JP2024059099A - Resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

Abstract

[Problem] To provide a resin composition capable of realizing a polyimide film (cured relief pattern) having high resolution and capable of suitably imprinting a mark with a green laser. [Solution] A resin composition containing the following components: (A) a polyimide precursor represented by general formula (A1); (B) a dye; (C) a photopolymerization initiator; and (D) a solvent; wherein a prebaked film obtained by drying a coating of the resin composition at 110°C for 240 seconds has an average UV transmittance (a) of 15% or more at a wavelength of 365 to 436 nm in a 10 μm film thickness, and a polyimide film obtained by heating the prebaked film at 230°C for 2 hours in a nitrogen atmosphere has an average UV transmittance (b) of 40% or less at a wavelength of 500 to 600 nm in a 10 μm film thickness. [Selected Figure] Figure 1

Description

The present invention relates to a resin composition, a method for producing a cured relief pattern, and a semiconductor device.

Semiconductor devices (hereinafter sometimes simply referred to as "elements" in this specification) are mounted on printed circuit boards in various ways depending on the purpose. Conventional elements were generally produced by wire bonding, in which thin wires connect the external terminals (pads) of the element to the lead frame. However, today, as elements have become faster and the operating frequencies have reached the GHz range, differences in the wiring length of each terminal during mounting have come to affect the operation of the element. As a result, when mounting elements for high-end applications, it has become necessary to precisely control the length of the mounting wiring. However, it has been difficult to meet this requirement using wire bonding.

Flip-chip mounting has therefore been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on top of the rewiring layer, and then the chip is flipped over and mounted directly onto a printed circuit board. With flip-chip mounting, the wiring distance can be precisely controlled. For this reason, flip-chip mounting is being adopted for high-end devices that handle high-speed signals, and for mobile phones and other devices due to its small mounting size, and demand for this technology is rapidly expanding.

Conventionally, polyimide, which has excellent heat resistance and electrical properties, has been used as an insulating material for electronic components, and as a passivation film, surface protection film, and interlayer insulation film for semiconductor devices. In order to form a relief pattern on the surface of the resin that constitutes the passivation film, surface protection film, and interlayer insulation film, and to engrave characters and marks such as the product specifications, lot number, and date of manufacture of the semiconductor device on the surface, a laser device equipped with a green laser with a wavelength of 532 nm is generally used. In order to be able to form and engrave the desired relief pattern when processed with a laser, it is required that the passivation film, surface protection film, and interlayer insulation film have absorption at the laser wavelength.

Here, a method is known in which a polyimide film is colored to give the polyimide film appropriate light absorption. For example, Patent Document 1 discloses that a polyimide film is colored by incorporating dyes such as C.I. Solvent Blue 63, C.I. Solvent Red 18, and C.I. Disperse Yellow 201. Patent Document 2 discloses that a mark can be engraved by a green laser by incorporating dyes such as OIL GREEN 502 and OIL BLACK BS.

Patent No. 6891880 Japanese Patent No. 5501938

However, when coloring a polyimide film by adding dye, it is difficult to obtain a cured relief pattern with high resolution. In addition, if the amount of dye added is reduced to achieve high resolution, there is also the problem that it is not possible to engrave a mark with a green laser.

The object of the present invention is to provide a resin composition that can realize a polyimide film (cured relief pattern) that has high resolution and can be suitably engraved with a mark using a green laser. It is also an object of the present invention to provide a method for producing a cured relief pattern using such a resin composition, and a semiconductor device.

｛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、重合性基、又は炭素数１～４の飽和脂肪族基であり、ただし、Ｒ_１及びＲ_２は、同時に水素原子ではない。｝で表されるポリイミド前駆体；
（Ｂ）染料；
（Ｃ）光重合開始剤；及び
（Ｄ）溶媒；
を含む、樹脂組成物であって、
前記樹脂組成物の塗膜を１１０℃で２４０秒間に亘って乾燥して得られるプリベーク膜の、１０μｍ膜厚換算の波長３６５～４３６ｎｍにおける平均ＵＶ透過率（ａ）が１５％以上であり、かつ、
前記プリベーク膜を２３０℃で２時間に亘って窒素雰囲気下で加熱して得られるポリイミド膜の、１０μｍ膜厚換算の波長５００～６００ｎｍにおける平均ＵＶ透過率（b’）４０％以下である、樹脂組成物。
［２］
前記プリベーク膜を２３０℃で２時間に亘って窒素雰囲気下で加熱して得られるポリイミド膜の、１０μｍ膜厚換算の波長５３２ｎｍのＵＶ透過率（ｂ）が４０％以下である、項目１に記載の樹脂組成物。
［３］
前記一般式（Ａ１）において、前記Ｒ_１及びＲ_２が、下記一般式（Ｒ_ｈ）：

｛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の整数である。｝で表される構造を含む、項目１又は２に記載の樹脂組成物。
［４］
前記一般式（Ａ１）において、前記Ｘが、下記式（２）：

で表される構造を含む、項目１～３のいずれか１項に記載の樹脂組成物。
［５］
前記一般式（Ａ１）において、前記Ｙが、下記式（８）：
及び／又は下記式（９）：
で表される構造を含む、項目１～４のいずれか１項に記載の樹脂組成物。
［６］
前記（Ｂ）成分の含有量が、（Ａ）成分１００質量部に対して、０．５～３０質量部である、項目１～５のいずれか１項に記載の樹脂組成物。
［７］
前記（Ｃ）成分の含有量が、（Ａ）成分１００質量部に対して、０．１～１００質量部である、項目１～６のいずれか１項に記載の樹脂組成物。
［８］
前記（Ｂ）成分が、アジン系染料誘導体、及びアントラセン系染料誘導体の少なくとも一方を含む、項目１～７のいずれか１項に記載の樹脂組成物。
［９］
前記（Ｄ）成分が、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、γ－ブチロラクトン（ＧＢＬ）、ジメチルスルホキシド（ＤＭＳＯ）、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、及び乳酸エチルから成る群より選択される少なくとも１つである、項目１～８のいずれか１項に記載の樹脂組成物。
［１０］
（１）項目１～９のいずれか１項に記載の樹脂組成物を基板に塗布することにより、樹脂組成物膜を形成する工程と、
（２）前記樹脂組成物膜を露光、及び現像する工程により、又は前記樹脂組成物膜にレーザー照射する工程により、レリーフパターンを形成する工程と、
（３）前記レリーフパターンを加熱して硬化レリーフパターンを形成する工程と、
を有する、硬化レリーフパターンの製造方法。
［１１］
前記（１）工程では、銅又は銅合金から形成されて成る前記基板に、前記樹脂組成物を塗布する、項目１０に記載の硬化レリーフパターンの製造方法。
［１２］
項目１～９のいずれか１項に記載の樹脂組成物から得られる硬化レリーフパターンを絶縁層として有する、半導体装置。 One aspect of the present invention is as follows.
[1]
Ingredients below:
(A) The following general formula (A1):

A polyimide precursor represented by the formula: {wherein X is a tetravalent organic group, Y is a divalent organic group, and R ₁ and R ₂ are each independently a hydrogen atom, a polymerizable group, or a saturated aliphatic group having 1 to 4 carbon atoms, with the proviso that R ₁ and R ₂ are not both hydrogen atoms.}
(B) dye;
(C) a photoinitiator; and (D) a solvent;
A resin composition comprising:
A prebaked film obtained by drying a coating film of the resin composition at 110° C. for 240 seconds has an average UV transmittance (a) of 15% or more at a wavelength of 365 to 436 nm in a 10 μm film thickness; and
The prebaked film is heated at 230° C. for 2 hours in a nitrogen atmosphere to obtain a polyimide film, which has an average UV transmittance (b') of 40% or less at a wavelength of 500 to 600 nm in a 10 μm-thickness equivalent.
[2]
2. The resin composition according to item 1, wherein the polyimide film obtained by heating the prebaked film at 230° C. for 2 hours under a nitrogen atmosphere has a UV transmittance (b) of 40% or less at a wavelength of 532 nm in a 10 μm film thickness.
[3]
In the general formula (A1), R ₁ and R ₂ are represented by the following general formula (R _h ):

{wherein R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p represents an integer of 2 to 10.}. The resin composition according to item 1 or 2,
[4]
In the general formula (A1), the X is represented by the following formula (2):

The resin composition according to any one of items 1 to 3, comprising a structure represented by:
[5]
In the general formula (A1), the Y is represented by the following formula (8):
And/or the following formula (9):
The resin composition according to any one of items 1 to 4, comprising a structure represented by:
[6]
6. The resin composition according to any one of items 1 to 5, wherein the content of the (B) component is 0.5 to 30 parts by mass relative to 100 parts by mass of the (A) component.
[7]
7. The resin composition according to any one of claims 1 to 6, wherein the content of the (C) component is 0.1 to 100 parts by mass relative to 100 parts by mass of the (A) component.
[8]
8. The resin composition according to any one of items 1 to 7, wherein the component (B) includes at least one of an azine dye derivative and an anthracene dye derivative.
[9]
The resin composition according to any one of items 1 to 8, wherein the component (D) is at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), 3-methoxy-N,N-dimethylpropanamide, and ethyl lactate.
[10]
(1) A step of forming a resin composition film by applying the resin composition according to any one of items 1 to 9 to a substrate;
(2) forming a relief pattern by exposing and developing the resin composition film or by irradiating the resin composition film with a laser;
(3) heating the relief pattern to form a hardened relief pattern; and
The method for producing a cured relief pattern comprising:
[11]
Item 11. The method for producing a cured relief pattern according to item 10, wherein in the step (1), the resin composition is applied to the substrate made of copper or a copper alloy.
[12]
10. A semiconductor device having, as an insulating layer, a cured relief pattern obtained from the resin composition according to any one of items 1 to 9.

According to the present invention, it is possible to provide a resin composition capable of producing a polyimide film (cured relief pattern) having high resolution and capable of suitably imprinting a mark with a green laser. In addition, according to the present invention, it is possible to provide a method for producing a cured relief pattern using such a resin composition, and a semiconductor device.

1 is a schematic cross-sectional view showing one aspect of a semiconductor device according to an embodiment of the present invention. 1 is a schematic plan view showing one aspect of a semiconductor device according to an embodiment of the present invention; 1 is a diagram illustrating an example of a manufacturing process for the semiconductor device according to the present embodiment. 11 is a schematic cross-sectional view showing another aspect of the semiconductor device according to the embodiment. FIG.

Hereinafter, the embodiment of the present invention (hereinafter referred to as "the present embodiment") will be specifically described, but the present invention is not limited thereto, and various modifications are possible within the scope of the present invention. In this specification, when a structure represented by the same symbol in a certain general formula exists in a molecule, it may be the same or different from each other. In this specification, a numerical range described using "~" represents a numerical range including the numerical values before and after "~" as the lower limit and upper limit. In addition, in this specification, in a numerical range described in stages, the upper limit or lower limit described in a certain numerical range may be replaced by the upper limit or lower limit of another numerical range described in stages. In addition, in this specification, the upper limit or lower limit described in a certain numerical range may be replaced by a value shown in an example.
In this specification, the aspect expressed as the "face side" based on a given face includes an aspect in contact with the face, as well as an aspect in which any member is interposed between the face and the face. The scale, shape, length, and the like shown in the drawings may be exaggerated for greater clarity.

[Resin composition]

｛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、重合性基、又は炭素数１～４の飽和脂肪族基であり、ただし、Ｒ_１及びＲ_２は、同時に水素原子ではない。｝で表されるポリイミド前駆体；
（Ｂ）染料；
（Ｃ）光重合開始剤；及び
（Ｄ）溶媒；
を含む、樹脂組成物であって、
前記樹脂組成物の塗膜、１１０℃で２４０秒間に亘って乾燥して得られるプリベーク膜の、１０μｍ膜厚換算の波長３６５～４３６ｎｍにおける平均ＵＶ透過率（ａ）が１５％以上であり、かつ、
前記プリベーク膜を２３０℃で２時間に亘って窒素雰囲気下で加熱して得られるポリイミド膜の、１０μｍ膜厚換算の波長５００～６００ｎｍにおける平均ＵＶ透過率（ｂ’）が４０％以下である。
このような樹脂組成物によれば、高い解像性を有する、かつ、グリーンレーザーによってマークを好適に刻印することができるポリイミド膜（硬化レリーフパターン）を実現可能である。
一態様において、前記プリベーク膜を２３０℃で２時間に亘って窒素雰囲気下で加熱して得られるポリイミド膜の、１０μｍ膜厚換算の波長５３２ｎｍのＵＶ透過率（ｂ）は、４０％以下である。これによれば、高い解像性を有する、かつ、グリーンレーザーによってマークを好適に刻印することができるポリイミド膜（硬化レリーフパターン）を実現し易い。 The resin composition of the present embodiment is
Ingredients below:
(A) The following general formula (A1):

A polyimide precursor represented by the formula: {wherein X is a tetravalent organic group, Y is a divalent organic group, and R ₁ and R ₂ are each independently a hydrogen atom, a polymerizable group, or a saturated aliphatic group having 1 to 4 carbon atoms, with the proviso that R ₁ and R ₂ are not both hydrogen atoms.}
(B) dye;
(C) a photoinitiator; and (D) a solvent;
A resin composition comprising:
A coating film of the resin composition and a prebaked film obtained by drying at 110° C. for 240 seconds have an average UV transmittance (a) of 15% or more at a wavelength of 365 to 436 nm in a 10 μm film thickness; and
The prebaked film is heated at 230° C. for 2 hours in a nitrogen atmosphere to obtain a polyimide film, which has an average UV transmittance (b') of 40% or less at a wavelength of 500 to 600 nm in terms of a 10 μm film thickness.
Such a resin composition can provide a polyimide film (cured relief pattern) that has high resolution and allows marks to be suitably engraved thereon with a green laser.
In one embodiment, the polyimide film obtained by heating the prebaked film at 230° C. for 2 hours in a nitrogen atmosphere has a UV transmittance (b) of 40% or less at a wavelength of 532 nm in a 10 μm film thickness. This makes it easy to realize a polyimide film (cured relief pattern) that has high resolution and allows marks to be suitably engraved by a green laser.

[UV transmittance]
<Average UV transmittance (a)>
In this embodiment, the prebaked film has an average UV transmittance (a) of 15% or more at wavelengths of 365 to 436 nm. The average UV transmittance (a) at wavelengths of 365 to 436 nm can be regarded as an index showing the degree of transmission of the exposure light in the photolithography process. The average UV transmittance (a) of 15% or more at the prebaked film indicates that the exposure light can suitably reach the bottom of the prebaked film. In other words, it indicates that the prebaked film is suitably exposed, and further, that a relief pattern with high resolution can be obtained by developing such a prebaked film. The high resolution of the relief pattern is maintained even after heating (curing). Therefore, a prebaked film having an average UV transmittance (a) of 15% or more can provide a cured relief pattern with high resolution. From this viewpoint, the average UV transmittance (a) at wavelengths of 365 nm to 436 nm is preferably 20% or more, more preferably 30% or more. The average UV transmittance (a) may be 100% or less, or may be 99% or less.

The average UV transmittance (a) at 365 to 436 nm can be controlled by the raw material types of the resin composition and their content ratios. The average UV transmittance (a) at wavelengths of 365 to 436 nm is calculated based on the method in the examples. The drying conditions (110°C and 240 seconds) are selected from the perspective of obtaining a suitable pre-baked film.

<Average UV transmittance (b')>
In this embodiment, the prebaked film has an average UV transmittance (b') of 40% or less at wavelengths of 500 to 600 nm. The average UV transmittance (b') can be regarded as an index showing the degree of coloration in the polyimide film, and an average UV transmittance (b') of 40% or less indicates that the polyimide film is suitably colored to an extent that it can absorb laser light having a wavelength (wavelength 500 to 600 nm) that can be used as a green laser. Since the average UV transmittance (b') is the average transmittance converted into a 10 μm film thickness at wavelengths of 500 to 600 nm, a value of 40% or less allows marks to be suitably engraved by a green laser marker. From this viewpoint, the average UV transmittance (b) is preferably 30% or less, more preferably 25% or less.

<UV transmittance (b)>
In a preferred embodiment of the present invention, the UV transmittance (b) is 40% or less. The UV transmittance (b) can be regarded as an index showing the degree of coloration in the polyimide film, and a UV transmittance (b) of 40% or less indicates that the polyimide film is suitably colored to such an extent that it can suitably absorb laser light from a green laser having a wavelength of 532 nm. The UV transmittance (b) is the transmittance converted to a 10 μm film thickness at a wavelength of 532 nm, so that a value of 40% or less makes it easy to engrave a mark using a green laser marker. From this viewpoint, the UV transmittance (b) is preferably 30% or less, more preferably 25% or less.

The UV transmittance (b) and the average UV transmittance (b') can be controlled by the raw material types of the resin composition and their content ratios. The UV transmittance (a) is calculated based on the method in the examples. The heating (curing) conditions (230°C, 2 hours, and in a nitrogen atmosphere) are selected from the perspective of obtaining a polyimide film in an optimal manner.

[Component (A): Polyimide precursor]
The component (A) in this embodiment is a polyimide precursor represented by the above general formula (A1), which makes it easier for the photopolymerization initiator (C) to act effectively during exposure, and as a result, makes it easier to obtain a cured relief pattern excellent in various properties.

｛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の整数である。｝で表される構造を含むことが好ましい。これによれば、本発明の効果を奏し易くなる。 In the general formula (A1), R ₁ and R ₂ are represented by the following general formula (R _h ):

It is preferable that the compound contains a structure represented by the following formula: {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 of 2 to 10.} This makes it easier to achieve the effects of the present invention.

<X in the above general formula (A1)>
In the above general formula (A1), the tetravalent organic group represented by X is, for example, an organic group derived from the tetracarboxylic dianhydride that is the raw material of component (A). Such an organic group is preferably an organic group having 6 to 40 carbon atoms, and more preferably
(1) _one -COOR group and one -CONH- group are attached to the same ring;
(2) _one -COOR group and one -CONH- group are in the ortho position to each other;
In the above (1), 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 or different. In this context, the "ring" is preferably a benzene ring. In addition, R ₁ in the -COOR ₁ group in this context is preferably a monovalent organic group represented by the above general formula (R _h ).

で表される構造が挙げられる。Ｘ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 particularly preferably a group represented by the following formula:

X may be one type or a combination of two or more types.

で表される構造を含むことが、良好な膜物性を発現する観点から好ましい。 Among them, in the general formula (A1), X is the following formula (2):

From the viewpoint of exhibiting good film properties, it is preferable that the copolymer contains a structure represented by the following formula:

In this embodiment, from the viewpoint of exhibiting good film properties, the X is represented by the following formulas (1) to (3):
It is preferable that the compound contains at least one structure selected from the group represented by:

In the present embodiment, from the viewpoint of exhibiting good film properties (for example, film elongation), in the component (A), the above X is represented by the following formula (2):
In other words, the component (A) preferably contains a structure derived from ODPA (4,4'-oxydiphthalic anhydride).

When at least one of _R1 and _R2X in the above general formula (A1) is a monovalent organic group represented by the above general formula ( _Rh ), _R3 in the general formula ( _Rh ) is preferably a hydrogen atom or a methyl group, and _R4 and _R5 are each preferably a hydrogen atom from the viewpoint of photosensitive properties. Also, p is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

｛上記式中、Ａは、それぞれ独立に、メチル基（－ＣＨ_３）、エチル基（－Ｃ_２Ｈ_５）、プロピル基（－Ｃ_３Ｈ_７）、ブチル基（－Ｃ_４Ｈ_９）、又はトリフルオロメチル基（－ＣＦ_３）である。｝で表される構造が挙げられる。Ｙは、１種でも２種以上の組み合わせでも構わない。 <Y in the above general formula (A1)>
In the above general formula (A1), the divalent organic group represented by Y is, for example, an organic group derived from a diamine which is a raw material for the component (A). Such an organic group is preferably an aromatic group having 6 to 40 carbon atoms, for example, a group represented by the following formula:

In the above formula, each A is independently a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ), a butyl group (-C ₄ H ₉ ), or a trifluoromethyl group (-CF ₃ ). Y may be one type or a combination of two or more types.

｛上記式中、Ａは、それぞれ独立に、メチル基（－ＣＨ_３）、エチル基（－Ｃ_２Ｈ_５）、プロピル基（－Ｃ_３Ｈ_７）、ブチル基（－Ｃ_４Ｈ_９）、又はトリフルオロメチル基（－ＣＦ_３）である。｝で表される群から選択される少なくとも一つの構造を含むことが好ましい。 In this embodiment, from the viewpoint of exhibiting good film properties, the above Y is represented by the following general formulas (4) to (7):

It is preferable that the compound contains at least one structure selected from the group represented by the following formula: {In the above formula, each A is independently a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ), a butyl group (-C ₄ H ₉ ), or a trifluoromethyl group (-CF ₃ ).}.

In particular, in the present embodiment, from the viewpoint of exhibiting good film properties (for example, film elongation), in the component (A), the above Y is represented by the following formula (8):
And/or the following formula (9):
That is, the component (A) preferably contains a structure derived from DADPE (4,4'-diaminodiphenyl ether) and/or a structure derived from m-TB (2,2'-dimethyl-4,4'-diaminobiphenyl).

<Examples of combinations of X and Y in general formula (A1)>
In this embodiment, in general formula (A1), the X is represented by the following formula (2):
and wherein Y is a structure represented by the following formula (8):
It is preferable that the copolymer contains a structure represented by the following formula (1):

In the present embodiment, in general formula (A1), X is represented by the following formula (2):
and wherein Y is represented by the following formula (9):
And the following formula (10):
From the viewpoint of exhibiting good film properties, it is preferable that the polymerizable compound contains at least one structure selected from the group represented by the following formula:

Including the above, examples of combinations of X and Y in this embodiment are as follows. These combinations make it easy to improve various properties of the resin composition and/or the cured relief pattern obtained therefrom. The combination of X and Y in a given number and the combination of X and Y in another number may be used in combination.

<Physical Properties of Component (A)>
The weight average molecular weight of the (A) component is preferably 1,000 or more, more preferably 5,000 or more, and also preferably 100,000 or less, from the viewpoint of heat resistance and mechanical properties of the polyimide film obtained after heating (curing). From the viewpoint of solubility in organic solvents, the weight average molecular weight of the (A) component is more preferably 50,000 or less. The resin composition of the present embodiment has photosensitivity, and from the viewpoint of compatibility between exposure sensitivity, resolution of the pattern obtained after exposure and development, and film properties after heating (curing) for such a pattern, the weight average molecular weight of the (A) component is preferably 6,000 or more, 7,000 or more, or 8,000 or more, and also preferably 40,000 or less, 30,000 or less, or 22,000 or less. The "weight average molecular weight" is calculated as a polystyrene equivalent value by gel permeation chromatography (GPC).

[Component (B): Dye]
The resin composition of this embodiment contains the above-mentioned component (B). The dye as component (B) is different from a "pigment" which is defined as not interacting with the solvent and not dissolving in the solvent in that it dissolves in the solvent (mainly water). As component (B), a dye (particularly an organic dye) having a maximum absorption wavelength in the vicinity of 450 to 800 nm is preferably used.

Specific examples of the (B) component include at least one dye derivative selected from the group consisting of azines, azomethines, anthracenes, quinacridones, dioxazines, diketopyrrolopyrroles, anthrapyridones, isoindolinones, indanthrones, perinones, perylenes, indigo, thioindigo, quinophthalones, quinolines, and triphenylmethanes. Among these, preferred examples of the (B) component include at least one of azine dye derivatives and anthracene dye derivatives. These (B) components are highly compatible with the (A) component, making it easy to improve the film elongation of the polyimide film.

Component (B) is preferably a combination of multiple organic dyes that satisfy at least one of the following: favorable absorption of wavelengths in the visible range, favorable compatibility with polymers such as component (A), and low scattering properties for laser light. Furthermore, component (B) preferably contains an organic dye that does not fade easily when exposed to high temperatures during the heating (curing) process of component (A) or high temperatures during melting due to irradiation with laser light, has excellent heat resistance, and favorable absorption of the wavelength of laser light. The "laser light" referred to here may be, for example, laser light from a green laser with a wavelength of 532 nm.

Examples of azine dye derivatives include black azine condensation mixtures (e.g., black azine condensation mixtures such as those described in the Color Index as C.I. Solvent Black 5, C.I. Solvent Black 7, and C.I. Acid Black 2). Such azine dye derivatives can be obtained, for example, by oxidizing and dehydrating condensation of aniline, aniline hydrochloride, and nitrobenzene in the presence of iron chloride at a reaction temperature of 160 to 180°C.

As the anthracene-based dye derivative, the anthracene-based dye derivative shown below is particularly preferred because it exhibits good heat resistance and has high absorbance at 532 nm. That is, as the anthracene-based dye derivative, an anthracene-based oil-soluble dye is preferred, and specifically,
C.I. Solvent Blue 11, 12, 13, 14, 26, 35, 36, 44, 45, 48, 49, 58, 59, 63, 68, 69, 70, 78, 79, 83, 87, 90, 94, 97, 98, 101, 102, 104, 105, 122, 129, and 132;
C.I. Disperse Blue 14, 35, 102, and 197;
C.I. Solvent Violet 13, 14, 15, 26, 30, 31, 33, 34, 36, 37, 38, 40, 41, 42, 45, 47, 48, 51, 59, and 60;
Preferred are dyes commercially available under the color indexes C.I. Disperse Violet 1, 4, 26 and 31.

As component (B), the following red dyes are preferred because they have high absorbance at 532 nm. Specifically, preferred examples include commercially available dyes with color indexes of C.I. Solvent Red 1, 3, 8, 18, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, and 122.

From the viewpoint of easily achieving the effects of the present invention, the content of the (B) component is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the (A) component. If the content of the (B) component is equal to or greater than the above lower limit, it is easy to engrave a mark with a green laser marker, and if the content of the (B) component is equal to or less than the above upper limit, it is easy to prevent deterioration of the film properties of the obtained polyimide film. The (B) component may be used alone or in combination of two or more kinds.

[Component (C): Photopolymerization initiator]
The resin composition of the present embodiment further contains the above-mentioned component (C). The component (C) can generate radicals by absorbing a specific wavelength and decomposing. By further containing the component (C), the resin composition of the present embodiment can be suitably used as a photosensitive resin composition.

As the component (C),
Benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone;
Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone;
Thioxanthone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone;
benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal and other benzil derivatives;
Benzoin, benzoin derivatives such as benzoin methyl ether, etc.;
Oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime;
N-arylglycines such as N-phenylglycine;
Peroxides such as benzoyl perchloride;
Aromatic biimidazoles Photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide;
Among them, oximes are more preferable from the viewpoint of photosensitivity. It is also preferable that the resin composition of the present embodiment and the component (C) of the present embodiment do not contain titanocenes from the viewpoint of storage stability.

Among the oximes, from the viewpoint of adhesion between the resin composition and the substrate, the following formulae (C1) to (C6):
{In the formula, R ₃₉ is a methyl group or a phenyl group, R ₄₀ is each independently a monovalent organic group having 1 to 12 carbon atoms, Z is a sulfur or oxygen atom, R ₄₁ is a methyl group, a phenyl group or a divalent organic group, and R ₄₂ to R ₄₄ are each independently a hydrogen atom or a monovalent organic group.} is more preferable.

From the viewpoint of optimally expressing the function of component (C), and therefore of easily achieving the effects of the present invention, the resin composition preferably contains 0.1 to 100 parts by mass, and more preferably 1 to 50 parts by mass, of component (C) per 100 parts by mass of component (A).

[Component (D); Solvent]
The resin composition of the present embodiment contains the above-mentioned component (D).
As the component (D), for example, from the viewpoint of solubility in the component (A), a polar organic solvent is preferable. Specific examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide (DMSO), diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone (GBL), α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, and N-cyclohexyl-2-pyrrolidone. These can be used alone or in combination of two or more kinds.

In addition, from the viewpoint of improving the storage stability of the resin composition, alcohols are preferably used as the component (D). Suitable alcohols are those that have an alcoholic hydroxyl group in the molecule and do not have an olefinic double bond. Specifically,
Alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol;
Lactic acid esters such as ethyl lactate;
Propylene glycol monoalkyl ethers such as 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, and propylene glycol 2-(n-propyl) ether;
Monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol-n-propyl ether;
2-Hydroxyisobutyric acid esters;
Di-alcohols such as ethylene glycol and propylene glycol;
Among these, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethyl alcohol are preferred, and in particular, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether are more preferred.

Component (D) is used in an amount of 30 to 1,500 parts by mass, preferably 100 to 1,000 parts by mass, per 100 parts by mass of component (A), depending on the coating thickness and/or viscosity of the resin composition. When component (D) contains an alcohol that does not have an olefinic double bond, the proportion of the alcohol that does not have an olefinic double bond in the total amount of component (D) is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the proportion of the alcohol that does not have an olefinic double bond is 5% by mass or more, the storage stability of the resin composition is good, and when it is 50% by mass or less, the solubility of component (A) is good.

Considering the above factors comprehensively, among the (D) components, at least one selected from the group consisting of NMP, GBL, DMSO, 3-methoxy-N,N-dimethylpropanamide, and ethyl lactate is particularly preferred. The (D) component may be used alone or in combination of two or more types.

[Component (E); Other Components]
The resin composition of the present embodiment may further contain a component other than the above (A) to (D) (component (E); other component) in addition to the above components (A) to (D).

Examples of the component (E) include a crosslinking agent having an unsaturated bond. This makes it easier to use the resin composition of the present embodiment as a photosensitive resin composition. In addition, examples of the component (E) include:
Resins other than component (A);
Sensitizers;
Adhesive aid;
Polymerization inhibitors;
Azole compounds;
Hindered phenol compounds;
The component (E) may be used alone, or in combination of two or more types.

((E-1) Crosslinking Agent)
The resin composition of the present embodiment may contain a crosslinking agent having a photopolymerizable unsaturated bond from the viewpoint of improving the physical properties and resolution of the polyimide film (cured relief pattern). Examples of such crosslinking agents include (meth)acrylic compounds that can undergo a radical polymerization reaction with the component (D). Examples of such compounds include:
Mono- or di(meth)acrylates of ethylene glycol or polyethylene glycol, including diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate;
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;
Neopentyl glycol di(meth)acrylate;
Mono- or di(meth)acrylate 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 ethylene oxide or propylene oxide adducts of these compounds;
etc. are preferably mentioned.

The content of the crosslinking agent having a photopolymerizable unsaturated bond is preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, per 100 parts by mass of component (A). The crosslinking agent having a photopolymerizable unsaturated bond may be used alone or in combination of two or more kinds.

((E-2) Resins other than component (A))
The resin composition of the present embodiment may contain a resin component other than the component (A). Such a resin component is, for example, a polyimide, a polyoxazole, a polyoxazole precursor, a phenolic resin, a polyamide, an epoxy resin, a siloxane resin, an acrylic resin, etc. When the resin composition contains a polyimide as the component (E), the polyimide may be a polyimide having a skeleton derived from the skeleton of the component (A), or may be a polyimide not having the skeleton.

The amount of resin components other than component (A) is preferably 0.01 to 20 parts by mass per 100 parts by mass of component (A). The resin components other than component (A) may be used alone or in combination of two or more kinds.

((E-3) Sensitizer)
When the resin composition of the present embodiment is used as a photosensitive resin composition, the resin composition may optionally contain a sensitizer in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylamine ... 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-bis(7-dimethylaminocoumarin), ... Nyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Examples of such an alkyl ether compound include 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, and 3',4'-dimethylacetanilide.

The content of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of component (A). The sensitizer may be used alone or in combination of two or more kinds.

((E-4) Adhesive assistant)
In order to improve the adhesion between the resin composition and the substrate, the resin composition may optionally contain an adhesive aid. Examples of the adhesive aid include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, and N-[3-(triethoxysilyl)propyl]phthala. Examples of suitable adhesives include silane coupling agents such as midic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyl trimethoxysilane, as well as aluminum-based adhesive assistants such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate. Among these, silane coupling agents are preferred from the viewpoint of adhesion.

The content of the adhesive aid is preferably 0.5 to 25 parts by mass per 100 parts by mass of component (A). The adhesive aid may be used alone or in combination of two or more kinds.

((E-5) Polymerization inhibitor)
The resin composition of the present embodiment is in a solution state because it contains an organic solvent as the component (C). In this case, in order to improve the stability of the viscosity and photosensitivity during storage, the resin composition may optionally contain a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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 2,2,6,6-tetramethylpiperidine 1-oxyl.

The content of the thermal polymerization inhibitor is preferably 0.005 to 12 parts by mass per 100 parts by mass of component (A). The thermal polymerization inhibitor may be used alone or in combination of two or more types.

((E-6) Azole Compounds)
When the substrate to which the resin composition of the present embodiment is applied contains copper or a copper alloy, the resin composition may optionally contain an azole compound to suppress discoloration of the copper surface. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 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, and the like. benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Among them, at least one selected from the group consisting of tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole is preferred.

From the viewpoint of adhesion, the content of the azole compound is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A). When the content of the azole compound is 0.1 parts by mass or more, when the resin composition of this embodiment is formed on a substrate, discoloration of the copper or copper alloy contained in the substrate is easily suppressed, and when the content is 20 parts by mass or less, the resin composition is likely to exhibit good storage stability. The azole compounds may be used alone or in combination of two or more kinds.

((E-7) Hindered phenol compound)
In order to suppress discoloration of the substrate surface, the resin composition of the present embodiment may optionally contain a hindered phenol compound in place of or together with the azole compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-buthion, and the like. 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-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N' hexamethylene bis(3,5-di-t-butyl-4-hydroxyphenyl)propionate, di-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)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tri Azine-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- Examples of the tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione include 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. 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 is preferred.

From the viewpoint of adhesion between the resin composition and the substrate, the content of the hindered phenol compound is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A). When the content of the hindered phenol compound is 0.1 parts by mass or more, when the resin composition of this embodiment is formed on a substrate, discoloration of the copper or copper alloy contained in the substrate is easily suppressed, and when the content is 20 parts by mass or less, the resin composition is likely to exhibit good storage stability.

[Method of preparing component (A)]
The component (A) can be prepared by each step.
(1) A tetracarboxylic acid dianhydride having a desired tetravalent organic group X is reacted with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an "acid/ester body").
(2) The acid/ester compound is subjected to amide polycondensation with a diamine having a divalent organic group Y.
In the above (1), saturated aliphatic alcohols may be used in combination with the alcohols having a photopolymerizable group. These compounds may be used alone or in combination of two or more.

<Preparation of Acid/Ester>
(Tetracarboxylic acid dianhydride having a tetravalent organic group X)
Examples of tetracarboxylic dianhydrides having a tetravalent organic group X suitable for preparing an acid/ester include pyromellitic anhydride, diphenylether-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, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane.

(Alcohols having a photopolymerizable group)
Examples of alcohols having a photopolymerizable group suitable for preparing an acid/ester body include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t ... 1-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

(Saturated fatty alcohols)
Examples of the saturated aliphatic alcohols that can be used optionally include saturated aliphatic alcohols having 1 to 4 carbon atoms. Specifically, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol are preferred.

(Reaction solvent and reaction conditions)
The tetracarboxylic dianhydride and the alcohol may be stirred and mixed, preferably in the presence of a basic catalyst such as pyridine, in a suitable reaction solvent at a temperature of 20 to 50° C. for 4 to 10 hours. This allows the esterification reaction of the acid anhydride to proceed, and the desired acid/ester can be suitably obtained.

The reaction solvent is preferably a solvent capable of dissolving the raw materials (tetracarboxylic dianhydride and alcohols) and the product, that is, the acid/ester. More preferably, it is a solvent capable of dissolving the polyimide precursor, which is the amide polycondensation product of the acid/ester and the diamine. Examples of such reaction solvents include NMP, N,N-dimethylacetamide, N,N-dimethylformamide, DMSO, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. Among these,
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Examples of esters include methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate;
Examples of lactones include GBL;
Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran;
Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene;
Hydrocarbons include, for example, hexane, heptane, benzene, toluene, and xylene;
etc.

<Preparation of component (A)>
An appropriate dehydration condensation agent is added to and mixed with the acid/ester (typically, the acid/ester in a solution state dissolved in the above-mentioned reaction solvent), preferably under ice cooling, to convert the acid/ester into a polyacid anhydride intermediate. A diamine having a divalent organic group Y dissolved or dispersed in a separate solvent is added dropwise to the acid/ester, and the two are subjected to amide polycondensation to obtain the target component (A).

Examples of dehydration condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

Examples of diamines having a divalent organic group Y include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diamino Diphenyl sulfone, 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 zene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and the like;
These benzene rings have some of their hydrogen atoms substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogen atoms, or the like (substituted compounds);
Mixtures of these;
etc.

Specific examples of the substitutes include 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and the like;
Mixtures of these;
etc.

In order to improve the adhesion between the resin composition and the substrate, diaminosiloxanes may be used in combination with diamines containing a divalent organic group Y when preparing component (A). Specific examples of diaminosiloxanes include 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, etc.

After the amide polycondensation is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution may be filtered off as necessary, and then a suitable poor solvent (e.g., water, aliphatic lower alcohol, or a mixture thereof) may be added to the solution containing the polymer to precipitate the polymer component. Furthermore, the polymer may be purified by repeating redissolution and reprecipitation operations as necessary, and then vacuum dried to isolate the desired component (A). To improve the degree of purification, the solution containing the polymer may be passed through a column packed with an anion and/or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

The weight average molecular weight of component (A) is preferably 1,000 or more, more preferably 5,000 or more, and preferably 100,000 or less, as a polystyrene equivalent value by GPC, from the viewpoint of heat resistance and mechanical properties of the polyimide film (cured relief pattern) obtained after heating. From the viewpoint of solubility in the developer, the weight average molecular weight is more preferably 50,000 or less. From the viewpoint of compatibility between sensitivity and resolution, the weight average molecular weight is preferably 6,000 to 40,000, more preferably 7,000 to 30,000, and even more preferably 8,000 to 22,000. Tetrahydrofuran or NMP is recommended as the developing solvent for GPC. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

[Method for producing cured relief pattern]
One aspect of this embodiment is a method for producing a cured relief pattern.
The manufacturing method of this embodiment includes the following steps:
(1) applying the resin composition to a substrate to form a resin composition film;
(2) exposing the resin composition film to light;
(3) developing the exposed resin composition film to form a relief pattern;
(4) heat treating the relief pattern to form a hardened relief pattern.
By adopting this manufacturing method,
(5) In the step of irradiating the surface of the cured relief pattern with a laser to perform laser printing, the resin surface can be easily printed.

[Step (1)]
In this step, the resin composition is applied to a substrate to form a resin composition film. After the resin composition is applied to the substrate, it may be dried as necessary. In this step, it is preferable to apply the photosensitive resin composition to the substrate made of copper or a copper alloy.

The substrate may be, for example,
Metal substrates made of silicon, aluminum, copper, copper alloys, etc.;
Resin substrates such as epoxy, polyimide, and polybenzoxazole;
a substrate having a metal circuit formed on the resin substrate;
A substrate in which multiple metals or metal and resin are laminated in multiple layers;
etc.

The coating method may be a method that has been conventionally used for coating a resin composition, for example,
Coating methods using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc.;
Spray application method using a spray coater;
etc.

When drying the resin composition, the drying method is
Air dry;
Heat drying in an oven or on a hot plate;
Vacuum drying;
The drying is preferably carried out under conditions that do not easily cause imidization of the component (A). Specifically, when air drying or heat drying is carried out, drying can be carried out under conditions of 20° C. to 140° C. for 1 minute to 1 hour.

[Step (2) and Step (3)]
In this process, a relief pattern is formed by exposing and developing the resin composition film, or by irradiating the resin composition film with a laser. This process is suitable when the resin composition is used as a photosensitive resin. That is, a relief pattern can be suitably formed by performing a photolithography process (exposure and development process) or a process (laser drilling process) of performing laser drilling using a high energy density such as a carbon dioxide laser, a UV laser, or a green laser.

The photolithography process can be performed by an exposure apparatus. Examples of the exposure apparatus include contact aligners, mirror projections, and steppers.

In the exposure process, the resin composition film is irradiated with exposure light from a light beam. The resin composition film can be irradiated with exposure light through a photomask or reticle on which a pattern is formed, or directly. The light beam used for exposure is an ultraviolet light source, etc.

After the exposure step, for the purpose of improving the photosensitivity, a post-exposure bake (PEB) and/or a pre-development bake may be performed at any temperature and for any time, as necessary. An example of the baking conditions is a temperature of 40 to 120°C and a time of 10 to 240 seconds.

In the development process, the unexposed portions of the resin composition film after exposure are removed with a developer. Development methods include conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment.

After the development step, a post-development bake may be performed at any temperature and for any time combination, as necessary, for the purpose of adjusting the shape of the relief pattern, etc. An example of the post-development bake conditions is a temperature of 80 to 130°C and a time of 0.5 to 10 minutes.

The developer is preferably a good solvent for the resin composition, or a combination of the good solvent and a poor solvent. As good solvents, NMP, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, GBL, α-acetyl-γ-butyrolactone, etc. are preferred. As poor solvents, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferred. When a good solvent and a poor solvent are used in combination, the ratio of the poor solvent to the good solvent may be adjusted depending on the solubility of the resin component in the resin composition. Each solvent may be used alone or in combination of two or more.

In the laser drilling process, it is preferable to use a green laser wavelength of 532 nm, since this makes it easier to achieve high throughput and minimize damage to the semiconductor device. The resin composition of this embodiment has an absorption wavelength of 532 nm, so a relief pattern can be suitably formed using a green laser.

[Step (4)]
In this step, the relief pattern obtained by the above development is heated to form a cured relief pattern, in which the component (A) is imidized to convert it into a cured relief pattern containing polyimide.

Heating methods include a variety of methods, such as using a hot plate, an oven, or a temperature-programmable oven. An example of heating conditions is a temperature of 200°C to 400°C and a time of 30 minutes to 5 hours. The gas in the atmosphere during heating may be air or an inert gas such as nitrogen or argon.

[Step (5)]
In this process, the film surface of the cured relief pattern can be irradiated with a laser. That is, the product specifications, lot number, and manufacturing date of the semiconductor device can be engraved on the surfaces of the resins constituting the passivation film, surface protection film, and interlayer insulating film, etc.

Laser processing using high energy density such as carbon dioxide laser, UV laser, green laser, etc. can be preferably used. In particular, the use of a green laser wavelength of 532 nm is preferable because it is easy to achieve high throughput and minimize damage to the semiconductor device. In order to be able to form the desired relief pattern during laser processing and to be able to engrave, it is required that the passivation film, surface protection film, interlayer insulating film, etc. have absorption at the laser wavelength.

The passivation layer, surface protection layer, and interlayer insulating film produced through the above steps (1) to (4) and, if necessary, step (5) can be produced as a multi-layer passivation layer, surface protection layer, and interlayer insulating film by repeating the steps multiple times. The photosensitive resin composition may be used in all repeated steps of the passivation layer, surface protection layer, and interlayer insulating film produced through the above steps, or may be used only in a specific repeated step. In a preferred embodiment, the photosensitive resin composition is used in the outermost passivation layer, surface protection layer, and interlayer insulating film produced through the repeated steps.

[Semiconductor device]
One aspect of the present embodiment is a semiconductor device having, as an insulating layer, a cured relief pattern obtained from the resin composition described above. The semiconductor device has, for example, a substrate that is a semiconductor element, and the cured relief pattern described above disposed on the substrate.

The semiconductor device can be manufactured, for example, by using a semiconductor element as a substrate and by a method that includes the above-mentioned method for manufacturing a cured relief pattern as part of the manufacturing process of the semiconductor device. The semiconductor device can be manufactured by forming the cured relief pattern formed by the above-mentioned method for manufacturing a cured relief pattern as, 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 protective film for a semiconductor device having a bump structure; and further combining the above-mentioned method for manufacturing a semiconductor device.

[Outline of configuration]
1A is a schematic cross-sectional view of a semiconductor device 1, FIG. 1B is an enlarged schematic view of a field a in FIG. 1, and FIG.
The semiconductor device 1 includes:
A semiconductor chip 2;
a sealing material 3 in contact with the semiconductor chip 2;
The semiconductor device further includes a rewiring layer 4 that is disposed on at least one surface side of the semiconductor chip 2 and the sealing material 3 and has an area larger than that of the semiconductor chip 2 in a plan view in the thickness direction.
The semiconductor device 1 is a Fan-Out type device, or further a Wafer Level Chip Size Package (WLCSP) type device.
Each component will be described below in order.

<Semiconductor chip>
The semiconductor chip 2 is made of a semiconductor such as silicon. A plurality of semiconductor chips 2 may be arranged, and for example, Fig. 1(a) illustrates a semiconductor device 1 in which two semiconductor chips 2 are arranged in parallel along the surface direction (direction perpendicular to the thickness direction). The plurality of semiconductor chips 2 and the respective components associated therewith may be the same or different.

In FIG. 1(a), the semiconductor chip 2 is shown in a cubic shape having one surface 2a, another surface 2b opposite to the one surface 2a, and four side surfaces 2c between the one surface 2a and the other surface 2b. The one surface 2a contacts the rewiring layer 4, the other surface 2b contacts the terminals 9 and the protective layer 8, and the four side surfaces 2c contact the sealing material 3.

<Protective Layer>
The protective layer 8 is disposed between the other surface 2b of the semiconductor chip 2 and the rewiring layer 4, and serves to protect the semiconductor chip 2 from physical impact. In Fig. 1(a) , a plurality of terminals 9 that ensure electrical continuity with the wiring 5 in the rewiring layer 4 are disposed on the other surface 2b, and the protective layer 8 is disposed on the other surface 2b side so as to fill in the spaces between these terminals 9. Assuming that the semiconductor chip 2 is viewed in a plan view in the thickness direction from the one surface 2a side (as viewed from the arrow A in Fig. 1 ), the protective layer 8 is hidden behind the semiconductor chip 2 and cannot be observed.

The protective layer 8 can be composed of at least one compound selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. However, the composition of the protective layer 8 is not limited to the above, and the protective layer 8 itself can be omitted.

<Sealing material>
The sealing material 3 is in contact with the four side surfaces 2c of the semiconductor chip 2, and in this embodiment, is also in contact with the protective layer 8 and the redistribution layer 4. The sealing material 3 is preferably in contact with the insulating layer 6. Wiring 5 penetrates the sealing material in the thickness direction, and this wiring 5 is electrically connected to the wiring 5 in the redistribution layer 4.

The sealing material 3 can be made of, for example, epoxy resin. However, the configuration of the sealing material 3 is not limited to this.

<Rewiring Layer>
The redistribution layer 4 includes an intermediate layer (e.g., wiring 5) electrically connected to the semiconductor chip 2, and an insulating layer 6 in contact with the intermediate layer. As can be understood from the size relationship between the area S1 of the redistribution layer 4 and the area S2 of the semiconductor chip 2 in Fig. 2, the redistribution layer 4 has a larger area than the semiconductor chip 2 when viewed in a plan view in the thickness direction (as viewed from the arrow A in Fig. 1(a)). Note that the redistribution layer 4 in this embodiment does not include a printed wiring board.

The redistribution layer 4 preferably has a multi-layer structure (e.g., 3 to 9 layers). In FIG. 1(b), a three-layer redistribution layer 4 is shown having a first insulating layer 6-1, a second insulating layer, and a third insulating layer 6-3 from the semiconductor chip 2 and sealing material 3 side. The third insulating layer 6-3 corresponds to the outermost layer, and this outermost layer is configured as region 6a. The first insulating layer 6-1 and the second insulating layer 6-2 are configured as the other region 6b. The number of layers of the redistribution layer 4 corresponds to the number of insulating layer formation steps described below.

Here, in the semiconductor device 1, the region 6a, and therefore the insulating layer 6-3, which is the outermost layer, is composed of a photosensitive resin composition, which is one aspect of this embodiment. When a predetermined marking (such as the product specifications, lot number, and date of manufacture of the semiconductor device) is applied to the insulating layer, which is the outermost layer, the marking has excellent visibility.

The wiring 5 (wires 5-1 and 5-2 in FIG. 1B) is made of a highly conductive material, and in this embodiment, copper is used. The thickness of the redistribution layer 4, including the wiring 5, is about 3 to 30 μm.

(First Redistribution Layer and Second Redistribution Layer)
The semiconductor device 1 includes two redistribution layers 4 that face each other via a semiconductor chip 2. One is a first redistribution layer 4A disposed on one surface 2a of the semiconductor chip 2, and the other is a second redistribution layer 4B disposed on the other surface 2b of the semiconductor chip 2 with a protective layer 8 interposed therebetween.
The first redistribution layer 4A and the second redistribution layer 4B each have a surface (first surface 4a) on the semiconductor chip 2 side and a surface (second surface 4b) opposite to the first surface 4a. The second surface 4b is suitable for providing various electronic components. A RAM (including a DRAM, indicated by the symbol D in FIG. 1) may be provided on the second surface 4b of the first redistribution layer 4A, and an external connection terminal 7 may be provided on the second surface 4b of the second redistribution layer 4B.

A sealing material 3 is disposed between the first redistribution layer 4A and the second redistribution layer 4B, and the wiring 5 penetrating the sealing material 3 is electrically connected to both the wiring 5 in the first redistribution layer 4A and the wiring 5 in the second redistribution layer 4B.

In this specification, the configuration that can be adopted for both the first redistribution layer 4A and the second redistribution layer 4B is also simply referred to as a "redistribution layer". However, the configuration described simply as a "redistribution layer" may be adopted only for the first redistribution layer 4A, only for the second redistribution layer 4B, or both for the first redistribution layer 4A and the second redistribution layer 4B. The first redistribution layer 4A and the second redistribution layer 4B, and the configurations associated therewith, may be different from each other. Just as the protective layer 8 is disposed between the second redistribution layer 4B and the semiconductor chip 2, a protective layer may also be disposed between the first redistribution layer 4A and the semiconductor chip 2. In FIG. 1(a), the region 6a is illustrated only for the first redistribution layer 4A, but only the second redistribution layer 4B, and also the second redistribution layer 4B, may have a configuration corresponding to the region 6a.

(Insulating layer)
The insulating layer 6 is disposed between the wirings 5 in the redistribution layer 4, and serves to prevent unintended conduction between the wirings 5. The insulating layer 6 can be made of a photosensitive resin composition which is one aspect of this embodiment. This makes it easier to improve the adhesion between the insulating layer 6 and the intermediate layer after irradiation with a green laser.

When the redistribution layer 4 is viewed in cross section, the insulating layer 6 may include an Nth insulating layer (N is an integer equal to or greater than 1) from the semiconductor chip 2 side. The composition, characteristics, film thickness, etc. of each insulating layer may be the same or different.

In the insulating layer 6, the layer made of the photosensitive resin composition, which is one aspect of this embodiment, may be a single layer or multiple layers. From the viewpoint of visibility of the marking applied by the green laser, the layer made of the photosensitive resin composition, which is one aspect of this embodiment, is preferably disposed on the second surface 4b side of the rewiring layer 4, in other words, on the outermost layer side.

The insulating layer 6 may have a layer (other layer) made of a resin composition different from the photosensitive resin composition which is one aspect of this embodiment. Here, for example, in FIG. 1(b), the first insulating layer 6-1 and the second insulating layer 6-2 are configured as the other layers.

<Method of Manufacturing Semiconductor Device>
The method for manufacturing the semiconductor device 1 includes the steps of:
A first step of preparing a semiconductor chip 2;
a second step of disposing a first redistribution layer 4A, which has an area larger than that of the semiconductor chip 2 in a plan view in the thickness direction and includes an intermediate layer (e.g., a wiring 5) electrically connected to the semiconductor chip 2 and an insulating layer 6 in contact with the intermediate layer, on one surface 2a of the semiconductor chip 2;
a third step of covering the semiconductor chip 2 with a sealing material 3 so that the other surface 2b of the semiconductor chip 2 is exposed;
a fourth step of disposing a second redistribution layer 4B, which has an area larger than that of the semiconductor chip 2 in a plan view in the thickness direction, and which includes an intermediate layer (e.g., a wiring 5) electrically connected to the semiconductor chip 2 and an insulating layer 6 in contact with the intermediate layer, on the other surface 2b side of the semiconductor chip 2;
In the second and fourth steps, the rewiring layer 4 may be formed and then the semiconductor chip 2 may be mounted on the rewiring layer 4, or the rewiring layer 4 may be formed on the semiconductor chip 2 as a base.

Here, in the second step, it is preferable to form the insulating layer 6 in the rewiring layer 4 using the photosensitive resin composition which is one aspect of this embodiment, and from the viewpoint of visibility of the printing made by the green laser, it is more preferable to form the insulating layer 6 which constitutes the outermost layer of the rewiring layer 4 using the photosensitive resin composition. The third step preferably includes a step of forming a protective layer 8 on the semiconductor chip 2 (protective layer forming step), and a step of covering the semiconductor chip 2 on which the protective layer 8 has been formed with an encapsulant 3 so that at least a part of the protective layer 8 is exposed (encapsulation structure forming step). The fourth step preferably includes a step of disposing the rewiring layer 4 on the protective layer 8 side (rewiring layer forming step).

The method for manufacturing the semiconductor device in this embodiment will be described with reference to FIG. 3. FIG. 3 shows an example of a manufacturing process for the semiconductor device 1 in this embodiment. In the following description, the photosensitive resin composition may be either positive or negative.

(1) First Step In Fig. 3A1, a wafer 10 that has been subjected to a previous process is prepared. A photosensitive resin composition (a photosensitive composition for forming a protective layer) is applied to the wafer 10, and a relief pattern is formed by exposure and development (protective layer formation step). In Fig. 3B1, the wafer 10 on which the relief pattern has been formed is diced to form a plurality of semiconductor chips 2. Thus, the semiconductor chips 2 are prepared (first step).

(2) Second Step In FIG. 3A2, a carrier C is prepared. The carrier C is made of, for example, glass. An adhesive layer C1 for temporarily fixing the semiconductor package may be formed on the carrier C. A photosensitive resin composition (a photosensitive composition for forming an insulating layer) is applied onto the adhesive layer C1, and a relief pattern is formed by exposure and development (relief pattern forming step). A relief pattern is formed through exposure and development of the photosensitive resin composition, and this is heated to form a cured relief pattern (insulating layer forming step). Furthermore, wiring is formed in a location where the cured relief pattern is not formed (wiring forming step). By repeating the insulating layer forming step and the wiring forming step, a multi-layer insulating layer is formed. As a result, a rewiring layer 4 (first rewiring layer 4A) having an area larger than the semiconductor chip 2 in a plan view in the thickness direction is arranged on one side of the semiconductor chip 2 (second step).

One embodiment of the second step will be described by taking the rewiring layer shown in FIG.
First, a non-permanent material pattern is formed using a predetermined non-permanent material on the pattern of the insulating layer (the third insulating layer 6-3 shown in FIG. 1(b)) on the adhesive layer C1. Then, wiring 5-2 is formed by plating or the like.
After removing the non-permanent material pattern, a photosensitive resin composition is applied onto the insulating layer 6-3 so as to cover the wiring 5-2. The applied photosensitive resin composition is exposed to light, developed, and cured to produce an insulating layer (the second insulating layer 6-2 shown in FIG. 1(b)) having a pattern in which the wiring 5-2 is exposed at the bottom of the pattern.
Thereafter, wiring 5-1 is formed between the patterns of insulating layer 6-2, and the above process is repeated to produce the rewiring layer shown in Fig. 1(b), which is one aspect of this embodiment. The non-permanent material pattern can be produced using a conventionally known photosensitive resin composition.

Here, the insulating layer 6 in contact with the adhesive layer C1 corresponds to the outermost layer of the first redistribution layer 4A, and this insulating layer 6 is composed of a photosensitive resin composition, which is one aspect of this embodiment. In the figure, the wiring exposed on the surface of the first redistribution layer 4A facing the semiconductor chip 2 is omitted from the illustration.

(3) Third step In FIG. 3C, the semiconductor chip 2 is attached to the first rewiring layer 4A at a predetermined interval so that the first rewiring layer 4A and the side of the semiconductor chip 2 on which the protective layer is not formed are in contact. Next, a metal pillar (wiring) having a height equivalent to the height of the semiconductor chip 2 is formed on the first rewiring layer 4A, and then a molding resin 12 is applied from the top of the semiconductor chip 2 to the first rewiring layer 4A, and molded and sealed as shown in FIG. 3D. The molding resin 12 is polished by a CMP process or the like to the extent that the protective layer 8 of the semiconductor chip 2 and the metal pillar (not shown) are exposed (FIG. 3E). As a result, the semiconductor chip 2 is covered with the sealing material 3 so that the other surface 2b of the semiconductor chip 2 is exposed (third step).

(4) Fourth step: After that, a photosensitive resin composition 13 is applied to the protective layer 8 side of the semiconductor chip (FIG. 3F), and the redistribution layer 4 (second redistribution layer 4B) is formed in the same manner as described above. As a result, the redistribution layer 4 (second redistribution layer 4B) having an area larger than that of the semiconductor chip 2 in a plan view in the thickness direction is disposed on the other surface 2b side of the semiconductor chip 2 (fourth step).

In FIG. 3G, dicing is performed between each semiconductor chip 2. After that, the adhesive layer C1 formed on the carrier C is peeled off. This allows a semiconductor device (semiconductor IC) 1 to be obtained as shown in FIG. 3H. In this embodiment, a plurality of fan-out type semiconductor devices 1 can be obtained by the manufacturing method shown in FIG. 3. Note that, before dicing between each semiconductor chip 2, a plurality of external connection terminals 7 corresponding to each semiconductor chip 2 may be provided on the rewiring layer 4.

Although the configuration of the semiconductor device 1 has been described above, the configuration is not limited to the above.
4 is a schematic cross-sectional view showing another embodiment of a semiconductor device. The illustrated semiconductor device 1A includes the first redistribution layer 4A and the second redistribution layer, the second redistribution layer 4B, and does not include the first redistribution layer. The sealing material 3 contacts not only the four side surfaces 2c of the semiconductor chip 2 but also the one surface 2a, that is, the sealing material 3 covers the surfaces of the semiconductor chip 2 except for the other surface 2b. In addition to the semiconductor device 1, such a semiconductor device 1A is also included in this embodiment.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. The physical properties of the resin compositions in the examples were measured and evaluated according to the following methods.

(1) UV transmittance of cured relief pattern The resin composition was applied onto a quartz plate by spin coating using a coater developer (D-Spin 60A type, manufactured by SOKUDO Corporation) to obtain a film of the resin composition. The film was dried (prebaked) at 110° C. for 240 seconds to obtain a prebaked film having a thickness of about 14 μm on the quartz plate. The average UV transmittance (a) of the prebaked film at wavelengths of 365 to 436 nm converted into a 10 μm film thickness was calculated using a UV-visible spectrophotometer (Shimadzu Corporation, UV-1800).

The prebaked film was heated (cured) in a nitrogen atmosphere at 230°C for 2 hours using a temperature-programmed curing furnace (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) to obtain a polyimide film (cured relief pattern) approximately 10 μm thick on the quartz plate. The UV transmittance (b) of the polyimide film at a wavelength of 532 nm converted to a 10 μm film thickness and the average UV transmittance (b') at wavelengths of 500 to 600 nm converted to a 10 μm film thickness were calculated using a UV-visible spectrophotometer (Shimadzu Corporation, UV-1800).

(2) Preparation of a cured relief pattern on Cu A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti film and a 400 nm thick Cu film in this order using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Corporation). Next, a negative photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO Co., Ltd.), and prebaked on a hot plate at 110° C. for 240 seconds to form a coating film with a thickness of about 14 μm. This coating film was irradiated with energy of 1500 mJ/cm ² using a test pattern mask with Prisma GHI (manufactured by Ultratech Co., Ltd.). Next, this coating film was spray-developed with a coater developer (D-Spin 60A type, manufactured by SOKUDO Co., Ltd.) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The wafer on which the relief pattern was formed on Cu was heated (cured) in a temperature-rising programmable curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) at 230° C. for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern made of resin with a thickness of about 10 μm on Cu.

(3) Resolution of the cured relief pattern on Cu The cured relief pattern obtained by the above method was observed under an optical microscope to determine the size of the minimum opening pattern. At this time, if the area of the opening of the obtained pattern was 1/2 or more of the corresponding pattern mask opening area, it was considered to be resolved, and the length of the mask opening side corresponding to the resolved opening having the smallest area was taken as the resolution. Resolutions less than 20 μm were rated as "excellent," those between 20 μm and 100 μm were rated as "good," and those 100 μm or more were rated as "poor."

(4) Visibility of mark engraved by green laser A mark was engraved on the polyimide film on the quartz plate obtained by the above method by irradiating a laser at an intensity of 2.4 W using a green laser device (MD-T1000W, manufactured by Keyence Corporation). When the letter "A" was printed in a large size of 0.5 mm x 0.5 mm and a small size of 0.1 mm x 0.1 mm, the case where the letter was distinguishable in both the large and small sizes was rated "excellent", the case where the letter in the small size was crushed and could not be distinguished, but the letter in the large size was distinguishable was rated "good", and the case where the letter in both the large size and the small size was crushed and could not be distinguished was rated "unacceptable".

<Production Example 1> (Component (A): Polymer A-1)
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of GBL were added, and 79.1 g of pyridine was added while stirring at room temperature to cause a reaction. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and then left to stand for a further 16 hours to obtain a reaction mixture.

Next, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of GBL and a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of GBL were prepared. The above solution was added to the reaction mixture while stirring under ice cooling over 40 minutes, and then the above suspension was added while stirring over 60 minutes. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of GBL was added to obtain a mixed solution. The precipitate formed in the mixed solution was removed by filtration to obtain a reaction solution.

The resulting reaction solution was added to 3 L of ethanol to produce a precipitate containing a crude polymer. The produced crude polymer was filtered and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the precipitate was filtered and then vacuum dried to obtain powdered polymer A-1. The weight average molecular weight (Mw) of polymer A-1 was 20,000.

<Production Example 2> (Component (A): Polymer A-2)
Polymer A-2 was obtained in the same manner as in Production Example 1, except that 147.1 g of 3,3′,4′-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example 1. The weight average molecular weight (Mw) of Polymer A-2 was 22,000.

<Production Example 3> (Component (A): Polymer A-3)
Polymer A-3 was obtained in the same manner as in Production Example 1, except that 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (190.7 g) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example 1. The weight average molecular weight (Mw) of Polymer A-3 was 21,000.

<Production Example 4> (Component (A): Polymer A-4)
Polymer A-4 was obtained in the same manner as in Production Example 1, except that 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) (98.6 g) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example 1. The weight average molecular weight (Mw) of Polymer A-4 was 21,000.

<Production Example 5> (Component (A): Polymer A-5)
Polymer A-5 was obtained in the same manner as in Production Example 1, except that p-phenylenediamine (p-PD) (50.2 g) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example 1. The weight average molecular weight (Mw) of Polymer A-5 was 21,000.

<Production Example 6> (Component (A): Polymer A-6)
Polymer A-6 was obtained in the same manner as in Production Example 1, except that 160.1 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example 1. The weight average molecular weight (Mw) of Polymer A-6 was 21,000.

<Production Example 7> (Component (A): Polymer A-7)
Polymer A-7 was obtained in the same manner as in Production Example 1, except that 54.5 g of pyromellitic anhydride (PMDA) and 77.6 g of 4,4'-oxydiphthalic dianhydride (ODPA) were used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA), and 98.6 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE). The weight average molecular weight (Mw) of Polymer A-7 was 21,000.

<Production Example 8> (Component (A): Polymer A-8)
Polymer A-8 was obtained in the same manner as in Production Example 1, except that 77.6 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 73.6 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The weight average molecular weight (Mw) of Polymer A-8 was 20,000.

Example 1
As the component (A), polymer A-1 (100 parts by mass) and
As the component (B), B-1 (3.0 parts by mass)
As the component (C), C-1 (4.0 parts by mass)
As other components, tetraethylene glycol dimethacrylate (8 parts by mass) and N-phenyldiethanolamine (4 parts by mass) were added.
Component (D) was dissolved in D-1 (a mixture of GBL and DMSO in a weight ratio of 80:20) to obtain a negative photosensitive resin composition. The viscosity of the resin composition was about 3.5 Pa·s. The composition was evaluated according to the above-mentioned method. The results are shown in Table 1.
In the table, the blending amount of component (B) is shown in parts by mass based on 100 parts by mass of component (A).

<Examples 2 to 35 and Comparative Examples 1 to 13>
Negative-type photosensitive resin compositions of Examples 2 to 38 and Comparative Examples 1 to 3 were obtained in the same manner as in Example 1, except that the raw materials shown in Table 1 were mixed. The compositions were evaluated according to the methods described above. The results are shown in Table 1.

Each number in the table below represents the following compound.
Component (A): Polyimide precursor A-1/A-2: A mixture of 50 parts by mass each of A-1 and A-2 A-1/A-5: A mixture of 50 parts by mass each of A-1 and A-5

Component (B): Dye
B-1: Solvent Black 7
(C.I. Solvent Black 7)
B-2: Disperse Violet 26
(C.I. Disperse Violet 26)
B-3: Solvent Red 24
(C.I. Solvent Red 24)
B-4: Solvent Black 3
(C.I. Solvent Black 3)
B-5: Solvent Green 3
(C.I. Solvent Green 3)

Component (C): Photopolymerization initiator
C-1: Photopolymerization initiator represented by the above formula
C-2: Photopolymerization initiator represented by formula (C4)
C-3: Photopolymerization initiator represented by formula (C6)

Component (D): Solvent D-2: N-methylpyrrolidone D-3: A mixture of N-methylpyrrolidone and ethyl lactate in a weight ratio of 80:20 D-4: 3-methoxy-N,N-dimethylpropanamide D-5: A mixture of 3-methoxy-N,N-dimethylpropanamide and DMSO in a weight ratio of 80:20

As shown in the table, the resin composition of the example can provide a prebaked film having a specific average UV transmittance (a) and a polyimide film having a specific average UV transmittance (b'). It has been confirmed that the polyimide film (cured relief pattern) exhibits high resolution and has good visibility of the green laser mark.

In addition, the resin composition of the example was used to successfully fabricate an insulating layer for the semiconductor device shown in FIG. 1, and thus the semiconductor device shown in FIG. 1 could be successfully fabricated.

By using the resin composition according to the present invention, a cured relief pattern with high resolution can be obtained, and marks can be engraved using a green laser marker. The present invention can be suitably used in the field of photosensitive materials that are useful for manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

1, 1A Semiconductor device 2 Semiconductor chip 2a One side 2b Other side 2c Four side surfaces 3 Sealing material 4 Rewiring layer 4A First rewiring layer 4B Second rewiring layer 4a First surface 4b Second surface 5, 5-1, 5-2 Wiring 6 Insulating layer 6a Region 6b Other region 6-1 First insulating layer 6-2 Second insulating layer 6-3 Third insulating layer (outermost layer)
7 External connection terminal 8 Protective layer 9 Terminal 10 Wafer 11 Support 12 Molding resin 13 Photosensitive resin composition C Carrier C1 Adhesive layer D DRAM

Claims (12)

Ingredients below:
(A) The following general formula (A1):

A polyimide precursor represented by the formula: {wherein X is a tetravalent organic group, Y is a divalent organic group, and R ₁ and R ₂ are each independently a hydrogen atom, a polymerizable group, or a saturated aliphatic group having 1 to 4 carbon atoms, with the proviso that R ₁ and R ₂ are not both hydrogen atoms.}
(B) dye;
(C) a photoinitiator; and (D) a solvent;
A resin composition comprising:
A prebaked film obtained by drying a coating film of the resin composition at 110° C. for 240 seconds has an average UV transmittance (a) of 15% or more at a wavelength of 365 to 436 nm in a 10 μm film thickness; and
The prebaked film is heated at 230° C. for 2 hours in a nitrogen atmosphere to obtain a polyimide film, which has an average UV transmittance (b') of 40% or less at a wavelength of 500 to 600 nm in terms of a 10 μm film thickness. The resin composition according to claim 1, wherein the polyimide film obtained by heating the prebaked film at 230°C for 2 hours in a nitrogen atmosphere has a UV transmittance (b) of 40% or less at a wavelength of 532 nm in a 10 μm film thickness. In the general formula (A1), R ₁ and R ₂ are represented by the following general formula (R _h ):

The resin composition according to claim 1, comprising a structure represented by the following formula: {wherein R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p represents an integer of 2 to 10.}. In the general formula (A1), the X is represented by the following formula (2):

The resin composition according to claim 1 , comprising a structure represented by: In the general formula (A1), the Y is represented by the following formula (8):
And/or the following formula (9):
The resin composition according to claim 1 , comprising a structure represented by: The resin composition according to claim 1, wherein the content of the (B) component is 0.5 to 30 parts by mass per 100 parts by mass of the (A) component. The resin composition according to claim 1, wherein the content of the (C) component is 0.1 to 100 parts by mass per 100 parts by mass of the (A) component. The resin composition according to claim 1, wherein the component (B) contains at least one of an azine dye derivative and an anthracene dye derivative. The resin composition according to claim 1, wherein the component (D) is at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), dimethylsulfoxide (DMSO), 3-methoxy-N,N-dimethylpropanamide, and ethyl lactate. (1) A step of forming a resin composition film by applying the resin composition according to any one of claims 1 to 9 to a substrate;
(2) forming a relief pattern by exposing and developing the resin composition film or by irradiating the resin composition film with a laser;
(3) heating the relief pattern to form a hardened relief pattern;
The method for producing a cured relief pattern comprising: The method for producing a cured relief pattern according to claim 10, wherein in step (1), the resin composition is applied to the substrate made of copper or a copper alloy. A semiconductor device having, as an insulating layer, a cured relief pattern obtained from the resin composition according to any one of claims 1 to 9.

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