JP7169844B2 - Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

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. , and semiconductor devices.

BACKGROUND ART Conventionally, polyimide resins, which have excellent heat resistance, electrical properties and mechanical properties, have been used as insulating materials for electronic parts, passivation films, surface protective films, interlayer insulating films, etc. 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, exposing, developing and curing the composition for thermal imidation. can be formed. Such a photosensitive polyimide precursor composition has the feature of enabling a significant reduction in the process compared to conventional non-photosensitive polyimide materials.

By the way, a semiconductor device (hereinafter also referred to as "element") is mounted on a printed circuit board by various methods according to the purpose. A conventional element is generally manufactured by a wire bonding method in which a fine wire is used to connect an external terminal (pad) of the element to a lead frame. However, today, when the speed of devices has increased and the operating frequency has reached GHz, the difference in the wiring length of each terminal in mounting affects the operation of the device. Therefore, in mounting elements for high-end applications, it is necessary to accurately control the length of the mounting wiring, and it has become difficult to satisfy this requirement with wire bonding.

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 thereon, the chip is flipped over, and the chip is directly mounted on a printed circuit board. . Since this flip-chip mounting can accurately control the wiring distance, it has been adopted for high-end devices that handle high-speed signals, and for mobile phones due to its small mounting size, and demand is growing rapidly. . More recently, a pre-processed wafer is diced to produce individual chips, the individual chips are reconstructed on a support, sealed with mold resin, and a rewiring layer is formed after removing the support. A semiconductor chip mounting technique called fan-out wafer level package (FOWLP) has been proposed (for example, Patent Document 1). The fan-out wafer level package has the advantage of being able to reduce the height of the package, as well as high-speed transmission and cost reduction.

JP 2005-167191 A

However, due to the recent diversification of package mounting technology, the number of types of supports has increased, and rewiring layers have become multi-layered. There was a problem that the resolution deteriorated greatly. Therefore, there has been a problem that the degradation of the resolution causes disconnection in the rewiring layer, which causes signal delay or a decrease in yield. In addition, when the desired resolution is not obtained when laminating the rewiring layer, the layer is peeled off with a chemical solution and laminated again. There is a problem that the film at the part is damaged and the film thickness is reduced. In addition, since the exposure process and the development process are repeated due to the multi-layer structure, there is a problem of deterioration of the mold resin and deterioration of adhesion.

The present invention provides a photosensitive resin that exhibits good resolution even when there is a shift in the depth of focus, exhibits good chemical resistance, and provides a cured relief pattern that suppresses deterioration of the mold resin and deterioration of adhesion. An object of the present invention 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 can be 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) a polyimide precursor;
(B) a photopolymerization initiator having a g-line absorbance of 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent of 0.01 to 0.1; elastic resin composition.
[2] The photosensitive resin composition according to Aspect 1, wherein the photopolymerization initiator (B) has a g-line absorbance of 0.015 to 0.04.
[3] The photosensitive resin composition according to Aspect 1 or 2, wherein the photopolymerization initiator (B) has a g-line absorbance of 0.015 to 0.03.
[4] Aspects 1 to 1 above, wherein a 0.001 wt% solution of the photopolymerization initiator (B) using N-methyl-2-pyrrolidone as a solvent has an h-line absorbance of 0.15 to 0.5. 4. The photosensitive resin composition according to 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 according to any one of aspects 1 to 5 above.
[7] The photosensitive resin composition according to any one of the above aspects 1 to 6, further comprising (C) a cross-linking agent.
[8] The g-line absorbance measured for a 10 μm thick film obtained after applying the (A) polyimide precursor as a single solution and pre-baking is 0.001 to 0.1, and the h-line absorbance is 0.001. The photosensitive resin composition according to any one of the above aspects 1 to 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, the following general formula (R1)

(In 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.) 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) be. }, the photosensitive resin composition according to any one of aspects 1 to 7 above, which is a polyimide precursor containing a structure represented by }.
[10] X is the following structure:

The photosensitive resin composition according to aspect 9 above, comprising:
[11] X is the following structure:

The photosensitive resin composition according to aspect 9 above, comprising:
[12] Y is the following structure:

The photosensitive resin composition according to any one of aspects 9 to 11 above, comprising:
[13] Y has the following structure:

The photosensitive resin composition according to any one of aspects 9 to 11 above, comprising:
[14] X is the following structure:

including
Y is the following structure:

The photosensitive resin composition according to aspect 9 above, comprising:
[15] Any one of the above aspects 1 to 14, wherein the total content of (B) the photopolymerization initiator and (C) the cross-linking 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 according to .
[16] (A) a polyimide precursor;
(B) a photopolymerization initiator whose 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent has a g-line absorbance of 0.01 to 0.1. A photosensitive resin composition for out-wafer level packaging.
[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 a photosensitive resin composition.
[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, and the following general formula (R1):

(In 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 general formula (R1) be. } The photosensitive resin composition according to aspect 17 above, which is a polyimide precursor containing a structure represented by:
[19] X is the following structure:

The photosensitive resin composition according to aspect 18 above, comprising:
[20] X is the following structure:

The photosensitive resin composition according to aspect 18 above, comprising:
[21] Y is the following structure:

The photosensitive resin composition according to any one of aspects 18 to 20 above.
[22] Y is the following structure:

The photosensitive resin composition according to any one of aspects 18 to 20 above.
[23] X is the following structure:

including
Y is the following structure:

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

According to the present invention, a photosensitive resin that exhibits good resolution even when there is a deviation in the depth of focus, exhibits good chemical resistance, and gives a cured relief pattern that suppresses deterioration of the mold resin and deterioration of adhesion. A composition, a method for 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 present specification, structures represented by the same reference numerals in general formulas may be the same or different from each other when a plurality of structures are present in the molecule.

<Photosensitive resin composition>
A photosensitive resin composition according to an aspect of the present invention contains (A) a polyimide precursor and (B) a photopolymerization initiator. In one aspect, the photopolymerization initiator (B) has a g-line absorbance of 0.01 to 0.1 in a 0.001 wt % solution using N-methyl-2-pyrrolidone as a solvent. Moreover, the photosensitive resin composition may further contain (C) a cross-linking agent in addition to the above components.
According to such a photosensitive resin composition, it is possible to obtain a cured relief pattern that has improved focus margin and chemical resistance, and that can suppress deterioration of the epoxy resin used as the mold resin and deterioration of adhesion.

The photosensitive resin composition according to one 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 form in which a rewiring layer (which has wiring and an insulating film) is formed larger than the outline of the semiconductor chip (that is, is fanned out from the semiconductor chip). . In a fan-out type semiconductor device, the insulating film of the rewiring layer needs to adhere well not only to the semiconductor chip but also to the mold resin as the sealing material. The photosensitive resin composition of the present disclosure is particularly suitable as an insulating film for a rewiring layer, since deterioration of the mold resin can be suppressed and the composition adheres well to the mold resin. Accordingly, in one aspect, the photosensitive resin composition of the present disclosure is a photosensitive resin composition for fan-out wafer level packaging.

[(A) polyimide precursor]
The (A) polyimide precursor according to this 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 coated as a single solution, and the g-line absorbance measured for a 10 μm thick film obtained after pre-baking is preferably 0.001 to 0.1. Furthermore, it is more 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 ) preferably contains a polyimide precursor.

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

The (A) polyimide precursor according to the present embodiment is mainly composed of, for example, at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. is preferred. Here, the main component means that these resins are contained in an amount of 60% by mass or more, preferably 80% by mass or more, based on the total resin. Moreover, other resins may be included as necessary.

(A) The weight-average molecular weight of the 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 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.

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 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, 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). } is an ester-type polyimide precursor containing a structure represented by }.

In the above general formula (A1), the tetravalent organic group represented by X is preferably an organic group having 6 to 40 carbon atoms, more preferably one of -COOR ₁ and -CONH- groups. are attached to the same aromatic ring and both are ortho-positioned 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. . An 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。 The tetravalent organic group represented by X is more preferably the following formula:

Examples include, but are not limited to, structures represented by each of the above. Moreover, the structure of X may be one type or a combination of two or more types.

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 the tetravalent organic group represented by X in the general formula (A1):

or the following structure:

is particularly preferred.
By having such a structure, the polyimide precursor has improved heat resistance and photosensitivity, and in the cured relief pattern obtained, the focus margin and chemical resistance are improved, and deterioration and adhesion of the epoxy resin used as the mold resin are improved. can suppress the decrease in

In general formula (A1) above, the divalent organic group represented by Y is preferably a C ₆ to C ₄₀ aromatic group, 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 ), an ethyl group (--C ₂ H ₅ ), a propyl group (--C ₃ H ₇ ), or a butyl group (--C ₄ H ₉ ). }, but not limited thereto. Moreover, the structure of Y may be one type or a combination of two or more types.

R ₃ in the general formula (R1) is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are each preferably a hydrogen atom 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, from the viewpoint of photosensitive characteristics.

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 is a polyimide precursor, and in general formula (A1), the divalent organic group represented by Y has the following structure:

or the following structure:

is particularly preferred.
By having such a structure, the polyimide precursor has improved heat resistance and photosensitivity, and in the cured relief pattern obtained, the focus margin and chemical resistance are improved, and deterioration and adhesion of the epoxy resin used as the mold resin are improved. can suppress the decrease in

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。 The photosensitive resin composition, in the general formula (A1),
X is the following structure:

including
Y has the following structure:

It is most preferred to include
By having such a structure of the polyimide precursor, the heat resistance and photosensitivity are further improved, the focus margin and chemical resistance are further improved in the cured relief pattern obtained, and the deterioration of the epoxy resin used as the mold resin is reduced. A decrease in adhesion can be suppressed more reliably.

[(A) Preparation method of polyimide precursor]
The ester bond type polyimide precursor, for example, first, a tetracarboxylic dianhydride having a desired tetravalent organic group X, and an alcohol having a photopolymerizable group (e.g., unsaturated double bond) A partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester form) is prepared by reacting them. After that, this acid/ester form and diamines having a divalent organic group Y are subjected to amide polycondensation to obtain. Saturated aliphatic alcohols may optionally be used in combination with the alcohols having photopolymerizable groups.

(Preparation of acid/ester form)
In the present invention, the tetracarboxylic dianhydride having a tetravalent organic group X, which is suitably used for preparing the ester bond type polyimide precursor, includes, for example, pyromellitic anhydride, diphenyl ether-3,3 ',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic 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 limited thereto. not a thing In addition, these may be used alone, or two or more of them may be used in combination.

In the present invention, alcohols having a photopolymerizable group that are suitably used for preparing the 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, 1-methacryloyloxy-3-propyl alcohol, 2- methacrylamide ethyl 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.

Saturated aliphatic alcohols having 1 to 4 carbon atoms are preferred as the saturated aliphatic alcohols that can optionally be used together with the alcohols having a photopolymerizable group. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.

The above tetracarboxylic dianhydride suitable for the present invention and the above alcohol are reacted preferably 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 long time, the esterification reaction of the acid anhydride proceeds and the desired acid/ester can be obtained.

As the reaction solvent, those capable of completely dissolving the tetracarboxylic dianhydride and alcohol as starting materials and the acid/ester body as the product are preferred. More preferably, the solvent completely dissolves the polyimide precursor, which is the amide polycondensation product of the acid/ester compound and the diamine. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, carbonization Hydrogens etc. can be mentioned. Specific examples of these include:
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like;
Examples of esters include methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, and the like;

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

(Preparation of polyimide precursor)
A suitable dehydration condensation agent is added to the acid/ester compound (typically in a solution state dissolved in the reaction solvent), preferably under ice cooling, and mixed to convert the acid/ester compound into a polyanhydride. and Then, a diamine having a divalent organic group Y, which is preferably used in the present invention, is separately dissolved or dispersed in a solvent and added dropwise thereto, and the two 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 described above.
Examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N '-disuccinimidyl carbonate and the like.
As described above, the intermediate polyacid anhydride is obtained.

In the present invention, the diamines having a divalent organic group Y that are 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, 4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4 , 4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 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)hexafluoropropane, 2,2-bis[4-(4-amino phenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolysine sulfone, 9,9- bis(4-aminophenyl)fluorene and the like;
and those in which some of the 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 substituent include 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. Diamines are not limited to the above examples.

Diaminosiloxanes are used for the purpose of improving the adhesion between the coating film formed from the photosensitive resin composition and various substrates. Used in combination with diamines containing Specific examples of such diaminosiloxanes include 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane. can.

After the completion of the amide polycondensation reaction, water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are filtered out if necessary, and the solution containing the polymer components is added with a suitable poor solvent such as water, fat, or the like. Group lower alcohol, mixture thereof, etc.) is added to precipitate the polymer component, and if necessary, the polymer is purified by repeating operations such as redissolution and reprecipitation, followed by vacuum drying. Thus, the desired polyimide precursor is isolated. At that time, for the purpose of improving storage stability and resolution, acid compounds such as carboxylic acids and sulfonic acids, salt compounds such as carboxylates and sulfonates, and base compounds such as aliphatic amines and aromatic amines. , aliphatic amine salts, aromatic amine salts and other salt compounds may also be added. In order to improve the degree of purification, the polymer solution may be passed through a column packed with anion and/or cation exchange resins swollen with a suitable organic solvent to remove ionic impurities.
Examples of the carboxylic acid include formic acid, oxalic acid, and maleic acid. Sulfonic acids include p-toluenesulfonic acid and methanesulfonic acid.
Carboxylate includes sodium formate, sodium oxalate and the like. Examples of sulfonates include sodium p-toluenesulfonate and pyridine p-toluenesulfonate.
Aliphatic amines include triethylamine, tributylamine, and the like. Aromatic amines include aniline, bisaniline, and the like.
Aliphatic amine salts include triethylamine hydrochloride, tributylamine hydrochloride and the like. Aromatic amine salts include aniline hydrochloride, bisaniline hydrochloride, and the like.

From the viewpoint of the heat resistance and mechanical properties of the film obtained after the heat treatment, 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. 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 monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko.

Regarding the (A) polyimide precursor synthesized by such a method, the g-line and h-line absorbance of the pre-baked film formed independently takes various values depending on the molecular structure. However, the g-line and h-line absorbance of the mixture is the arithmetic mean of the g-line and h-line absorbance of each component. (A) The g-line absorbance of a 10 μm thick film after pre-baking of the polyimide precursor should be 0.001 to 0.1, and the h-line absorbance should be 0.001 to 0.5, while maintaining a balance with thermophysical properties. can be done.

｛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) Photoinitiator]
Next, the (B) photopolymerization initiator according to the present embodiment will be described.
In one aspect, the photopolymerization initiator (B) has a g-line absorbance of 0.01 to 0.1 in a 0.001 wt % solution using N-methyl-2-pyrrolidone as a solvent.
(B) The absorbance of the photopolymerization initiator can 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 normal spectrophotometer. can.
In the photopolymerization initiator (B) according to the present embodiment, the g-line absorbance of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent is 0.015 from the viewpoint of focus margin and chemical resistance. 0.020 or more is preferable. The g-line absorbance is preferably 0.09 or less, preferably 0.08 or less, preferably 0.07 or less, preferably 0.06 or less, preferably 0.05 or less, preferably 0.04 or less, and 0.04 or less. 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 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent. ~0.5 is preferred. The h-line absorbance is preferably 0.15 to 0.4, 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 absorbance, but from the viewpoint of chemical resistance, it preferably has an oxime structure in its 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, preferably has a structure represented by the following general formula (B1). In one aspect, 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 these, Ar is preferably a phenylene group, R7 and R8 are preferably monovalent organic groups having 1 to 4 carbon atoms, and R6 is preferably a monovalent organic group having 1 to 3 carbon atoms. .

According to the present embodiment, a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent has a g-line absorbance of 0.01 to 0.1 (B) By using a photopolymerization initiator, The reason why the focus margin and chemical resistance are improved and the deterioration of the epoxy resin used as the mold resin and the deterioration of the adhesion are suppressed is not clear. They think as follows.
Since the i-line and ghi-line used for normal exposure have higher energy than the g-line and h-line, when they reach the epoxy resin side through the polyimide film, they may damage the epoxy resin, Part of the resin evaporates, and gas accumulates at the interface between the polyimide and the epoxy resin, which is thought to reduce adhesion. Therefore, when g-line and h-line are used for exposure, damage to the epoxy resin can be suppressed.
Although the reason why the chemical resistance is good in the present embodiment is not clear, for example, by having a specific absorbance at g-line and h-line, in the case of a negative photosensitive resin composition, cross-linking of the exposed portion It is thought that it easily progresses, easily takes a three-dimensional network structure, and develops chemical resistance.

By using the photopolymerization initiator (B) according to the present embodiment, the focus margin and chemical resistance are improved, and the deterioration of the epoxy resin that is the mold resin and the decrease in adhesion are suppressed. Good expression tends to occur when the g-line absorbance of the body is 0.01 to 0.1.
The (B) photopolymerization initiator according to the present embodiment is not limited as long as it has the absorbance, but the photosensitive resin composition is generally treated under yellow light with a wavelength of 500 nm or less cut. A lower absorbance at 500 nm is preferable. 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 according to one aspect of the present invention can also be expressed as follows.
The photosensitive resin composition comprises (A) a polyimide precursor, (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 }. Moreover, the photosensitive resin composition may further contain (C) a cross-linking agent in addition to the above components.
According to such a photosensitive resin composition, it is possible to obtain a cured relief pattern that has improved focus margin and chemical resistance, and that can suppress deterioration of the epoxy resin used as the mold resin and deterioration of adhesion.

[(C) Crosslinking agent]
As the (C) cross-linking agent optionally used in the present invention, any compound having a plurality of functional groups in the molecule can be mentioned. Examples of functional groups include acrylic, methacrylic, epoxy, methylol, allyl, vinyl, and maleimide groups.

Examples of cross-linking agents having one cross-linkable group include ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, and ML-TBC (trade names, Honshu Kagaku Kogyo ( Co., Ltd.), Pa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc., and DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (the above, trade names, Asahi Yukuzai Kogyo Co., Ltd.), 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, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (above , trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (above, trade name, Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. TriML-P, TriML-35XL, TriML-TrisCR-HAP (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), etc. TM-BIP-A (trade name, Asahi Organic Chemicals Industry Co., Ltd.) ), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (the above , trade name, manufactured by Sanwa Chemical Co., Ltd.), etc., and HML-TPPHBA, HML-TPHAP (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MW-390, and Nikalac MW-100LM. (these are trade names, manufactured by Sanwa Chemical Co., Ltd.).

Among these, those containing at least two crosslinkable groups are preferred in the present invention, and particularly preferred are 46DMOC, 46DMOEP (trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-MBPC, and DML-MBOC. , DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, products Name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (above, trade name, Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc., TriML-P, TriML-35XL (Above, product name, manufactured by Honshu Chemical Industry Co., Ltd.), etc., TM-BIP-A (product name, manufactured by Asahi Organic Chemical Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML -BPA, TMOM-BP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nicalac MX-280, Nicalac MX-270 (trade names, manufactured by Sanwa Chemical Co., Ltd.), etc., HML-TPPHBA, HML-TPHAP (these are trade names, manufactured by Honshu Kagaku Kogyo Co., Ltd.) and the like. Still more preferably, Nicalac MX-290, Nicalac MX-280, Nicalac MX-270 (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (the above , trade name, manufactured by Shikoku Kasei Co., Ltd.), Nicalac MW-390, and Nicalac MW-100LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

The amount of the cross-linking agent (C) is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, per 100 parts by mass of the resin (A).

Further, in the photosensitive resin composition, the total content of (B) the photopolymerization initiator and (C) the cross-linking agent is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor component. Preferably.

[(D) Other components]
The photosensitive resin composition may further contain components other than the above components (A) to (C).
The photosensitive resin composition is typically used as a liquid photosensitive resin composition prepared by dissolving each of the above components and optionally further optional components in a solvent to form a varnish. Therefore, (D) other components include solvents, and for example, resins other than the above (A) photosensitive polyimide precursor, sensitizers, monomers having photopolymerizable unsaturated bonds, adhesion aids , thermal polymerization inhibitors, azole compounds, hindered phenol compounds, and the like.

Examples of the solvent include polar organic solvents and alcohols.
As the solvent, it is preferable to use a polar organic solvent 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, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like, and these can be used alone or in combination of two or more.

As the solvent in the present invention, a solvent containing alcohols is preferable 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 no 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;
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, and propylene glycol-1-(n-propyl) ether are more preferred.

The solvent is, for example, 30 to 1500 parts by mass, preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the polyimide precursor (A), 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 total solvent is preferably 5 to 50% by mass, more preferably 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 improved, and when it is 50% by mass or less, (A) dissolution of the polyimide precursor becomes better.

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

A sensitizer can be arbitrarily added to the photosensitive resin composition according to the present embodiment in order to improve 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-dimethylamino thinner mylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)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, diphenylacetamide, benzanilide, N-methylacetanilide, 3' , 4′-dimethylacetanilide and the like. These can be used singly or in combination, for example of 2 to 5 types.

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

In order to improve the resolution of the relief pattern, the resin composition may optionally contain a photopolymerizable unsaturated bond-containing monomer. 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;
mono- or di(meth)acrylates of propylene glycol or polypropylene glycol;
mono-, di- or tri(meth)acrylates of glycerol;
cyclohexane di(meth)acrylate;
Diacrylate and dimethacrylate of 1,4-butanediol, di(meth)acrylate of 1,6-hexanediol;

di(meth)acrylates of neopentyl glycol;
mono- or di(meth)acrylates of bisphenol A;
benzene trimethacrylate;
isobornyl (meth)acrylate;
acrylamide and its derivatives;
methacrylamide and its derivatives;
trimethylolpropane tri(meth)acrylate;
di- or tri(meth)acrylates 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 monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the blending amount is (A) the 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 the present embodiment and the base material, the photosensitive resin composition may optionally contain an adhesion aid. Examples of adhesion promoters 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- Silanes such as 1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane Coupling agents, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

Among these adhesion promoters, the silane coupling agent is more preferable from the viewpoint of adhesion. When the photosensitive resin composition contains an adhesion aid, the blending 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 the viscosity and photosensitivity during storage. can be arbitrarily blended. Thermal polymerization inhibitors include, for example, 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 amount of the thermal polymerization inhibitor to be added to the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor (A).

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 arbitrarily blended in order to suppress discoloration of the copper surface. Examples of azole compounds 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-dimethylbenzyl)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, hydroxy phenylbenzotriazole, 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-tetrazole, 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 singly or as a mixture of two or more.

When the photosensitive resin composition according to the present embodiment contains the azole compound, the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor (A). From the viewpoint of sensitivity characteristics, 0.5 to 5 parts by mass is more preferable. When the amount of the azole compound (A) blended with respect to 100 parts by mass of the 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, and on the other hand, when it is 10 parts by mass or less, the 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 arbitrarily blended instead of the azole compound or together with the azole compound. Hindered phenol compounds include, for example, 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), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 -thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],

N,N'hexamethylenebis(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-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)- trion,

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-hydroxy-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 and the like are mentioned, but are not limited to these. 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 preferred.

The 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 from the viewpoint of photosensitivity characteristics, it is 0.5 to 10 parts by mass. is more preferred. (A) When the amount of the hindered phenol compound per 100 parts by mass of the polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, copper or copper Discoloration and corrosion of the alloy are prevented, and when the amount is 20 parts by mass or less, excellent photosensitivity of the photosensitive resin composition is maintained.

<Method for manufacturing cured relief pattern>
The present invention also provides a method of manufacturing a cured relief pattern.
A method for producing an effect relief pattern according to the invention comprises, for example, the following steps:
(1) a coating step of applying the above-described negative photosensitive resin composition of the present disclosure onto a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer with g-line and/or h-line;
(3) a developing step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) The relief pattern is heat-treated to form a hardened relief pattern, and a heating step is performed in the order described above.
Typical aspects of each step are described below.

(1) Coating step In this step, a photosensitive resin composition is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer.
As the substrate, for example, a metal substrate made of silicon, aluminum, copper, copper alloy, etc.;
Resin substrates such as epoxy, polyimide, and polybenzoxazole;
A substrate in which a metal circuit is formed on the resin substrate;
A substrate or the like in which a plurality of metals or metals and resins are laminated in multiple layers can be used.
As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, or a method of spray coating with a spray coater. 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 using an oven or a hot plate, and vacuum drying are used. Moreover, the drying of the coating film is desirably carried out under such conditions that imidization of (A) the 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. As described above, a photosensitive resin layer can be formed on the substrate.

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

After exposure, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and/or pre-development baking may be performed at any combination of temperature and time, if necessary. The range of baking conditions is preferably a temperature of 40 to 120° C. and a time of 10 seconds to 240 seconds.

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

A developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. Good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like. Preferred solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water. 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. Moreover, two or more kinds of each solvent can be used, for example, several kinds can 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 the heat curing method, various methods such as a method using a hot plate, a method using an oven, and a method using a heating oven capable of setting a temperature program can be selected. Heating can be performed, for example, at 200° C. to 400° C. for 30 minutes to 5 hours. As the atmospheric gas for heat curing, air may be used, or an inert gas such as nitrogen or argon may be used.
A cured relief pattern can be produced in the manner described above.

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

The photosensitive resin composition according to one aspect of the present invention is applied to semiconductor devices as described above, as well as applications such as interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. It is also useful for

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these. The 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 (converted to standard polystyrene). The column used for the measurement is Shodex 805M/806M series manufactured by Showa Denko KK, Shodex STANDARD SM-105 manufactured by Showa Denko KK is selected as the standard monodisperse polystyrene, and N-methyl-2-pyrrolidone is used as the developing solvent. The detector used was Shodex RI-930 (trade name) manufactured by Showa Denko.

(2) Absorbance measurement The absorbance of the photopolymerization initiator (B) is adjusted by adjusting a 0.001 wt% NMP solution, filling a 1 cm quartz cell, and scanning using a UV-1800 device manufactured by Shimadzu Corporation. Measurement was performed at a medium speed and a sampling pitch of 0.5 nm.
The absorbance of the polyimide precursor was measured by coating it on quartz glass so as to form a 10 μm-thick film after pre-baking. When the thickness of the formed film is not 10 μm, the absorbance obtained for the film is converted to the case of 10 μm thickness according to Lambert-Beer's law to obtain the g-line and h-line absorbance of 10 μm thickness. rice field.

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

An i-line cut filter or a gh-line cut filter is attached to this spin-coated film using a reticle with a test pattern having a circular pattern with a mask size of 6 μm in diameter, and using an equal-magnification projection exposure apparatus Prisma GHI S/N5503 (manufactured by Ultratec). , Examples 1 to 9 were irradiated with energy of 40 mJ/cm ² of g and h rays, and Comparative Examples 1 and 2 were irradiated with energy of 120 mJ/cm ² of i rays. At this time, the focus was moved by 4 μm from the surface of the spin-coated film toward the bottom of the film with respect to each exposure dose.
Next, the coating film formed on the sputtered Cu wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and polyamic acid ester is obtained. A round recessed relief pattern was obtained. The development time of the spray development was defined as 1.4 times the minimum time for developing the resin composition in the unexposed area of the 10 μm spin-coated film.

Regarding whether or not the circular recessed relief pattern with a mask size of 6 μm obtained above can be opened, a pattern that satisfies both the following criteria (I) and (II) is judged to be acceptable, and the thickness of the focus margin that gives the acceptable pattern was described in the results.
(I) The area of the pattern opening is 1/2 or more of the corresponding pattern mask opening area.
(II) The pattern cross section does not slack, and undercut, swelling, and bridging do not occur.

(4) Chemical resistance evaluation The pattern obtained above is heat-treated at 200 ° C. for 2 hours in a nitrogen atmosphere using a temperature-rising programmable cure furnace (VF-2000, manufactured by Koyo Lindbergh, Japan). This gave a cured relief pattern of polyimide about 7-8 μm thick on the silicon wafer.
This relief pattern was immersed in chemicals (DMSO: 70% by weight, 2-aminoethanol: 25% by weight, TMAH: 5% by weight) at 50 ° C. for 5 minutes, and then measured with a Tencor P-15 type step meter (KLA Tencor Co., Ltd. A dissolution rate (nm/min) was calculated by comparing the film thickness with that before the chemical treatment.

(5) Encapsulant Degradation Test R4000 series manufactured by Nagase Chemtex Co., Ltd. was prepared as an epoxy-based encapsulant.
Next, the sealing material was spin-coated on the aluminum-sputtered silicon wafer so as to have a thickness of about 150 microns, and was thermally cured at 130° C. to cure the epoxy-based sealing material.
The photosensitive resin compositions prepared in Examples and Comparative Examples were coated on the epoxy-based cured film so that the final film thickness was 10 microns. The entire surface of the coated photosensitive resin composition was exposed to 100 mJ/cm ² of g and h lines in Examples 1 to 9, and 100 mJ/cm ² of i line in Comparative Examples 1 and 2. Time heat curing was performed to prepare a first cured film having a thickness of 10 microns.
The photosensitive resin composition used in forming the cured film of the first layer is applied onto the cured film of the first layer, and the entire surface is exposed to light under the same conditions as in the formation of the cured film of the first layer, followed by thermal curing. , to prepare a second cured film having a thickness of 10 microns.
The degree of deterioration was evaluated by checking the presence or absence of voids in the epoxy portion after cutting the cross section of the test piece after the second layer cured film was formed with an FIB device (manufactured by JEOL Ltd., JIB-4000). . A sample with no voids was rated as ◯, and a sample with at least one void was rated as x.

(6) Adhesion test with encapsulant An epoxy resin was applied on the photosensitive resin cured film of the sample prepared in the encapsulant deterioration test, and then a pin was set up and a take-off tester (Quad Group Co., Ltd., Sebastian 5 type) was used to conduct an adhesion test.
Evaluation: Adhesion strength of 70 MPa or more ... Adhesion ◎
50 MPa or more - less than 70 MPa ... Adhesion ○
30 MPa or more and less than -50 MPa ... Adhesion △
Less than 30 MPa 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 N-ethylcarbazole in 40 ml CH ₂ Cl ₂ was added 2.73 parts terephthaloyl chloride and 3.76 parts AlCl ₃ . After stirring overnight at room temperature, 2.21 parts acetyl chloride and 3.76 parts AlCl ₃ are 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, then dried over anhydrous magnesium sulfate. After concentrating the solvent, 5.91 parts (76.3%) of a pale yellow-green solid was obtained. This solid was used in 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

a. in 30 ml of ethanol. 0.76 parts of hydroxylammonium chloride and 0.86 parts of pyridine were added to 3.0 parts of the acyl derivative obtained in . 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 with anhydrous magnesium sulfate, it was concentrated to obtain 2.80 parts (89%) of a pale yellowish white solid. This solid was used in the next reaction without being purified.

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. 1.5 parts of the oxime derivative obtained in (1) was dissolved in 25 parts of DMF. To this solution, 0.59 parts of acetyl chloride was added, and then 0.78 parts of triethylamine was added dropwise at 10°C or lower. 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 give 1.05 parts (61.8%) of a pale yellow solid (initiator B1). λmax was 345 nm, and the melting point was 191-202°C.
This initiator B1 had a g-line absorbance of 0.025 and an h-line absorbance of 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. λmax was 366 nm and the melting point was 205-218°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> ((A) Synthesis of polyimide precursor (polymer A-1))
Put 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2-liter separable flask, add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature. While adding 79.1 g of pyridine, a reaction mixture was obtained. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand still for 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was 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 with stirring over 60 minutes. 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. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

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

<Production Example 4> (Synthesis of polyimide precursor (polymer A-2))
Production Example 2 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride in Production Example 2 above. Polymer A-2) was obtained by carrying out the reaction in the same manner as described in 1.
When the weight average molecular weight (Mw) of this polymer A-2 was measured, it was 22,000. This polymer had a g-line absorbance of 0.02 and an h-line absorbance of 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 4,4′-diaminodiphenyl ether (DADPE) was replaced with 1,4-phenylenediamine (50.2 g) in Production Example 2 above, Polymer A-3) was obtained.
When the weight average molecular weight (Mw) of this polymer A-3 was measured, it was 21,000. This polymer had a g-line absorbance of 0.01 and an h-line absorbance of 0.02.

架橋剤Ｃ１：

Initiator B3: Adeka Optomer NCI831 (g line: 0.001, h line: 0.127)
Initiator B4: PBG305 (g line: 0.001, h line: 0.001)

Crosslinker C1:

<Example 1>
A mixture consisting of 50 g of polymer A-1 and 50 g of polymer A-2 as components (A), initiator B1 (4 g) as component (B), and 16 g of tetraethylene glycol dimethacrylate as other components, gamma-butyrolactone and DMSO. A photosensitive resin composition solution was prepared by dissolving in a solvent (weight ratio 75:25) and adjusting the amount of the solvent so that the viscosity was about 35 poise.
This 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>
Evaluation was performed in the same manner as in Example 1, except that the resin composition solution was used at the ratio shown in Table 1. The evaluation results are shown in Table 1.

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

Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the gist 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 producing electric/electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (23)

(A) a polyimide precursor;
(B) a photopolymerization initiator having a g-line absorbance of 0.01 to 0.1 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent ,
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, the following general formula (R1)

(In 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.) 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) be. } is a polyimide precursor containing a structure represented by a photosensitive resin composition. 2. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (B) has a g-line absorbance of 0.015 to 0.04. 3. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (B) has a g-line absorbance of 0.015 to 0.03. Any one of claims 1 to 3, wherein a 0.001 wt% solution of the (B) photopolymerization initiator using N-methyl-2-pyrrolidone as a solvent has an h-line absorbance of 0.15 to 0.5. 1. The photosensitive resin composition according to claim 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 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 according to any one of claims 1 to 5. 7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (C) a cross-linking 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 pre-baking is 0.001 to 0.1, and the h-line absorbance is 0.001 to 0.001. 5, the photosensitive resin composition according to any one of claims 1 to 7. The X is the following structure:

The photosensitive resin composition according to any one of claims 1 to 8 . The X is the following structure:

The photosensitive resin composition according to any one of claims 1 to 8 . Y is the following structure:

The photosensitive resin composition according to any one of claims 1 to 10 , comprising Y is the following structure:

The photosensitive resin composition according to any one of claims 1 to 10 , comprising The X is the following structure:

including
Y is the following structure:

The photosensitive resin composition according to any one of claims 1 to 8 . The total content of (B) a photopolymerization initiator and (C) a cross-linking agent with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 to 20 parts by mass, according to any one of claims 1 to 13 The photosensitive resin composition described. (A) a polyimide precursor;
(B) a photopolymerization initiator having a g-line absorbance of 0.01 to 0.1 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent ,
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, and the following general formula (R1):

(In 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 general formula (R1) be. A photosensitive resin composition for a fan-out wafer level package , which is a polyimide precursor containing a structure represented by } . (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 (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, and the following general formula (R1):

(In 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 general formula (R1) be. } is a polyimide precursor containing a structure represented by a photosensitive resin composition. The X is the following structure:

The photosensitive resin composition according to claim 16 , comprising The X is the following structure:

The photosensitive resin composition according to claim 16 , comprising Y is the following structure:

The photosensitive resin composition according to any one of claims 16 to 18 , comprising Y is the following structure:

The photosensitive resin composition according to any one of claims 16 to 18 , comprising The X is the following structure:

including
Y is the following structure:

The photosensitive resin composition according to claim 16 , comprising The following steps:
(1) a coating step of applying the photosensitive resin composition according to any one of claims 1 to 21 onto a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer with g-line and/or h-line;
(3) a developing step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a hardened relief pattern, comprising a heating step of heating the relief pattern to form a hardened relief pattern. 23. A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to claim 22 .