JP2021167926A - Photosensitive resin composition, cured product including the same, method for producing patterned cured product and method for producing electronic component - Google Patents

Abstract

To provide a photosensitive resin composition that is be cured at a low temperature of 200°C or lower to give a cured product that can have sufficient adhesion to a copper wire even after left standing at 175°C for 500 hours and offers excellent adhesion and migration resistance, a cured product including the same, a method for producing a patterned cured product, and a method for producing an electronic component.SOLUTION: A photosensitive resin composition contains (A) thermoplastic resin, (B) a compound containing a hydroxy group and a triazole skeleton, and (C) photoinitiator. The photosensitive resin composition preferably further contains (D) a polymerizable monomer having an aliphatic cyclic skeleton and (E) a thermal polymerization initiator. A method for producing a patterned cured product has the steps of: applying the photosensitive resin composition to a substrate and drying it to form a photosensitive resin film; subjecting the photosensitive resin film to pattern exposure to form a resin film; developing the pattern-exposed resin film with an organic solvent to form a patterned resin film; and heating the patterned resin film.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive resin composition, a cured product using the photosensitive resin composition, a method for producing a patterned cured product, and a method for producing an electronic component.

Conventionally, polyimide or polybenzoxazole having excellent heat resistance, electrical properties, mechanical properties, etc. has been used as a surface protective film and an interlayer insulating film of a semiconductor element. In recent years, photosensitive resin compositions in which photosensitive properties have been imparted to these resins themselves have been used, and by using this, the manufacturing process of a cured pattern can be simplified and complicated manufacturing processes can be shortened (for example, Patent Documents). 1).
By the way, in recent years, the miniaturization of transistors, which has supported the high performance of computers, has reached the limit of the scaling law, and a laminated device structure in which semiconductor elements are three-dimensionally laminated for further high performance and high speed. Is attracting attention (see, for example, Non-Patent Document 1).
Among the laminated device structures, the multi-die fanout wafer level package (Multi-die Fanout Wafer Level Packaging) is a package manufactured by collectively encapsulating a plurality of dies in one package, and has been conventionally proposed. It is attracting a lot of attention because it can be expected to have lower cost and higher performance than the fan-out wafer level package (manufactured by sealing one die in one package).
In the production of multi-die fan-out wafer level packages, low temperature curability is strongly required from the viewpoint of protecting high-performance dies, protecting encapsulants with low heat resistance, and improving yield (for example, patent documents). 2).
Further, the demand for long-term reliability of the fan-out package is increasing (for example, Patent Document 3). The long-term reliability here is the adhesion between the metal rewiring layer and the polyimide layer, and is a test in which the metal rewiring layer and the polyimide layer are kept at a high temperature for 500 hours under the condition of 175 ° C.

Japanese Unexamined Patent Publication No. 2009-265520 International Publication No. 2008/111470 Japanese Patent No. 6419383

"Semiconductor Technology Yearbook 2013 Packaging / Mounting", Nikkei BP, p. 41-50

An object of the present invention is to ensure adhesion between the copper wiring and the cured product of the photosensitive resin composition even after low-temperature curing at 200 ° C. or lower and after leaving at a high temperature of 175 ° C. for 500 hours. It is an object of the present invention to provide a photosensitive resin composition capable of forming a cured product having excellent migration resistance, a method for producing a cured product and a patterned cured product using the same, and a method for producing an electronic component.

According to the present invention, the following photosensitive resin composition, a cured product using the same, a manufacturing method, and the like are provided.
[1] A photosensitive resin composition containing (A) a thermoplastic resin, (B) a compound containing a hydroxyl group and a triazole skeleton, and (C) a photoinitiator.
[2] The photosensitive resin composition according to the above [1], wherein the compound containing the hydroxyl group of the component (B) and the triazole skeleton is represented by the following general formula (1).

（一般式（１）中、Ｒ_１〜Ｒ_４は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基である。）
［３］ 前記（Ｂ）成分の水酸基とトリアゾール骨格を含有する化合物が下記一般式（２）で表される上記［１］又は［２］に記載の感光性樹脂組成物。

(In the general formula (1), R _{1 to} R ₄ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms.)
[3] The photosensitive resin composition according to the above [1] or [2], wherein the compound containing the hydroxyl group of the component (B) and the triazole skeleton is represented by the following general formula (2).

[4] The thermoplastic resin of the component (A) contains a polyimide precursor having a structural unit represented by the following general formula (3) or a polyimide having a structural unit represented by the following general formula (4). The photosensitive resin composition according to any one of [1] to [3].

（一般式（３）及び一般式（４）中、Ｘ_１は４価の芳香族基であって、−ＣＯＯＲ_５基と−ＣＯＮＨ−基とは互いにオルト位置にあり、−ＣＯＯＲ_６基と−ＣＯ−基とは互いにオルト位置にある。Ｙ_１は２価の芳香族基である。Ｒ_５及びＲ_６は、それぞれ独立に、水素原子、下記一般式（５）で表される基、又は炭素数１〜４の脂肪族炭化水素基であり、Ｒ_５、Ｒ_６の少なくとも一方が前記一般式（５）で表される基である。）

(In the general formula (3) and the general formula (4), X ₁ is a tetravalent aromatic group, and the -COOR ₅ group and the -CONH- group are in ortho positions with each other, and the -COOR ₆ group and- The CO- group is in the ortho position with each other. Y ₁ is a divalent aromatic group. R ₅ and R ₆ are independently hydrogen atoms, groups represented by the following general formula (5), or groups represented by the following general formula (5). It is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and _{at least one of R 5} and R ₆ is a group represented by the general formula (5).

（一般式（５）中、Ｒ_７〜Ｒ_９はそれぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基であり、ｍは１〜１０の整数である。）
［５］ 更に、（Ｄ）脂肪族環状骨格を有する重合性モノマを含む上記［１］〜［４］のいずれか一項に記載の感光性樹脂組成物。
［６］ 更に、（Ｅ）熱重合開始剤を含む上記［１］〜［５］のいずれか一項に記載の感光性樹脂組成物。

(In the general formula (5), R _{7 to} R ₉ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10.)
[5] The photosensitive resin composition according to any one of the above [1] to [4], further comprising (D) a polymerizable monoma having an aliphatic cyclic skeleton.
[6] The photosensitive resin composition according to any one of the above [1] to [5], further comprising (E) a thermal polymerization initiator.

[7] A step of applying the photosensitive resin composition according to any one of the above [1] to [6] onto a substrate and drying to form a photosensitive resin film, and a pattern of the photosensitive resin film. It includes a step of exposing to obtain a resin film, a step of developing the resin film after pattern exposure with an organic solvent to obtain a pattern resin film, and a step of heat-treating the pattern resin film. , A method for producing a cured pattern.
[8] The method for producing a pattern cured product according to the above [7], wherein the temperature of the heat treatment step is 200 ° C. or lower.
[9] A cured product obtained by curing the photosensitive resin composition according to any one of the above [1] to [6].
[10] The cured product according to the above [9], wherein the cured product is a pattern cured product.
[11] Production of a pattern cured product using the cured product produced by the method for producing a pattern cured product according to the above [7] or [8] as any of an interlayer insulating film, a cover coat layer, and a surface protective film. Method.
[12] A method for manufacturing an electronic component, which comprises a step of manufacturing a pattern cured product used for any of the interlayer insulating film, the cover coat layer, and the surface protective film according to the above [11].

According to the present invention, even if the temperature is cured at a low temperature of 200 ° C. or lower, the adhesion between the copper wiring and the cured product of the photosensitive resin composition can be ensured even after being left at a high temperature of 175 ° C. for 500 hours, and the adhesiveness and adhesion can be ensured. Provided are a photosensitive resin composition capable of forming a cured product having excellent migration resistance, a method for producing a patterned cured product applied to an interlayer insulating layer, a cover coat layer, a surface protective film, etc. using the photosensitive resin composition, a cured product, and electronic parts. can.

It is a manufacturing process diagram of the electronic component which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the photosensitive resin composition of the present invention, a method for producing a pattern cured product using the same, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component will be described in detail. The present invention is not limited to the following embodiments.
As used herein, the term "A or B" may include either A or B, and may include both. Further, in the present specification, the term "process" is used not only as an independent process but also as a term as long as the desired action of the process is achieved even when it cannot be clearly distinguished from other processes. included.
The numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. Further, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means quantity. Further, the exemplary materials may be used alone or in combination of two or more unless otherwise specified.
As used herein, the term "(meth) acrylic group" means "acrylic group" and "methacrylic group".

The photosensitive resin composition of the present invention is (A) a thermoplastic resin (hereinafter, also referred to as “(A) component”) (B) a compound containing a hydroxyl group and a triazole skeleton (hereinafter, also referred to as “(B) component”). ), (C) Photoinitiator (hereinafter, also referred to as "(C) component") is contained.
As a result, even if the temperature is cured at a low temperature of 200 ° C. or lower, the adhesion between the copper wiring and the cured product of the photosensitive resin composition can be ensured even after being left at a high temperature of 175 ° C. for 500 hours. An excellent cured product can be formed.
In the present specification, the (A) thermoplastic resin refers to a compound having a glass transition point (Tg) or a melting point (Tm), and the main skeleton is not limited and may have a reactive substituent. Define.
Further, as an arbitrary effect, a cured product having excellent chemical resistance and a high residual film ratio after curing can be formed.
The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

(Component (A): Thermoplastic resin)
The component (A) preferably contains a polyimide precursor having a structural unit represented by the following general formula (3) and the following general formula (4) and a ring-closed polyimide. As a result, the i-ray transmittance is high, and a good cured product can be formed even when cured at a low temperature of 200 ° C. or lower.
The content of the structural unit represented by the general formula (3) is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% or more, based on all the structural units of the component (A). It is more preferably mol% or more. The upper limit is not particularly limited, and may be 100 mol%.

（一般式（３）中、Ｘ_１は４価の芳香族基であって、−ＣＯＯＲ_５基と−ＣＯＮＨ−基とは互いにオルト位置にあり、−ＣＯＯＲ_６基と−ＣＯ−基とは互いにオルト位置にある。Ｙ_１は２価の芳香族基である。Ｒ_５及びＲ_６は、それぞれ独立に、水素原子、下記一般式（５）で表される基、又は炭素数１〜４の脂肪族炭化水素基であり、Ｒ_５、Ｒ_６の少なくとも一方が前記一般式（５）で表される基である。）

(In the general formula (3), X ₁ is a tetravalent aromatic group, the -COOR ₅ group and the -CONH- group are in ortho positions with each other, and the -COOR ₆ group and the -CO- group are mutually. At the ortho position, Y ₁ is a divalent aromatic group. R ₅ and R ₆ are each independently a hydrogen atom, a group represented by the following general formula (5), or a group having 1 to 4 carbon atoms. It is an aliphatic hydrocarbon group, and _{at least one of R 5} and R ₆ is a group represented by the general formula (5).)

（一般式（５）中、Ｒ_７〜_９はそれぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基であり、ｍは１〜１０の整数である。）
一般式（３）中のＸ_１の４価の芳香族基は、４価の芳香族炭化水素基でもよく、４価の芳香族複素環式基でもよい。４価の芳香族炭化水素基が好ましい。
一般式（３）中のＸ_１の４価の芳香族炭化水素基としては、例えば以下の一般式（６）の基が挙げられるが、これらに限定されるものではない。

(In the general formula (5), R ₇ to ₉ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10.)
Tetravalent aromatic groups X ₁ in the general formula (3) may be a tetravalent aromatic hydrocarbon group or a tetravalent aromatic heterocyclic group. A tetravalent aromatic hydrocarbon group is preferred.
The tetravalent aromatic hydrocarbon group of X ₁ in general formula (3), for example, groups of the following general formula (6) include, but are not limited thereto.

一般式（６）中、Ｘ及びＹは、それぞれ独立に、各々が結合するベンゼン環と共役しない２価の基又は単結合を示す。Ｚはエーテル基（−Ｏ−）又はスルフィド基（−Ｓ−）であり、エーテル基（−Ｏ−）が好ましい。
一般式（６）においてＸ及びＹの、各々が結合するベンゼン環と共役しない２価の基は、−Ｏ−、−Ｓ−、メチレン基、ビス（トリフルオロメチル）メチレン基、又はジフルオロメチレン基であることが好ましく、−Ｏ−であることがより好ましい。
一般式（３）中のＹ_１の２価の芳香族基は、２価の芳香族炭化水素基でもよく、２価の芳香族複素環式基でもよい。２価の芳香族炭化水素基が好ましい。
一般式（３）中のＹ_１の２価の芳香族炭化水素基としては、例えば、以下の一般式（７）の基が挙げられるが、これに限定されるものではない。

In the general formula (6), X and Y each independently represent a divalent group or a single bond that is not conjugate with the benzene ring to which they are bonded. Z is an ether group (-O-) or a sulfide group (-S-), and an ether group (-O-) is preferable.
In the general formula (6), the divalent groups of X and Y that are not conjugated to the benzene ring to which they are bonded are -O-, -S-, methylene group, bis (trifluoromethyl) methylene group, or difluoromethylene group. Is preferable, and —O— is more preferable.
Divalent aromatic group for Y ₁ in general formula (3) may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. A divalent aromatic hydrocarbon group is preferred.
Examples of the divalent aromatic hydrocarbon group for Y ₁ in general formula (3), for example, there may be mentioned groups of the following general formula (7), but is not limited thereto.

（一般式（７）中、Ｒ_１０〜Ｒ_１７は、それぞれ独立に水素原子、１価の脂肪族炭化水素基又はハロゲン原子を有する１価の有機基である。）
一般式（７）のＲ_１０〜Ｒ_１７の１価の脂肪族炭化水素基（好ましくは炭素数１〜１０、より好ましくは炭素数１〜６）としては、メチル基などが挙げられる。例えば、Ｒ_１０及びＲ_１３〜Ｒ_１７が水素原子であり、Ｒ_１１、Ｒ_１２が１価の脂肪族炭化水素基であってもよい。
一般式（７）中のＲ_１０〜Ｒ_１７のハロゲン原子（好ましくはフッ素原子）を有する１価の有機基は、ハロゲン原子を有する１価の脂肪族炭化水素基（好ましくは炭素数１〜１０、より好ましくは炭素数１〜６）が好ましく、トリフルオロメチル基などが挙げられる。
一般式（３）中のＲ_５及びＲ_６の炭素数１〜４（好ましくは１又は２）の脂肪族炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、２−プロピル基、ｎ−ブチル基などが挙げられる。
一般式（３）中のＲ_５及びＲ_６の少なくとも一方が、一般式（５）で表される基であり、ともに一般式（５）で表される基であることが好ましい。
一般式（５）中のＲ_７〜Ｒ_９の炭素数１〜３（好ましくは１又は２）の脂肪族炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、２−プロピル基などが挙げられ、メチル基が好ましい。
一般式（３）で表される構造単位を有するポリイミド前駆体は、例えば下記一般式（８）で表されるテトラカルボン酸二無水物と、下記一般式（９）で表されるジアミノ化合物とを、Ｎ−メチル−２−ピロリドンなどの有機溶媒中にて反応させポリアミド酸を得て、下記一般式（１０）で表される化合物を加え、有機溶媒中で反応させ部分的にエステル基を導入することで得られる。

(In the general formula (7), R _{10 to} R ₁₇ are monovalent organic groups each independently having a hydrogen atom, a monovalent aliphatic hydrocarbon group or a halogen atom.)
Examples of the monovalent aliphatic hydrocarbon group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms _{) of R 10 to} R ₁₇ of the general formula (7) include a methyl group and the like. For example, R ₁₀ and R _{13 to} R ₁₇ may be hydrogen atoms, and R ₁₁ and R ₁₂ may be monovalent aliphatic hydrocarbon groups.
_{The monovalent organic group having a halogen atom (preferably a fluorine atom) of R 10 to} R _{17 in} the general formula (7) is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms). , More preferably 1 to 6) carbon atoms, and examples thereof include a trifluoromethyl group.
Examples of the aliphatic hydrocarbon radical of the general formula (3) _{R 5} and 1 to 4 carbon atoms _{R 6} in (preferably 1 or 2), methyl group, ethyl group, n- propyl group, 2-propyl, Examples thereof include an n-butyl group.
It is preferable that at least one of R ₅ and R _{6 in} the general formula (3) is a group represented by the general formula (5), and both are groups represented by the general formula (5).
_{Examples of the aliphatic hydrocarbon group having 1 to 3 (preferably 1 or 2) carbon atoms of R 7 to} R _{9 in} the general formula (5) include a methyl group, an ethyl group, an n-propyl group and a 2-propyl group. However, a methyl group is preferable.
The polyimide precursor having the structural unit represented by the general formula (3) includes, for example, a tetracarboxylic acid dianhydride represented by the following general formula (8) and a diamino compound represented by the following general formula (9). Is reacted in an organic solvent such as N-methyl-2-pyrrolidone to obtain a polyamic acid, a compound represented by the following general formula (10) is added, and the reaction is carried out in an organic solvent to partially form an ester group. Obtained by introducing.

（一般式（８）中の、Ｘ_１は一般式（３）のＸ_１に対応する基である。一般式（９）中の、Ｙ_１は一般式（３）で定義したとおりである。一般式（１０）中の、Ｒは上述の一般式（３）で表される基のＲ_５、Ｒ_６に相当する基である。）
一般式（８）で表されるテトラカルボン酸二無水物及び一般式（９）で表されるジアミノ化合物は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
（Ａ）成分は、一般式（３）で表される構造単位以外の構造単位を有してもよい。
一般式（３）で表される構造単位以外の構造単位としては、一般式（１１）で表される構造単位などが挙げられる。

(General formula in (8), _{X 1} is a group corresponding to _{X 1} in the general formula (3). General Formula (9) in the, _{Y 1} is as defined in formula (3). In the general formula (10), R is a group corresponding to _{R 5} and R _{6 of the groups represented by the above general formula (3).)}
The tetracarboxylic dianhydride represented by the general formula (8) and the diamino compound represented by the general formula (9) may be used alone or in combination of two or more.
The component (A) may have a structural unit other than the structural unit represented by the general formula (3).
Examples of the structural unit other than the structural unit represented by the general formula (3) include the structural unit represented by the general formula (11).

一般式（１１）中、Ｘ_２は４価の芳香族基であって、−ＣＯＯＲ_５１基と−ＣＯＮＨ−基とは互いにオルト位置にあり、−ＣＯＯＲ_５２基と−ＣＯ−基とは互いにオルト位置にある。Ｙ_２は２価の芳香族基である。Ｒ_５１及びＲ_５２は、それぞれ独立に、水素原子又は炭素数１〜４の脂肪族炭化水素基である。）
一般式（１１）のＸ_２の４価の芳香族基は、一般式（３）中のＸ_１の４価の芳香族基と同様のものが挙げられる。
一般式（１１）中のＲ_５１及びＲ_５２の炭素数１〜４の脂肪族炭化水素基は、一般式（３）中のＲ_５及びＲ_６の炭素数１〜４の脂肪族炭化水素基と同様のものが挙げられる。
一般式（３）で表される構造単位以外の構造単位は、１種単独で用いてもよく、２種以上を組み合わせてもよい。
一般式（３）で表される構造単位以外の構造単位の含有量は、（Ａ）成分の全構成単位に対して、５０モル％未満であることが好ましい。
（Ａ）成分において、全カルボキシ基及び全カルボキシエステル基に対して、一般式（５）で表される基でエステル化されたカルボキシ基の割合が、５０モル％以上であることが好ましく、６０〜１００モル％がより好ましく、７０〜９０モル％が更に好ましい。
（Ａ）成分の分子量に特に制限はないが、数平均分子量で１０，０００〜２００，０００であることが好ましい。
数平均分子量は、例えばゲルパーミエーションクロマトグラフィーによって測定することができ、標準ポリスチレン検量線を用いて換算することによって求めることができる。

In the general formula (11), X ₂ is a tetravalent aromatic group, the -COOR ₅₁ group and the -CONH- group are in ortho positions with each other, and the -COOR ₅₂ group and the -CO- group are ortho with each other. In position. Y ₂ is a divalent aromatic group. R ₅₁ and R ₅₂ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 4 carbon atoms. )
_{Examples of the X 2} tetravalent aromatic group of the general formula (11) include those similar to the _{X 1} tetravalent aromatic group of the general formula (3).
The aliphatic hydrocarbon groups having 1 to 4 carbon atoms _{of R 51} and R _{52 in} the general formula (11) are the aliphatic hydrocarbon groups having 1 to 4 carbon atoms in _{R 5} and R _{6 in the general formula (3).} The same can be mentioned.
As the structural unit other than the structural unit represented by the general formula (3), one type may be used alone, or two or more types may be combined.
The content of the structural unit other than the structural unit represented by the general formula (3) is preferably less than 50 mol% with respect to all the structural units of the component (A).
In the component (A), the ratio of the carboxy group esterified with the group represented by the general formula (5) to the total carboxy group and the total carboxy ester group is preferably 50 mol% or more, preferably 60. ~ 100 mol% is more preferable, and 70 to 90 mol% is further preferable.
The molecular weight of the component (A) is not particularly limited, but the number average molecular weight is preferably 10,000 to 200,000.
The number average molecular weight can be measured, for example, by gel permeation chromatography and can be determined by conversion using a standard polystyrene calibration curve.

(Component (B): Compound containing hydroxyl group and triazole skeleton)
The photosensitive resin composition of the present invention preferably contains a compound (B) containing a hydroxyl group and a triazole skeleton, and preferably contains a component (B) represented by the following general formula (1). As a result, even if the resin is cured at 200 ° C. or lower, the adhesion between the copper wiring and the cured product layer of the photosensitive resin composition can be ensured even after being left at a high temperature of 175 ° C. for 500 hours.
The compound containing the hydroxyl group of the component (B) and the triazole skeleton preferably has a first-class hydroxyl group with the azole skeleton in that oxidation at the interface between the copper wiring and the resin can be prevented.

（一般式（１）中、Ｒ_１〜Ｒ_４は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基である。）
樹脂の酸化防止効果を高めるため、水酸基は２つ含むことが好ましい。
これにより、銅と樹脂の密着性向上に加え、銅及び樹脂の酸化を抑制する効果を新規に付与することができる。
（Ｂ）成分は、下記一般式（２）で表される化合物を含むことができる。

(In the general formula (1), R _{1 to} R ₄ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms.)
In order to enhance the antioxidant effect of the resin, it is preferable to contain two hydroxyl groups.
As a result, in addition to improving the adhesion between the copper and the resin, it is possible to newly impart the effect of suppressing the oxidation of the copper and the resin.
The component (B) can include a compound represented by the following general formula (2).

（Ｂ）成分は、１種単独で用いてもよく、２種以上を組み合わせてもよい。
（Ｂ）成分の含有量は、（Ａ）成分１００質量部に対して、０．１〜２０質量部が好ましい。より好ましくは０．３〜１０質量部、更に好ましくは０．５〜５質量部である。
上記範囲内である場合、２００℃以下の硬化においても樹脂の硬化度を保ちつつ、銅と樹脂の密着性と酸化防止効果を兼ね備えられる。

The component (B) may be used alone or in combination of two or more.
The content of the component (B) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably 0.3 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass.
When it is within the above range, the degree of curing of the resin is maintained even when the temperature is 200 ° C. or lower, and the adhesion between the copper and the resin and the antioxidant effect can be obtained.

(Component (C): photoinitiator)
The present invention contains (C) a photoinitiator.
Examples of the component (C) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone, 2,2'-diethoxyacetophenone, and 2-. Acetphenone derivatives such as hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethylketal, benzyl-β-methoxy Benzyl derivatives such as ethyl acetal, benzoins, benzoin derivatives such as benzoin methyl ether, and 1-phenyl-1,2-butandion-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-Diphenylpropanthrion-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropantrion-2- (o-benzoyl) oxime, etanone, 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), oxime esters such as compounds represented by the following formula (12) are preferable, but are limited thereto. It is not something that is done.

特に高感度の点で、オキシムエステル類が好ましい。
（Ｃ）成分は、１種単独で用いてもよく、２種以上を組み合わせてもよい。
（Ｃ）成分の含有量は、（Ａ）成分１００質量部に対して、０．１〜２０質量部であることが好ましく、より好ましくは０．１〜１０質量部であり、更に好ましくは０．１〜５質量部である。
上記範囲内の場合、光架橋が厚膜方向で均一となりやすく、実質的なレリーフパターンを得やすくなる。

Oxime esters are particularly preferable in terms of high sensitivity.
The component (C) may be used alone or in combination of two or more.
The content of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0 with respect to 100 parts by mass of the component (A). .1 to 5 parts by mass.
Within the above range, the photocrosslinking tends to be uniform in the thick film direction, and a substantial relief pattern can be easily obtained.

((D) Polymerizable monoma having an aliphatic cyclic skeleton)
The present invention may include a polymerizable monoma having (D) an aliphatic cyclic skeleton (preferably 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms). As a result, hydrophobicity can be imparted to the cured product that can be formed, and a decrease in adhesion between the cured product and the substrate in a high temperature and high humidity environment can be suppressed.
The component (D) has a group containing a polymerizable unsaturated double bond (preferably two or more) (preferably a (meth) acryloyl group because it can be polymerized by a photopolymerization initiator). It is preferable to contain a polymerizable monoma having an aliphatic cyclic skeleton, and in order to improve the crosslink density and photosensitivity and suppress the swelling of the pattern after development, a few groups containing a polymerizable unsaturated double bond are used. It is preferable to have.
The component (D) preferably contains a polymerizable monoma represented by the following general formula (13).

（一般式（１３）中、Ｒ_１８及びＲ_１９は、それぞれ独立に、炭素数１〜４の脂肪族炭化水素基又は下記一般式（５）で表される基である。ｎ１は０又は１であり、ｎ２は０〜２の整数であり、ｎ１＋ｎ２は１以上（好ましくは２又は３）である。ｎ１個のＲ_１８及びｎ２個のＲ_１９の少なくとも１つ（好ましくは２又は３）は、下記一般式（５）で表される基である。）
Ｒ_１９が２つの場合、２つのＲ_１９は同一でもよく、異なっていてもよい。

(In the general formula (13), R ₁₈ and R ₁₉ are independently aliphatic hydrocarbon groups having 1 to 4 carbon atoms or groups represented by the following general formula (5). N1 is 0 or 1. in it, n2 is an integer of 0 to 2, n1 + n2 is 1 or more (preferably 2 or 3) at least one a is .n1 one of _{R 18} and n2 one _{R 19} (preferably 2 or 3) , A group represented by the following general formula (5).)
When _{there are two R 19s} , the two R _19s may be the same or different.

（一般式（５）中、Ｒ_７〜Ｒ_９はそれぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基であり、ｍは１〜１０の整数である。）
（Ｄ）成分は下記一般式（１４）で表される重合性モノマを含むことがより好ましい。

(In the general formula (5), R _{7 to} R ₉ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10.)
It is more preferable that the component (D) contains a polymerizable monoma represented by the following general formula (14).

また、（Ｄ）成分として、例えば、以下の重合性モノマを用いてもよい。

Further, as the component (D), for example, the following polymerizable monomas may be used.

一般式（１５）中、Ｒ_２０〜Ｒ_２３は、それぞれ独立に、炭素数１〜４の脂肪族炭化水素基又は、上記式（５）で表される基である。ｎ３は１〜３の整数（好ましくは２又は３）である。ｎ４は１〜３の整数（好ましくは２又は３）である。ｎ５及びｎ６は０又は１である。ｎ５＋ｎ６は１以上（好ましくは２）である。
Ｒ_２０が２以上存在する場合、２以上のＲ_２０は同一でもよく、異なっていてもよい。
Ｒ_２１が２以上存在する場合、２以上のＲ_２１は同一でもよく、異なっていてもよい。
ｎ３個のＲ_２０の少なくとも１つ（好ましくは２又は３）は、上記式（５）で表される基である。
ｎ４個のＲ_２１の少なくとも１つ（好ましくは２又は３）は、上記式（５）で表される基である。
ｎ５個のＲ_２２及びｎ６個のＲ_２３の少なくとも１つ（好ましくは２又は３）は、上記式（５）で表される基である。
一般式（１３）のＲ_１８及びＲ_１９及び一般式（１５）のＲ_２０〜Ｒ_２３の炭素数１〜４の脂肪族炭化水素基としては、一般式（３）のＲ_５及びＲ_６の炭素数１〜４の脂肪族炭化水素基と同様のものが挙げられる。
（Ｄ）成分は、１種単独で用いてもよく、２種以上を組み合わせてもよい。
（Ｄ）成分の含有量は、（Ａ）成分１００質量部に対して、１〜５０質量部が好ましい。硬化物の疎水性の観点から、より好ましくは３〜５０質量部、更に好ましくは５〜３５質量部である。
上記範囲内である場合、実質的なレリーフパターンが得られやすく、未露光部の現像残渣を抑制しやすい。

In the general formula (15), R _{20 to} R ₂₃ are independently aliphatic hydrocarbon groups having 1 to 4 carbon atoms or groups represented by the above formula (5). n3 is an integer of 1-3 (preferably 2 or 3). n4 is an integer of 1-3 (preferably 2 or 3). n5 and n6 are 0 or 1. n5 + n6 is 1 or more (preferably 2).
If R ₂₀ is present 2 or more, 2 or more _{R 20} may be the same or different.
When _{two or more R 21s} are present, the two or more R _21s may be the same or different.
At least one (preferably 2 or 3) of n3 R _20s is a group represented by the above formula (5).
At least one (preferably 2 or 3) of n4 R _21s is a group represented by the above formula (5).
At least one (preferably 2 or 3) of n5 R ₂₂ and n 6 R ₂₃ is a group represented by the above formula (5).
As the aliphatic hydrocarbon groups having 1 to 4 carbon atoms _{of R 18} and R ₁₉ of the general formula (13) _{and R 20 to} R ₂₃ of the general formula (15 _{), R 5} and R ₆ of the general formula (3) Examples thereof include those similar to the aliphatic hydrocarbon group having 1 to 4 carbon atoms.
The component (D) may be used alone or in combination of two or more.
The content of the component (D) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). From the viewpoint of hydrophobicity of the cured product, it is more preferably 3 to 50 parts by mass, still more preferably 5 to 35 parts by mass.
When it is within the above range, a substantial relief pattern can be easily obtained, and development residue in the unexposed portion can be easily suppressed.

(Component (E): Thermal polymerization initiator)
The photosensitive resin composition of the present invention may further contain (E) a thermal polymerization initiator from the viewpoint of accelerating the polymerization reaction.
As the component (E), it is not decomposed by heating (drying) for removing the solvent at the time of film formation, but is decomposed by heating at the time of curing to generate radicals. A compound that promotes the polymerization reaction of the component (B) is preferable.
The component (E) preferably has a decomposition temperature of 110 ° C. or higher and 200 ° C. or lower, and more preferably 110 ° C. or higher and 175 ° C. or lower from the viewpoint of promoting the polymerization reaction at a lower temperature. Specific examples include ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di (t-hexyl peroxide) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1, Peroxyketals such as 1-di (t-butylperoxy) cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutylhydroperoxides, cumene hydroperoxides, p-methane hydroperoxides, dicumyl peroxides, di. Dialkyl peroxides such as -t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, peroxy such as di (4-t-butylcyclohexyl) peroxydicarbonate and di (2-ethylhexyl) peroxydicarbonate. Dicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa Peroxyesters such as Noate, bis (1-phenyl-1-methylethyl) peroxide and the like can be mentioned. Examples of commercially available products include the trade names "Park Mill D", "Park Mill P", and "Park Mill H" (all manufactured by NOF CORPORATION).
When the component (E) is contained, the content of the component (E) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A), and is 0 to ensure good flux resistance. .2 to 20 parts by mass is more preferable, and 0.3 to 10 parts by mass is further preferable from the viewpoint of suppressing a decrease in solubility due to decomposition during drying.

((F) component: solvent)
The photosensitive resin composition of the present invention contains (F) a solvent.
As the component (F), N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, Examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethylketone, diisobutylketone, methylamylketone, N-dimethylmorpholin and the like. Usually, there is no particular limitation as long as other components can be sufficiently dissolved.
Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N, N-dimethylformamide from the viewpoint of excellent solubility of each component and coating property at the time of forming a photosensitive resin film. , N, N-dimethylacetamide is preferably used.
Further, as the component (F), a compound represented by the following general formula (16) may be used.

（一般式（１６）中、Ｒ_４１〜Ｒ_４３は、それぞれ独立に、炭素数１〜１０のアルキル基である。）
一般式（１６）中におけるＲ_４１〜Ｒ_４３の炭素数１〜１０（好ましくは炭素数１〜３）であるアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などを挙げることができる。
一般式（１６）で表される化合物は、３−メトキシ−Ｎ，Ｎ−ジメチルプロパンアミド（例えば、商品名「ＫＪＣＭＰＡ−１００」（ＫＪケミカルズ株式会社製））であることが好ましい。
（Ｆ）成分は、１種単独で用いてもよく、２種以上を組み合わせてもよい。
（Ｆ）成分の含有量は、特に制限されないが、一般的に（Ａ）成分１００質量部に対して、５０〜１０００質量部である。

(In the general formula (16), R _{41 to} R ₄₃ are independently alkyl groups having 1 to 10 carbon atoms.)
Examples _{of the alkyl group having 1 to 10 carbon atoms (preferably 1 to 3 carbon atoms) of R 41 to R 43} in the general formula (16) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-. Examples thereof include a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The compound represented by the general formula (16) is preferably 3-methoxy-N, N-dimethylpropanamide (for example, trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)).
The component (F) may be used alone or in combination of two or more.
The content of the component (F) is not particularly limited, but is generally 50 to 1000 parts by mass with respect to 100 parts by mass of the component (A).

(Coupling agent, surfactant or leveling agent, rust preventive, and polymerization inhibitor)
The photosensitive resin composition of the present invention may contain a coupling agent, a surfactant or a leveling agent, a rust preventive agent, a polymerization inhibitor and the like.
Usually, the coupling agent itself polymerizes in the step of reacting with the component (A) to crosslink or heat-treat the coupling agent after development. Thereby, the adhesiveness between the obtained cured product and the substrate can be further improved.
Preferred coupling agents include compounds having a urea bond (-NH-CO-NH-). As a result, even when curing is performed at a low temperature of 200 ° C. or lower, the adhesiveness to the substrate can be further improved.
The compound represented by the following general formula (17) is more preferable in that it is excellent in developing adhesiveness when cured at a low temperature.

（一般式（１７）中、Ｒ_３１及びＲ_３２は、それぞれ独立に炭素数１〜５のアルキル基である。aは１〜１０の整数であり、ｂは１〜３の整数である。）
一般式（１７）で表される化合物の具体例としては、ウレイドメチルトリメトキシシラン、ウレイドメチルトリエトキシシラン、２−ウレイドエチルトリメトキシシラン、２−ウレイドエチルトリエトキシシラン、３−ウレイドプロピルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、４−ウレイドブチルトリメトキシシラン、４−ウレイドブチルトリエトキシシランなどが挙げられ、好ましくは３−ウレイドプロピルトリエトキシシランである。

(In the general formula (17), R ₃₁ and R ₃₂ are independently alkyl groups having 1 to 5 carbon atoms. A is an integer of 1 to 10, and b is an integer of 1 to 3.)
Specific examples of the compound represented by the general formula (17) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxy. Examples thereof include silane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, preferably 3-ureidopropyltriethoxysilane.

As the silane coupling agent, a silane coupling agent having a hydroxy group or a glycidyl group may be used. When a silane coupling agent having a hydroxy group or a glycidyl group and a silane coupling agent having an intramolecular urea bond are used in combination, the adhesiveness of the cured product during low temperature curing to the substrate can be further improved.
Examples of the silane coupling agent having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, and t-. Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, t-butylmethylphenylsilanol, ethyl n-propylphenyl Silanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, t-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, t-butyldiphenylsilanol, Phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) Benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene , 1,4-Bis (dibutylhydroxysilyl) benzene, and compounds represented by the following general formula (18). In particular, the compound represented by the general formula (18) is preferable in order to further improve the adhesiveness to the substrate.

（一般式（１８）中、Ｒ_３３はヒドロキシ基又はグリシジル基を有する１価の有機基であり、Ｒ_３１及びＲ_３２は、それぞれ独立に炭素数１〜５のアルキル基である。ｃは１〜１０の整数であり、ｄは１〜３の整数である。）
一般式（１８）で表される化合物としては、ヒドロキシメチルトリメトキシシラン、ヒドロキシメチルトリエトキシシラン、２−ヒドロキシエチルトリメトキシシラン、２−ヒドロキシエチルトリエトキシシラン、３−ヒドロキシプロピルトリメトキシシラン、３−ヒドロキシプロピルトリエトキシシラン、４−ヒドロキシブチルトリメトキシシラン、４−ヒドロキシブチルトリエトキシシラン、グリシドキシメチルトリメトキシシラン、グリシドキシメチルトリエトキシシラン、２−グリシドキシエチルトリメトキシシラン、２−グリシドキシエチルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、４−グリシドキシブチルトリメトキシシラン、４−グリシドキシブチルトリエトキシシランなどが挙げられる。

(In the general formula (18), R ₃₃ is a monovalent organic group having a hydroxy group or a glycidyl group, and R ₃₁ and R ₃₂ are independently alkyl groups having 1 to 5 carbon atoms. C is 1 It is an integer of 10 and d is an integer of 1 to 3.)
Examples of the compound represented by the general formula (18) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, and 3 -Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2 -Glysidoxyethyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, etc. Can be mentioned.

The silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a nitrogen atom, and a silane coupling agent having an amino group or an amide bond is preferable.
Examples of the silane coupling agent having an amino group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, and bis (2-glycidoxy). Examples thereof include methyl) -3-aminopropyltrimethoxysilane, bis (2-glycidoxymethyl) -3-aminopropyltriethoxysilane, and bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane.
The silane coupling agents having an amide _{bond, R 36 - (CH 2)} e -CO-NH- (CH 2) f -Si (OR 37) 3 (R 36 is a hydroxy group or a glycidyl group, e and f is an integer of 1 to 3 independently of each other, and R ₃₇ is a methyl group, an ethyl group or a propyl group).

The silane coupling agent may be used alone or in combination of two or more.
When a silane coupling agent is used, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and 0, based on 100 parts by mass of the component (A). .3 to 10 parts by mass is more preferable.

By containing a surfactant or a leveling agent, coatability (for example, suppression of striation (unevenness of film thickness)) and developability can be improved. Examples of the surfactant or leveling agent include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. F171 "," F173 "," R-08 "(above, manufactured by DIC Co., Ltd.), trade name" Florard FC430 "," FC431 "(above, manufactured by Sumitomo 3M Co., Ltd.), trade name" Organosiloxane Polymer KP341 ", Examples thereof include "KBM303", "KBM403", and "KBM803" (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
The surfactant or leveling agent may be used alone or in combination of two or more.
When a surfactant or a leveling agent is contained, the content of the surfactant or the leveling agent is preferably 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the component (A). More preferably, 0.05 to 3 parts by mass is further preferable.

By containing a rust preventive, it is possible to suppress corrosion and prevent discoloration of copper and copper alloys. Examples of the rust preventive include a triazole derivative and a tetrazole derivative.
The rust preventive here is different from the component (B).
The rust preventive may be used alone or in combination of two or more. When a rust inhibitor is used, the content of the rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and 0.5 parts by mass with respect to 100 parts by mass of the component (A). ~ 3 parts by mass is more preferable.

By using a polymerization inhibitor, good storage stability can be ensured.
Examples of the polymerization inhibitor include a radical polymerization inhibitor and a radical polymerization inhibitor.
Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2-. Examples thereof include naphthylamine, cuperon, 2,5-torquinone, tannic acid, parabenzylaminophenol, nitrosoamines and the like.
The polymerization inhibitor may be used alone or in combination of two or more.
When a polymerization inhibitor is contained, the content of the polymerization inhibitor is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and 0. 05 to 5 parts by mass is more preferable.

The photosensitive resin composition of the present invention essentially comprises components (A) to (C) and optionally components (D) to (F), a coupling agent, a surfactant, a leveling agent, a rust preventive, and the like. And a polymerization inhibitor, and may contain other unavoidable impurities as long as the effects of the present invention are not impaired.

For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the photosensitive resin composition of the present invention.
Ingredients (A) to (E),
Components (A) to (F) or
It may consist of the components (A) to (E), and optionally the component (F), a coupling agent, a surfactant, a leveling agent, a rust preventive, and a polymerization inhibitor.

(Manufacturing method of cured product and pattern cured product)
The cured product of the present invention can be obtained by curing the above-mentioned photosensitive resin composition.
The cured product of the present invention may be used as a patterned cured product or as a cured product without a pattern.
The film thickness of the cured product of the present invention is preferably 5 to 20 μm.
In the method for producing a cured pattern of the present invention, the above-mentioned photosensitive resin composition is applied onto a substrate and dried to form a photosensitive resin film, and the photosensitive resin film is pattern-exposed to form a resin film. The process includes a step of developing the resin film after pattern exposure with an organic solvent to obtain a pattern resin film, and a step of heat-treating the pattern resin film.
Thereby, a pattern cured product can be obtained. A method for producing a cured product without a pattern includes, for example, a step of forming the above-mentioned photosensitive resin film and a step of heat treatment. Further, a step of exposing may be provided. Examples of the substrate include a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), _{a metal oxide insulator substrate such as a TiO 2} substrate and a SiO ₂ substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.
The coating method is not particularly limited, but it can be applied using a spinner or the like.
Drying can be performed using a hot plate, an oven, or the like.
The drying temperature is preferably 90 to 150 ° C., and more preferably 90 to 120 ° C. from the viewpoint of ensuring the dissolution contrast.
The drying time is preferably 30 seconds to 5 minutes. Drying may be performed twice, and the temperatures may be different for each.
As a result, a photosensitive resin film obtained by forming the above-mentioned photosensitive resin composition into a film can be obtained.
The film thickness of the photosensitive resin film is preferably 5 to 100 μm, more preferably 6 to 50 μm, and even more preferably 7 to 30 μm.
In the pattern exposure, for example, a predetermined pattern is exposed through a photomask.
Examples of the active light beam to be irradiated include ultraviolet rays such as i-rays, visible rays, and radiation, but i-rays are preferable. As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine and the like can be used.

By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, the unexposed portion is removed with a developing solution.
As the organic solvent used as the developing solution, the good solvent of the photosensitive resin film can be used alone, or the good solvent and the poor solvent can be appropriately mixed and used.
Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, Cyclopentanone, cyclohexanone and the like can be mentioned. Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and water.
A surfactant may be added to the developer.
The amount to be added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developing solution.
The development time can be, for example, twice the time required for the photosensitive resin film to be immersed in a developing solution and completely dissolved.
The developing time varies depending on the component (A) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 20 seconds to 5 minutes from the viewpoint of productivity.
After development, it may be washed with a rinsing liquid.
As the rinsing liquid, distilled water, toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like may be used alone or in an appropriate mixture, or may be combined stepwise. ..

A cured pattern can be obtained by heating the pattern resin film.
When the component (A) is a polyimide precursor, a dehydration ring closure reaction is caused by a heat treatment step to obtain a normally corresponding polyimide.
The temperature of the heat treatment is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., further preferably 200 ° C. or lower, or even more preferably 160 to 200 ° C. Within the above range, damage to the substrate and the device can be suppressed to a small extent, the device can be produced with a high yield, and energy saving of the process can be realized.
The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
Within the above range, the cross-linking reaction or the dehydration ring closure reaction can be sufficiently proceeded.
The atmosphere of the heat treatment may be the atmosphere or an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the patterned resin film.
Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace and the like.

The cured product of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating layer, a cover coat layer, a surface protective film, or the like.
Highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, and laminates using one or more selected from the group consisting of the passion film, buffer coat film, interlayer insulation layer, cover coat layer, surface protection film, and the like. It is possible to manufacture electronic components such as devices (multi-die fan-out wafer level packages, etc.).

(Manufacturing method of electronic parts)
An example of a manufacturing process of a semiconductor device which is an electronic component of the present invention will be described with reference to the drawings.
FIG. 1 is a manufacturing process diagram of a semiconductor device having a multi-layer wiring structure, which is an electronic component according to an embodiment of the present invention.
In FIG. 1, a semiconductor substrate 1 such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. It is formed. After that, the interlayer insulating film 4 is formed on the semiconductor substrate 1.
Next, a photosensitive resin layer 5 such as a rubber chloride type or a phenol novolac type is formed on the interlayer insulating film 4, and the window 6A is provided so that the interlayer insulating film 4 of a predetermined portion is exposed by a known photographic etching technique. Be done.
The interlayer insulating film 4 in which the window 6A is exposed is selectively etched to provide the window 6B.
Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.
Further, using a known photographic etching technique, the second conductor layer 7 is formed and electrically connected to the first conductor layer 3.
When forming a multi-layer wiring structure having three or more layers, the above steps can be repeated to form each layer.
Next, using the above-mentioned photosensitive resin composition, the window 6C is opened by pattern exposure to form the surface protective film 8. The surface protective film 8 protects the second conductor layer 7 from external stress, α rays, and the like, and the obtained semiconductor device is excellent in reliability.
In the above example, the interlayer insulating film can also be formed by using the photosensitive resin composition of the present invention.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. The present invention is not limited to the following examples.

(Synthesis example)
7.07 g of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) N-methyl- It was dissolved in 30 g of 2-pyrrolidone (NMP) and stirred at 30 ° C. for 4 hours and then at room temperature (25 ° C.) overnight to obtain polyamic acid. To this, 9.45 g of trifluoroacetic anhydride was added under water cooling, the mixture was stirred at 45 ° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. This reaction solution was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor A1.
The number average molecular weight was determined by gel permeation chromatography under the following conditions in terms of standard polystyrene. The number average molecular weight of A1 was 40,000.

(Measurement by gel permeation chromatography)
The measurement was carried out using a solution of 1 mL of a solvent (tetrahydrofuran (THF) / dimethylformamide (DMF) = 1: 1 (volume ratio)) with respect to 0.5 mg of A1.
Measuring device: Detector Hitachi, Ltd. L4000UV
Pump: Hitachi, Ltd. L6000
Shimadzu Corporation C-R4A Chromatopac
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.3 _{mol / L), H 3} PO ₄ (0.06 mol / L)
Flow velocity: 1.0 mL / min
Detector: UV270nm

Further, the esterification rate of A1 (reaction rate of the carboxy group of ODPA with HEMA) was calculated by performing NMR measurement under the following conditions. The esterification rate was 80 mol% with respect to the total carboxy group of the polyamic acid. (The remaining 20 mol% is a carboxy group)
(NMR measurement)
Measuring equipment: AV400M manufactured by Bruker Biospin
Magnetic field strength: 400MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: Dimethyl sulfoxide (DMSO)

(Examples 1 to 10, Comparative Examples 1 to 3)
(Preparation of photosensitive resin composition)
The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared with the components and blending amounts shown in Table 1.
The blending amount in Table 1 is the mass part of each component with respect to 100 parts by mass of A1.

Each component used is as follows.
Component (A): Thermoplastic resin A1 obtained in the above synthetic example was used.

(B) Component: Compound containing hydroxyl group and triazole skeleton B1: Trade name "TT-LYK"(2,2'-[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol, below Ceremony, manufactured by Johoku Chemical Industry Co., Ltd.)

Ｂ２：商品名「ＴＴ−ＬＸ」（１−［Ｎ,Ｎ−ビス（２−エチルヘキシル）アミノメチル］メチルベンゾトリアゾール、下記式、城北化学工業株式会社製）

B2: Product name "TT-LX" (1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, the following formula, manufactured by Johoku Chemical Industry Co., Ltd.)

（Ｃ）成分：光開始剤
Ｃ１：エタノン，１−[９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル]−，１−（０−アセチルオキシム）商品名「ＯＸＥ０２」（ＢＡＳＦジャパン株式会社製）
Ｃ２：１−フェニル−１，２−プロパンジオン−２−（Ｏ−エトキシカルボニル）オキシム商品名「Ｇ−１８２０（ＰＤＯ）」（Ｌａｍｂｓｏｎ株式会社製）
Ｃ３：２−メチル−１−[４−（メチルチオ）フェニル]−２−モルフォリノプロパン−１−オン商品名「Ｉｒｇ９０７」（ＢＡＳＦジャパン株式会社製）
（Ｄ）成分：脂肪族環状骨格を有する重合性モノマ
Ｄ１：商品名「Ａ−ＤＣＰ」（トリシクロデカンジメタノールジアクリレート、下記式、新中村化学株式会社製）

(C) Ingredient: Photoinitiator C1: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime) Trade name "OXE02" (Made by BASF Japan Ltd.)
C2: 1-Phenyl-1,2-Propanedione-2- (O-ethoxycarbonyl) Oxime Trade name "G-1820 (PDO)" (manufactured by Rambson Co., Ltd.)
C3: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one Trade name "Irg907" (manufactured by BASF Japan Ltd.)
(D) Ingredient: Polymerizable monoma having an aliphatic cyclic skeleton D1: Trade name "A-DCP" (tricyclodecanedimethanol diacrylate, the following formula, manufactured by Shin-Nakamura Chemical Co., Ltd.)

（Ｅ）成分：熱重合開始剤
Ｅ１：商品名「パークミルＤ」（ジクミルパーオキサイド、下記式、日油株式会社製）

(E) Ingredient: Thermal polymerization initiator E1: Product name "Park Mill D" (Dicumyl peroxide, the following formula, manufactured by NOF CORPORATION)

（Ｆ）成分：溶剤
Ｆ１：商品名「Ｎ−メチル−２−ピロリドン」（三菱ケミカル株式会社製）

(F) Ingredient: Solvent F1: Product name "N-methyl-2-pyrrolidone" (manufactured by Mitsubishi Chemical Corporation)

(Manufacturing of cured product)
The obtained photosensitive resin composition was spin-coated on a silicon wafer using a spin coater (product name "MS-A200", manufactured by Mikasa Co., Ltd.), and was spin-coated on a hot plate at 105 ° C. for 2 minutes and 115 ° C. for 2 minutes. After drying, a photosensitive resin film having a dry film thickness of 11 to 15 μm was formed. (Aim for 10 μm after curing)
The development time was set to twice the time required for the obtained photosensitive resin film to be immersed in cyclopentanone and completely dissolved.
Exposure is performed using an aligner exposure machine (product name "ML-320 FSAT" (manufactured by Sanaga Denki Seisakusho)), and then the exposed resin film is exposed to a developing machine (product name "AD-3000" (manufactured by Mikasa Co., Ltd.). )), After paddle development with cyclopentanone for the above development time, rinse washing with propylene glycol monomethyl ether acetate (PGMEA) to obtain a resin film.
The obtained resin film is heated in a nitrogen oven (product name "Inert Gas Oven" (manufactured by Koyo Thermo System Co., Ltd.)) at 200 ° C. for 2 hours (temperature rise: 5 ° C./min) in a nitrogen atmosphere to cure the product (cured product). After curing, a film thickness of 10 μm) was obtained.

(Remaining film ratio after curing)
In the cured product manufacturing step, the silicon wafer was exposed by scratching the resin portion, and the height from the exposed silicon wafer surface to the film surface before and after curing was measured using a contact film thickness meter.
The residual film ratio was calculated based on the obtained film thickness before and after curing.
Remaining film ratio (%) = (film thickness after curing / film thickness before curing) x 100

(Adhesion (HTS resistance) evaluation)
Electroplating was performed on a silicon wafer sputtered with Ti at a thickness of 50 nm and Cu at a thickness of 150 nm using a plating solution manufactured by Okuno Pharmaceutical Industry Co., Ltd. (trade name “Top Lucina”).
(Spatter conditions: Product name "SIV-500" (manufactured by ULVAC, Inc.)
Condition Ti: 4kW, 30sccm, 869mm / min, 60s
Cu: 4kW, 30sccm, 1005mm / min, 120s
(Electroplating conditions: 1.76V, 10A, 510 seconds (5 μm thickness))
The plated substrate was pickled with a 10 mass% sulfuric acid aqueous solution for 10 seconds, washed with running water for 1 minute, compressed air was sprayed to drain water well, and then dried on a hot plate at 80 ° C. for 5 minutes. The surface was then treated with a plasma cleaner. Then, a cured resin product was produced on the plated substrate by the same method as described above.
(Plasma cleaner condition: Product name "AP-1000" (manufactured by Nordson)
Condition O ₂ : 500 sccm
Output: 100W
Processing time: 180 seconds
Vacuum degree: 150mTorr)
The prepared evaluation substrate was heated in an oven (product name "HISPEC HIGH TEMPERATURE CHAMBER" (manufactured by Kusumoto Kasei Co., Ltd.)) for 0,100,200,500 hours at 175 ° C. in an air atmosphere (HTS (High Temperature Storage (HTS)). High temperature storage)) Test).
The test pieces at the initial stage and after the HTS test were subjected to a grid test according to the JIS standard "JIS K5400-8.5 (JIS D0202)" to evaluate the adhesion.
The evaluation criteria are as follows: "A" for those without peeling, "B" for those with partial peeling (peeling <50/100 squares), and those with peeling (peeling> 50/100 squares). Was evaluated as "C".
The measurement results of the residual film ratio and the adhesion of HTS resistance are shown in Table 1 together with the formulation of the photosensitive resin composition.

Comparative Example 1 which does not contain the compound containing the hydroxyl group and the triazole skeleton of the component (B) is inferior in the high temperature storage stability of HTS resistance, and the effect is not so great in Comparative Examples 2 and 3 which contain the triazole skeleton but do not have the hydroxyl group. However, in the present invention using a compound containing a hydroxyl group and a triazole skeleton, it is excellent in HTS resistance and high temperature storage stability.

The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer or a surface protective film, and the interlayer insulating film, a cover coat layer or a surface protective film of the present invention can be used for an electronic component or the like. Can be done.

1: Semiconductor substrate 2: Protective film 3: First conductor layer 4: Interlayer insulating film 5: Photosensitive resin layer 6A, 6B, 6C: Window 7: Second conductor layer 8: Surface protective film

Claims (12)

A photosensitive resin composition containing (A) a thermoplastic resin, (B) a compound containing a hydroxyl group and a triazole skeleton, and (C) a photoinitiator. The photosensitive resin composition according to claim 1, wherein the compound containing the hydroxyl group of the component (B) and the triazole skeleton is represented by the following general formula (1).

(In the general formula (1), R _{1 to} R ₄ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms.) The photosensitive resin composition according to claim 1 or 2, wherein the compound containing the hydroxyl group of the component (B) and the triazole skeleton is represented by the following general formula (2).

Claims 1 to 1, wherein the thermoplastic resin of the component (A) contains a polyimide precursor having a structural unit represented by the following general formula (3) or a polyimide having a structural unit represented by the following general formula (4). The photosensitive resin composition according to any one of 3.

(In the general formula (3) and the general formula (4), X ₁ is a tetravalent aromatic group, and the -COOR ₅ group and the -CONH- group are in ortho positions with each other, and the -COOR ₆ group and- The CO- group is in the ortho position with each other. Y ₁ is a divalent aromatic group. R ₅ and R ₆ are independently hydrogen atoms, groups represented by the following general formula (5), or groups represented by the following general formula (5). It is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and _{at least one of R 5} and R ₆ is a group represented by the general formula (5).

(In the general formula (5), R _{7 to} R ₉ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10.) The photosensitive resin composition according to any one of claims 1 to 4, further comprising (D) a polymerizable monoma having an aliphatic cyclic skeleton. The photosensitive resin composition according to any one of claims 1 to 5, further comprising (E) a thermal polymerization initiator. The step of applying the photosensitive resin composition according to any one of claims 1 to 6 onto a substrate and drying it to form a photosensitive resin film, and pattern-exposing the photosensitive resin film to a resin film. Production of a cured pattern product, which comprises a step of obtaining the pattern resin film, a step of developing the resin film after the pattern exposure with an organic solvent to obtain the pattern resin film, and a step of heat-treating the pattern resin film. Method. The method for producing a cured pattern according to claim 7, wherein the temperature of the heat treatment step is 200 ° C. or lower. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 6. The cured product according to claim 9, wherein the cured product is a pattern cured product. A method for producing a patterned cured product, wherein the cured product produced by using the method for producing a patterned cured product according to claim 7 or 8 is used as any of an interlayer insulating film, a cover coat layer, and a surface protective film. A method for manufacturing an electronic component, which comprises a step of manufacturing a pattern cured product used for any of the interlayer insulating film, the cover coat layer, and the surface protective film according to claim 11.

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