JP7309010B2 - 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 composition. , 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, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards by various methods according to their purposes. A conventional element is generally manufactured by a wire bonding method in which a thin 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 2). 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 is a problem that the resolution is greatly deteriorated, and the resolution obtained is remarkably different depending on the difference of the base material. 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.

The present invention provides a photosensitive resin composition that exhibits good resolution even when there is a shift in the depth of focus, exhibits good resolution regardless of the underlying substrate, and exhibits good chemical resistance. It is an object of the present invention to provide a method for forming a cured relief pattern using a photosensitive resin composition, and a semiconductor device having the cured relief pattern.

（式中、Ｒａは炭素数１～１０の１価の有機基を表し、Ｒｂは炭素数１～２０の有機基を表し、Ｒｃは炭素数１～１０、Ｒｄは炭素数１～１０の有機基を表す。）
で表される構造である、［１］または［２］に記載の感光性樹脂組成物。
［４］
前記（Ｂ）光重合開始剤は、一般式（Ｂ）中のＲｃが炭素数３～１０の飽和脂環構造を含有する、［３］に記載の感光性樹脂組成物。
［５］
前記（Ａ）成分が下記一般式（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る。但し、Ｒ_１及びＲ_２の両者が同時に水素原子であることはない。｝で表される構造を含むポリイミド前駆体である、［１］～［４］のいずれかに記載の感光性樹脂組成物。
［６］
前記Ｘは下記構造：

を含む、［５］に記載の感光性樹脂組成物。
［７］
前記Ｘは下記構造：

を含む、［５］に記載の感光性樹脂組成物。
［８］
前記Ｙは下記構造：

を含む、［５］～［７］のいずれかに記載の感光性樹脂組成物。
［９］
前記Ｙは下記構造：

を含む、［５］～［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：

を含み、
前記Ｙは下記構造：

を含む、［５］に記載の感光性樹脂組成物。
［１１］
更に（Ｃ）重合禁止剤を含有する、［１］～［１０］のいずれかに記載の感光性樹脂組成物。
［１２］
前記（Ｃ）重合禁止剤が、芳香族性水酸基を含有する化合物、ニトロソ化合物、Ｎ－オキシド化合物、キノン化合物、Ｎ－オキシル化合物、およびフェノチアジン化合物から選択される少なくとも１種である、［１１］に記載の感光性樹脂組成物。
［１３］
前記（Ｃ）重合禁止剤が、芳香族性水酸基を含有する化合物である、［１１］又は［１２］に記載の感光性樹脂組成物。
［１４］
更に（Ｄ）アルコール性水酸基を２個以上含有する化合物を含む、［１］～［１３］のいずれかに記載の感光性樹脂組成物。
［１５］
前記（Ｄ）アルコール性水酸基を２個以上含有する化合物が、アルドース、ケトース、ピラノース、フラノース、およびアルジトールからなる群から選択される少なくとも１種である、［１４］に記載の感光性樹脂組成物。
［１６］
前記（Ａ）成分１００質量部に対する（Ｂ）成分及び（Ｃ）成分の合計含有量が０．１～２０質量部である、［１１］～［１５］のいずれかに記載の感光性樹脂組成物。
［１７］
前記（Ａ）ポリイミド前駆体の前記０．１ｗｔ％溶液のｉ線吸光度が０．１８～０．５である、［１］～［１６］のいずれかに記載の感光性樹脂組成物。
［１８］
前記（Ａ）ポリイミド前駆体の前記０．１ｗｔ％溶液のｉ線吸光度が０．１８～０．４である、［１］～［１７］のいずれかに記載の感光性樹脂組成物。
［１９］
前記（Ａ）ポリイミド前駆体の前記０．１ｗｔ％溶液のｉ線吸光度が０．１８～０．３である、［１］～［１８］のいずれかに記載の感光性樹脂組成物。
［２０］
前記（Ａ）ポリイミド前駆体の前記０．１ｗｔ％溶液のｉ線吸光度が０．１８～０．２である、［１］～［１９］のいずれかに記載の感光性樹脂組成物。
［２１］
前記（Ａ）ポリイミド前駆体の前記０．１ｗｔ％前記溶液のｉ線吸光度をＤＡとし、
前記（Ｂ）光重合開始剤の０．００１ｗｔ％Ｎ－メチルピロリドン溶液のｉ線吸光度をＤＢとしたとき、
前記ＤＡとＤＢの和（ＤＡ＋ＤＢ）が０．２５～０．９０である、［１］～［２０］のいずれかに記載の感光性樹脂組成物。
［２２］
［１］～［２１］のいずれかに記載の感光性樹脂組成物を硬化することを含む、ポリイミドの製造方法。
［２３］
以下の工程：
（１）［１］～［２１］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。
［２４］
［２３］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。
［２５］
以下の成分：
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る。但し、Ｒ_１及びＲ_２の両者が同時に水素原子であることはない。｝
で表される（Ａ）ポリイミド前駆体；
下記一般式（Ｂ）：

{（式中、Ｒａは炭素数１～１０の１価の有機基を表し、Ｒｂは炭素数１～２０の有機基を表し、Ｒｃは炭素数１～１０、Ｒｄは炭素数１～１０の有機基を表す。）}
または（Ｂ１）：

｛式中、Ｒｅは炭素数１～２０の１価の有機基を表し、Ｒｆは炭素数１～１０の有機基を表す。｝
で表される（Ｂ）光重合開始剤；
（Ｄ）アルコール性水酸基を２個以上含有する化合物；および
（Ｅ）γ―ブチロラクトン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール、アセト酢酸エチル、こはく酸ジメチル、マロン酸ジメチル、Ｎ，Ｎ－ジメチルアセトアセトアミド、ε―カプロラクトン、および１，３－ジメチル―２－イミダゾリジノン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミドからなる群から選択される少なくとも１種の溶媒；
を含有することを特徴とする感光性樹脂組成物。
［２６］
（Ｅ）上記群から選択される少なくとも２種の溶媒を含む、［２５］に記載の感光性樹脂組成物。
［２７］
前記Ｙが、下記構造：

または下記構造：

｛式中、Ａは炭素数１～６のハロゲン原子を含んでいても良い有機基を示す｝
を含む、［２５］または［２６］に記載の感光性樹脂組成物。
［２８］
［２５］～［２７］のいずれかに記載の感光性樹脂組成物を硬化することを含む、ポリイミドの製造方法。
［２９］
以下の工程：
（１）［２５］～［２７］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。
［３０］
［２９］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 specific polyimide precursor and a specific initiator, and have completed the present invention. That is, the present invention is as follows.
[1]
Ingredients for:
(A) a polyimide precursor having an i-line absorbance of 0.1 wt% N-methylpyrrolidone solution of 0.1 to 0.6; and (B) a photopolymerization initiator having a carbazole structure;
A photosensitive resin composition comprising:
[2]
The photosensitive resin composition according to [1], wherein the 0.1 wt % solution of the polyimide precursor (A) has an i-line absorbance of 0.18 to 0.6.
[3]
The (B) photopolymerization initiator has the following general formula (B):

(Wherein, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents an organic group having 1 to 20 carbon atoms, Rc represents 1 to 10 carbon atoms, and Rd represents an organic group having 1 to 10 carbon atoms. represents a group.)
The photosensitive resin composition according to [1] or [2], which is a structure represented by
[4]
The photosensitive resin composition according to [3], wherein in the photopolymerization initiator (B), Rc in the general formula (B) contains a saturated alicyclic structure having 3 to 10 carbon atoms.
[5]
The component (A) 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 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. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. The photosensitive resin composition according to any one of [1] to [4], which is a polyimide precursor containing a structure represented by }.
[6]
The X is the following structure:

The photosensitive resin composition according to [5], comprising:
[7]
The X is the following structure:

The photosensitive resin composition according to [5], comprising:
[8]
Y is the following structure:

The photosensitive resin composition according to any one of [5] to [7].
[9]
Y is the following structure:

The photosensitive resin composition according to any one of [5] to [7].
[10]
The X is the following structure:

including
Y is the following structure:

The photosensitive resin composition according to [5], comprising:
[11]
The photosensitive resin composition according to any one of [1] to [10], further comprising (C) a polymerization inhibitor.
[12]
The (C) polymerization inhibitor is at least one selected from aromatic hydroxyl-containing compounds, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazine compounds, [11] The photosensitive resin composition according to .
[13]
The photosensitive resin composition according to [11] or [12], wherein the (C) polymerization inhibitor is a compound containing an aromatic hydroxyl group.
[14]
The photosensitive resin composition according to any one of [1] to [13], further comprising (D) a compound containing two or more alcoholic hydroxyl groups.
[15]
The photosensitive resin composition according to [14], wherein the (D) compound containing two or more alcoholic hydroxyl groups is at least one selected from the group consisting of aldose, ketose, pyranose, furanose, and alditol. .
[16]
The photosensitive resin composition according to any one of [11] to [15], wherein the total content of components (B) and (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass of component (A). thing.
[17]
The photosensitive resin composition according to any one of [1] to [16], wherein the 0.1 wt % solution of the (A) polyimide precursor has an i-line absorbance of 0.18 to 0.5.
[18]
The photosensitive resin composition according to any one of [1] to [17], wherein the 0.1 wt % solution of the (A) polyimide precursor has an i-line absorbance of 0.18 to 0.4.
[19]
The photosensitive resin composition according to any one of [1] to [18], wherein the 0.1 wt % solution of the (A) polyimide precursor has an i-line absorbance of 0.18 to 0.3.
[20]
The photosensitive resin composition according to any one of [1] to [19], wherein the 0.1 wt % solution of the (A) polyimide precursor has an i-line absorbance of 0.18 to 0.2.
[21]
The i-line absorbance of the 0.1 wt% solution of the (A) polyimide precursor is DA,
When the i-line absorbance of the 0.001 wt% N-methylpyrrolidone solution of the photopolymerization initiator (B) is DB,
The photosensitive resin composition according to any one of [1] to [20], wherein the sum of DA and DB (DA+DB) is 0.25 to 0.90.
[22]
[1] A method for producing a polyimide, comprising curing the photosensitive resin composition according to any one of [21].
[23]
The following steps:
(1) a coating step of applying the photosensitive resin composition according to any one of [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;
(3) a developing step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) a heating step of heating the relief pattern to form a cured relief pattern;
A method for producing a cured relief pattern, comprising:
[24]
A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to [23].
[25]
Ingredients for:
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 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. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. }
(A) a polyimide precursor represented by;
The following general formula (B):

{(Wherein, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents an organic group having 1 to 20 carbon atoms, Rc represents 1 to 10 carbon atoms, and Rd represents 1 to 10 carbon atoms. represents an organic group.)}
or (B1):

{In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents an organic group having 1 to 10 carbon atoms. }
(B) a photopolymerization initiator represented by;
(D) compounds containing two or more alcoholic hydroxyl groups; ε-caprolactone, and at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide solvent of;
A photosensitive resin composition comprising:
[26]
(E) The photosensitive resin composition according to [25], containing at least two solvents selected from the above group.
[27]
wherein Y is the following structure:

Or the structure below:

{Wherein, A represents an organic group optionally containing a halogen atom having 1 to 6 carbon atoms}
The photosensitive resin composition according to [25] or [26].
[28]
[25] A method for producing a polyimide, comprising curing the photosensitive resin composition according to any one of [27].
[29]
The following steps:
(1) A coating step of applying the photosensitive resin composition according to any one of [25] to [27] onto a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer;
(3) a developing step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a hardened relief pattern, comprising: a heating step of heating the relief pattern to form a hardened relief pattern.
[30]
A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to [29].

According to the present invention, a photosensitive resin composition that exhibits good resolution even when there is a shift in the depth of focus, exhibits good resolution regardless of the underlying substrate, and exhibits good chemical resistance, A method for forming a cured relief pattern using a photosensitive resin composition and a semiconductor device having the cured relief pattern can be provided.

The present embodiment will be specifically described below. Throughout this 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 first aspect according to this embodiment will be described.
The photosensitive resin composition according to the first aspect of the present invention comprises (A) a polyimide precursor having an i-line absorbance of 0.1 wt% N-methylpyrrolidone solution of 0.1 to 0.6, and (B) carbazole and a photopolymerization initiator having a structure.
Moreover, the photosensitive resin composition of the present invention may further contain (C) a polymerization inhibitor in addition to the above components.
Moreover, the photosensitive resin composition of the present invention may further contain (D) a compound containing two or more alcoholic hydroxyl groups.
According to such a photosensitive resin composition, it is possible to obtain a cured relief pattern with good focus margin and good resolution, and with improved chemical resistance.

[(A) polyimide precursor]
The (A) polyimide precursor according to the present embodiment will be described.
The (A) polyimide precursor according to the present embodiment has an i-line absorbance of 0.1 to 0.6 in a 0.1 wt% N-methylpyrrolidone solution, and (B) cure relief due to the action of a photopolymerization initiator. It is not limited as long as it can form a pattern.
Here, the absorbance can be measured by dissolving the polyimide precursor in N-methylpyrrolidone at a concentration of 0.1 wt % and using a 1 cm quartz cell with a normal spectrophotometer.
The i-line absorbance of the 0.1 wt% solution of (A) the polyimide precursor according to the present embodiment is not limited as long as it is 0.1 to 0.6, but from the viewpoint of the coverage of the inorganic film, it is 0.18. ~0.6 is preferred. Further, from the viewpoint of developability when the film thickness is increased, 0.18 to 0.5 is preferable, and 0.18 to 0.4 is more preferable. The i-line absorbance may be from 0.18 to 0.3, or from 0.18 to 0.2.

(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.

｛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る。但し、Ｒ_１及びＲ_２の両者が同時に水素原子であることはない。｝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。 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):

{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):

(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. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. } 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 a cycloaliphatic 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を向上させることができる。 In particular, in the photosensitive resin composition of the present invention, the tetravalent organic group represented by X in the general formula (A1) has the following structure:

or the following structure:

is particularly preferred.
When the polyimide precursor has such a structure, the heat resistance and photosensitivity are improved, and the resulting cured relief pattern can be improved in focus margin and chemical resistance.

In general formula (A1) above, the divalent organic group represented by Y is preferably an aromatic group having 6 to 40 carbon atoms.

｛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を向上させることができる。 Particularly in the photosensitive resin composition of the present invention, the polyimide precursor has the following structure:

or the following structure:

is particularly preferred.
When the polyimide precursor has such a structure, the heat resistance and photosensitivity are improved, and the resulting cured relief pattern can be improved in focus margin and chemical resistance.

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させることができる。 In the photosensitive resin composition of the present invention, 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, the polyimide precursor can further improve heat resistance and photosensitivity, and further improve the focus margin and chemical resistance of the obtained cured relief pattern.

[(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-mentioned tetracarboxylic dianhydride suitable for the present invention and the above-mentioned alcohol are reacted preferably in the presence of a basic catalyst such as pyridine, preferably in a suitable reaction solvent, at a temperature of 20-50° C., at a temperature of 4-10°C. 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, and xylene. 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 of the present invention and various substrates. It is used in combination with diamines containing an organic group Y. Specific examples of such diaminosiloxanes include 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane. can.

After the completion of the amide polycondensation reaction, water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are optionally filtered off, and then a suitable poor solvent, such as water, is added to the solution containing the polymer component. Aliphatic lower alcohols, mixtures thereof, etc.) are added, the polymer components are precipitated, and if necessary, the polymer is purified by repeating operations such as redissolution and reprecipitation, followed by vacuum drying. By carrying out, the desired polyimide precursor is isolated. 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.

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.

（式中、Ｒａは炭素数１～１０の１価の有機基を表し、Ｒｂは炭素数１～２０の有機基を表し、Ｒｃは炭素数１～１０、Ｒｄは炭素数１～１０の有機基を表す。）
Ｒａは炭素数１～１０の１価の有機基であれば限定されないが、耐熱性の観点から、炭素数１～５のアルキル基が好ましく、メチル基、エチル基、プロピル基がより好ましい。
Ｒｂは炭素数１～２０の有機基であれば限定されないが、解像度の観点から、炭素数６～２０の芳香族基、炭素数５～２０の複素環化合物に由来する１価の有機基が好ましい。
Ｒｃは炭素数１～１０の有機基であれば限定されない。その中で、解像性の観点から炭素数３～１０の飽和脂環構造を含有する１価の有機基がより好ましい。
Ｒｄは、炭素数１～１０の有機基であれば限定されない。その中で、解像性の観点から、炭素数１～３の有機基が好ましく、メチル基、エチル基、プロピル基がより好ましい。 [(B) Photoinitiator]
Next, the component (B) according to this embodiment will be described.
The (B) component according to this embodiment is a photopolymerization initiator having a carbazole structure.
(B) The photopolymerization initiator is not limited as long as it has a carbazole structure, but preferably has an oxime structure.
More specifically, (B) the photopolymerization initiator more preferably has a structure represented by the following general formula (B).

(Wherein, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents an organic group having 1 to 20 carbon atoms, Rc represents 1 to 10 carbon atoms, and Rd represents an organic group having 1 to 10 carbon atoms. represents a group.)
Ra is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of heat resistance, it is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group.
Rb is not limited as long as it is an organic group having 1 to 20 carbon atoms, but from the viewpoint of resolution, a monovalent organic group derived from an aromatic group having 6 to 20 carbon atoms and a heterocyclic compound having 5 to 20 carbon atoms is used. preferable.
Rc is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, a monovalent organic group containing a saturated alicyclic structure having 3 to 10 carbon atoms is more preferable from the viewpoint of resolution.
Rd is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, from the viewpoint of resolution, an organic group having 1 to 3 carbon atoms is preferable, and a methyl group, an ethyl group and a propyl group are more preferable.

(A) a polyimide precursor having a 0.1 wt% N-methylpyrrolidone solution i-line absorbance of 0.1 to 0.6 according to the present embodiment, and (B) light represented by the general formula (B) Although it is not clear why the polymerization initiator has excellent focus margin, exhibits good resolution regardless of the underlying substrate, and exhibits good chemical resistance, the present inventors have made the following assumptions. thinking.
In general, polyimide precursors with a 0.1 wt% solution i-line absorbance of 0.1 to 0.6 have high transmittance, and especially when the underlying substrate is a metal such as copper or aluminum, the resolution is poor due to reflected light. By selecting a specific initiator, good resolution can be obtained regardless of the base material. Further, it is believed that the tertiary amine portion of the heterocyclic ring of the initiator according to this embodiment improves the imidization rate during heat curing, thereby improving the chemical resistance.

In the present embodiment, the i-line absorbance of (B) the 0.001 wt % N-methylpyrrolidone solution of the photopolymerization initiator is preferably 0.01 to 0.5 from the viewpoint of the coverage of the inorganic film. Furthermore, from the viewpoint of developability when the film thickness is increased, 0.01 to 0.2 is preferable. The i-line absorbance is preferably 0.02 to 0.2, more preferably 0.03 to 0.15.

In particular, in the photosensitive resin composition according to the present embodiment, (A) the i-line absorbance of the 0.1 wt% N-methylpyrrolidone solution of the polyimide precursor is DA, and (B) the photopolymerization initiator is 0.001 wt. When the i-line absorbance of the % N-methylpyrrolidone solution is DB, the sum of DA and DB (DA+DB) is preferably 0.25 to 0.90.
Thereby, the photosensitive resin composition can optimally absorb the i-line, and the focus margin can be further improved.

[(C) polymerization inhibitor]
In this embodiment, a polymerization inhibitor can be added. By adding a polymerization inhibitor, good resolution can be obtained regardless of the base material.
Examples of the polymerization inhibitor according to the present embodiment include aromatic hydroxyl group-containing compounds, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazine compounds.
Compounds containing aromatic hydroxyl groups include 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl ) propionate, N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3′,3″,5,5′ , 5″-hexa-tert-butyl-a,a′,a″-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2 ,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, catechol, tert-butyl-catechol, 4,4′,4″ -(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol, 3,9 -bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5, 5] undecane, hydroquinone, methylhydroquinone, t-butylhydroquinone, di-t-butyl-p-cresol, pyrogallol, 4,4-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis ( 4-methyl-6-t-butylphenol), phenolic resins, and cresol resins.

Nitroso compounds include nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitroso-diphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitrosopyrrolidine, Nt-butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperidine , 4-nitrosomorpholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N-nitrosophenylhydroxyamine cerium salt and N-nitrosophenylhydroxyamine aluminum salt, Examples include 2,4,6-Tris-t-butyl-nitrosobenzene, N-nitrosodiphenylamine.

N-oxide compounds include phenyl-t-butyl nitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine Examples include N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide.

Examples of quinone compounds include p-benzoquinone, p-xyloquinone, p-toluquinone, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone, 2-tert-butyl-p-benzoquinone, 2, 5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-1,4-benzoquinone, thymoquinone, 2,5-di-tert-amylbenzoquinone, 2-bromo-1,4-benzoquinone , 2,5-dibromo-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, 2-bromo-5-methyl-1,4-benzoquinone , tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone, 2-chloro-5-methyl-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2 ,5-dihydroxy-1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone , tetrahydroxy-1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-anthraquinone, 2-methyl-1,4-naphthoquinone, 5,8-dihydroxy- 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 5-hydroxy-2-methyl-1,4-naphthoquinone, 1-nitroanthraquinone, anthraquinone, 1-amino Examples include anthraquinone, 1,2-benzoanthraquinone, 1,4-diaminoanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthraquinone, 2-methylanthraquinone, and 5,12-naphthacenequinone.

N-oxyl compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6 ,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4- hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, piperidine 1-oxyl free radical, 4-oxo-2, 2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethyl Piperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, pyrrolidine 1-oxyl free radical compounds, 3-carboxyl free radical (3-carboxy- 2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

Phenothiazine compounds include phenothiazine, 10-methylphenothiazine, 2-methylthiophenothiazine, 2-chlorophenothiazine, 2-ethylthiophenothiazine, 2-(trifluoromethyl)phenothiazine, and 2-methoxyphenothiazine.

Compounds containing aromatic hydroxyl groups and nitroso compounds are preferred, and compounds containing aromatic hydroxyl groups are particularly preferred, from the viewpoints of the residual film ratio after development and resolution.
As the compound containing an aromatic hydroxyl group, 4-methoxyphenol and 2,6-di-tert-butyl-4-methylphenol are preferred, and 4-methoxyphenol is particularly preferred.

Further, in the photosensitive resin composition of the present invention, the total content of (B) the photopolymerization initiator and (C) the polymerization inhibitor is (A) with respect to 100 parts by mass of the polyimide precursor component, 0.1 to It is preferably 20 parts by mass.

[(D) compound containing two or more alcoholic hydroxyl groups]
The photosensitive resin composition of the present invention may further contain (D) a compound containing two or more alcoholic hydroxyl groups, in addition to the above components (A) to (C).
The compound containing two or more alcoholic hydroxyl groups according to the second aspect is not limited as long as it has two or more alcoholic hydroxyl groups in its molecular structure.
Examples of such compounds include glycerin, 1,2,3-butanetriol, 1,3,5-pentanetriol, and 1,2,6-hexanetriol.
Also, aldose, ketose, pyranose, furanose, alditol and the like can be exemplified. Specifically, it is preferably at least one selected from the group consisting of xylitol ((2R,3R,4S)-pentane-1,2,3,4,5-pentol) and D-glucose.
By adding these compounds, when combined with the above photopolymerization initiator, there is a tendency that the adhesiveness to the mold resin used for the fanout structure is improved.

[(E) other components]
The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (D).
The photosensitive resin composition of the present invention is typically used as a liquid photosensitive resin composition formed into a varnish by dissolving each of the above components and optionally further optional components in a solvent. . Therefore, the (E) other component may include a solvent, for example, a resin other than the above (A) photosensitive polyimide precursor, a sensitizer, a cross-linking agent, a monomer having a photopolymerizable unsaturated bond, Adhesion aids, azole compounds, hindered phenol compounds and the like can be mentioned.
Examples of the cross-linking agent include any compound having multiple functional groups in the molecule. Examples of functional groups include acrylic, methacrylic, epoxy, methylol, allyl, vinyl, and maleimide groups.

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.

Depending on the desired coating thickness and viscosity of the photosensitive resin composition, the solvent is in the range of, for example, 30 to 1500 parts by weight, preferably 100 to 1,000 parts by weight with respect to 100 parts by weight of the polyimide precursor (A). 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 of the present invention 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 aids, the silane coupling agent is more preferable from the point 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 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. When the amount of the hindered phenol compound (A) per 100 parts by mass of the polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, Discoloration and corrosion of copper or copper alloys are prevented, while excellent photosensitivity of the photosensitive resin composition is maintained when the content is 20 parts by mass or less.

The i-line absorbance of a 0.1 wt % N-methylpyrrolidone solution of the photosensitive resin composition according to the present embodiment is preferably 0.01 to 1.2 from the viewpoint of coverage of the inorganic film. Further, from the viewpoint of developability when the film thickness is increased, 0.01 to 1.0 is preferable. The i-line absorbance may be from 0.1 to 0.9, or from 0.2 to 0.8.

｛一般式（２）中、Ｘ^１、及びＹ^１は、一般式（Ａ１）中のＸ、及びＹと同じである。一般式（Ａ１）中の好ましいＸ、Ｙは、同じ理由により、一般式（２）のポリイミドにおいても好ましい。繰り返し単位数ｍは、特に限定は無いが、２～１５０の整数であってもよい。 <Method for producing polyimide and polyimide>
The present invention also provides a method for producing polyimide.
The method for producing polyimide in the present invention includes curing the photosensitive resin composition described above.
The structure of the polyimide formed from the photosensitive resin composition (polyimide precursor composition) is represented by the following general formula (2).

{X ¹ and Y ¹ in general formula (2) are the same as X and Y in general formula (A1). Preferred X and Y in general formula (A1) are also preferred in polyimide of general formula (2) for the same reason. The number of repeating units m is not particularly limited, but may be an integer of 2-150.

<Method for manufacturing cured relief pattern>
The present invention also provides a method of manufacturing a cured relief pattern.
The method for producing a cured relief pattern in the present invention includes, for example, the following steps:
(1) a coating step of applying the above-described photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer;
(3) a developing step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) The 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, the photosensitive resin composition of the present invention is applied onto a substrate, and if necessary, dried 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 160° 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-described method for producing a hardened relief pattern of the present invention.
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. The semiconductor device of the present invention is a semiconductor having a cured relief pattern formed by the cured relief pattern manufacturing method described above, for example, a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure. It can be manufactured by forming it as a device protective film or the like and combining it with a known method for manufacturing a semiconductor device.

The photosensitive resin composition of the present invention is useful not only for application to semiconductor devices as described above, but also for applications such as interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. be.

A second aspect according to the present embodiment will be described.
The photosensitive resin composition of the second aspect includes (A1) a polyimide precursor, (B) a photopolymerization initiator having a specific structure, (D) a compound containing two or more alcoholic hydroxyl groups, and (E ) γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, N,N-dimethylacetoacetamide, ε-caprolactone and 1,3-dimethyl-2-imidazolidinone, and at least one solvent selected from the group consisting of 3-methoxy-N,N-dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide. (E) More preferably, at least two solvents are included.
According to such a photosensitive resin composition, it is possible to obtain a cured relief pattern with improved adhesion and durability of the encapsulant.
It is explained below.

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

（一般式（Ｒ１）中、Ｒ_３、Ｒ_４、及びＲ_５は、それぞれ独立に、水素原子又は炭素数１～３の有機基であり、ｐは２～１０から選ばれる整数である。）で表される１価の有機基、又は炭素数１～４の飽和脂肪族基である。但し、Ｒ_１及びＲ_２の両者が同時に水素原子であることはない。｝
この中で、好ましいポリイミド前駆体としては、第一の態様と同様のものを例示することができる。 [(A1) polyimide precursor]
The polyimide precursor according to the second aspect is not limited as long as it contains a structure represented by 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. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. }
Among these, the same polyimide precursor as in the first embodiment can be exemplified as a preferable polyimide precursor.

または下記構造：

｛式中、Ａは炭素数１～６のハロゲン原子を含んでいても良い有機基を示す｝
で表される構造を含むことがより好ましい。
Ａは炭素数１～６のハロゲン原子を含んでも良い有機基であれば限定されない。このような置換基として、メチル基、エチル基、プロピル基などのアルキル基、トリフルオロメチル基などのフッ素原子含有アルキル基などを例示することができる。 Among these, in particular Y is the following structure:

Or the structure below:

{Wherein, A represents an organic group optionally containing a halogen atom having 1 to 6 carbon atoms}
It is more preferable to include a structure represented by
A is not limited as long as it is an organic group having 1 to 6 carbon atoms which may contain a halogen atom. Examples of such substituents include alkyl groups such as methyl group, ethyl group and propyl group, and fluorine atom-containing alkyl groups such as trifluoromethyl group.

｛式中、Ｒａ、Ｒｂ、Ｒｃ、Ｒｄは前述の通りである。｝

｛式中、Ｒｅは炭素数１～２０の１価の有機基を表し、Ｒｆは炭素数１～１０の１価有機基を表す。｝
Ｒａは炭素数１～１０の１価の有機基であれば限定されないが、耐熱性の観点から、炭素数１～５のアルキル基が好ましく、メチル基、エチル基、プロピル基がより好ましい。
Ｒｂは炭素数１～２０の有機基であれば限定されないが、解像度の観点から、炭素数６～２０の芳香族基、炭素数５～２０の複素環化合物に由来する１価の有機基が好ましい。
Ｒｃは炭素数１～１０の有機基であれば限定されない。その中で、解像性の観点から炭素数３～１０の飽和脂環構造を含有する１価の有機基がより好ましい。
Ｒｄは、炭素数１～１０の有機基であれば限定されない。その中で、解像性の観点から、炭素数１～３の有機基が好ましく、メチル基、エチル基、プロピル基がより好ましい。
Ｒｅは炭素数１～２０の１価の有機基であれば限定されない。この中で、耐薬品性の観点から、飽和炭化水素基を含むことが好ましい。
Ｒｆは、炭素数１～１０の有機基であれば限定されない。その中で、解像性の観点から、炭素数１～３の有機基が好ましく、メチル基、エチル基、プロピル基がより好ましい。 [(B) Photoinitiator]
The (B) photopolymerization initiator according to the second aspect is not limited as long as it has an oxime structure and further includes a heteroatom, but includes a structure represented by the following general formula (B) or (B1) .

{In the formula, Ra, Rb, Rc, and Rd are as described above. }

{In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents a monovalent organic group having 1 to 10 carbon atoms. }
Ra is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of heat resistance, it is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group.
Rb is not limited as long as it is an organic group having 1 to 20 carbon atoms, but from the viewpoint of resolution, a monovalent organic group derived from an aromatic group having 6 to 20 carbon atoms and a heterocyclic compound having 5 to 20 carbon atoms is used. preferable.
Rc is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, a monovalent organic group containing a saturated alicyclic structure having 3 to 10 carbon atoms is more preferable from the viewpoint of resolution.
Rd is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, from the viewpoint of resolution, an organic group having 1 to 3 carbon atoms is preferable, and a methyl group, an ethyl group and a propyl group are more preferable.
Re is not limited as long as it is a monovalent organic group having 1 to 20 carbon atoms. Among these, from the viewpoint of chemical resistance, it is preferable to contain a saturated hydrocarbon group.
Rf is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, from the viewpoint of resolution, an organic group having 1 to 3 carbon atoms is preferable, and a methyl group, an ethyl group and a propyl group are more preferable.

(D) Compound Containing Two or More Alcoholic Hydroxyl Groups The compound containing two or more alcoholic hydroxyl groups according to the second aspect is not limited as long as it has two or more alcoholic hydroxyl groups in its molecular structure.
Examples of such compounds include 1,2,3-butanetriol, 1,3,5-pentanetriol, and 1,2,6-hexanetriol.
(D) When the compound containing two or more alcoholic hydroxyl groups is a polyhydric alcohol compound such as aldose, ketose, pyranose, furanose, or alditol, oxidation of copper or copper alloy is particularly suppressed even in a high-temperature environment, and adhesion is improved. be kept. This is probably because they have primary hydroxyl groups and a large number of secondary hydroxyl groups, and these compounds do not denature even at high temperatures. Specific examples of aldose include erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose and talose. Among aldoses, compounds that can form a pyranose structure or a furanose structure by intramolecular hemiacetal reaction can be used in the pyranose or furanose structure to obtain the effects of the present invention in the same manner as aldoses. Specific examples of pyranose include allopyranose, altropyranose, glucopyranose, mannopyranose, glopyranose, idopyranose, galactopyranose, and talopyranose. Specific examples of furanose include ribofuranose, arabinofuranose, xylofuranose, lyxofuranose and the like. Specific examples of ketose include erythrulose, xylulose, ribulose, psicose, fructose, sorbose, tagatose, sedoheptulose, colyose and the like. Specific examples of alditol include glycerin, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, glucitol, mannitol, iditol, galactitol, and talitol. Among these, alditols, in particular, have primary hydroxyl groups at both ends, so that the effect of the present invention can be obtained remarkably.
By adding these compounds, when combined with the above photopolymerization initiator, there is a tendency that the adhesiveness to the mold resin used for the fanout structure is improved.

Although the reason why the addition of the present compound according to the second aspect improves the adhesion to the mold resin is not clear, the present inventors believe as follows.
Epoxy resin is generally used as the molding resin, and the remaining epoxy groups and hydroxyl groups interact with each other. It is believed that the interaction between the hydroxyl groups of the adhesive enhances the adhesiveness.
Solvents according to the second aspect include γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, N,N-dimethylacetoacetamide, ε-caprolactone, and 1,3- It is at least one selected from dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide. The use of these solvents is preferred because it tends to improve the coverage of the inorganic film.

The photosensitive resin composition according to the second aspect can be configured in the same manner as the photosensitive resin composition according to the first aspect with respect to components other than those described above and the content of each component.
Using the photosensitive resin composition according to the second aspect, a cured relief pattern can be produced in the same manner as in the first aspect described above. Additionally, a semiconductor device can be provided comprising the resulting cured relief pattern.

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, the standard monodisperse 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 (A) The absorbance of the polyimide precursor was measured by adjusting a 0.1 wt% NMP solution, filling a 1 cm quartz cell, and then using a UV-1800 device manufactured by Shimadzu Corporation, scanning speed Measurements were taken at medium speed and sampling pitch of 0.5 nm. Here, when two kinds of polymers described in Examples and Comparative Examples were mixed, the absorbance of the mixed polymer mixed at each weight ratio was measured.

(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 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 17 μm±0. A 2 μm spin-coated film was produced.

Using a reticle with a test pattern having a circular pattern with a mask size of 6 μm in diameter, this spin-coated film was exposed with a life-size projection exposure apparatus Prisma GHI S/N5503 (manufactured by Ultratech). 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 17 μm spin-coated film.

Regarding whether or not the round recessed relief pattern with a mask size of 15 μm obtained above can be opened, a pattern that satisfies both the following criteria (I) and (II) is judged to be acceptable. 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) Resolution 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 0.1 µm thick film. Al was sputtered to prepare a sputtered Al wafer substrate.
Similarly, a 6-inch wafer was coated with an epoxy-based encapsulant (R4000 series, manufactured by Nagase Chemtex Co., Ltd.) to a thickness of about 150 microns and cured at 130°C.
A spin-coated film of 17 μm±0.2 μm was formed on each of the sputtered Cu wafer substrate, the sputtered Al substrate, and the epoxy encapsulant-coated substrate in the same manner as in (3) Focus margin evaluation above. Using a reticle with a test pattern having a circular pattern with a mask size of 12 μm and 100 μm in diameter, this spin-coated film was exposed to 200 mJ/cm ² to 50 mJ/cm ² with a life-size projection exposure apparatus Prisma GHI S/N5503 (manufactured by Ultratec). Exposure to 800 mJ/cm ² in increments, and whether or not the sputtered Cu wafer substrate and the sputtered Al substrate can be opened according to the judgment criteria in (3) above. The case where there was no cut was regarded as passed.
The allowable exposure amount was defined as an acceptable exposure amount for all of the sputtered Cu wafer substrate, the sputtered Al substrate, and the epoxy encapsulant-coated substrate, and the range was calculated.

(5) 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 curing furnace (VF-2000, manufactured by Koyo Lindbergh, Japan). This gave a cured relief pattern of polyimide about 11 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.

(6) Inorganic Film Coverability Evaluation A test pattern with a film thickness of 5 μm and a via size of 7 μm was formed on a 6-inch silicon wafer by performing coating, exposure, development and heat curing by the methods described above. Using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Corp.), a 0.4 μm-thick Ti layer was sputtered on this test pattern to obtain a sputtered Ti-coated polyimide cured relief pattern.
This pattern was immersed in the chemical used in the chemical resistance evaluation above at 65° C. for 30 minutes, and then the appearance was observed. A case where the Ti coating was sufficient and no change in appearance was evaluated as ⊚, a case where 10% or less of the total peeling or floating was observed, a Δ when 30% or less, and an X when over 30%.

(7) Encapsulating Material Deterioration Test R4000 series manufactured by Nagase Chemtex Co., Ltd. was prepared as an epoxy-based encapsulating material. 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 composition prepared in each example and each comparative example was applied onto the epoxy-based cured film so that the final film thickness was 10 microns. For Examples 9 to 16 and Comparative Example 4, the entire surface of the coated photosensitive resin composition was exposed under the exposure condition of 300 mJ/cm ² . After that, it was thermally cured at 200° C. for 2 hours to form a first cured film having a thickness of 10 microns.

On the cured film of the first layer, the photosensitive resin composition used in the formation of the cured film of the first layer is applied, and the entire surface is exposed under the same conditions as the cured film of the first layer, and then cured by heat. 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.

(8) Adhesion Test with Encapsulating Material A pin was set on the sample prepared in the encapsulating material deterioration test, and an adhesion test was performed using a take-off tester (Sebastian 5, manufactured by Quad Group). That is, the adhesiveness between the epoxy-based encapsulant and the cured relief pattern prepared from the photosensitive resin composition prepared in each example and each comparative example was tested.
Evaluation: Adhesion strength of 70 MPa or more ... Adhesion ◎
50 MPa or more - less than 70 MPa ... adhesion strength ○
30 MPa or more and less than -50 MPa ... Adhesion △
Less than 30 MPa Adhesion ×

<Production Example 1> ((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 and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and dried in a vacuum 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. A 0.1 wt % solution of this polymer had an i-line absorbance of 0.18.

<Production Example 2> (Synthesis of polyimide precursor (polymer A-2))
Production Example 1 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride in Production Example 1 above. Polymer A-2) was obtained by carrying out the reaction in the same manner as described in 1.
The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 22,000. A 0.1 wt % solution of this polymer had an i-line absorbance of 1.2.

<Production Example 3>
20.0 g of ODPA (dried at 140°C for 12 hours), 18.6 g of HEMA, 0.05 g of hydroquinone, 10.7 g of pyridine and 140 g of diglyme were mixed and heated at a temperature of 60°C for 18 hours. After stirring for hours, a diester of ODPA and HEMA was produced. After chlorination of the resulting diester with SOCl2, a solution of 11.08 g of DADPE in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. Then, 5 L of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 L of water for 30 minutes and filtered again.
The resulting polyimide precursor was then dried under reduced pressure at 45° C. for 3 days to obtain polymer A-3. A 0.1 wt % solution of this polymer had an i-line absorbance of 0.09.

<Production Example 4>
Synthesis was carried out in the same manner as in Production Example 1 except that 4,4'-diamino-2,2'-dimethylbiphenyl (90.98 g) was used instead of DADPE in Production Example 1 above, and polymer A-4 was obtained. got

<Production Example 5>
Same as Production Example 1 except that fluoric anhydride (229.2 g) was used instead of ODPA and 2.2′-bis(trifluoromethyl)benzidine (148.51 g) was used instead of DADPE. was synthesized by the method to obtain a polymer A-5.

Photoinitiator B1: ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H
-Carbazol-3-yl]-1-(O-acetyloxime) (trade name: IRGACURE OXE-02 (hereinafter simply referred to as "OXE-02"), manufactured by Ciba Japan)
Photopolymerization initiator B2: 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]propanone-1-(O-acetyloxime) (trade name: PBG-304) , by Changzhou Power Electronics Co., Ltd.)
Photopolymerization initiator B3: 3-cyclopentylpropanone-1-(6-2-formylthiophene-9-ethylcarbazol-3-yl)-1-oxime acetate (trade name: PBG-314, manufactured by Changzhou Power Electronics Co., Ltd.) )
Photopolymerization initiator B4: 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(Obenzoyloxime) (trade name: PBG-305, manufactured by Changzhou Power Electronics Co., Ltd.)
Photoinitiator B5: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime polymerization inhibitor C1: 4-methoxyphenol polymerization inhibitor C2: 2-nitroso-1-naphthol alcoholic Compound containing two or more hydroxyl groups D1: xylitol D2: D-glucose solvent E1: γ-butyrolactone solvent E2: dimethyl sulfoxide

<Example 1>
100 g of polymer A-1 as component (A), initiator B1 (4 g) as component (B), 14 g of tetraethylene glycol dimethacrylate (M4G) as other components, and a mixed solvent of gamma-butyrolactone and DMSO (weight ratio: 75:25), and the amount of the solvent was adjusted so that the viscosity was about 35 poise, to prepare a photosensitive resin composition solution.
This composition was evaluated by the method described above. The evaluation results are shown in Table 1.

<Examples 2 to 8, Comparative Examples 1 to 3>
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, the examples satisfying the conditions of the first aspect of the present invention gave good results in terms of focus margin, resolution, and chemical resistance, but the comparative examples showed satisfactory results. no results were obtained.

<Examples 9 to 16, Comparative Example 4>
A resin composition solution was prepared at the ratio shown in Table 2 and evaluated by the method described above. The evaluation results are shown in Table 2.

As is clear from Table 2, in the examples satisfying the conditions of the second aspect of the present invention, good results were obtained in both the encapsulating material deterioration test and the adhesion test with the encapsulating material. The example did not give satisfactory results.

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 (6)

Ingredients for:
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 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. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. }
Represented by (A) a polyimide precursor having a monovalent organic group represented by the general formula (R1) ;
The following general formula (B):

{(Wherein, Ra represents an alkyl group having 1 to 5 carbon atoms, Rb represents an aromatic group having 6 to 20 carbon atoms or a monovalent organic group derived from a heterocyclic compound having 5 to 20 carbon atoms, Rc represents an organic group having 1 to 10 carbon atoms, and Rd represents an organic group having 1 to 3 carbon atoms. )}
(B) a photopolymerization initiator represented by;
(D) having a primary hydroxyl group and at least one selected from the group consisting of aldose, ketose, pyranose, furanose and alditol ; and (E) γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate , dimethyl succinate, dimethyl malonate, N,N-dimethylacetoacetamide, ε-caprolactone, and 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy- at least one solvent selected from the group consisting of N,N-dimethylpropanamide;
contains
A photosensitive resin composition characterized by being used by adhering to a molding resin containing an epoxy resin . (E) The photosensitive resin composition according to claim 1, comprising at least two solvents selected from the above group. wherein Y is the following structure:

Or the structure below:

{Wherein, A represents an organic group optionally containing a halogen atom having 1 to 6 carbon atoms}
The photosensitive resin composition according to claim 1 or 2, comprising. A method for producing a polyimide, comprising curing the photosensitive resin composition according to any one of claims 1 to 3. The following steps:
(1) a coating step of applying the photosensitive resin composition according to any one of claims 1 to 3 onto a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer;
(3) a developing step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a hardened relief pattern, comprising: a heating step of heating the relief pattern to form a hardened relief pattern. A method of manufacturing a semiconductor device, comprising the method of manufacturing a cured relief pattern according to claim 5 .