JP6949050B2 - 2-layer photosensitive layer roll - Google Patents

Description

The present invention relates to a photosensitive layer roll.

Conventionally, a photolithography method has been generally known as an image forming method used for patterning semiconductor devices, liquid crystal display elements, printed wiring boards, and the like. In the photolithography method, usually, a method of applying a solution of a photosensitive resin composition on a substrate such as a copper-clad laminate and drying it, or a layer composed of a support and a photosensitive resin composition (hereinafter, "photosensitive layer"). A photosensitive resin laminate (hereinafter, also referred to as “dry film resist”) in which a photosensitive resin laminate (hereinafter, also referred to as “dry film resist”) in which a cover film is sequentially laminated is used. The latter is often used in the manufacture of printed wiring boards.

The dry film resist may be stored in the form of a roll (see Patent Document 1). Patent Document 1 describes a photosensitive layer and a non-adhesive outer layer having a thickness of one-fifth or less of the thickness of the photosensitive layer in order to reduce the manufacturing cost by omitting the cover film from the roll of the dry film resist. A photosensitive composite containing the above in order has been proposed.

From the viewpoint of handling the dry film resist, the dry film resist is not adhesive at room temperature, and it is required to exhibit fluidity when the dry film resist is thermocompression bonded to a substrate or the like (that is, at the time of laminating) (that is, at the time of laminating). See Patent Document 2). Patent Document 2 proposes a photosensitive coverlay film that is not adhesive at a substrate temperature of 20 ° C. and whose position can be easily corrected even when placed on a substrate.

Further, Patent Document 3 confirms that a phenol resin having a specific structure in the photosensitive resin composition is used in combination with a nonionic surfactant to achieve both low-temperature curability and chemical resistance of the cured film. Has been done.

Japanese Unexamined Patent Publication No. 2001-175000 Japanese Unexamined Patent Publication No. 2003-149803 Japanese Unexamined Patent Publication No. 2013-190697

Usually, the photosensitive resin laminate is manufactured in the form of a roll and is slit to a required width for use. However, in the case of a conventional photosensitive resin laminate in which the photosensitive layer is formed of at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, when slitting occurs. There is a problem that wrinkles or cracks occur and it is difficult to slit so that the cross section becomes smooth.

｛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、かつ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。｝
で表される構造を繰り返し単位として有する、［１４］に記載の感光層ロール。
［１６］
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、ｎ１は０〜４の整数であって、ｎ１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、ｎ１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、かつ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、［１５］に記載の感光層ロール。
［１７］
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、［１５］又は［１６］に記載の感光層ロール。
［１８］
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、［１７］に記載の感光層ロール。
［１９］
前記フェノール樹脂が、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、ｎ２は１〜３の整数であり、ｎ３は０〜２の整数であり、ｍ１は１〜５００の整数であり、２≦（ｎ２＋ｎ３）≦４であり、ｎ３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、ｎ４は１〜３の整数であり、ｎ５は０〜２の整数であり、ｎ６は０〜３の整数であり、ｍ２は１〜５００の整数であり、２≦（ｎ４＋ｎ５）≦４であり、ｎ５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、ｎ６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、［１５］〜［１８］のいずれか１項に記載の感光層ロール。
［２０］
支持体フィルムと、
前記支持体フィルム上に設けられた、感光性樹脂組成物を含む感光層と、
を有する感光層ロールであって、
前記感光性樹脂組成物がフェノール樹脂、ポリイミド前駆体、ポリベンズオキサゾール前駆体、及び可溶性ポリイミドから成る群から選択される少なくとも１つの樹脂を含み、かつ前記支持体フィルムの両面は、前記感光層と接している、感光層ロール。
［２１］
前記感光層中に含まれる有機溶媒の量が、前記感光層の総量に対して０．１質量％以上１５質量％以下である、［２０］に記載の感光層ロール。
［２２］
前記感光層中に含まれる有機溶媒の量が、前記感光層の総量に対して１質量％以上１５質量％以下である、［２１］に記載の感光層ロール。
［２３］
前記感光性樹脂組成物が前記フェノール樹脂を含む、［２１］又は［２２］に記載の感光層ロール。
［２４］
前記有機溶媒が、γ−ブチロラクトン、アセトン、メチルエチルケトン、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシド、プロピレングリコールモノメチルエーテル、ｔｅｒｔ−ブチルアルコール及びテトラヒドロフルフリルアルコールから成る群から選択される少なくとも一つを含む、［２１］〜［２３］のいずれか１項に記載の感光層ロール。
［２５］
前記有機溶媒が、γ−ブチロラクトン、アセトン、メチルエチルケトン、Ｎ−メチル−２−ピロリドン及びジメチルスルホキシドからなる群から選択される少なくとも一つを含む、［２４］に記載の感光層ロール。
［２６］
前記感光性樹脂組成物が前記ポリイミド前駆体を含む、［２０］〜［２５］のいずれか１項に記載の感光層ロール。
［２７］
前記感光性樹脂組成物が前記ポリベンズオキサゾール前駆体を含む、［２０］〜［２５］のいずれか１項に記載の感光層ロール。
［２８］
前記感光性樹脂組成物が前記可溶性ポリイミドを含む、［２０］〜［２５］のいずれか１項に記載の感光層ロール。
［２９］
前記感光性樹脂組成物がフェノール樹脂を含む、［２０］〜［２５］のいずれか１項に記載の感光層ロール。
［３０］
前記フェノール樹脂が、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、かつ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。｝
で表される構造を繰り返し単位として有する、［２９］に記載の感光層ロール。
［３１］
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、ｎ１は０〜４の整数であって、ｎ１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、ｎ１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、かつ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、［３０］に記載の感光層ロール。
［３２］
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、［３０］又は［３１］に記載の感光層ロール。
［３３］
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、［３２］に記載の感光層ロール。
［３４］
前記フェノール樹脂が、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、ｎ２は１〜３の整数であり、ｎ３は０〜２の整数であり、ｍ１は１〜５００の整数であり、２≦（ｎ２＋ｎ３）≦４であり、ｎ３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、ｎ４は１〜３の整数であり、ｎ５は０〜２の整数であり、ｎ６は０〜３の整数であり、ｍ２は１〜５００の整数であり、２≦（ｎ４＋ｎ５）≦４であり、ｎ５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、ｎ６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、［３０］〜［３３］のいずれか１項に記載の感光層ロール。
［３５］
［１］〜［３４］のいずれか１項に記載の感光層ロールをスリッターでスリットしてスリット感光層ロールを製造するスリット感光層ロールの製造方法。
［３６］
前記スリッターの歯が加熱されている、［３５］に記載のスリット感光層ロールの製造方法。
［３７］
前記スリッターの歯が１００℃以上に加熱されている、［３６］に記載のスリット感光層ロールの製造方法。
［３８］
以下の工程：
［１］〜［３４］のいずれか１項に記載の感光層ロールが、前記感光層の前記支持体フィルムが設けられた側とは反対側にカバーフィルムを有する場合には、前記カバーフィルムを剥離する工程と、
前記カバーフィルムを有さない前記感光層ロールをスリッターでスリットする工程と、
スリットされた前記感光層ロールに、前記剥離したカバーフィルム又は前記剥離したカバーフィルムとは別のカバーフィルムを貼る工程と、
を含むスリット感光層ロールの製造方法。
［３９］
前記スリッターの歯が加熱されている、［３８］に記載のスリット感光層ロールの製造方法。
［４０］
前記スリッターの歯が１００℃以上に加熱されている、［３９］に記載のスリット感光層ロールの製造方法。The present inventors have found that the above problems can be solved by adjusting the melt viscosity of the photosensitive layer or removing the cover film, and have completed the present invention. That is, the present invention is as follows.
[1]
Support film and
A photosensitive layer containing a photosensitive resin composition provided on the support film and
It is a photosensitive layer roll having
The photosensitive resin composition contains at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and the photosensitive layer has a melt viscosity of 500 Pa · s or less. A photosensitive layer roll, which is a layer having a temperature point of
[2]
The photosensitive layer roll according to [1], wherein the photosensitive layer is a layer having a temperature point at which the melt viscosity is 350 Pa · s or less.
[3]
The photosensitive layer roll according to [1] or [2], wherein the photosensitive layer has a melt viscosity at 100 ° C. of 500 Pa · s or less.
[4]
The photosensitive layer roll according to [3], wherein the photosensitive layer has a melt viscosity at 100 ° C. of 350 Pa · s or less.
[5]
Any one of [1] to [4], wherein the cover film is provided on the side of the photosensitive layer opposite to the side on which the support film is provided, and the softening temperature of the cover film is 90 ° C. or higher. The photosensitive layer roll according to.
[6]
The photosensitive layer roll according to [5], wherein the softening temperature of the cover film is 110 ° C. or higher.
[7]
Item 2. The photosensitive layer according to any one of [1] to [6], wherein the amount of the organic solvent contained in the photosensitive layer is 0.1% by mass or more and 15% by mass or less with respect to the total amount of the photosensitive layer. Layer roll.
[8]
The photosensitive layer roll according to [7], wherein the amount of the organic solvent contained in the photosensitive layer is 1% by mass or more and 15% by mass or less with respect to the total amount of the photosensitive layer.
[9]
The organic solvent comprises at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol. , [7] or [8].
[10]
The photosensitive layer roll according to [9], wherein the organic solvent comprises at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethyl sulfoxide.
[11]
The photosensitive layer roll according to any one of [1] to [10], wherein the photosensitive resin composition contains the polyimide precursor.
[12]
The photosensitive layer roll according to any one of [1] to [10], wherein the photosensitive resin composition contains the polybenzoxazole precursor.
[13]
The photosensitive layer roll according to any one of [1] to [10], wherein the photosensitive resin composition contains the soluble polyimide.
[14]
The photosensitive layer roll according to any one of [1] to [10], wherein the photosensitive resin composition contains the phenol resin.
[15]
The phenol resin has 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 , And 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, and 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. }
The photosensitive layer roll according to [14], which has the structure represented by (1) as a repeating unit.
[16]
X in the general formula (1) 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, n1 is an integer of 0 to 4, and R ₆ is a halogen atom when n1 is an integer of 1 to 4. hydroxyl, or a monovalent organic group, a is at least one R ₆ hydroxyl groups, n1 may be different in a plurality of R ₆ in the case where an integer of 2 to 4 the same, respectively. }
The divalent group represented by, 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. 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 optionally substituted with a hydrogen atom, fluorine. Aliphatic group having 3 to 20 carbon atoms which may be substituted with an atom, 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 layer roll according to [15], which is a divalent organic group selected from the group consisting of divalent groups represented by.
[17]
X in the general formula (1) is the following formula (6):

The photosensitive layer roll according to [15] or [16], which is a divalent organic group represented by.
[18]
X in the general formula (1) is the following formula (7):

The photosensitive layer roll according to [17], which is a divalent organic group represented by.
[19]
The phenol resin 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, n2 is an integer of 1 to 3, and n3 is 0 to 0. It is an integer of 2, m1 is an integer of 1 to 500, 2 ≦ (n2 + n3) ≦ 4, and R ₁₁ when n3 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 selected independently from the group consisting of hydrocarbon groups and alkoxy groups, and n4 is an integer of 1 to 3. When n5 is an integer of 0 to 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and R ₁₃ when n6 is 2 or 3 may be the same or different. }
The photosensitive layer roll according to any one of [15] to [18], which has both of the repeating units represented by (1) in the same resin skeleton.
[20]
Support film and
A photosensitive layer containing a photosensitive resin composition provided on the support film and
It is a photosensitive layer roll having
The photosensitive resin composition contains at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and both sides of the support film are formed with the photosensitive layer. Photosensitive layer roll in contact.
[21]
The photosensitive layer roll according to [20], wherein the amount of the organic solvent contained in the photosensitive layer is 0.1% by mass or more and 15% by mass or less with respect to the total amount of the photosensitive layer.
[22]
The photosensitive layer roll according to [21], wherein the amount of the organic solvent contained in the photosensitive layer is 1% by mass or more and 15% by mass or less with respect to the total amount of the photosensitive layer.
[23]
The photosensitive layer roll according to [21] or [22], wherein the photosensitive resin composition contains the phenol resin.
[24]
The organic solvent comprises at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol. , The photosensitive layer roll according to any one of [21] to [23].
[25]
The photosensitive layer roll according to [24], wherein the organic solvent comprises at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethyl sulfoxide.
[26]
The photosensitive layer roll according to any one of [20] to [25], wherein the photosensitive resin composition contains the polyimide precursor.
[27]
The photosensitive layer roll according to any one of [20] to [25], wherein the photosensitive resin composition contains the polybenzoxazole precursor.
[28]
The photosensitive layer roll according to any one of [20] to [25], wherein the photosensitive resin composition contains the soluble polyimide.
[29]
The photosensitive layer roll according to any one of [20] to [25], wherein the photosensitive resin composition contains a phenol resin.
[30]
The phenol resin has 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 , And 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, and 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. }
The photosensitive layer roll according to [29], which has the structure represented by (2) as a repeating unit.
[31]
X in the general formula (1) 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, n1 is an integer of 0 to 4, and R ₆ is a halogen atom when n1 is an integer of 1 to 4. hydroxyl, or a monovalent organic group, a is at least one R ₆ hydroxyl groups, n1 may be different in a plurality of R ₆ in the case where an integer of 2 to 4 the same, respectively. }
The divalent group represented by, 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. 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 optionally substituted with a hydrogen atom, fluorine. Aliphatic group having 3 to 20 carbon atoms which may be substituted with an atom, the following general formula (2):

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

It is a divalent organic group selected from the group consisting of divalent groups represented by. }
The photosensitive layer roll according to [30], which is a divalent organic group selected from the group consisting of divalent groups represented by.
[32]
X in the general formula (1) is the following formula (6):

The photosensitive layer roll according to [30] or [31], which is a divalent organic group represented by.
[33]
X in the general formula (1) is the following formula (7):

The photosensitive layer roll according to [32], which is a divalent organic group represented by.
[34]
The phenol resin 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, n2 is an integer of 1 to 3, and n3 is 0 to 0. It is an integer of 2, m1 is an integer of 1 to 500, 2 ≦ (n2 + n3) ≦ 4, and R ₁₁ when n3 is 2, may be the same or different. }
The repeating unit represented by, and the following general formula (9):

{In formula (9), R ₁₂ and R ₁₃ are monovalent groups having 1 to 10 carbon atoms selected independently from the group consisting of hydrocarbon groups and alkoxy groups, and n4 is an integer of 1 to 3. When n5 is an integer of 0 to 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and R ₁₃ when n6 is 2 or 3 may be the same or different. The photosensitive layer roll according to any one of [30] to [33], which has both of the repeating units represented by} in the same resin skeleton.
[35]
A method for producing a slit photosensitive layer roll, wherein the photosensitive layer roll according to any one of [1] to [34] is slit with a slitter to produce a slit photosensitive layer roll.
[36]
The method for producing a slit photosensitive layer roll according to [35], wherein the teeth of the slitter are heated.
[37]
The method for producing a slit photosensitive layer roll according to [36], wherein the teeth of the slitter are heated to 100 ° C. or higher.
[38]
The following steps:
When the photosensitive layer roll according to any one of [1] to [34] has a cover film on the side of the photosensitive layer opposite to the side on which the support film is provided, the cover film is used. The process of peeling and
The step of slitting the photosensitive layer roll without the cover film with a slitter, and
A step of attaching the peeled cover film or a cover film different from the peeled cover film to the slitted photosensitive layer roll.
A method for manufacturing a slit photosensitive layer roll including.
[39]
The method for producing a slit photosensitive layer roll according to [38], wherein the teeth of the slitter are heated.
[40]
The method for producing a slit photosensitive layer roll according to [39], wherein the teeth of the slitter are heated to 100 ° C. or higher.

According to the present invention, it is possible to provide a photosensitive layer roll that is less likely to cause wrinkles or cracks at the time of slitting and can be slit so that the cross section is smooth.

<First Embodiment: Two-layer photosensitive layer roll>

The photosensitive layer roll according to the first embodiment of the present invention contains a support film and at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide. It is formed by sequentially laminating two layers with a photosensitive layer formed from a photosensitive resin composition.

In this embodiment, the photosensitive layer roll does not include a cover film. Since the photosensitive layer is laminated on one side of the support film and the other side of the support film (that is, the back surface of the support or the surface on which the photosensitive layer is not laminated) is exposed, both sides of the support film are exposed. Will come into contact with the photosensitive layer.
Hereinafter, a photosensitive layer roll that does not include a cover film and in which both sides of the support film are in contact with the photosensitive layer will be described as a two-layer photosensitive layer roll.

Since the conventional photosensitive layer roll is provided with a cover film, wrinkles are likely to occur on the cover film at the time of slitting, and particularly when the slitter teeth are heated and slit, large wrinkles are likely to occur on the cover film. was there.
In order to solve the above problems, the two-layer photosensitive layer roll according to the first embodiment is characterized in that it does not include a cover film.

<Support film>
The support film according to the present embodiment 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 “polyethylene terephthalate film”) can be used. , "PET film") is preferred.

From the viewpoint of transferring the photosensitive layer from the two-layer photosensitive layer roll to the substrate when performing the photolithography method, it is preferable that at least one surface of the support film is subjected to a mold release treatment. The mold release treatment in the present embodiment is a mold release agent such as a silicone-based surfactant, a silicone-based compound such as a silicone resin, a fluorine-based surfactant, a fluorine-containing compound such as a fluorine resin, and an alkyd resin of a support film. It refers to a chemical treatment that coats the surface thinly, or a physical treatment such as corona treatment of 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.

<Photosensitive layer>
The photosensitive layer is a support film, preferably at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide on the release-treated surface of the support film. It is formed by applying a photosensitive resin composition containing.
Hereinafter, the components contained in the photosensitive resin composition will be described.

｛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、かつ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。｝で表される構造を繰り返し単位として有することが好ましい。
式（１）で表される構造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ズ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し、ひいては感光層の熱溶融性に寄与する。
熱溶融性に優れた感光層は、スリット時、特にスリッターの歯を加熱してスリットした際に、切断面にクラックが発生し難く、断面が平滑になるようにスリットできるため好ましい。[Photosensitive resin composition containing phenol resin] [Component (A): phenol resin]
Generally, the phenol resin is a thermosetting resin formed from a phenol compound and an aldehyde compound.
In the present embodiment, from the viewpoint of thermal meltability of the photosensitive layer, the phenol resin (A) is used in 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 , And 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, and 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. } Is preferably provided as a repeating unit.
The phenol resin (A) having a repeating unit having a structure represented by the formula (1) can be cured at a lower temperature than, for example, a polyimide resin and a polybenzoxazole resin, and has good elongation. It enables the formation of a film and thus contributes to the thermal meltability of the photosensitive layer.
A photosensitive layer having excellent heat-meltability is preferable because cracks are less likely to occur on the cut surface and the cross section can be made smooth when slitting, particularly when the slitter teeth are heated and slit.

｛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。In the above general formula (1), R ₁ 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, and is alkaline-soluble. From the viewpoint, a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an aromatic group 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 an integer of 1 to 3, and 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 an integer of 0 to 3, and is preferably 0 or 1 from the viewpoint of alkali solubility and elongation. 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、ｎ１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、かつ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有機基であることが好ましい。
式（４）中のＷとしては、硬化膜の伸度及び熱溶融性の観点から、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 toughness of the film after curing and heat meltability.

{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, n1 is an integer of 0 to 4, and R ₆ is a halogen atom _{when n 1 is an integer of 1 to 4.} , hydroxyl group, or a monovalent organic group, at least one R ₆ is hydroxyl group, 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. 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 optionally substituted with a hydrogen atom, fluorine. Aliphatic group having 3 to 20 carbon atoms which may be substituted with an atom, 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 divalent groups.
The W in the formula (4) is a single bond, an alkylene oxide group represented by the general formula (2), and an ester group in the above formula (5) from the viewpoint of elongation and thermal meltability of the cured film. , A divalent organic group selected from the group consisting of an amide group and a sulfonyl group.

で表される２価の有機基であることがより好ましく、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 and thermal meltability 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、ｎ２は１〜３の整数であり、ｎ３は０〜２の整数であり、ｍ１は１〜５００の整数であり、２≦（ｎ２＋ｎ３）≦４であり、ｎ３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、ｎ４は１〜３の整数であり、ｎ５は０〜２の整数であり、ｎ６は０〜３の整数であり、ｍ２は１〜５００の整数であり、２≦（ｎ４＋ｎ５）≦４であり、ｎ５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、ｎ６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, from the viewpoint of heat meltability and alkali solubility of the photosensitive layer, the phenol resin (A) is described by 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, n2 is an integer of 1 to 3, and n3 is 0 to 0. It is an integer of 2, m1 is an integer of 1 to 500, 2 ≦ (n2 + n3) ≦ 4, and R ₁₁ when n3 is 2, may be the same or different. }
The repeating unit represented by, and the following general formula (9):

{In formula (9), R ₁₂ and R ₁₃ are monovalent groups having 1 to 10 carbon atoms selected independently from the group consisting of hydrocarbon groups and alkoxy groups, and n4 is an integer of 1 to 3. When n5 is an integer of 0 to 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and R ₁₃ when n6 is 2 or 3 may be the same or different. }
It is particularly preferable to have both of the repeating units represented by (1) in the same resin skeleton.

M1 of the general formula (8) and m2 of the above 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, block or these. Can be arranged in a combination of. m1 and m2 are independently integers of 1 to 500 from the viewpoint of alkali solubility and elongation of the cured product, the lower limit is preferably 2, more preferably 3, and the upper limit is preferably. It is 450, more preferably 400, and even more preferably 350. Each of m1 and m2 is preferably 2 or more independently from the viewpoint of toughness and thermal meltability of the cured film, 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 molar ratio of the structure represented by the general formula (8). The higher the value, the better the physical properties of the film after curing, and the better the heat resistance and thermal meltability. The higher the molar ratio of the structure represented by the general formula (9), the better the alkali solubility and curing. Excellent in later pattern shape. Therefore, as the range of the ratio of the structure represented by the general formula (8) to the structure represented by the general formula (9), m ₁ : m ₂ = 90: 10 to 20:80 is the physical characteristic of the film after curing. From the viewpoint, m ₁ : m ₂ = 80: 20 to 40:60 is more preferable from the viewpoint of film physical characteristics after curing, alkali solubility and thermal meltability, and m ₁ : m ₂ = 70: 30 to 50: 50 is particularly preferable from the viewpoint of film physical characteristics after curing, pattern shape, alkali solubility and thermal meltability.

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. More typically, these monomer components can be synthesized by subjecting them to 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 polymerized component. From the viewpoint of reaction control and stability of the obtained phenol resin (A) and the photosensitive resin composition, the charged molar ratio (phenol compound: copolymer component) of the phenol compound and the above-mentioned copolymer component is 5: 1. It is preferably ~ 1.01: 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. be. The weight average molecular weight is preferably 700 or more from the viewpoint of the elongation of the cured film, while the weight average molecular weight is 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition. Is preferable.
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, dibenzylketone, 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-Norbornadiene, Tetrahydroindene, 5-Etilidene-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, dehydrohalation, or dealcoholization, or by polymerizing while cleaving an unsaturated bond. A catalyst may be used during the polymerization of the phenol compound and the copolymerization component.
Examples of acidic catalysts include hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, phosphite, 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.
Examples of alkaline catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, piperazine, 1 , 4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonen, ammonia, hexa Methylenetetramine and the like can be mentioned.
In the present embodiment, the amount of the catalyst used to obtain the phenol resin (A) is the total number of moles of the copolymerization components, 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, but are not limited to, bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and dipropylene glycol. Examples thereof include dimethyl ether, cyclohexanone, cyclopentanone, 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 preferably 40 ° C. to 250 ° C., more preferably 100 ° C. to 200 ° C., and the reaction time is approximately 1 hour to 1 hour. It is preferably 10 hours.

In addition, the phenol resin (A) is a phenol compound which is not a raw material of the structure of the general formula (1), and is a total molar amount of the phenol compound which is a raw material of the phenol resin (A), for example, as long as the effect of the present invention is not impaired. It may be 30% or less of the number, and may be further used and polymerized.

In the present embodiment, in the above general formula (1), when a is 1, a phenol resin selected from the group consisting of novolak resin and polyhydroxystyrene resin (hereinafter, phenol resin) in order to improve alkali solubility. (Also referred to as (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, 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. The polyparavinylphenol is not particularly limited as long as it is a polymer containing paravinylphenol as a polymerization unit. The polymerization unit other than paravinylphenol that can constitute polyparavinylphenol may be any compound copolymerizable with paravinylphenol as long as it does not contradict the object of the present invention. Compounds that can be copolymerized with paravinylphenol include, for example, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, 2-ethoxyethylta acrylate, t-butyl acrylate, and 1,5-pentanediol di. Acrylate, N, N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1,3-propanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2- Dimethylol propanediacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2-di (p-hydroxyphenyl) -propanedimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2-2 -Di (p-hydroxyphenyl) -propane dimethacrylate, triethylene glycol dimethacrylate, polyoxypropyltrimethylol propanetriacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate Acrylate, Butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimetaacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol Of trimethacrylate, 1-phenylethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylpropan trimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol dimethacrylate Acrylate esters such as; styrene and substituted styrenes such as 2-methylstyrene and vinyltoluene; vinyl esters such as vinyl acrylates and vinyl methacrylates; orthovinyl phenols and metavinylphenols. Monomer such as vinylphenol other than paravinylphenol; is mentioned, but is not limited thereto.

The weight average molecular weight of the phenol resin (A') (that is, the phenol resin selected from the group consisting of the novolak resin and the polyhydroxystyrene resin) is preferably 700 to 100,000, more preferably 1,500 to 80. It is 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 group consisting of 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 radiation 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 − 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 and the like are preferable.
As the diaryliodonium salts, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate and the like are preferable.
Examples of triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfo. Nart, 4-phenylthiophenyldiphenyltrifluoroacetate and the like are preferable.
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, and diazonaphthoquinone compound. Specific examples include 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds of phenols.

(2) Sulfone Compound Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples include 4-trisphenacyl sulfone, mesitylphenacyl sulfone, 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 of the sulfonic acid compound include benzointosylate, 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 Specific examples of the oxime ester compound include 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. Is preferable, and it is 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 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. Therefore, the positive photoacid generator (B) is preferably a quinonediazide compound.

Examples of the quinone diazide compound include a compound having a 1,2-benzoquinone diazido structure or a 1,2-naphthoquinone diazide structure (a compound having the latter structure is hereinafter also referred to as an “NQD compound”). These compounds are described, 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 naphthoquinonediazide sulfonic acid into a sulfonyl chloride with chlorsulfonic acid, thionyl chloride or the like according to a conventional method, and subjecting the obtained naphthoquinone diazidosulfonyl 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, 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。｝
で表されるものが挙げられる。Examples of preferable NQD compounds from the viewpoint of the physical characteristics of the cured film such as sensitivity and elongation include 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. }
The one represented by is mentioned.

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, sulfoxides, 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, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, Ethyl acetate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, tert-butyl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpho Phosphor, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesityrene and the like can be used. Among them, γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone from the viewpoints of resin solubility, resin composition stability, adhesion to substrate, thermal meltability, storage stability, and blocking property. , Dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol are preferable, and among these, γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide are particularly preferable.

[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 of the silicone-type surfactant include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (trade name, manufactured by Shin-Etsu Chemical 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, manufactured by Big Chemie Japan), 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. When the amount of the silicone-type surfactant (D) used 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 according to the present embodiment 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 according to the present embodiment is heat-cured, or the cross-linking agent itself is a cross-linking network. It is a compound that forms. The cross-linking agent (E) is not limited as long as it is a compound that can be thermally cross-linked. In general, 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.

Examples of the cross-linking agent (E) include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, and phenol-xylylene type epoxy resin, which are oxylan compounds. Naftor-xylylene type epoxy resin, phenol-naphthol 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, Trimethylol propanepolyglucidyl ether, 1,1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol triglycidyl ether, orthosecondary butylphenylglycidyl ether, 1,6-bis (2,3-epoxy) Epoxy) Naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-212, 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 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Praxel G402, PUE101, PUE105 (above, product) Name, manufactured by Daicel Chemical Industry Co., Ltd., Epicron (registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850- 1000 (above, trade name, manufactured by DIC), Denacol (registered trademark) 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), Epolite (registered trademark) 70P, Epolite 100MF (above, trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

The cross-linking agent (E) includes isocyanate group-containing compounds 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and isophorone. Diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (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.

The cross-linking agent (E) includes 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5, which are bismaleimide compounds. 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'-diphenylsulfone bismaleimide, 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.), etc. Be done.

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 the compounding amount is 40 parts by mass or less, the stability of the composition in a varnish state and the elongation of the thermosetting film are good. Is good.

The thermoacid generator is preferably blended in the resin composition from the viewpoint of exhibiting good thermophysical and mechanical properties of the cured product even when the curing temperature is lowered.
The thermoacid generator is not limited as long as it is a compound that generates an acid by heat, but for example, allyl chloroacetate, n-butyl chloroacetate, t-butyl chloroacetate, ethyl chloroacetate, methyl chloroacetate, benzyl chloroacetate. , Isopropyl chloroacetate, 2-methoxyethyl chloroacetate, methyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, 2-ethoxyethyl trichloroacetate, t-butyl cyanoacetate, t-butyl methacrylate, ethyl trifluoroacetate, trifluoro Methyl acetate, phenyl trifluoroacetate, vinyl trifluoroacetate, isopropyl trifluoroacetate, allyl trifluoroacetate, ethyl benzoate, methyl benzoate, t-butyl benzoate, methyl 2-chlorobenzoate, ethyl 2-chlorobenzoate , 4-Chlorobenzoate ethyl, 2,5-dichlorobenzoate ethyl, 2,4-dichlorobenzoate methyl 2,4-dichlorobenzoate ethyl, p-fluorobenzoate methyl, p-fluorophenylcarboxylic acid t-butyl, pentafluoro Carbolate esters such as methyl propionate, ethyl pentafluoropropionate, t-butyl crotonate; cyclic carboxylic acid esters such as phenolphthaline and timolphthalene; ethyl methanesulphonate, methyl methanesulphonate, methanesulphonic acid 2-methoxyethyl, 2-isopropoxyethyl methanesulfonic acid, phenyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, 2-phenylethyl p-toluenesulfonate, p-toluenesulfonic acid n-propyl, n-butyl p-toluenesulfonate, t-butyl p-toluenesulfonate, n-hexyl p-toluenesulfonate, n-heptyl p-toluenesulfonate, n-octyl p-toluenesulfonate, p -Toluenesulfonate 2-methoxyethyl, p-toluenesulfonate propargyl, p-toluenesulfonate 3-butynyl, trifluoromethanesulfonate ethyl, trifluoromethanesulfonate n-butyl, perfluorobutane sulfonate ethyl, perfluorobutane sulfone Methyl acid acid, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluorophosphate, trimethylsulfonium methylsulfate, tri-p-sulfonium trifluoromethane Sulfonic acid esters such as sulfonate, trimethylsulfonium trifluoromethanesulfonate, pyridinium-p-toluenesulfonate, ethyl perfluorooctane sulfonate; 1,4-butane sulton, 2,4-butane sulton, 1,3-propane sulton, phenol Cyclic sulfonic acid esters such as red, bromocresol green, and bromocresol purple; aromatic carboxylic acid anhydrides such as 2-sulfobenzoic acid anhydride, p-toluene sulfonic acid anhydride, and phthalic acid anhydride, and the like. ..

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). The portion is more preferable. When the blending amount is 0.1 part by mass or more, the effect of maintaining the pattern shape after thermosetting is good, while when the blending amount is 30 parts by mass or less, the lithography performance is not adversely affected and the composition Good stability.

Examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd .: trade name KBM803, manufactured by Chisso Co., Ltd .: trade name Sila Ace S810), 3-mercaptopropyltriethoxysilane (Azumax Co., Ltd.). Manufactured by: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: trade name LS1375, manufactured by Azumax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Asmax Co., Ltd.) : Product name SIM6473.5C), Mercaptomethylmethyldimethoxysilane (manufactured by Azumax Co., Ltd .: Product name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane , 3-Mercaptopropyldiethoxypropoxysilane, 3-Mercaptopropylethoxydipropoxysilane, 3-Mercaptopropyldimethoxypropoxysilane, 3-Mercaptopropylmethoxydipropoxysilane, 2-Mercaptoethyltrimethoxysilane, 2-Mercaptoethyldiethoxy Methoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydi Propoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: trade name LS3610, Azumax Co., Ltd .: trade name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (Azumax Co., Ltd .: trade 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-Dimethoxypropoxysilylpropyl) urea, N- (3-methoxydipropoxy) Cyrilpropyl) 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 .: trade name SLA0598.0) ), M-Aminophenyltrimethoxysilane (manufactured by Azumax Co., Ltd .: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azumax Co., Ltd .: trade name SLA0599.1) Aminophenyltrimethoxysilane (Azumax Co., Ltd.) Manufactured by: trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azumax Co., Ltd .: trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) 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, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), 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, di-t- Butoxydiacetoxysilane, di-i-butoxyaluminoxytrier Toxisilane, bis (pentazionate) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilane Diol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethyl Phenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol , Tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol and the like. These may be used alone or in combination of two or more.

表される化合物が好ましい。
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 the following formula:

The compound represented is preferred.
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. -Hydroxy5-norbornene-2,3-dicarboxylic acid imide and the like can be mentioned. Examples of compounds having a carboxyl group include 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).

｛式（１１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、炭素数１〜３０の飽和脂肪族基、芳香族基、炭素−炭素不飽和二重結合を有する一価の有機基、又は、炭素−炭素不飽和二重結合を有する一価のイオンであり、Ｘ^１は４価の有機基であり、Ｙ^１は２価の有機基であり、ｍは１以上の整数であり、そしてｍは２以上が好ましく、５以上がより好ましい。｝
で表される繰り返し単位を含むポリアミド酸エステルを用いることができる。[Photosensitive resin composition containing a polyimide precursor and / or an alkali-soluble polyimide]
(A) Polyimide precursor Examples of the photosensitive resin used in the polyimide precursor composition include polyamide and polyamic acid ester. For example, as the polyamic acid ester, the following general formula (11):

{In formula (11), R ¹ and R ² are monovalent organics each independently having a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, and a carbon-carbon unsaturated double bond. A group or a monovalent ion having a carbon-carbon unsaturated double bond, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is an integer of 1 or more. Yes, and m is preferably 2 or more, more preferably 5 or more. }
A polyamic acid ester containing a repeating unit represented by is used.

^{When R 1} and R ^{2 of the} above general formula (11) are present as monovalent cations, O is negatively charged (that is, exists as ^{−O −).} Further, X ¹ and Y ¹ may contain a hydroxyl group.

｛一般式（１２）中、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜５の有機基であり、そしてｍ_１は、１〜２０の整数である。｝
で表される１価の有機基、又は下記一般式（１３）：

｛一般式（１３）中、Ｒ_６、Ｒ_７及びＲ_８は、それぞれ独立に、水素原子又は炭素数１〜５の有機基であり、そしてｍ_２は、１〜２０の整数である。｝
で表される１価の有機基の末端にアンモニウムイオンを有する構造である。 ^{R 1} and R ² in the general formula (11) are more preferably the following general formula (12):

{In general formula (12), R ₃ , R ₄ and R ₅ are independently hydrogen atoms or organic groups having 1 to 5 carbon atoms, and m ₁ is an integer of 1 to 20. }
A monovalent organic group represented by, or the following general formula (13):

{In general formula (13), R ₆ , R ₇ and R ₈ are independently hydrogen atoms or organic groups having 1 to 5 carbon atoms, and m ₂ is an integer of 1 to 20. }
It is a structure having an ammonium ion at the end of a monovalent organic group represented by.

A plurality of polyamic acid esters represented by the general formula (11) may be mixed. Further, a polyamic acid ester obtained by copolymerizing polyamic acid esters represented by the general formula (11) may be used.

｛式（４）中、Ｒ_９は酸素原子、硫黄原子、２価の有機基のいずれかである。｝
で表される少なくとも１つの構造を含む４価の有機基であることが好ましい。 ^{From the viewpoint of thermal meltability, X 1} in the formula (11) is preferably a tetravalent organic group containing an aromatic group. Specifically, X ¹ is expressed by the following general formulas (2) to (4):

{In formula (4), R ₉ is either an oxygen atom, a sulfur atom, or a divalent organic group. }
It is preferably a tetravalent organic group containing at least one structure represented by.

_{R 9} in the general formula (4) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom. R ₉ may contain a hydroxyl group.

で表される構造を含む４価の有機基が特に好ましい。From the viewpoint of thermal meltability, X ¹ is expressed by the following general formula (5):

A tetravalent organic group containing the structure represented by is particularly preferable.

｛式（６）中、Ｒ_１０、Ｒ_１１、Ｒ_１２及びＲ_１３は、水素原子、炭素数が１〜５の１価の脂肪族基であり、同一であっても異なっていてもよい。｝

｛式（７）中、Ｒ_１４〜Ｒ_２１は、水素原子、ハロゲン原子、炭素数が１〜５の１価の有機基であり、互いに異なっていても、同一であってもよい。｝

｛式（８）中、Ｒ_２２は２価の基であり、Ｒ_２３〜Ｒ_３０は、水素原子、ハロゲン原子、炭素数が１〜５の１価の脂肪族基であり、同一であっても異なっていてもよい。）
で表される少なくとも１つの構造を含む２価の有機基であることが好ましい。Y ¹ in the formula (11), from the viewpoint of adhesion between the interlayer insulating film and the sealing material is preferably a divalent organic group containing an aromatic group. Specifically, Y ¹ is expressed by the following general formulas (6) to (8):

{In formula (6), R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different. }

{In formula (7), R _{14 to} R ₂₁ are hydrogen atoms, halogen atoms, and monovalent organic groups having 1 to 5 carbon atoms, which may be different from each other or the same. }

{In formula (8), R ₂₂ is a divalent group, and R _{23 to} R ₃₀ are hydrogen atoms, halogen atoms, and monovalent aliphatic groups having 1 to 5 carbon atoms, which are the same. May also be different. )
It is preferably a divalent organic group containing at least one structure represented by.

_{R 22} in the general formula (8) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom.

で表される構造を含む２価の有機基が特に好ましい。From the viewpoint of heat-fusible, the ^{Y 1,} the following general formula (9):

A divalent organic group containing the structure represented by is particularly preferable.

In the above polyamic acid ester, X ¹ in the repeating unit is derived from the tetracarboxylic dianhydride used as a raw material, and Y ¹ is derived from the diamine used as a raw material.

The tetracarboxylic acid dianhydride used as a raw material is not limited, for example, pyromellitic anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic acid dianhydride, benzophenone-3, 3', 4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3', 4,4'-tetracarboxylic acid Dianhydride, diphenylmethane-3,3', 4,4'-tetracarboxylic acid dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-anhydride) Phthalic acid) -1,1,1,3,3,3-hexafluoropropane and the like can be mentioned. Further, these may be used alone or in combination of two or more.

Examples of the diamine used as a raw material include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl. Sulfur, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4 '-Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-Aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl, 4 , 4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) ) Benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) Aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, 1,4-bis Examples thereof include (3-aminopropyldimethylsilyl) benzene, ortho-trizine sulfone, 9,9-bis (4-aminophenyl) fluorene and the like. Some of the hydrogen atoms on these benzene rings may be substituted. Further, these may be used alone or in combination of two or more.

In the synthesis of the polyamic acid ester (A), it is usually preferable to use a method in which the tetracarboxylic acid diester obtained by performing the esterification reaction of the tetracarboxylic acid dianhydride described later is directly subjected to the condensation reaction with the diamine. ..

The alcohols used in the esterification reaction of the above tetracarboxylic acid dianhydride are alcohols having an olefinic double bond, and specifically, 2-hydroxyethyl methacrylate, 2-methacryloyloxyethyl alcohol, and glycerin diacrylate. , Glycerin dimethacrylate, etc., but is not limited thereto. These alcohols can be used alone or in combination of two or more.

As a specific method for synthesizing the polyamic acid ester (A) used in the present embodiment, a conventionally known method can be adopted. As the synthesis method, for example, the method shown in International Publication No. 00/4439 pamphlet can be mentioned. That is, the tetracarboxylic acid diester is once converted into a tetracarboxylic acid diester diate product, and the tetracarboxylic acid diester diate product and diamine are subjected to a condensation reaction in the presence of a basic compound to obtain a polyamic acid ester (A). To manufacture. Moreover, as a synthesis method, a method of producing a polyamic acid ester (A) by subjecting a tetracarboxylic acid diester and a diamine to a condensation reaction in the presence of an organic dehydrating agent can be mentioned.

Examples of organic dehydrating agents include dicyclohexylcarbodiimide (DCC), diethylcarbodiimide, diisopropylcarbodiimide, ethylcyclohexylcarbodiimide, diphenylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-cyclohexyl-3- (3). -Dimethylaminopropyl) Carbodiimide hydrochloride and the like.

The weight average molecular weight of the polyamic acid ester (A) used in the present embodiment is preferably 6,000 to 150,000, more preferably 7,000 to 50,000, and 7,000 to 20, It is more preferably 000.

(B1) Photoinitiator In the case of a negative type photosensitive resin, a photoinitiator is added to the resin composition. Photoinitiators include, for example, benzophenone derivatives such as benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; 2,2'-diethoxyacetophenone, and 2 -Acetophenone derivatives such as hydroxy-2-methylpropiophenone; thioxanthone derivatives such as 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl, benzyldimethylketal, benzyl-β Benzyl derivatives such as −methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; 2,6-di (4'-diazidobenzal) -4-methylcyclohexanone, and 2,6'-di (4'-diazidobenzal) cyclohexanone, etc. Azides; 1-phenyl-1,2-butandion-2- (O-methoxycarbonyl) oxime, 1-phenylpropandion-2- (O-methoxycarbonyl) oxime, 1-phenylpropandion-2- (O-methoxycarbonyl) oxime Ethoxycarbonyl) oxime, 1-phenylpropandion-2- (O-benzoyl) oxime, 1,3-diphenylpropanthrion-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanthrion-2- Oximes such as (O-benzoyl) oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoylperoxide; aromatic biimidazoles; and titanocene are used. Of these, the above-mentioned oximes are preferable in terms of light sensitivity.

The amount of the photoinitiator added is preferably 1 to 40 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the polyamic acid ester (A). By adding 1 part by mass or more of the photoinitiator to 100 parts by mass of the polyamic acid ester (A), the light sensitivity is excellent. Further, by adding 40 parts by mass or less of the photoinitiator, the thick film curability is excellent.

(B2) Photoacid generator In the case of a positive photosensitive resin, a photoacid generator is added to the resin composition. When the resin composition contains a photoacid generator, acid is generated in the ultraviolet exposed portion, and the solubility of the exposed portion in the alkaline aqueous solution is increased. Thereby, the resin can be used as a positive photosensitive resin composition.

Examples of the photoacid generator include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like. Among these, the quinone diazide compound is preferably used from the viewpoint of exhibiting an excellent dissolution inhibitory effect and obtaining a highly sensitive positive photosensitive resin composition. Moreover, you may contain 2 or more kinds of photoacid generators.

(C) Solvent The solvent (C) is the same as the solvent described in the above item [Photosensitive resin composition containing phenol resin]. The type and amount of the preferable solvent are also the same as those described in the above item [Photosensitive resin composition containing phenol resin].

｛式（１）中、Ｘ^１、Ｙ^１、及びｍは、上記一般式（１１）中で定義されたＸ^１、Ｙ^１、及びｍと同じでよく、例えば、Ｘ^１は４価の有機基であり、Ｙ^１は２価の有機基であり、ｍは１以上の整数である。｝
で表される。
一般式（１１）中の好ましいＸ^１、Ｙ^１、及びｍは、一般式（１１）について説明された理由と同じ理由により、一般式（１）で表されるポリイミドにおいても好ましい。<Polyimide>
The structure of the cured relief pattern formed from the polyimide precursor composition is described in the following general formula (1):

{In formula (1), X ¹ , Y ¹ , and m may be the same as X ¹ , Y ¹ , and m defined in the above general formula (11), for example, X ¹ is a tetravalent organic. It is a group, Y ¹ is a divalent organic group, and m is an integer of 1 or more. }
It is represented by.
Preferred X ¹ , Y ¹ , and m in the general formula (11) are also preferable in the polyimide represented by the general formula (1) for the same reason as described for the general formula (11).

In the case of alkali-soluble polyimide, the end of the polyimide may be replaced with a hydroxyl group.

｛式（１４）中、ＵとＶは、それぞれ独立に、２価の有機基である。｝
で表される繰り返し単位を含むポリ（ｏ−ヒドロキシアミド）を用いることができる。[Photosensitive resin composition containing polybenzoxazole precursor]
(A) Polybenzoxazole Precursor The photosensitive resin used in the polybenzoxazole precursor composition includes the following general formula (14):

{In formula (14), U and V are independently divalent organic groups. }
A poly (o-hydroxyamide) containing a repeating unit represented by is used.

From the viewpoint of thermal meltability, U in the formula (14) is preferably a divalent organic group having 1 to 30 carbon atoms, and is a chain alkylene group having 1 to 15 carbon atoms (however, a chain alkylene group). The hydrogen atom may be substituted with a halogen atom), and a chain alkylene group having 1 to 8 carbon atoms and having a part or all of the hydrogen atom substituted with a fluorine atom is particularly preferable.

｛式（６）中、Ｒ_１０、Ｒ_１１、Ｒ_１２及びＲ_１３は、水素原子、炭素数が１〜５の１価の脂肪族基であり、同一であっても異なっていてもよい。｝

｛式（７）中、Ｒ_１４〜Ｒ_２１は、水素原子、ハロゲン原子、炭素数が１〜５の１価の有機基であり、互いに異なっていても、同一であってもよい。｝

｛式（８）中、Ｒ_２２は２価の基であり、Ｒ_２３〜Ｒ_３０は、水素原子、ハロゲン原子、炭素数が１〜５の１価の脂肪族基であり、同一であっても異なっていてもよい。｝
で表される少なくとも１つの構造を含む２価の有機基である。Further, from the viewpoint of thermal meltability, V in the formula (14) is preferably a divalent organic group containing an aromatic group, and more preferably the following general formulas (6) to (8):

{In formula (6), R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different. }

{In formula (7), R _{14 to} R ₂₁ are hydrogen atoms, halogen atoms, and monovalent organic groups having 1 to 5 carbon atoms, which may be different from each other or the same. }

{In formula (8), R ₂₂ is a divalent group, and R _{23 to} R ₃₀ are hydrogen atoms, halogen atoms, and monovalent aliphatic groups having 1 to 5 carbon atoms, which are the same. May also be different. }
It is a divalent organic group containing at least one structure represented by.

_{R 22} in the general formula (8) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom.

で表される構造を含む２価の有機基が特に好ましい。From the viewpoint of thermal meltability, V is expressed by the following general formula (9):

A divalent organic group containing the structure represented by is particularly preferable.

From the viewpoint of thermomeltability, V is preferably a divalent organic group having 1 to 40 carbon atoms, more preferably a divalent chain aliphatic group having 1 to 40 carbon atoms, and 2 having 1 to 20 carbon atoms. Valuable chain aliphatic groups are particularly preferred.

Polybenzoxazole precursors can generally be synthesized from dicarboxylic acid derivatives and hydroxy group-containing diamines. Specifically, a polybenzoxazole precursor can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with diamines. As the dihalide derivative, a dichloride derivative is preferable.

The dichloride derivative can be synthesized by allowing a halogenating agent to act on the dicarboxylic acid derivative. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride and the like, which are used in ordinary acid chloride reaction of carboxylic acid, can be used.

As a method for synthesizing a dichloride derivative, there are a method of reacting a dicarboxylic acid derivative with the above halogenating agent in a solvent, a method of reacting in an excess halogenating agent, and then a method of distilling off the excess.

Examples of the dicarboxylic acid used for the dicarboxylic acid derivative include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4. '-Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5- tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n -Butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2 -Methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid , Octafluoroadiponic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid , Dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecandioic acid, eikosandioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosane Examples thereof include diacid, pentacosandioic acid, hexacosandioic acid, heptacosandioic acid, octacosandioic acid, nonakosandioic acid, triacontanedioic acid, hentoriacontanedioic acid, dotoriacontanedioic acid and diglycolic acid. These may be mixed and used.

Examples of the hydroxy group-containing diamine include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, and bis (3-amino-4-hydroxyphenyl). Propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino) -4-Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3 -Hexafluoropropane and the like can be mentioned. These may be mixed and used.

(B2) Photoacid generator The photoacid generator has a function of increasing the solubility of an alkaline aqueous solution in a light-irradiated portion. Examples of the photoacid generator include a diazonaphthoquinone compound, an aryldiazonium salt, a diallyliodonium salt, a triarylsulfonium salt and the like. Of these, the diazonaphthoquinone compound is preferable because of its high sensitivity.

(C) Solvent The solvent (C) is the same as the solvent described in the above item [Photosensitive resin composition containing phenol resin]. The type and amount of the preferable solvent are also the same as those described in the above item [Photosensitive resin composition containing phenol resin].

｛式（１０）中、Ｕ及びＶは、上記一般式（１４）中で定義されたＵ及びＶと同じである。｝
で表される。一般式（１４）中の好ましいＵ及びＶは、一般式（１４）について説明されら理由と同じ理由により、一般式（１０）のポリベンズオキサゾールにおいても好ましい。<Polybenzoxazole>
The structure of the cured relief pattern formed from the polybenzoxazole precursor composition is described in the following general formula (10):

{In formula (10), U and V are the same as U and V defined in the above general formula (14). }
It is represented by. The preferred U and V in the general formula (14) are also preferred in the polybenzoxazole of the general formula (10) for the same reasons as described for the general formula (14).

The photosensitive resin composition according to the first embodiment may contain at least one selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and is thermally meltable. From the viewpoint, it is preferable to contain a phenol resin.

<Second Embodiment: Low Melt Viscosity Photosensitive Layer Roll>
The photosensitive layer roll according to the second embodiment of the present invention is
Support film and
A photosensitive layer containing a photosensitive resin composition provided on the support film, and
The photosensitive resin composition contains at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and the photosensitive layer has a melt viscosity of 500 Pa. -A layer having a temperature point of s or less.

Since the conventional photosensitive layer roll has a high melt viscosity of the photosensitive layer, there is a problem that cracks are likely to occur even when the slitter teeth are heated and slit at the time of slitting.
In order to solve the above problems, the photosensitive layer roll according to the second embodiment is characterized in that the photosensitive layer is a layer having a temperature point having a melt viscosity of 500 Pa · s or less.

The photosensitive layer according to the present embodiment is a layer having a temperature point at which the melt viscosity is 500 Pa · s or less. The photosensitive layer is preferably a layer having a temperature point having a melt viscosity of 450 Pa · s or less, preferably a layer having a temperature point of 400 Pa · s or less, and having a temperature point of 350 Pa · s or less. It is preferably a layer having a temperature point of 300 Pa · s or less, preferably a layer having a temperature point of 250 Pa · s or less, and a temperature point of 200 Pa · s or less. It is preferable that the layer has. By lowering the melt viscosity of the photosensitive layer, it is possible to suppress the occurrence of cracks when the slits, particularly the teeth of the slitter, are heated and slit.

The photosensitive layer of the present embodiment has a melt viscosity at 100 ° C. of preferably 500 Pa · s or less, preferably 450 Pa · s or less, preferably 400 Pa · s or less, and 350 Pa · s or less. It is preferably 300 Pa · s or less, preferably 250 Pa · s or less, preferably 200 Pa · s or less, preferably 150 Pa · s or less, and 100 Pa · s or less. It is preferable to have.

The photosensitive layer roll according to the second embodiment may have a cover film on the side of the photosensitive layer opposite to the side on which the support film is provided.

If a cover film is provided, wrinkles may occur during slitting, especially when the slitter teeth are heated and slit. Therefore, a cover film should not be provided or a cover film with a high softening temperature should be used. Is preferable.

The softening point temperature of the cover film is preferably 90 ° C. or higher, preferably 100 ° C. or higher, preferably 110 ° C. or higher, preferably 120 ° C. or higher, and preferably 130 ° C. or higher. preferable. The material of the cover film is not particularly limited as long as it satisfies the above softening point temperature.

The melt viscosity of the photosensitive layer can be adjusted by the type and / or amount of the organic solvent contained in the photosensitive layer. The details will be described below. Other points are the same as those described in the above item <First embodiment: Two-layer photosensitive layer roll>.

<Manufacturing and use of photosensitive layer roll>
A method for producing a photosensitive film according to this embodiment will be described.
The photosensitive layer can be formed by applying the photosensitive resin composition as a liquid photosensitive resin composition onto a support film.
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 (C) can be removed by heating, for example. From the viewpoint of the remaining amount of the organic solvent in the photosensitive layer, when the organic solvent is removed, the heating temperature is preferably about 70 to 150 ° C., more preferably 100 to 140 ° C., and / or the heating time. It is preferably about 1 to 30 minutes, more preferably about 3 to 20 minutes, and even more preferably about 4 to 10 minutes.

The thickness of the photosensitive layer varies depending on the application, but the thickness after removing the solvent is preferably about 1 to 30 μm. The photosensitive film may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, a gas barrier layer, or a cover film between the support film and the photosensitive layer.
The photosensitive film can be wound around a core having a cylindrical shape or the like and stored as a photosensitive layer roll in a roll shape. The winding core is not particularly limited as long as it is conventionally used, and the material thereof is, for example, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene common weight). Examples include plastics such as coalescing). 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, from the viewpoint of edge fusion resistance, a moisture-proof end face separator is provided. It is preferable to install it. Further, when packing the photosensitive film or the photosensitive layer roll, it is preferable to wrap it in a black sheet having low moisture permeability.

<Slit of photosensitive layer roll>
A slit photosensitive layer roll can be manufactured by slitting the produced photosensitive layer roll to a desired width with a slitter.
From the viewpoint of suppressing wrinkles or cracks on the cut surface of the slitter, it is preferable that the teeth of the slitter are heated. The heating temperature of the slitter teeth may be 80 ° C. or higher, 90 ° C. or higher, 100 ° C. or higher, 110 ° C. or higher, 120 ° C. or higher. It may be 130 ° C. or higher.

If the photosensitive layer roll includes a cover film, the cover film may wrinkle during slitting, and the cover film may wrinkle significantly, especially when the slitter teeth are heated and slit. There is. From the viewpoint of suppressing the wrinkles of the cover film generated at the time of slitting, the method for manufacturing the slit photosensitive layer roll is as follows:
When the photosensitive layer roll has a cover film on the side of the photosensitive layer opposite to the side on which the support film is provided, a step of peeling the cover film and a step of peeling the cover film.
The step of slitting the photosensitive layer roll without the cover film with a slitter, and
A step of attaching the peeled cover film or a cover film different from the peeled cover film to the slitted photosensitive layer roll.
Is preferably included.

<Lamination of photosensitive layer on base material>
As a method of laminating the photosensitive layer of the slit photosensitive layer roll on the substrate, the photosensitive layer is heated to about 70 to 130 ° C. and about 0.1 to 1 MPa on the substrate (that is, about 1 to 10 kgf / cm ² ). A method of crimping with a laminator or the like at the pressure of the above can be mentioned. The laminating step may be performed under reduced pressure. The surface of the base material on which the photosensitive layer is laminated is not particularly limited.

Since the two-layer photosensitive layer roll according to the first embodiment does not have a cover film, the photosensitive layer may stick to the support film (blocking risk). On the other hand, if the adhesiveness of the photosensitive layer is lowered, there is a risk that the photosensitive layer will not adhere to the substrate when it is laminated. That is, it is desirable that the two-layer photosensitive layer roll according to the first embodiment has low adhesiveness at room temperature, which is a storage state, and exhibits high adhesiveness when heated when laminated on a substrate.

The amount of residual organic solvent in the photosensitive layer is 0.1% by mass or more and 15% by mass with respect to the total amount of the photosensitive layer from the viewpoint of achieving both adhesiveness at room temperature and formation of a photosensitive film that is easily melted by heat. It is preferably 0.3% by mass or more and 15% by mass or less, preferably 0.5% by mass or more and 15% by mass or less, and 0.8% by mass or more and 15% by mass or less. It is preferably 1% by mass or more and 15% by mass or less, preferably 3% by mass or more and 14% by mass or less, preferably 3% by mass or more and 13% by mass or less, and 5% by mass. More preferably 13% by mass or less. When the amount of the residual organic solvent in the photosensitive layer is within the above range, the adhesiveness is low at room temperature, and the photosensitive layer is less likely to adhere to the support film when the photosensitive layer roll is produced. When laminated on top, it exhibits high meltability and high adhesion.

The organic solvent remaining in the photosensitive layer may be the solvent (C) described above, which is the solubility of the resin, the stability of the resin composition, the adhesiveness to the substrate, the thermal meltability, the storage stability, and the blocking. From the viewpoint of sex, γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol are preferable, and among these, γ-butyrolactone, acetone, Methylethylketone, N-methyl-2-pyrrolidone and dimethylsulfoxide are particularly preferred.

Similarly, in the case of the low melt viscosity photosensitive layer roll according to the second embodiment, the melt viscosity is high at room temperature, the adhesiveness of the photosensitive layer is low, and the slits, particularly the teeth of the slitter, are heated and slit. It is desired that cracks are unlikely to occur at a low melt viscosity. The amount of residual organic solvent in the preferable photosensitive layer is the same as the above range. The melt viscosity of the photosensitive layer can be adjusted by the amount of the organic solvent contained in the photosensitive layer. The larger the amount of the organic solvent contained in the photosensitive layer, the lower the melt viscosity of the photosensitive layer. The amount of the organic solvent in the photosensitive layer can be controlled by adjusting the heating temperature and / or the heating time for removing the organic solvent. In addition to this, the melt viscosity of the photosensitive layer can be adjusted by a method of lowering the molecular weight of the polymer, a method of increasing low molecular weight components such as a non-thermosetting plasticizer, and the like.

The photosensitive layer laminated on the substrate in this way is irradiated with active rays in an image form through a negative or positive mask pattern to form an exposed portion. At this time, when the support existing on the photosensitive layer is transparent to the active light, the active light can be irradiated through the support, and when the support exhibits light shielding property to the active light. Irradiates the photosensitive layer with active light rays after removing the support.

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 preferable. After the exposure, the coating film may be heated again at 80 to 140 ° C., if necessary.

Next, the development can be performed 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.
Examples of the developing solution include 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. An aqueous solution of a quaternary ammonium salt such as hydroxide and, if necessary, a water-soluble organic solvent such as methanol and ethanol, or an aqueous solution to which an appropriate amount of a surfactant is added can be used. Of these, an aqueous solution of tetramethylammonium hydroxide is preferable. The concentration of tetramethylammonium hydroxide is preferably 0.5 to 10% by mass, 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, for example, distilled water, methanol, ethanol, isopropanol and the like can be used, and these 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.

The method for producing a cured relief pattern using the photosensitive layer roll according to the first or second embodiment is 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, and a fan-out type. Rewiring layer for wafer level package (FOWLP), protective film for flip chip equipment, high density substrate, protective film for equipment with bump structure, interlayer insulating film for multi-layer circuit, cover coat of flexible copper upholstery, solder resist It can be suitably used for producing a film, a liquid crystal alignment film, and the like.
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") 121 in a separable flask with a capacity of 0.5 liter Dean-Stark apparatus. .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. with an oil bath, generation of methanol was confirmed from the reaction solution, and the reaction solution was stirred at 140 ° C. for 2 hours as it was.
Next, the reaction vessel was cooled in the air, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluent was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, washed with water and dehydrated as appropriate, and then vacuum-dried to obtain a copolymer (phenol) composed of phloroglucinol / BMMB. Resin (A-1)) was obtained in a yield of 70%.

[Synthesis Example 2]
<Synthesis of phenol resin (A-2)>
Synthesis was carried out in the same manner as in Synthesis Example 1 except that 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate was used instead of phloroglucinol in Synthesis Example 1, and 3,5-dihydroxybenzoic acid was used. A copolymer composed of methyl / 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-toluenesulfonic acid. 3.81 g (0.02 mol) 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, the generation of methanol was confirmed from the reaction solution, and the reaction solution was stirred at 120 ° C. for 3 hours.
Next, 24.9 g (0.150 mol) of 2,6-bis (hydroxymethyl) -p-cresol and 249 g of PGME were mixed and stirred in another container, and the solution was uniformly dissolved by using a dropping funnel. The mixture was added dropwise to the separable flask over 1 hour, and after the addition, the mixture was further stirred for 2 hours.
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.

[Synthesis Example 4]
<Synthesis of polyimide precursor (A-5)>
In a separable flask having a capacity of 2 L, 87.2 g (0.4 mol) of pyromellitic dianhydride, 59.3 g (0.8 mol) of isobutyl alcohol, and 320 g of γ-butyrolactone (hereinafter, also referred to as “GBL”) are placed. The mixture was mixed and stirred at room temperature (25 ° C.) to dissolve the mixture, and 63.3 g (0.8 mol) of pyridine was added while stirring under ice-cooling.

Next, a solution prepared by dissolving 165 g (0.8 mol) of dicyclohexylcarbodiimide in 120 g of GBL was added to the separable flask in 40 minutes while stirring under ice-cooling. Subsequently, a suspension of 74.5 g (0.37 mol) of 4,4'-diaminodiphenyl ether suspended in 150 g of GBL was added to the separable flask for 60 minutes while stirring under ice-cooling. After stirring at room temperature for 2 hours, 30 ml of ethyl alcohol is added to the separable flask, the mixture is stirred for 1 hour, 250 ml of dimethylacetamide (hereinafter referred to as "DMAc") and 400 ml of tetrahydrofuran (THF) are added, and then precipitation is performed. It was removed by suction filtration to obtain a reaction solution. The obtained reaction solution was added to 15 L of ethyl alcohol, the generated precipitate was filtered off, and then vacuum dried to obtain a polyimide precursor (A-5).

[Synthesis Example 5]
<Synthesis of polybenzoxazole precursor (A-6)>
In a separable flask with a capacity of 2 L, add 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane 197.8 g (0.54 mol), pyridine 75.9 g (0.96 mol), and DMAc 692 g. It was mixed and stirred at room temperature (25 ° C.) to dissolve it.

A solution prepared by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride in 88 g of dimethyl diglycol (hereinafter, also referred to as “DMDG”) was added dropwise to the obtained mixed solution. Dropped from the funnel. The time required for dropping was 40 minutes, and the reaction liquid temperature was 28 ° C. at the maximum.
After completion of the dropwise addition, the reaction was warmed to 50 ° C. by a water bath and stirred for 18 hours, subjected to measurement of the IR spectrum of the reaction solution, the characteristic absorption of an imide group 1385Cm ^-1 and 1772 cm ^-1 appeared It was confirmed.

Next, the reaction solution was cooled to 8 ° C. by a water bath, and a solution prepared by separately dissolving 142.3 g (0.48 mol) of 4,4'-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added to the reaction solution from the dropping funnel. Dropped. The time required for dropping was 80 minutes, and the reaction liquid temperature was 12 ° C. at the maximum.
Three hours after the completion of the dropping, the reaction solution was added dropwise to 12 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water and dehydrated as appropriate, and then vacuum-dried to prepare a polybenzoxazole precursor. Body (A-6) was obtained.

<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: Novolac resin, polystyrene-equivalent weight average molecular weight (Mw) = 10,600 (manufactured by Asahi Organic Materials Co., Ltd., product name EP-4080G)
A-5: Polyimide precursor A-6: Polybenzoxazole precursor

｛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。｝<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. }

<Solvent (C)>
C-1: γ-Butyrolactone (GBL)
C-2: Methyl ethyl ketone C-3: Acetone C-4: N, N-dimethylformamide

<Surfactant (D)>
D-1: Silicone type surfactant DBE821 (trade name, manufactured by Gelest)
D-2: Silicone type surfactant DBE224 (trade name, manufactured by Gelest)

<Crosslinking agent (E)>
E-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluryl (manufactured by Sanwa Chemical Co., Ltd., trade name; Nicarac MX-270)

[Preparation of photosensitive resin composition]
As shown in Table 1 below, the resin (A), the photoacid generator (B), the surfactant (D), and the cross-linking agent (E) were dissolved in the solvent (C) to make a thickness of 0.1 μm. A positive photosensitive resin composition was prepared by filtering with a filter.

[Support film]
As a support film, a PET film "PET25X" (manufactured by Lintec Corporation, width 290 mm, thickness 25 μm) that had been mold-released with a silicone compound was prepared.

[Preparation of photosensitive film]
(Example 1)
As the support film, "PET25X", which is a release-treated PET film, was used, and a solution of a photosensitive resin composition having the composition shown in Table 1 above was applied on the release-treated surface. Next, the PET film coated with the solution of the photosensitive resin composition was dried with hot air at 120 ° C. for 5 minutes to form a photosensitive layer. At that time, the thickness of the photosensitive layer after heating was adjusted to 10 μm. A photosensitive film having a width of 300 mm having the above composition is linearly formed on a cylindrical plastic tube having an outer diameter of 3.5 inches by using a pressure roll arranged parallel to the winding axis width direction. Pressure was applied and the film was wound up to 1000 m with a tension of 7 kg to obtain a photosensitive film roll.

(Examples 2 to 13)
Each photosensitive film roll was prepared according to the same procedure as in Example 1 except that the components, compositions and drying conditions shown in Table 1 were used.

(Comparative Examples 1 to 3)
Same as Example 1 except that the components, compositions and drying conditions shown in Table 1 above were used, and a cover film having a softening temperature of 90 ° C. was provided on the photosensitive layer when obtaining a photosensitive film roll. Each photosensitive film roll was prepared according to the procedure.

<Amount of residual solvent>
The photosensitive film is unwound from the photosensitive film rolls produced in Examples and Comparative Examples, the photosensitive layer is peeled from the support film, and the peeled photosensitive layer is gas chromatographed (manufactured by Agilent Technologies, Inc., trade name " 6890N ") was analyzed, and the amount of residual solvent (parts by mass) with respect to 100 parts by mass of the photosensitive layer was measured.
<Melting viscosity>
The photosensitive film is unwound from the photosensitive film rolls produced in Examples and Comparative Examples, the photosensitive layer is peeled from the support film, and the peeled photosensitive layer is released by a melt viscosity measuring device (TA Instruments Japan). It was measured under the following conditions using a product name "DHR-2" manufactured by Co., Ltd.). Table 1 shows the melt viscosities at a temperature of 100 ° C.
・ Sample shape Film thickness: 0.5 mmt
Diameter: 25 mm disk, measurement conditions Start temperature: 50 ° C
Temperature rise rate: 5 ° C / min
End temperature: 220 ° C
Distortion: 0.1%
Frequency: 1Hz
Load: 0.5N (± 0.1N)

<Storage stability>
The photosensitive film rolls produced in Examples and Comparative Examples were stored at room temperature (25 ° C.) for 1 month or longer, and then the unwinding of the rolls was visually observed and evaluated according to the following criteria.
S (Remarkably good): In roll form, the photosensitive layer does not adhere to the back surface of the support film even when stored at room temperature for 1 month or longer.
A (Good): When stored in a roll form at room temperature for 1 month, a part of the photosensitive layer adheres to the back surface of the support film.

<Removability of support film>
A photosensitive film was unwound from the photosensitive film rolls 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.
S (Remarkably good): Peeling and removal is possible without the photosensitive layer adhering to the support film.
A (Good): A part of the photosensitive layer, which is peeled off with the photosensitive layer attached to the support film.
B (defective): The entire surface of the photosensitive layer is peeled off with the photosensitive layer attached to the support film.

<Crack at slit>
The photosensitive film rolls prepared in Examples and Comparative Examples were slit with a slitter in which the teeth were heated to 100 ° C. The occurrence of cracks at the time of slitting and the aesthetic appearance of the cut surface were visually evaluated.
S (significantly good): No cracks occur and the cut surface is smooth.
A (good): No cracks have occurred, but the cut surface has some irregularities.
B (defective): A crack has occurred.

<Wrinkles on the cover film>
The photosensitive film roll produced in the comparative example was slit with a slitter having teeth heated to 100 ° C., and the wrinkles generated on the cover film were visually evaluated.
A (good): No wrinkles occur on the cover film.
B (defective): The cover film was wrinkled.

<Evaluation result>
The characteristics evaluation results for each Example and Comparative Example are shown in Table 1 above.

The photosensitive layer roll 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 rewiring layer for a wafer level package, a protective film for a flip chip device, and a high height. It can be suitably used as a density substrate, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.

Claims (38)

Support film and
A photosensitive layer containing a photosensitive resin composition provided on the support film and
It is a photosensitive layer roll having
The photosensitive resin composition contains at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and the photosensitive layer has a melt viscosity of 500 Pa · s or less. It is a layer having a temperature point, contains 0.1 to 16% by mass of an organic solvent with respect to the total amount of the photosensitive layer, and covers the photosensitive layer on the side opposite to the side on which the support film is provided. A photosensitive layer roll having a film and having a softening temperature of the cover film of 110 ° C. or higher. The photosensitive layer roll according to claim 1, wherein the photosensitive layer is a layer having a temperature point at which the melt viscosity is 350 Pa · s or less. The photosensitive layer roll according to claim 1 or 2, wherein the photosensitive layer has a melt viscosity at 100 ° C. of 150 Pa · s or more and 500 Pa · s or less. The photosensitive layer roll according to claim 3, wherein the photosensitive layer has a melt viscosity at 100 ° C. of 150 Pa · s or more and 350 Pa · s or less. Wherein the amount of said organic solvent contained in the photosensitive layer is, the is 15 wt% or less than 0.1% by mass of the total amount of the photosensitive layer, the photosensitive layer according to any one of claims 1 to 4 roll. Wherein the amount of said organic solvent contained in the photosensitive layer is 15 mass% or less 1 wt% or more, based on the total amount of the photosensitive layer, the photosensitive layer roll of claim 5. The organic solvent, .gamma.-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide, comprises at least one selected from propylene glycol monomethyl ether, and tert- butyl alcohol or al group consisting photosensitive according to claim 5 or 6 Layer roll. The photosensitive layer roll according to claim 7, wherein the organic solvent contains at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone , and dimethyl sulfoxide. The photosensitive layer roll according to any one of claims 1 to 8, wherein the photosensitive resin composition contains the polyimide precursor. The photosensitive layer roll according to any one of claims 1 to 8, wherein the photosensitive resin composition contains the polybenzoxazole precursor. The photosensitive layer roll according to any one of claims 1 to 8, wherein the photosensitive resin composition contains the soluble polyimide. The photosensitive layer roll according to any one of claims 1 to 8, wherein the photosensitive resin composition contains the phenol resin. The phenol resin has 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 , And 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, and 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. }
The photosensitive layer roll according to claim 12, further comprising the structure represented by. X in the general formula (1) 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, n1 is an integer of 0 to 4, and R ₆ is a halogen atom when n1 is an integer of 1 to 4. hydroxyl, or a monovalent organic group, a is at least one R ₆ hydroxyl groups, n1 may be different in a plurality of R ₆ in the case where an integer of 2 to 4 the same, respectively. }
The divalent group represented by, 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. 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 optionally substituted with a hydrogen atom, fluorine. Aliphatic group having 3 to 20 carbon atoms which may be substituted with an atom, 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 layer roll according to claim 13, which is a divalent organic group selected from the group consisting of divalent groups represented by. X in the general formula (1) is the following formula (6):

The photosensitive layer roll according to claim 13 or 14, which is a divalent organic group represented by. X in the general formula (1) is the following formula (7):

The photosensitive layer roll according to claim 15, which is a divalent organic group represented by. The phenol resin 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, n2 is an integer of 1 to 3, and n3 is 0 to 0. It is an integer of 2, m1 is an integer of 1 to 500, 2 ≦ (n2 + n3) ≦ 4, and R ₁₁ when n3 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 selected independently from the group consisting of hydrocarbon groups and alkoxy groups, and n4 is an integer of 1 to 3. When n5 is an integer of 0 to 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and R ₁₃ when n6 is 2 or 3 may be the same or different. }
The photosensitive layer roll according to any one of claims 13 to 16, which has both of the repeating units represented by the above in the same resin skeleton. Support film and
A photosensitive layer containing a photosensitive resin composition provided on the support film and
It is a photosensitive layer roll having
The photosensitive resin composition is a phenolic resin, a polyimide precursor, polybenzoxazole precursors, and at least one resin selected from the group consisting of a soluble polyimide, both sides of the front Symbol support film, and the photosensitive layer A photosensitive layer roll that is in contact with the photosensitive layer and contains 0.1 to 16% by mass of an organic solvent with respect to the total amount of the photosensitive layer. Wherein the amount of said organic solvent contained in the photosensitive layer is 15 mass% or less than 0.1% by mass of the total amount of the photosensitive layer, the photosensitive layer roll of claim 18. Wherein the amount of said organic solvent contained in the photosensitive layer is 15 mass% or less 1 wt% or more, based on the total amount of the photosensitive layer, the photosensitive layer roll of claim 19. The photosensitive layer roll according to claim 19 or 20, wherein the photosensitive resin composition contains the phenol resin. The organic solvent, .gamma.-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide, propylene glycol monomethyl ether, and at least one selected from tert- butyl alcohol or al group consisting, either of claims 19 to 21 1 The photosensitive layer roll according to the section. 22. The photosensitive layer roll according to claim 22, wherein the organic solvent comprises at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone , and dimethyl sulfoxide. The photosensitive layer roll according to any one of claims 18 to 23, wherein the photosensitive resin composition contains the polyimide precursor. The photosensitive layer roll according to any one of claims 18 to 23, wherein the photosensitive resin composition contains the polybenzoxazole precursor. The photosensitive layer roll according to any one of claims 18 to 23, wherein the photosensitive resin composition contains the soluble polyimide. The photosensitive layer roll according to any one of claims 18 to 23, wherein the photosensitive resin composition contains a phenol resin. The phenol resin has 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 , And 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, and 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. }
The photosensitive layer roll according to claim 27, which has the structure represented by. X in the general formula (1) 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, n1 is an integer of 0 to 4, and R ₆ is a halogen atom when n1 is an integer of 1 to 4. hydroxyl, or a monovalent organic group, a is at least one R ₆ hydroxyl groups, n1 may be different in a plurality of R ₆ in the case where an integer of 2 to 4 the same, respectively. }
The divalent group represented by, 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. 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 optionally substituted with a hydrogen atom, fluorine. Aliphatic group having 3 to 20 carbon atoms which may be substituted with an atom, the following general formula (2):

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

It is a divalent organic group selected from the group consisting of divalent groups represented by. }
28. The photosensitive layer roll according to claim 28, which is a divalent organic group selected from the group consisting of divalent groups represented by. X in the general formula (1) is the following formula (6):

The photosensitive layer roll according to claim 28 or 29, which is a divalent organic group represented by. X in the general formula (1) is the following formula (7):

The photosensitive layer roll according to claim 30, which is a divalent organic group represented by. The phenol resin 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, n2 is an integer of 1 to 3, and n3 is 0 to 0. It is an integer of 2, m1 is an integer of 1 to 500, 2 ≦ (n2 + n3) ≦ 4, and R ₁₁ when n3 is 2, may be the same or different. }
The repeating unit represented by, and the following general formula (9):

{In formula (9), R ₁₂ and R ₁₃ are monovalent groups having 1 to 10 carbon atoms selected independently from the group consisting of hydrocarbon groups and alkoxy groups, and n4 is an integer of 1 to 3. When n5 is an integer of 0 to 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and R ₁₃ when n6 is 2 or 3 may be the same or different. The photosensitive layer roll according to any one of claims 28 to 31, which has both of the repeating units represented by} in the same resin skeleton. A method for producing a slit photosensitive layer roll, wherein the photosensitive layer roll according to any one of claims 1 to 22 is slit with a slitter to produce a slit photosensitive layer roll. The method for producing a slit photosensitive layer roll according to claim 33, wherein the teeth of the slitter are heated. The method for producing a slit photosensitive layer roll according to claim 34, wherein the teeth of the slitter are heated to 100 ° C. or higher. The following steps:
When the photosensitive layer roll according to any one of claims 1 to 22 has a cover film on the side of the photosensitive layer opposite to the side on which the support film is provided, the cover film is peeled off. Process and
The step of slitting the photosensitive layer roll without the cover film with a slitter, and
A step of attaching the peeled cover film or a cover film different from the peeled cover film to the slitted photosensitive layer roll.
A method for manufacturing a slit photosensitive layer roll including. The method for producing a slit photosensitive layer roll according to claim 36, wherein the teeth of the slitter are heated. The method for producing a slit photosensitive layer roll according to claim 37, wherein the teeth of the slitter are heated to 100 ° C. or higher.