WO2018117047A1 - Two-layer photosensitive layer roll - Google Patents

Abstract

This photosensitive layer roll has a support body film, and a photosensitive layer that is provided on the support body film and includes a photosensitive resin composition, wherein the photosensitive resin composition includes at least one resin selected from the group consisting of a phenolic resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and the photosensitive layer is a layer that has a temperature at which the melt viscosity thereof becomes 500Pa∙s or less.

Description

2-layer photosensitive layer roll

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 solution of a photosensitive resin composition is applied on a substrate such as a copper clad laminate and dried, or a layer comprising a support and a photosensitive resin composition (hereinafter referred to as “photosensitive layer”). And a method of laminating a photosensitive resin laminate (hereinafter, also referred to as “dry film resist”) in which a cover film is sequentially laminated, if necessary, on a substrate. The latter is frequently used in the production of printed wiring boards.

The dry film resist may be stored in the form of a roll (see Patent Document 1). Patent Document 1 discloses a photosensitive layer and a non-adhesive outer layer having a thickness of 1/5 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 dry film resist. There has been proposed a photosensitive composite containing in order.

From the viewpoint of handling the dry film resist, the dry film resist is not sticky 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, during lamination) ( Patent Document 2). Patent Document 2 proposes a photosensitive cover lay film that is not sticky at a substrate temperature of 20 ° C. and that can be easily corrected even when placed on the substrate.

Patent Document 3 confirms compatibility between low-temperature curability and chemical resistance of a cured film by using a phenol resin having a specific structure in a photosensitive resin composition in combination with a nonionic surfactant. Has been.

Japanese Patent Laid-Open No. 2001-175000 JP 2003-149803 A JP 2013-190697 A

Usually, the photosensitive resin laminate is manufactured in the form of a roll and is used by being slit to a required width. 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, There was a problem that wrinkles or cracks occurred and it was difficult to slit the cross section to be smooth.

The present inventors have found that the above problem 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]
A support film;
A photosensitive layer comprising a photosensitive resin composition provided on the support film;
A photosensitive layer roll comprising:
The photosensitive resin composition includes 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.
[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 photosensitive layer has a cover film on the side 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 described in 1.
[6]
The photosensitive layer roll according to [5], wherein the softening temperature of the cover film is 110 ° C. or higher.
[7]
The photosensitive layer according to any one of [1] to [6], wherein the amount of the organic solvent contained in the photosensitive layer is from 0.1% by mass to 15% by mass 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 based on the total amount of the photosensitive layer.
[9]
The organic solvent includes 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 includes 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 is represented by the following general formula (1):

{In 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 of 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R _{1 s} 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, the following general formula (2) :

(In formula (2), p is an integer of 1 to 10) and a divalent alkylene oxide group represented by the formula (2) and a divalent organic group selected from the group consisting of divalent organic groups having an aromatic ring. Represents an organic group. }
The photosensitive layer roll according to [14], wherein the photosensitive layer roll has a structure represented by:
[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 each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. A monovalent aliphatic group having 1 to 10 carbon atoms substituted by an atom, n1 is an integer of 0 to 4, and n1 is an integer of 1 to 4, R ₆ is a halogen atom, A hydroxyl group or a monovalent organic group, at least one R ₆ is a hydroxyl group, and when n1 is an integer of 2 to 4, a plurality of R ₆ may be the same or different. }
And a divalent group represented by the following general formula (4):

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

(In the formula (2), p is an integer of 1 to 10) and the following formula (5):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: }
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 a hydrocarbon group and an alkoxy group, n2 is an integer of 1 to 3, and n3 is 0 to And m1 is an integer of 1 to 500, 2 ≦ (n2 + n3) ≦ 4, and when n3 is 2, R ₁₁ may be the same or different. } And the following general formula (9):

{In Formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n4 is an integer of 1 to 3 N5 is an integer from 0 to 2, n6 is an integer from 0 to 3, m2 is an integer from 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and when n6 is 2 or 3, R ₁₃ may be the same or different. }
The photosensitive layer roll according to any one of [15] to [18], wherein both of the repeating units represented by formula (1) are contained in the same resin skeleton.
[20]
A support film;
A photosensitive layer comprising a photosensitive resin composition provided on the support film;
A photosensitive layer roll comprising:
The photosensitive resin composition includes at least one resin selected from the group consisting of a phenolic resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and both sides of the support film have the photosensitive layer and The 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 from 0.1% by mass to 15% by mass 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 based on 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 includes 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. , [21] to [23].
[25]
The photosensitive layer roll according to [24], wherein the organic solvent contains 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 is represented by the following general formula (1):

{In 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 of 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R _{1 s} 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, the following general formula (2) :

(In formula (2), p is an integer of 1 to 10) and a divalent alkylene oxide group represented by the formula (2) and a divalent organic group selected from the group consisting of divalent organic groups having an aromatic ring. Represents an organic group. }
The photosensitive layer roll according to [29], having a structure represented by:
[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 each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. A monovalent aliphatic group having 1 to 10 carbon atoms substituted by an atom, n1 is an integer of 0 to 4, and n1 is an integer of 1 to 4, R ₆ is a halogen atom, A hydroxyl group or a monovalent organic group, at least one R ₆ is a hydroxyl group, and when n1 is an integer of 2 to 4, a plurality of R ₆ may be the same or different. }
And a divalent group represented by the following general formula (4):

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

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

A divalent organic group selected from the group consisting of divalent groups represented by the formula: }
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 a hydrocarbon group and an alkoxy group, n2 is an integer of 1 to 3, and n3 is 0 to And m1 is an integer of 1 to 500, 2 ≦ (n2 + n3) ≦ 4, and when n3 is 2, R ₁₁ may be the same or different. }
And a repeating unit represented by the following general formula (9):

{In Formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n4 is an integer of 1 to 3 N5 is an integer from 0 to 2, n6 is an integer from 0 to 3, m2 is an integer from 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and when n6 is 2 or 3, R ₁₃ may be the same or different. } The photosensitive layer roll according to any one of [30] to [33], having both of the repeating units represented by
[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 slit photosensitive layer roll manufacturing method according to [35], wherein the slitter teeth are heated.
[37]
The slit photosensitive layer roll manufacturing method according to [36], wherein the slitter teeth 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 opposite to the side on which the support film is provided of the photosensitive layer, the cover film is A peeling step;
Slitting the photosensitive layer roll without the cover film with a slitter;
A process of applying a peeled cover film or a cover film different from the peeled cover film to the slit photosensitive layer roll;
A method for producing a slit photosensitive layer roll comprising:
[39]
The slit photosensitive layer roll manufacturing method according to [38], wherein the slitter teeth are heated.
[40]
The slit photosensitive layer roll manufacturing method according to [39], wherein the slitter teeth are heated to 100 ° C or higher.

According to the present invention, it is possible to provide a photosensitive layer roll which can be slit so that the cross section is smooth without causing wrinkles or cracks in the slit.

<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 the present 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 side of the support or the side where the photosensitive layer is not laminated) is exposed, both sides of the support film Will be in contact with the photosensitive layer.
Hereinafter, a photosensitive layer roll in which both sides of the support film are in contact with the photosensitive layer without including the cover film 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 in the cover film at the time of slitting, and particularly when heating and slitting the slitter teeth, large wrinkles are likely to be generated in 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. For example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. , “PET film”).

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 the support film is subjected to a release treatment on at least one surface. The mold release treatment in the present embodiment is a silicone-based surfactant, a silicone-based compound such as a silicone resin, a fluorine-based surfactant, a fluorine-containing compound such as a fluororesin, or a mold release agent such as an alkyd resin. It refers to a chemical treatment that coats the surface thinly, or a physical treatment such as corona treatment of the support film.
When a release agent is coated on the support film, it is preferable to coat thinly as long as the release effect can be obtained. After coating, the release agent may be fixed to the support film by heat or UV treatment. More preferably, an undercoat layer is applied to the support film before coating the release agent.

<Photosensitive layer>
The photosensitive layer is 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 support film, preferably on the release-treated surface of the support film. It is formed by apply | coating the photosensitive resin composition containing this.
Hereinafter, the components contained in the photosensitive resin composition will be described.

[Photosensitive resin composition containing phenolic resin] [(A) component: phenolic resin]
Generally, a phenol resin is a thermosetting resin formed from a phenol compound and an aldehyde compound.
In the present embodiment, the phenol resin (A) is represented by the following general formula (1):

{In 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 of 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R _{1 s} 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, the following general formula (2) :

(In formula (2), p is an integer of 1 to 10) and a divalent alkylene oxide group represented by the formula (2) and a divalent organic group selected from the group consisting of divalent organic groups having an aromatic ring. Represents an organic group. } As a repeating unit.
The phenol resin (A) having a repeating unit having the structure represented by the formula (1) can be cured at a low temperature and has a good elongation as compared with, for example, a polyimide resin and a polybenzoxazole resin. A film can be formed, which contributes to the heat melting property of the photosensitive layer.
A photosensitive layer excellent in heat melting property is preferable because, when slitting, particularly when the slitter teeth are heated and slit, the cut surface hardly cracks and can be slit so that the cross section becomes smooth.

In the 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 has an alkali solubility. From the viewpoint, a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms that 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 each independently a hydrogen atom, a chain aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or 3 to 3 carbon atoms. 20 represents an alicyclic group or an aromatic group having 6 to 20 carbon atoms, and R ₁₇ represents a divalent chain aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, A divalent alicyclic group having 3 to 20 carbon atoms or a divalent aromatic group having 6 to 20 carbon atoms is represented. } Is preferably a monovalent substituent selected from the group consisting of four groups represented by:

In the present embodiment, in the 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 hydroxyl groups may be any of ortho, meta, and para positions. When a is 3, the substitution position between the hydroxyl groups may be any of 1,2,3-position, 1,2,4-position, 1,3,5-position, and the like.

In the present embodiment, in the 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 ₁ may be the same or different.
Further, in the present embodiment, in the general formula (1), a and b satisfy the relationship of 1 ≦ (a + b) ≦ 4.

In the present embodiment, in the general formula (1), X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, or a divalent chain having 3 to 20 carbon atoms. A divalent organic group selected from the group consisting of an alicyclic group, an alkylene oxide group represented by the general formula (2), and a divalent organic group having an aromatic ring. Among these divalent organic groups, X is represented by the following general formula (3) from the viewpoint of the toughness of the film after curing and the viewpoint of the heat melting property.

{In Formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. R ₆ in the case of a monovalent aliphatic group having 1 to 10 carbon atoms substituted by an atom, n1 is an integer of 0 to 4, and n ₁ is an integer of 1 to 4, is a halogen atom , A hydroxyl group, or a monovalent organic group, at least one R ₆ is a hydroxyl group, and when n ₁ is an integer of 2 to 4, a plurality of R ₆ may be the same or different. } And the following general formula (4):

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

(In the formula (2), p is an integer of 1 to 10) and the following formula (5):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: } Is preferably an organic group selected from the group consisting of divalent groups represented by:
W in formula (4) is a single bond, an alkylene oxide group represented by the above general formula (2), or an ester group in the above formula (5) from the viewpoint of the elongation and heat melting property of the cured film. And a divalent organic group selected from the group consisting of an amide group and a sulfonyl group.

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 is represented by the following formula (6) from the viewpoint that the pattern forming property of the resin composition is good and from the viewpoint of the elongation and the heat melting property of the cured film after curing:

Is more preferably a divalent organic group represented by the following formula (7):

The divalent organic group represented by the formula is particularly preferred.

Regarding the ratio between the portion containing the phenolic hydroxyl group and the portion represented by X in the general formula (1), particularly from the viewpoint of elongation, the portion represented by X in the structure represented by the general formula (1) The ratio is preferably 20% by mass or more, and more preferably 30% by mass or more.
The ratio is preferably 80% by mass or less, more preferably 70% by mass or less, from the viewpoint of alkali solubility. Further, from the viewpoint of the heat melting property and alkali solubility of the photosensitive layer, the phenol resin (A) is represented 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 a hydrocarbon group and an alkoxy group, n2 is an integer of 1 to 3, and n3 is 0 to And m1 is an integer of 1 to 500, 2 ≦ (n2 + n3) ≦ 4, and when n3 is 2, R ₁₁ may be the same or different. }
And a repeating unit represented by the following general formula (9):

{In Formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n4 is an integer of 1 to 3 N5 is an integer from 0 to 2, n6 is an integer from 0 to 3, m2 is an integer from 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and when n6 is 2 or 3, R ₁₃ may be the same or different. }
It is particularly preferred to have both of the repeating units represented by

M1 in the general formula (8) and m2 in the general formula (9) represent the total number of each repeating unit in the main chain of the phenol resin (A). That is, in the phenol resin (A), the repeating unit in parentheses in the structure represented by the general formula (8) and the repeating unit in parentheses in the structure represented by the general formula (9) are random, block, or these Can be arranged in combination. m1 and m2 are each independently an integer of 1 to 500 from the viewpoint of alkali solubility and the elongation of the cured product, and the lower limit is preferably 2, more preferably 3, and the upper limit is preferably 450, more preferably 400, and still more preferably 350. m1 and m2 are each independently preferably 2 or more from the viewpoint of the toughness and heat melting property of the cured film, and preferably 450 or less from the viewpoint of solubility in an aqueous alkali 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 molar ratio of the structure represented by the general formula (9), the better the alkali solubility, and the better the physical properties of the film after curing. Excellent pattern shape later. Therefore, the range of the ratio between the structure represented by the general formula (8) and the structure represented by the general formula (9) is m ₁ : m ₂ = 90: 10 to 20:80. From the viewpoint, m ₁ : m ₂ = 80: 20 to 40:60 is more preferable from the viewpoint of film physical properties after curing, alkali solubility, and heat melting property, and m ₁ : m ₂ = 70: 30 to 50: 50 is particularly preferred from the viewpoints of film physical properties after curing, pattern shape, alkali solubility and heat melting property.

The phenol resin (A) is typically a phenol compound and a copolymer component, specifically a compound having an aldehyde group (including a compound that decomposes to form an aldehyde compound like trioxane), a ketone group One or more compounds selected from the group consisting of: a compound having 2 groups, a compound having 2 methylol groups in the molecule, a compound having 2 alkoxymethyl groups in the molecule, and a compound having 2 haloalkyl groups in the molecule; More typically, these monomer components can be synthesized by a polymerization reaction. For example, an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, a haloalkyl compound, etc. with respect to phenol and / or a phenol derivative (hereinafter also collectively referred to as “phenol compound”) as shown below A phenol resin (A) can be obtained by polymerizing the copolymer component. In this case, in the above general formula (1), the moiety represented by the structure in which the OH group and an arbitrary R ₁ group are bonded to the aromatic ring is derived from the phenol compound, and the moiety represented by X is the above-mentioned common group. It comes from the polymerization component. From the viewpoint of reaction control and the stability of the obtained phenol resin (A) and the photosensitive resin composition, the charged molar ratio of the phenol compound and the copolymer component (phenol compound: 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. is there. 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 preferred.
The weight average molecular weight is measured by gel permeation chromatography (GPC), and can be calculated from a calibration curve prepared using standard polystyrene.

In this embodiment, examples of the phenol compound that can be used to obtain the phenol resin (A) include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, nitrobenzylphenol, and cyano. Benzylphenol, adamantanephenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (hydroxyphenyl) -5 -Methyl-5-norbornene-2,3-dicarboximide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, Ethyl loxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitrobenzylcatechol, methylresorcinol , Ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxy Benzami , Dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N- (dihydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (dihydroxyphenyl) -5-methyl-5-norbornene-2, 3-dicarboximide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1, 2, 4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, tri Examples include butyl hydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, and trihydroxybenzonitrile.

Examples of the aldehyde compound include acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxyl Examples include aldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde, and the like.

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

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-tert-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, livi , Arabitol, allitol, 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-norbornene-2,2-dimethanol, 5-norbornene-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-dihydroxy Dodecane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydride) Xoxymethyl) cyclohexene, 1,6-bis (hydroxymethyl) adamantane, 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'-hydroxymethylanili 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, Examples include dipropylene 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-tert-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 (methoxy) Methyl) butyric acid, 2,2-bis (methoxymethyl) -5-norbornene, 2,3-bis (methoxymethyl) -5-norbornene, 1,4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxy) Methyl) cyclohexene, 1,6-bis (methoxymethyl) adamantane, 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) diphenyl Oether, 4,4′-bis (methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4′-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4′-methoxymethylanilide, 4,4′-bis (methoxy) Methyl) 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 dimethyl ether Ter, 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-dimethacrylate, 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-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl cyanurate, diallyl isocyanurate, isocyanurate Allyl, diallyl propyl etc. isocyanuric acid.

Examples of the haloalkyl compound include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, 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.

A phenol resin (A) can be obtained by condensing the above-mentioned phenol compound and copolymerization component by dehydration, dehydrohalogenation or dealcoholization, or by polymerizing the unsaturated bond with cleavage. A catalyst may be used during the polymerization of the phenol compound and the copolymer component.
Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1 Examples include '-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, and boron trifluoride / ether complex.
Examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, piperazine, 1 , 4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, ammonia, hexa And methylenetetramine.
In this embodiment, the amount of the catalyst used to obtain the phenol resin (A) is the total number of moles of copolymerization components, preferably aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds and haloalkyls. 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 conducting the synthesis reaction of the phenol resin (A), an organic solvent can be used as necessary. Specific examples of organic solvents 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, dipropylene glycol. Examples include dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone and the like. The amount of these organic solvents to be 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. In the synthesis reaction of the phenol resin (A), the reaction temperature is preferably 40 ° C. to 250 ° C., more preferably in the range of 100 ° C. to 200 ° C., and the reaction time is about 1 hour to It is preferably 10 hours.

The phenol resin (A) is a phenol compound that does not become a raw material having the structure of the general formula (1) as long as it does not impair the effects of the present invention. It may be 30% or less of the number and further used for polymerization.

In the present embodiment, when a is 1 in the general formula (1), a phenol resin selected from the group consisting of a novolac resin and a polyhydroxystyrene resin (hereinafter referred to as a phenol resin) in order to improve alkali solubility. (Also referred to as (A ′)) can be mixed with the phenolic 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 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 further preferable.

The 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 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.

The polyhydroxystyrene resin is preferably polyparavinylphenol. The polyparavinylphenol is not particularly limited as long as it is a polymer containing paravinylphenol as a polymerization unit. The polymer units other than paravinylphenol that can constitute polyparavinylphenol may be any compound that can be copolymerized with paravinylphenol as long as the object of the present invention is not adversely affected. Compounds that can be copolymerized with paravinylphenol include, for example, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, 2-ethoxyethyl acrylate, t-butyl acrylate, 1,5-pentanediol diester. Acrylate, N, N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1,3-propanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2- Dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2-di ( -Hydroxyphenyl) -propane dimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2--2-di (p-hydroxyphenyl) -propane dimethacrylate, triethylene glycol dimethacrylate, polyoxypropyltrimethylolpropane Triacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol tri Methacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate, 1-phenylethylene-1,2 Esters of acrylic acid, such as dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol dimethacrylate; styrene, and for example Monomers such as, substituted styrenes such as 2-methylstyrene and vinyltoluene; vinyl esters such as vinyl acrylate and vinyl methacrylate; vinylphenols other than paravinylphenol, such as orthovinylphenol and metavinylphenol; However, it is not limited to these.

The weight average molecular weight of the phenol resin (A ′) (that is, a phenol resin selected from the group consisting of a novolak resin and a polyhydroxystyrene resin) is preferably 700 to 100,000, more preferably 1,500 to 80. 2,000, 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, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.
In addition, the phenol resin selected from the group which consists of a novolak resin and a polyhydroxy styrene resin may be used individually by 1 type, and may be used in mixture of 2 or more types.

[Photoacid generator (B)]
In the present embodiment, the photosensitive resin composition is a composition that can form a resin pattern in response to actinic rays (that is, radiation) represented by ultraviolet rays, electron beams, X-rays, and the like. The photosensitive resin composition may be either a negative type (that is, a non-irradiated part is eluted by development) or a positive type (that is, an irradiated part is eluted by development).

In this embodiment, when the photosensitive resin composition is used as a negative 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 crosslinking reaction between (A) and the crosslinking agent, the radiation irradiated portion becomes insoluble in the developer. Examples of the photoacid generator (B) that can be used in 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- - styryl) - bis (4,6-trichloromethyl) -s-triazine and the like;

(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-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4 -Methoxyphenylphenyliodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) Iodonium trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, etc .;

(Iii) Triarylsulfonium salts Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluene Sulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium Trifluoroacetate 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyl Diphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, and the like.

Among these compounds, trichloromethyl-s-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 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.
Triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfone. Nert, 4-phenylthiophenyl diphenyl trifluoroacetate and the like are preferable.
In addition, 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 compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. 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, mesityl phenacyl sulfone, bis (phenacylsulfonyl) methane, and the like.

(3) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl-p-toluene sulfonate and the like.

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

(5) Oxime ester compound As an oxime ester compound, specifically, 2- [2- (4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methyl Phenyl) acetonitrile (trade name “Irgacure PAG121” by Ciba Specialty Chemicals), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty) Chemicals trade name “Irgacure PAG103”), [2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name) "Irgacure PAG 108 ”), α- (n-octanesulfonyloxyimino) -4-methoxybenzylcyanide (trade name“ CGI725 ”manufactured by Ciba Specialty Chemicals) and the like.

(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 (5) oxime ester compound is particularly preferable.
In this 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. The amount is preferably 1 to 40 parts by mass. If the blending amount is 0.1 parts by mass or more, a sensitivity improvement effect can be obtained satisfactorily. If the blending amount is 50 parts by mass or less, the mechanical properties of the cured film are good.

In this 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 these, a quinonediazide compound is preferable from the viewpoint of physical properties after curing. This is because the quinonediazide compound is thermally decomposed during curing and the amount remaining in the cured film is extremely low. Therefore, the positive photoacid generator (B) is preferably a quinonediazide compound.

Examples of the quinonediazide compound include a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure (hereinafter, a compound having the latter structure is also referred to as “NQD compound”). These compounds are described in, for example, 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”), and 1, It is at least one compound selected from the group consisting of 2-naphthoquinonediazide-5-sulfonic acid ester.

The NQD compound can be obtained by converting naphthoquinone diazide sulfonic acid into sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method, and subjecting the obtained naphthoquinone diazide sulfonyl chloride to 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, and the like such as triethylamine The reaction can be carried out in the presence of a basic catalyst for esterification, and the resulting product can be obtained by washing with water and drying.

Examples of preferred NQD compounds from the viewpoint of cured film properties such as sensitivity and elongation include the following general formula group:

{Wherein Q is a hydrogen atom or the following group of formulas:

The naphthoquinone diazide sulfonate group represented by any of the above, but not all Q are hydrogen atoms at the same time. }
The thing represented by is mentioned.

As the NQD compound, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl group. A mixture with an ester compound can also be used.
The NQD compounds 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 composition. It is ˜70 parts by mass, more preferably 1 to 40 parts by mass, still more preferably 5 to 30 parts by mass. If this amount used is 0.1 parts by mass or more, good sensitivity is 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, for example, N-methyl-2- Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, Ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, tert-butyl alcohol Coal, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. Can be used. Among them, from the viewpoints of resin solubility, resin composition stability, adhesion to a substrate, heat melting property, storage stability, and blocking property, γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone. Dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol are preferred, and among these, γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethyl sulfoxide are particularly preferred.

[Silicone type surfactant (D)]
The silicone type surfactant is a surfactant having a siloxane bond and a silicon-carbon bond in the molecule. Examples thereof include a dimethylsiloxane ethyleneoxy graft compound, a dimethylsiloxane propyleneoxy graft compound, and a (hydroxyethyleneoxypropyl) methylsiloxane-dimethylsiloxane compound.

Specific examples of silicone type surfactants include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), SH- 28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, trade name, manufactured by Toray Dow Corning Silicone), SILWET L-77, L-7001 FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nihon Unicar), DBE-814, DBE-224, DBE-621, CMS-626 , CMS-222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DB -712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (trade names, manufactured by BYK Chemie Japan), Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Among these, a dimethylsiloxane ethyleneoxy graft compound and a dimethylsiloxane propyleneoxy graft compound are preferable from the viewpoint of applicability of the composition varnish. These silicone type surfactants can be used singly 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 applicability of the composition varnish to the support. The amount is preferably 0.02 to 10 parts by mass. If the usage-amount of a silicone type surfactant (D) is 30 mass parts or less, the residue and pattern floating at the time of image development can be suppressed.

[Other ingredients]
The photosensitive resin composition according to the present embodiment can contain a crosslinking agent (E), a thermal acid generator, a silane coupling agent, a dye, a dissolution accelerator, and the like as necessary.
The crosslinking agent (E) can be crosslinked with the phenol resin (A) when the relief pattern formed using the photosensitive resin composition according to the present embodiment is heat-cured, or the crosslinking agent itself is a crosslinked network. Is a compound that forms The crosslinking agent (E) is not limited as long as it is a compound that can be thermally crosslinked. Generally, the crosslinking agent has two or more crosslinking groups in the molecule, and can further improve the thermal properties, mechanical properties, and chemical resistance of a cured film formed from the photosensitive resin composition.

Examples of the crosslinking agent (E) include Cymel (registered trademark) 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 (above, manufactured by Mitsui Cytec), Nikarac (registered trademark) MX-270, -280, -290, Nikalac MS-11, Nikalac MW-30, -100, -300, -390, -750 (above, manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DMLPCHP, DML-POP, D L-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAF-MF Honshu Chemical Industry Co., Ltd.), benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis ( Hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxy) Methyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl benzoate methoxymethyl, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, and the like.

As the crosslinking agent (E), phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol type epoxy resins, trisphenol type epoxy resins, tetraphenol type epoxy resins, phenol-xylylene type epoxy resins, which are oxirane compounds, Naphthol-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, Trimethylolpropane polyglycidyl ether, 1,1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, Lyserol triglycidyl ether, ortho secondary butyl phenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (above, trade name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (above , 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 15 H70, YX-315-75 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (above, trade name, manufactured by Daicel Chemical Industries, 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 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

The crosslinking agent (E) includes isocyanate group-containing compounds such as 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone. Diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (trade name, manufactured by Mitsui Chemicals) Duranate (registered trademark) 17B-60PX, TPA-B80E, MF- B60X, MF-K60X, E402-B80T (above, trade name, manufactured by Asahi Kasei Chemicals) and the like.

The crosslinking agent (E) includes bismaleimide compounds such as 4,4′-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5, 5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, 4,4′- Diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, BMI-1000, BMI-1100, BMI- 2000, BMI-2300, BMI-3 00, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (trade names, Daiwa Kasei Kogyo Co., Ltd.), and the like.

The blending amount when the crosslinking agent (E) is used 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). If the blending amount is 0.1 parts by mass or more, the thermophysical properties and mechanical strength of the thermosetting film are good, and if it is 40 parts by mass or less, the stability of the composition in the varnish state and the elongation of the thermosetting film. Is good.

The thermal acid generator is preferably blended in the resin composition from the viewpoint of developing the good thermal properties and mechanical properties of the cured product even when the curing temperature is lowered.
The thermal acid generator is not limited as long as it is a compound that generates an acid by heat. 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, ethyl 2,5-dichlorobenzoate, methyl 2,4-dichlorobenzoate, ethyl p-fluorobenzoate, methyl p-fluorobenzoate, t-butyl pentachlorophenylcarboxylate, methyl pentafluoropropionate, pentafluoro Carboxylic acid esters such as ethyl propionate and t-butyl crotonate; Cyclic carboxylic acid esters such as phenolphthalein and thymolphthalein; Ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, methane 2-isopropoxyethyl sulfonate, phenyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, 2-phenylethyl p-toluenesulfonate, n-propyl p-toluenesulfonate, p- Toluth N-butyl phonate, t-butyl p-toluenesulfonate, n-hexyl p-toluenesulfonate, n-heptyl p-toluenesulfonate, n-octyl p-toluenesulfonate, 2-methoxy p-toluenesulfonate Ethyl, propargyl p-toluenesulfonate, 3-butynyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, ethyl perfluorobutanesulfonate, methyl perfluorobutanesulfonate, benzyl (4- Hydroxyphenyl) methylsulfonium hexafluoroantimonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluorophosphate, trimethylsulfonium methylsulfate, tri-p-sulfonium trifluoromethane Sulfonates such as sulfonate, trimethylsulfonium trifluoromethanesulfonate, pyridinium-p-toluenesulfonate, ethyl perfluorooctanesulfonate; 1,4-butane sultone, 2,4-butane sultone, 1,3-propane sultone, phenol Cyclic sulfonic acid esters such as red, bromocresol green and bromocresol purple; aromatic carboxylic acid anhydrides such as 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, phthalic anhydride, etc. .

The amount of the thermal acid generator used is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the (A) phenol resin. Part is more preferred. If the blending amount is 0.1 parts by mass or more, the effect of maintaining the pattern shape after thermosetting is good. On the other hand, if 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 Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name of Sila Ace S810), 3-mercaptopropyltriethoxysilane (Amax Co., Ltd.). Product name: SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: product name LS1375, manufactured by Amax Co., Ltd .: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation) : Trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by AMAX Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylene Xylodimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercapto Ethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Amax Co., Ltd .: trade name SIU9055.0) N- (3-trimethoxysilylpropyl) urea (manufactured by AMAX 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 Silylpropyl) 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 Amax Co., Ltd .: trade name SLA0598.0 ), M-aminophenyltrimethoxysilane (Amax Co., Ltd.) : Trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Amax Co .: trade name SLA0599.1) Aminophenyltrimethoxysilane (trade name SLA0599.2), 2- (trimethoxy) (Silylethyl) pyridine (manufactured by AMAX 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- Butoxy Lan, 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 (triethoxy Silyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytrie Toxisilane, bis (pentadionato) 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.

As the silane coupling agent, among the above silane coupling agents, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxy are used from the viewpoint of storage stability. Diphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following formula:

The compounds represented are preferred.
The amount of the silane coupling agent used 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, and malachite green. The blending amount of the dye 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 the compound having a hydroxyl group include the ballast agent used in the above-mentioned naphthoquinone diazide compound, paracumylphenol, bisphenols, resorcinols, and linear phenol compounds such as MtrisPC and MtetraPC, TrisP-HAP, TrisP -Non-linear phenolic compounds such as PHBA, TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2-5 phenol substitutes of diphenylmethane, 1-5 phenol substitutes of 3,3-diphenylpropane, A compound obtained by reacting 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane with 5-norbornene-2,3-dicarboxylic anhydride at a molar ratio of 1: 2, bis- ( 3-amino-4-hydroxyphenyl) sulfone and 1,2-cyclo Compounds obtained by reacting xyldicarboxylic anhydride with a molar ratio of 1: 2, N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxy 5-norbornene-2,3-dicarboxylic imide, etc. Can be mentioned. Examples of the compound 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 the 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 (A) phenol resin.

[Photosensitive resin composition containing polyimide precursor and / or alkali-soluble polyimide]
(A) Polyimide precursor As photosensitive resin used for a polyimide precursor composition, polyamide, polyamic acid ester, etc. can be mentioned. For example, as a polyamic acid ester, the following general formula (11):

{In Formula (11), R ¹ and R ² are each independently a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a monovalent organic group having a carbon-carbon unsaturated double bond. 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. And m is preferably 2 or more, more preferably 5 or more. }
The polyamic acid ester containing the repeating unit represented by these can be used.

In the above general formula (11), when R ¹ and R ² are present as monovalent cations, O is negatively charged (ie, present as —O 2 ^— ). X ¹ and Y ¹ may contain a hydroxyl group.

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 each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m ₁ is an integer of 1 to 20. }
Or a monovalent organic group represented by the following general formula (13):
{In General Formula (13), R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m ₂ is an integer of 1 to 20. }
The structure which has an ammonium ion at the terminal of the monovalent organic group represented by these.

A plurality of polyamic acid esters represented by the general formula (11) may be mixed. Moreover, you may use the polyamic acid ester which copolymerized the polyamic acid ester represented by General formula (11).

X ¹ in formula (11) is preferably a tetravalent organic group containing an aromatic group from the viewpoint of heat melting property. Specifically, X ¹ represents the following general formulas (2) to (4):

{In Formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group. }
It is preferable that it is a tetravalent organic group containing at least 1 structure represented by these.

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.

From the viewpoint of heat melting property, X ¹ represents the following general formula (5):

The tetravalent organic group containing the structure represented by these is especially preferable.

Y ¹ in Formula (11) is preferably a divalent organic group containing an aromatic group from the viewpoint of adhesion between the interlayer insulating film and the sealing material. Specifically, Y ¹ represents the following general formulas (6) to (8):

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

{In Formula (7), R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a monovalent organic group 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, R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, and are the same. May be different. )
It is preferable that it is a divalent organic group containing at least 1 structure represented by these.

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

From the viewpoint of heat melting property, Y ¹ is represented by the following general formula (9):

A divalent organic group having a structure represented by the formula is particularly preferred.

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

The tetracarboxylic dianhydride used as a raw material is not limited, but examples thereof include pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3, 3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic acid Dianhydride, diphenylmethane-3,3 ′, 4,4′-tetracarboxylic 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. 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. Sulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 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, -Bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4 -(4-aminophenoxy) phenyl) hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene and the like. Some of the hydrogen atoms on these benzene rings may be substituted. These may be used alone or in combination of two or more.

In the synthesis of the polyamic acid ester (A), generally, a method in which a tetracarboxylic acid diester obtained by performing an esterification reaction of a tetracarboxylic dianhydride described later is directly subjected to a condensation reaction with a diamine can be preferably used. .

The alcohols used in the esterification reaction of the tetracarboxylic dianhydride are alcohols having an olefinic double bond, specifically 2-hydroxyethyl methacrylate, 2-methacryloyloxyethyl alcohol, glycerin diacrylate. Glycerin dimethacrylate and the like, but is not limited thereto. These alcohols can be used alone or in admixture 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 employed. Examples of the synthesis method include the method shown in International Publication No. 00/43439. That is, once the tetracarboxylic acid diester is converted into a tetracarboxylic acid diester diacid chloride, the tetracarboxylic acid diester diacid chloride and diamine are subjected to a condensation reaction in the presence of a basic compound, and the polyamic acid ester (A) To manufacture. Examples of the synthesis method include a method of producing the polyamic acid ester (A) by a method in which a tetracarboxylic acid diester and a diamine are subjected to a condensation reaction in the presence of an organic dehydrating agent.

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 this embodiment is preferably 6,000 to 150,000, more preferably 7,000 to 50,000, and 7,000 to 20,000. More preferably, it is 000.

(B1) Photoinitiator In the case of a negative photosensitive resin, a photoinitiator is added to the resin composition. Examples of the photoinitiator include benzophenone, benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, and fluorenone; 2,2′-diethoxyacetophenone, and 2 Acetophenone derivatives such as hydroxy-2-methylpropiophenone; thioxanthone derivatives such as 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl, benzyldimethyl ketal, benzyl-β Benzyl derivatives such as methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; 2,6-di (4′-diazidobenzal) -4-methylcyclohexanone, and 2, Azides such as' -di (4'-diazidobenzal) cyclohexanone; 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-methoxycarbonyl) oxime 1-phenylpropanedione-2- (O-ethoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, Oximes such as 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl peroxide; aromatic biimidazoles As well as titanocenes. Of these, the above oximes are preferred in terms of photosensitivity.

The addition amount of the photoinitiator is preferably 1 to 40 parts by mass, and 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 photosensitivity is excellent. Moreover, it is excellent in thick film curability by adding 40 mass parts or less of photoinitiators.

(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, an acid is generated in the ultraviolet-exposed part, and the solubility of the exposed part in the alkaline aqueous solution is increased. Thereby, resin can be used as a positive photosensitive resin composition.

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

(C) Solvent (C) The solvent is the same as the solvent described in the above item [Photosensitive resin composition containing phenol resin]. The types and amounts of preferred solvents are also the same as the types and amounts described in the above item [Photosensitive resin composition containing phenol resin].

<Polyimide>
The structure of the cured relief pattern formed from the polyimide precursor composition has 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 General Formula (11). For example, X ¹ is a tetravalent organic compound. Y ¹ is a divalent organic group, and m is an integer of 1 or more. }
It is represented by
Preferable 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 terminal of the polyimide may be substituted with a hydroxyl group.

[Photosensitive resin composition containing polybenzoxazole precursor]
(A) Polybenzoxazole precursor As a photosensitive resin used for a polybenzoxazole precursor composition, the following general formula (14):

{In Formula (14), U and V are each independently a divalent organic group. }
Poly (o-hydroxyamide) containing a repeating unit represented by the following formula can be used.

From the viewpoint of heat melting, 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 (provided that The hydrogen atom may be substituted with a halogen atom), more preferably a chain alkylene group having 1 to 8 carbon atoms and partially or entirely substituted with fluorine atoms.

From the viewpoint of heat melting property, 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 a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different. }

{In Formula (7), R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a monovalent organic group 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, R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, and are the same. May be different. }
It is a divalent organic group containing at least one structure represented by these.

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

From the viewpoint of heat melting property, V is the following general formula (9):

A divalent organic group having a structure represented by the formula is particularly preferred.

From the viewpoint of heat melting, 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. A valent chain aliphatic group is particularly preferred.

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

The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorideation 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 and the halogenating agent in a solvent, a method of reacting in an excess halogenating agent, and then 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, methylsuccin 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethyl Glutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6 -Tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid , Hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hen Icosandioic acid, docosandioic acid, tricosandioic acid, tetracosandioic acid, pentacosandioic acid, hexacosandioic acid, heptacosandioic acid, octacosandioic acid, nonacosandioic acid, triacontanedioic acid, entriacontanedioic acid, dotriacontane A diacid, diglycolic acid, etc. are mentioned. You may mix and use these.

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. You may mix and use these.

(B2) Photoacid generator The photoacid generator has a function of increasing the aqueous alkali solubility of the light irradiation part. Examples of the photoacid generator include a diazonaphthoquinone compound, an aryldiazonium salt, a diaryliodonium salt, and a triarylsulfonium salt. Of these, diazonaphthoquinone compounds are preferred because of their high sensitivity.

(C) Solvent (C) The solvent is the same as the solvent described in the above item [Photosensitive resin composition containing phenol resin]. The types and amounts of preferred solvents are also the same as the types and amounts described in the above item [Photosensitive resin composition containing phenol resin].

<Polybenzoxazole>
The structure of the cured relief pattern formed from the polybenzoxazole precursor composition is represented by the following general formula (10):

{In Formula (10), U and V are the same as U and V defined in General Formula (14) above. }
It is represented by Preferred U and V in the general formula (14) are also preferable in the polybenzoxazole of the general formula (10) for the same reason as described for the general formula (14).

The photosensitive resin composition according to the first embodiment may include at least one selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide. It is preferable that a phenol resin is included from a viewpoint.

<Second Embodiment: Low Melt Viscosity Photosensitive Layer Roll>
The photosensitive layer roll according to the second embodiment of the present invention comprises:
A support film;
A photosensitive layer comprising a photosensitive resin composition provided on the support film;
And the photosensitive resin composition includes 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. -It is a layer which has a temperature point used as 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 slitting the slitter teeth when 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 at which the melt viscosity is 500 Pa · s or less.

The photosensitive layer according to this 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 where the melt viscosity is 450 Pa · s or less, preferably a layer having a temperature point of 400 Pa · s or less, and has a temperature point of 350 Pa · s or less. 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 it is a layer which has. By lowering the melt viscosity of the photosensitive layer, it is possible to suppress the occurrence of cracks when the slits, especially slitter teeth, are slit by heating.

The photosensitive layer of this embodiment preferably has a melt viscosity at 100 ° C. of 500 Pa · s or less, preferably 450 Pa · s or less, preferably 400 Pa · s or less, and 350 Pa · s or less. Preferably, it is 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. Preferably there is.

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 when slitting, especially when slitter teeth are heated, so do not provide a cover film or use a cover film with a high softening temperature. Is preferred.

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 130 ° C. or higher. preferable. The material of the cover film is not particularly limited as long as it satisfies the 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. Details will be described later. About another point, it is the same as the structure demonstrated by the said item <1st Embodiment: 2 layer photosensitive layer roll>.

<Preparation 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 on 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. The removal of the solvent (C) can be performed by heating, for example. From the viewpoint of the remaining amount of 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 is It is preferably about 1 minute to 30 minutes, more preferably about 3 minutes to 20 minutes, and further preferably about 4 minutes to 10 minutes.

The thickness of the photosensitive layer varies depending on the use, 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, or a gas barrier layer or a cover film between the support film and the photosensitive layer.
For example, the photosensitive film can be wound around a core having a cylindrical shape or the like, and stored in a roll shape as a photosensitive layer roll. The core is not particularly limited as long as it is conventionally used. Examples of the material include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer). And the like. At the time of storage, it is preferable that the support film is wound up so as to be the outermost side. Moreover, it is preferable to install an end face separator from the viewpoint of protecting the end face on the end face of the photosensitive film (photosensitive film roll) wound in a roll shape. It is preferable to install. Moreover, when packing a photosensitive film or a photosensitive layer roll, it is preferable to wrap and package it in a black sheet with low moisture permeability.

<Slit of photosensitive layer roll>
A slit photosensitive layer roll can be produced by slitting the produced photosensitive layer roll to a desired width with a slitter.
From the viewpoint of suppressing wrinkles or cracks at the slitting surface, the slitter teeth are preferably 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. Or 130 ° C. or higher.

When the photosensitive layer roll has a cover film, wrinkles may occur in the cover film when slitting, especially when slitting by slitting the slitter teeth, large wrinkles may occur in the cover film There is. From the viewpoint of suppressing the wrinkle of the cover film generated at the time of slitting, the manufacturing method of the slit photosensitive layer roll includes the following steps:
When the photosensitive layer roll has a cover film on the side opposite to the side where the support film of the photosensitive layer is provided, a step of peeling the cover film;
Slitting the photosensitive layer roll without the cover film with a slitter;
A step of applying a cover film different from the peeled cover film or the peeled cover film to the slit photosensitive layer roll;
It is preferable to contain.

<Lamination of photosensitive layer on substrate>
As a method of laminating the photosensitive layer of the slit photosensitive layer roll onto the substrate, the substrate is heated to about 70 to 130 ° C. while the photosensitive layer is heated to about 0.1 to 1 MPa (that is, about 1 to 10 kgf / cm ² ). For example, a method of pressure bonding using a laminator or the like at the pressure of The laminating step may be performed under reduced pressure. The surface of the substrate on which the photosensitive layer is laminated is not particularly limited.

In the case of the two-layer photosensitive layer roll according to the first embodiment, since there is no cover film, the photosensitive layer may adhere to the support film (there is a risk of blocking). On the other hand, if the adhesiveness of the photosensitive layer is lowered, there is a possibility that the photosensitive layer does not adhere when the photosensitive layer is laminated on the substrate. 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 adhesion when heated when laminated on a substrate.

The amount of the 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 adhesion at room temperature and formation of a photosensitive film that is easily melted by heat. Is preferably 0.3 mass% or more and 15 mass% or less, more preferably 0.5 mass% or more and 15 mass% or less, and 0.8 mass% or more and 15 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 preferably 5% by mass. More preferred is 13% by mass or less. When the amount of the residual organic solvent in the photosensitive layer is within the above range, the adhesive layer has low adhesiveness at room temperature, and the photosensitive layer hardly sticks 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, and the solubility of the resin, the stability of the resin composition, the adhesion to the substrate, the heat melting property, the storage stability, and the blocking. From the viewpoint of properties, γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol are preferred, and among these, γ-butyrolactone, acetone, Methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethyl sulfoxide are particularly preferred.

Similarly, in the case of the low melt viscosity photosensitive layer roll according to the second embodiment, when having a high melt viscosity at room temperature, the adhesiveness of the photosensitive layer is low, and slitting is performed by heating slits, particularly slitter teeth. For this, it is desired that cracks hardly occur at a low melt viscosity. The amount of residual organic solvent in the preferred 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 greater the amount of 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, it is possible to adjust the melt viscosity of the photosensitive layer by a method of decreasing the molecular weight of the polymer or a method of increasing low molecular components such as a plasticizer that is not thermally cured.

In this way, the photosensitive layer laminated on the substrate is irradiated with an actinic ray in an image form through a negative or positive mask pattern to form an exposed portion. In this case, when the support present on the photosensitive layer is transparent to the actinic ray, the actinic ray can be irradiated through the support, and the support exhibits a light shielding property against the actinic ray. Irradiates the photosensitive layer with actinic rays after removing the support.

As the active light source, 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 a single or a mixture of two or more actinic 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. as necessary.

Next, development can be performed by using a developer and selecting from a method such as an immersion method, a paddle method, or a spray method. By developing, 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 applied photosensitive resin layer to obtain a relief pattern.
Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia water, 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 an aqueous solution to which a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added as required can be used. Among these, tetramethylammonium hydroxide aqueous solution 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 is formed with a relief pattern by washing with a rinse solution and removing the developer. As a rinse liquid, distilled water, methanol, ethanol, isopropanol etc. can be used, for example, These can be used individually or in combination of 2 or more types.
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, and more preferably 250 ° C. or lower.

A method for producing a cured relief pattern using a photosensitive layer roll according to the first or second embodiment includes a surface protective film, an interlayer insulating film, a rewiring insulating film, a fan-out type semiconductor device, a display device, and a light emitting device. Rewiring layer for wafer level package (FOWLP), protective film for flip chip device, high-density substrate, protective film for devices with bump structure, interlayer insulating film for multilayer circuit, cover coat for flexible copper-clad board, solder resist The film can be suitably used for producing a liquid crystal alignment film and the like.
The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. The present invention can be variously modified 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 equipped with a Dean-Stark apparatus having a volume of 0.5 liter. 0.2 g (0.5 mol), diethylsulfate 3.9 g (0.025 mol), and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70 ° C. to dissolve the solid matter.

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 atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluted solution was dropped into 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 produce a copolymer of phloroglucinol / BMMB (phenol Resin (A-1)) was obtained with a yield of 70%.

[Synthesis Example 2]
<Synthesis of phenol resin (A-2)>
Synthesis was performed 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 synthesized. A copolymer consisting 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 Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen. 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 matter.

The mixed solution was heated to 120 ° C. with an oil bath, generation of methanol was confirmed from the reaction solution, and the reaction solution was stirred at 120 ° C. for 3 hours as it was.
Next, in another container, 24.9 g (0.150 mol) of 2,6-bis (hydroxymethyl) -p-cresol and 249 g of PGME were mixed and stirred, and the uniformly dissolved solution was added using a dropping funnel. The solution 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 performed, and a copolymer (resin resin (A-3)) composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol was obtained with a yield of 77%. Got in.

[Synthesis Example 4]
<Synthesis of polyimide precursor (A-5)>
In a 2 L separable flask, 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”) were added. The mixture was mixed and stirred at room temperature (25 ° C.), dissolved, and 63.3 g (0.8 mol) of pyridine was added with stirring under ice cooling.

Next, a solution obtained by dissolving 165 g (0.8 mol) of dicyclohexylcarbodiimide in 120 g of GBL was added to the above separable flask over 40 minutes while stirring under ice-cooling. Subsequently, a suspension obtained by suspending 74.5 g (0.37 mol) of 4,4′-diaminodiphenyl ether in 150 g of GBL was added to the above separable flask over 60 minutes with stirring under ice cooling. After stirring for 2 hours at room temperature, 30 ml of ethyl alcohol was added to the above separable flask and stirred for 1 hour. Further, 250 ml of dimethylacetamide (hereinafter referred to as “DMAc”) and 400 ml of tetrahydrofuran (THF) were added. Removal by suction filtration gave a reaction solution. The resulting reaction solution was added to 15 L of ethyl alcohol, and the resulting precipitate was filtered off and dried under vacuum to obtain a polyimide precursor (A-5).

[Synthesis Example 5]
<Synthesis of polybenzoxazole precursor (A-6)>
In a 2 L separable flask, 197.8 g (0.54 mol) 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75.9 g (0.96 mol) pyridine, and 692 g DMAc were added. The mixture was stirred and dissolved at room temperature (25 ° C.).

A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of dimethyl diglycol (hereinafter also referred to as “DMDG”) separately was added dropwise to the obtained mixed solution. It was dripped from the funnel. The time required for the dropping was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
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. with a water bath, and a solution prepared by 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 a dropping funnel. It was dripped. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C.
Three hours after the completion of the dropping, the above reaction solution is dropped into 12 L of water under high-speed stirring to disperse and precipitate the polymer, which is recovered, appropriately washed with water and dehydrated, followed by vacuum drying to obtain 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: Resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol copolymer, polystyrene-reduced 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

<Photoacid generator (B)>
B-1: Photoacid generator represented by the following formula:

{In the formula, 83% of Q is the following:

The remainder 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) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)

[Preparation of photosensitive resin composition]
As shown in the following Table 1, the resin (A), the photoacid generator (B), the surfactant (D), and the crosslinking agent (E) are dissolved in the solvent (C), and 0.1 μm A positive photosensitive resin composition was prepared by filtration through a filter.

[Support film]
As a support film, a PET film “PET25X” (manufactured by Lintec Corporation, width 290 mm, thickness 25 μm) subjected to release treatment with a silicone compound was prepared.

[Preparation of photosensitive film]
Example 1
“PET25X”, which is a release-treated PET film, was used as a support film, and a solution of a photosensitive resin composition having the composition shown in Table 1 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 set to 10 μm. A photosensitive film having a width of 300 mm having the above composition is linearly formed on a plastic tube by using a pressure roll disposed in a cylindrical plastic tube having an outer diameter of 3.5 inches in parallel with the winding axis width direction. Pressure was applied, and the film was wound up by 1000 kg with a tension of 7 kg to obtain a photosensitive film roll.

(Examples 2 to 13)
Each photosensitive film roll was produced 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 that 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 produced according to the procedure.

<Residual solvent amount>
The photosensitive film was unwound from the photosensitive film roll produced in each of Examples and Comparative Examples, the photosensitive layer was peeled off from the support film, and the peeled photosensitive layer was gas chromatographed (trade name “manufactured by Agilent Technologies, Inc., trade name“ 6890N ") and the amount of residual solvent (parts by mass) relative to 100 parts by mass of the phenol resin was measured.
<Melt viscosity>
The photosensitive film was unwound from the photosensitive film rolls prepared in the examples and comparative examples, the photosensitive layer was peeled off from the support film, and the peeled photosensitive layer was melted by a melt viscosity measuring device (TE Instruments Japan). Using a product name “DHR-2” manufactured by Co., Ltd., measurement was performed under the following conditions. Table 1 shows the melt viscosity at a temperature of 100 ° C.
・ Sample shape Film thickness: 0.5mmt
Diameter: 25 mm disk / measurement conditions Start temperature: 50 ° C.
Temperature increase rate: 5 ° C / min
End temperature: 220 ° C
Strain: 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 unrolling of the rolls was visually observed and evaluated according to the following criteria.
S (remarkably good): The photosensitive layer does not adhere to the back surface of the support film even when stored in a roll form at room temperature for 1 month or more.
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.

<Peelability of support film>
The photosensitive film was unwound from the photosensitive film roll produced in each of the examples and comparative examples, and the photosensitive layer was laminated on a glass plate while being heated to 130 ° C., thereby producing a sample for property evaluation in which the photosensitive layer was transferred. Subsequently, the support film was peeled off from the sample for property evaluation, and the transfer state of the photosensitive layer was visually evaluated.
S (remarkably good): Peeling and removal are possible without the photosensitive layer adhering to the support film.
A (good): A part of the photosensitive layer, peeled off with the photosensitive layer attached to the support film.
B (defect): Peeled with the photosensitive layer adhering to the support film over the entire surface of the photosensitive layer.

<Crack at slit>
The photosensitive film roll produced in each of the examples and comparative examples was slit with a slitter whose teeth were heated to 100 ° C. The occurrence of cracks when slitting and the appearance of the cut surface were evaluated visually.
S (remarkably good): no crack is generated and the cut surface is smooth.
A (good): Cracks are not generated, but the cut surface is slightly uneven.
B (defect): A crack occurred.

<Wrinkle of cover film>
The photosensitive film roll produced in the comparative example was slit with a slitter having teeth heated to 100 ° C., and wrinkles generated on the cover film were visually evaluated.
A (good): The cover film does not wrinkle.
B (defect): The cover film was wrinkled.

<Evaluation results>
For each example and comparative example, the result of each characteristic evaluation is shown in Table 1 above.

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

Claims (40)

1. A support film;
   A photosensitive layer comprising a photosensitive resin composition provided on the support film;
   A photosensitive layer roll comprising:
   The photosensitive resin composition includes 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.
2. 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.
3. The photosensitive layer roll according to claim 1, wherein the photosensitive layer has a melt viscosity at 100 ° C. of 500 Pa · s or less.
4. The photosensitive layer roll according to claim 3, wherein the photosensitive layer has a melt viscosity at 100 ° C. of 350 Pa · s or less.
5. The cover film according to any one of claims 1 to 4, further comprising a cover film on a side of the photosensitive layer opposite to the side on which the support film is provided, and a softening temperature of the cover film being 90 ° C or higher. Photosensitive layer roll.
6. The photosensitive layer roll according to claim 5, wherein a softening temperature of the cover film is 110 ° C. or higher.
7. The photosensitive layer roll according to any one of claims 1 to 6, wherein an 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 a total amount of the photosensitive layer. .
8. The photosensitive layer roll according to claim 7, wherein the amount of the organic solvent contained in the photosensitive layer is from 1% by mass to 15% by mass with respect to the total amount of the photosensitive layer.
9. The organic solvent includes 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 claim 7 or 8.
10. The photosensitive layer roll according to claim 9, wherein the organic solvent contains 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 claims 1 to 10, wherein the photosensitive resin composition contains the polyimide precursor.
12. The photosensitive layer roll according to any one of claims 1 to 10, wherein the photosensitive resin composition contains the polybenzoxazole precursor.
13. The photosensitive layer roll according to any one of claims 1 to 10, wherein the photosensitive resin composition contains the soluble polyimide.
14. The photosensitive layer roll according to any one of claims 1 to 10, wherein the photosensitive resin composition contains the phenol resin.
15. The phenol resin is represented by the following general formula (1):
    

    

    {In 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 of 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R _{1 s} 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, the following general formula (2) :
    

    

    (In formula (2), p is an integer of 1 to 10) and a divalent alkylene oxide group represented by the formula (2) and a divalent organic group selected from the group consisting of divalent organic groups having an aromatic ring. Represents an organic group. }
    The photosensitive layer roll according to claim 14, having a structure represented by:
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 each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. A monovalent aliphatic group having 1 to 10 carbon atoms substituted by an atom, n1 is an integer of 0 to 4, and n1 is an integer of 1 to 4, R ₆ is a halogen atom, A hydroxyl group or a monovalent organic group, at least one R ₆ is a hydroxyl group, and when n1 is an integer of 2 to 4, a plurality of R ₆ may be the same or different. }
    And a divalent group represented by the following general formula (4):
    

    

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

    

    (In the formula (2), p is an integer of 1 to 10) and the following formula (5):
    

    

    A divalent organic group selected from the group consisting of divalent groups represented by the formula: }
    The photosensitive layer roll according to claim 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 claim 15, which is a divalent organic group represented by the formula:
18. X in the general formula (1) is the following formula (7):
    

    

    The photosensitive layer roll according to claim 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 a hydrocarbon group and an alkoxy group, n2 is an integer of 1 to 3, and n3 is 0 to And m1 is an integer of 1 to 500, 2 ≦ (n2 + n3) ≦ 4, and when n3 is 2, R ₁₁ may be the same or different. } And the following general formula (9):
    

    

    {In Formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n4 is an integer of 1 to 3 N5 is an integer from 0 to 2, n6 is an integer from 0 to 3, m2 is an integer from 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and when n6 is 2 or 3, R ₁₃ may be the same or different. }
    The photosensitive layer roll according to any one of claims 15 to 18, wherein both of the repeating units represented by formula (1) are contained in the same resin skeleton.
20. A support film;
    A photosensitive layer comprising a photosensitive resin composition provided on the support film;
    A photosensitive layer roll comprising:
    The photosensitive resin composition includes at least one resin selected from the group consisting of a phenolic resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and both sides of the support film have the photosensitive layer and The photosensitive layer roll in contact.
21. 21. The photosensitive layer roll according to claim 20, wherein the amount of the organic solvent contained in the photosensitive layer is from 0.1% by mass to 15% by mass with respect to the total amount of the photosensitive layer.
22. The photosensitive layer roll according to claim 21, wherein the amount of the organic solvent contained in the photosensitive layer is from 1% by mass to 15% by mass with respect to the total amount of the photosensitive layer.
23. The photosensitive layer roll according to claim 21 or 22, wherein the photosensitive resin composition contains the phenol resin.
24. The organic solvent includes 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 claims 21 to 23.
25. 25. The photosensitive layer roll according to claim 24, wherein the organic solvent contains 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 claims 20 to 25, wherein the photosensitive resin composition contains the polyimide precursor.
27. The photosensitive layer roll according to any one of claims 20 to 25, wherein the photosensitive resin composition contains the polybenzoxazole precursor.
28. The photosensitive layer roll according to any one of claims 20 to 25, wherein the photosensitive resin composition contains the soluble polyimide.
29. The photosensitive layer roll according to any one of claims 20 to 25, wherein the photosensitive resin composition contains a phenol resin.
30. The phenol resin is represented by the following general formula (1):
    

    

    {In 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 of 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R _{1 s} 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, the following general formula (2) :
    

    

    (In formula (2), p is an integer of 1 to 10) and a divalent alkylene oxide group represented by the formula (2) and a divalent organic group selected from the group consisting of divalent organic groups having an aromatic ring. Represents an organic group. }
    The photosensitive layer roll according to claim 29, having a structure represented by the formula:
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 each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. A monovalent aliphatic group having 1 to 10 carbon atoms substituted by an atom, n1 is an integer of 0 to 4, and n1 is an integer of 1 to 4, R ₆ is a halogen atom, A hydroxyl group or a monovalent organic group, at least one R ₆ is a hydroxyl group, and when n1 is an integer of 2 to 4, a plurality of R ₆ may be the same or different. }
    And a divalent group represented by the following general formula (4):
    

    

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

    

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

    

    A divalent organic group selected from the group consisting of divalent groups represented by the formula: }
    The photosensitive layer roll according to claim 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 claim 30 or 31, which is a divalent organic group represented by the formula:
33. X in the general formula (1) is the following formula (7):
    

    

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

    

    {In Formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n4 is an integer of 1 to 3 N5 is an integer from 0 to 2, n6 is an integer from 0 to 3, m2 is an integer from 1 to 500, 2 ≦ (n4 + n5) ≦ 4, and n5 is 2. R ₁₂ may be the same or different, and when n6 is 2 or 3, R ₁₃ may be the same or different. The photosensitive layer roll according to any one of claims 30 to 33, having both of the repeating units represented by
35. A method for producing a slit photosensitive layer roll, wherein the photosensitive layer roll according to any one of claims 1 to 34 is slit with a slitter to produce a slit photosensitive layer roll.
36. 36. The method for producing a slit photosensitive layer roll according to claim 35, wherein the slitter teeth are heated.
37. The method for producing a slit photosensitive layer roll according to claim 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 claims 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 peeled off. Process,
    Slitting the photosensitive layer roll without the cover film with a slitter;
    A process of applying a peeled cover film or a cover film different from the peeled cover film to the slit photosensitive layer roll;
    A method for producing a slit photosensitive layer roll comprising:
39. The method for producing a slit photosensitive layer roll according to claim 38, wherein the slitter teeth are heated.
40. 40. The method for producing a slit photosensitive layer roll according to claim 39, wherein the slitter teeth are heated to 100 ° C. or higher.