JP6902826B2 - Photosensitive film - Google Patents

Description

The present invention relates to a positive photosensitive film.

As an image forming method used for patterning semiconductor devices, liquid crystal display elements, printed wiring boards, etc., positive photosensitive using a photosensitive resin composition containing a novolak type phenol resin and 1,2-quinonediazide as a raw material. A method using a resin composition is generally known (see, for example, Patent Document 1).
The positive photosensitive resin composition can be developed with an alkaline aqueous solution, and the change in image size due to swelling during development is more negative than that of the photosensitive resin composition requiring development with a solvent. It is extremely smaller than the type photosensitive resin composition, and its dimensional controllability is relatively easy.

Recently, the positive photosensitive resin composition has a fine pattern processing when laminating the photosensitive resin composition layer on the base material, and is excellent in followability to the flexible base material. It is strongly desired to make a dry film and laminate it by a hot roll laminate or a vacuum laminate method. However, when a conventional photosensitive resin composition containing a phenol resin as a main component is made into a dry film, the adhesive force with the support film tends to be high. Therefore, thermal transfer is performed while pressure bonding onto the substrate using a laminator. At that time, the photosensitive layer made of the photosensitive resin composition may partially remain on the support film, and defects may occur in the image pattern formed by using the photosensitive resin composition. Further, when a release-processed support film having high peelability is used, poor application to the support film may occur, and defects may occur in the image pattern. Therefore, it is difficult to achieve both coatability on the support film and peelability from the support film.

On the other hand, a fluorine-based surfactant is added to the photosensitive resin composition to improve the coatability on the release-treated support film, and the photosensitive layer can be sufficiently peeled off from the support film. It is known that a high-quality, defect-free photosensitive film can be formed. (Patent Document 2)
Further, Patent Document 3 confirms that the chemical resistance is improved by using a phenol resin having a specific structure in combination with a nonionic surfactant.

Japanese Unexamined Patent Publication No. 2000-105466 Japanese Unexamined Patent Publication No. 2012-226148 Japanese Unexamined Patent Publication No. 2013-190697

However, the phenol resin having a specific structure has insufficient applicability to the release-treated support film having high peelability. Further, there is no description that a phenol resin having a specific structure is made into a dry film and laminated by a laminating method.
Therefore, in the present invention, the photosensitive resin composition containing a phenol resin having a specific structure has good applicability to a highly releasable support film, and the photosensitive layer can be peeled from the support film. An object of the present invention is to provide a photosensitive film having sufficiently high properties and capable of forming a defect-free pattern.

｛式（１）中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ_１は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基から成る群から選ばれる１価の置換基を表し、ｂが２又は３である場合の複数のＲ_１は、それぞれ同じでも異なっていてもよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の鎖状脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（２）：

（式（２）中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び芳香族環を有する２価の有機基から成る群から選ばれる２価の有機基を表す。｝で表される繰り返し単位を有するフェノール樹脂（Ａ）、光酸発生剤（Ｂ）、溶剤（Ｃ）、及びシリコーン型界面活性剤（Ｄ）を含有する感光性樹脂組成物からなる感光層と、保護フィルムと、がこの順に積層されてなり、前記感光層が前記支持体フィルムの離型処理層上に配されており、
前記感光性樹脂組成物が、更に架橋剤（Ｅ）を含む、感光性フィルム。
［２］
前記一般式（１）中の、Ｘが、下記一般式（３）：

｛式（３）中、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基であり、ｎ_１は０〜４の整数であって、ｎ_１が１〜４の整数である場合のＲ_６は、ハロゲン原子、水酸基、又は１価の有機基であり、少なくとも１つのＲ_６は水酸基であり、ｎ_１が２〜４の整数である場合の複数のＲ_６はそれぞれ同じでも異なっていてもよい。｝で表される２価の基、及び下記一般式（４）：

｛式（４）中、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基を表し、Ｗは、単結合、フッ素原子で置換されていてもよい炭素数１〜１０の鎖状脂肪族基、フッ素原子で置換されていてもよい炭素数３〜２０の脂環式基、下記一般式（２）：

（式（２）中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び下記式（５）：

で表される２価の基から成る群から選ばれる２価の有機基である。｝で表される２価の基から成る群から選ばれる２価の有機基である、［１］に記載の感光性フィルム。
［３］
少なくとも一方の面に、シリコーン系化合物、フッ素含有化合物、及びアルキッド樹脂から成る群より選択される少なくとも１種を含む離型剤で支持体フィルムの表面をコートする化学処理、又は支持体フィルムをコロナ処理する物理処理により、離型処理層が配された該支持体フィルムと、下記一般式（１）：

｛式（１）中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ _１ は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基から成る群から選ばれる１価の置換基を表し、ｂが２又は３である場合の複数のＲ _１ は、それぞれ同じでも異なっていてもよく、
前記一般式（１）中の、Ｘが、下記式（６）：

で表される２価の有機基である繰り返し単位を有するフェノール樹脂（Ａ）、光酸発生剤（Ｂ）、溶剤（Ｃ）、及びシリコーン型界面活性剤（Ｄ）を含有する感光性樹脂組成物からなる感光層と、保護フィルムと、がこの順に積層されてなり、前記感光層が前記支持体フィルムの離型処理層上に配されている、感光性フィルム。
［４］
前記一般式（１）中の、Ｘが、下記式（７）：

で表される２価の有機基である、［３］に記載の感光性フィルム。
［５］
前記フェノール樹脂（Ａ）が、下記一般式（８）：

｛式（８）中、Ｒ_１１は炭化水素基及びアルコキシ基から成る群から選ばれる炭素数１〜１０の１価の基であり、ｎ_２は１〜３の整数であり、ｎ_３は０〜２の整数であり、ｍ_１は１〜５００の整数であり、２≦（ｎ_２＋ｎ_３）≦４であり、ｎ_３が２である場合のＲ_１１はそれぞれ同じでも異なっていてもよい。｝で表される繰り返し単位、及び下記一般式（９）：

｛式（９）中、Ｒ_１２及びＲ_１３はそれぞれ独立に炭化水素基及びアルコキシ基から成る群から選ばれる炭素数１〜１０の１価の基であり、ｎ_４は１〜３の整数であり、ｎ_５は０〜２の整数であり、ｎ_６は０〜３の整数であり、ｍ_２は１〜５００の整数であり、２≦（ｎ_４＋ｎ_５）≦４であり、ｎ_５が２である場合のＲ_１２はそれぞれ同じでも異なっていてもよく、ｎ_６が２又は３である場合のＲ_１３はそれぞれ同じでも異なっていてもよい。｝で表される繰り返し単位の両方を同一樹脂骨格内に有するフェノール樹脂である、［３］または［４］に記載の感光性フィルム。
［６］
前記シリコーン型界面活性剤が、ジメチルシロキサンエチレンオキシグラフト化合物、及び／又はジメチルシロキサンプロピレンオキシグラフト化合物である、［１］〜［５］のいずれかに記載の感光性フィルム。
As a result of diligent studies and repeated experiments in view of the above-mentioned problems of the prior art, the present inventor has obtained a support film in which at least one surface has been mold-released, and (A) a phenol resin having a specific structure. A photosensitive layer composed of a photosensitive resin composition containing (B) a photoacid generator, (C) a solvent, and (D) a silicone-type surfactant, and a protective film are laminated in this order to form a photosensitive layer. Has found that a photosensitive film formed on the release-treated surface of the support film can be obtained, and has completed the present invention. That is, the present invention is as follows.
[1]
A chemical treatment in which the surface of the support film is coated with a release agent containing at least one selected from the group consisting of a silicone-based compound, a fluorine-containing compound, and an alkyd resin on at least one surface, or a corona of the support film. The support film on which the release treatment layer is arranged by the physical treatment to be treated, and the following general formula (1):

{In the formula (1), a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₁ is 1 having 1 to 20 carbon atoms. valent organic group, a halogen atom, represents a monovalent substituent selected from the group consisting of a nitro group and a cyano group, a plurality of R ₁ when b is 2 or 3, which may be the same or different , X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (2):

(In formula (2), p is an integer of 1 to 10) A divalent alkylene oxide group selected from the group consisting of a divalent alkylene oxide group and a divalent organic group having an aromatic ring. Represents an organic group. } And a photosensitive layer composed of a photosensitive resin composition containing a phenol resin (A) having a repeating unit represented by}, a photoacid generator (B), a solvent (C), and a silicone-type surfactant (D). , And the protective film are laminated in this order, and the photosensitive layer is arranged on the release processing layer of the support film .
A photosensitive film in which the photosensitive resin composition further contains a cross-linking agent (E).
[2]
In the general formula (1), X is the following general formula (3):

{In formula (3), R ₂ , R ₃ , R ₄ and R ₅ are independently hydrogen atoms, monovalent aliphatic groups having 1 to 10 carbon atoms, or some or all of hydrogen atoms are fluorine. It is a monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, n ₁ is an integer of 0 to 4, and R ₆ is a halogen _{when n 1 is an integer of 1 to 4.} atom, a hydroxyl group, or a monovalent organic group, a is at least one R ₆ hydroxyl groups, a plurality of R ₆ may be the same or different when n ₁ is an integer of 2 to 4. }, And the following general formula (4):

{In formula (4), R ₇ , R ₈ , R ₉ and R ₁₀ are independently hydrogen atoms, monovalent aliphatic groups having 1 to 10 carbon atoms, or some or all of hydrogen atoms are fluorine. It represents a monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, and W is a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and a fluorine atom. Aliphatic group having 3 to 20 carbon atoms which may be substituted with, the following general formula (2):

(In the formula (2), p is an integer of 1 to 10.) A divalent alkylene oxide group represented by the formula (2), and the following formula (5):

It is a divalent organic group selected from the group consisting of divalent groups represented by. } The photosensitive film according to [1], which is a divalent organic group selected from the group consisting of divalent groups represented by.
[3]
A chemical treatment in which the surface of the support film is coated with a release agent containing at least one selected from the group consisting of a silicone-based compound, a fluorine-containing compound, and an alkyd resin on at least one surface, or a corona of the support film. The support film on which the release treatment layer is arranged by the physical treatment to be treated, and the following general formula (1):

{In the formula (1), a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₁ is 1 having 1 to 20 carbon atoms. valent organic group, a halogen atom, represents a monovalent substituent selected from the group consisting of a nitro group and a cyano group, a plurality of R ₁ when b is 2 or 3, which may be the same or different ,
In the general formula (1), X is the following formula (6):

A photosensitive resin composition containing a phenol resin (A), a photoacid generator (B), a solvent (C), and a silicone-type surfactant (D) having a repeating unit which is a divalent organic group represented by A photosensitive film in which a photosensitive layer made of an object and a protective film are laminated in this order, and the photosensitive layer is arranged on a mold release processing layer of the support film.
[4]
In the general formula (1), X is the following formula (7):

The photosensitive film according to [3 ], which is a divalent organic group represented by.
[5]
The phenol resin (A) has the following general formula (8):

{In formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of hydrocarbon groups and alkoxy groups, n ₂ is an integer of 1 to 3, and n ₃ is 0. It is an integer of ~ 2, m ₁ is an integer of 1 to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and _{R 11 when n 3} is 2 may be the same or different. .. } And the following general formula (9):

{In formula (9), R ₁₂ and R ₁₃ are monovalent groups having 1 to 10 carbon atoms independently selected from the group consisting of hydrocarbon groups and alkoxy groups, respectively, and n ₄ is an integer of 1 to 3. Yes, n ₅ is an integer from 0 to 2, n ₆ is an integer from 0 to 3, m ₂ is an integer from 1 to 500, 2 ≤ (n ₄ + n ₅ ) ≤ 4, and n _{5 R 12} when is 2 may be the same or different, and _{R 13 when n 6} is 2 or 3 may be the same or different. The photosensitive film according to [3] or [4], which is a phenol resin having both of the repeating units represented by} in the same resin skeleton.
[6]
The photosensitive film according to any one of [1] to [5], wherein the silicone-type surfactant is a dimethylsiloxane ethyleneoxygraft compound and / or a dimethylsiloxanepropyleneoxygraft compound.

According to the present invention, the coatability of the photosensitive layer made of the photosensitive resin composition to the release-treated support film is improved, the peelability of the photosensitive layer from the support film is sufficiently high, and there are no defects. A photosensitive film can be provided.

It is a schematic cross-sectional view which shows one Embodiment of the photosensitive film of this invention.

The photosensitive film of the present invention is a photosensitive film containing a support film having a release treatment layer arranged on at least one surface, a phenol resin having a specific structure, a photoacid generator, a solvent, and a silicone-type surfactant. The photosensitive layer made of the sex resin composition and the protective film are laminated in this order, and the photosensitive layer is formed on the release treatment layer of the support film.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are designated by the same reference numerals, and duplicate description will be omitted. In addition, the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios in the drawings are not limited to the ratios shown.

FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive film of the present invention. The photosensitive film 1 shown in FIG. 1 has a structure in which a photosensitive layer 11 is laminated on a support film 10 and a protective film 12 is further laminated on a surface of the photosensitive layer 11 opposite to the support film 10. The photosensitive layer 11 is a layer made of the photosensitive resin composition of the present embodiment described later.

<Support film>
The support film 10 according to the present embodiment is subjected to a mold release treatment on at least one surface to form a mold release treatment layer 10a. Here, the mold release treatment in the present embodiment is supported by a silicone-based surfactant, a silicone-based compound such as a silicone resin, a fluorine-based surfactant, a fluorine-containing compound such as a fluororesin, and a mold release agent such as an alkyd resin. It refers to a chemical treatment that thinly coats the surface of the body film, or a physical treatment that corona-treats the support film.
When the release agent is coated on the support film, it is preferable to coat it as thinly as possible to obtain the effect of release. After coating, the release agent may be fixed to the support film by heat or UV treatment. It is more preferable to apply an undercoat layer to the support film before coating the release agent.
The support film before the mold release treatment is not particularly limited as long as the surface is smooth, and for example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used, and among them, a polyethylene terephthalate film. (Hereinafter referred to as "PET film") is preferable.

｛式（１）中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ_１は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基から成る群から選ばれる１価の置換基を表し、ｂが２又は３である場合の複数のＲ_１は、それぞれ同じでも異なっていてもよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の鎖状脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（２）：

（式（２）中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び芳香族環を有する２価の有機基から成る群から選ばれる２価の有機基を表す。｝で表される繰り返し単位を有する。上記の繰り返し単位を有するフェノール樹脂（Ａ）は、例えばポリイミド樹脂及びポリベンゾオキサゾール樹脂と比べて低温での硬化が可能であり、かつ良好な伸度を有する硬化膜の形成を可能にする。
上記一般式（１）において、Ｒ_１は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基から成る群から選ばれる１価の置換基であれば限定されない。アルカリ溶解性の観点から、ハロゲン原子、ニトロ基、シアノ基、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基、炭素数６〜２０の芳香族基、及び下記一般式（１０）：

｛式（１０）中、Ｒ_１４、Ｒ_１５及びＲ_１６は、それぞれ独立に、水素原子、不飽和結合を有していてもよい炭素数１〜１０の鎖状脂肪族基、炭素数３〜２０の脂環式基、又は炭素数６〜２０の芳香族基を表し、そしてＲ_１７は、不飽和結合を有していてもよい炭素数１〜１０の２価の鎖状脂肪族基、炭素数３〜２０の２価の脂環式基、又は炭素数６〜２０の２価の芳香族基を表す。｝で表される４つの基から成る群から選ばれる１価の置換基であることが好ましい。 <Photosensitive layer>
The photosensitive layer 11 supports a photosensitive resin composition containing (A) a phenol resin having a specific structure, (B) a photoacid generator, (C) a solvent, and (D) a silicone-type surfactant as a component. It is formed by applying it to the release-treated surface of the body film 10. Hereinafter, each component will be described in detail.
[Component (A): Phenol resin having a specific structure]
In the present embodiment, the phenol resin (A) is represented by the following general formula (1):

{In the formula (1), a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₁ is 1 having 1 to 20 carbon atoms. valent organic group, a halogen atom, represents a monovalent substituent selected from the group consisting of a nitro group and a cyano group, a plurality of R ₁ when b is 2 or 3, which may be the same or different , X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (2):

(In formula (2), p is an integer of 1 to 10) A divalent alkylene oxide group selected from the group consisting of a divalent alkylene oxide group and a divalent organic group having an aromatic ring. Represents an organic group. } Has a repeating unit. The phenol resin (A) having the above repeating unit can be cured at a lower temperature than, for example, a polyimide resin and a polybenzoxazole resin, and can form a cured film having good elongation.
In the above general formula (1), R ₁ is not limited as long as it is a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group and a cyano group. From the viewpoint of alkali solubility, halogen atoms, nitro groups, cyano groups, aliphatic groups having 1 to 10 carbon atoms which may have unsaturated bonds, aromatic groups having 6 to 20 carbon atoms, and the following general formula (10):

{In formula (10), R ₁₄ , R ₁₅ and R ₁₆ are independent hydrogen atoms, chain aliphatic groups having 1 to 10 carbon atoms which may have unsaturated bonds, and 3 to 10 carbon atoms, respectively. 20 alicyclic group, or an aromatic group having 6 to 20 carbon atoms, and R ₁₇ is a divalent chain aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, It represents a divalent aliphatic group having 3 to 20 carbon atoms or a divalent aromatic group having 6 to 20 carbon atoms. } Is preferably a monovalent substituent selected from the group consisting of four groups.

In the present embodiment, in the above general formula (1), a is not limited as long as it is an integer of 1 to 3, but 2 is preferable from the viewpoint of alkali solubility and elongation. When a is 2, the substitution position between the hydroxyl groups may be any of the ortho, meta, and para positions. When a is 3, the substitution positions of the hydroxyl groups may be any of 1,2,3-positions, 1,2,4-positions, 1,3,5-positions, and the like.

In the present embodiment, in the above general formula (1), b is not limited as long as it is an integer of 0 to 3, but is preferably 0 or 1 from the viewpoint of alkali solubility and elongation. Further, when b is 2 or 3, the plurality of R _1s may be the same or different.
Further, in the present embodiment, in the above general formula (1), a and b satisfy the relationship of 1 ≦ (a + b) ≦ 4.

｛式（３）中、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基であり、ｎ_１は０〜４の整数であって、ｎ_１が１〜４の整数である場合のＲ_６は、ハロゲン原子、水酸基、又は１価の有機基であり、少なくとも１つのＲ_６は水酸基であり、ｎ_１が２〜４の整数である場合の複数のＲ_６はそれぞれ同じでも異なっていてもよい。｝で表される基、及び下記一般式（４）：

｛式（４）中、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基を表し、Ｗは、単結合、フッ素原子で置換されていてもよい
炭素数１〜１０の鎖状脂肪族基、フッ素原子で置換されていてもよい炭素数３〜２０の脂環式基、下記一般式（２）：

（式（２）中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び下記式（５）：

で表される２価の基から成る群から選ばれる２価の有機基である。｝で表される基から成る群から選ばれる有機基であることが好ましい。
Ｗとしては、硬化膜の伸度の観点から、単結合、上記一般式（２）で表されるアルキレンオキシド基、並びに上記式（５）のうちエステル基、アミド基及びスルホニル基から成る群から選ばれる２価の有機基、が好ましい。 In the present embodiment, in the above general formula (1), X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, and a divalent group having 3 to 20 carbon atoms. It is a divalent organic group selected from the group consisting of an alicyclic group, an alkylene oxide group represented by the above general formula (2), and a divalent organic group having an aromatic ring. Among these divalent organic groups, X is represented by the following general formula (3): from the viewpoint of the toughness of the film after curing.

{In formula (3), R ₂ , R ₃ , R ₄ and R ₅ are independently hydrogen atoms, monovalent aliphatic groups having 1 to 10 carbon atoms, or some or all of hydrogen atoms are fluorine. It is a monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, n ₁ is an integer of 0 to 4, and R ₆ is a halogen _{when n 1 is an integer of 1 to 4.} atom, a hydroxyl group, or a monovalent organic group, a is at least one R ₆ hydroxyl groups, a plurality of R ₆ may be the same or different when n ₁ is an integer of 2 to 4. } And the following general formula (4):

{In formula (4), R ₇ , R ₈ , R ₉ and R ₁₀ are independently hydrogen atoms, monovalent aliphatic groups having 1 to 10 carbon atoms, or some or all of hydrogen atoms are fluorine. It represents a monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, and W is a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, or a fluorine atom. Aliphatic group having 3 to 20 carbon atoms which may be substituted with, the following general formula (2):

(In the formula (2), p is an integer of 1 to 10.) A divalent alkylene oxide group represented by the formula (2), and the following formula (5):

It is a divalent organic group selected from the group consisting of divalent groups represented by. } Is preferably an organic group selected from the group consisting of groups represented by.
From the viewpoint of the elongation of the cured film, W is composed of a single bond, an alkylene oxide group represented by the general formula (2), and a group consisting of an ester group, an amide group and a sulfonyl group in the above formula (5). The selected divalent organic group is preferred.

で表される２価の有機基であることがより好ましく、さらに下記式（７）：

で表される２価の有機基であることが特に好ましい。 In the present embodiment, in the general formula (1), X is preferably a divalent organic group represented by the general formula (3) or (4), and is represented by the general formula (4). The divalent organic group to be formed has the following formula (6): from the viewpoint of good pattern forming property of the resin composition and from the viewpoint of the elongation of the cured film after curing.

It is more preferable that it is a divalent organic group represented by the following formula (7):

It is particularly preferable that it is a divalent organic group represented by.

｛式（８）中、Ｒ_１１は炭化水素基及びアルコキシ基から成る群から選ばれる炭素数１〜１０の１価の基であり、ｎ_２は１〜３の整数であり、ｎ_３は０〜２の整数であり、ｍ_１は１〜５００の整数であり、２≦（ｎ_２＋ｎ_３）≦４であり、ｎ_３が２である場合のＲ_１１は同じであっても異なっていてもよい。｝で表される構造及び下記一般式（９）：

｛式（９）中、Ｒ_１２及びＲ_１３はそれぞれ独立に炭化水素基及びアルコキシ基から成る群から選ばれる炭素数１〜１０の１価の基であり、ｎ_４は１〜３の整数であり、ｎ_５は０〜２の整数であり、ｎ_６は０〜３の整数であり、ｍ_２は１〜５００の整数であり、２≦（ｎ_４＋ｎ_５）≦４であり、ｎ_５が２である場合のＲ_１２は同じでも異なっていてもよく、ｎ_６が２又は３である場合のＲ_１３は同じでも異なっていてもよい。｝で表される構造の両方を同一樹脂骨格内に有することが特に好ましい。 Regarding the ratio of the part containing the phenolic hydroxyl group to the part represented by X in the general formula (1), particularly from the viewpoint of elongation, the part represented by X in the structure represented by the general formula (1). The ratio of is preferably 20% by mass or more, and more preferably 30% by mass or more. From the viewpoint of alkali solubility, the above ratio is preferably 80% by mass or less, more preferably 70% by mass or less. Further, the phenol resin (A) has the following general formula (8):

{In formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of hydrocarbon groups and alkoxy groups, n ₂ is an integer of 1 to 3, and n ₃ is 0. It is an integer of ~ 2, m ₁ is an integer of 1 to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and _{R 11 when n 3} is 2 is the same but different. May be good. } And the following general formula (9):

{In formula (9), R ₁₂ and R ₁₃ are monovalent groups having 1 to 10 carbon atoms independently selected from the group consisting of hydrocarbon groups and alkoxy groups, respectively, and n ₄ is an integer of 1 to 3. Yes, n ₅ is an integer from 0 to 2, n ₆ is an integer from 0 to 3, m ₂ is an integer from 1 to 500, 2 ≤ (n ₄ + n ₅ ) ≤ 4, and n _{5 R 12} when is 2 may be the same or different, and _{R 13 when n 6} is 2 or 3 may be the same or different. It is particularly preferable to have both of the structures represented by} in the same resin skeleton.

_{M 1} of the general formula (8) _{and m 2} of the general formula (9) represent the total number of each repeating unit in the main chain of the phenol resin (A). That is, in the phenol resin (A), the repeating unit in parentheses in the structure represented by the general formula (8) and the repeating unit in parentheses in the structure represented by the general formula (9) are random blocks. Alternatively, they can be arranged in a combination thereof. m ₁ and m ₂ are independently integers of 1 to 500 from the viewpoint of alkali solubility and elongation of the cured product, and the lower limit is preferably 2, more preferably 3, and the upper limit is. It is preferably 450, more preferably 400, and even more preferably 350. Each of m ₁ and m ₂ is preferably 2 or more independently from the viewpoint of toughness of the film after curing, and is preferably 450 or less from the viewpoint of solubility in an alkaline aqueous solution.

In the phenol resin (A) having both the structure represented by the general formula (8) and the structure represented by the general formula (9) in the same resin skeleton, the structure represented by the general formula (8). The higher the molar ratio of the structure, the better the physical properties of the film after curing and the better the heat resistance. The higher the molar ratio of the structure represented by the general formula (9), the better the alkali solubility and the curing. Excellent in later pattern shape. Therefore, the range of the ratio between the structure represented by the general formula (8) and the structure represented by the general formula (9) is m ₁ : m ₂ = 90: 10 to 20:80 after curing. It is preferable from the viewpoint of physical properties, m ₁ : m ₂ = 80: 20 to 40:60 is more preferable from the viewpoint of film physical properties after curing and alkali solubility, and m ₁ : m ₂ = 70: 30 to 50:50 is preferable. It is particularly preferable from the viewpoint of film physical characteristics after curing, pattern shape, and alkali solubility.

The phenol resin (A) is typically a phenol compound, a copolymerization component (specifically, a compound having an aldehyde group (including a compound that decomposes to produce an aldehyde compound such as trioxane), and a ketone group. One or more compounds selected from the group consisting of a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule) And more typically, a monomer component composed of these can be synthesized by carrying out a polymerization reaction. For example, aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds, haloalkyl compounds, etc., with respect to phenols and / or phenol derivatives (hereinafter collectively referred to as "phenolic compounds") as shown below. The phenolic resin (A) can be obtained by polymerizing the copolymerization components of the above. In this case, in the general formula (1), part of OH groups and any R ₁ group is represented by the structure is bonded to an aromatic ring derived from the phenolic compounds, moieties represented by X above co It will be derived from the polymer component. From the viewpoint of reaction control and the stability of the obtained phenol resin (A) and the photosensitive resin composition, the charged molar ratio of the phenol compound and the above-mentioned copolymer component. Phenol compound: copolymer component is 5: 1-1. It is preferably 0.01: 1, more preferably 2.5: 1 to 1.1: 1. In the present embodiment, the weight average molecular weight of the phenol resin (A) is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. is there. The weight average molecular weight is preferably 700 or more from the viewpoint of the elongation of the cured film, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.
The weight average molecular weight can be measured by gel permeation chromatography (GPC) and calculated from a calibration curve prepared using standard polystyrene.

In the present embodiment, examples of the phenolic compound that can be used to obtain the phenolic resin (A) include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, nitrobenzylphenol, and cyano. Benzylphenol, adamantanphenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboxyimide, N- (hydroxyphenyl) -5 -Methyl-5-norbornen-2,3-dicarboxyimide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone , Hydroxybenzonitrile, resorcinol, xylenol, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitrobenzylcatechol, methylresorcinol, ethylresorcinol, hexylresorcinol, benzylresorcinol, nitrobenzylresorcinol, hydroquinone, caffeic acid, dihydroxy Dihydroxybenzoate, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N- (dihydroxyphenyl) -5-Norbornene-2,3-dicarboxyimide, N- (dihydroxyphenyl) -5-methyl-5-Norbornene-2,3-dicarboxyimide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoro Methylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, fluoroglucolcinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, trihydroxybenzoate Ethyl phosphate, Trich Examples thereof include butyl droxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, and trihydroxybenzonitrile.

Examples of the aldehyde compound include acetaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde, pentanal, hexanal, trioxane, glioxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutylaldehyde, benzaldehyde, glyoxylic acid, and 5-norbornene-2-carboxy. Examples thereof include aldehyde, malondialdehyde, succindialdehyde, glutaaldehyde, salicylaldehyde, naphthoaldehyde, terephthalaldehyde and the like.

Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butin-2-one, 2-norbornanone, and the like. Examples thereof include adamantanone and 2,2-bis (4-oxocyclohexanone) propane.

Examples of the methylol compound include 2,6-bis (hydroxymethyl) -p-cresol, 2,6-bis (hydroxymethyl) -4-ethylphenol, and 2,6-bis (hydroxymethyl) -4-propyl. Phenol, 2,6-bis (hydroxymethyl) -4-n-butylphenol, 2,6-bis (hydroxymethyl) -4-t-butylphenol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, 2, , 6-bis (hydroxymethyl) -4-ethoxyphenol, 2,6-bis (hydroxymethyl) -4-propoxyphenol, 2,6-bis (hydroxymethyl) -4-n-butoxyphenol, 2,6- Bis (hydroxymethyl) -4-t-butoxyphenol, 1,3-bis (hydroxymethyl) urea, libitol, arabitol, alitol, 2,2-bis (hydroxymethyl) butyric acid, 2-benzyloxy-1,3- Propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-norbornen- 2,2-dimethanol, 5-norbornen-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis (hydroxymethyl) durene , 2-Nitro-p-xylylene glycol, 1,10-dihydroxydecane, 1,12-dihydroxydodecane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexene, 1,6 -Bis (hydroxymethyl) adamantan, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis (hydroxymethyl) -1,4-dimethoxybenzene, 2,3-bis (hydroxymethyl) Naphthalene, 2,6-bis (hydroxymethyl) naphthalene, 1,8-bis (hydroxymethyl) anthracene, 2,2'-bis (hydroxymethyl) diphenyl ether, 4,4'-bis (hydroxymethyl) diphenyl ether, 4, 4'-bis (hydroxymethyl) diphenylthioether, 4,4'-bis (hydroxymethyl) benzophenone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl, 4-hydroxymethylbenzoic acid-4'-hydroxymethylanilide , 4,4'-bis (hydroxymethyl) phenylurea, 4,4'-bis (hydroxymethyl) phenylurethane, 1,8-bis (hydroxymethyl) anthracene, 4,4'-bis (hydroxymethyl) biphenyl, 2,2'-dimethyl-4,4'-bis (hydroxymethyl) biphenyl, 2,2-bis (4-hydroxymethylphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, di Examples thereof include propylene glycol, tripropylene glycol and tetrapropylene glycol.

Examples of the alkoxymethyl compound include 2,6-bis (methoxymethyl) -p-cresol, 2,6-bis (methoxymethyl) -4-ethylphenol, and 2,6-bis (methoxymethyl) -4-. Propylphenol, 2,6-bis (methoxymethyl) -4-n-butylphenol, 2,6-bis (methoxymethyl) -4-t-butylphenol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6-bis (methoxymethyl) -4-propoxyphenol, 2,6-bis (methoxymethyl) -4-n-butoxyphenol, 2,6 -Bis (methoxymethyl) -4-t-butoxyphenol, 1,3-bis (methoxymethyl) urea, 2,2-bis (methoxymethyl) butyric acid, 2,2-bis (methoxymethyl) -5-norbornen, 2,3-bis (methoxymethyl) -5-norbornen, 1,4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxymethyl) cyclohexene, 1,6-bis (methoxymethyl) adamantan, 1,4 -Bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 2,6-bis (methoxymethyl) -1,4-dimethoxybenzene, 2,3-bis (methoxymethyl) naphthalene, 2,6 -Bis (methoxymethyl) naphthalene, 1,8-bis (methoxymethyl) anthracene, 2,2'-bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl ether, 4,4'-bis ( Methoxymethyl) diphenylthioether, 4,4'-bis (methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylanilide, 4,4' -Bis (methoxymethyl) phenylurea, 4,4'-bis (methoxymethyl) phenylurethane, 1,8-bis (methoxymethyl) anthracene, 4,4'-bis (methoxymethyl) biphenyl, 2,2'- Dimethyl-4,4'-bis (methoxymethyl) biphenyl, 2,2-bis (4-methoxymethylphenyl) propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethylate , Dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether and the like.

Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrate, 2,4-hexadiene-1-ol, and methyl. Cyclohexadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2 , 5-Norborneadiene, Tetrahydroindene, 5-Etylidene-2-Norbornene, 5-Vinyl-2-Norbornene, Triallyl cyanurate, Dialyl isocyanurate, Triallyl isocyanurate, Dialylpropyl isocyanurate and the like.

Examples of the haloalkyl compound include xylene chloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, and the like. Examples thereof include bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis (chloroethyl) ether, diethylene glycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether, and tetraethylene glycol bis (chloroethyl) ether.

The phenol resin (A) can be obtained by condensing the above-mentioned phenol compound and the copolymerization component by dehydration, dehalogenated hydrogen, or dealcoholization, or by polymerizing while cleaving the unsaturated bond. , A catalyst may be used at the time of polymerization. Acidic catalysts include, for example, hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfate, diethylsulfate, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1. '-Diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex and the like can be mentioned. On the other hand, examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, and the like. Piperazin, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonen, Examples thereof include ammonia and hexamethylenetetramine.
In the present embodiment, the amount of catalyst used to obtain the phenolic resin (A) is the total number of moles of the copolymerization component, preferably an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound and a haloalkyl. It is preferably in the range of 0.01 mol% to 100 mol% with respect to 100 mol% of the total number of moles of the compound. When carrying out the synthetic reaction of the phenol resin (A), an organic solvent can be used if necessary. Specific examples of the organic solvent that can be used include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, and the like. Examples thereof include, but are not limited to, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone and the like. The amount of these organic solvents used is usually 10 parts by mass to 1000 parts by mass, preferably 20 parts by mass to 500 parts by mass, when the total mass of the charged raw materials is 100 parts by mass. Further, in the synthetic reaction of the phenol resin (A), the reaction temperature is usually preferably 40 ° C. to 250 ° C., more preferably 100 ° C. to 200 ° C., and the reaction time is approximately 1 hour. It is preferably 10 hours.

The phenol resin (A) may be obtained by further polymerizing a phenol compound that does not serve as a raw material for the structure of the general formula (1) within a range that does not impair the effects of the present invention. The range that does not impair the effects of the present invention is, for example, 30% or less of the total number of moles of the phenol compound that is the raw material of the phenol resin (A).

In the present embodiment, when a is 1, in the above general formula (1), a phenol resin selected from a novolak resin and a polyhydroxystyrene resin in order to improve alkali solubility (hereinafter, phenol resin (A'). ) Can be mixed with the phenol resin (A).
The mixing ratio of the phenol resin (A) and the phenol resin (A') is preferably in the range of (A) / (A') = 10/90 to 90/10 in terms of mass ratio. This mixing ratio is preferably (A) / (A') = 10/90 to 90/10 from the viewpoint of solubility in an alkaline aqueous solution and elongation of the cured film, and (A) / ( A') = 20/80 to 80/20 is more preferable, and (A) / (A') = 30/70 to 70/30 is even more preferable.

The above novolak resin can be obtained by condensing phenols and formaldehyde in the presence of an acidic catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and 2 , 3-Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples thereof include trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like. Specific examples of the novolak resin include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin and the like.

Polyparavinylphenol is preferable as the polyhydroxystyrene resin. Polyparavinylphenol is not particularly limited as long as it is a polymer containing paravinylphenol as a polymerization unit. As the polymerization unit other than paravinylphenol that can constitute polyparavinylphenol, any compound that can be copolymerized with paravinylphenol is possible as long as it does not contradict the object of the present invention, and for example, methyl acrylate and methyl. Metaacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, 2-ethoxyethylta acrylate, t-butyl acrylate, 1,5-pentanediol diacrylate, N, N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1, 3-Propanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropanediacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol Triacrylate, 2,2-di (p-hydroxyphenyl) -propanedimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2--2-di (p-hydroxyphenyl) -propanedimethacrylate, triethylene glycol Dimethacrylate, polyoxypropyltrimethylol propanetriacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate , 1,2,4-butanetriol trimetaacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol trimetaacrylate, 1-phenylethylene-1,2-dimethacrylate, Acrylate esters such as pentaerythritol tetramethacrylate, trimethylpropan trimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol dimethacrylate; styrene and, for example, 2-methyl. Substituted styrenes such as styrene and vinyltoluene; vinyl esters such as vinyl acrylates and vinyl methacrylates; vinyl phenols other than paravinylphenols such as orthovinylphenols and metavinylphenols; It is not limited to.

The weight average molecular weight of the phenol resin (A') (that is, the phenol resin selected from the novolak resin and the polyhydroxystyrene resin) is preferably 700 to 100,000, more preferably 1,500 to 80,000. , More preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the elongation of the cured film, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.
The phenol resin selected from the novolak resin and the polyhydroxystyrene resin may be used alone or in combination of two or more.

[Photoacid generator (B)]
In the present embodiment, the photosensitive resin composition is a composition capable of forming a resin pattern in response to active light rays (that is, radiation) typified by ultraviolet rays, electron beams, X-rays, and the like. The photosensitive resin composition may be either a negative type (that is, one in which the unirradiated portion is eluted by development) or a positive type (that is, one in which the irradiated portion is eluted by development).
In the present embodiment, when the photosensitive resin composition is used as a negative type photosensitive resin composition, the photoacid generator (B) is irradiated with irradiation to generate an acid, and the generated acid is the phenol resin. By causing a cross-linking reaction between (A) and the cross-linking agent, the irradiated portion becomes insoluble in the developing solution. Examples of the photoacid generator (B) that can be used for the negative type include the following compounds:

(I) Trichloromethyl-s-triazines Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) ) -Bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4) , 6-Trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloro Methyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) bis (4,6-trichloromethyl-s-triazine) , 2- (2-Methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2-( 3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3,4) 5-Trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2 -(3-Methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine etc;

(Ii) Diaryliodonium salts Diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxy Phenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenyliodonium trifluoromethaneshonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4 -Methenylphenyl phenyliodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) Iodonium trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, etc .;

(Iii) Triarylsulfonium salts Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluene Sulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium Trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4- Phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, etc.

Among these compounds, trichloromethyl-s-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine and 2- (4-chlorophenyl) -bis (4). 6-Trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6) -Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, etc., as diaryliodonium salts, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethane Sulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, etc., and as triarylsulfonium salts, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4- Suitable examples include methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate and the like.
In addition to this, the following compounds can also be used as the photoacid generator (B).

(1) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound and the like, and specific examples thereof include 1,2-naphthoquinone diazide of phenols. A 4-sulfonic acid ester compound can be mentioned.

(2) Sulfone Compound Examples of the sulfone compound include β-ketosulfone compound, β-sulfonylsulfone compound and α-diazo compound of these compounds. Specific examples thereof include 4-trisphenacyl sulfone and mesitylphena. Examples thereof include silsulfone and bis (phenacylsulfonyl) methane.

(3) Sulfonic Acid Compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates and the like. Preferred specific examples include benzointosilate, pyrogalloltristrifluoromethanesulfonate, o-nitrobenzyltrifluoromethanesulfonate, o-nitrobenzyl-p-toluenesulfonate and the like.

(4) Sulfonimide compound Examples of the sulfoneimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, and N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned.

(5) Oxime ester compound As the oxime ester compound, specifically, 2- [2- (4-methylphenylsulfonyloxyimine)]-2,3-dihydrothiophene-3-iriden] -2- (2-methyl) Phenyl) acetonitrile (Ciba Specialty Chemicals, Inc. trade name "Irgacure PAG121"), [2- (propylsulfonyloxyimine) -2,3-dihydrothiophene-3-iriden] -2- (2-methylphenyl) acetonitrile (Ciba Specialty) Chemicals trade name "Irgacure PAG103"), [2- (n-octanesulfonyloxyimine) -2,3-dihydrothiophene-3-iriden] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name "Irgacure PAG108"), α- (n-octanesulfonyloxyimine) -4-methoxybenzyl cyanide (trade name "CGI725", Ciba Specialty Chemicals, Inc.) and the like can be mentioned.

(6) Diazomethane Compound Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.
From the viewpoint of sensitivity, the above-mentioned (5) oxime ester compound is particularly preferable.
In the present embodiment, when the photosensitive resin composition is a negative type, the blending amount of the photoacid generator (B) with respect to 100 parts by mass of the phenol resin (A) is 0.1 to 50 parts by mass. It is preferably 1 to 40 parts by mass, and more preferably 1 to 40 parts by mass. When the compounding amount is 0.1 part by mass or more, the effect of improving the sensitivity can be obtained satisfactorily, and when the compounding amount is 50 parts by mass or less, the mechanical properties of the cured film are good.

In the present embodiment, the photosensitive resin composition can also be used as a positive photosensitive resin composition. In this case, the photoacid generators and / or quinonediazide compounds represented by the above (i) to (iii) and (1) to (6) are preferably used. Among them, the quinone diazide compound is preferable from the viewpoint of physical properties after curing. This is because the quinone diazide compound is thermally decomposed at the time of curing, and the amount remaining in the film after curing is extremely low.

The positive photoacid generator (B) is preferably a quinonediazide compound. Examples of the quinone diazide compound include compounds having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure (a compound having the latter structure is also referred to as “NQD compound” below), and these are mentioned. Compounds are known, for example, in US Pat. No. 2,772,972, US Pat. No. 2,797,213, US Pat. No. 3,669,658, and the like. The NQD compound includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a compound having a plurality of phenolic hydroxyl groups (hereinafter, also referred to as “polyhydroxy compound”) described in detail below, and 1, of the polyhydroxy compound. It is at least one compound selected from the group consisting of 2-naphthoquinonediazide-5-sulfonic acid ester.

The NQD compound is obtained by converting naphthoquinonediazidesulfonic acid into a sulfonyl chloride with chlorsulfonic acid, thionyl chloride or the like according to a conventional method, and subjecting the obtained naphthoquinonediazidesulfonyl chloride to a condensation reaction with a polyhydroxy compound. For example, a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran, such as triethylamine. It can be obtained by reacting in the presence of a basic catalyst to carry out esterification, and washing the obtained product with water and drying it.

｛式中、Ｑは、水素原子、又は下記式群：

のいずれかで表されるナフトキノンジアジドスルホン酸エステル基であるが、全てのＱが同時に水素原子であることはない。｝。 Examples of preferable NQD compounds from the viewpoint of the physical characteristics of the cured film such as sensitivity and elongation include those represented by the following general formula group.

{In the formula, Q is a hydrogen atom, or the following formula group:

Although it is a naphthoquinone diazide sulfonic acid ester group represented by any of the above, not all Qs are hydrogen atoms at the same time. }.

Further, as the NQD compound, a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group in the same molecule can also be used, and a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound can be used. It can also be used in combination with an ester compound.
The NQD compound may be used alone or in combination of two or more.
In the present embodiment, the amount of the photoacid generator (B) used when the photosensitive resin composition is positive is preferably 0.1 with respect to 100 parts by mass of the phenol resin (A) of the present composition. It is ~ 70 parts by mass, more preferably 1 to 40 parts by mass, and further preferably 5 to 30 parts by mass. If the amount used is 0.1 parts by mass or more, good sensitivity can be obtained, and if it is 70 parts by mass or less, the mechanical properties of the cured film are good.

[Solvent (C)]
Examples of the solvent (C) include amides, dichloromethanes, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like, and examples thereof include N-methyl-2-. Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methylethylketone, methylisobutylketone, cyclopentanone, cyclohexanone, methylacetate, ethyl acetate, butylacetate, diethyl oxalate, Ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1 , 2-Dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, methylylene and the like can be used. Among them, N-methyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, methylethylketone, butyl acetate, ethyl lactate, γ-butyrolactone from the viewpoint of resin solubility, stability of resin composition, and adhesion to substrate. , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

In the photosensitive resin composition of the present invention, the amount of the solvent (C) used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass with respect to 100 parts by mass of the phenol resin (A). Yes, more preferably in the range of 125-500 parts by mass.

[Silicone-type surfactant (D)]
The silicone-type surfactant is a surfactant having a siloxane bond and a silicon-carbon bond in the molecule. For example, a dimethylsiloxane ethyleneoxygraft compound, a dimethylsiloxanepropyleneoxygraft compound, a (hydroxyethyleneoxypropyl) methylsiloxane-dimethylsiloxane compound and the like can be mentioned.

Specific examples include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.), SILWET L-77, L-7001, FZ-2105, FZ- 2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nippon Unicar Co., Ltd.), DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF -352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (above, product name, Big Chemie Japan) (Manufactured by), Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Among these, a dimethylsiloxane ethyleneoxygraft compound and a dimethylsiloxanepropyleneoxygraft compound are preferable from the viewpoint of coatability of the composition varnish. These silicone-type surfactants may be used alone or in combination of two or more.

The amount of the silicone-type surfactant (D) used is 0.01 to 30 parts by mass with respect to 100 parts by mass of the phenol resin (A) from the viewpoint of coatability of the composition varnish to the support. It is preferably 0.02 to 10 parts by mass, more preferably 0.02 to 10 parts by mass. If it is 30 parts by mass or less, it is possible to suppress the residue and pattern floating during development.

[Other ingredients]
The photosensitive resin composition of the present invention can contain a cross-linking agent (E), a thermoacid generator, a silane coupling agent, a dye, a dissolution accelerator and the like, if necessary.
The cross-linking agent (E) can be cross-linked with the phenol resin (A) when the relief pattern formed by using the photosensitive resin composition of the present invention is heat-cured, or the cross-linking agent itself forms a cross-linking network. Such a compound. The cross-linking agent has two or more cross-linking groups in the molecule, and can further improve the thermal properties, mechanical properties, and chemical resistance of the cured film formed from the photosensitive resin composition.

Examples of the cross-linking agent (E) include Cymel® 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, which are compounds containing a methylol group and / or an alkoxymethyl group. 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300, My Coat 102, 105 (all manufactured by Mitsui Cytec), Nicarac (registered trademark) MX-270, -280, -290, Nikarak MS-11, Nicarac MW-30, -100, -300, -390, -750 (all manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DMLPCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM- BP, TMOM-BPA, TML-BPAF-MF (manufactured by Honshu Kagaku Kogyo Co., Ltd.), benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxy) Methyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis Examples thereof include (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, and dimethylbis (methoxymethyl) biphenyl.

In addition, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol which are oxylan compounds. -Naftor type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylpropanpolyglucidyl ether, 1 , 1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol triglycidyl ether, orthosecondary butylphenylglycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl Ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN- 1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051 , Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315-75 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Praxel G402, PUE101, PUE105 (above, trade name, Daicel Chemical Industry Co., Ltd.) , Epoxy® 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (above, trade name, DIC) EX-201, EX-251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX -614, EX-614B, EX-711, EX-731, EX-810, EX-911, EM-150 (above, trade name, manufactured by Nagase ChemteX Corporation), Epoxy (Noboru) Recorded trademark) 70P, Epolite 100MF (above, trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

In addition, isocyanate group-containing compounds such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and takenate ( Registered trademarks) 500, 600, Cosmonate (registered trademark) NBDI, ND (above, trade name, manufactured by Mitsui Chemicals, Inc.) Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402- B80T (above, trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like can be mentioned.

In addition, bismaleimide compounds such as 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4 '-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4' -Diphenylsulphonbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI- 3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (above, trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and the like can be mentioned. However, the cross-linking agent (E) is not limited to these as long as it is a compound that can be thermally cross-linked.

When the cross-linking agent (E) is used, the blending amount is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the phenol resin (A). When the blending amount is 0.1 part by mass or more, the thermosetting and mechanical strength of the thermosetting film are good, and when it is 40 parts by mass or less, the stability of the composition in a varnish state and the elongation of the thermosetting film Is good.

The thermoacid generator is preferably blended from the viewpoint of exhibiting good thermophysical and mechanical properties of the cured product even when the curing temperature is lowered.
Examples of the thermoacid generator include allyl chloroacetate, n-butyl chloroacetate, t-butyl chloroacetate, ethyl chloroacetate, methyl chloroacetate, benzyl chloroacetate, isopropyl chloroacetate, 2-methoxyethyl chloroacetate, methyl dichloroacetate, and the like. Methyl trichloroacetate, ethyl trichloroacetate, 2-ethoxyethyl trichloroacetate, t-butyl cyanoacetate, t-butyl methacrylate, ethyl trifluoroacetate, methyl trifluoroacetate, phenyl trifluoroacetate, vinyl trifluoroacetate, trifluoroacetic acid Isopropyl, allyl trifluoroacetate, ethyl benzoate, methyl benzoate, t-butyl benzoate, methyl 2-chlorobenzoate, ethyl 2-chlorobenzoate, ethyl 4-chlorobenzoate, ethyl 2,5-dichlorobenzoate , Methyl 2,4-dichlorobenzoate, ethyl p-fluorobenzoate, methyl p-fluorobenzoate, t-butyl pentachlorophenylcarboxylic acid, methyl pentafluoropropionate, ethyl pentafluoropropionate, t-butyl crotonate, etc. Carboxylic acid esters; cyclic carboxylic acid esters such as phenolphthaline and timolphthalene; ethyl methanesulphonate, methyl methanesulphonate, 2-methoxyethyl methanesulphonate, 2-isopropoxyethyl methanesulphonic acid, p- Phenyl toluene sulfonate, ethyl p-toluene sulfonate, methyl p-toluene sulfonate, 2-phenyl ethyl p-toluene sulfonate, n-propyl p-toluene sulfonate, n-butyl p-toluene sulfonate, p-toluene T-butyl sulfonate, n-hexyl p-toluene sulfonate, n-heptyl p-toluene sulfonate, n-octyl p-toluene sulfonate, 2-methoxyethyl p-toluene sulfonate, propargyl p-toluene sulfonate, 3-butynyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, ethyl perfluorobutanesulfonate, methyl perfluorobutanesulfonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate , Benzyl (4-hydroxyphenyl) methylsulfonium hexafluorophosphate, trimethylsulfonium methylsulfate, tri-p-sulfonium trifluoromethanesulfonate, trimethylsulfonium trifluoromethanesul Sulfonic acid esters such as honato, pyridinium-p-toluenesulfonate, ethyl perfluorooctane sulfonate; 1,4-butane sulton, 2,4-butane sulton, 1,3-propane sulton, phenol red, bromocresol green, bromo Cyclic sulfonic acid esters such as cresol purple; aromatic carboxylic acid anhydrides such as 2-sulfobenzoic acid anhydride, p-toluenesulfonic acid anhydride, and phthalic acid anhydride, etc., but acid is generated by heat. It is not limited as long as it is a compound.

When a thermoacid generator is used, the blending amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and 1 to 5 parts by mass with respect to 100 parts by mass of the phenol resin (A). It is more preferably a part. When the compounding amount is 0.1 part by mass or more, the effect of maintaining the pattern shape after thermosetting is good, while when the compounding amount is 30 parts by mass or less, the lithography performance is not adversely affected and the composition Good stability.

As the silane coupling agent, 3-mercaptopropyltrimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd .: trade name KBM803, manufactured by Chisso Co., Ltd .: trade name Sila Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azumax Co., Ltd .: Product name SIM6475.0), 3-Mercaptopropylmethyldimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd .: product name LS1375, manufactured by Azumax Co., Ltd .: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Asmax Co., Ltd .: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azumax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3 -Mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane , 2-Mercaptoethylethoxydimethoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethylethoxydipropoxysilane, 2-Mercaptoethyldimethoxypropoxysilane, 2-Mercaptoethylmethoxydipropoxysilane , 4-Mercaptobutyltrimethoxysilane, 4-Mercaptobutyltriethoxysilane, 4-Mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: trade name LS3610, Azumax Co., Ltd.) Company: Product name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (Azumax Co., Ltd .: Product name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- ( 3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N-( 3-Dimethoxypropoxysilylpropyl) urea, N- ( 3-methoxydipropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3) -Tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3) -Trimethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Azumax Co., Ltd .: Product name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azumax Co., Ltd .: product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azumax Co., Ltd .: product name SLA0599.1) Aminophenyltrimethoxy Silane (manufactured by Azumax Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azumax Co., Ltd .: trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxy) Cyrilmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane , Tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrax (methoxyethoxysilane), tetrax (methoxy-n-propoxy) Silane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, Bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide , Ethyl butoxydiacetoki Silanol, di-i-butoxyaluminoxytriethoxysilane, bis (pentazionate) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol , N-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p- Trillsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-Butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyl Examples thereof include, but are not limited to, diphenylsilanol and triphenylsilanol. These may be used alone or in combination of two or more.

シランカップリング剤を使用する場合の配合量としては、フェノール樹脂（Ａ）１００質量部に対して、０．０１〜２０質量部が好ましい。 Among the above-mentioned silane coupling agents, the silane coupling agent includes phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, and diethoxy from the viewpoint of storage stability. Diphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent represented by the following structure are preferable.

When a silane coupling agent is used, the blending amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the phenol resin (A).

Examples of the dye include methyl violet, crystal violet, malachite green and the like. The amount of the dye to be blended is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the phenol resin (A).

As the dissolution accelerator, a compound having a hydroxyl group or a carboxyl group is preferable. Examples of compounds having a hydroxyl group include ballast agents used in the above-mentioned naphthoquinone diazide compounds, paracumylphenols, bisphenols, resorcinols, linear phenol compounds such as MtrisPC and MterraPC, TrisP-HAP, and TrisP. Non-linear phenol compounds such as −PHBA and TrisP-PA (all manufactured by Honshu Kagaku Kogyo Co., Ltd.), 2 to 5 phenol substitutions of diphenylmethane, 1 to 5 phenol substitutions of 3,3-diphenylpropane, Bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, a compound obtained by reacting 5-norbornene-2,3-dicarboxylic acid anhydride with a molar ratio of 1: 2. Compounds obtained by reacting 3-amino-4-hydroxyphenyl) sulfone with 1,2-cyclohexyldicarboxylic acid anhydride at a molar ratio of 1: 2, N-hydroxysuccinimide, N-hydroxyphthalateimide, N. Examples thereof include -hydroxy 5-norbornen-2,3-dicarboxylic acid imide and the like. Examples of compounds having a carboxyl group are 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2. − (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, itaconic acid and the like can be mentioned.
When a dissolution accelerator is used, the blending amount is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the phenol resin (A).

<Protective film>
As the protective film 12, for example, a polymer film such as polyethylene, polypropylene, polyethylene terephthalate, or polyester can be used. Further, as with the support film, a polymer film that has undergone a mold release treatment may be used. From the viewpoint of flexibility when the photosensitive film is wound into a roll, a polyethylene film is particularly preferable as the protective film 12.
The thickness of the protective film 12 is preferably 10 to 100 μm, and particularly preferably 15 to 80 μm.

Next, a method for producing the photosensitive film 1 of the present embodiment will be described.
The photosensitive layer 11 can be formed by applying the photosensitive resin composition as a liquid photosensitive resin composition onto the support film 10.
Examples of the coating method include a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. Further, the solvent can be removed by heating, for example, and the heating temperature in that case is preferably about 70 to 150 ° C., and the heating time is preferably about 1 to about 30 minutes.

The thickness of the photosensitive layer 11 varies depending on the application, but the thickness after removing the solvent is preferably about 1 to 30 μm. The photosensitive film 1 is an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer between the support film 10 and the photosensitive layer 11 and / or between the photosensitive layer 11 and the protective film 12. Alternatively, a protective layer may be further provided.
The photosensitive film 1 can be wound around a core such as a cylinder and stored in a roll shape. The winding core is not particularly limited as long as it is conventionally used, and for example, plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). And so on. At the time of storage, it is preferable that the support film is wound so as to be the outermost. Further, it is preferable to install an end face separator on the end face of the photosensitive film (photosensitive film roll) wound in a roll shape from the viewpoint of end face protection, and in addition, a moisture-proof end face separator is installed from the viewpoint of edge fusion resistance. It is preferable to do so. Further, when packing the photosensitive film 1, it is preferable to wrap it in a black sheet having low moisture permeability.

As a method of laminating the photosensitive layer 11 on the base material, after removing the protective film 12, the photosensitive layer 11 is heated to about 70 to 130 ° C. and about 0.1 to 1 MPa (1 to 10 kgf / cm) on the base material. A method of crimping with a laminator or the like at a pressure of about ^{2) can be mentioned.} Such a laminating step may be performed under reduced pressure. The surface of the base material on which the photosensitive layer 11 is laminated is not particularly limited.

The amount of residual organic solvent in the photosensitive layer 11 formed in this manner is preferably 1% by mass or more and 20% by mass or less from the viewpoint of lamination on the substrate and contrast between the exposed portion and the unexposed portion. More preferably, it is 2% by mass or more and 15% by mass or less, and further preferably 5% by mass or more and 12% by mass or less.

The amount of the residual organic solvent is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 20 parts by mass or less, and further preferably 6 parts by mass with respect to 100 parts by mass of the phenol resin. It is 10 parts or more and 16 parts by mass or less.

The photosensitive layer 11 laminated on the substrate in this way is irradiated with active light rays in an image form through a negative or positive mask pattern to form an exposed portion. At this time, when the support 10 existing on the photosensitive layer 11 is transparent to the active light, the active light can be irradiated through the support 10, and the support 10 has a light-shielding property with respect to the active light. In the case of, the photosensitive layer 11 is irradiated with active light rays after the support 10 is removed.

As the light source of the active light, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably in the g-line, h-line or i-line region of the mercury lamp, and may be used alone or in combination of two or more chemical rays. As the exposure apparatus, an aligner, a parallel exposure machine, a mirror projection, and a stepper are particularly preferable. After the exposure, the coating film may be heated again at 80 to 140 ° C., if necessary.

Next, development can be carried out by selecting from a method such as a dipping method, a paddle method, and a spray method using a developing solution. By development, an exposed portion (in the case of a positive type) or an unexposed portion (in the case of a negative type) can be eluted and removed from the coated photosensitive resin layer to obtain a relief pattern.
The developing solution includes inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, tetramethylammonium hydroxide and tetrabutylammonium hydroxide. An aqueous solution of a quaternary ammonium salt such as, and if necessary, a water-soluble organic solvent such as methanol or ethanol, or an aqueous solution to which an appropriate amount of a surfactant is added can be used. Among these, an aqueous solution of tetramethylammonium hydroxide is preferable, and the concentration of the tetramethylammonium hydroxide is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass.

After the development, the substrate on which the relief pattern is formed can be obtained by washing with a rinsing solution and removing the developing solution. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol and the like can be used alone or in combination of two or more.
Finally, a cured relief pattern can be obtained by heating the relief pattern thus obtained. The heating temperature is preferably 150 ° C. or higher and 300 ° C. or lower, more preferably 250 ° C. or lower.

In the method for producing a cured relief pattern of the present invention, the photosensitive resin composition can be cured even by heating at a lower temperature, so that it can be suitably used for heat-sensitive semiconductor devices, printed wiring boards, and display devices. You can.
Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above embodiment. The present invention can be modified in various ways without departing from the gist thereof.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Synthesis Example 1]
<Synthesis of phenol resin (A-1)>
Phloroglucinol 100.9 g (0.8 mol), 4,4'-bis (methoxymethyl) biphenyl (hereinafter also referred to as "BMMB") in a separable frasslasco with a Dean-Stark apparatus having a capacity of 0.5 liter. 121.2 g (0.5 mol), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70 ° C. to dissolve the solid substance.
The mixed solution was heated to 140 ° C. in an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 140 ° C. for 2 hours.
Next, the reaction vessel was cooled in the air, and 100 g of tetrahydrofuran was separately added thereto and stirred. The above reaction diluent is added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, washed with water as appropriate, dehydrated, and then vacuum-dried. A copolymer (phenol resin) composed of phloroglucinol / BMMB. (A-1)) was obtained in a yield of 70%.

[Synthesis Example 2]
<Synthesis of phenol resin (A-2)>
Using 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate instead of phloroglucinol in Synthesis Example 1, synthesis was carried out in the same manner as in Synthesis Example 1, and methyl 3,5-dihydroxybenzoate / A copolymer composed of BMMB (phenol resin (A-2)) was obtained in a yield of 65%.

[Synthesis Example 3]
<Synthesis of phenol resin (A-3)>
A separable flask with a capacity of 1.0 L with a Dean-Stark apparatus was replaced with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, and p-toluenesulfone were used. 3.81 g (0.02 mol) of acid and 116 g of propylene glycol monomethyl ether (hereinafter, also referred to as PGME) were mixed and stirred at 50 ° C. to dissolve the solid substance.
The mixed solution was heated to 120 ° C. in an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 120 ° C. for 3 hours.
Next, 24.9 (0.150 mol) g of 2,6-bis (hydroxymethyl) -p-cresol and 249 g of PGME were mixed and stirred in another container, and the uniformly dissolved solution was prepared using a dropping funnel. The mixture was added dropwise to a separable flask in 1 hour, and the mixture was further stirred for 2 hours after the addition.
After completion of the reaction, the same treatment as in Synthesis Example 1 was carried out to obtain a copolymer (phenol resin (A-3)) composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%. I got it in.

[Example]
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
<Phenol resin (A) and (A')>
A-1: Copolymer composed of phloroglucinol / BMMB, polystyrene-equivalent weight average molecular weight (Mw) = 15,000
A-2: Copolymer composed of methyl 3,5-dihydroxybenzoate / BMMB, polystyrene-equivalent weight average molecular weight (Mw) = 21,000
A-3: Copolymer composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol, polystyrene-equivalent weight average molecular weight (Mw) = 9,900
A-4: Phenol / biphenylene resin, polystyrene-equivalent weight average molecular weight (Mw) = 2,400 (manufactured by Meiwa Kasei Co., Ltd., product name MEH-7851M)
A-5: Novolac resin, polystyrene-equivalent weight average molecular weight (Mw) = 10,600 (manufactured by Asahi Organic Materials Co., Ltd., product name EP-4080G)

（式中、Ｑの内８３％が以下の：

で表される構造であり、残余が水素原子である。）
Ｂ−２：オキシムエステル化合物（ＢＡＳＦ社製、商品名；イルガキュア ＰＡＧ１２１） <Photoacid generator (B)>
B-1: Photoacid generator represented by the following formula:

(In the formula, 83% of Q is as follows:

The structure is represented by, and the residue is a hydrogen atom. )
B-2: Oxime ester compound (manufactured by BASF, trade name; Irgacure PAG121)

<Solvent (C)>
C-1: γ-Butyrolactone (GBL)
<Silicone type surfactant (D)>
D-1: Silicone type surfactant DBE821 (trade name, manufactured by Gelest)
D-2: Silicone type surfactant DBE224 (trade name, manufactured by Gelest)
D-3: Silicone type surfactant SILWET FZ-2105 (trade name, manufactured by Nippon Unicar Co., Ltd.)
D-4: Fluorine-type surfactant PF-656 (trade name, manufactured by OMNOVA Solutions)
D-5: Fluorine-type surfactant Futergent 251 (trade name, manufactured by Neos)

<Crosslinking agent (E)>
E-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluryl (manufactured by Sanwa Chemical Co., Ltd., trade name; Nicarac MX-270)
As shown in Table 1, the phenol resin (A), the photoacid generator (B), the surfactant (D), and the cross-linking agent (E) are dissolved in the solvent (C) and filtered through a 0.1 μm filter. Then, positive photosensitive resin compositions 1 to 20 were prepared.

The following films were prepared as the support film and the protective film.
-PET film "PET25X" released from a silicone compound: manufactured by Lintec Corporation, width 290 mm, thickness 25 μm.
-Polyethylene film "GF-858": manufactured by Tamapoli Co., Ltd., width 290 mm, thickness 33 μm.

[Preparation of photosensitive film]
(Example 1)
Using the solution of the photosensitive resin composition 1, a photosensitive film was prepared according to the following procedure. First, a release-treated PET film "PET25X" was used as the support film, and the solution of the photosensitive resin composition 1 was applied onto the release-treated surface. Next, the PET film coated with the solution of the photosensitive resin composition 1 was held in a hot air convection dryer set at 130 ° C. to form a photosensitive layer. At that time, the thickness of the photosensitive layer after heating was adjusted to 10 μm. Then, "GF-858" was placed as a protective film on the formed photosensitive layer and pressed with a roll. In this way, the photosensitive film of Example 1 was obtained.

(Examples 2 to 15)
Using the support film shown in Table 2, the solution of the photosensitive resin composition, and the protective film, each photosensitive film was prepared according to the same procedure as in Example 1.

(Comparative Examples 1 to 5)
Using the support film shown in Table 3, the solution of the photosensitive resin composition, and the protective film, each photosensitive film was prepared according to the same procedure as in Example 1.

<Applicability to support film>
A solution of the photosensitive resin composition was applied onto the support film so that the thickness of the photosensitive layer after drying was 10 μm, and the coatability was evaluated according to the following criteria.
A: The solution of the photosensitive resin composition can be uniformly applied.
B: There is a part of repellent (some parts are not applied).
C: There are many repellents (some parts are not applied).

<Removability of protective film>
After storing the photosensitive films prepared in Examples and Comparative Examples at 23 ° C. for 20 hours, the protective film was peeled off and the transferred state of the photosensitive layer was visually evaluated.
A: There is no peeling of the photosensitive layer from the support film, and the peelability is good.
B: The protective film adheres firmly to the photosensitive layer, and part or all of the photosensitive layer is peeled off from the support film.

<Removability of support film>
The protective film was removed from the photosensitive films prepared in Examples and Comparative Examples, and the photosensitive layer was laminated on a glass plate while being heated to 130 ° C. to prepare a characteristic evaluation sample to which the photosensitive layer was transferred. Next, the support film was peeled off from the characteristic evaluation sample, and the transfer state of the photosensitive layer was visually evaluated.
A: Peeling can be removed without the photosensitive layer adhering to the support film.
B: A part or the entire surface of the photosensitive layer is peeled off with the photosensitive layer attached to the support film.

<Amount of residual solvent>
The protective film was removed from the photosensitive films prepared in Examples and Comparative Examples, respectively. Next, the photosensitive layer was peeled off from the support film, and the peeled photosensitive layer was subjected to gas chromatography (manufactured by Agilent Technologies, Inc., trade name "6890N") to measure the amount of residual solvent with respect to 100 parts by mass of phenol resin. ..

<Developability of exposed area>
The support film was peeled off from the characteristic evaluation sample, and the photosensitive layer was formed at an ^{exposure of 300 mJ / cm 2} using an exposure machine (manufactured by ORC Manufacturing Co., Ltd., trade name "HMW-801") equipped with a high-pressure mercury lamp. The resist film was obtained by exposure. Next, it was developed with a developing machine PD-1000 (Mikasa Co., Ltd.) at 23 ° C. using a 2.38 mass% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials Co., Ltd.) for 50 seconds, and exposed. The state of the resist film in the portion was visually evaluated according to the following criteria.
A: No residue of the resist film was observed on the glass surface, and the developability was good.
B: The resist film remained on the glass surface, and the developability was not good.

<Resolution>
The support film was peeled off from the characteristic evaluation sample, and the photosensitive layer was formed at an ^{exposure of 300 mJ / cm 2} using an exposure machine (manufactured by ORC Manufacturing Co., Ltd., trade name "HMW-801") equipped with a high-pressure mercury lamp. The resist film was obtained by exposure. Next, development was carried out in a developing machine PD-1000 (Mikasa Co., Ltd.) at 23 ° C. using a 2.38 mass% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials Co., Ltd.) for 50 seconds, and relief was performed. I got a pattern. The relief pattern was observed with an optical microscope and evaluated according to the following criteria.
A: The relief pattern of 10 μm square is resolved.
B: The relief pattern of 10 μm square is not resolved.

<Chemical resistance evaluation>
The support film was peeled off from the above-mentioned characteristic evaluation sample. Next, a photosensitive layer was exposed with an ^{exposure amount of 300 mJ / cm 2} using an exposure machine equipped with a high-pressure mercury lamp (manufactured by ORC Manufacturing Co., Ltd., trade name: HMW-801) to obtain a resist film. Next, development was carried out in a developing machine PD-1000 (Mikasa Co., Ltd.) at 23 ° C. using a 2.38 mass% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials Co., Ltd.) for 50 seconds, and pure. After rinsing with water, it was cured in a vertical curing furnace VF200B (manufactured by Koyo Thermo System Co., Ltd.) at 220 ° C. for 1 hour in a nitrogen atmosphere to obtain a cured relief pattern.
The obtained cured relief pattern was evaluated for chemical resistance to PGMEA and GBL. The processing conditions are as follows.
[PGMEA]
Room temperature x 10 minutes, immersion [GBL]
After immersion treatment at 80 ° C. for 10 minutes, washing with water, and drying in a 50% RH atmosphere at 23 ° C. for 5 hours or more, the appearance of the curing pattern (observed with an optical microscope) and the change in film thickness (needle-type profilometer KLA-) (Measured by Tencor P-15) was examined. The evaluation criteria are as follows.
A: There is no change in the pattern crack, and both the film loss (that is, the film thickness decrease) and the swelling (that is, the film thickness increase) are less than 5%.
B: No pattern cracks occur, but film reduction or swelling of 5% or more and less than 10% is observed.
C: There is pattern cracking, or 10% or more of film loss or swelling is observed.
Tables 2 and 3 show the results of each characteristic evaluation for each Example and Comparative Example.

As is clear from Tables 2 and 3, in Comparative Examples 1 to 3 in which a fluorine-based surfactant was used as the surfactant, the coatability to the support film and the chemical resistance were not sufficient.
Further, in Comparative Example 4 containing no surfactant, the coatability was poor and the characteristics of the coating film could not be evaluated.
On the other hand, in Examples 1 to 16 in which the silicone-type surfactant was used, in Example 13 (0.02 parts by mass) in which the content of the surfactant was low, the chemical resistance to GBL was further lower. At 16 (0.01 parts by mass), the coatability and chemical resistance to GBL were slightly low, but all of the others had excellent coatability, peelability, developability, resolution and chemical resistance. You can see that there is.
Therefore, a phenol resin having a specific structure as represented by the general formula (1) and a silicone-type surfactant are used, and the amount used is 0.01 part by mass or more with respect to 100 parts by mass of the phenol resin. It was confirmed that particularly good characteristics can be obtained by doing so.

Therefore, a support film having at least one surface demolded, and a photosensitive layer composed of a photosensitive resin composition containing a phenol resin having a specific structure, a photoacid generator, a solvent, and a silicone-type surfactant. , The protective film is laminated in this order, and the photosensitive layer is formed on the release-treated surface of the support film. The photosensitive film of the present invention improves the coatability to the support film and is photosensitive. The layer has sufficiently high peelability from the support film, and a defect-free photosensitive film is obtained.

1 ... photosensitive film, 10 ... support film, 11 ... photosensitive layer, 12 ... protective film.

The photosensitive resin film of the present invention includes a surface protective film for a semiconductor device, a display device and a light emitting device, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film for a device having a bump structure, and a multilayer. It can be suitably used as an interlayer insulating film of a circuit, a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.

Claims (6)

A chemical treatment in which the surface of the support film is coated with a release agent containing at least one selected from the group consisting of a silicone-based compound, a fluorine-containing compound, and an alkyd resin on at least one surface, or a corona of the support film. The support film on which the release treatment layer is arranged by the physical treatment to be treated, and the following general formula (1):

{In the formula (1), a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₁ is 1 having 1 to 20 carbon atoms. valent organic group, a halogen atom, represents a monovalent substituent selected from the group consisting of a nitro group and a cyano group, a plurality of R ₁ when b is 2 or 3, which may be the same or different , X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (2):

(In formula (2), p is an integer of 1 to 10) A divalent alkylene oxide group selected from the group consisting of a divalent alkylene oxide group and a divalent organic group having an aromatic ring. Represents an organic group. } And a photosensitive layer composed of a photosensitive resin composition containing a phenol resin (A) having a repeating unit represented by}, a photoacid generator (B), a solvent (C), and a silicone-type surfactant (D). , And the protective film are laminated in this order, and the photosensitive layer is arranged on the release processing layer of the support film .
A photosensitive film in which the photosensitive resin composition further contains a cross-linking agent (E). In the general formula (1), X is the following general formula (3):

{In formula (3), R ₂ , R ₃ , R ₄ and R ₅ are independently hydrogen atoms, monovalent aliphatic groups having 1 to 10 carbon atoms, or some or all of hydrogen atoms are fluorine. It is a monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, n ₁ is an integer of 0 to 4, and R ₆ is a halogen _{when n 1 is an integer of 1 to 4.} atom, a hydroxyl group, or a monovalent organic group, a is at least one R ₆ hydroxyl groups, a plurality of R ₆ may be the same or different when n ₁ is an integer of 2 to 4. }, And the following general formula (4):

{In formula (4), R ₇ , R ₈ , R ₉ and R ₁₀ are independently hydrogen atoms, monovalent aliphatic groups having 1 to 10 carbon atoms, or some or all of hydrogen atoms are fluorine. It represents a monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, and W is a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and a fluorine atom. Aliphatic group having 3 to 20 carbon atoms which may be substituted with, the following general formula (2):

(In the formula (2), p is an integer of 1 to 10.) A divalent alkylene oxide group represented by the formula (2), and the following formula (5):

It is a divalent organic group selected from the group consisting of divalent groups represented by. The photosensitive film according to claim 1, which is a divalent organic group selected from the group consisting of divalent groups represented by. A chemical treatment in which the surface of the support film is coated with a release agent containing at least one selected from the group consisting of a silicone-based compound, a fluorine-containing compound, and an alkyd resin on at least one surface, or a corona of the support film. The support film on which the release treatment layer is arranged by the physical treatment to be treated, and the following general formula (1):

{In the formula (1), a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₁ is 1 having 1 to 20 carbon atoms. valent organic group, a halogen atom, represents a monovalent substituent selected from the group consisting of a nitro group and a cyano group, a plurality of R ₁ when b is 2 or 3, which may be the same or different ,
In the general formula (1), X is the following formula (6):

A photosensitive resin composition containing a phenol resin (A), a photoacid generator (B), a solvent (C), and a silicone-type surfactant (D) having a repeating unit which is a divalent organic group represented by A photosensitive film in which a photosensitive layer made of an object and a protective film are laminated in this order, and the photosensitive layer is arranged on a mold release processing layer of the support film. In the general formula (1), X is the following formula (7):

The photosensitive film according to claim 3 , which is a divalent organic group represented by. The phenol resin (A) has the following general formula (8):

{In formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of hydrocarbon groups and alkoxy groups, n ₂ is an integer of 1 to 3, and n ₃ is 0. It is an integer of ~ 2, m ₁ is an integer of 1 to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and _{R 11 when n 3} is 2 may be the same or different. .. } And the following general formula (9):

{In formula (9), R ₁₂ and R ₁₃ are monovalent groups having 1 to 10 carbon atoms independently selected from the group consisting of hydrocarbon groups and alkoxy groups, respectively, and n ₄ is an integer of 1 to 3. Yes, n ₅ is an integer from 0 to 2, n ₆ is an integer from 0 to 3, m ₂ is an integer from 1 to 500, 2 ≤ (n ₄ + n ₅ ) ≤ 4, and n _{5 R 12} when is 2 may be the same or different, and _{R 13 when n 6} is 2 or 3 may be the same or different. The photosensitive film according to claim 3 or 4 , which is a phenol resin having both of the repeating units represented by} in the same resin skeleton. The photosensitive film according to any one of claims 1 to 5, wherein the silicone-type surfactant is a dimethylsiloxane ethyleneoxygraft compound and / or a dimethylsiloxanepropyleneoxygraft compound.

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