JP2019109494A - Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

Abstract

To provide a photosensitive resin composition that gives a cured relief pattern that shows excellent resolution even when there is a deviation in focus depth, and expresses excellent chemical resistance, and prevents degradation of a mold resin and decrease in adhesion, a method of forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device including the cured relief pattern.SOLUTION: A photosensitive resin composition has (A) a polyimide precursor, and (B) a photopolymerization initiator where a 0.001 wt.% solution obtained by using N-methyl-2-pyrrolidone as a solvent has a g line absorbance of 0.01-0.1.SELECTED DRAWING: None

Description

  The present invention relates to, for example, an insulating material for electronic components, and 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 it. , And a semiconductor device.

  Heretofore, polyimide resins having excellent heat resistance, electrical properties and mechanical properties have been used for insulating materials of electronic parts, passivation films of semiconductor devices, surface protective films, interlayer insulating films and the like. Among the polyimide resins, those provided in the form of a photosensitive polyimide precursor composition facilitate heat-resistant relief pattern films by thermal imidization treatment by application, exposure, development, and curing of the composition. It can be formed. Such a photosensitive polyimide precursor composition has a feature of enabling significant process reduction as compared to conventional non-photosensitive polyimide materials.

  By the way, semiconductor devices (hereinafter, also referred to as "elements") are mounted on a printed circuit board by various methods according to the purpose. Conventional devices are generally manufactured by a wire bonding method in which thin wires are connected from the external terminals (pads) of the devices to the lead frame. However, as the speed of elements has advanced and the operating frequency has reached GHz, the difference in the wiring length of each terminal in mounting has come to affect the operation of the elements. Therefore, in the case of the mounting of elements for high-end applications, it becomes necessary to control the length of the mounting wiring accurately, and it has become difficult to meet the requirement in the wire bonding.

  Therefore, there has been proposed flip chip mounting in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped and mounted directly on a printed circuit board. . In this flip-chip mounting, since the wiring distance can be accurately controlled, the demand is rapidly expanding because it is adopted for high-end devices that handle high-speed signals or for small-sized mounting due to its small mounting size. . More recently, the pre-processed wafer is diced to produce individual chips, the individual chips are reassembled on the support and sealed with a mold resin, and the support is peeled off to form a redistribution layer. A semiconductor chip mounting technique called a fan-out wafer level package (FOWLP) is proposed (for example, Patent Document 1). The fan-out wafer level package has an advantage that the height of the package can be reduced and high speed transmission and cost reduction can be achieved.

JP, 2005-167191, A

  However, in recent years, with the diversification of package mounting techniques, the types of supports are diversified, and in addition, rewiring layers are multilayered, so that when the photosensitive resin composition is exposed, a shift in focus depth occurs. There is a problem that the resolution is greatly deteriorated. Therefore, there is a problem that the rewiring layer is broken due to the deterioration of the resolution to cause a signal delay or a decrease in the yield. In addition, when the rewiring layer is laminated, if the desired resolution can not be obtained, the layer is peeled off by the chemical solution and laminated again, but the lower layer is formed by the chemical solution. There was a problem that the film of the part was damaged and the film thickness decreased. Moreover, in order to become a multilayer, since the exposure process and the image development process were repeated, there existed a subject which causes degradation of mold resin and the fall of adhesiveness.

  The present invention is a photosensitive resin which exhibits a good resolution even when a shift in focus depth occurs, exhibits a good chemical resistance, and provides a cured relief pattern capable of suppressing deterioration of a mold resin and a decrease in adhesion. An object is to provide a composition, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.

｛式中、Ｒ_６〜Ｒ_８はそれぞれ独立に炭素数１〜６の１価の有機基を表し、Ａｒは直接結合であるか、または、フェニレン、ナフチレン、およびチエニレンから選択される少なくとも１種の２価の基を表す。｝で表される、上記態様１〜５のいずれかに記載の感光性樹脂組成物。
［７］ （Ｃ）架橋剤を更に含有する、上記態様１〜６のいずれかに記載の感光性樹脂組成物。
［８］ 前記（Ａ）ポリイミド前駆体を単独の溶液として塗布し、プリベークした後に得られる１０μｍ厚フィルムについて測定したｇ線吸光度が０．００１〜０．１であり、ｈ線吸光度が０．００１〜０．５である、上記態様１〜７のいずれかに記載の感光性樹脂組成物。
［９］ 前記（Ａ）ポリイミド前駆体が下記一般式（Ａ１）：

｛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り、但し、Ｒ_１及びＲ_２の少なくとも一方が一般式（Ｒ１）で表される１価の有機基である。｝で表される構造を含むポリイミド前駆体である、上記態様１〜７のいずれかに記載の感光性樹脂組成物。
［１０］ 前記Ｘは下記構造：

を含む、上記態様９に記載の感光性樹脂組成物。
［１１］ 前記Ｘは下記構造：

を含む、上記態様９に記載の感光性樹脂組成物。
［１２］ 前記Ｙは下記構造：

を含む、上記態様９〜１１のいずれかに記載の感光性樹脂組成物。
［１３］ 前記Ｙは下記構造：

を含む、上記態様９〜１１のいずれかに記載の感光性樹脂組成物。
［１４］ 前記Ｘは下記構造：

を含み、
前記Ｙは下記構造：

を含む、上記態様９に記載の感光性樹脂組成物。
［１５］ 前記（Ａ）ポリイミド前駆体１００質量部に対する（Ｂ）光重合開始剤及び（Ｃ）架橋剤の合計含有量が０．１〜２０質量部である、上記態様１〜１４のいずれかに記載の感光性樹脂組成物。
［１６］ （Ａ）ポリイミド前駆体と、
（Ｂ）Ｎ−メチル−２−ピロリドンを溶媒として用いた０．００１ｗｔ％溶液のｇ線吸光度が０．０１〜０．１である、光重合開始剤と、を含有することを特徴とするファンアウトウエハレベルパッケージ用感光性樹脂組成物。
［１７］ （Ａ）ポリイミド前駆体と、
（Ｂ）下記一般式（Ｂ１）：

｛式中、Ｒ_６〜Ｒ_８はそれぞれ独立に炭素数１〜６の１価の有機基を表し、Ａｒは直接結合であるか、または、フェニレン、ナフチレン、およびチエニレンから選択される少なくとも１種の２価の基を表す。｝で表される光重合開始剤と、を含有することを特徴とする感光性樹脂組成物。
［１８］ 前記（Ａ）ポリイミド前駆体が下記一般式（Ａ１）：

｛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Ｃ_１〜Ｃ_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Ｃ_１〜Ｃ_４の飽和脂肪族基であり、但し、Ｒ_１及びＲ_２の少なくとも一方が一般式（Ｒ１）で表される１価の有機基である。｝で表される構造を含むポリイミド前駆体である、上記態様１７に記載の感光性樹脂組成物。
［１９］ 前記Ｘは下記構造：

を含む、上記態様１８に記載の感光性樹脂組成物。
［２０］ 前記Ｘは下記構造：

を含む、上記態様１８に記載の感光性樹脂組成物。
［２１］ 前記Ｙは下記構造：

を含む、上記態様１８〜２０のいずれかに記載の感光性樹脂組成物。
［２２］ 前記Ｙは下記構造：

を含む、上記態様１８〜２０のいずれかに記載の感光性樹脂組成物。
［２３］ 前記Ｘは下記構造：

を含み、
前記Ｙは下記構造：

を含む、上記態様１８に記載の感光性樹脂組成物。
［２４］ 以下の工程：
（１）上記態様１〜２３のいずれかに記載の感光性樹脂組成物を基板上に塗布し、該基板上に感光性樹脂層を形成する塗布工程と、
（２）該感光性樹脂層をｇ線及び／又はｈ線で露光する露光工程と、
（３）該露光後の感光性樹脂層を現像してレリーフパターンを形成する現像工程と、
（４）該レリーフパターンを加熱処理することによって硬化レリーフパターンを形成する加熱工程と
を含むことを特徴とする、硬化レリーフパターンの製造方法。
［２５］ 上記態様２４に記載の製造方法により得られる硬化レリーフパターンを有してなることを特徴とする、半導体装置。 The present inventors have found that the above object is achieved by combining a polyimide precursor and a specific initiator, and have completed the present invention. That is, the present invention includes the following aspects.
[1] (A) polyimide precursor,
(B) Photosensitivity characterized by containing a photopolymerization initiator having a g-line absorbance of 0.01 to 0.1 of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent Resin composition.
[2] The photosensitive resin composition according to the above aspect 1, wherein the g-line absorbance of the (B) photopolymerization initiator is 0.015 to 0.04.
[3] The photosensitive resin composition according to the above aspect 1 or 2, wherein the g-line absorbance of the (B) photopolymerization initiator is 0.015 to 0.03.
[4] The above embodiments 1 to 6, wherein the h-line absorbance of the 0.001 wt% solution of the (B) photopolymerization initiator using N-methyl-2-pyrrolidone as a solvent is 0.15 to 0.5. 3. The photosensitive resin composition as described in any one of 3.
[5] The photosensitive resin composition according to any one of the above aspects 1 to 4, wherein the (B) photopolymerization initiator has an oxime structure.
[6] The photopolymerization initiator (B) has the following general formula (B1):

Wherein R _{6 to} R ₈ each independently represent a monovalent organic group having 1 to 6 carbon atoms, and Ar is a direct bond, or at least one selected from phenylene, naphthylene, and thienylene Represents a divalent group of ] The photosensitive resin composition in any one of the said aspect 1-5 represented by}.
[7] The photosensitive resin composition according to any one of the above aspects 1 to 6, which further comprises (C) a crosslinking agent.
[8] The g-line absorbance measured for a 10 μm thick film obtained after applying (A) the polyimide precursor as a single solution and prebaking is 0.001 to 0.1, and h-line absorbance is 0.001 The photosensitive resin composition in any one of the said aspect 1-7 which is -0.5.
[9] The (A) polyimide precursor has the following general formula (A1):

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

(In general formula (R1), R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10). Or a saturated aliphatic group having 1 to 4 carbon atoms, provided that at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (R 1) is there. ] The photosensitive resin composition in any one of the said aspect 1-7 which is a polyimide precursor containing the structure represented by}.
[10] The above X has the following structure:

The photosensitive resin composition according to the above-mentioned aspect 9, which comprises
[11] Said X has the following structure:

The photosensitive resin composition according to the above-mentioned aspect 9, which comprises
[12] Said Y has the following structure:

The photosensitive resin composition as described in any one of the said aspect 9-11 containing these.
[13] Said Y has the following structure:

The photosensitive resin composition as described in any one of the said aspect 9-11 containing these.
[14] The aforementioned X has the following structure:

Including
Said Y is the following structure:

The photosensitive resin composition according to the above-mentioned aspect 9, which comprises
[15] Any one of the above embodiments 1 to 14, wherein the total content of the (B) photopolymerization initiator and the (C) crosslinking agent is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor The photosensitive resin composition as described in-.
[16] (A) a polyimide precursor,
(B) A fan comprising: a photopolymerization initiator having a g-line absorbance of 0.01 to 0.1 of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent Photosensitive resin composition for out-wafer level package.
[17] (A) a polyimide precursor,
(B) the following general formula (B1):

Wherein R _{6 to} R ₈ each independently represent a monovalent organic group having 1 to 6 carbon atoms, and Ar is a direct bond, or at least one selected from phenylene, naphthylene, and thienylene Represents a divalent group of And a photopolymerization initiator represented by the formula:
[18] The (A) polyimide precursor has the following general formula (A1):

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

(In the general formula (R1), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a C _{1 to} C ₃ organic group, and p is an integer selected from 2 to 10.) Or a C _{1 to} C ₄ saturated aliphatic group, provided that at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (R 1) is there. 18. The photosensitive resin composition according to the above-mentioned aspect 17, which is a polyimide precursor containing a structure represented by
[19] Said X has the following structure:

20. The photosensitive resin composition according to the above-mentioned aspect 18, which comprises
[20] Said X has the following structure:

20. The photosensitive resin composition according to the above-mentioned aspect 18, which comprises
[21] Said Y has the following structure:

20. The photosensitive resin composition in any one of the said aspect 18-20 containing C. and.
[22] Said Y has the following structure:

20. The photosensitive resin composition in any one of the said aspect 18-20 containing C. and.
[23] Said X has the following structure:

Including
Said Y is the following structure:

20. The photosensitive resin composition according to the above-mentioned aspect 18, which comprises
[24] The following steps:
(1) applying the photosensitive resin composition according to any one of the above embodiments 1 to 23 onto a substrate, and forming a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer with g-rays and / or h-rays;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of: heating the relief pattern to form a cured relief pattern.
[25] A semiconductor device characterized by comprising a cured relief pattern obtained by the manufacturing method according to the above-mentioned aspect 24.

  According to the present invention, a photosensitive resin which exhibits a good resolution even when a shift in focus depth occurs, exhibits a good chemical resistance, and provides a cured relief pattern capable of suppressing deterioration of a mold resin and a decrease in adhesion. A composition, a method of forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern 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 formula may be identical to or different from one another when a plurality of structures are present in the molecule.

<Photosensitive resin composition>
The photosensitive resin composition according to one aspect of the present invention contains (A) a polyimide precursor and (B) a photopolymerization initiator. In one embodiment, the (B) photopolymerization initiator has a g-line absorbance of 0.01 to 0.1 of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent. The photosensitive resin composition may further contain (C) a crosslinking agent in addition to the above components.
According to such a photosensitive resin composition, it is possible to obtain a cured relief pattern capable of improving the focus margin and the chemical resistance, and suppressing the deterioration of the epoxy resin as the mold resin and the decrease in the adhesiveness.

  The photosensitive resin composition according to an aspect of the present invention is suitably used for a fan-out wafer level package (FOWLP) type (also referred to as a fan-out type) semiconductor device. FOWLP is a package in which a redistribution layer (which has a wiring and an insulating film) is formed larger than the outer shape of a semiconductor chip (that is, it is fan-out from the semiconductor chip) . In the fan-out type semiconductor device, the insulating film of the rewiring layer needs to be well adhered not only to the semiconductor chip but also to the mold resin as a sealing material. The photosensitive resin composition of the present disclosure can suppress deterioration of the mold resin and adheres well to the mold resin, and is particularly suitable as an insulating film for a rewiring layer. Therefore, in one aspect, the photosensitive resin composition of the present disclosure is a photosensitive resin composition for fan-out wafer level package.

[(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 not limited as long as it can form a cured relief pattern by the action of the (B) photopolymerization initiator.
The (A) polyimide precursor according to the present embodiment is preferably applied as a single solution, and the g-line absorbance measured on a 10 μm thick film obtained after prebaking is preferably 0.001 to 0.1. It is further preferable that the h-line absorbance is 0.001 to 0.5.
From the viewpoint of obtaining a wide focus margin in the cured relief pattern obtained from the photosensitive resin composition and from the viewpoint of expressing good chemical resistance, the photosensitive resin composition of the present embodiment satisfies the above requirements (A It is preferable to contain a polyimide precursor.

(A) The g-line and h-line absorbances of a 10 μm thick film after prebaking of a polyimide precursor alone can be measured with a conventional spectrophotometer for a coating formed on quartz glass. When the thickness of the formed film is not 10 μm, the absorbance obtained for the film is converted to the thickness of 10 μm according to the Lambert-Beer's law to determine the 10 μm thick g-line and h-line absorbances. be able to.
When the g-line absorbance is 0.001 or more, it is preferable in order to sufficiently exhibit mechanical properties and thermal properties when forming a polyimide film after curing the polyimide precursor. If the g-line absorbance is 0.1 or less, the light reaches the bottom of the coating, and for example, in the case of a negative type, the bottom tends to be sufficiently cured, which is preferable. From the viewpoint of mechanical properties and development resolution, 0.001 to 0.05 is preferable, and 0.005 to 0.03 is more preferable.
If the h-line absorbance is 0.001 or more, it is preferable in order to sufficiently exhibit mechanical properties and thermal properties when forming a polyimide film after curing the polyimide precursor. If the h-line absorbance is 0.5 or less, the light reaches the bottom of the coating, and for example, in the case of a negative type, the bottom tends to be sufficiently cured, which is preferable. From the viewpoint of mechanical properties and development resolution, 0.001 to 0.3 is preferable, and 0.005 to 0.2 is more preferable.

  The (A) polyimide precursor according to the present embodiment contains, as a main component, at least one resin selected from the group consisting of, for example, polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. Is preferred. Here, the main component means containing 60% by mass or more of these resins with respect to the entire resin, and preferably containing 80% by mass or more. Moreover, you may contain other resin as needed.

  The weight average molecular weight of the (A) polyimide precursor is preferably 1,000 or more as a polystyrene conversion value by gel permeation chromatography from the viewpoint of heat resistance and mechanical properties of a film obtained after heat treatment. More preferably, it is 5,000 or more. The upper limit is preferably 100,000 or less. From the viewpoint of solubility in a developer, the weight average molecular weight is more preferably 50,000 or less.

  In the resin composition according to the present embodiment, one of the most preferable (A) polyimide precursors from the viewpoint of heat resistance and photosensitivity is a compound represented by the following general formula (A1):

｛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）

（式中、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り、但し、Ｒ_１及びＲ_２の少なくとも一方が一般式（Ｒ１）で表される１価の有機基である。｝で表される構造を含む、エステル型のポリイミド前駆体である。

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

(Wherein, 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). It is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms, provided that at least one of R ₁ and R ₂ is a monovalent organic group represented by General Formula (R1). It is an ester type polyimide precursor containing the structure represented by}.

In the above general formula (A1), the tetravalent organic group represented by X is preferably an organic group having a carbon number of 6 to 40, more preferably _one of —COOR ₁ group and —CONH— group Are bonded to the same aromatic ring, and both are in the ortho position with each other, which is 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.

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。 More preferably, as the tetravalent organic group represented by X, the following formula:

The structures represented by each of the above are included, but are not limited thereto. In addition, the structure of X may be one kind or a combination of two or more kinds.

又は下記構造：

を含むことが特に好ましい。
ポリイミド前駆体がこのような構造を有することにより、耐熱性および感光性が向上し、得られる硬化レリーフパターンにおいて、フォーカスマージンおよび耐薬品性が向上し、モールド樹脂であるエポキシ樹脂の劣化や密着性の低下を抑えることができる。 In particular, the photosensitive resin composition has the following structure as a tetravalent organic group represented by X in the above general formula (A1):

Or the following structure:

It is particularly preferred to include
When the polyimide precursor has such a structure, the heat resistance and the photosensitivity are improved, and in the cured relief pattern obtained, the focus margin and the chemical resistance are improved, and the deterioration and the adhesion of the epoxy resin which is a mold resin are achieved. Can reduce the

In the above general formula (A1), the divalent organic group represented by Y is preferably a C _{6 to} C ₄₀ aromatic group, and for example, the following formula:

｛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 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).} The structures represented by each of} can be mentioned, but it is not limited thereto. The structure of Y may be one kind or a combination of two or more kinds.

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

又は下記構造：

を含むことが特に好ましい。
ポリイミド前駆体がこのような構造を有することにより、耐熱性および感光性が向上し、得られる硬化レリーフパターンにおいて、フォーカスマージンおよび耐薬品性が向上し、モールド樹脂であるエポキシ樹脂の劣化や密着性の低下を抑えることができる。 In particular, in the photosensitive resin composition, the polyimide precursor has a divalent organic group represented by Y in the general formula (A1) and the following structure:

Or the following structure:

It is particularly preferred to include
When the polyimide precursor has such a structure, the heat resistance and the photosensitivity are improved, and in the cured relief pattern obtained, the focus margin and the chemical resistance are improved, and the deterioration and the adhesion of the epoxy resin which is a mold resin are achieved. Can reduce the

を含み、
Ｙは下記構造：

を含むことが最も好ましい。
ポリイミド前駆体がこのような構造を有することにより、耐熱性および感光性がさらに向上し、得られる硬化レリーフパターンにおいて、フォーカスマージンおよび耐薬品性がさらに向上し、モールド樹脂であるエポキシ樹脂の劣化や密着性の低下をさらに確実に抑えることができる。 In the photosensitive resin composition, in the above general formula (A1),
X has the following structure:

Including
Y has the following structure:

Most preferably.
When the polyimide precursor has such a structure, the heat resistance and the photosensitivity are further improved, and in the cured relief pattern obtained, the focus margin and the chemical resistance are further improved, and the degradation of the epoxy resin which is a mold resin or The reduction in adhesion can be further reliably suppressed.

[(A) Preparation Method of Polyimide Precursor]
For example, the ester bond type polyimide precursor first comprises: 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 an acid / ester). Thereafter, it is obtained by subjecting this acid / ester body and a diamine having a divalent organic group Y to amide polycondensation. A saturated aliphatic alcohol may optionally be used in combination with the above-described alcohol having a photopolymerizable group.

(Preparation of acid / ester)
Examples of tetracarboxylic acid dianhydride having a tetravalent organic group X suitably used to prepare an ester bond type polyimide precursor in the present invention include, for example, pyromellitic anhydride, 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 , Diphenyl sulfone-3,3 ', 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3', 4,4'-tetracarboxylic acid dianhydride, 2,2-bis (3,4 -Phthalic anhydride propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane, etc. may be mentioned, but it is limited thereto It is not a thing. In addition, it is possible to use two or more of them in combination, as a matter of course.

  Examples of alcohols having a photopolymerizable group, which are suitably used to prepare an ester bond type polyimide precursor in the present invention, include, for example, 2-acryloyloxyethyl alcohol, 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- 3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like can be mentioned.

  As saturated aliphatic alcohol which can be optionally used with alcohol which has the said photopolymerizable group, C1-C4 saturated aliphatic alcohol is preferable. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.

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

As the above-mentioned reaction solvent, preferred are those capable of completely dissolving tetracarboxylic acid dianhydride and alcohols as raw materials and acid / ester as product. More preferably, it is a solvent in which a polyimide precursor which is an amide polycondensation product of the acid / ester form 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, carbonized Hydrogens etc. can be mentioned. Examples of these are
As ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc .;
As esters, for example, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate etc .;

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

(Preparation of Polyimide Precursor)
A suitable dehydration condensation agent is added to and mixed with the above-mentioned acid / ester (typically in the form of a solution dissolved in the above reaction solvent), preferably under ice cooling, to obtain an acid / ester as a polyanhydride. I assume. Subsequently, a solution obtained by separately dissolving or dispersing a diamine having a divalent organic group Y suitably used in the present invention in a solvent is added dropwise thereto, and the desired polyimide precursor is obtained by subjecting both to amide polycondensation. You can get Diaminosiloxanes may be used in combination with the diamines having the divalent organic group Y.
As the above-mentioned dehydration condensation agent, for example, dicyclohexyl carbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N '-Disuccinimidyl carbonate etc. are mentioned.
As described above, an intermediate polyacid anhydride is obtained.

  In the present invention, examples of diamines having a divalent organic group Y which can be suitably used for the reaction with the polyacid anhydride 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'-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- (4-amino-4-phenyl) phenyl] sulfone] 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 and the like;
And those in which a part of hydrogen atoms on these benzene rings 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 substituted compound 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 mixtures thereof and the like. The diamines are not limited to the above examples.

  Diaminosiloxanes are for the purpose of improving the adhesion between a coating film formed of a photosensitive resin composition and various substrates, and in the preparation of (A) photosensitive polyimide precursor, the above divalent organic group Y is used. In combination with diamines including Specific examples of such diaminosiloxanes include, for example, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetraphenyldisiloxane, etc. it can.

After completion of the amide polycondensation reaction, the water absorption by-product of the dehydration condensation agent coexisting in the reaction solution is separated by filtration if necessary, and a poor solvent suitable for a solution containing a polymer component such as water, fat Lower alcohol, its mixed solution, etc.) to precipitate the polymer component, and if necessary, repeat operations such as re-dissolution and re-precipitation operation etc. to purify the polymer and then vacuum-dry it Thus, the desired polyimide precursor is isolated. At that time, for the purpose of improving storage stability and resolution, acid compounds such as carboxylic acid and sulfonic acid, salt compounds such as carboxylic acid salt and sulfonic acid salt, and base compounds such as aliphatic amine and aromatic amine Salt compounds such as aliphatic amine salts and aromatic amine salts can also be added. In order to improve the degree of purification, the solution of this polymer may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.
Examples of the carboxylic acid include formic acid, oxalic acid and maleic acid. As a sulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and the like can be mentioned.
Examples of the carboxylate include sodium formate and sodium oxalate. As a sulfonate, sodium p-toluenesulfonic acid, p-toluenesulfonic acid pyridine salt and the like can be mentioned.
Examples of aliphatic amines include triethylamine and tributylamine. The aromatic amines include aniline and bisaniline.
Examples of aliphatic amine salts include triethylamine hydrochloride, tributylamine hydrochloride and the like. As an aromatic amine salt, aniline hydrochloride, bis aniline hydrochloride, etc. are mentioned.

  The weight average molecular weight of the ester bond type polyimide precursor is preferably 1,000 or more as a polystyrene conversion value by gel permeation chromatography from the viewpoint of the heat resistance and mechanical properties of the film obtained after heat treatment. More preferably, it is 5,000 or more. The upper limit is preferably 100,000 or less. From the viewpoint of solubility in a developer, the weight average molecular weight is more preferably 50,000 or less. Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as a developing solvent for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodispersed polystyrene. As standard monodispersed polystyrene, it is recommended to select from Showa Denko organic solvent based standard sample STANDARD SM-105.

  With respect to the (A) polyimide precursor synthesized by such a method, the g-line and h-line absorbances of the prebaked film formed alone take various values depending on the molecular structure. However, since the g-line and h-line absorbances of the mixture are the arithmetic mean of the g-line and h-line absorbances of the respective components, mechanical properties can be obtained by combining two or more types of (A) polyimide precursors in an appropriate ratio. Make the g-line absorbance of the 10 μm thick film of the (A) polyimide precursor to 0.001 to 0.1 and the h-line absorbance to 0.001 to 0.5 while keeping balance with the thermal properties etc. Can.

｛式中、Ｒ_６〜Ｒ_８はそれぞれ独立に炭素数１〜６の１価の有機基を表し、Ａｒは直接結合であるか、または、フェニレン、ナフチレン、およびチエニレンから選択される少なくとも１種の２価の基を表す。｝
これらの中でＡｒはフェニレン基であることが好ましく、Ｒ７およびＲ８は炭素数１〜４の１価の有機基が好ましく、Ｒ６は炭素数１〜３の１価の有機基であることが好ましい。 [(B) Photopolymerization initiator]
Next, the (B) photopolymerization initiator according to the present embodiment will be described.
In one embodiment, the (B) photopolymerization initiator has a g-line absorbance of 0.01 to 0.1 of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent.
(B) The absorbance of the photopolymerization initiator may be measured by dissolving the compound in N-methyl-2-pyrrolidone at a concentration of 0.001 wt% and using a 1 cm quartz cell with a conventional spectrophotometer. it can.
The (B) photopolymerization initiator according to the present embodiment has a g-line absorbance of 0.015 wt% of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent, from the viewpoint of focus margin and chemical resistance. The above is preferable, and 0.020 or more is preferable. The g-line absorbance is preferably 0.09 or less, preferably 0.08 or less, more preferably 0.07 or less, preferably 0.06 or less, preferably 0.05 or less, preferably 0.04 or less, and 0. 03 or less is preferable.
From the viewpoint of focus margin and chemical resistance, the (B) photopolymerization initiator according to the present embodiment has an h-line absorbance of 0.15 of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent. It is preferable that it is -0.5. The h-line absorbance is preferably 0.15 to 0.4, and more preferably 0.15 to 0.3.
The (B) photopolymerization initiator according to the present embodiment is not limited as long as it has the above-mentioned absorbance, but from the viewpoint of chemical resistance, it is preferable to have an oxime structure in the structure.
The (B) photopolymerization initiator according to the present embodiment is not limited as long as the g-line absorbance of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent is 0.01 to 0.1. In one aspect, a structure represented by the following general formula (B1) is preferable. In one embodiment, the (B) photopolymerization initiator is a compound represented by the following general formula (B1).

Wherein R _{6 to} R ₈ each independently represent a monovalent organic group having 1 to 6 carbon atoms, and Ar is a direct bond, or at least one selected from phenylene, naphthylene, and thienylene Represents a divalent group of }
Among them, Ar is preferably a phenylene group, R 7 and R 8 are preferably a C 1-4 monovalent organic group, and R 6 is preferably a C 1-3 monovalent organic group. .

By using (B) a photopolymerization initiator having a g-line absorbance of 0.01 to 0.1 of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent according to the present embodiment, Although it is not clear why the focus margin and the chemical resistance are improved and the deterioration of the epoxy resin which is the mold resin and the deterioration of the adhesion are suppressed, for example, the reason for the deterioration and the adhesion of the epoxy resin is the present invention The people think as follows.
The i-line and ghi line used for normal exposure have higher energy than g- and h-line, so when they reach the epoxy resin side through the polyimide film, they damage the epoxy resin or the damaged epoxy It is believed that the gas is accumulated at the interface between the polyimide and the epoxy resin by the volatilization of a part of the resin, thereby reducing the adhesion. Therefore, when it exposes using g line | wire and h line | wire, the damage of an epoxy resin can be suppressed.
Although the reason why the chemical resistance is good in the present embodiment is not clear, for example, in the case of a negative photosensitive resin composition, the crosslinking of the exposed portion is caused by having specific absorbance at the g line and h line. It is thought that it is easy to progress, easy to adopt a three-dimensional network structure, and develop chemical resistance.

The use of the (B) photopolymerization initiator according to the present embodiment improves the focus margin and the chemical resistance, and tends to suppress the deterioration of the epoxy resin which is a mold resin and the decrease in adhesion. When the g-line absorbance of the body is 0.01 to 0.1, it tends to be expressed well.
The photopolymerization initiator (B) according to the present embodiment is not limited as long as it has the above-mentioned absorbance, but the photosensitive resin composition is generally handled under yellow light which is cut at a wavelength of 500 nm or less in general. The absorbance at 500 nm is preferably low. Specifically, the absorbance at 500 nm of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent is preferably 0.1 or less, more preferably 0.05 or less, and particularly preferably 0.02 or less.

｛式中、Ｒ_６〜Ｒ_８はそれぞれ独立に炭素数１〜６の１価の有機基を表し、Ａｒは直接結合であるか、または、フェニレン、ナフチレン、およびチエニレンから選択される少なくとも１種の２価の基を表す。｝を含有する。また、感光性樹脂組成物は、上記の成分以外に、（Ｃ）架橋剤を更に含有していてもよい。
このような感光性樹脂組成物によれば、フォーカスマージンおよび耐薬品性が向上し、モールド樹脂であるエポキシ樹脂の劣化や密着性の低下を抑えることができる硬化レリーフパターンを得ることができる。 In addition, the photosensitive resin composition which concerns on 1 aspect of this invention can also be represented as follows.
The photosensitive resin composition comprises (A) a polyimide precursor, and (B) a photopolymerization initiator represented by the following general formula (B1):

Wherein R _{6 to} R ₈ each independently represent a monovalent organic group having 1 to 6 carbon atoms, and Ar is a direct bond, or at least one selected from phenylene, naphthylene, and thienylene Represents a divalent group of Containing}. The photosensitive resin composition may further contain (C) a crosslinking agent in addition to the above components.
According to such a photosensitive resin composition, it is possible to obtain a cured relief pattern capable of improving the focus margin and the chemical resistance, and suppressing the deterioration of the epoxy resin as the mold resin and the decrease in the adhesiveness.

[(C) crosslinker]
As the (C) crosslinking agent optionally used in the present invention, any compound having a plurality of functional groups in the molecule can be mentioned. Here, examples of the functional group include acryl group, methacryl group, epoxy group, methylol group, allyl group, vinyl group and maleimide group.

  As the crosslinking agent, for example, one having one crosslinkable group, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (all trade names, Honshu Chemical Industry ( DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (above, trade name, Asahi organic material, etc.) having two such as Pa-type benzoxazine (trade name, Shikoku Kasei Kogyo Co., Ltd.), etc. DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis -C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, ML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, Sanko Corporation) Manufactured by Sumitomo Chemical Co., Ltd., B-a type benzoxazine, B-m type benzoxazine (all trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6- TriML-P, TriML-35 XL, TriML-Tris CR-HAP (all trade names, Honshu Chemical Industry Co., Ltd.) as having dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, T L-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, trade name, Honshu Chemical Industry Co., Ltd. product), Nikalac MX-280, Nikalac MX-270 (above, trade name, Inc.) HML-TPPHBA, HML-TPHAP (all trade names, Honshu Chemical Industry Co., Ltd.), Nikalac MW-390, Nikalac MW-100 LM (all trade names, trade names, etc.) Sanwa Chemical Co., Ltd.).

  Among them, in the present invention, those containing at least two crosslinkable groups are preferable, and 46DMOC, 46DMOEP (all trade names, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC are particularly preferable. , DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (all products) Name, Honshu Chemical Industry Co., Ltd., Nicarak MX-290 (trade name, Sanwa Chemical Co., Ltd.), B-a type benzoxazine, B-m type benzoxazine (all, trade name, Shikoku Kasei Kogyo Co., Ltd.) Ltd.) 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-creso , 2,6-diacetoxymethyl-p-cresol, etc., TriML-P, TriML-35 XL (above, trade name, Honshu Chemical Industry Co., Ltd. product), etc., TM-BIP-A (trade name, Asahi organic material) Industrial Co., Ltd., TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (all trade names, Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc. may be mentioned, such as -270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) and the like. Furthermore, more preferably, Nikalac MX-290, Nikalac MX-280, Nikalac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), B-a type benzoxazine, B-m type benzoxazine (more than , Trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., Nikalac MW-390, Nikalac MW-100LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.) and the like.

  It is preferable that it is 1-40 mass parts with respect to 100 mass parts of (A) resin, and, as for the compounding quantity of (C) crosslinking agent, More preferably, it is 2-30 mass parts.

  In the photosensitive resin composition, the total content of (B) photopolymerization initiator and (C) crosslinking agent is 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) polyimide precursor component. Is preferred.

[(D) Other ingredients]
The photosensitive resin composition may further contain components other than the components (A) to (C).
The photosensitive resin composition is typically used as a liquid photosensitive resin composition in which each of the above-described components and optional components further used as necessary are dissolved in a solvent to form a varnish. Therefore, as the (D) other components, solvents can be mentioned, for example, resins other than the above-mentioned (A) photosensitive polyimide precursor, sensitizers, monomers having a photopolymerizable unsaturated bond, adhesion assistants And thermal polymerization inhibitors, azole compounds, hindered phenol compounds and the like.

Examples of the solvent include polar organic solvents, alcohols and the like.
As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in (A) 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, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like can be mentioned, and these can be used alone or in combination of two or more.

From the viewpoint of improving the storage stability of the photosensitive resin composition, the solvent in the present invention is preferably a solvent containing an alcohol. Alcohols which can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond. Specific examples thereof include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol and the like;
Lactate 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;
Dialcohols such as ethylene glycol and propylene glycol can be mentioned. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters and ethyl alcohol are preferred, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, in particular, And propylene glycol-1- (n-propyl) ether are more preferred.

  The above solvent is, for example, in the range of 30 to 1,500 parts by mass, preferably 100 to 1,000 parts by weight per 100 parts by mass of the (A) polyimide precursor, depending on the desired coating 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 more preferably Preferably it is 10-30 mass%. When the content of the alcohol having no olefin double bond is 5% by mass or more, the storage stability of the photosensitive resin composition becomes good, and when it is 50% by mass or less, the dissolution of the polyimide precursor (A) Sex is good.

  The photosensitive resin composition according to the present embodiment may further contain a resin component other than the (A) polyimide precursor described above. Examples of the resin component that can be contained include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, acrylic resin and the like. 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.

  In the photosensitive resin composition according to the present embodiment, a sensitizer can be optionally blended in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, 2,6-bis (4′-diethylaminobenzal) ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnana Myrylene 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, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 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 An acetamide, benzanilide, N-methyl acetanilide, 3 ', 4'- dimethyl acetanilide etc. are mentioned. These can be used alone or in combination of, for example, 2 to 5 types.

  It is preferable that the compounding quantity in case the photosensitive resin composition contains the sensitizer for improving a photosensitivity is 0.1-25 mass parts with respect to 100 mass parts of (A) polyimide precursors. .

The resin composition 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 which undergoes a radical polymerization reaction by a photopolymerization initiator is preferable. In particular, ethylene glycol or polyethylene glycol mono- or di- (meth) acrylates, including, but not limited to, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate;
Propylene glycol or polypropylene glycol mono or di (meth) acrylate;
Mono-, di- or tri (meth) acrylate of glycerol;
Cyclohexane di (meth) acrylate;
1, 4-butanediol diacrylate and dimethacrylate, 1, 6-hexanediol di (meth) acrylate;

Di (meth) acrylate of neopentyl glycol;
Bisphenol A mono- or di (meth) acrylates;
Benzene trimethacrylate;
Isobornyl (meth) acrylate;
Acrylamide and its derivatives;
Methacrylamide and its derivatives;
Trimethylolpropane tri (meth) acrylate;
Di- or tri (meth) acrylate of glycerol;
Di-, tri-, or tetra (meth) acrylates of pentaerythritol;
And compounds such as ethylene oxide or propylene oxide adducts of these compounds.

  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) polyimide precursor The amount is preferably 1 to 50 parts by mass with respect to 100 parts by mass.

  In order to improve the adhesion between the film formed from the photosensitive resin composition according to this embodiment and the substrate, an adhesion auxiliary agent can be optionally blended in the photosensitive resin composition. Examples of adhesion assistants 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) propyl succinic anhydride, silane coupling agents such as N-phenylaminopropyl trimethoxysilane, and aluminum tris (ethyl aceto) And aluminum-based adhesion aids such as acetate), aluminum tris (acetylacetonate) and ethylacetoacetate aluminum diisopropylate.

  Among these adhesion assistants, it is more preferable to use a silane coupling agent from the viewpoint of adhesion. When the photosensitive resin composition contains an adhesion | attachment adjuvant, the range of 0.5-25 mass parts is preferable with respect to 100 mass parts of (A) polyimide precursors.

  When the photosensitive resin composition according to the present embodiment is in the form of a solution containing a solvent in particular, a thermal polymerization inhibitor is added to the photosensitive resin composition in order to improve the viscosity and stability of the photosensitivity during storage. Can be blended arbitrarily. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic 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.

  As a compounding quantity of the thermal-polymerization inhibitor in the case of mix | blending with the photosensitive resin composition, the range of 0.005-12 mass parts is preferable with respect to 100 mass parts of (A) photosensitive polyimide precursors.

  When the substrate to which the resin composition according to the present embodiment is applied uses, for example, a substrate made of copper or a copper alloy, an azole compound can be optionally blended 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, 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-dimeth -Benzyl) 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 one or more selected from tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

  It is preferable that the compounding quantity in case the photosensitive resin composition concerning this Embodiment contains the said azole compound is 0.1-20 mass parts with respect to 100 mass parts of (A) polyimide precursors, From the viewpoint of sensitivity characteristics, 0.5 to 5 parts by mass is more preferable. When the compounding quantity with respect to 100 mass parts of (A) polyimide precursors of an azole compound is 0.1 mass part or more, when the photosensitive resin composition concerning this 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, the excellent photosensitivity of the photosensitive resin composition is maintained.

  In order to suppress 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 hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl-3- (3,5-di-tert-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), triethylene glycol-bis [3- (3) -Tert-Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-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-hydrocinnamamide), 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-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-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 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- (1 H, 3 H, 5 H) -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, it is not limited thereto. 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 etc. are particularly preferred.

  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 light sensitivity characteristics. Is more preferred. When the compounding quantity with respect to 100 mass parts of (A) polyimide precursors of a hindered phenol compound is 0.1 mass part or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, copper or copper Discoloring and corrosion of the alloy are prevented, while when it is 20 parts by mass or less, the excellent photosensitivity of the photosensitive resin composition is maintained.

<Method of producing hardened relief pattern>
The invention also provides a method of making a cured relief pattern.
The method for producing an effect relief pattern in the present invention may be, for example, the following steps:
(1) applying the above-described negative photosensitive resin composition of the present disclosure on a substrate, and forming a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer with g-ray and / or h-ray;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A step of heating the relief pattern to form a cured relief pattern is carried out in the order described above.
Hereinafter, typical embodiments of each step will be described.

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

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

(2) Exposure process At this process, the photosensitive resin layer formed above is exposed. As the exposure apparatus, for example, an exposure apparatus such as a contact aligner, a mirror projection, a stepper or the like is used. The exposure can be performed directly through a photomask or reticle having a pattern. The light beam used for exposure is, for example, an ultraviolet light source.

  After exposure, post exposure bake (PEB) and / or post development bake may be performed according to any combination of temperature and time as needed for the purpose of improving photosensitivity and the like. The range of baking conditions is preferably 40 to 120 ° C. for 10 seconds to 240 seconds, but the range is not limited to this range as long as it does not inhibit various properties of the photosensitive resin composition of the present embodiment.

(3) Development Step In this step, the unexposed area of the photosensitive resin layer after exposure is removed by development. As a development method for developing the photosensitive resin layer after exposure (irradiation), a conventional development method of photoresist can be selected and used. For example, a rotary spray method, a paddle method, an immersion method with ultrasonic treatment, and the like. In addition, after development, post-development baking may be performed according to any combination of temperature and time as needed, for the purpose of adjusting the shape of the relief pattern and the like. The post-development baking temperature can be, for example, 80 to 130 ° C., and the time can be, for example, 0.5 to 10 minutes.

  As a developing solution to be used for development, a good solvent for the photosensitive resin composition, or a combination of the good solvent and the poor solvent is preferable. As a good solvent, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone etc. 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. In addition, two or more types of each solvent, for example, several types may be used in combination.

(4) Heating step In this step, the relief pattern obtained by the above development is heated to dilute the photosensitive component, and (A) the polyimide precursor is imidized to convert it into a cured relief pattern made of polyimide. .
As a method of heat curing, various methods can be selected such as using a hot plate, using an oven, and using a temperature rising oven capable of setting a temperature program. Heating can be performed, for example, at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. As an atmosphere gas at the time of heat curing, air may be used, or an inert gas such as nitrogen or argon may be used.
As described above, a cured relief pattern can be produced.

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

  The photosensitive resin composition according to one aspect of the present invention is used in 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 the application to semiconductor devices as described above. It is also useful.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Physical properties of 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 (in terms of standard polystyrene). The column used for the measurement is Shodex 805 M / 806 M series manufactured by Showa Denko, and the standard monodispersed polystyrene is Shodex STANDARD SM-105 manufactured by Showa Denko KK, and the developing solvent is N-methyl-2-pyrrolidone. The detector used was Shodex RI-930 (trade name) manufactured by Showa Denko.

(2) Absorbance Measurement The absorbance of the photopolymerization initiator (B) was prepared by preparing a 0.001 wt% NMP solution, filling a 1 cm quartz cell, and scanning using a Shimadzu UV-1800 apparatus. The measurement was performed at a medium speed and a sampling pitch of 0.5 nm.
The absorbance of the polyimide precursor was measured after being prebaked on quartz glass so as to be a 10 μm thick film. When the thickness of the formed film is not 10 μm, the absorbance obtained for the film is converted to the thickness of 10 μm according to Lambert-Beer's law to determine the g-line and h-line absorbances of 10 μm thickness. The

(3) Focus margin evaluation 200 nm thick Ti, 400 nm on a 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva) A thick Cu was sputtered in this order to prepare a sputtered Cu wafer substrate.
A photosensitive resin composition is spin coated on the sputter Cu wafer substrate using a spin coater (D-spin 60A type, manufactured by SOKUDO), heat dried at 110 ° C. for 180 seconds, and a film thickness of 10 μm ± 0.2 μm. The spin-coated film of

An i-line cut filter or gh-line cut filter is attached to this spin coat film using a reticle with a test pattern having a circular pattern with a mask size of 6 μm in diameter by the same magnification projection exposure system PrismaGHI S / N 5503 (manufactured by Ultratech Co., Ltd.) in examples 1 to 9 g, and h line 40 mJ / cm ^2, was irradiated with an energy of Comparative examples 1 and 2 in the i-line 120 mJ / cm ^2. At this time, exposure was performed by moving the focus by 4 μm toward the film bottom with reference to the surface of the spin coat film for each exposure amount.
Next, the coated film formed on the sputtered Cu wafer is spray-developed with cyclopentanone using a developing machine (D-SPIN 636, manufactured by Dainippon Screen), rinsed with propylene glycol methyl ether acetate, and then polyamic acid ester A round relief concave relief pattern was obtained. The development time for spray development was defined as 1.4 times the minimum time for developing the resin composition in the unexposed area in the above-mentioned 10 μm spin-coated film.

Whether or not the mask shape obtained above has an open concave relief pattern with a mask size of 6 μm determines that a pattern satisfying both of the following criteria (I) and (II) is a pass, and the thickness of the focus margin giving a pass pattern In the results.
(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 wide and there is no undercut, swelling or bridging.

(4) Chemical resistance evaluation The pattern obtained above is heat treated at 200 ° C. for 2 hours in a nitrogen atmosphere using a programmed temperature curing furnace (VF-2000, manufactured by Koyo Lindberg, Japan). Thus, a cured relief pattern of about 7 to 8 μm thick polyimide was obtained on a silicon wafer.
This relief pattern is immersed in a drug (DMSO: 70% by weight, 2-aminoethanol: 25% by weight, TMAH: 5% by weight) for 5 minutes at 50 ° C., and then a Tencor P-15 step difference meter (CAEL ETCOL CORP.) It measured as a dissolution rate (nm / min) by performing film thickness measurement using the product made and comparing with before chemical processing.

(5) Sealing Material Deterioration Test The Nagase Chemtex R4000 series was prepared as an epoxy-based sealing material.
The encapsulant was then spin-coated on an aluminum sputtered silicone wafer to a thickness of about 150 microns and thermally cured at 130 ° C. to cure the epoxy encapsulant.
The photosensitive resin compositions prepared in Examples and Comparative Examples were coated on the cured epoxy resin film to a final film thickness of 10 microns. The exposed photosensitive resin composition is exposed to light at 100 mJ / cm ² in Examples 1 to 9 and 100 mJ / cm ² in Comparative Examples 1 and ^{2 under} the exposure conditions of i line 100 mJ / cm ² , and then 200 ° C. 2 It was thermally cured for a time to prepare a 10-μm thick first-layer cured film.
The photosensitive resin composition used in the formation of the first cured film is coated on the first cured film, exposed to light under the same conditions as in the formation of the first cured film, and then thermally cured. A second cured film having a thickness of 10 microns was produced.
After cutting the cross section of the test piece after the formation of the second layer of the cured film with a FIB apparatus (JIB-4000 manufactured by Nippon Denshi Co., Ltd.), the degree of deterioration was evaluated by confirming the presence or absence of voids in the epoxy part . A sample in which no void was observed was marked with 、, and a sample in which even one void was observed was marked ×.

(6) Adhesion test with sealing material An epoxy resin is applied on the photosensitive resin cured film of the sample prepared in the sealing material deterioration test, and then a pin is set, and a take-off tester (Sebastian manufactured by Quad Group, Inc.) The adhesion test was conducted using a 5 type).
Evaluation: Adhesive strength 70 MPa or more ・ ・ ・ Adhesion 密 着
50MPa or more-less than 70MPa · · · adhesion ○
30MPa or more-less than 50MPa ... adhesion force △
Less than 30MPa · · · adhesion ×

ＣＨ_２Ｃｌ_２ ４０ｍｌ中のＮ−エチルカルバゾール５．００部に、テレフタル酸クロリド２．７３部及びＡｌＣｌ_３ ３．７６部を加えた。室温で一晩攪拌したのち、アセチルクロリド２．２１部及びＡｌＣｌ_３ ３．７６部を加えた。この反応混合物を室温で４時間攪拌した。次いで、反応混合物を氷水に注いだ。生成物を酢酸エチルで抽出した。酢酸エチル層を飽和ＮａＨＣＯ_３水溶液及び食塩水で洗浄し、その後無水硫酸マグネシウムで乾燥した。溶媒を濃縮後、淡黄緑色固体５．９１部（７６．３％）を得た。この固体を未精製のまま次の反応に用いた。 <Production Example 1>
a. Synthesis of carbazole derivative (acyl form)

To 5.00 parts of N-ethylcarbazole in 40 ml of CH ₂ Cl ₂ was added 2.73 parts of terephthalic acid chloride and 3.76 parts of AlCl ₃ . After stirring overnight at room temperature, 2.21 parts of acetyl chloride and 3.76 parts of AlCl ₃ were added. The reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was then poured into ice water. The product was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous NaHCO ₃ solution and brine and then dried over anhydrous magnesium sulfate. After concentration of the solvent, 5.91 parts (76.3%) of pale yellowish green solid was obtained. This solid was used for the next reaction without purification.

エタノール３０ｍｌ中のａ．で得られたアシル体３.０部に、塩化ヒドロキシルアンモニウム０.７６部及びピリジン０.８６部を加えた。１０時間還流したのち、反応混合物を氷水に注いだ。得られた固体を濾取し、水で洗浄し、酢酸エチルに溶解した。無水硫酸マグネシウムで乾燥したのち、濃縮し、淡黄白色固体２.８０部（８９％）を得た。この固体を未精製のまま、次の反応に用いた。 b. Synthesis of oxime form

A. In 30 ml of ethanol To 3.0 parts of the acyl compound obtained in the above, 0.76 parts of hydroxylammonium chloride and 0.86 parts of pyridine were added. After refluxing for 10 hours, the reaction mixture was poured into ice water. The resulting solid was collected by filtration, washed with water and dissolved in ethyl acetate. After drying over anhydrous magnesium sulfate, concentration was performed to obtain 2.80 parts (89%) of a pale yellowish white solid. This solid was used in the next reaction without purification.

ｂ．で得られたオキシム体１．５部をＤＭＦ２５部に溶解した。この溶液に、塩化アセチル０．５９部を加え、次いでトリエチルアミン０．７８部を１０℃以下で滴下した。室温で４時間攪拌したのち、反応混合物を水に注ぎ、析出固体をろ過した。ろ物を、ＣＨ_２Ｃｌ_２−ヘキサン（２：１）を用いて、シリカゲルカラムクロマトグラフィーにより精製して、淡黄色固体１．０５部（６１．８％）を得た（開始剤Ｂ１）。λｍａｘは３４５ｎｍ、融点は１９１〜２０２℃であった。
この開始剤Ｂ１のｇ線吸光度は０．０２５、ｈ線吸光度は０．１６であった。 c. Synthesis of oxime ester

b. In 25 parts of DMF was dissolved 1.5 parts of the oxime obtained in the above. To this solution was added 0.59 parts of acetyl chloride, and then 0.78 parts of triethylamine was dropped at 10 ° C. or less. After stirring at room temperature for 4 hours, the reaction mixture was poured into water and the precipitated solid was filtered. The filtrate was purified by silica gel column chromatography using CH ₂ Cl ₂ -hexane (2: 1) to obtain 1.05 parts (61.8%) of a pale yellow solid (initiator B1). The λmax was 345 nm, and the melting point was 191 ° C to 202 ° C.
The g-line absorbance of the initiator B1 was 0.025, and the h-line absorbance was 0.16.

｛式中、Ａは下記式で表される２価の有機基を表し、Ｂ、Ｃはエチル基を表し、Ｄはメチル基を表す。

<Production Example 2>
A compound (B2) having the following structure was synthesized by the same synthesis method as in Production Example 1. The λmax was 366 nm and the melting point was 205 to 218 ° C. The g-line absorbance was 0.024, and the h-line absorbance was 0.17.

In the formula, A represents a divalent organic group represented by the following formula, B and C represent an ethyl group, and D represents a methyl group.

<Production Example 3> (Synthesis of (A) Polyimide Precursor (Polymer A-1))
155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) is placed in a 2-liter separable flask, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone are added and stirred at room temperature While adding 79.1 g of pyridine, a reaction mixture was obtained. After completion of the reaction exotherm, the mixture was allowed to cool to room temperature and left to stand for additional 16 hours.

  Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone is added to the reaction mixture with stirring over 40 minutes, 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 with 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 solution.

The resulting reaction solution was added to 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer. The resulting crude polymer was collected by filtration, dissolved in 1.5 liters of tetrahydrofuran and then dissolved by adding p-toluenesulfonic acid pyridine salt (2.0 g). The resulting crude polymer solution is purified using a cation exchange resin (manufactured by Organo Corporation) and then dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate is collected by filtration and then vacuum dried. Thus, a powdery polymer A-1 was obtained.
It was 20,000 when the weight average molecular weight (Mw) of this polymer A-1 was measured. The g-line absorbance of this polymer was 0.01, and the h-line absorbance was 0.04.

<Production Example 4> (Synthesis of Polyimide Precursor (Polymer A-2))
In the above Preparation Example 2 except for using 147.1 g of 3,3′4,4′-biphenyltetracarboxylic acid dianhydride instead of 155.1 g of 4,4′-oxydiphthalic acid dianhydride The reaction was carried out in the same manner as described in 1 to obtain a polymer A-2).
It was 22,000 when the weight average molecular weight (Mw) of this polymer A-2 was measured. The g-line absorbance of this polymer was 0.02, and the h-line absorbance was 0.152.

<Production Example 5> (Synthesis of Polyimide Precursor (Polymer A-3))
By carrying out the reaction in the same manner as in Production Example 1 except that in the above Production Example 2, 4,4′-diaminodiphenyl ether (DADPE) is replaced with 1,4-phenylenediamine (50.2 g), Polymer A-3) was obtained.
It was 21,000 when the weight average molecular weight (Mw) of this polymer A-3 was measured. The g-line absorbance of this polymer was 0.01, and the h-line absorbance was 0.02.

架橋剤Ｃ１：

Initiator B3: Adeka Optomer NCI 831 (g-line: 0.001, h-line: 0.127)
Initiator B4: PBG 305 (g-line: 0.001, h-line: 0.001)

Crosslinker C1:

Example 1
50 g of polymer A-1 and 50 g of polymer A-2 as component (A), initiator B1 (4 g) as component (B), 16 g of tetraethylene glycol dimethacrylate as another component, and a mixture of gamma butyrolactone and DMSO It was made into the photosensitive resin composition solution by melt | dissolving in a solvent (weight ratio 75:25), and adjusting the quantity of a solvent so that a viscosity might be about 35 poise.
The composition was evaluated by the method described above. The evaluation results are shown in Table 1.

<Examples 2 to 9, Comparative Examples 1 to 2>
The evaluation was conducted in the same manner as in Example 1 except that the resin composition solution was used in the proportion described in Table 1. The evaluation results are shown in Table 1.

  As apparent from Table 1, (B) the photopolymerization initiator has a structure of the general formula (B1), and / or the g-line absorbance is 0.01 to 0.1, of Examples 1 to 9 It has been found that the cured relief pattern obtained from the photosensitive resin composition can improve the focus margin and the chemical resistance, and can suppress the deterioration of the epoxy resin as the mold resin and the deterioration of the adhesion.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the meaning of invention.

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

Claims (25)

(A) a polyimide precursor,
(B) Photosensitivity characterized by containing a photopolymerization initiator having a g-line absorbance of 0.01 to 0.1 of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent Resin composition.   The photosensitive resin composition according to claim 1, wherein the g-line absorbance of the (B) photopolymerization initiator is 0.015 to 0.04.   The photosensitive resin composition according to claim 1 or 2, wherein the g-line absorbance of the (B) photopolymerization initiator is 0.015 to 0.03.   The h-line absorbance of a 0.001 wt% solution of the (B) photopolymerization initiator using N-methyl-2-pyrrolidone as a solvent is 0.15 to 0.5. Or the photosensitive resin composition according to item 1.   The photosensitive resin composition according to any one of claims 1 to 4, wherein the (B) photopolymerization initiator has an oxime structure. The (B) photopolymerization initiator is represented by the following general formula (B1):

Wherein R _{6 to} R ₈ each independently represent a monovalent organic group having 1 to 6 carbon atoms, and Ar is a direct bond, or at least one selected from phenylene, naphthylene, and thienylene Represents a divalent group of ] The photosensitive resin composition of any one of Claims 1-5 represented by}.   The photosensitive resin composition according to any one of claims 1 to 6, further comprising (C) a crosslinking agent.   The (A) polyimide precursor is applied as a single solution, and the g-line absorbance measured for a 10 μm thick film obtained after prebaking is 0.001 to 0.1, and the h-line absorbance is 0.001 to 0. The photosensitive resin composition according to any one of claims 1 to 7, which is 5. The (A) polyimide precursor has the following general formula (A1):

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

(In general formula (R1), R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10). Or a saturated aliphatic group having 1 to 4 carbon atoms, provided that at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (R 1) is there. ] The photosensitive resin composition of any one of Claims 1-7 which is a polyimide precursor containing the structure represented by}. Said X is the following structure:

The photosensitive resin composition according to claim 9, comprising Said X is the following structure:

The photosensitive resin composition according to claim 9, comprising Said Y is the following structure:

The photosensitive resin composition of any one of Claims 9-11 containing these. Said Y is the following structure:

The photosensitive resin composition of any one of Claims 9-11 containing these. Said X is the following structure:

Including
Said Y is the following structure:

The photosensitive resin composition according to claim 9, comprising   The total content of (B) a photopolymerization initiator and (C) a crosslinking agent with respect to 100 mass parts of said (A) polyimide precursors is 0.1-20 mass parts, It is any one of Claims 1-14. Photosensitive resin composition as described. (A) a polyimide precursor,
(B) A fan comprising: a photopolymerization initiator having a g-line absorbance of 0.01 to 0.1 of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent Photosensitive resin composition for out-wafer level package. (A) a polyimide precursor,
(B) the following general formula (B1):

Wherein R _{6 to} R ₈ each independently represent a monovalent organic group having 1 to 6 carbon atoms, and Ar is a direct bond, or at least one selected from phenylene, naphthylene, and thienylene Represents a divalent group of And a photopolymerization initiator represented by the formula: The (A) polyimide precursor has the following general formula (A1):

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

(In the general formula (R1), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a C _{1 to} C ₃ organic group, and p is an integer selected from 2 to 10.) Or a C _{1 to} C ₄ saturated aliphatic group, provided that at least one of R ₁ and R ₂ is a monovalent organic group represented by the general formula (R 1) is there. The photosensitive resin composition of Claim 17 which is a polyimide precursor containing the structure represented by}. Said X is the following structure:

The photosensitive resin composition according to claim 18, comprising Said X is the following structure:

The photosensitive resin composition according to claim 18, comprising Said Y is the following structure:

The photosensitive resin composition according to any one of claims 18 to 20, which comprises Said Y is the following structure:

The photosensitive resin composition according to any one of claims 18 to 20, which comprises Said X is the following structure:

Including
Said Y is the following structure:

The photosensitive resin composition according to claim 18, comprising The following steps:
(1) applying the photosensitive resin composition according to any one of claims 1 to 23 on a substrate, and forming a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer with g-rays and / or h-rays;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of: heating the relief pattern to form a cured relief pattern.   A semiconductor device characterized by comprising a cured relief pattern obtained by the manufacturing method according to claim 24.