JP2014122276A - Adamantane skeleton-containing compound, silicone skeleton-containing polymer compound, negative resist material, photocurable dry film, pattern formation method and coating for protection of electric/electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical amplification type negative resist material that improves the problem of peeling on a substrate.SOLUTION: A silicone skeleton-containing polymer compound has repeating units represented by general formula (1) and has a weight average molecular weight of 3,000-500,000.

Description

  The present invention relates to an adamantane skeleton-containing compound; a silicone skeleton-containing polymer compound obtained by using the compound; the silicone that can be patterned by ultraviolet exposure at a wavelength of 500 nm or less (near-ultraviolet and far-ultraviolet region) such as i-line and g-line Chemically amplified negative resist material using a skeleton-containing polymer compound and method for producing the same; Photocurable dry film formed using the resist material and method for producing the same; On the substrate using the resist material or dry film A method for forming a pattern by forming a resist film or a photocurable resin layer on the substrate; and further, a protective film for wiring, circuits, substrates, etc. using the cured film obtained from the resist film or the photocurable resin layer. Is.

  The pattern of the negative resist material to be formed is used for the purpose of a protective film covering the wiring, circuit, substrate, etc., but the wiring covered by the pattern of the negative resist material, on the Cu metal layer of the circuit, the substrate There is often a problem of peeling off due to poor adhesion on the Al metal electrode present on the SiN substrate, which is an insulating substrate for wiring and circuits to be covered. However, the pattern formed by the chemically amplified negative resist material of the present invention or the dry film obtained using this resist material can greatly improve the substrate adhesion.

  Furthermore, the protective film according to the present invention has a heat resistance, chemical resistance, insulation, and flexibility, so that it can be used for semiconductor devices including rewiring, insulating films for multilayer printed boards, solder masks, coverlay films. In addition to an insulating film for embedding a silicon substrate through wiring (TSV), it is effective for bonding substrates.

  As various electronic devices such as personal computers, digital cameras, and mobile phones are miniaturized and have high performance, demands for further miniaturization, thinning, and high density of semiconductor elements are rapidly increasing. For this reason, it is possible to cope with an increase in the substrate area for improving productivity, and in a high-density mounting technology such as a chip size package, a chip scale package (CSP), or three-dimensional stacking, the substrate has fine irregularities with a high aspect ratio. Development of a photosensitive insulating material that can cope with such a structure is desired.

  As a photosensitive insulating material as described above, it can be applied over a wide range of film thickness by spin coating methods commonly used in semiconductor device manufacturing processes, and fine patterns can be formed in a wide wavelength range. Photocurable resin composition that provides a film for protecting electrical and electronic parts that is excellent in flexibility, heat resistance, electrical properties, adhesion, reliability, and chemical resistance (Patent Document 1: Japanese Patent Application Laid-Open No. 2008-184571) Has been proposed. This spin coating method has an advantage that a film can be easily formed on a substrate.

  On the other hand, the photocurable resin composition that provides the above-mentioned coating film for protecting electric / electronic parts is used on a substrate with a film thickness of 1 to 100 μm. Since the viscosity of the composition becomes very high, film formation on a substrate by a spin coating method has practical limitations and becomes difficult.

  In addition, when the photocurable resin composition is applied to a substrate having an uneven surface by the spin coating method, it is difficult to cover the substrate almost uniformly. For this reason, a gap between the photocurable resin layers is likely to be generated at the stepped portion on the substrate, and further improvement in flatness and step coverage has been awaited. Further, as another application method in place of the spin coating method, a spray method (Patent Document 2: Japanese Patent Application Laid-Open No. 2009-200315) has been proposed. However, in principle, defects such as height differences due to substrate irregularities, film cuts at the pattern edge, and pinholes at the bottom of the recesses are likely to occur, and the problems related to flatness and step coverage are still sufficiently solved. There is no place.

  Further, in recent years, in a high-density mounting technology such as a chip size package, a chip scale package (CSP), or three-dimensional stacking, a fine and high aspect ratio pattern is formed on a substrate, and a metal such as copper is stacked on the obtained pattern. Therefore, technology for rewiring from the chip is prosperous. With the increasing density and integration of chips, there is a strong demand for miniaturization of the pattern line width and the contact hole size for connecting between substrates in the rewiring technology. Lithography technology is generally used as a method for obtaining a fine pattern. In particular, a chemically amplified negative resist material is suitable for obtaining a fine pattern. In addition, the pattern used for rewiring is an electrical device that has excellent flexibility, heat resistance, electrical properties, adhesion, reliability, and chemical resistance, while having a characteristic of permanently curing between device chips and chips. -Since it is necessary to work as a coating for protecting electronic parts, the negative resist type is suitable for obtaining resist patterns.

  Therefore, it is a pattern forming material that can process fine rewiring and is used for the formation of a coating film for protecting electrical and electronic parts that has excellent flexibility, heat resistance, electrical properties, adhesion, reliability, and chemical resistance. An amplification type negative resist material can be mentioned.

  On the other hand, a chemically amplified negative resist material that can form a fine pattern used when processing rewiring and is useful as a coating for protecting electrical and electronic components covers Cu wiring previously processed on a substrate. Or covering an Al electrode present on the substrate. In addition, the substrate on which the wiring and electrodes are provided includes an insulating substrate such as SiN, and it is necessary to cover the SiN substrate widely. However, the adhesion between the chemically-amplified negative resist material coating film layer and these substrates is still insufficient, and the problem of the resist material coating film layer peeling off on the substrate is often encountered.

  Therefore, it is possible to make the pattern finer in the rewiring technology as the density and integration of the chip increases, and it is a chemically amplified negative resist material that is useful as a coating for protecting electrical and electronic components, but it has excellent adhesion on the substrate. A dramatic improvement is desired.

JP 2008-184571 A JP 2009-200315 A

The present invention has been made in view of the above circumstances, can form a fine pattern, and has a problem of peeling on a metal wiring such as Cu and Al, an electrode, and a substrate, particularly on a substrate such as SiN. To provide a chemically amplified negative resist material that can be improved, a silicone skeleton-containing polymer compound suitably used as a base resin of the negative resist material, and an adamantane skeleton-containing compound effective for obtaining this polymer compound Objective.
It is another object of the present invention to provide a method by which the resist material can be easily applied on a substrate by spin coating to form a fine pattern.
In addition, a photocurable dry film using the resist material, a manufacturing method thereof, and a resist having a wide film thickness using a photocurable dry film using the composition, even on a substrate having irregularities. Another object is to provide a fine pattern forming method by applying layers.
Another object is to provide a film for protecting electrical and electronic parts such as wiring, circuits and substrates using a cured film obtained by post-curing the pattern obtained by the pattern forming method at a low temperature. To do.

  As a result of intensive studies to achieve the above object, the present inventors have found that a chemically amplified negative resist material containing the following components (A) to (D) can form a fine pattern, and Cu It has been found that the problem of delamination encountered on metal wiring, electrodes, and substrates such as Si and Al, especially on substrates such as SiN, can be greatly improved. Furthermore, the present inventors have found that the cured film obtained by the pattern forming method is excellent as a film for protecting electrical / electronic parts, and have made the present invention.

  Accordingly, the present invention provides the following silicone skeleton-containing polymer compound, chemically amplified negative resist material, pattern formation method using the resist material, photocurable dry film, and pattern formation using the photocurable dry film Methods and coatings for protecting electrical and electronic components are provided. Furthermore, an adamantane skeleton-containing compound is provided.

（式中、Ｒ¹〜Ｒ⁴は同一でも異なっていてもよい炭素数１〜８の１価炭化水素基を示す。ｍは１〜１００の整数である。ａ、ｂ、ｃ、ｄは０又は正数、ｅ、ｆは正数であり、かつ、ａ、ｂ、ｃ、ｄは同時に０になることがない。但し、ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＝１である。Ｘは下記一般式（２）で示される有機基、Ｙは下記一般式（３）で示される有機基、Ｗは下記式（４ａ）もしくは式（４ｂ）で示される有機基である。）

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｎは０又は１である。Ｒ⁵及びＲ⁶はそれぞれ炭素数１〜４のアルキル基又はアルコキシ基であり、相互に異なっていても同一でもよい。ｋは０、１、２のいずれかである。）

（式中、Ｖは

のいずれかより選ばれる２価の有機基であり、ｐは０又は１である。Ｒ⁷及びＲ⁸はそれぞれ炭素数１〜４のアルキル基又はアルコキシ基であり、相互に異なっていても同一でもよい。ｈは０、１、２のいずれかである。）

〔２〕
（Ａ）〔１〕記載の一般式（１）で示される繰り返し単位を有する重量平均分子量が３，０００〜５００，０００のシリコーン骨格含有高分子化合物、
（Ｂ）ホルムアルデヒド又はホルムアルデヒド−アルコールにより変性されたアミノ縮合物、１分子中に平均して２個以上のメチロール基又はアルコキシメチロール基を有するフェノール化合物、及び多価フェノールの水酸基をグリシドキシ基に置換した化合物から選ばれる１種又は２種以上の架橋剤、
（Ｃ）波長１９０〜５００ｎｍの光によって分解し、酸を発生する光酸発生剤、
（Ｄ）溶剤
を含有してなる化学増幅型ネガ型レジスト材料。
〔３〕
式（１）において、０．１≦ａ≦０．８、０．１≦ｂ≦０．８、０≦ｃ、０≦ｄ、０＜ｅ≦０．８、０＜ｆ≦０．８である〔２〕記載の化学増幅型ネガ型レジスト材料。
〔４〕
（１）〔２〕又は〔３〕記載の化学増幅型ネガ型レジスト材料を基板上に塗布し、レジスト皮膜を形成する工程、
（２）次いで加熱処理後、フォトマスクを介して波長１９０〜５００ｎｍの高エネルギー線もしくは電子線でレジスト皮膜を露光する工程、
（３）加熱処理した後、現像液を用いて現像する工程
を含むパターン形成方法。
〔５〕
更に、（４）現像によりパターン形成された皮膜を、温度１００〜２５０℃において後硬化する工程を含む〔４〕記載のパターン形成方法。
〔６〕
膜厚１０〜１００μｍである光硬化性樹脂層が支持フィルム及び保護フィルムで挟まれた構造を有する光硬化性ドライフィルムであって、光硬化性樹脂層の形成に用いられる組成物が〔２〕又は〔３〕記載の化学増幅型ネガ型レジスト材料であることを特徴とする光硬化性ドライフィルム。
〔７〕
（ｉ）〔２〕又は〔３〕記載の（Ａ）〜（Ｄ）成分を含有する化学増幅型ネガ型レジスト材料を支持フィルム上に連続的に塗布し、光硬化性樹脂層を形成する工程、
（ｉｉ）上記光硬化性樹脂層を連続的に乾燥させる工程、
（ｉｉｉ）更に、上記光硬化性樹脂層上に上記保護フィルムを貼り合わせる工程
を含む光硬化性ドライフィルムの製造方法。
〔８〕
（ｉ）〔７〕記載の光硬化性ドライフィルムから保護フィルムを剥離することにより露出した光硬化性樹脂層を基板に密着させる工程、
（ｉｉ）上記支持フィルムを介してもしくは上記支持フィルムを剥離した状態で、フォトマスクを介して光硬化性樹脂層を波長１９０〜５００ｎｍの高エネルギー線もしくは電子線で露光する工程、
（ｉｉｉ）露光後の加熱処理を行う工程、
（ｉｖ）現像液にて現像する工程
を含むパターン形成方法。
〔９〕
更に、（ｖ）現像によりパターン形成された皮膜を、温度１００〜２５０℃において後硬化する工程を含む〔８〕記載のパターン形成方法。
〔１０〕
基板が、開口幅が１０〜１００μｍであり、かつ、深さが１０〜１２０μｍである溝及び／又は孔を有する基板である〔８〕又は〔９〕記載のパターン形成方法。
〔１１〕
開口幅が１０〜１００μｍであり、かつ、深さが１０〜１２０μｍである溝及び／又は孔を有する基板に〔６〕記載の光硬化性ドライフィルムの光硬化性樹脂層が積層されてなる積層体。
〔１２〕
〔４〕，〔５〕，〔８〕，〔９〕，〔１０〕のいずれかに記載のパターン形成方法により得られた硬化皮膜からなる電気・電子部品保護用皮膜。
〔１３〕
下記式（２０）で表されるジアリル基を有するアダマンタン骨格含有化合物である１，３−ビス（４−アリロキシフェニル）アダマンタン化合物。

[1]
A silicone skeleton-containing polymer compound having a repeating unit represented by the following general formula (1) and having a weight average molecular weight of 3,000 to 500,000.

(Wherein, .m showing a monovalent hydrocarbon group R ¹ to R ⁴ is 1-8 carbon atoms, which may be the same or different is an integer of 1~100 .a, b, c, d is 0 Or, a positive number, e, f are positive numbers, and a, b, c, d are not simultaneously 0. However, a + b + c + d + e + f = 1, X is represented by the following general formula (2) An organic group, Y is an organic group represented by the following general formula (3), and W is an organic group represented by the following formula (4a) or (4b).)

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ⁵ and R ⁶ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be different or the same. k is 0, 1, or 2. )

(Where V is

And a p is 0 or 1. R ⁷ and R ⁸ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be different or the same. h is 0, 1, or 2. )

[2]
(A) A silicone skeleton-containing polymer compound having a weight average molecular weight of 3,000 to 500,000 having a repeating unit represented by the general formula (1) according to [1],
(B) An amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, and a hydroxyl group of a polyhydric phenol substituted with a glycidoxy group One or more cross-linking agents selected from compounds,
(C) a photoacid generator that decomposes with light having a wavelength of 190 to 500 nm to generate an acid;
(D) A chemically amplified negative resist material containing a solvent.
[3]
In the formula (1), 0.1 ≦ a ≦ 0.8, 0.1 ≦ b ≦ 0.8, 0 ≦ c, 0 ≦ d, 0 <e ≦ 0.8, 0 <f ≦ 0.8 A chemically amplified negative resist material according to [2].
[4]
(1) A step of applying a chemically amplified negative resist material according to [2] or [3] on a substrate to form a resist film,
(2) Next, after the heat treatment, a step of exposing the resist film with a high energy beam or electron beam having a wavelength of 190 to 500 nm through a photomask,
(3) A pattern forming method including a step of developing using a developer after heat treatment.
[5]
Further, (4) The pattern forming method according to [4], further comprising a step of post-curing the film patterned by development at a temperature of 100 to 250 ° C.
[6]
A photocurable dry film having a structure in which a photocurable resin layer having a thickness of 10 to 100 μm is sandwiched between a support film and a protective film, wherein the composition used for forming the photocurable resin layer is [2]. Alternatively, a photocurable dry film, which is a chemically amplified negative resist material according to [3].
[7]
(I) A step of continuously applying a chemically amplified negative resist material containing the components (A) to (D) described in [2] or [3] on a support film to form a photocurable resin layer ,
(Ii) a step of continuously drying the photocurable resin layer;
(Iii) Furthermore, the manufacturing method of the photocurable dry film including the process of bonding the said protective film on the said photocurable resin layer.
[8]
(I) a step of closely attaching a photocurable resin layer exposed by peeling a protective film from the photocurable dry film according to [7] to a substrate;
(Ii) a step of exposing the photocurable resin layer with a high energy beam or an electron beam having a wavelength of 190 to 500 nm through a photomask in a state where the support film is peeled off or via the support film;
(Iii) a step of performing a heat treatment after exposure;
(Iv) A pattern forming method including a step of developing with a developer.
[9]
Furthermore, (v) The pattern formation method as described in [8] including the process of post-curing the film | membrane patterned by image development at the temperature of 100-250 degreeC.
[10]
The pattern forming method according to [8] or [9], wherein the substrate is a substrate having a groove and / or a hole having an opening width of 10 to 100 μm and a depth of 10 to 120 μm.
[11]
Lamination obtained by laminating a photocurable resin layer of a photocurable dry film according to [6] on a substrate having a groove and / or a hole having an opening width of 10 to 100 μm and a depth of 10 to 120 μm. body.
[12]
[4], [5], [8], [9], [10] An electrical / electronic component protective coating comprising a cured coating obtained by the pattern forming method according to any one of [10].
[13]
1,3-bis (4-allyloxyphenyl) adamantane compound which is an adamantane skeleton-containing compound having a diallyl group represented by the following formula (20).

  According to the present invention, it is possible to provide a chemically amplified negative resist material capable of drastically improving the problem of peeling on a metal wiring such as Cu or Al, an electrode, a substrate, particularly a substrate such as SiN, It is possible to form a fine pattern in a wide wavelength range, and it is possible to make the pattern finer in the rewiring technology as the density and integration of the chip increases. An amplification negative resist material, a photocurable dry film, and a pattern forming method can be provided.

It is explanatory drawing which shows the adhesiveness measuring method in an Example.

（式中、Ｒ¹〜Ｒ⁴は同一でも異なっていてもよい炭素数１〜８の１価炭化水素基を示す。ｍは１〜１００の整数である。ａ、ｂ、ｃ、ｄは０又は正数、ｅ、ｆは正数であり、かつ、ａ、ｂ、ｃ、ｄは同時に０になることがない。但し、ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＝１である。更に、Ｘは下記一般式（２）で示される有機基、Ｙは下記一般式（３）で示される有機基、Ｗは下記式（４ａ）もしくは式（４ｂ）で示される有機基である。）

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｎは０又は１である。Ｒ⁵及びＲ⁶はそれぞれ炭素数１〜４のアルキル基又はアルコキシ基であり、相互に異なっていても同一でもよい。ｋは０、１、２のいずれかである。）

（式中、Ｖは

のいずれかより選ばれる２価の有機基であり、ｐは０又は１である。Ｒ⁷及びＲ⁸はそれぞれ炭素数１〜４のアルキル基又はアルコキシ基であり、相互に異なっていても同一でもよい。ｈは０、１、２のいずれかである。）

The silicone skeleton-containing polymer compound according to the present invention has a weight average molecular weight of 3,000 to 500,000 having a repeating unit represented by the following general formula (1).

(Wherein, .m showing a monovalent hydrocarbon group R ¹ to R ⁴ is 1-8 carbon atoms, which may be the same or different is an integer of 1~100 .a, b, c, d is 0 Or, a positive number, e, f are positive numbers, and a, b, c, d are not simultaneously 0. However, a + b + c + d + e + f = 1, and X is represented by the following general formula (2). The organic group shown, Y is the organic group shown by the following general formula (3), and W is the organic group shown by the following formula (4a) or (4b).)

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ⁵ and R ⁶ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be different or the same. k is 0, 1, or 2. )

(Where V is

And a p is 0 or 1. R ⁷ and R ⁸ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be different or the same. h is 0, 1, or 2. )

In the formula, R ^{1 to} R ⁴ represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, which may be the same or different. Specifically, linear, branched or cyclic alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, cyclohexyl group, vinyl group, allyl group, propenyl And straight chain, branched or cyclic alkenyl groups such as a butenyl group, hexenyl group and cyclohexenyl group, aryl groups such as a phenyl group and a tolyl group, and aralkyl groups such as a benzyl group and a phenylethyl group.

Moreover, m is an integer of 1-100, Preferably it is an integer of 1-80 from a compatible viewpoint with the crosslinking agent mentioned later and a photo-acid generator, and a photocurable viewpoint. From the viewpoint of adhesion to the substrate, electrical characteristics, and reliability, a, b, c, and d are 0 or a positive number, e and f are positive numbers, and a, b, c, and d are simultaneously 0. Never become.
In this case, 0 ≦ a ≦ 0.8, 0.1 ≦ b ≦ 0.8, 0 ≦ c, 0 ≦ d, 0 <e ≦ 0.8, 0 <f ≦ 0.8, Preferably 0 ≦ a ≦ 0.8, more preferably 0.1 ≦ a ≦ 0.8, particularly preferably 0.3 ≦ a ≦ 0.7, preferably 0.1 ≦ b ≦ 0.8, More preferably, 0.1 ≦ b ≦ 0.5, preferably 0 ≦ c ≦ 0.5, particularly preferably 0 ≦ c ≦ 0.2, preferably 0 ≦ d ≦ 0.5, particularly preferably. Is 0 ≦ d ≦ 0.2, preferably 0 <e <0.8, particularly preferably 0 <e ≦ 0.5, preferably 0 <f <0.8, particularly preferably 0 <f. ≦ 0.5. However, a + b + c + d + e + f = 1.
Regarding the above-mentioned a, b, c, d, e, f, i. 0.1 ≦ a ≦ 0.8 and 0.1 ≦ b ≦ 0.8, c and d are 0, 0 <e <0.8, 0 <f <0.8,
ii. 0.1 ≦ a ≦ 0.7, 0.1 ≦ b ≦ 0.5, 0 <c ≦ 0.2, 0 <d ≦ 0.2, 0 <e ≦ 0.5, 0 <f ≦ 0. 5
Are preferred.

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｎは０又は１である。Ｒ⁵及びＲ⁶はそれぞれ炭素数１〜４のアルキル基又はアルコキシ基であり、相互に異なっていても同一でもよい。ｋは０、１、２のいずれかである。）
Ｒ⁵及びＲ⁶の具体例としては、メチル基、エチル基、イソプロピル基、ｔｅｒｔ−ブチル基、メトキシ基、エトキシ基、イソプロピルオキシ基等が挙げられる。

（式中、Ｖは

のいずれかより選ばれる２価の有機基であり、ｐは０又は１である。Ｒ⁷及びＲ⁸はそれぞれ炭素数１〜４のアルキル基又はアルコキシ基であり、相互に異なっていても同一でもよい。ｈは０、１、２のいずれかである。）
Ｒ⁷及びＲ⁸の具体例としては、Ｒ⁵又はＲ⁶と同様なものが挙げられる。

Further, X, Y, and W are each selected from organic groups represented by the following general formula (2), general formula (3), formula (4a), or formula (4b).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ⁵ and R ⁶ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be different or the same. k is 0, 1, or 2. )
Specific examples of R ⁵ and R ⁶ include methyl group, ethyl group, isopropyl group, tert-butyl group, methoxy group, ethoxy group, isopropyloxy group and the like.

(Where V is

And a p is 0 or 1. R ⁷ and R ⁸ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be different or the same. h is 0, 1, or 2. )
Specific examples of R ⁷ and R ⁸ include the same as R ⁵ or R ⁶ .

  The weight average molecular weight of the silicone skeleton-containing polymer compound of the present invention is 3,000 from the viewpoint of the compatibility and photocurability of a resist material using the same and the mechanical properties of a cured product obtained from the resist material. ˜500,000, preferably 5,000 to 300,000. In the present invention, the weight average molecular weight is a polystyrene equivalent value determined by gel permeation chromatography (GPC).

と、あるいはこのハイドロジェンシルフェニレン及び下記一般式（６）のジヒドロオルガノシロキサン

（式中、Ｒ³、Ｒ⁴及びｍは、上記と同一である。）
と、下記一般式（７）で示されるジアリル基を有する特定のエポキシ基含有化合物

（式中、Ｖ、Ｒ⁷、Ｒ⁸、ｐ、ｈは、上記と同一である。）
と、下記一般式（８）で示されるジアリル基を有する特定のフェノール化合物

（式中、Ｚ、Ｒ⁵、Ｒ⁶、ｎ、ｋは、上記と同一である。）
と、更に下記式（９ａ）もしくは式（９ｂ）で表されるジアリル基を有するビス（４−ヒドロキシフェニル）アダマンタン骨格含有化合物

とを、触媒の存在下にいわゆる「ハイドロシリレーション」重合反応を行うことにより、製造することができる。 The silicone skeleton-containing polymer compound of the present invention is a hydrogensilphenylene (1,4-bis (dimethylsilyl) benzene) represented by the following formula (5):

Or this hydrogensilphenylene and dihydroorganosiloxane of the following general formula (6)

(Wherein R ³ , R ⁴ and m are the same as above).
And a specific epoxy group-containing compound having a diallyl group represented by the following general formula (7)

(In the formula, V, R ⁷ , R ⁸ , p and h are the same as above.)
And a specific phenol compound having a diallyl group represented by the following general formula (8)

(In the formula, Z, R ⁵ , R ⁶ , n, and k are the same as above.)
And a bis (4-hydroxyphenyl) adamantane skeleton-containing compound having a diallyl group represented by the following formula (9a) or (9b):

Can be produced by carrying out a so-called “hydrosilylation” polymerization reaction in the presence of a catalyst.

  The weight average molecular weight of the silicone skeleton-containing polymer of the present invention has a specific epoxy group-containing compound having a diallyl group represented by the above formula (7) and a diallyl group represented by the above formula (8). The total number of allyl groups of the specific phenol compound and the bis (4-hydroxyphenyl) adamantane skeleton-containing compound having a diallyl group represented by the above formulas (9a) and (9b), and the hydro gen represented by the above formula (5) It can be easily controlled by adjusting the ratio (total number of allyl groups / total number of hydrosilyl groups) of gensylphenylene and the dihydroorganosiloxane represented by the above formula (6) with the total number of hydrosilyl groups. Alternatively, during the polymerization of the specific epoxy group-containing compound having a diallyl group, the specific phenol compound having a diallyl group, the specific isocyanuric acid skeleton-containing compound having a diallyl group, and hydrogensilphenylene and dihydroorganosiloxane, for example, By using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as the molecular weight modifier, the weight average molecular weight can be easily controlled.

In the above polymerization reaction, examples of the catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; H ₂ PtCl ₄ · xH ₂ O, H ₂ PtCl ₆ · xH ₂ O, NaHPtCl ₆ · xH ₂ O, KHPtCl ₆ · xH ₂ O, Na ₂ PtCl ₆ · xH ₂ O, K ₂ PtCl ₄ · xH ₂ O, PtCl ₄ · xH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · xH ₂ O (wherein x is preferably an integer of 0 to 6, and particularly preferably 0 or 6. Platinum chloride, chloroplatinic acid and chloroplatinate, etc .; alcohol-modified chloroplatinic acid (US Pat. No. 3,220,972) A complex of chloroplatinic acid and an olefin (US Pat. No. 3,159,601, US Pat. No. 3,159,662, US Pat. No. 3,775,452); Platinum group such as palladium Metal supported on a support such as alumina, silica, carbon, etc .; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (so-called Wilkinson's catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane (Especially a complex with a vinyl group-containing cyclic siloxane).

  The amount of the catalyst used is a catalyst amount, and is usually preferably 0.001 to 0.1% by mass with respect to the total amount of the reaction polymer as a platinum group metal.

In the above polymerization reaction, a solvent may be used as necessary. As the solvent, for example, hydrocarbon solvents such as toluene and xylene are preferable.
The polymerization temperature is preferably 40 to 150 ° C., particularly 60 to 120 ° C., from the viewpoint that the catalyst is not deactivated and the polymerization can be completed in a short time.
Although the polymerization time depends on the kind and amount of the polymer, it is preferably completed in about 0.5 to 100 hours, particularly 0.5 to 30 hours, in order to prevent moisture from being involved in the polymerization system. When the solvent is used after completion of the polymerization reaction in this way, the silicone skeleton-containing polymer compound represented by the formula (1) of the present invention can be obtained by distilling off the solvent.

  In addition, when the weight average molecular weight of the silicone skeleton-containing polymer compound is decreased, the viscosity of the silicone skeleton-containing polymer compound is decreased. Therefore, the viscosity of the resin layer formed using the chemically amplified negative resist material using the silicone skeleton-containing polymer compound also decreases. In addition, when the proportion of molecular units containing linear polysiloxane [b, d, and f in the general formula (1)] in the molecule of the silicone skeleton-containing polymer compound increases, the relative aromatics such as silphenylene The ratio of the molecular unit containing the compound [a, c and e in the general formula (1)] decreases, and the viscosity of the silicone skeleton-containing polymer compound decreases. Therefore, the viscosity of the resin layer formed using the chemically amplified negative resist material using the silicone skeleton-containing polymer compound also decreases. Further, when the molecular chain length of the linear polysiloxane is increased in the molecule of the silicone skeleton-containing polymer compound, that is, when the value of m in the general formula (1) is increased, the viscosity of the silicone skeleton-containing polymer compound is increased. Will decline. Therefore, the viscosity of the resin layer formed using the chemically amplified negative resist material using the silicone skeleton-containing polymer compound also decreases.

  Note that the bis (4-hydroxyphenyl) adamantane skeleton-containing compound having a diallyl group represented by the above formulas (9a) and (9b) is easily synthesized by the following method. That is, industrially available 2,2-bis (4-hydroxyphenyl) adamantane represented by the following formula (10) or 1,3-bis (4-hydroxyphenyl) adamantane represented by the following formula (19) 2,2-bis (4-allyloxyphenyl) adamantane represented by the following formula (11) is obtained by dissolving in 2 equivalents of allyl halide such as allyl bromide and a solvent and reacting in the presence of a base such as potassium carbonate. Alternatively, 1,3-bis (4-allyloxyphenyl) adamantane represented by the following formula (20) can be obtained. Incidentally, 2-bis (4-allyloxyphenyl) adamantane represented by the formula (11) is disclosed in JP-A-10-130371. Further, 1,3-bis (4-allyloxyphenyl) adamantane represented by the formula (20) is a novel substance.

  Thereafter, the obtained 2,2-bis (4-allyloxyphenyl) adamantane represented by the following formula (11) or 1,3-bis (4-allyloxyphenyl) adamantane represented by the following formula (20) was converted to N Bis (4-hydroxyphenyl) adamantane skeleton having a diallyl group represented by formulas (9a) and (9b) by dissolving in N, diethylaniline and aging at high temperature to cause a Claisen rearrangement reaction The compound can be easily obtained.

The present invention provides a chemically amplified negative resist material containing the following components (A) to (D) using the silicone skeleton-containing polymer compound.
(A) The above silicone skeleton-containing polymer compound,
(B) An amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, and a hydroxyl group of a polyhydric phenol substituted with a glycidoxy group One or more cross-linking agents selected from compounds,
(C) a photoacid generator that decomposes with light having a wavelength of 190 to 500 nm to generate an acid;
(D) Solvent

  Here, (B) as the crosslinking agent, an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in a molecule, and a polyhydric phenol 1 type (s) or 2 or more types selected from the compound which substituted the hydroxyl group of this by the glycidoxy group can be used.

  Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include melamine condensate modified with formaldehyde or formaldehyde-alcohol, or urea condensate modified with formaldehyde or formaldehyde-alcohol.

  Preparation of the melamine condensate modified with formaldehyde or formaldehyde-alcohol is, for example, first modified by methylolating a melamine monomer with formalin according to a known method, or further alkoxylated with alcohol to modify the following general formula: The modified melamine represented by (12) is used. In addition, as said alcohol, a lower alcohol, for example, C1-C4 alcohol, is preferable.

（式中、Ｒ¹¹は同一でも異なってもよく、メチロール基、炭素数１〜４のアルコキシ基を含むアルコキシメチル基又は水素原子であるが、少なくとも１つはメチロール基又は上記アルコキシメチル基である。）
上記Ｒ¹¹としては、例えば、メチロール基、メトキシメチル基、エトキシメチル基等のアルコキシメチル基及び水素原子等が挙げられる。

(In the formula, R ¹¹ may be the same or different and is a methylol group, an alkoxymethyl group containing 1 to 4 carbon atoms or a hydrogen atom, but at least one is a methylol group or the above alkoxymethyl group. .)
Examples of R ¹¹ include a methylol group, an alkoxymethyl group such as a methoxymethyl group, an ethoxymethyl group, and a hydrogen atom.

Specific examples of the modified melamine of the general formula (12) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine and the like.
Subsequently, the modified melamine of the general formula (12) or this multimer (for example, an oligomer such as a dimer or a trimer) is subjected to addition condensation polymerization with formaldehyde until a desired molecular weight is obtained according to a conventional method. A melamine condensate modified with formaldehyde-alcohol is obtained.

The urea condensate modified with formaldehyde or formaldehyde-alcohol is prepared by, for example, modifying a urea condensate having a desired molecular weight with methylol with formaldehyde or modifying the urea condensate with alcohol with a known method. Denature.
Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include, for example, methoxymethylated urea condensate, ethoxymethylated urea condensate, propoxymethylated urea condensate and the like.
In addition, 1 type, or 2 or more types of these modified melamine condensates and modified urea condensates can also be mixed and used.

Subsequently, as an example of a phenol compound having two or more methylol groups or alkoxymethylol groups on average in one molecule, (2-hydroxy-5-methyl) -1,3-benzenedimethanol, 2,2 ′, 6,6′-tetramethoxymethylbisphenol A and the like can be mentioned.
One or more of these phenol compounds can be used as a crosslinking agent.
In addition, the said crosslinking agent can be used 1 type or in combination of 2 or more types.

On the other hand, as a compound in which the hydroxyl group of polyhydric phenol is substituted with a glycidoxy group, the hydroxyl group of bisphenol A, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane is epitheliated in the presence of a base. 1,1′-diglycidoxybisphenol A obtained by reacting with chlorohydrin, tris (4-glycidoxyphenyl) methane, 1,1,1-tris (4-glycidoxyphenyl) ethane, etc. Can be mentioned.
One or two types of compounds in which the hydroxyl group of these polyphenols is substituted with a glycidoxy group can be used as a crosslinking agent.

  The crosslinking agent is a component that causes a curing reaction with the above-described silicone skeleton-containing polymer compound and can easily form a pattern, and further increases the strength of the cured product. The weight average molecular weight of such a crosslinking agent is preferably from 150 to 10,000, particularly from 200 to 3,000, from the viewpoint of photocurability and heat resistance.

  The blending amount of the crosslinking agent is 0.5 to 50 masses with respect to 100 mass parts of the silicone skeleton-containing polymer compound from the viewpoint of reliability as a film for protecting electrical and electronic parts that has undergone photocuring and post-curing. Parts, particularly 1 to 30 parts by weight.

  (C) As a photo-acid generator, what generate | occur | produces an acid by light irradiation with a wavelength of 190-500 nm, and this becomes a curing catalyst can be used. Since the resist material of the present invention is excellent in compatibility with the photoacid generator, various types of photoacid generators can be used. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonates. Derivatives, triazine derivatives and the like.

As said onium salt, the compound represented by following General formula (13) is mentioned, for example.
(R ¹² ) _j M ⁺ K ⁻ (13)
Wherein R ¹² is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, which may have a substituent. M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and j represents 2 or 3.

In R ¹² , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-oxocyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the aryl group include a phenyl group; an alkoxyphenyl group such as o-, m- or p-methoxyphenyl group, ethoxyphenyl group, m- or p-tert-butoxyphenyl group; 2-, 3- or 4- Examples thereof include alkylphenyl groups such as methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group. Examples of the aralkyl group include groups such as a benzyl group and a phenethyl group.

Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions; fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; tosylate and benzene Examples thereof include aryl sulfonates such as sulfonate, 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate; alkyl sulfonates such as mesylate and butane sulfonate.

（式中、Ｒ¹³は同一でも異なってもよく、炭素数１〜１２の直鎖状、分岐状もしくは環状のアルキル基もしくはハロゲン化アルキル基、炭素数６〜１２のアリール基もしくはハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を表す。） Examples of the diazomethane derivative include compounds represented by the following general formula (14).

(In the formula, R ¹³ may be the same or different and is a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, aryl group or halogenated aryl group having 6 to 12 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms.)

Examples of the alkyl group in R ¹³ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. Examples of the aryl group include a phenyl group; an alkoxyphenyl group such as o-, m- or p-methoxyphenyl group, ethoxyphenyl group, m- or p-tert-butoxyphenyl group; 2-, 3- or 4- Examples thereof include alkylphenyl groups such as methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

Specifically, as a photoacid generator, for example, trifluoromethanesulfonic acid diphenyliodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p -Tert-butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, trifluoromethane Tris (p-tert-butoxyphenyl) sulfonium sulfonate, p-toluenesulfonate triphenylsulfonium, p-tolue Sulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfone Triphenylsulfonium acid, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2 -Oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, p-toluene Onium salts such as dimethylphenylsulfonium sulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, diphenyl (4-thiophenoxyphenyl) sulfonium hexafluoroantimonate; bis (benzenesulfonyl) diazomethane, bis ( p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec- Butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropyl Rusulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1- Diazomethane derivatives such as cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane Bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenes) Sulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis- (p-toluenesulfonyl) -2-methyl-3,4-pentanediol Lioxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α- Dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, Bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylg Oxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctane Sulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -Α-dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl) -Glyoxime derivatives such as α-dimethylglyoxime; α- (benzenesulfur Oxime sulfonate derivatives such as onium oxyimino) -4-methylphenylacetonitrile; β- such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane Ketosulfone derivatives; disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; nitrobenzylsulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate; 1,2,3 -Sulfonic acid ester derivatives such as tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene; Imido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene 2,3-dicarboximido-yl-triflate, 5-norbornene 2,3-dicarboximido-yl-tosylate, 5-norbornene 2,3 -Imido-yl-sulfonate derivatives such as dicarboximido-yl-n-butylsulfonate, n-trifluoromethylsulfonyloxynaphthylimide; (5- (4-methylphenyl) sulfonyloxyimino-5H-thiophen-2-ylidene )-(2-methylphenyl) acetonitrile, (5- (4- (4-methylphenylsulfonyloxy) phenylsulfonyloxyimino) -5H-thiophen-2-ylidene)-(2-methylphenyl) -acetonitrile Sulfonate, 2-methyl- And 2 [(4-methylphenyl) sulfonyl] -1-[(4-methylthio) phenyl] -1-propane. Among these, imido-yl-sulfonates, iminosulfonates, oxime sulfonates and the like are preferably used.
The said photo-acid generator can use 1 type (s) or 2 or more types.

  The compounding amount of the photoacid generator is 0.05 to 20 parts by mass with respect to 100 parts by mass of the silicone skeleton-containing polymer compound, from the viewpoint of light absorption of the photoacid generator itself and photocurability in a thick film. 0.2-5 mass parts is especially preferable.

(D) As a solvent, what can melt | dissolve the silicone frame containing polymer compound mentioned above, a crosslinking agent, and a photo-acid generator can be used.
For example, ketones such as cyclohexanone, cyclopentanone, methyl-2-n-amyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, etc. Alcohols such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxypropio Ethyl acetate tert- butyl, tert- butyl propionate, propylene glycol - monobutyl -tert- butyl ether acetate, etc. esters such as γ- butyrolactone and the like, can be used alone or in combination of two or more thereof. In particular, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone or a mixed solvent thereof, which is most excellent in solubility of the photoacid generator, is preferable.

  From the viewpoint of compatibility, viscosity, and coatability of the resist material, the amount of the solvent is 50 to the total 100 parts by mass of the silicone skeleton-containing polymer compound, the crosslinking agent, and the photoacid generator. 2,000 parts by mass, particularly 100 to 1,000 parts by mass are preferred.

  Furthermore, in this invention, a basic compound can be added as (E) component as needed. As said basic compound, the compound which can suppress the diffusion rate at the time of the acid which generate | occur | produces from a photo-acid generator diffuses a resist film is suitable. Then, by blending the basic compound, the resolution can be improved, the sensitivity change after exposure can be suppressed, the substrate and environment dependency can be reduced, and the exposure margin and pattern shape can be improved.

  Examples of the basic compound include primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, and sulfonyl groups. Examples thereof include nitrogen-containing compounds, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and compounds represented by the following general formula (15).

ここで、Ｒ³⁰⁰、Ｒ³⁰²、Ｒ³⁰⁵は炭素数１〜４の直鎖状又は分岐状のアルキレン基であり、Ｒ³⁰¹、Ｒ³⁰⁴は水素原子又は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基であり、ヒドロキシル基、エーテル結合、エステル結合、ラクトン環を１あるいは複数含んでいてもよい。Ｒ³⁰³は単結合又は炭素数１〜４の直鎖状もしくは分岐状のアルキレン基であり、Ｒ³⁰⁶は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基であり、ヒドロキシル基、エーテル結合、エステル結合、ラクトン環を１あるいは複数含んでいてもよい。なお、＊は結合末端を示す。 N (α) _q (β) _3-q (15)
In the formula, q = 1, 2, or 3. The side chain α may be the same or different, and is any substituent represented by the following general formulas (16) to (18). The side chains β may be the same or different and each represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether bond or a hydroxyl group. Further, the side chains α may be bonded to form a ring.

Here, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are hydrogen atoms or linear and branched groups having 1 to 20 carbon atoms. Or a cyclic alkyl group, which may contain one or a plurality of hydroxyl groups, ether bonds, ester bonds and lactone rings. R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxyl group, One or a plurality of ether bonds, ester bonds and lactone rings may be contained. In addition, * shows a bond terminal.

  Specifically, primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Examples include amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

  Secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, Examples include dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine and the like.

  Tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, tri Hexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, Examples thereof include N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like.

  Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like.

  Aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline). 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline , N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2 , 4-Dimethyl Roll, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methyl, etc.) Imidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, Methylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, Piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quino Phosphocarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives And adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

  Examples of the nitrogen-containing compound having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine and the like).

  Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

  Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine , Diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1 -Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidine Tanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxy Yurolidine, 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Is exemplified.

Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like.
Examples of imide derivatives include phthalimide, succinimide, maleimide and the like.

Examples of the compound represented by the general formula (15) include tris [2- (methoxymethoxy) ethyl] amine, tris [2- (2-methoxyethoxy) ethyl] amine, and tris [2- (2-methoxyethoxymethoxy). ) Ethyl] amine, tris [2- (1-methoxyethoxy) ethyl] amine, tris [2- (1-ethoxyethoxy) ethyl] amine, tris [2- (1-ethoxypropoxy) ethyl] amine, tris [2 -{2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13, 18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 1,4,10,13-tetraoxa-7,16-diazabi Crooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) Amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2- Pivaloyloxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) amine , Tris [2- (2-oxopropoxy) ethyl] amine, tris [2- Methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N -Bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2 -Methoxyethoxycarbonyl) Tylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N- Bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxy) Ethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- ( 2-oxopropoxycarbonyl) ethylamine, N, N-bis ( -Hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- [(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyl) Oxyethyl) 2- (2-formyloxyate) Sicarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxy) Ethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) Ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2 -(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N- Methylbis (2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) Examples thereof include, but are not limited to, amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone.
The said basic compound can use 1 type (s) or 2 or more types.

  The blending amount of the basic compound is preferably 0 to 3 parts by mass, particularly 0.01 to 1 part by mass with respect to 100 parts by mass of the silicone skeleton-containing polymer compound from the viewpoint of sensitivity.

  In addition to the above components (A) to (E), an additive component may be further blended in the chemically amplified negative resist material. Examples of the additive component include light absorbers commonly used for improving light absorption efficiency such as surfactants and photoacid generators commonly used for improving coatability.

  The surfactant is preferably a nonionic one, for example, a fluorine-based surfactant, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, fluorine-containing organosiloxane. Compounds and the like.

  As these, commercially available products can be used. For example, Florard “FC-4430” (manufactured by Sumitomo 3M Limited), Surflon “S-141” and “S-145” (above, Asahi Glass Co., Ltd.) ), Unidyne "DS-401", "DS-4031" and "DS-451" (manufactured by Daikin Industries, Ltd.), MegaFuck "F-8151" (manufactured by DIC Corporation), "X- 70-093 "(manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, Fluorard “FC-4430” (manufactured by Sumitomo 3M Limited) and “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.) are preferable.

  Examples of the light absorber include diaryl sulfoxide, diaryl sulfone, 9,10-dimethylanthracene, 9-fluorenone and the like.

  In the chemically amplified negative resist material of the present invention, the preparation is performed by a usual method. The above-mentioned chemically amplified negative resist material can be prepared by stirring and mixing the components described above and then filtering with a filter or the like. When manufacturing the dry film mentioned later, it can prepare similarly using this resist material.

In order to form a pattern using the negative resist material of the present invention, a known lithography technique can be employed. For example, a pattern such as a silicon wafer, a SiO ₂ substrate, a SiN substrate, or a copper wiring is formed. A resist film having a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm is applied to the substrate by spin coating and prebaked at 80 to 130 ° C. for about 50 to 600 seconds. Form. Next, a mask for forming a target pattern is placed over the resist film, and high energy rays having a wavelength of 190 to 500 nm such as i-line and g-line are exposed to an exposure amount of about 1 to 5,000 mJ / cm ² , preferably Irradiation is performed so as to be about 100 to 2,000 mJ / cm ² . Next, if necessary, post-exposure baking (PEB) may be performed on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably 80 to 120 ° C. for 1 to 5 minutes. By exposing in this way, the exposed part is crosslinked to form an insolubilized pattern insoluble in the following solvent as a developer.

  Then, it develops with a developing solution. As the developer, the above-described solvent used when the chemically amplified negative resist material of the present invention is prepared can be used. For example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as propylene glycol monomethyl ether are preferable. Development can be performed by a normal method, for example, by immersing a substrate on which a pattern is formed in the developer. Thereafter, washing, rinsing, drying, and the like are performed as necessary to obtain a resist film having a desired pattern. In addition, when it is not necessary to form a pattern, for example, when it is desired to form a simple uniform film, it may be performed by the same method as described in the pattern forming method except that the photomask is not used.

  Further, the resist film is post-cured at a temperature of 100 to 250 ° C., preferably 150 to 220 ° C., more preferably 170 to 190 ° C., using the obtained pattern using an oven or a hot plate. If the post-curing temperature is 100 to 250 ° C., the cross-linking density of the resist film can be increased and the remaining volatile components can be removed, which is preferable from the viewpoints of adhesion to the substrate, heat resistance and strength, and electrical characteristics. The post-curing time can be 10 minutes to 10 hours.

  The cured film thus obtained is excellent in flexibility, adhesion to the substrate, heat resistance, electrical properties, mechanical strength and chemical resistance to the solder flux liquid, and it is a semiconductor element using it as a protective film. It is also excellent in reliability, can prevent cracking especially during temperature cycle tests, and is suitably used as a protective film for electrical / electronic parts, semiconductor elements and the like.

  The present invention can further form a photocurable dry film using the resist material.

  First, the structure of the photocurable dry film of the present invention will be described. The photocurable dry film has a structure in which a photocurable resin layer is sandwiched between a support film and a protective film. And as said photocurable resin layer, it can obtain using the said resist material effective in formation of the film | membrane for electric / electronic component protection, and the obtained dry film has a fine pattern in a wide film thickness and wavelength range. It can be formed and is excellent in flexibility, heat resistance, electrical properties, adhesion, reliability and chemical resistance by post-curing at low temperature.

  In the present invention, the photocurable resin layer of the photocurable dry film obtained using the resist material is a solid, and the photocurable resin layer does not contain a solvent. There is no possibility of remaining between the inside of the layer and the uneven substrate. And, as the semiconductor elements are becoming smaller, thinner, and multilayered, the interlayer insulating layer, which is the scope of application of the present invention, tends to be thin, but considering the flatness and the step coverage on an uneven substrate. An appropriate film thickness range exists. Therefore, the film thickness of the photocurable resin layer is 10 to 100 μm, preferably 10 to 70 μm, particularly preferably 10 to 50 μm, from the viewpoint of flatness and step coverage.

  In addition, the viscosity and fluidity of the photocurable resin layer are closely related, and the photocurable resin layer can exhibit appropriate fluidity in an appropriate viscosity range, and enters deep inside a narrow gap. I can go.

  Therefore, when the photocurable dry film of the present invention is closely attached to a substrate having unevenness, the photocurable resin layer is coated following the unevenness, and high flatness can be achieved. In particular, when the main component of the photocurable resin layer is a photocurable silicone composition, a low surface tension is a characteristic, so that higher flatness can be achieved. Furthermore, when the photocurable resin layer is brought into close contact with the substrate in a vacuum environment, the generation of the gaps can be more effectively prevented.

  Next, the manufacturing method of the photocurable dry film of this invention and the pattern formation method using the dry film are described.

  In the photocurable dry film of the present invention, the chemical amplification type negative resist material used for forming the photocurable resin layer is prepared by stirring and mixing the components as described above, and then filtering with a filter or the like. Thus, a photocurable resin layer forming material can be prepared.

  The support film used in the photocurable dry film of the present invention may be a single film or a multilayer film in which a plurality of polymer films are laminated. Examples of the material include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Polyethylene terephthalate having appropriate flexibility, mechanical strength, and heat resistance is preferable. Further, these films may be subjected to various treatments such as corona treatment or a release agent. Commercially available products can be used, for example, Therapy WZ (RX), Therapy BX8 (R) (above, manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (above, manufactured by Toyobo Co., Ltd.), Pew Rex G31, Purex G71T1 (above, manufactured by Teijin DuPont Films Co., Ltd.), PET38 × 1-A3, PET38 × 1-V8, PET38 × 1-X08 (above, manufactured by Nipper Corp.) and the like.

  The protective film used in the photocurable dry film of the present invention can be the same as the above-described support film, but polyethylene terephthalate and polyethylene having moderate flexibility are preferable. These can use a commercial item, and what was already illustrated as a polyethylene terephthalate, As a polyethylene, GF-8 (made by Tamapoly Co., Ltd.) and PE film 0 type (made by Nipper Co., Ltd.) are mentioned, for example. .

  The thickness of the support film and the protective film is preferably 10 to 100 μm, particularly preferably 25 to 50 μm, from the viewpoints of the stability of the photocurable dry film production and curling against the winding core, so-called curl prevention.

  Next, the manufacturing method of the photocurable dry film in this invention is demonstrated. Generally, a film coater for producing a pressure-sensitive adhesive product can be used as the photocurable dry film production apparatus. Examples of the film coater include a comma coater, a comma reverse coater, a multi coater, a die coater, a lip coater, a lip reverse coater, a direct gravure coater, an offset gravure coater, a three bottom reverse coater, and a four bottom reverse coater. It is done.

  When the support film was unwound from the unwinding shaft of the film coater and passed through the coater head of the film coater, the resist material was applied with a predetermined thickness on the support film to form a photocurable resin layer. Thereafter, the photocurable resin layer that has been passed through a hot-air circulating oven at a predetermined temperature and a predetermined time and dried on the support film, together with a protective film unwound from another unwinding shaft of the film coater, is predetermined. The film is passed through a laminating roll at a pressure of 1 and bonded to the photocurable resin layer on the support film, and then wound on a winding shaft of the film coater. In this case, the temperature is preferably 25 to 150 ° C., the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5 MPa.

  Furthermore, the pattern formation method of the photocurable dry film in this invention is demonstrated. The protective film is peeled from the photocurable dry film of the present invention, the photocurable resin layer is adhered to the substrate, exposed, subjected to post-exposure heat treatment (post-exposure baking (hereinafter referred to as PEB)), developed, Furthermore, if necessary, the film is post-cured to form a pattern, and the final target electric / electronic component protecting film is obtained.

First, a photocurable dry film is adhered to a substrate using a film sticking apparatus. Examples of the substrate include silicon wafers, TSV silicon wafers, plastics, ceramics, and various metal circuit boards. Particularly, a substrate having a groove or a hole having an opening width of 10 to 100 μm and a depth of 10 to 120 μm. Can be mentioned. As said film sticking apparatus, a vacuum laminator is preferable. The photocurable dry film is attached to the film application device, and the photocurable resin layer exposed by peeling off the protective film of the photocurable dry film is exposed to a predetermined pressure in a vacuum chamber having a predetermined degree of vacuum. Using a sticking roll, the substrate is brought into close contact with a table at a predetermined temperature. The temperature is preferably 60 to 120 ° C., the pressure is preferably 0 to 5.0 MPa, and the vacuum is preferably 50 to 500 Pa. After the adhesion, a pattern can be formed using a known lithography technique. Here, in order to efficiently perform the photocuring reaction of the photocurable resin layer or to improve the adhesion between the photocurable resin layer and the substrate, preheating (prebaking) may be performed as necessary. . Pre-baking can be performed, for example, at 40 to 140 ° C. for about 1 minute to 1 hour. Next, the film is exposed and cured with light having a wavelength of 190 to 500 nm through a photomask in a state where the support film is peeled off through the support film. For example, the photomask may be formed by cutting a desired pattern. The material of the photomask is preferably one that shields light having a wavelength of 190 to 500 nm, and for example, chromium is preferably used, but is not limited thereto. Examples of the light having a wavelength of 190 to 500 nm include light of various wavelengths generated by a radiation generator, for example, ultraviolet light such as g-line and i-line, and far-ultraviolet light (248 nm and 193 nm). The wavelength is preferably 248 to 436 nm. The exposure amount is preferably, for example, 10 to 3,000 mJ / cm ² . By exposing in this way, the exposed part is crosslinked to form an insolubilized pattern insoluble in the following solvent as a developer.

  Further, post-exposure heat treatment (PEB) is performed to increase the development sensitivity. The heat treatment after the exposure can be performed at 40 to 140 ° C. for 0.5 to 10 minutes, for example.

  Then, it develops with a developing solution. As the developer, a solvent of a resist material used for forming a photocurable resin layer in the photocurable dry film of the present invention can be used. For example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as propylene glycol monomethyl ether are preferable. Development can be performed by a normal method, for example, by immersing a substrate on which a pattern is formed in the developer. Thereafter, washing, rinsing, drying, and the like are performed as necessary to obtain a film of the photocurable resin layer having a desired pattern. In addition, when it is not necessary to form a pattern, for example, when it is desired to form a simple uniform film, it may be performed by the same method as described in the pattern forming method except that the photomask is not used.

  Moreover, the obtained pattern is post-cured at a temperature of 100 to 250 ° C., preferably 150 to 220 ° C., more preferably 170 to 190 ° C., using an oven or a hot plate. If the post-curing temperature is 100 to 250 ° C., the crosslinking density of the film of the photocurable resin layer can be increased, and the remaining volatile components can be removed, which is preferable from the viewpoint of adhesion to the substrate, heat resistance and strength, and electrical properties. . The post-curing time can be 10 minutes to 10 hours.

  The cured film thus obtained is also excellent in flexibility, adhesion to the substrate, heat resistance, electrical properties, mechanical strength and chemical resistance to the solder flux solution, and a semiconductor element using it as a protective film In particular, it is excellent in reliability, can prevent the occurrence of cracks during the temperature cycle test, and can be suitably used as a protective film for electrical / electronic parts, semiconductor elements and the like.

  The dry film of the present invention can be effectively applied to a substrate having grooves and holes as described above. Therefore, the present invention can be applied to grooves and / or grooves having an opening width of 10 to 100 μm and a depth of 10 to 120 μm. The present invention provides a laminate in which a cured layer of a photocurable resin formed of the photocurable dry film is laminated on a substrate having holes.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following example. In addition, in the following example, a part shows a mass part.
I. Preparation of Chemically Amplified Negative Resist Material The chemical structural formulas of compounds (M-1) to (M-10) used in the following synthesis examples are shown.

[Synthesis Example 1]
In a 500 mL three-necked flask purged with nitrogen, 51 g (159 mmol) of 1,3-bis (4-hydroxyphenyl) adamantane, 42.4 g (350 mmol) of allyl bromide, 100 g of acetone, and 80 g of THF (tetrahydrofuran) were weighed. After stirring at room temperature and dissolution, 44.0 g of potassium carbonate was added and heated to 70 ° C. After aging for 25 hours, the mixture was allowed to cool to room temperature, 200 g of ultrapure water and 50 g of toluene were added, and the mixture was transferred to a 1 L separatory funnel. The organic layer was taken out and the aqueous layer was extracted with 200 g of ethyl acetate. The organic layers were combined and separated and washed with 200 g of ultrapure water twice. The organic layer was concentrated under reduced pressure, 200 g of methanol was added to the remaining solid, and the mixture was stirred at room temperature for 1 hour. The crystals were filtered off and dried to obtain 52.4 g of Compound (M-6), yield 82.3%. I got it.
In a 300 mL three-necked flask purged with nitrogen, 50.0 g (125 mmol) of the compound (M-6) and 100 g of N, N-diethylaniline were weighed. The mixture was heated to 170 ° C., aged for 30 hours, allowed to cool to room temperature, added with 100 g of ethyl acetate, and transferred to a 500 mL separatory funnel. The liquid separation operation was repeated three times with 100 g of 10% by mass hydrochloric acid, and then the liquid separation washing with 100 g of ultrapure water was repeated three times. The organic layer was concentrated under reduced pressure, 100 g of hexane was added to the remaining solid, heated to 80 ° C., stirred for 1 hour, allowed to cool to room temperature, the crystals were filtered off and dried to give compound (M-7). Obtained 46.2 g, yield 92.4%.
The compound (M-7) was identified by ¹ H-NMR (600 MHz) (JEOL-600 JEOL).

[Synthesis Example 2]
In a 500 mL three-necked flask purged with nitrogen, 2,2-bis (4-hydroxyphenyl) adamantane 40 g (125 mmol), allyl bromide 33.2 g (275 mmol), acetone 100 g, and THF 80 g were weighed. After stirring at room temperature to obtain a suspension, 34.5 g of potassium carbonate was added and heated to 70 ° C. After aging for 30 hours, the mixture was allowed to cool to room temperature, 200 g of ultrapure water and 50 g of toluene were added, and the mixture was transferred to a 1 L separatory funnel. The organic layer was taken out and the aqueous layer was extracted with 200 g of ethyl acetate. The organic layers were combined and separated and washed with 200 g of ultrapure water twice. The organic layer was concentrated under reduced pressure, 200 g of methanol was added to the remaining solid content, and the mixture was stirred at room temperature for 1 hour. The crystals were filtered off and dried to give 46.1 g of Compound (M-8), yield 92.1%. I got it.
46 g (115 mmol) of the compound (M-8) and 92 g of N, N-diethylaniline were weighed in a 300 mL three-necked flask purged with nitrogen. After heating to 170 ° C. and aging for 15 hours, the mixture was allowed to cool to room temperature, 100 g of ethyl acetate was added, and the mixture was transferred to a 500 mL separatory funnel. The liquid separation operation was repeated three times with 100 g of 10% by mass hydrochloric acid, and then the liquid separation washing with 100 g of ultrapure water was repeated three times. The organic layer was concentrated under reduced pressure, 140 g of hexane was added to the remaining solid content, and the mixture was stirred at room temperature for 1 hour. The crystals were filtered off and dried to give 40.5 g of Compound (M-9), yield 88.0. %.
The compound (M-9) was identified by ¹ H-NMR (600 MHz) (JEOL-600 JEOL).

Synthesis Example 3 Synthesis of Silicone Skeletal-Containing Polymer Compound Solution (A-1) 70 g of Compound (M-1) was added to 330 g of toluene in a 2 L flask equipped with a stirrer, thermometer, nitrogen displacement device and reflux condenser. Then, 15.9 g of compound (M-7), 104.4 g of compound (M-3) and 1.2 g of compound (M-4) were added and heated to 60 ° C. Thereafter, 0.4 g of a carbon-supported platinum catalyst (5% by mass) was added, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C., the mixture was further heated to 90 ° C. for 3 hours, and again 60 ° C. Then, 0.4 g of a carbon-supported platinum catalyst (5% by mass) was added, and 25.7 g of the compound (M-5) was dropped into the flask over 1 hour. At this time, the temperature in the flask rose to 65 to 67 ° C. After completion of dropping, the mixture was further aged at 90 ° C. for 3 hours, cooled again to 60 ° C. and aged for 7 days. On the 2nd, 3rd, 4th, and 5th days of aging, 0.4 g of carbon-supported platinum catalyst (5% by mass) was added. Thereafter, 350 g of methyl isobutyl ketone was added to the reaction solution, and the platinum catalyst was removed by pressure-filtering the reaction solution with a filter. Furthermore, 150 g of pure water was added to the obtained silicone skeleton-containing polymer compound solution, and the mixture was stirred and allowed to stand to remove the lower aqueous layer. This separation water washing operation was repeated 6 times to remove the trace acid component in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and 1,000 g of cyclopentanone was added, followed by concentration under reduced pressure to obtain a cyclopentanone solution having a solid concentration of 65 to 70% by mass. A silicone skeleton-containing polymer compound solution (A-1) containing pentanone as a main solvent was obtained. When the molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC, it was a weight average molecular weight of 29,000 in terms of polystyrene. Further, in the formula (1), a = 0.578, b = 0.201, c = 0, d = 0, e = 0.164, f = 0.057.

Synthesis Example 4 Synthesis of Silicone Skeletal-Containing Polymer Compound Solution (A-2) 70 g of Compound (M-1) was added to 330 g of toluene in a 2 L flask equipped with a stirrer, thermometer, nitrogen displacement device and reflux condenser. After dissolution, 53.8 g of compound (M-7), 165.8 g of compound (M-3) and 1.8 g of compound (M-4) were added, and the mixture was heated to 60 ° C. Thereafter, 0.6 g of carbon-supported platinum catalyst (5% by mass) was added, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C., the mixture was further heated to 90 ° C. for 3 hours, and again to 60 ° C. Then, 0.6 g of a carbon-supported platinum catalyst (5% by mass) was added, and 39.3 g of the compound (M-5) was dropped into the flask over 1 hour. At this time, the temperature in the flask rose to 65 to 67 ° C. After completion of dropping, the mixture was further aged at 90 ° C. for 3 hours, cooled again to 60 ° C. and aged for 7 days. In the middle of aging 2, 3, 4 and 5, 0.6 g of carbon-supported platinum catalyst (5% by mass) was added. Thereafter, 530 g of methyl isobutyl ketone was added to the reaction solution, and the platinum catalyst was removed by pressure-filtering the reaction solution with a filter. Furthermore, 230 g of pure water was added to the obtained silicone skeleton-containing polymer compound solution, and the mixture was stirred and allowed to stand to remove the lower aqueous layer. This separation water washing operation was repeated 6 times to remove the trace acid component in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and 1,000 g of cyclopentanone was added, followed by concentration under reduced pressure to obtain a cyclopentanone solution having a solid concentration of 65 to 70% by mass. A silicone skeleton-containing polymer compound solution (A-2) containing pentanone as a main solvent was obtained. When the molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC, it was a weight average molecular weight of 29,000 in terms of polystyrene. In the formula (1), a = 0.375, b = 0.132, c = 0, d = 0, e = 0.365, and f = 0.128.

[Synthesis Example 5] Synthesis of silicone skeleton-containing polymer compound solution (A-3) Cyclopenta synthesized in the same manner as in Synthesis Example 3 except that compound (M-7) was replaced with 15.9 g of compound (M-9). A silicone skeleton-containing polymer compound solution (A-3) containing non as a main solvent was obtained. When the molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC, the weight average molecular weight was 28,000 in terms of polystyrene. Further, in the formula (1), a = 0.578, b = 0.201, c = 0, d = 0, e = 0.164, f = 0.057.

[Synthesis Example 6] Synthesis of silicone skeleton-containing polymer compound solution (A-4) Cyclopenta synthesized in the same manner as in Synthesis Example 4 except that compound (M-7) was replaced with 53.8 g of compound (M-9). A silicone skeleton-containing polymer compound solution (A-4) containing non as a main solvent was obtained. When the molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC, the weight average molecular weight was 28,000 in terms of polystyrene. In the formula (1), a = 0.375, b = 0.132, c = 0, d = 0, e = 0.365, and f = 0.128.

[Synthesis Example 7] Synthesis of silicone skeleton-containing polymer compound solution (A-5) 70 g of compound (M-1) was added to 330 g of toluene in a 2 L flask equipped with a stirrer, thermometer, nitrogen displacement device and reflux condenser. Then, 7.9 g of compound (M-7), 8.3 g of compound (M-10), 105.9 g of compound (M-3) and 1.2 g of compound (M-4) were added, and the mixture was heated to 60 ° C. Warm up. Thereafter, 0.4 g of a carbon-supported platinum catalyst (5% by mass) was added, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C., the mixture was further heated to 90 ° C. for 3 hours, and again 60 ° C. Then, 0.4 g of a carbon-supported platinum catalyst (5% by mass) was added, and 25.7 g of the compound (M-5) was dropped into the flask over 1 hour. At this time, the temperature in the flask rose to 65 to 67 ° C. After completion of the dropwise addition, the mixture was further aged at 90 ° C. for 3 hours, cooled to room temperature, 350 g of methyl isobutyl ketone was added, and the platinum catalyst was removed by pressure filtration of the reaction solution through a filter. Furthermore, 150 g of pure water was added to the obtained silicone skeleton-containing polymer compound solution, and the mixture was stirred and allowed to stand to remove the lower aqueous layer. This separation water washing operation was repeated 6 times to remove the trace acid component in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and 1,000 g of cyclopentanone was added, followed by concentration under reduced pressure to obtain a cyclopentanone solution having a solid concentration of 65 to 70% by mass. A silicone skeleton-containing polymer compound solution (A-5) containing pentanone as a main solvent was obtained. When the molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC, the weight average molecular weight was 30,000 in terms of polystyrene. In the formula (1), a = 0.777, b = 0.201, c = 0.082, d = 0.029, e = 0.082, and f = 0.029.

[Comparative Synthesis Example 1] Synthesis of silicone skeleton-containing polymer compound solution (A-6) 797 g of compound (M-1) was added to toluene in a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device and reflux condenser. After dissolving in 2,500 g, Compound (M-2) 140.6 g, Compound (M-3) 1,214.4 g, and Compound (M-4) 13.3 g were added and heated to 60 ° C. Thereafter, 3.5 g of a carbon-supported platinum catalyst (5% by mass) was added, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C., the mixture was further heated to 90 ° C. for 3 hours, and again to 60 ° C. Then, 3.5 g of carbon-supported platinum catalyst (5% by mass) was added, and 285.2 g of compound (M-5) was added dropwise into the flask over 1 hour. At this time, the temperature in the flask rose to 65 to 67 ° C. After completion of dropping, the mixture was further aged at 90 ° C. for 3 hours, cooled to room temperature, 2,800 g of methyl isobutyl ketone was added, and the platinum catalyst was removed by pressure filtration of the reaction solution through a filter. Furthermore, 1,300 g of pure water was added to the obtained silicone skeleton-containing polymer compound solution, and the mixture was stirred and allowed to stand to remove the lower aqueous layer. This separation water washing operation was repeated 6 times to remove the trace acid component in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and after adding 3,300 g of cyclopentanone, the solution was concentrated under reduced pressure to obtain a cyclopentanone solution having a solid concentration of 65 to 70% by mass. A silicone skeleton-containing polymer compound solution (A-6) containing pentanone as a main solvent was obtained. When the molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC, the weight average molecular weight was 31,000 in terms of polystyrene. In the formula (1), a = 0.742, b = 0.258, c = 0, d = 0, e = 0, and f = 0.

[Comparative Synthesis Example 2] Synthesis of silicone skeleton-containing polymer compound solution (A-7) 150 g of compound (M-1) was added to toluene in a 2 L flask equipped with a stirrer, thermometer, nitrogen displacement device and reflux condenser. After dissolving in 700 g, 26.1 g of compound (M-2), 373.4 g of compound (M-3), and 2.4 g of compound (M-4) were added, and the mixture was heated to 60 ° C. Thereafter, 0.6 g of carbon-supported platinum catalyst (5% by mass) was added, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C., the mixture was further heated to 90 ° C. for 3 hours, and again to 60 ° C. Then, 0.7 g of a carbon-supported platinum catalyst (5% by mass) was added, and 45.5 g of the compound (M-5) was dropped into the flask over 20 minutes. At this time, the temperature in the flask rose to 65 to 67 ° C. After completion of the dropwise addition, the mixture was further aged at 90 ° C. for 3 hours, cooled to room temperature, 670 g of methyl isobutyl ketone was added, and the platinum catalyst was removed by pressure filtration of the reaction solution through a filter. Furthermore, 300 g of pure water was added to the obtained silicone skeleton-containing polymer compound solution, and the mixture was stirred and allowed to stand to remove the lower aqueous layer. This separation water washing operation was repeated 6 times to remove the trace acid component in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and after adding 780 g of cyclopentanone, the solution was concentrated under reduced pressure to obtain a cyclopentanone solution having a solid concentration of 65 to 70% by mass. As a main solvent, a silicone skeleton-containing polymer compound solution (A-7) was obtained. When the molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC, it was a weight average molecular weight of 29,000 in terms of polystyrene. In the formula (1), a = 0.614, b = 0.386, c = 0, d = 0, e = 0, and f = 0.

[Comparative Synthesis Example 3] Synthesis of silicone skeleton-containing polymer compound solution (A-8) 150 g of compound (M-1) was added to toluene in a 3 L flask equipped with a stirrer, thermometer, nitrogen displacement device and reflux condenser. After dissolving in 850 g, 88.8 g of compound (M-2), 355.2 g of compound (M-3), and 3.9 g of compound (M-4) were added and heated to 60 ° C. Thereafter, 0.7 g of a carbon-supported platinum catalyst (5% by mass) was added, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C., the mixture was further heated to 90 ° C. for 3 hours, and again 60 ° C. Then, 0.7 g of a carbon-supported platinum catalyst (5% by mass) was added, and 84.2 g of the compound (M-5) was dropped into the flask over 30 minutes. At this time, the temperature in the flask rose to 65 to 67 ° C. After completion of dropping, the mixture was further aged at 90 ° C. for 3 hours, cooled to room temperature, 770 g of methyl isobutyl ketone was added, and the platinum catalyst was removed by pressure filtration of the reaction solution through a filter. Furthermore, 350 g of pure water was added to the obtained silicone skeleton-containing polymer compound solution, and the mixture was stirred and allowed to stand to remove the lower aqueous layer. This separation water washing operation was repeated 6 times to remove the trace acid component in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and after adding 930 g of cyclopentanone, the solution was concentrated under reduced pressure to obtain a cyclopentanone solution having a solid concentration of 65 to 70% by mass. As a main solvent, a silicone skeleton-containing polymer compound solution (A-8) was obtained. When the molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC, the weight average molecular weight was 34,000 in terms of polystyrene. In the formula (1), a = 0.740, b = 0.260, c = 0, d = 0, e = 0, and f = 0.

  Using the solution of the polymer compound synthesized in Synthesis Examples 3 to 7 above, a crosslinking agent, a photoacid generator, and an amine compound are blended in the composition and blending amount shown in Table 1, and cyclopenta is added as a solvent to be added. The resist material of 45 mass% in terms of resin was prepared by blending non. Then, after stirring, mixing, and dissolving, microfiltration was performed with a 0.5 μm filter made of Teflon (registered trademark) to obtain a resist material.

  Further, as a comparative example, a solution of the polymer compound synthesized in the above Comparative Synthesis Examples 1 to 3, a crosslinking agent, a photoacid generator, and an amine compound are blended, and cyclopentanone is blended as a solvent to be added. After stirring, mixing and dissolving, microfiltration was performed with a 0.5 μm filter made of Teflon (registered trademark) to obtain a resist material. The composition and amount of the comparative example are also shown in Table 1.

In addition, the photoacid generator (PAG-1), the crosslinking agent (XL-1), and the basic compound (amine-1) described in Table 1 are as follows.

II. Exposure, Pattern Formation The resist material can be applied onto the substrate by rotating the substrate after dispensing 5 mL of the resist material onto the silicon substrate. That is, the spin coating method. It is possible to easily adjust the film thickness of the resist film on the substrate by adjusting the rotation speed. The resist material was applied on a silicon substrate to a thickness of 20 μm.
The resist material was dispensed and spin coated on the substrate, and then pre-baked on a hot plate at 100 ° C. for 2 minutes. Next, using a mask aligner (product name: MA-8) manufactured by SUSS Microtech Co., Ltd., a mask capable of forming 20 μm holes in a 1: 1 and vertical arrangement was mounted, and broadband light exposure was performed. . Next, the substrate was exposed at 110 ° C. for 2 minutes, then heated (PEB) and cooled. Thereafter, paddle development was performed three times for 1 minute using isopropyl alcohol (IPA) to perform patterning. Next, the obtained pattern on the substrate was post-cured using an oven at 180 ° C. for 2 hours while purging with nitrogen.
Similarly, patterning was performed on a SiN substrate and a Cu substrate instead of the silicon substrate.

  Next, each board | substrate was cut out so that the shape of the obtained hole pattern could be observed, and the hole pattern shape was observed using the scanning electron microscope (SEM). Table 2 shows the optimum exposure amount (exposure amount in terms of 365 nm light) with which the hole pattern has the same diameter as the mask size of 20 μm.

  As shown in Table 2, when patterning of a composition not using the silicone skeleton-containing polymer compound of the present invention was attempted, significant pattern peeling was observed on the SiN substrate and the Cu substrate, and patterning was impossible. . Therefore, it is clear that the adhesion between the pattern or film using the resist material and the substrate is improved by using the silicone skeleton-containing polymer compound of the present invention.

  Next, for the photocurable dry film, using the solution of the polymer compound synthesized in Synthesis Examples 3 to 7 in the same manner as described above, the crosslinking agent and the photoacid were again prepared with the compositions and blending amounts described in Table 1. Add the amine compound to the generator (unlike the above, do not mix cyclopentanone as a solvent), and then stir, mix and dissolve, then microfilter with a 1.0μm filter made of Teflon (registered trademark) and resist. Obtained material.

  Also, as a comparative example, a solution of the polymer compound synthesized in Comparative Synthesis Examples 1 to 3, a crosslinking agent, a photoacid generator, and an amine compound were blended in the same manner (unlike the above, cyclopentanone was blended as a solvent) No), stirring, mixing and dissolving, and then microfiltration was performed with a 1.0 μm filter made of Teflon (registered trademark) to obtain a resist material.

III. Production of Photocurable Dry Film Using a die coater as a film coater and a polyethylene terephthalate film (thickness: 38 μm) as a support film, the resist materials 1 to 8 shown in Table 1 were applied on the support film with a coating thickness of 50 μm. Subsequently, the photocurable resin layer was formed on the support film by allowing the hot air circulation oven (length 4m) set to 100 degreeC to pass through in 5 minutes. Furthermore, a polyethylene film (thickness: 50 μm) was bonded as a protective film from above the photocurable resin layer at a pressure of 1 MPa using a laminate roll to prepare a photocurable dry film.
In addition, the film thickness of the said photocurable resin layer is 50 micrometers. The example of a film is collectively shown in Table 3 as an Example and a comparative example.

IV. Exposure and pattern formation Next, as summarized in Table 3, each of the photocurable dry films using the resist materials listed in Examples and Comparative Examples was peeled off the protective film, and manufactured by Takatori Corporation. Using a vacuum laminator (product name: TEAM-100RF), the vacuum chamber was set to a degree of vacuum of 100 Pa, and the photocurable resin layer on the support film was brought into close contact with the silicon substrate at a temperature of 100 ° C. After returning to normal pressure, the substrate was cooled to 25 ° C., removed from the vacuum laminator, and the support film was peeled off.
Next, after peeling off the support film, pre-baking was performed on a hot plate at 100 ° C. for 5 minutes. Next, using a mask aligner (product name: MA-8) manufactured by SUSS Microtech Co., Ltd., a mask capable of forming 40 μm holes in a vertical and horizontal 1: 1 arrangement was mounted, and broadband light exposure was performed. . Next, the substrate was exposed at 130 ° C. for 5 minutes and then heated (PEB) to cool. Thereafter, patterning was performed by spray development using propylene glycol monomethyl ether acetate (PGMEA) for 5 minutes. Next, post-curing was performed using an oven at 180 ° C. for 2 hours while purging with nitrogen.
Similarly, patterning was performed after laminating the photocurable dry film produced as described above on a SiN substrate and a Cu substrate instead of the silicon substrate.

  Next, each board | substrate was cut out so that the shape of the obtained hole pattern could be observed, and the hole pattern shape was observed using the scanning electron microscope (SEM). Table 3 shows the optimum exposure amount (exposure amount in terms of 365 nm light) with which the hole pattern has the same diameter as the mask size of 40 μm.

  As shown in Table 3, even in the photocurable dry film having a composition not using the silicone skeleton-containing polymer compound of the present invention, the pattern and the film were observed to be remarkably peeled on the SiN substrate and the Cu substrate. Was impossible. Therefore, it is clear that by using the silicone skeleton-containing polymer compound of the present invention, the photocurable dry film using the resist material also improves the adhesion between the pattern or film and the substrate.

V. Embedding Performance A 6-inch silicon wafer was prepared in which 200 circular holes each having an opening diameter of 10 to 100 μm (in 10 μm increments) and a depth of 10 to 120 μm (in 10 μm increments) were formed. About the photocurable dry film of Examples 6-10 in the said Table 3, the protective film is peeled off, The inside of a vacuum chamber is used using the vacuum laminator (product name: TEAM-100RF) made from Takatori Corporation. The degree of vacuum was set to 100 Pa, and the photocurable resin layer on the support film was adhered to the substrate at a temperature condition of 100 ° C. After returning to normal pressure, the substrate was cooled to 25 ° C., removed from the vacuum laminator, and the support film was peeled off.
Next, after peeling off the support film, pre-baking was performed on a hot plate at 100 ° C. for 5 minutes. Then, using the mask aligner (product name: MA-8) manufactured by SUSS Microtech Co., Ltd., the substrate was irradiated with broadband light with an exposure amount (wavelength 365 nm) described in Table 4. Next, the substrate was exposed to 110 ° C. for 5 minutes, then heated (PEB) and cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Next, post-curing was performed using an oven at 180 ° C. for 2 hours while purging with nitrogen. The obtained substrate was diced to obtain a cross section of the circular hole, and the cross section of the circular hole was observed using a scanning electron microscope (SEM) to evaluate the presence or absence of defects. The results are shown in Table 4.
As shown in Table 4, it is filled without any defects, and it can be judged that the embedding performance as a coating for protecting electric / electronic parts is good.

VI. Electrical characteristics (dielectric breakdown strength)
About the photocurable dry film with a film thickness of 50 micrometers of Examples 6-10 in the said Table 3, the protective film is peeled off and the photocurable resin layer on a support film is JIS K by the temperature conditions of 100 degreeC. It was made to adhere to the substrate specified in 6249. And the said board | substrate was cooled to room temperature and the support film was peeled. Next, after peeling off the support film, pre-baking was performed on a hot plate at 100 ° C. for 5 minutes. Furthermore, the substrate was irradiated with broadband light having an exposure amount of 1,000 mJ / cm ² (wavelength 365 nm) through a quartz photomask using the mask aligner. Next, the substrate was subjected to PEB at 110 ° C. for 5 minutes and cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Next, post-curing was performed using an oven at 180 ° C. for 2 hours while purging with nitrogen, to prepare a substrate for measuring dielectric breakdown strength. And according to the measuring method prescribed | regulated to JISK6249, the dielectric breakdown strength was measured. The results are shown in Table 5.
As shown in Table 5, the electrical properties as the electrical / electronic component protecting film were all good.

VII. Adhesiveness About the photocurable dry film having a film thickness of 50 μm of Examples 6 to 10 in Table 3 above, the protective film is peeled off, and the vacuum chamber is set to a vacuum degree of 100 Pa using the vacuum laminator. The photocurable resin layer on the support film was brought into close contact with an untreated 6-inch silicon wafer under a temperature condition of 100 ° C. After returning to normal pressure, the substrate was cooled to 25 ° C., removed from the vacuum laminator, and the support film was peeled off. Next, after peeling off the support film, pre-baking was performed on a hot plate at 100 ° C. for 5 minutes. Furthermore, the substrate was irradiated with broadband light having an exposure amount of 1,000 mJ / cm ² (wavelength 365 nm) through a quartz photomask using the mask aligner. Next, the substrate was subjected to PEB at 110 ° C. for 5 minutes and cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Subsequently, post-curing was performed using an oven at 180 ° C. for 2 hours while purging with nitrogen, to obtain a post-pattern cured film having a diameter of 300 μm and a height of 50 μm. The post-patterned cured film was evaluated for initial adhesion by using a bond tester (product name: Dage series 4000-PXY) manufactured by Dage, England, based on the resistance force applied when the pattern cured film was peeled from the substrate. The measurement conditions were a measurement speed of 50.0 μm / sec and a measurement height of 3.0 μm. FIG. 1 is an explanatory view showing an adhesion measuring method. In the figure, reference numeral 1 denotes a silicon (Si) substrate, 2 denotes a post-pattern cured film, 3 denotes a measurement jig for a bond tester, and 4 denotes a moving direction of the measurement jig. The obtained numerical value is an average value of 15-point measurement, and the higher the numerical value, the higher the adhesion of the post pattern cured film to the substrate.
Furthermore, a solder flux liquid is applied to the post pattern cured film on the substrate, heated at 220 ° C. for 30 seconds, cooled, washed with pure water, and dried at room temperature for 2 hours using the above bond tester. Then, the adhesiveness after deterioration was evaluated in the same manner as in the initial stage by the resistance applied when the pattern was peeled from the substrate.
In addition, about five kinds of photocurable dry films, adhesiveness is evaluated by comparing initial numerical values, and by comparing behaviors in which numerical values decrease from initial to post-degradation, the adhesive flux and solder flux liquid are compared. Chemical resistance was also evaluated. The results are shown in Table 5.
As shown in Table 5, the adhesion as an electric / electronic component protecting film was good.

VIII. Crack resistance About the photocurable dry film having a film thickness of 50 μm in Examples 6 to 10 in Table 3 above, the protective film was peeled off, and the vacuum chamber was set to a vacuum degree of 100 Pa using the vacuum laminator. The photocurable resin layer on the support film was brought into close contact with the substrate used for the embedding property under a temperature condition of 100 ° C. After returning to normal pressure, the substrate was cooled to 25 ° C., removed from the vacuum laminator, and the support film was peeled off.
Next, after peeling off the support film, pre-baking was performed on a hot plate at 100 ° C. for 5 minutes. Next, the substrate was irradiated with broadband light having an exposure amount of 1,000 mJ / cm ² (wavelength 365 nm) through a quartz photomask using the mask aligner. Next, the substrate was subjected to PEB at 110 ° C. for 5 minutes and cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Next, post-curing was performed using an oven at 180 ° C. for 2 hours while purging with nitrogen.
The substrate on which this cured film was formed was put into a temperature cycle tester with −55 to + 150 ° C. as one cycle, and the presence or absence of cracks in the cured film was examined up to 1,000 cycles. The results are shown in Table 5.
As shown in Table 5, the crack resistance as a coating for protecting electric / electronic parts was good.

IX. Release liquid resistance About the photocurable dry film with a film thickness of 50 μm of Examples 6 to 10 in Table 3 above, the protective film was peeled off, and the inside of the vacuum chamber was set at a vacuum degree of 100 Pa using the vacuum laminator. The photocurable resin layer on the support film was brought into close contact with an untreated 6-inch silicon wafer under the temperature condition of 100 ° C. After returning to normal pressure, the substrate was cooled to 25 ° C., removed from the vacuum laminator, and the support film was peeled off.
Next, after peeling off the support film, pre-baking was performed on a hot plate at 100 ° C. for 5 minutes. Next, the substrate was irradiated with broadband light having an exposure amount of 1,000 mJ / cm ² (wavelength 365 nm) through a quartz photomask using the mask aligner. Next, the substrate was subjected to PEB at 110 ° C. for 5 minutes and cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Subsequently, it was post-cured using an oven at 180 ° C. for 2 hours while purging with nitrogen to obtain a 15 mm × 15 mm square pattern cured film.
And after immersing the said board | substrate in NMP (N-methylpyrrolidone) at room temperature for 1 hour, the external appearance and the film thickness change were investigated and stripping solution tolerance was evaluated. The results are shown in Table 5.
As shown in Table 5, all of the stripping solution resistance as a film for protecting electrical and electronic parts was good.

DESCRIPTION OF SYMBOLS 1 Silicon (Si) board | substrate 2 Post pattern hardening film of 300 micrometers in diameter x 50 micrometers in height 3 Measuring jig of a bond tester 4 Movement direction of a measuring jig

Claims (13)

A silicone skeleton-containing polymer compound having a repeating unit represented by the following general formula (1) and having a weight average molecular weight of 3,000 to 500,000.

(Wherein, .m showing a monovalent hydrocarbon group R ¹ to R ⁴ is 1-8 carbon atoms, which may be the same or different is an integer of 1~100 .a, b, c, d is 0 Or, a positive number, e, f are positive numbers, and a, b, c, d are not simultaneously 0. However, a + b + c + d + e + f = 1, X is represented by the following general formula (2) An organic group, Y is an organic group represented by the following general formula (3), and W is an organic group represented by the following formula (4a) or (4b).)

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ⁵ and R ⁶ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be different or the same. k is 0, 1, or 2. )

(Where V is

And a p is 0 or 1. R ⁷ and R ⁸ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be different or the same. h is 0, 1, or 2. )

(A) a silicone skeleton-containing polymer compound having a repeating unit represented by the general formula (1) according to claim 1 and having a weight average molecular weight of 3,000 to 500,000,
(B) An amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, and a hydroxyl group of a polyhydric phenol substituted with a glycidoxy group One or more cross-linking agents selected from compounds,
(C) a photoacid generator that decomposes with light having a wavelength of 190 to 500 nm to generate an acid;
(D) A chemically amplified negative resist material containing a solvent.   In the formula (1), 0.1 ≦ a ≦ 0.8, 0.1 ≦ b ≦ 0.8, 0 ≦ c, 0 ≦ d, 0 <e ≦ 0.8, 0 <f ≦ 0.8 The chemically amplified negative resist material according to claim 2. (1) A step of applying a chemically amplified negative resist material according to claim 2 or 3 on a substrate to form a resist film,
(2) Next, after the heat treatment, a step of exposing the resist film with a high energy beam or electron beam having a wavelength of 190 to 500 nm through a photomask,
(3) A pattern forming method including a step of developing using a developer after heat treatment.   Furthermore, (4) The pattern formation method of Claim 4 including the process of postcuring the film | membrane patterned by image development at the temperature of 100-250 degreeC.   A photocurable dry film having a structure in which a photocurable resin layer having a thickness of 10 to 100 μm is sandwiched between a support film and a protective film, wherein the composition is used for forming the photocurable resin layer. Alternatively, a photocurable dry film, which is the chemically amplified negative resist material according to 3. (I) a step of continuously applying a chemically amplified negative resist material containing the components (A) to (D) according to claim 2 or 3 on a support film to form a photocurable resin layer;
(Ii) a step of continuously drying the photocurable resin layer;
(Iii) Furthermore, the manufacturing method of the photocurable dry film including the process of bonding the said protective film on the said photocurable resin layer. (I) a step of closely attaching a photocurable resin layer exposed by peeling a protective film from the photocurable dry film according to claim 7 to the substrate;
(Ii) a step of exposing the photocurable resin layer with a high energy beam or an electron beam having a wavelength of 190 to 500 nm through a photomask in a state where the support film is peeled off or via the support film;
(Iii) a step of performing a heat treatment after exposure;
(Iv) A pattern forming method including a step of developing with a developer.   The pattern forming method according to claim 8, further comprising a step of (v) post-curing the film patterned by development at a temperature of 100 to 250 ° C.   The pattern forming method according to claim 8 or 9, wherein the substrate has a groove and / or a hole having an opening width of 10 to 100 µm and a depth of 10 to 120 µm.   Lamination obtained by laminating a photocurable resin layer of a photocurable dry film according to claim 6 on a substrate having a groove and / or a hole having an opening width of 10 to 100 µm and a depth of 10 to 120 µm. body.   A film for protecting electrical / electronic parts comprising a cured film obtained by the pattern forming method according to any one of claims 4, 5, 8, 9, and 10. 1,3-bis (4-allyloxyphenyl) adamantane compound which is an adamantane skeleton-containing compound having a diallyl group represented by the following formula (20).

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