comparative Examples 1 and 2 were synthesized in the same manner as in Example 1 except for the conditions described in Table 1. The obtained Mw and Mw/Mn are shown in Table 1.

[Measurement of terminal capping rate]
The solution after the reaction was measured by gas chromatography, and assuming that all of the dimethylmaleic anhydride consumed in the reaction was bound to the polymer terminal, the ratio of the actual consumption to the theoretical consumption of dimethylmaleic anhydride was calculated. It is defined as the capping rate of the polymer terminal by dimethyl maleic anhydride.

[Solubility in organic solvents]
The solubility in γ-butyl lactone (GBL) of the negative photosensitive polymers obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was evaluated according to the following criteria. Table 1 shows the results.
(Evaluation criteria for solubility)
○: 5% by mass or more of polymer dissolved △: 1 to 5% by mass of polymer dissolved ×: Less than 1% by mass of polymer dissolved

[Hydrolysis resistance]
The rate of decrease in the weight average molecular weight of the negative photosensitive polymers obtained in Examples and Comparative Examples was measured under the following conditions. Table 1 shows the results.
(Conditions (no addition of triethylamine))
400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of the negative photosensitive polymer, and the mixture was stirred at 100°C for 6 hours.
Formula: [(weight average molecular weight before test - weight average molecular weight after test) / weight average molecular weight before test] × 100

(Conditions (addition of triethylamine))
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 were added to 100 parts by mass of the negative photosensitive polymer, and the mixture was stirred at 100°C for 6 hours. Calculated by the formula.
Formula: [(weight average molecular weight before test - weight average molecular weight after test) / weight average molecular weight before test] × 100

[Growth rate]
The polymer solution (100 parts by mass of polymer) obtained in Examples and Comparative Examples was spin-coated on the surface of a silicon wafer, prebaked at 120°C for 4 minutes, and then heat-treated at 200°C for 120 minutes under nitrogen to prepare a film. .
A tensile test (stretching speed: 5 mm/min) was performed in an atmosphere of 23° C. on a test piece (6.5 mm×60 mm×10 μm thick) cut out from the obtained film. The tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. Five test pieces were measured, the tensile elongation was calculated from the breaking distance and the initial distance, and the maximum and average values of the elongation were obtained. Table 1 shows the results.

As shown in Table 1, the negative photosensitive polymers of the present invention obtained in Examples are excellent in solubility in organic solvents and elongation. It was inferred that the decrease in physical strength was suppressed.

The following compounds were used in the preparation of the negative photosensitive resin composition.
Photosensitive agent: 1-chloro-4-propoxythioxanthone (SPEEDCURE CPTX (trade name) manufactured by Lambson, UK)
・Solvent: Cyclopentanone

[Synthesis Example 1]
(Synthesis of maleic anhydride-modified norbornene monomer (DMMIBuNB, 1-[4-(5-2-norbornyl)butyl]-3,4-dimethyl-pyrrole-2,5-dione))
Dimethylmaleic anhydride (42.6 g, 0.34 mol) was dissolved in toluene (300 mL) at room temperature in a 500 mL round bottom flask. The solution was placed under a nitrogen gas atmosphere to remove oxygen. The reaction flask was placed in an ice bath to prevent excessive heating resulting from the exothermic reaction. Once the dimethylmaleic anhydride dissolved, a dropping funnel containing 5-norbornene-2-butylamine (49.6 g, 0.30 mol) was fitted and the norbornene compound was added dropwise to the reaction flask over 3 hours. The dropping funnel was removed and the flask was fitted with a Dean-Stark tube and reflux condenser. The solution was heated to reflux in an oil bath set at 125° C. and the reaction was stirred at that temperature for 18 hours. About 6 mL of water was collected in the Dean-Stark tube during this time. 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 applied to a flash chromatography column (250 g silica gel) and eluted with a solvent mixture of 1.7 liters of cyclohexane/ethyl acetate (95/5 wt ratio). The elution solvent was removed using an evaporator, followed by drying under vacuum at 45° C. for 18 hours to give 80.4 g (92.7% yield) of the desired product. A reaction formula is shown below.

(Synthesis of polymer (DMMI-PNB))
24.6 g of 1-[4-(5-2-norbornyl)butyl]-3,4-dimethyl-pyrrole-2,5-dione) obtained by the above method, triethylsilane 3 .1 g, 13.5 g of toluene and 4.5 g of ethyl acetate were charged. Further, 0.065 g of [Pd(P(iPr)3)2(OCOCH3)(NCCH3)]tetrakis(pentafluorophenyl)borate at a concentration of 2.1 wt%, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate A mixed solution was prepared by adding 3.8 g of toluene and 1.3 g of ethyl acetate to 0.043 g, added to a reaction vessel and reacted at 70° C. for 3 hours to obtain a polymer solution. The conversion 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, reprecipitated with methanol, filtered, and vacuum-dried at 50° C. to obtain 18 g of polymer (DMMI-PNB).

[Example 5]
(Preparation of negative photosensitive resin composition)
The polymer solution of Example 1 (polymer DMMI-PI 12.0 parts by mass), the polymer of Synthesis Example 1 (DMMI-PNB), and the components shown in Table 2 were mixed in the amounts shown in Table 2 to give a photosensitive polymer. A resin composition was prepared.
The obtained negative type photosensitive resin composition was spin-coated on the surface of a silicon wafer so that the film thickness after drying was 10 μm, prebaked at 120° C. for 4 minutes, and then exposed at 1500 mJ/cm ² with a high-pressure mercury lamp. After that, heat treatment was performed at 200° C. for 120 minutes in a nitrogen atmosphere to prepare a film.

[Glass transition temperature (Tg)]
A test piece of 8 mm × 40 mm was cut out from the film obtained in Example 5, and the test piece was subjected to dynamic viscoelasticity measurement (DMA device, manufactured by TA Instruments, Q800) at a heating rate of 5. A dynamic viscoelasticity measurement was performed at °C/min and a frequency of 1 Hz, and the temperature at which the loss tangent tan δ showed the maximum value was measured as the glass transition temperature.

[Growth rate]
A test piece (6.5 mm×60 mm×10 μm thick) cut out from the film obtained in Example 5 was subjected to a tensile test (stretching speed: 5 mm/min) in an atmosphere of 23° C. The tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. The strength was obtained by measuring five test pieces and averaging the stress at the breaking point. The tensile elongation was calculated from the breaking distance and the initial distance, and the average and maximum values of the elongation were obtained.
Furthermore, the test piece cut out from the film obtained in Example 5 was subjected to HAST (unsaturated pressurized steam test) for 96 hours under conditions of a temperature of 130 ° C. and a relative humidity of 85% RH. Similarly, the average value and maximum value of the elongation rate were determined.

(Dielectric loss tangent Df)
The photosensitive resin composition of Example 5 was applied onto a substrate, the coating film was dried at 120°C for 10 minutes, subjected to PLA exposure (540 mJ), and cured in a nitrogen atmosphere at 200°C for 2 hours to form a film having a thickness of 100 µm. got the film. The dielectric loss tangent at 10 GHz of the obtained film was measured by the cavity resonator method.

[Evaluation of patterning characteristics]
It was confirmed as follows that the photosensitive resin composition of Example 5 could be sufficiently patterned by exposure and development.
The photosensitive resin composition of Example 5 was applied onto an 8-inch silicon wafer using a spin coater. After the application, it was pre-baked on a hot plate at 120° C. for 4 minutes in the atmosphere to obtain a coating film having a thickness of about 8.0 μm.
This coating film was irradiated with an i-line through a mask having a via pattern with a width of 20 μm. An i-line stepper (NSR-4425i manufactured by Nikon Corporation) was used for irradiation.
After exposure, spray development was carried out using cyclopentanone as a developer for 120 seconds, and the unexposed areas were removed by dissolution to obtain a via pattern.
A cross section of the obtained via pattern was observed using a desktop SEM. The width at the middle height between the bottom surface of the via pattern and the opening was defined as the via width, and evaluation was made according to the following criteria.
Good patterning property: 20 μm via pattern opens Poor patterning property: 20 μm via pattern does not open The coating film obtained from the photosensitive resin composition of Example 5 had good patterning property.

As shown in Table 2, the film obtained from the negative photosensitive resin composition containing the negative photosensitive polymer of the present invention has excellent low dielectric loss tangent and excellent elongation, and further has hydrolysis resistance. Since it contains an excellent negative type photosensitive polymer, it has been clarified that the mechanical strength is excellent even after the HAST test. Moreover, it was confirmed that the patterning property was also favorable and it was suitably used as a negative photosensitive resin composition.

This application claims priority based on Japanese Patent Application No. 2021-105687 filed on June 25, 2021, and the entire disclosure thereof is incorporated herein.

100 semiconductor device 30 interlayer insulating film 32 passivation film 34 top layer wiring 40 rewiring layer 42 insulating layer 44 insulating layer 46 rewiring 50 UBM layer 52 bump

Claims

(A) contains a polyimide;
The polyimide (A) is
a structural unit (a1) represented by the following general formula (a1);
a structural unit (a2) represented by the following general formula (a2);
At least one of both ends is a group represented by the following general formula (t), a negative photosensitive resin composition.

(In general formula (a1), Y is a divalent organic group.
In general formula (a2), R 1 to R 4 each independently represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R 1 and R 2 are different groups; R3 and R4 are different groups.
X 1 represents 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; , a plurality of X 1 may be the same or different.
In 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. * indicates a bond. )
The negative 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.
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). 3. The negative photosensitive resin composition according to Item 1 or 2.

(In general formula (a1-1), R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R 7 and a plurality of R 8 may be the same or different, R 9 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; may be the same or different, and * indicates a bond.
In general formula (a1-2), each of R 10 and R 11 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R 11 may be the same or different. * indicates a bond.
In general formula (a1-3), Z 1 represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond. )
3. The negative photosensitive resin composition according to claim 1, wherein Y in the general formula (a1) is a divalent organic group represented by the following general formula (a1-4).

(In general formula (a1-4), Z2 represents a divalent aromatic group. * represents a bond.)
The negative photosensitive resin composition according to claim 1 or 2, wherein both ends of the polyimide (A) are groups represented by the general formula (t).
3. The negative photosensitive resin composition according to claim 1, wherein said polyimide (A) further comprises a structural unit (a3) represented by general formula (a3).

(In general formula (a3), R 5 and R 6 each independently represent a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a hydroxyl group, and multiple R 5 and multiple R 6 are the same X represents a single bond, an alkylene group having 1 to 4 carbon atoms, or a haloalkylene group having 1 to 4 carbon atoms, and m and n each independently represent 0 or 1.)
The divalent organic group in Q 2 of the general formula (t) is a structural unit (a2) represented by the general formula (a2) or a structural unit (a3) represented by the general formula (a3). The negative photosensitive resin composition according to claim 6.
The negative photosensitive resin composition according to claim 1 or 2, wherein the polyimide (A) contains a structural unit represented by the following general formula (1).

(In general formula (1), R 1 to R 4 and X 1 have the same meanings as in general formula (a2), and Y has the same meaning as in general formula (a1).)
The negative photosensitive resin composition according to claim 6, wherein the polyimide (A) contains a structural unit represented by the following general formula (2).

(In general formula (2), R 5 to R 6 , X, m, and n are synonymous with general formula (a3), and Y is synonymous with general formula (a1).)
The negative photosensitive resin composition according to claim 1 or 2, further comprising a cross-linking agent (B) (excluding the polyimide (A)) having a substituted or unsubstituted maleimide group.
The negative photosensitive resin composition according to claim 10, wherein the cross-linking agent (B) contains a structural unit represented by the following general formula (b).

(In general formula (b), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q 1 represents a single bond or a divalent organic group, G 1 , G 2 and G 3 each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and m is 0, 1 or 2.)
12. The negative photosensitive resin composition according to claim 11, wherein the divalent organic group of Q 1 is an alkylene group having 1 to 8 carbon atoms or a (poly)alkylene glycol chain.
The negative photosensitive resin composition according to claim 1 or 2, further comprising a photosensitizer (C).
The negative photosensitive resin composition according to claim 1 or 2, further comprising a silane coupling agent (D).
a structural unit (a1) represented by the following general formula (a1);
a structural unit (a2) represented by the following general formula (a2);
At least one of both ends is a group represented by the following general formula (t), a negative photosensitive polymer.

(In general formula (a1), Y is a divalent organic group. In general formula (a2), R 1 to R 4 are each independently an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. is an alkoxy group, R 1 and R 2 are different groups, and R 3 and R 4 are different groups.
X 1 represents 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; , a plurality of X 1 may be the same or different.
In 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. * indicates a bond. )
The negative 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.
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). 17. The negative photosensitive polymer according to Item 15 or 16.

(In general formula (a1-1), R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R 7 and a plurality of R 8 may be the same or different, R 9 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; may be the same or different, and * indicates a bond.
In general formula (a1-2), each of R 10 and R 11 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R 11 may be the same or different. * indicates a bond.
In general formula (a1-3), Z 1 represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond. )
17. The negative photosensitive polymer according to claim 15, wherein Y in general formula (a1) is a divalent organic group represented by general formula (a1-4) below.

(In general formula (a1-4), Z2 represents a divalent aromatic group. * represents a bond.)
The negative photosensitive polymer according to claim 15 or 16, wherein both ends are groups represented by the general formula (t).
17. The negative photosensitive polymer according to claim 15, further comprising a structural unit (a3) represented by general formula (a3).

(In general formula (a3), R 5 and R 6 each independently represent a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a hydroxyl group, and multiple R 5 and multiple R 6 are the same X represents a single bond, an alkylene group having 1 to 4 carbon atoms, or a haloalkylene group having 1 to 4 carbon atoms, and m and n each independently represent 0 or 1.)
The divalent organic group in Q 2 of the general formula (t) is a structural unit (a2) represented by the general formula (a2) or a structural unit (a3) represented by the general formula (a3). 21. The negative photosensitive polymer of claim 20.
17. The negative photosensitive polymer according to claim 15 or 16, comprising a structural unit represented by the following general formula (1).

(In general formula (1), R 1 to R 4 and X 1 have the same meanings as in general formula (a2), and Y has the same meaning as in general formula (a1).)
21. The negative photosensitive polymer according to claim 20, comprising a structural unit represented by general formula (2) below.

(In general formula (2), R 5 to R 6 , X, m, and n are synonymous with general formula (a3), and Y is synonymous with general formula (a1).)
17. The negative photosensitive polymer according to claim 15 or 16, wherein the weight average molecular weight reduction rate measured under the following conditions is less than 50%.
(conditions)
400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water are added to 100 parts by mass of the negative photosensitive polymer, and the mixture is stirred at 100°C for 6 hours. .
Formula: [(weight average molecular weight before test - weight average molecular weight after test) / weight average molecular weight before test] × 100
A cured film comprising a cured product of the negative photosensitive resin composition according to claim 1 or 2.
A semiconductor device comprising a resin film containing a cured product of the negative photosensitive resin composition according to claim 1 or 2.
an interlayer insulating film;
A resin film containing a cured product of the negative photosensitive resin composition according to claim 1 or 2, provided on the interlayer insulating film;
a rewiring embedded in the resin film;
A semiconductor device comprising: