JP2020064205A - Photosensitive resin composition and method for producing cured relief pattern - Google Patents

Abstract

To provide a photosensitive resin composition that gives a cured relief pattern that shows excellent sensitivity and suppresses decrease in adhesion to a mold resin, and a cured relief pattern forming method using the photosensitive resin composition.SOLUTION: A negative photosensitive resin composition contains (A) a polyimide precursor having a (meth) acryloyl group; (B) a sulfonyl group-containing compound; and (C) a photopolymerization initiator.SELECTED DRAWING: None

Description

  The present invention relates to, for example, an insulating material for electronic parts, a photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, and a method for producing a cured relief pattern using the same. It is about.

  BACKGROUND ART Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, and mechanical characteristics has been used as an insulating material for electronic parts, a passivation film, a surface protective film, an interlayer insulating film, and the like for semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor composition can easily form a heat-resistant relief pattern film by applying the composition, exposing, developing, and thermally imidizing by curing. Can be formed. Such a photosensitive polyimide precursor composition has a feature that it enables a significant reduction in process steps as compared with a conventional non-photosensitive polyimide material.

  By the way, a semiconductor device (hereinafter, also referred to as “element”) is mounted on a printed board by various methods according to the purpose. A conventional element is generally manufactured by a wire bonding method in which a thin wire is connected from an external terminal (pad) of the element to a lead frame. However, as the speed of the device has increased and the operating frequency has reached GHz, the difference in the wiring length of each terminal in mounting has come to influence the operation of the device. Therefore, in mounting an element for high-end use, it is necessary to accurately control the length of mounting wiring, and it is difficult for wire bonding to meet the requirement.

  Therefore, flip chip mounting has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the rewiring layer, and then the chip is flipped over and directly mounted on a printed circuit board. . In this flip-chip mounting, the wiring distance can be controlled accurately, so it has been adopted in high-end devices handling high-speed signals, or in mobile phones due to its small mounting size, and the demand is rapidly expanding. . More recently, dicing a preprocessed wafer to produce individual chips, rebuilding individual chips on a support and sealing with mold resin, peeling the support, and then forming a rewiring layer A semiconductor chip mounting technology called a fan-out wafer level package (FOWLP) has been proposed (for example, Patent Document 1). The fan-out wafer level package has the advantages that the height of the package can be reduced, and high-speed transmission and cost reduction can be achieved.

JP 2005-167191 A

  However, due to the diversification of package mounting technology in recent years, the types of supports are diversified and the rewiring layer is multi-layered, so that the sensitivity is greatly reduced when the photosensitive resin composition is exposed. was there. Therefore, there is a problem that disconnection occurs in the rewiring layer due to deterioration of resolution, signal delay occurs, or yield is lowered. Further, there is a problem that the adhesiveness with the mold resin is deteriorated.

  The present invention provides a photosensitive resin composition which exhibits good sensitivity and gives a cured relief pattern in which the reduction in adhesion to a mold resin is suppressed, and a method for forming a cured relief pattern using the photosensitive resin composition. The purpose is to

｛式中、Ｘは４価の有機基であり、Ｙは２価の有機基であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、下記一般式（Ｒ１）：

（一般式（Ｒ１）中、Ｒ_３、Ｒ_４、及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、ｐは２〜１０から選ばれる整数である。）で表される１価の有機基、又は炭素数１〜４の飽和脂肪族基である。但し、Ｒ_１及びＲ_２の両者が同時に水素原子であることはない。｝
［２］
前記Ｘが、下記一般式（１）で表される構造を含む、［１］に記載の感光性樹脂組成物。

［３］
前記Ｙが、下記一般式（２）で表される構造を含む、［２］に記載の感光性樹脂組成物。

［４］
前記Ｘが、下記一般式（３）で表される構造を含む、［１］に記載の感光性樹脂組成物。

［５］
前記Ｙが、下記一般式（２）で表される構造を含む、［４］に記載の感光性樹脂組成物。

［６］
前記Ｙが、下記一般式（２）または一般式（４）で表される構造のうち少なくとも１つを含む、［１］〜［５］のいずれかに記載のネガ型感光性樹脂組成物。

（式中、Ｒ_９〜Ｒ_１２は、水素原子又は炭素数１〜４の１価の脂肪族基であり、互いに異なっていても、同一であってもよい。）
［７］
前記（Ａ）ポリイミド前駆体において、前記Ｘが下記一般式（１）である第１のポリイミド前駆体と、前記Ｘが下記一般式（３）である第２のポリイミド前駆体とを含む、［１］〜［６］のいずれかに記載のネガ型感光性樹脂組成物。

［８］
前記第１のポリイミド前駆体における前記Ｙと、前記第２のポリイミド前駆体における前記Ｙが、下記一般式（２）で表される構造：

を含む、［７］に記載のネガ型感光性樹脂組成物。
［９］
前記（Ａ）ポリイミド前駆体の重量平均分子量が、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算において、８０００〜２２０００である、
［１］〜［８］のいずれかに記載のネガ型感光性樹脂組成物。
［１０］
前記（Ｂ）スルホニル基含有化合物が、ｐ−トルエンスルホン酸、ｐ−トルエンスルホン酸無水物、及びメタンスルホン酸からなる群から選択される少なくとも１種である、［１］〜［９］のいずれかに記載のネガ型感光性樹脂組成物。
［１１］
前記（Ｂ）スルホニル基含有化合物が、ｐ−トルエンスルホン酸である、［１０］に記載のネガ型感光性樹脂組成物。
［１２］
前記（Ｂ）スルホニル基含有化合物が、ｐ−トルエンスルホン酸無水物である、［１０］に記載のネガ型感光性樹脂組成物。
［１３］
前記（Ｂ）スルホニル基含有化合物が、メタンスルホン酸である、［１０］に記載のネガ型感光性樹脂組成物。
［１４］
１００質量部の前記（Ａ）ポリイミド前駆体と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１〜３０質量部の前記（Ｂ）スルホニル基含有化合物と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１〜２０質量部の前記（Ｃ）光重合開始剤と、
を含む、［１］〜［１３］のいずれかに記載のネガ型感光性樹脂組成物。
［１５］
［１］〜［１４］のいずれかに記載のネガ型感光性樹脂組成物を硬化するポリイミドの製造方法。
［１６］
（１）［１］〜［１４］のいずれかに記載のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）露光後の前記感光性樹脂層を現像して、レリーフパターンを形成する工程と、
（４）前記レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程と、
を含む、硬化レリーフパターンの製造方法。 The present inventors have found that the above object can be achieved by combining a polyimide precursor, a sulfonyl group-containing compound, and a photopolymerization initiator, and have completed the present invention. That is, the present invention is as follows.
[1]
The following ingredients:
(A) a polyimide precursor represented by the following general formula (A1);
(B) a sulfonyl group-containing compound; and (C) a photopolymerization initiator;
A negative photosensitive resin composition comprising:

{In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are each independently a hydrogen atom, the following general formula (R1):

(In the general formula (R1), R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.) Is a monovalent organic group represented by or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. }
[2]
The photosensitive resin composition according to [1], wherein the X includes a structure represented by the following general formula (1).

[3]
The photosensitive resin composition according to [2], wherein the Y includes a structure represented by the following general formula (2).

[4]
The photosensitive resin composition according to [1], wherein X includes a structure represented by the following general formula (3).

[5]
The photosensitive resin composition according to [4], wherein the Y contains a structure represented by the following general formula (2).

[6]
The negative photosensitive resin composition according to any one of [1] to [5], wherein Y contains at least one of the structures represented by the following general formula (2) or general formula (4).

(In formula, R < ₉ > -R < ₁₂ > is a hydrogen atom or a C1-C4 monovalent | monohydric aliphatic group, and they may mutually differ and may be the same.)
[7]
In the (A) polyimide precursor, the X includes a first polyimide precursor having the following general formula (1) and a second polyimide precursor having the X having the following general formula (3): The negative photosensitive resin composition according to any one of 1] to [6].

[8]
The structure in which the Y in the first polyimide precursor and the Y in the second polyimide precursor are represented by the following general formula (2):

The negative photosensitive resin composition according to [7], which comprises:
[9]
The weight average molecular weight of the (A) polyimide precursor is 8000 to 22000 in terms of polystyrene by gel permeation chromatography (GPC).
The negative photosensitive resin composition according to any one of [1] to [8].
[10]
Any of [1] to [9], wherein the (B) sulfonyl group-containing compound is at least one selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonic acid anhydride, and methanesulfonic acid. The negative photosensitive resin composition as described in 1.
[11]
The negative photosensitive resin composition according to [10], wherein the (B) sulfonyl group-containing compound is p-toluenesulfonic acid.
[12]
The negative photosensitive resin composition according to [10], wherein the (B) sulfonyl group-containing compound is p-toluenesulfonic acid anhydride.
[13]
The negative photosensitive resin composition according to [10], wherein the (B) sulfonyl group-containing compound is methanesulfonic acid.
[14]
100 parts by mass of the (A) polyimide precursor,
0.1 to 30 parts by mass of the (B) sulfonyl group-containing compound based on 100 parts by mass of the (A) polyimide precursor;
0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor;
The negative photosensitive resin composition according to any one of [1] to [13], which comprises:
[15]
A method for producing a polyimide, comprising curing the negative photosensitive resin composition according to any one of [1] to [14].
[16]
(1) A step of applying the negative photosensitive resin composition according to any one of [1] to [14] onto a substrate to form a photosensitive resin layer on the substrate,
(2) a step of exposing the photosensitive resin layer,
(3) a step of developing the photosensitive resin layer after exposure to form a relief pattern,
(4) a step of heating the relief pattern to form a cured relief pattern;
A method for producing a cured relief pattern, comprising:

  According to the present invention, a photosensitive resin composition showing good sensitivity and giving a cured relief pattern in which a decrease in adhesion to a mold resin is suppressed, and a method for forming a cured relief pattern using the photosensitive resin composition are provided. Can be provided.

  The present embodiment will be specifically described below. Throughout the specification, the structures represented by the same reference numerals in the general formulas may be the same or different from each other when a plurality of structures are present in the molecule.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention contains (A) a polyimide precursor, (B) a sulfonyl group-containing compound, and (C) a photopolymerization initiator.
According to such a photosensitive resin composition, it is possible to obtain a cured relief pattern that exhibits good sensitivity and can suppress a decrease in adhesion to an epoxy resin that is a mold resin.

｛式中、Ｘは４価の有機基であり、Ｙは２価の有機基であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、下記一般式（Ｒ１）：

（一般式（Ｒ１）中、Ｒ_３、Ｒ_４、及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、ｐは２〜１０から選ばれる整数である。）で表される１価の有機基、又は炭素数１〜４の飽和脂肪族基である。但し、Ｒ_１及びＲ_２の両者が同時に水素原子であることはない。｝
上記（Ａ）ポリイミド前駆体の構造であると、（Ｃ）光重合開始剤の作用のより硬化レリーフパターンを得ることができる。 [(A) Polyimide precursor]
The (A) polyimide precursor according to the present embodiment will be described.
The (A) polyimide precursor according to the present embodiment is a polyimide precursor represented by the following general formula (A1).

{In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are each independently a hydrogen atom, the following general formula (R1):

(In the general formula (R1), R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.) Is a monovalent organic group represented by or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. }
With the structure of the (A) polyimide precursor, a cured relief pattern can be obtained by the action of the (C) photopolymerization initiator.

のそれぞれで表される構造が挙げられるが、これらに限定されるものではない。また、Ｘの構造は、１種でも２種以上の組み合わせでも構わない。 In the general formula (A1), the tetravalent organic group represented by X is preferably an organic group having 6 to 40 carbon atoms, and more preferably _one of -COOR ₁ group and -CONH- group. And are bonded to the same aromatic ring and both are in the ortho position with respect to each other, either a tetravalent aromatic group or an alicyclic aliphatic group. In the former case, the aromatic ring to which the -COOR ₁ group is bonded and the aromatic ring to which the -COOR ₂ group is bonded may be the same aromatic ring or different aromatic rings. . The aromatic ring in this context is preferably a benzene ring.
The tetravalent organic group represented by X is more preferably the following formula:

And the structure represented by each of these are not limited thereto. The structure of X may be one kind or a combination of two or more kinds.

In the present embodiment, the polyimide precursor (A) preferably contains a structure in which X is represented by the following general formula (1) from the viewpoint of chemical resistance.

｛上記式中、Ａは、メチル基（−ＣＨ_３）、エチル基（−Ｃ_２Ｈ_５）、プロピル基（−Ｃ_３Ｈ_７）、又はブチル基（−Ｃ_４Ｈ_９）である。｝のそれぞれで表される構造が挙げられるが、これらに限定されるものではない。また、Ｙの構造は、１種でも２種以上の組み合わせでも構わない。 In the general formula (A1), the divalent organic group represented by Y is preferably a C _{6 to} C ₄₀ aromatic group, for example, the following formula:

{In the above formula, A is a methyl group _(-CH 3), ethyl group _{(-C 2 H} 5), propyl _{(-C 3 H} 7), is or butyl group _(-C 4 _{H 9).} }, But the structure is not limited thereto. The structure of Y may be one kind or a combination of two or more kinds.

（式中、Ｒ_９〜Ｒ_１２は、水素原子又は炭素数１〜４の１価の脂肪族基であり、互いに異なっていても、同一であってもよい。） In the present embodiment, it is preferable that Y contains at least one structure represented by the following general formula (2) or (4) from the viewpoint of developability.

(In formula, R < ₉ > -R < ₁₂ > is a hydrogen atom or a C1-C4 monovalent | monohydric aliphatic group, and they may mutually differ and may be the same.)

上記一般式（Ｒ１）中のＲ_３は、水素原子又はメチル基であることが好ましく、Ｒ_４及びＲ_５は、感光特性の観点からそれぞれ水素原子であることが好ましい。ｐは、感光特性の観点から２以上１０以下の整数であることが好ましく、より好ましくは２以上４以下の整数である。 In the present embodiment, it is preferable that X further includes a structure represented by the following general formula (3) from the viewpoint of adhesiveness with the underfill agent.

R ₃ in the general formula (R1) is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably hydrogen atoms from the viewpoint of photosensitivity. From the viewpoint of photosensitivity, p is preferably an integer of 2 or more and 10 or less, and more preferably an integer of 2 or more and 4 or less.

  It is more preferable that X includes a structure represented by the general formula (3), and Y further includes a structure represented by the general formula (2).

The polyimide precursor (A) preferably contains a first polyimide precursor in which X is the general formula (1) and a second polyimide precursor in which X is the general formula (3). That is, the first polyimide precursor contains a structure derived from BPDA (3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride), and the second polyimide precursor is ODPA (4,4′-oxydiphthalic acid). It is preferable to include a structure derived from acid anhydride).

を含むことが好ましい。 Then, the Y in the first polyimide precursor and the Y in the second polyimide precursor are represented by the following general formula (2):

It is preferable to include.

  The weight average molecular weight of the (A) polyimide precursor is preferably 1,000 or more in terms of polystyrene conversion by gel permeation chromatography from the viewpoint of heat resistance and mechanical properties of the film obtained after heat treatment. It is more preferably 5,000 or more. The upper limit is preferably 100,000 or less. From the viewpoint of solubility in a developing solution, the weight average molecular weight is more preferably 50,000 or less. From the viewpoint of compatibility of sensitivity and resolution, 6000 to 40000 is preferable, 7000 to 30000 is more preferable, and 8000 to 22000 is particularly preferable.

[(A) Method for Preparing Polyimide Precursor]
The ester bond-type polyimide precursor comprises, for example, a tetracarboxylic acid dianhydride having a desired tetravalent organic group X and an alcohol having a photopolymerizable group (for example, an unsaturated double bond). The reaction is carried out to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as acid / ester form). Then, it is obtained by subjecting this acid / ester compound and a diamine having a divalent organic group Y to amide polycondensation. Saturated aliphatic alcohols may optionally be used in combination with the alcohols having a photopolymerizable group.

(Preparation of acid / ester form)
In the present invention, the tetracarboxylic acid dianhydride having a tetravalent organic group X, which is preferably used for preparing an ester bond type polyimide precursor, includes, for example, pyromellitic dianhydride and diphenyl ether-3,3. ', 4,4'-Tetracarboxylic acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic acid dianhydride , Diphenylsulfone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3', 4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4) -Phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane, and the like, but are not limited thereto. Not a thing. In addition, these may be used alone or in combination of two or more kinds.

  In the present invention, alcohols having a photopolymerizable group, which are preferably used for preparing an ester bond type polyimide precursor, include, for example, 2-acryloyloxyethyl alcohol and 1-acryloyloxy-3-propyl alcohol. , 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2- Hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, -Methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy- Examples thereof include 3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

  As the saturated aliphatic alcohol which can be optionally used together with the alcohol having a photopolymerizable group, a saturated aliphatic alcohol having 1 to 4 carbon atoms is preferable. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.

  The above-mentioned tetracarboxylic dianhydride suitable for the present invention and the above alcohols are preferably mixed in the presence of a basic catalyst such as pyridine, preferably in a suitable reaction solvent at a temperature of 20 to 50 ° C. for 4 to 10 minutes. By stirring and mixing for a time, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester form can be obtained.

The reaction solvent is preferably one that completely dissolves the raw material tetracarboxylic dianhydride and alcohol, and the product acid / ester form. More preferably, it is a solvent in which the polyimide precursor, which is an amide polycondensation product of the acid / ester and diamine, is also completely dissolved. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, carbonization Examples thereof include hydrogens. Specific examples of these are:
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like;
Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate and the like;

Examples of lactones include γ-butyrolactone and the like;
As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like;
Examples of the halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene and the like;
As hydrocarbons, for example, hexane, heptane, benzene, toluene, xylene, etc.,
Each can be listed. These may be used alone or as a mixture of two or more, if necessary.

(Preparation of polyimide precursor)
The acid / ester compound (typically in a solution state dissolved in the reaction solvent) is charged and mixed with a suitable dehydration-condensation agent, preferably under ice cooling, to convert the acid / ester compound into a polyanhydride. And Next, a diamine having a divalent organic group Y, which is preferably used in the present invention, separately dissolved or dispersed in a solvent is dropped into this, and both are subjected to amide polycondensation to obtain the desired polyimide precursor. Can be obtained. Diaminosiloxanes may be used in combination with the diamines having the divalent organic group Y.
Examples of the dehydration condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N. Examples include'-disuccinimidyl carbonate and the like.
As described above, the polyanhydride which is an intermediate is obtained.

  In the present invention, the diamines having a divalent organic group Y, which are suitably used for the reaction with the polyanhydride obtained as described above, include, for example, p-phenylenediamine, m-phenylenediamine, 4, 4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4, 4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4 , 4'-diaminobenzophenone, 3,4'-diamino Benzophenone, 3,3'-benzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,

1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4- Aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10 -Bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) Xafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, 1,4-bis (3- Aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, etc .;
And those in which some of the hydrogen atoms on the benzene ring are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen atom or the like;
And mixtures thereof.

  Specific examples of the substitution product include, for example, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4. '-Diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc. And a mixture thereof and the like. The diamines are not limited to the above examples.

  The diaminosiloxanes are used for the purpose of improving the adhesion between the coating film formed from the photosensitive resin composition of the present invention and various substrates, when the (A) photosensitive polyimide precursor is prepared. Used in combination with diamines containing an organic group Y. Specific examples of such diaminosiloxanes include 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane. it can.

  After completion of the amide polycondensation reaction, the water-absorbing by-product of the dehydration-condensation agent coexisting in the reaction solution is filtered off if necessary, and then a poor solvent suitable for the solution containing the polymer component, such as water or fat. Group lower alcohol, a mixed solution thereof, etc.) to deposit a polymer component, and if necessary, the polymer is purified by repeating operations such as re-dissolving and re-precipitation, followed by vacuum drying. By doing so, the desired polyimide precursor is isolated. In order to improve the degree of purification, a solution of this polymer may be passed through a column packed by swelling an anion and / or cation exchange resin with a suitable organic solvent to remove ionic impurities.

The weight average molecular weight of the ester bond-type polyimide precursor is preferably 1,000 or more in terms of polystyrene by gel permeation chromatography from the viewpoint of heat resistance and mechanical properties of the film obtained after heat treatment. It is more preferably 5,000 or more. The upper limit is preferably 100,000 or less. From the viewpoint of solubility in a developing solution, the weight average molecular weight is more preferably 50,000 or less. From the viewpoint of compatibility of sensitivity and resolution, 6000 to 40000 is preferable, 7000 to 30000 is more preferable, and 8000 to 22000 is particularly preferable.
Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as a developing solvent for gel permeation chromatography. The molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. The standard monodisperse polystyrene is recommended to be selected from STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko KK.

[(B) Sulfonyl group-containing compound]
The (B) sulfonyl group-containing compound according to the present embodiment is not limited as long as it contains a sulfonyl group. Such compounds include sulfonic acids, sulfonates, sulfonamides, sulfonic anhydrides, and the like. Among these, sulfonic acid, sulfonate, and sulfonic acid anhydride are preferable from the viewpoint of sensitivity, and sulfonic acid and sulfonic acid anhydride are more preferable from the viewpoint of copper void suppression.
Examples of the sulfonic acid include methanesulfonic acid, p-toluenesulfonic acid, 4-acetylbenzenesulfonic acid, benzenesulfonic acid and N- (2-acetamido) -2-aminoethanesulfonic acid .
Examples of the sulfonate include sodium 4-acetylbenzenesulfonate, sodium p-toluenesulfonate, pyridine p-toluenesulfonate, and the like.

Examples of the sulfonic acid anhydride include trifluoromethanesulfonic acid anhydride , p-toluenesulfonic acid anhydride , benzenesulfonic acid anhydride and the like.
Examples of sulfonamides include 4-acetylbenzene sulfonamide.

In the present embodiment, it is not clear why the addition of a sulfonyl group-containing compound improves the sensitivity, but for example, when heated on a hot plate after the coating step, some of the side chains in the polyimide precursor are removed and the polyamide is removed. When it becomes an acid, it forms a strong hydrogen bond with a sulfonyl group-containing compound and suppresses the coloration of the polyimide precursor itself in order to suppress imidization, so that the exposure energy required in the exposure step can be suppressed. I'm estimating.
It is not clear why the addition of the sulfonyl compound in the present embodiment improves the adhesion, but it is presumed that the adhesion is improved by forming a hydrogen bond with a hydroxyl group or the like of a mold resin composed of an epoxy resin or the like. ing.
Although it is not clear why copper voids can be suppressed by adding a sulfonyl compound in the present embodiment, copper atoms and sulfonyl groups of the substrate suppress the migration of copper atoms by forming a complex and suppress the formation of copper voids. It is estimated that

[(C) Photopolymerization Initiator]
The (C) photopolymerization initiator according to the present embodiment will be described.
As the photopolymerization initiator according to this exemplary embodiment, a photopolymerization initiator that generates a radical by absorbing and decomposing a specific wavelength is preferably used.
(C) The photopolymerization initiator includes benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, benzophenone derivatives such as fluorenone, 2,2′-diethoxyacetophenone, 2- Acetophenone derivatives such as hydroxy-2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone, benzyl, benzyldimethylketal, benzyl-β-methoxy Benzyl derivatives such as ethyl acetal, benzoin, benzoin derivatives such as benzoin methyl ether, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1 -Phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propane Oxime such as dione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime , N-arylglycines such as N-phenylglycine, peroxides such as benzoylperchloride, aromatic biimidazoles, titanocenes, α- (n-octanesulfonyloxyimino) -4-methoxybenzylcyanide Preferred examples thereof include photoacid generators, etc., but are not limited thereto. Among the above photopolymerization initiators, oximes are more preferable in terms of photosensitivity.

（式中、Ｒ３９はメチル基又はフェニル基であり、Ｒ４０はそれぞれ独立に炭素数１〜１２の１価の有機基を表す。）

（式中、Ｚはイオウ又は酸素原子であり、そしてＲ₄₁はメチル基、フェニル基または２価の有機基を表し、Ｒ₄₂〜Ｒ₄₄は、それぞれ独立に、水素原子または１価の有機基を表す。）。

または式（８）

または式（９）

または式（１０）

Among the above oxime photopolymerization initiators, those having a structure represented by any of the following formulas (5) to (10) are most preferable from the viewpoint of adhesiveness.

(In the formula, R39 represents a methyl group or a phenyl group, and R40 independently represents a monovalent organic group having 1 to 12 carbon atoms.)

(In the formula, Z is a sulfur or oxygen atom, R ₄₁ represents a methyl group, a phenyl group or a divalent organic group, and R _{42 to} R ₄₄ are each independently a hydrogen atom or a monovalent organic group. Represents.).

Or formula (8)

Or formula (9)

Or formula (10)

[(D) Crosslinking agent]
Examples of the (D) crosslinking agent optionally used in the present invention include any compound having a plurality of functional groups in the molecule. Here, examples of the functional group include an acrylic group, a methacrylic group, an epoxy group, a methylol group, an allyl group, a vinyl group, and a maleimide group.

  The compounding amount of the (D) crosslinking agent is preferably 1 to 40 parts by mass, and more preferably 2 to 30 parts by mass, relative to 100 parts by mass of the (A) resin.

  Further, in the photosensitive resin composition of the present invention, the total content of the (D) crosslinking agent is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor component.

[(E) Other ingredients]
The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (D).
The photosensitive resin composition of the present invention is typically used as a varnish liquid photosensitive resin composition in which the above-mentioned components and optional components that are further used as necessary are dissolved in a solvent to form a varnish. . Therefore, as the other component (D), a solvent can be mentioned. For example, a resin other than the above (A) photosensitive polyimide precursor, a sensitizer, a monomer having a photopolymerizable unsaturated bond, an adhesion aid. , Thermal polymerization inhibitors, azole compounds, hindered phenol compounds and the like.

Examples of the solvent include polar organic solvents and alcohols.
As the solvent, a polar organic solvent is preferably used from the viewpoint of solubility in (A) the photosensitive polyimide precursor. Specifically, for example, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, Examples thereof include α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone and N-cyclohexyl-2-pyrrolidone, which can be used alone or in combination of two or more.

The solvent in the present invention is preferably a solvent containing alcohols from the viewpoint of improving the storage stability of the photosensitive resin composition. Alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and not having an olefinic double bond. Specific examples include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol;
Lactic acid esters such as ethyl lactate;

Propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- ( Propylene glycol monoalkyl ethers such as n-propyl) ether;
Monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether;
2-hydroxyisobutyric acid esters;
Examples thereof include dialcohols such as ethylene glycol and propylene glycol. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable, and particularly ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, And propylene glycol-1- (n-propyl) ether are more preferred.

  The solvent is, for example, in the range of 30 to 1500 parts by mass, preferably 100 to 1,000 parts, based on 100 parts by mass of the (A) polyimide precursor, depending on the desired coating film thickness and viscosity of the photosensitive resin composition. It can be used in the range of parts by mass. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the whole solvent is preferably 5 to 50% by mass, and It is preferably 10 to 30% by mass. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is good, and when it is 50% by mass or less, the (A) polyimide precursor is dissolved. Good quality.

  The photosensitive resin composition according to the present embodiment may further contain a resin component other than the above-mentioned (A) polyimide precursor. Examples of the resin component that can be contained include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

  The photosensitive resin composition according to the present embodiment may optionally contain a sensitizer in order to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthothiazole, 1,3-bis (4 ' Dimethylamino benzal) acetone, 1,3-bis (4'-diethylamino benzal) acetone,

3,3′-Carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3- Methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholino Benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p Dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenyl Examples include acetamide, benzanilide, N-methylacetanilide, 3 ′, 4′-dimethylacetanilide and the like. These can be used alone or in combination of, for example, 2 to 5 types.

  When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the compounding amount thereof is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. .

The resin composition of the present invention may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. As such a monomer, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable. Mono- or di (meth) acrylates of ethylene glycol or polyethylene glycol, including, but not limited to, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, among others;
Propylene glycol or polypropylene glycol mono or di (meth) acrylates;
Glycerol mono-, di- or tri (meth) acrylates;
Cyclohexane di (meth) acrylate;
1,4-butanediol diacrylate and dimethacrylate, 1,6-hexanediol di (meth) acrylate;

Neopentyl glycol di (meth) acrylate;
Bisphenol A mono- or di (meth) acrylate;
Benzene trimethacrylate;
Isobornyl (meth) acrylate;
Acrylamide and its derivatives;
Methacrylamide and its derivatives;
Trimethylolpropane tri (meth) acrylate;
Di- or tri (meth) acrylate of glycerol;
Pentaerythritol di-, tri- or tetra (meth) acrylate;
In addition, compounds such as ethylene oxide or propylene oxide adducts of these compounds can be mentioned.

  When the photosensitive resin composition according to the present embodiment contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the compounding amount is (A) a polyimide precursor. It is preferably 1 to 50 parts by mass with respect to 100 parts by mass.

  In order to improve the adhesiveness between the film formed from the photosensitive resin composition according to this embodiment and the substrate, an adhesion aid can be optionally added to the photosensitive resin composition. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl ) Succinimide, N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzene- 1,4-bis (N- [3 -Triethoxysilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic hydride, silane coupling agent such as N-phenylaminopropyltrimethoxysilane, and aluminum tris (ethylaceto) Acetate), aluminum tris (acetylacetonate), ethylacetoacetate aluminum diisopropylate, and other aluminum-based adhesion aids.

  Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the photosensitive resin composition contains an adhesion aid, the compounding amount is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

  When the photosensitive resin composition according to the present embodiment is in a solution state particularly containing a solvent, a thermal polymerization inhibitor is added to the photosensitive resin composition in order to improve the stability of viscosity and photosensitivity during storage. Can be arbitrarily mixed. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2 , 6-Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl- N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

  The blending amount of the thermal polymerization inhibitor when blended in the photosensitive resin composition is preferably 0.005 to 12 parts by mass with respect to 100 parts by mass of the (A) photosensitive polyimide precursor.

  When the substrate to which the resin composition according to the present embodiment is applied is, for example, a substrate made of copper or a copper alloy, an azole compound can be optionally mixed in order to suppress discoloration of the copper surface. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole and 4-t-butyl-. 5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxy Phenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5 -Bis (α, α-Dimethy Rubenzyl) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole , 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5 -Methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl -1H-tetrazole, 5-amino-1H- Torazoru, 1-methyl -1H- tetrazole, and the like. Particularly preferred is at least one selected from tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in a mixture of two or more.

  When the photosensitive resin composition according to the present embodiment contains the azole compound, the compounding amount thereof is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. From the viewpoint of sensitivity characteristics, 0.5 to 5 parts by mass is more preferable. When the compounding amount of the azole compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition according to the present embodiment is formed on copper or a copper alloy, Discoloration of the copper or copper alloy surface is suppressed, while when it is 10 parts by mass or less, excellent photosensitivity of the photosensitive resin composition is maintained.

  In order to suppress the discoloration of the copper surface, a hindered phenol compound can be optionally blended in place of the azole compound or together with the azole compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3- (3,5-di-t-butyl). -4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), triethyleneglycol-bis [3- (3 -T-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydro) Shifeniru) propionate], 2,2-thio - diethylene bis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate],

N, N ′ hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), 2, 2'-methylene-bis (4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris- (3. 5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene , 1,3,5-Tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1 , 3, 5 Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5- Tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5- Tris [4- (1-ethylpropyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione,

1,3,5-Tris [4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1 , 3,5-Tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3 , 5-Tris (4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1 , 3,5-Tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -Trione, 1,3,5-tris (4-t-butyl-6-ethyl-3- Droxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl- 3-Hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-) 5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione,

1,3,5-Tris (4-t-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-Tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-Tris (4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, etc. However, the present invention is not limited to this. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione and the like are particularly preferable.

  The compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and is 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. Is more preferable. When the compounding amount of the hindered phenol compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, Discoloration / corrosion of copper or a copper alloy is prevented, while when it is 20 parts by mass or less, excellent photosensitivity of the photosensitive resin composition is maintained.

  The negative photosensitive resin composition of the present invention comprises 100 parts by mass of (A) polyimide precursor and 0.1 to 30 parts by mass of (B) sulfonyl group based on 100 parts by mass of (A) polyimide precursor. It is preferable to contain the contained compound and 0.1 to 20 parts by mass of (C) a photopolymerization initiator. As a result, the negative photosensitive resin composition exhibits particularly good sensitivity and can provide a cured relief pattern in which the deterioration of the adhesion to the mold resin can be suppressed more effectively.

<Cured relief pattern manufacturing method>
The present invention also provides a method of making a cured relief pattern.
The method for producing an effect relief pattern according to the present invention includes, for example, the following steps:
(1) a coating step of coating the negative photosensitive resin composition of the present invention described above on a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer,
(3) a developing step of developing the exposed photosensitive resin layer to form a relief pattern,
(4) The heating step of forming a cured relief pattern by heating the relief pattern is performed in the order described above.
Hereinafter, typical aspects of each step will be described.

(1) Coating Step In this step, the photosensitive resin composition of the present invention is coated on a substrate and then dried if necessary to form a photosensitive resin layer.
As the substrate, for example, a metal substrate made of silicon, aluminum, copper, copper alloy, or the like;
Resin substrate of epoxy, polyimide, polybenzoxazole, etc .;
A substrate having a metal circuit formed on the resin substrate;
It is possible to use a substrate in which a plurality of metals or a metal and a resin are laminated in multiple layers.
As a coating method, a method which has been conventionally used for coating a photosensitive resin composition, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or a spray coater is used for spray coating. The method etc. can be used.

  If necessary, the photosensitive resin composition film can be dried. As the drying method, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used. Further, it is desirable to dry the coating film under the condition that imidization of the (A) polyimide precursor (polyamic acid ester) in the photosensitive resin composition does not occur. Specifically, when air drying or heat drying is performed, the drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. As described above, the photosensitive resin layer can be formed on the substrate.

(2) Exposure step In this step, the photosensitive resin layer formed above is exposed. As the exposure device, for example, an exposure device such as a contact aligner, a mirror projection or a stepper is used. The exposure can be done through a patterned photomask or reticle, or directly. The light beam used for exposure is, for example, an ultraviolet light source.

  After the exposure, for the purpose of improving the photosensitivity, a post-exposure bake (PEB) and / or a pre-development bake may be carried out, if desired, at any combination of temperature and time. The baking condition is preferably 40 to 120 ° C. and 10 to 240 seconds, but is not limited to this range as long as it does not impair the various properties of the photosensitive resin composition of the present embodiment.

(3) Development Step In this step, the unexposed portion of the photosensitive resin layer after exposure is removed by development. As a developing method for developing the photosensitive resin layer after exposure (irradiation), a conventionally known developing method for photoresist can be selected and used. For example, there are a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, and the like. Further, after development, for the purpose of adjusting the shape of the relief pattern or the like, a post-development baking may be performed at any combination of temperature and time, if necessary. The temperature of the post-development bake can be, for example, 80 to 130 ° C., and the time can be, for example, 0.5 to 10 minutes.

  The developer used for the development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and a poor solvent. As the good solvent, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are preferable and poor. As the solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Further, each solvent may be used in combination of two or more kinds, for example, several kinds.

(4) Heating Step In this step, the relief pattern obtained by the above development is heated to disperse the photosensitive component, and (A) the polyimide precursor is imidized to be converted into a cured relief pattern made of polyimide. .
As a method of heat curing, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising type oven capable of setting a temperature program can be selected. The heating can be performed, for example, at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as an atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used.
The cured relief pattern can be manufactured as described above. In particular, the cured relief pattern of the present invention has high sensitivity and more effectively suppresses the decrease in adhesion to the mold resin.

<Semiconductor device>
The present invention also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention.
The above semiconductor device can be, for example, a semiconductor device having a base material that is a semiconductor element and a cured relief pattern formed on the base material by the above-described cured relief pattern manufacturing method.
The semiconductor device can be manufactured, for example, by using a semiconductor element as a base material and including the method for manufacturing a cured relief pattern described above as a part of the process. In the semiconductor device of the present invention, the cured relief pattern formed by the above-described method for producing a cured relief pattern is provided with, for example, a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip-chip device protective film, or a semiconductor having a bump structure. It can be manufactured by forming it as a protective film of the device or the like and combining it with a known method for manufacturing a semiconductor device.

  INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coats of flexible copper clad boards, solder resist films, liquid crystal alignment films, etc., in addition to application to semiconductor devices as described above. is there.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. Physical properties of the photosensitive resin compositions in Examples, Comparative Examples and Production Examples were measured and evaluated according to the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) of each photosensitive resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement is Showa Denko's trade name Shodex 805M / 806M series, the standard monodisperse polystyrene is Showa Denko's Shodex STANDARD SM-105, and the developing solvent is N-methyl-2-pyrrolidone. As the detector, Showa Denko's trade name Shodex RI-930 was used.

(2) Sensitivity evaluation A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness: 625 ± 25 μm) was used with a sputtering device (L-440S-FHL type, manufactured by Canon Anelva) to obtain 200 nm Ti and 400 nm thickness. Cu was sputtered in this order to prepare a sputtered Cu wafer substrate.
The photosensitive resin composition was spin-coated on the sputtered Cu wafer substrate by using a spin coater (D-spin60A type, manufactured by SOKUDO), dried by heating at 110 ° C. for 180 seconds, and the film thickness was 10 μm ± 0.2 μm. A spin coat film of was prepared.

By using a reticle with a test pattern having a circular pattern on this spin coat film, a gh line cut filter was attached by a projection projection exposure apparatus Prisma GHI S / N5503 (manufactured by Ultratech), and the exposure amount was changed by 10 mJ / cm ^2. Exposed.
Then, the coating film formed on the sputtered Cu wafer was spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Co., Ltd.) using cyclopentanone, and rinsed with propylene glycol methyl ether acetate to give a polyamic acid ester. To obtain a round relief pattern. The development time of the spray development was defined as 1.4 times the minimum time required for the unexposed portion of the resin composition to develop in the 10 μm spin coat film.

Regarding the openability of the rounded concave relief pattern obtained above, a pattern satisfying both of the following criteria (I) and (II) was judged to be acceptable, and the sensitivity giving the minimum acceptable pattern is shown in the table.
(I) The area of the pattern opening is 1/2 or more of the corresponding pattern mask opening area.
(II) The cross section of the pattern is not slender, and neither undercut, swelling nor bridging occurs.

(3) Adhesion test An R4000 series manufactured by Nagase Chemtex Co., Ltd. was prepared as an epoxy-based encapsulating material.
Next, the encapsulant was spin-coated on the aluminum-sputtered silicone wafer so as to have a thickness of about 150 μm, and was thermally cured at 130 ° C. to cure the epoxy encapsulant.
The photosensitive resin compositions prepared in Examples and Comparative Examples were applied on the above epoxy-based cured film so that the final film thickness would be 10 μm. It was exposed with the exposure amount calculated in (2) above, developed in the same manner as in (2), and thermally cured at 200 ° C. for 2 hours.
When SEM observation (tilt angle of 30 degrees) was performed on the remaining pattern of 10 μm, the one in which the epoxy resin and the polyimide film were in close contact was ○, the one with a slight float was marked with Δ, and the one with a clear float was seen. It was set to x.

(4) High temperature storage test of the cured relief pattern on Cu and subsequent void area evaluation The wafer on which the cured relief pattern was formed on Cu was heated with a temperature programmed cure furnace (VF-2000 type, It was heated in air at 150 ° C. for 168 hours using a Koyo Lindbergh Company. Subsequently, using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.), the resin layer on Cu was entirely removed by plasma etching. The plasma etching conditions are as follows.
Output: 133W
Gas type and flow rate: O ₂ : 40 mL / min + CF ₄ : 1 mL / min Gas pressure: 50 Pa
Mode: Hard mode Etching time: 1800 seconds The Cu surface from which all the resin layers have been removed is observed by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and image analysis software (A image-kun, manufactured by Asahi Kasei Corporation) Was used to calculate the area of voids occupying the surface of the Cu layer.
When the total area of the voids when the photosensitive resin composition described in Comparative Example 1 was evaluated was 100%, the total area ratio of the voids was less than 50% was “A”, and 50% or more and less than 75%. Those with 75% or more and less than 100% were judged as “Δ”, and those with 100% or more were judged as “x”.

<Production Example 1> (Synthesis of (A) Polyimide Precursor (Polymer A-1))
155.1 g of 4,4′-oxydiphthalic acid dianhydride (ODPA) was placed in a separable flask having a capacity of 2 liters, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and the mixture was stirred at room temperature. While adding 79.1 g of pyridine, a reaction mixture was obtained. After the heat generation due to the reaction was completed, the mixture was allowed to cool to room temperature and left standing for 16 hours.

  Next, under ice-cooling, to the reaction mixture was added a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone over 40 minutes with stirring, followed by 4,4′-diaminodiphenyl ether ( A suspension of 93.0 g of DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and after stirring for 1 hour, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 liters of ethyl alcohol to generate a precipitate composed of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and dried in vacuum to obtain a powdery polymer A-1.
The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 20,000.

<Production Example 2> (Synthesis of Polyimide Precursor (Polymer A-2))
Production Example 1 except that 147.1 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4′-oxydiphthalic acid dianhydride in Production Example 1 above. Polymer A-2) was obtained by carrying out the reaction in the same manner as in the method described in 1.
The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 22,000.

<Production Example 3> (Synthesis of Polyimide Precursor (Polymer A-3))
By carrying out the reaction in the same manner as in Production Example 1 except that 4,4′-diaminodiphenyl ether (DADPE) was replaced with 1,4-phenylenediamine (50.2 g) in Production Example 1 above, Polymer A-3) was obtained.
The weight average molecular weight (Mw) of this polymer A-3 was measured and found to be 21,000.

<Production Example 4>
In the above Production Example 1, in place of 155.1 g of 4,4′-oxydiphthalic dianhydride, 73.6 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride and 4,4′-oxydiphthalic acid Polymer A-4) was obtained by carrying out the reaction in the same manner as in Production Example 1 except that dianhydride 77.6 was used.
The weight average molecular weight (Mw) of this polymer A-4 was measured and found to be 20,000.

Sulfonyl group-containing compound B1: p-toluenesulfonic acid sulfonyl group-containing compound B2: p-toluenesulfonic acid anhydride Sulfonyl group-containing compound B3: p-toluenesulfonic acid pyridine salt Initiator C1: O-benzoyl-N- (1- Methyl-2-oxo-2-phenylethylidene) hydroxylamine

<Example 1>
As component (A), polymer A-1 (100 g), as component (B), B1 (0.1 g), as photopolymerization initiator C1 (4 g), as other components, tetraethylene glycol dimethacrylate (abbreviated as M4G, 8 g), N -Phenyldiethanolamine (DEA, abbreviated as 4 g) is dissolved in a mixed solvent (weight ratio 75:25) consisting of gamma-butyrolactone and DMSO, and the amount of the solvent is adjusted so that the viscosity becomes about 35 poise, thereby improving the photosensitivity. A resin composition solution was prepared.
This composition was evaluated by the method described above. The evaluation results are shown in Table 1.

<Examples 2 to 7, Comparative Example 1>
Evaluation was carried out in the same manner as in Example 1 except that the resin composition solution was prepared in the proportions shown in Table 1. The evaluation results are shown in Table 1.

  Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be appropriately modified without departing from the spirit of the invention.

  INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for manufacturing electric / electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (16)

The following ingredients:
(A) a polyimide precursor represented by the following general formula (A1);
(B) a sulfonyl group-containing compound; and (C) a photopolymerization initiator;
A negative photosensitive resin composition comprising:

{In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are each independently a hydrogen atom, the following general formula (R1):

(In the general formula (R1), R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.) Is a monovalent organic group represented by or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. } The photosensitive resin composition according to claim 1, wherein the X includes a structure represented by the following general formula (1).

The photosensitive resin composition according to claim 2, wherein the Y includes a structure represented by the following general formula (2).

The photosensitive resin composition according to claim 1, wherein the X includes a structure represented by the following general formula (3).

The photosensitive resin composition according to claim 4, wherein the Y includes a structure represented by the following general formula (2).

The negative photosensitive resin composition according to claim 1, wherein the Y contains at least one structure represented by the following general formula (2) or general formula (4).

(In formula, R < ₉ > -R < ₁₂ > is a hydrogen atom or a C1-C4 monovalent | monohydric aliphatic group, and they may mutually differ and may be the same.) The polyimide precursor (A) includes a first polyimide precursor in which X is the following general formula (1) and a second polyimide precursor in which X is the following general formula (3). Item 7. The negative photosensitive resin composition according to any one of items 1 to 6.

The structure in which the Y in the first polyimide precursor and the Y in the second polyimide precursor are represented by the following general formula (2):

The negative photosensitive resin composition according to claim 7, which comprises:   The negative photosensitive resin according to any one of claims 1 to 8, wherein the weight average molecular weight of the (A) polyimide precursor is 8000 to 22000 in terms of polystyrene by gel permeation chromatography (GPC). Composition.   10. The (B) sulfonyl group-containing compound is at least one selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonic anhydride, and methanesulfonic acid. Negative type photosensitive resin composition according to the item.   The negative photosensitive resin composition according to claim 10, wherein the (B) sulfonyl group-containing compound is p-toluenesulfonic acid.   The negative photosensitive resin composition according to claim 10, wherein the (B) sulfonyl group-containing compound is p-toluenesulfonic acid anhydride.   The negative photosensitive resin composition according to claim 10, wherein the (B) sulfonyl group-containing compound is methanesulfonic acid. 100 parts by mass of the (A) polyimide precursor,
0.1 to 30 parts by mass of the (B) sulfonyl group-containing compound based on 100 parts by mass of the (A) polyimide precursor;
0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor;
The negative photosensitive resin composition according to claim 1, which comprises:   A method for producing a polyimide, which comprises curing the negative photosensitive resin composition according to claim 1. (1) A step of applying the negative photosensitive resin composition according to any one of claims 1 to 14 onto a substrate to form a photosensitive resin layer on the substrate,
(2) a step of exposing the photosensitive resin layer,
(3) a step of developing the photosensitive resin layer after exposure to form a relief pattern,
(4) a step of heating the relief pattern to form a cured relief pattern;
A method for producing a cured relief pattern, comprising: