KR20190085077A - 2 layer photosensitive layer roll - Google Patents

Abstract

Wherein the photosensitive layer roll comprises a support film and a photosensitive layer comprising a photosensitive resin composition formed on a support film, wherein the photosensitive resin composition comprises a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide group And the photosensitive layer is a layer having a temperature point at which the melt viscosity is 500 Pa · s or less.

Description

2 layer photosensitive layer roll

The present invention relates to a photosensitive layer roll.

Conventionally, photolithography has been known as an image forming method used for patterning semiconductor devices, liquid crystal display elements, printed wiring boards, and the like. In the photolithography method, usually, a method of applying a solution of a photosensitive resin composition onto a substrate such as a copper clad laminate or the like and drying, or a method of forming a layer comprising a support, a photosensitive resin composition (hereinafter also referred to as a "photosensitive layer" And a method of laminating a photosensitive resin laminate (hereinafter also referred to as a " dry film resist ") in which cover films are sequentially laminated as needed, is laminated on a substrate. In the production of a printed wiring board, the latter is commonly used.

The dry film resist may be stored in the form of a roll (see Patent Document 1). Patent Document 1 discloses a photosensitive film comprising a photosensitive layer and a photosensitive layer containing a non-tacky outer layer having a thickness of not more than 1/5 of the thickness of the photosensitive layer in order to reduce the manufacturing cost by omitting the cover film from the roll of the dry film resist Complexes have been proposed.

From the viewpoint of handling of a dry film resist, there is no tackiness to a dry film resist at room temperature, and it is required to exhibit fluidity when a dry film resist is thermocompression bonded to a substrate or the like (that is, when laminating) (see Patent Document 2) . Patent Document 2 proposes a photosensitive coverlay film which has no tackiness at a substrate temperature of 20 ° C and is easy to position even when placed on a substrate.

In Patent Document 3, both of low temperature curability and chemical resistance of a cured film are confirmed by using a phenolic resin having a specific structure in combination with a nonionic surface active agent in a photosensitive resin composition.

Japanese Laid-Open Patent Publication No. 2001-175000 Japanese Patent Application Laid-Open No. 2003-149803 Japanese Laid-Open Patent Publication No. 2013-190697

Usually, the photosensitive resin laminate is prepared in the form of a roll, and is slit into 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, And there is a problem that it is difficult to slit so that the cross section becomes smooth.

The present inventors have found out that the above problems can be solved by adjusting the melt viscosity of the photosensitive layer or by removing the cover film, thereby completing the present invention. That is, the present invention is as follows.

[One]

A support film,

A photosensitive layer formed on the support film and including a photosensitive resin composition,

As a photosensitive layer roll,

Wherein the photosensitive resin composition contains at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and the photosensitive layer has a melt viscosity of 500 Pa s or less The photosensitive layer being a layer having a temperature point at which the photosensitive layer is exposed.

[2]

The photosensitive layer roll according to [1], wherein the photosensitive layer is a layer having a temperature point at which a 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 캜 of 500 Pa s or less.

[4]

The photosensitive layer roll according to [3], wherein the photosensitive layer has a melt viscosity at 100 캜 of 350 Pa s or less.

[5]

The photosensitive layer roll according to any one of [1] to [4], wherein the photosensitive layer has a cover film on the side opposite to the side where the support film is formed, and the softening temperature of the cover film is 90 deg.

[6]

The photosensitive layer roll according to [5], wherein the softening temperature of the cover film is 110 占 폚 or higher.

[7]

The photosensitive layer roll according to any one of [1] to [6], wherein the amount of the organic solvent contained in the photosensitive layer is 0.1% by mass or more and 15% by mass or less based on the total amount of the photosensitive layer.

[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]

Wherein the organic solvent is at least one selected from the group consisting of? -Butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethylsulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol The photosensitive layer roll according to [7] or [8], further comprising at least one selected from the group consisting of

[10]

The photosensitive layer according to [9], wherein the organic solvent comprises at least one selected from the group consisting of? -Butyrolactone, acetone, methyl ethyl ketone, N-methyl- role.

[11]

The photosensitive layer roll according to any one of [1] to [10], wherein the photosensitive resin composition comprises the polyimide precursor.

[12]

The photosensitive layer roll according to any one of [1] to [10], wherein the photosensitive resin composition comprises the polybenzoxazole precursor.

[13]

The photosensitive layer roll according to any one of [1] to [10], wherein the photosensitive resin composition comprises the soluble polyimide.

[14]

The photosensitive layer roll according to any one of [1] to [10], wherein the photosensitive resin composition comprises the phenol resin.

[15]

Wherein the phenol resin is represented by the following general formula (1):

[Chemical Formula 1]

(1) wherein a is an integer of 1 to 3, b is an integer of 0 to 3, 1? (A + b)? 4, and R ₁ is a monovalent organic group having 1 to 20 carbon atoms A halogen atom, a nitro group and a cyano group, and a plurality of R _{1 s} when b is 2 or 3 may be the same or different and X is an unsaturated bond A bivalent aliphatic group having 2 to 10 carbon atoms and a bivalent alicyclic group having 3 to 20 carbon atoms,

(2)

A divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula (2) wherein p is an integer of 1 to 10, and a divalent organic group having an aromatic ring.

As a repeating unit, a structure represented by the following formula (1).

[16]

Wherein X in the general formula (1) is a group represented by the following general formula (3):

(3)

(In the 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 carbon number formed by substituting a part or all of hydrogen atoms with a fluorine atom and 1-10 aliphatic monovalent, n1 is an integer of 0 ~ 4, n1 is the case of 1 to 4 integer, R ₆ is a halogen atom, a hydroxyl group, or a monovalent organic group, at least one R ₆ is A plurality of R < ₆ > s may be the same or different when n1 is an integer of 2 to 4,

And a divalent group represented by the following general formula (4):

[Chemical Formula 4]

Wherein 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 carbon number of a hydrogen atom partially or entirely substituted with a fluorine atom W represents a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, a monovalent aliphatic group having 1 to 10 carbon atoms, (2) :

[Chemical Formula 5]

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

[Chemical Formula 6]

Is a divalent organic group selected from the group consisting of a divalent group represented by the formula:

Is a divalent organic group selected from the group consisting of a divalent group represented by the following formula (1).

[17]

Wherein X in the general formula (1) is a group represented by the following formula (6):

(7)

Is a divalent organic group represented by the following formula (15).

[18]

Wherein X in the general formula (1) is a group represented by the following formula (7):

[Chemical Formula 8]

Is a divalent organic group represented by the following formula (1).

[19]

Wherein the phenolic resin is represented by the following general formula (8):

[Chemical Formula 9]

(In the 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, n3 is an integer of 0 to 2, m1 . is an integer of 1 ~ 500, 2 ≤ (n2 + n3) ≤ 4 , and, R ₁₁ may be the same in each case of n3 is 2 and or different} repeat shown in units, and the following general formula (9):

[Chemical formula 10]

(In the 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, n 4 is an integer of 1 to 3, is an integer of 2, n6 is an integer of 0 ~ 3, m2 is an integer of 1 ~ 500, 2 ≤ (n4 + n5) ≤ 4 , and, R ₁₂ in the case where n5 is 2 and may be the or different in the same respectively , and R < ₁₃ > when n6 is 2 or 3 may be the same or different.

The photosensitive layer roll according to any one of the above-mentioned items [15] to [18], wherein both of the repeating units represented by the following formulas are within the same resin framework.

[20]

A support film,

A photosensitive layer formed on the support film and including a photosensitive resin composition,

As a photosensitive layer roll,

Wherein the photosensitive resin composition comprises at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and both surfaces of the support film are in contact with the photosensitive layer , Photosensitive layer roll.

[21]

The photosensitive layer roll according to [20], wherein the amount of the organic solvent contained in the photosensitive layer is 0.1% by mass or more and 15% by mass or less based on 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 comprises the phenolic resin.

[24]

Wherein the organic solvent is at least one selected from the group consisting of? -Butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethylsulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol , Wherein the photosensitive layer roll comprises at least one selected from the group consisting of the following. [21] to [23].

[25]

The photosensitive layer according to [24], wherein the organic solvent comprises at least one selected from the group consisting of? -Butyrolactone, acetone, methyl ethyl ketone, N-methyl- role.

[26]

The photosensitive layer roll according to any one of [20] to [25], wherein the photosensitive resin composition comprises the polyimide precursor.

[27]

The photosensitive layer roll according to any one of the items [20] to [25], wherein the photosensitive resin composition comprises the polybenzoxazole precursor.

[28]

The photosensitive layer roll according to any one of the items [20] to [25], wherein the photosensitive resin composition comprises the soluble polyimide.

[29]

The photosensitive layer roll according to any one of the items [20] to [25], wherein the photosensitive resin composition comprises a phenol resin.

[30]

 Wherein the phenol resin is represented by the following general formula (1):

(11)

(1) wherein a is an integer of 1 to 3, b is an integer of 0 to 3, 1? (A + b)? 4, and R ₁ is a monovalent organic group having 1 to 20 carbon atoms A halogen atom, a nitro group and a cyano group, and a plurality of R _{1 s} when b is 2 or 3 may be the same or different and X is an unsaturated bond A bivalent aliphatic group having 2 to 10 carbon atoms and a bivalent alicyclic group having 3 to 20 carbon atoms,

[Chemical Formula 12]

A divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula (2) wherein p is an integer of 1 to 10, and a divalent organic group having an aromatic ring.

As a repeating unit, a structure represented by the following formula (1).

[31]

Wherein X in the general formula (1) is a group represented by the following general formula (3):

[Chemical Formula 13]

(In the 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 carbon number formed by substituting a part or all of hydrogen atoms with a fluorine atom and 1-10 aliphatic monovalent, n1 is an integer of 0 ~ 4, n1 is the case of 1 to 4 integer, R ₆ is a halogen atom, a hydroxyl group, or a monovalent organic group, at least one R ₆ is A plurality of R < ₆ > s may be the same or different when n1 is an integer of 2 to 4,

And a divalent group represented by the following general formula (4):

[Chemical Formula 14]

Wherein 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 carbon number of a hydrogen atom partially or entirely substituted with a fluorine atom W represents a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, a monovalent aliphatic group having 1 to 10 carbon atoms, (2) :

[Chemical Formula 15]

(In the formula (2), p is an integer of 1 to 10.)

And a divalent alkylene oxide group represented by the following formula (5):

[Chemical Formula 16]

Is a divalent organic group selected from the group consisting of a divalent group represented by the formula:

Is a divalent organic group selected from the group consisting of a divalent group represented by the following formula (1).

[32]

Wherein X in the general formula (1) is a group represented by the following formula (6):

[Chemical Formula 17]

Is a divalent organic group represented by the following formula (1).

[33]

Wherein X in the general formula (1) is a group represented by the following formula (7):

[Chemical Formula 18]

Is a divalent organic group represented by the following formula (1).

[34]

Wherein the phenolic resin is represented by the following general formula (8):

[Chemical Formula 19]

(In the 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, n3 is an integer of 0 to 2, m1 is an integer from 1 to 500, and 2 ≤ (n2 + n3) ≤ 4 , is R ₁₁ may be the same or is different from each of the case where n3 is 2.}

And a repeating unit represented by the following general formula (9):

[Chemical Formula 20]

(In the 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, n 4 is an integer of 1 to 3, is an integer of 2, n6 is an integer of 0 ~ 3, m2 is an integer of 1 ~ 500, 2 ≤ (n4 + n5) ≤ 4 , and, R ₁₂ in the case where n5 is 2 and may be the or different in the same respectively , and R < ₁₃ > in the case of n6 being 2 or 3 may be the same or different, both of which are contained in the same resin skeleton, in the photosensitive layer rolls of any of [30] to [33] .

[35]

A process for producing a slit photosensitive layer roll, wherein the photosensitive layer roll according to any one of [1] to [34] is slit into a slit to produce a slit photosensitive layer roll.

[36]

And the teeth of the slitter are heated. The method of producing a slit photosensitive layer roll as set forth in [35].

[37]

And the teeth of the slitter are heated to 100 DEG C or higher.

[38]

The following steps:

When the photosensitive layer roll described in any one of [1] to [34] has a cover film on the side opposite to the side where the support film of the photosensitive layer is formed, the step of peeling the cover film,

A step of slitting the photosensitive layer roll having no cover film with a slitter,

A step of attaching the peeled cover film or a cover film different from the peeled cover film to the slit photosensitive layer roll

Wherein the slit photosensitive layer roll is formed by a method comprising the steps of:

[39]

And the teeth of the slitter are heated. The method of producing a slit photosensitive layer roll as set forth in [38].

[40]

The method of manufacturing a roll of a slit photosensitive layer according to [39], wherein the teeth of the slitter are heated to 100 DEG C or more.

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

≪ First Embodiment: Second layer photosensitive layer roll >

The photosensitive layer roll according to the first embodiment of the present invention comprises a support film and a photosensitive resin containing at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide And two layers of a photosensitive layer formed of a composition.

In the present embodiment, the photosensitive layer roll does not include a cover film. Both sides of the support film come in contact with the photosensitive layer 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 or the side where the photosensitive layer is not laminated) is exposed.

Hereinafter, the photosensitive layer roll in which both surfaces of the support film are in contact with the photosensitive layer without including a 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 in particular, when slits are formed by heating the teeth of the slitter, a large wrinkle easily occurs in the cover film .

In order to solve the above problems, the two-layer photosensitive layer roll according to the first embodiment 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, or polyester can be used. Among them, a polyethylene terephthalate film Hereinafter referred to as " PET film ").

From the viewpoint of transferring the photosensitive layer from the two-layer photosensitive layer roll to the base material when the photolithography method is carried out, it is preferable that at least one surface of the base film is subjected to the releasing treatment. The mold releasing treatment in the present embodiment is a chemical treatment in which the surface of a support film is thinly coated with a releasing agent such as a silicone compound such as a silicone surfactant or a silicone resin, a fluorine-containing compound such as a fluorine surfactant or a fluorine resin, Or a physical treatment such as corona treatment of a support film.

When the releasing agent is coated on the support film, it is preferable to thinly coat the releasing agent to the extent that the effect of release is obtained. After the coating, the releasing agent may be fixed to the support film by heat or UV treatment. It is more preferable to apply a primer layer to the support film before coating the release agent.

<Photosensitive Layer>

The photosensitive layer contains 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 Is formed by applying a photosensitive resin composition.

Hereinafter, the components contained in the photosensitive resin composition will be described.

[Photosensitive resin composition containing phenol resin] [Component (A): phenol resin]

Generally, phenolic resins are thermosetting resins formed from phenolic compounds and aldehyde compounds.

In the present embodiment, from the viewpoint of thermal fusibility of the photosensitive layer, the phenol resin (A) is represented by the following general formula (1):

[Chemical Formula 21]

(1) wherein a is an integer of 1 to 3, b is an integer of 0 to 3, 1? (A + b)? 4, and R ₁ is a monovalent organic group having 1 to 20 carbon atoms A halogen atom, a nitro group and a cyano group, and a plurality of R _{1 s} when b is 2 or 3 may be the same or different and X is an unsaturated bond A bivalent aliphatic group having 2 to 10 carbon atoms and a bivalent alicyclic group having 3 to 20 carbon atoms,

[Chemical Formula 22]

(Wherein p is an integer of 1 to 10), and a divalent organic group selected from the group consisting of a divalent organic group having an aromatic ring. Structure as a repeating unit.

The phenol resin (A) having a repeating unit having the structure represented by the formula (1) is a phenol resin having a repeating unit represented by the following formula (1), which can be cured at a low temperature as compared with, for example, a polyimide resin and a polybenzoxazole resin, And further contributes to the heat melting property of the photosensitive layer.

The photosensitive layer having excellent heat melting property is preferable because it is difficult for cracks to be generated in the cut surface when the slit is heated, particularly when the slit is heated and slit, so that the cross section can be slit smoothly.

In the general formula (1), R ₁ is a monovalent organic group having 1 to 20 carbon atoms, a monovalent organic group selected from the group consisting of a halogen atom, a nitro group and a cyano group, and from the viewpoint of alkali solubility, , A nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an aromatic group having 6 to 20 carbon atoms,

(23)

(In the formula (10), R ₁₄ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, a chain aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms, And R ₁₇ represents a divalent chain aliphatic group having 1 to 10 carbon atoms, a divalent aliphatic group having 3 to 20 carbon atoms, or a divalent aromatic group having 6 to 20 carbon atoms, which may have an unsaturated bond, Is a monovalent substituent selected from the group consisting of four groups represented by the following formula:

In the present embodiment, in Formula (1), a is an integer of 1 to 3, and preferably 2 from the viewpoint of alkali solubility and elongation. When a is 2, substitution positions between hydroxyl groups may be any of ortho, meta and para positions. When a is 3, substitution positions of the hydroxyl groups may be any of 1,2,3-position, 1,2,4-position and 1,3,5-position.

In the present embodiment, in the general formula (1), b is an integer of 0 to 3, and from the viewpoint of alkali solubility and elongation, 0 or 1 is preferable. When b is 2 or 3, plural R _{1 s} may be the same or different.

In the present embodiment, in the general formula (1), a and b satisfy the relationship 1? (A + b)? 4.

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

&Lt; EMI ID =

(In the 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 carbon number formed by substituting a part or all of hydrogen atoms with a fluorine atom and 1-10 aliphatic monovalent, n1 is an integer of 0 ~ 4, n1 is the case of 1 to 4 integer, R ₆ is a halogen atom, a hydroxyl group, or a monovalent organic group, at least one R ₆ is A plurality of R &lt; ₆ &gt; s may be identical to or different from each other when n1 is an integer of 2 to 4, and a group represented by the following general formula (4):

(25)

Wherein 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 carbon number of a hydrogen atom partially or entirely substituted with a fluorine atom W represents a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, a monovalent aliphatic group having 1 to 10 carbon atoms, (2) :

(26)

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

(27)

Is a divalent organic group selected from the group consisting of a divalent group represented by the following formula (1).

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

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 the divalent organic group represented by the general formula (4) From the viewpoint of good pattern forming property of the resin composition and from the viewpoint of elongation of the cured film after curing and thermal fusibility,

(28)

, More preferably a divalent organic group represented by the following formula (7):

[Chemical Formula 29]

Is particularly preferably a divalent organic group represented by the following formula

Regarding the ratio of the portion containing a phenolic hydroxyl group to the portion represented by X in the general formula (1), the proportion of the portion represented by X in the structure represented by the general formula (1) is preferably 20 mass% Or more, more preferably 30 mass% or more.

The above ratio is preferably 80 mass% or less, more preferably 70 mass% or less, from the viewpoint of alkali solubility. From the viewpoints of the heat melting property and the alkali solubility of the photosensitive layer, the phenol resin (A) preferably has the following general formula (8):

(30)

(In the 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, n3 is an integer of 0 to 2, m1 is an integer from 1 to 500, and 2 ≤ (n2 + n3) ≤ 4 , is R ₁₁ may be the same or is different from each of the case where n3 is 2.}

And a repeating unit represented by the following general formula (9):

(31)

(In the 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, n 4 is an integer of 1 to 3, is an integer of 2, n6 is an integer of 0 ~ 3, m2 is an integer of 1 ~ 500, 2 ≤ (n4 + n5) ≤ 4 , and, R ₁₂ in the case where n5 is 2 and may be the or different in the same respectively , and R &lt; ₁₃ &gt; when n6 is 2 or 3 may be the same or different.

Is contained in the same resin skeleton.

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 units in the parentheses in the structure represented by the general formula (8) and the repeating units in the parentheses in the structure represented by the general formula (9) are random, As shown in FIG. m1 and m2 are each independently an integer of 1 to 500 from the viewpoints of alkali solubility and elongation of the cured product, and the lower limit value is preferably 2, more preferably 3, and the upper limit value is preferably 450, 400, and more preferably 350. From the viewpoints of the toughness of the film after curing and the heat melting property, m1 and m2 are preferably independently from each other, and from the viewpoint of solubility in an aqueous alkali solution, it is preferable that m1 and m2 are 450 or less.

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 higher the molar ratio of the structure represented by the general formula (8) The film has good physical properties, is excellent in heat resistance and heat melting property, and the higher the molar ratio of the structure represented by formula (9), the better the alkali solubility and the better the pattern shape after curing. Accordingly, m ₁ : m ₂ = 90: 10 to 20: 80 is preferable in view of the physical properties of the film after curing, and m (m ₂ ) is preferably within the range of the ratio of the structure represented by formula (8) ₁ : m ₂ = 80: 20 to 40:60 are more preferable from the viewpoints of physical properties of the film after curing, alkali solubility and heat melting property, and m ₁ : m ₂ = 70:30 to 50:50, , Pattern shape, alkali solubility and heat melting property.

Typically, the phenol resin (A) is a compound having a phenol compound and a copolymerization component, specifically, a compound having an aldehyde group (including a compound that decomposes to produce an aldehyde compound such as trioxane), a compound having a ketone group, One or more compounds selected from the group consisting of a compound having two ortho groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule, and more typically, Can be synthesized by polymerization reaction. For example, an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, or a halo (meth) acrylate compound may be added to a phenol and / or phenol derivative (hereinafter collectively referred to as "phenol compound" A phenol resin (A) can be obtained by polymerizing a copolymerizable component such as an alkyl compound. In this case, in the general formula (1), the moiety represented by the structure in which the OH group and any R ₁ group are bonded to the aromatic ring is derived from the phenol compound, and the moiety represented by X is derived from the copolymerization component. From the viewpoint of reaction control and stability of the obtained phenol resin (A) and photosensitive resin composition, the injection molar ratio (phenol compound: copolymer component) of the phenol compound and the copolymer component is preferably 5: 1 to 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, and even more preferably 2,000 to 50,000. From the viewpoint of elongation of the cured film, the weight average molecular weight is preferably 700 or more. On the other hand, the weight average molecular weight is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

The weight average molecular weight can be calculated by a gel permeation chromatography (GPC) and a calibration curve prepared using standard polystyrene.

In the present embodiment, examples of the phenol compound which can be used for obtaining the phenol resin (A) include cresol, ethyl phenol, propyl phenol, butyl phenol, amyl phenol, cyclohexyl phenol, Nitrophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2, nitrophenol, 3-dicarboxyimide, N- (hydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboxyimide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, hydroxybenzoic acid Ethyl benzoate, ethyl benzoate, hydroxy benzoate benzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, , Hexylcatechol, benzyl But are not limited to, catechol, nitrobenzyl catechol, methyl resorcinol, ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate , Dihydroxybenzoic acid ethyl, dihydroxybenzoic acid butyl, dihydroxybenzoic acid propyl, dihydroxybenzoic acid benzyl, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, di (Dihydroxyphenyl) -5-norbornene-2,3-dicarboxyimide, N- (dihydroxyphenyl) -5-methyl-5-norbornene-2,3 And a pharmaceutically acceptable salt thereof selected from the group consisting of -dicarboximide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol , Trifluoromethylreso But are not limited to, benzoic acid, cyano, pyrogallol, fluoroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, butyl trihydroxybenzoate, Benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzonitrile, and the like.

The aldehyde compounds include, for example, acetaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutylaldehyde, benzaldehyde, Oxalic acid, 5-norbornene-2-carboxyaldehyde, malonaldialdehyde, succinodialdehyde, 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, and 2,2-bis (4-oxocyclohexyl) propane.

Examples of the methylol compound include 2,6-bis (hydroxymethyl) -p-cresol, 2,6-bis (hydroxymethyl) -4-ethylphenol, 2,6- Butylphenol, 2,6-bis (hydroxymethyl) -4-t-butylphenol, 2,6-bis (hydroxymethyl) Bis (hydroxymethyl) -4-methoxyphenol, 2,6-bis (hydroxymethyl) -4-ethoxyphenol, 2,6- (Hydroxymethyl) -4-n-butoxyphenol, 2,6-bis (hydroxymethyl) -4-t-butoxyphenol, 1,3-bis (hydroxymethyl) urea, ribitol, (Hydroxymethyl) butyric acid, 2-benzyloxy-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2- 2-nitro-1,3-propanediol, 5-norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol, penta Erythritol, 2-phenyl-1,3-propanediol, trimethylene Dihydroxydecane, 1,12-dihydroxydodecane, 1, 2-nitro-p-xylylene glycol, Bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexene, 1,6-bis (Hydroxymethyl) naphthalene, 2,6-bis (hydroxymethyl) -1,4-dimethoxybenzene, 2,3-bis (Hydroxymethyl) anthracene, 2,2'-bis (hydroxymethyl) diphenyl ether, 4,4'-bis (hydroxymethyl) diphenyl ether, (Hydroxymethyl) benzophenone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl, 4-hydroxymethylbenzoic acid-4'-hydroxymethylanilide, 4, 4'-bis (hydroxymethyl) phenylurea, 4,4'-bis (Hydroxymethyl) aniline, 4,4'-bis (hydroxymethyl) biphenyl, 2,2'-dimethyl-4,4'-bis Diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and the like can be given as examples of the polyhydric alcohols such as 2,2-bis (4-hydroxymethylphenyl) propane, ethylene glycol, have.

Examples of the alkoxymethyl compound include 2,6-bis (methoxymethyl) -p-cresol, 2,6-bis (methoxymethyl) -4-ethylphenol, 2,6- Butylphenol, 2,6-bis (methoxymethyl) -4-t-butylphenol, 2,6-bis (methoxymethyl) Bis (methoxymethyl) -4-methoxyphenol, 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6- Methoxymethyl) -4-n-butoxyphenol, 2,6-bis (methoxymethyl) -4-t-butoxyphenol, 1,3-bis (methoxymethyl) urea, 2,2- Bis (methoxymethyl) butyrate, 2,2-bis (methoxymethyl) -5-norbornene, 2,3- Bis (methoxymethyl) cyclohexane, 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxy) Methyl) benzene, 2,6-bis (methoxymethyl) -1,4-dimethoxybenzene, 2,3-bis (methoxymethyl) naphthalene, 2,6- Bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl ether, 4,4'-bis 4-methoxymethylbenzophenone, 4'-methoxymethylbenzophenone, 4'-methoxymethylbenzophenone, 4'-methoxymethylbenzophenone, 4'- Bis (methoxymethyl) anthracene, 4,4'-bis (methoxymethyl) phenylurea, 4,4'- (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, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether. Can.

Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrylate, Cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, methylcyclohexadiene, cyclohexadiene, cyclohexadiene, cyclohexadiene, Norbornene, 5-vinylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinylidene-2-norbornene, Norbornene, cyanuric acid triallyl, isocyanuric acid diallyl, isocyanuric acid triallyl, isocyanuric acid diallylpropionate and the like.

The haloalkyl compounds include, for example, xylylene dichloride, bischloromethyldimethoxybenzene, bischloromethylduren, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicar (Chloroethyl) ether, diethyleneglycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether, diethyleneglycol bis ) Ether, tetraethylene glycol bis (chloroethyl) ether, and the like.

The phenol resin (A) can be obtained by condensing the above-described phenol compound and the copolymerization component with dehydration, dehydrohalogenation, or alcohols, or polymerizing the unsaturated bond while cleavage. A catalyst may be used in the polymerization of the phenol compound and the copolymerization component.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfuric acid, acetic acid, oxalic acid, -Diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride-phenol complex, boron trifluoride-ether complex, and the like.

Examples of the alkaline catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, Diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Methylene tetramine and the like.

In the present embodiment, the amount of the catalyst used for obtaining the phenol resin (A) is preferably the total number of moles of the copolymerizable components, preferably the total number of moles of the copolymerizable components, But it is preferably in the range of 0.01 mol% to 100 mol% with respect to 100 mol% of the molar amount.

When the synthesis reaction of the phenol resin (A) is carried out, an organic solvent may be used if necessary. Specific examples of the organic solvent that can be used include, but are not limited to, bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene,? -Butyrolactone, N-methyl-2-pyrrolidone and the like. The amount of these organic solvents to be used is generally 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 raw material for injection is 100 parts by mass. In the synthesis reaction of the phenol resin (A), the reaction temperature is preferably from 40 to 250 ° C, more preferably from 100 to 200 ° C, and the reaction time is from about 1 to 10 Hour.

The phenol resin (A) can be obtained by copolymerizing a phenol compound which is not a raw material of the structure of the general formula (1) within the range that does not impair the effect of the present invention, Or 30% or less of the total number of moles of the phenol compound.

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 phenol resin (A ') may be mixed with the phenol resin (A).

The mixing ratio of the phenol resin (A) to the phenol resin (A ') is preferably in the range of (A) / (A') = 10/90 to 90/10 by mass ratio. (A) / (A ') = 10/90 to 90/10 in view of the solubility in an aqueous alkali solution and the elongation of the cured film, and (A) / (A') = 20 / More preferably 80 to 80/20, and still more preferably (A) / (A ') = 30/70 to 70/30.

The novolac resin can be obtained by condensation of phenols and formaldehyde in the presence of an acidic catalyst. Examples of the phenol include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, Phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, alpha -naphthol, beta -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 novolac resin, and the like.

As the polyhydroxystyrene resin, polyparabinyl phenol is preferable. The polyparabinylphenol is not particularly limited as long as it is a polymer containing parabinol phenol as a polymerization unit. The polymerization unit other than the paravinylphenol which can form the polyparabinylphenol may be any compound copolymerizable with the para-vinylphenol, as long as it is against the object of the present invention. Examples of the compound copolymerizable with para-vinylphenol include methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, 2-ethoxyethyl methacrylate, t-butyl acrylate , 1,5-pentanediol diacrylate, N, N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1,3-propanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate Acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylol propane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2- Hydroxyphenyl) -propanedimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2-2-di (p-hydroxyphenyl) -propane dimethacrylate, Ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyoxypropyl trimethylol propane triacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, butylene glycol dimethacrylate , 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate Acrylate, 1-phenylethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol Esters of acrylic acid, such as dimethacrylate; Styrene and substituted styrenes such as, for example, 2-methylstyrene and vinyltoluene; Vinyl esters such as vinyl acrylate and vinyl methacrylate; Vinyl phenols other than para-vinyl phenol, such as orthovinyl phenol and methvinyl phenol; , And the like, but are not limited thereto.

The weight average molecular weight of the phenol resin (A ') (that is, the phenol resin selected from the group consisting of the novolac resin and the polyhydroxystyrene resin) is preferably 700 to 100,000, more preferably 1,500 to 80,000, More preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of elongation of the cured film, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

The phenolic resins selected from the group consisting of novolac resins and polyhydroxystyrene resins may be used alone or in combination of two or more.

[Photo acid generator (B)]

In the present embodiment, the photosensitive resin composition is a composition capable of forming a resin pattern by being sensitive to an actinic ray (i.e., radiation) typified by ultraviolet rays, electron rays, X-rays and the like. The photosensitive resin composition may be either of a negative type (that is, a non-irradiated portion is eluted by development) or a positive type (that is, an irradiated portion is eluted by development).

In the present embodiment, when the photosensitive resin composition is used as a negative-type photosensitive resin composition, the photoacid generator (B) is irradiated with radiation to generate an acid, and the resulting acid undergoes a crosslinking reaction between the phenol resin (A) Thereby causing the irradiation part to become insoluble in the developer. Examples of the photoacid generator (B) usable in the negative type include the following compounds:

(i) trichloromethyl-s-triazine

Bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) Triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- Trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) Bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) -bis ) Bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) (4,6-trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis -Methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxy- beta -styryl) -bis (4,6-trichloro Methyl) -s- (4-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- , 6-trichloromethyl) -s-triazine, 2- (2-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine and the like;

(ii) diaryl iodonium salts

Diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrafluoroarsenate, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium trifluoroacetate, diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrafluoroborate, Phenyl iodonium p-toluenesulfonate, 4-methoxyphenyl phenyliodonium tetrafluoroborate, 4-methoxyphenyl phenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyl iodonium hexafluoroarsenate 4-methoxyphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, bis (4- iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate , Bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate and the like;

(iii) triarylsulfonium salts

Triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium hexafluorophosphate, Methoxyphenyldiphenylsulfonium hexafluorophosphate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoro 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4- Phenylthiophenyldiphenyl tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphate, 4-phenylthiophenyldiphenyl hexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfo Nate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, and the like.

Among these compounds, trichloromethyl-s-triazine derivatives include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-.beta.- -Styryl) -bis (4,6-trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) Do.

Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodide Trifluoroacetic acid and the like are preferable.

Examples of the triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfoniumtrifluoro Acetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, and the like are preferable.

In addition, as the photo acid generator (B), the following compounds may be used.

(1) diazoketone compound

Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, and a diazonaphthoquinone compound. Specific examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds of phenols.

(2) Sulfone compound

Examples of the sulfone compound include? -Ketosulfone compounds,? -Sulfonyl sulfone compounds, and? -Diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenacylsulfonyl) methane, and the like.

(3) Sulfonic acid compound

As the sulfonic acid compound, for example, alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates and the like can be given. Specific preferred examples of the sulfonic acid compound include benzoin tosylate, pyrogallol tris trifluoromethanesulfonate, o-nitrobenzyltrifluoromethanesulfonate, o-nitrobenzyl-p-toluenesulfonate, and the like .

(4) Sulfonimide compound

As sulfonimide compounds, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) Diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) Imide, and the like.

(5) Oxime ester compound

Specific examples of the oxime ester compound include 2- [2- (4-methylphenylsulfonyloxyimino)] - 2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals Inc., trade name "Irgacure PAG121" 2- (2-methylphenyl) acetonitrile (available from Ciba Specialty Chemicals, Inc. under the trade designation "Irgacure PAG103" (Irgacure PAG108 &quot; by Specialty Chemicals Inc.) and? - (n-octanesulfonyloxyimino) -4-methoxybenzyl cyanide (CGI725 by Ciba Specialty Chemicals).

(6) Diazomethane compound

Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane and the like.

From the viewpoint of sensitivity, the oxime ester compound (5) is particularly preferable.

In the present embodiment, when the photosensitive resin composition is a negative type, the compounding amount of the photoacid generator (B) relative to 100 parts by mass of the phenol resin (A) is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass desirable. When the amount is less than 0.1 part by mass, the effect of improving the sensitivity can be satisfactorily obtained. When the amount is less than 50 parts by mass, the mechanical properties of the cured film are good.

In the present embodiment, the photosensitive resin composition may be used as a positive photosensitive resin composition. In this case, photoacid generators and / or quinone diazide compounds represented by the above (i) to (iii) and (1) to (6) are used. Among them, a quinone diazide compound is preferable from the viewpoint of physical properties after curing. This is because the quinone diazide compound is pyrolyzed at the time of curing and the amount remaining in the film after curing is very low. Therefore, the positive-type photo acid generator (B) is preferably a quinone diazide compound.

As the quinone diazide compound, a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure (a compound having the latter structure, hereinafter also referred to as an "NQD compound" . These compounds are described in, for example, U.S. Patent No. 2,772,972, U.S. Patent No. 2,797,213, U.S. Patent No. 3,669,658, and the like. The NQD compound is a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a compound having a plurality of phenolic hydroxyl groups (hereinafter also referred to as &quot; polyhydroxy compound &quot; And 1,2-naphthoquinonediazide-5-sulfonic acid ester of the compound.

The NQD compound can be obtained by converting naphthoquinone diazidesulfonic acid with sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method and then condensing the resulting naphthoquinonediazide sulfonyl chloride with a polyhydroxy compound . For example, a predetermined amount of a polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinone diazide-4-sulfonyl chloride is dissolved in dioxane, acetone , Or tetrahydrofuran in the presence of a basic catalyst such as triethylamine to effect esterification, washing the obtained product with water and drying.

Examples of the NQD compound preferable from the viewpoint of physical properties of the cured film such as sensitivity and elongation are the following general groups:

(32)

(Wherein Q represents a hydrogen atom or a group represented by the following formula:

(33)

, All Q's may not be hydrogen atoms at the same time. &Lt; tb &gt; &lt; TABLE &gt;

.

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 may be used, or 4-naphthoquinone di A zidosulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be mixed and 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 a positive type is preferably 0.1 to 70 parts by mass, more preferably 0.1 to 70 parts by mass, per 100 parts by mass of the phenol resin (A) 1 to 40 parts by mass, and more preferably 5 to 30 parts by mass. When the amount is 0.1 part by mass or more, good sensitivity is obtained, and when 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 and hydrocarbons, and examples thereof include N-methyl- The solvent is preferably selected from the group consisting of N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, , Butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate,? -Butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, tert- Butyl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene and the like can be used. Among them, gamma -butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, and the like are preferable from the viewpoints of solubility of the resin, stability of the resin composition, adhesion to the substrate, thermal melting property, storage stability, Among them, gamma -butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, and the like are preferable. Don, and dimethylsulfoxide are particularly preferred.

[Silicone-type Surfactant (D)]

The silicon type surfactant is a surfactant having in its molecule a siloxane bond and a silicon-carbon bond. Examples thereof include dimethylsiloxane ethyleneoxy graft compounds, dimethylsiloxane propylene oxide graft compounds, (hydroxyethylene oxypropyl) methylsiloxane-dimethylsiloxane compounds, and the like.

Specific examples of the silicone type surfactant include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (trade name, SILWET L-77, L-7001, FZ-190, SH-190, SH-193, SZ-6032, SF-8428, DC- DBE-814, DBE-224, DBE-621, CMS-626, CMS-625, FZ-2164, FZ-2164, FZ- KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378 and BYK-333 (Trade name, manufactured by Chemie Japan), and Glanol (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.). Among these, dimethylsiloxane ethyleneoxy graft compound and dimethylsiloxane propyleneoxy graft compound are preferable from the viewpoint of coating property of the composition varnish. These silicone surfactants may be used singly or in combination of two or more.

The amount of the silicone type surfactant (D) to be used is preferably 0.01 to 30 parts by mass, more preferably 0.02 to 10 parts by mass, per 100 parts by mass of the phenol resin (A) from the viewpoint of the applicability of the composition varnish to the support Do. When the amount of the silicone type surfactant (D) used is less than 30 parts by mass, it is possible to suppress residue at the time of developing and pattern peeling.

[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 promoter, and the like, if necessary.

The crosslinking agent (E) is a compound capable of crosslinking with the phenol resin (A) when heat-curing a relief pattern formed using the photosensitive resin composition according to the present embodiment, or the crosslinking agent itself forms a crosslinking network. The crosslinking agent (E) is not limited as long as it is a thermally crosslinkable compound. Generally, the crosslinking agent can further improve thermal characteristics, mechanical properties, and chemical resistance of a cured film formed of a photosensitive resin composition, having two or more crosslinking groups in the molecule.

Examples of the crosslinking agent (E) include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300, Mycot 102, 105 (manufactured by Mitsui Cytec), NIKARAK (registered trademark) MX-270, -280, -290, DML-OPC, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-OXP, MS-11, NIKARAK MW-30, -100, -300, -390, DML-PSBP, DML-PTBP, DMLPCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC- BP, TMOM-BPA and TML-BPAF-MF (all manufactured by Honshu Chemical Industry Co., Ltd.), benzene dimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) Ether, bis (hydroxymethyl) benzophenone, hydroxymethylbenzyl hydroxymethylbenzoate, bis (hydroxymethyl) biphenyl, dimethyl bis (Methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis Phenol, methoxymethylbenzyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, and the like.

Examples of the crosslinking agent (E) include oxirane compounds such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylaniline type epoxy resin , 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) ethane tetraglycidyl ether, glycerol triglycidyl ether, ortho-secondary butyl (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001 , NC-3000H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000 and EOCN-4600 (trade names, Epikote (registered trademark) 1001, Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote 1031S, Epikote 180S65, Epikote 157H70, and YX-315 manufactured by Nippon Kayaku Co., (Trade names, manufactured by Daicel Chemical Industries, Ltd.), Epiclon (registered trademark) 830, 850, and 850 available from Japan Epoxy Resin Co., Ltd., EHPE3150, Fraxel G402, PUE101, and PUE105 EX-201, N-680, N-690, N-695, N-770, HP-7200, HP-820 and EXA-4850-1000 (trade names, , EX-251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX- (Trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like, and the like can be used.Can.

Examples of the crosslinking agent (E) include 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4'- (Registered trademark) 17B-60PX (trade name, manufactured by Mitsui Chemicals), N-methylpyrrolidone (trade name) manufactured by Mitsui Chemicals, Inc.), isophorone diisocyanate, hexamethylene diisocyanate, , TPA-B80E, MF-B60X, MF-K60X and E402-B80T (all trade names, manufactured by Asahi Chemical Industry Co., Ltd.).

Examples of the crosslinking agent (E) include 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3, Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2 , 2,4-trimethylhexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI -6000 and BMI-8000 (all trade names, manufactured by OWA Chemical Industry Co., Ltd.).

When the crosslinking agent (E) is used, the blending amount is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass, per 100 parts by mass of the phenol resin (A). When the blending amount is 0.1 parts by mass or more, the thermosetting film has good thermal properties and mechanical strength, and when it is 40 parts by mass or less, the stability of the composition in the varnish state and elongation of the thermosetting film are good.

The thermal acid generator is preferably incorporated in the resin composition from the viewpoint of exhibiting thermal properties and mechanical properties of a good cured product even when the curing temperature is lowered.

Examples of the thermal acid generator include, but are not limited to, allyl chloroacetate, n-butyl chloroacetate, t-butyl chloroacetate, ethyl chloroacetate, methyl chloroacetate, benzoyl chloroacetate, Propyl chloroformate, 2-methoxyethyl chloroacetate, methyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, 2-ethoxyethyl trichloroacetate, t-butyl cyanoacetate, t-butyl methacrylate, Butyl acetate, methyl trifluoroacetate, phenyl trifluoroacetate, vinyl trifluoroacetate, isopropyl trifluoroacetate, allyl trifluoroacetate, ethyl benzoate, methyl benzoate, t-butyl benzoate, methyl 2-chlorobenzoate , Ethyl 2-chlorobenzoate, ethyl 4-chlorobenzoate, ethyl 2,5-dichlorobenzoate, 2,4-dichloro A carboxylic acid ester such as methyl benzoate, ethyl p-fluorobenzoate, methyl p-fluorobenzoate, t-butyl pentachlorophenylcarboxylate, methyl pentafluoropropionate, ethyl pentafluoropropionate and t- Ryu; Cyclic carboxylic acid esters such as phenolphthalein and thymolphthalein; Methyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, 2-isopropoxyethyl methanesulfonate, phenyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, Propyl p-toluenesulfonate, n-butyl p-toluenesulfonate, n-hexyl p-toluenesulfonate, n-heptyl p-toluenesulfonate, n-octyl p- 2-methoxyethyl p-toluenesulfonate, propargyl p-toluenesulfonate, 3-butynyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, ethyl perfluorobutanesulfonate, (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluorophosphate, trimethylsulfonium methylsulfate, tri- p-sulfonium trifluoromethanesulfonate, trimethylsulfonium tri A perfluoro methane sulfonate, pyridinium -p--toluenesulfonate, sulfonic acid esters such as ethyl perfluoro octane sulfonic acid and the like; Cyclic sulfonic acid esters such as 1,4-butane sultone, 2,4-butane sultone, 1,3-propane sultone, phenol red, bromocresol green and bromocresol purple; Aromatic carboxylic acid anhydrides such as 2-sulfobenzoic acid anhydride, p-toluenesulfonic acid anhydride, and phthalic anhydride.

When the thermal acid generator is used, the amount is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 10 parts by mass, further preferably from 1 to 5 parts by mass, per 100 parts by mass of the phenol resin (A). When the blending amount is 0.1 parts by mass or more, the effect of maintaining the pattern shape after heat curing is good. On the other hand, when the blending amount is 30 parts by mass or less, there is no adverse effect on the lithography performance and the stability of the composition is good.

Examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (trade name: KBM803, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Syllace S810 manufactured by Chisso Co., Ltd.), 3-mercaptopropyltriethoxysilane 3-mercaptopropylmethyldimethoxysilane (trade name: LS1375, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: SIM6474.0, manufactured by Ajax Co., Ltd.), mercaptomethyltrimethoxysilane (Trade name: SIM6473.5C), mercaptomethyl methyldimethoxysilane (trade name: SIM6473.0, manufactured by Ajax Co., Ltd.), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane , 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxy Silane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercapto Mercaptoethyltrimethoxypropyltrimethoxysilane, ethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., (3-trimethoxysilylpropyl) urea (manufactured by Ajax Co., Ltd .: SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea , N- (3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) ) Urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- N- (3-trimethoxysilylethyl) urea, N- (3-trimethoxysilylethyl) urea, N- N- (3-methoxydipropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- N- (3-triethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, 3- Aminophenyltrimethoxysilane (trade name: SLA0599.0, manufactured by Asmax Co., Ltd.), p-aminophenyltrimethoxysilane (manufactured by Asmax Co., Ltd., trade name: SLA0598.0) Manufacture (Trimethoxysilylethyl) pyridine (trade name: SIT8396.0, manufactured by Ajax Co., Ltd.), 2- (trimethylsilylethyl) pyridine (trade name: SLA0599.1), aminophenyltrimethoxysilane (trade name: SLA0599.2, (3-triethoxysilylmethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, N-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-n-butoxysilane, tetraisopropylsilane, , Tetra-t-butoxy silane, tetrakis (methoxyethoxy silane), tetrakis (methoxy n-propoxy silane), tetrakis (ethoxyethoxy silane), tetrakis (methoxyethoxy (Trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) Bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (tri (Pentadionate) titanium-O, O'-bis (oxy) silane, di-t-butoxy diacetoxysilane, di- Ethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilane diol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol , n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propyl Butylphenylsilane, methylphenylsilanol, phenylphenylsilanol, ethylphenylphenylsilanol, phenylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, Diphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol and the like. These may be used singly or in combination.

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

(34)

Are preferred.

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

As the dissolution promoting agent, a compound having a hydroxyl group or a carboxyl group is preferable. Examples of the compound having a hydroxyl group include a ballast agent used in the naphthoquinone diazide compound described above and a cyclic phenol compound such as para-cumylphenol, bisphenol, resorcinol, and MtrisPC, MtetraPC, TrisP-HAP (All manufactured by Honshu Chemical Industry Co., Ltd.) such as TrisP-PHBA and TrisP-PA, 2 to 5 phenol substituents of diphenylmethane, 1 to 5 phenol substituents of 3,3-diphenylpropane, 2 , A compound obtained by reacting 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane with 5-norbornene-2,3-dicarboxylic anhydride in a molar ratio of 1: 2, Amino-4-hydroxyphenyl) sulfone and 1,2-cyclohexyldicarboxylic anhydride in a molar ratio of 1: 2, a compound obtained by reacting N-hydroxysuccinic acid imide, N-hydroxyphthalic acid imide, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, and the like. Examples of the compound having a carboxyl group include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy- -Methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid,? -Methoxyphenylacetic acid, O-acetylmandelic acid and itaconic acid.

When the dissolution promoter is used, the blending amount is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the phenol resin (A).

[Photosensitive resin composition comprising polyimide precursor and / or alkali-soluble polyimide]

(A) a polyimide precursor

Examples of the photosensitive resin used in the polyimide precursor composition include polyamide, polyamide acid ester, and the like. For example, as the polyamide acid ester, a compound represented by the following general formula (11):

(35)

(In the formula (11), R ¹ and R ² each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, a monovalent organic group having a carbon-carbon unsaturated double bond, X ¹ is a tetravalent organic group; Y ¹ is a divalent organic group; m is an integer of 1 or more; and m is preferably 2 or more, and more preferably 5 or more. }

A polyamide acid ester containing a repeating unit represented by the following general formula (1) can be used.

When R ¹ and R ² in the general formula (11) exist as a monovalent cation, O has a negative charge (that is, exists as -O-). X ¹ and Y ¹ may contain a hydroxyl group.

R ¹ and R ² in the general formula (11) are more preferably those represented by the following general formula (12):

(36)

(In the 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):

(37)

(In the 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.

Is a structure having an ammonium ion at the end of a monovalent organic group represented by the formula

A plurality of polyamic acid esters represented by the general formula (11) may be mixed. Polyamide acid esters obtained by copolymerizing polyamide acid esters represented by the general formula (11) may also be used.

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

(38)

[Chemical Formula 39]

(40)

(In the formula (4), R ₉ represents an oxygen atom, a sulfur atom or a divalent organic group.)

Is a tetravalent organic group containing at least one structure represented by the formula

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 is represented by the following general formula (5):

(41)

Is a tetravalent organic group containing a structure represented by the formula

Y ¹ in the 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 is a group represented by the following general formulas (6) to (8):

(42)

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

(43)

(In the formula (7), R ₁₄ to R ₂₁ are each a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 5 carbon atoms, and may be the same or different.}

(44)

(In the formula (8), R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different.}

Is a divalent organic group containing at least one structure represented by the formula

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 preferably a compound represented by the following general formula (9):

[Chemical Formula 45]

Is particularly preferably a divalent organic group containing a structure represented by the formula

In the polyamide 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.

Examples of the tetracarboxylic acid dianhydride used as the raw material include, but are not limited to, anhydrous pyromellitic acid, 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 dianhydride, diphenylmethane-3,3 ', 4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4-anhydrophthalic acid) propane, 2,2-bis 3,4-anhydrophthalic 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 the raw material include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diamino di Phenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'- Diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4 ' Diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) Biphenyl, 4,4-bis (3-aminophenoxy ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- Bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2- Propane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, 1,4- -Aminopropyldimethylsilyl) benzene, ortho-toluidine sulfone, and 9,9-bis (4-aminophenyl) fluorene. Or a part 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), a method in which a tetracarboxylic acid diester obtained by subjecting an esterification reaction of a tetracarboxylic acid dianhydride described later to a condensation reaction with a diamine is used .

The alcohols used in the esterification reaction of the tetracarboxylic dianhydride are alcohols having an olefinic double bond and specifically include 2-hydroxyethyl methacrylate, 2-methacryloyloxyethyl alcohol, glycerin di Acrylate, glycerin dimethacrylate, and the like, but are not limited thereto. These alcohols may be used alone or in combination of two or more.

As a specific method for synthesizing the polyamide acid ester (A) used in the present embodiment, conventionally known methods can be employed. As for the synthesis method, for example, the method described in WO 00/43439 pamphlet can be mentioned. That is, the tetracarboxylic acid diester is converted into a tetracarboxylic acid diester dicarboxylic acid salt, the tetracarboxylic acid diester dicarboxylic acid salt and diamine are subjected to condensation reaction in the presence of a basic compound to obtain a polyamic acid ester (A) . As a synthesis method, a method of producing a polyamide acid ester (A) by a method in which a tetracarboxylic acid diester and a diamine are provided in a condensation reaction in the presence of an organic dehydrating agent.

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

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

(B1) Photoinitiator

In the case of a negative type photosensitive resin, a photoinitiator is added to the resin composition. Examples of photoinitiators include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; Acetophenone derivatives such as 2,2'-diethoxyacetophenone, and 2-hydroxy-2-methylpropiophenone; Thioxanthone derivatives such as 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; Benzyl derivatives such as benzyl, benzyldimethyl ketal and benzyl- beta -methoxyethyl acetal; Benzoin derivatives such as benzoin methyl ether; Azide such as 2,6-di (4'-diazobenzal) -4-methylcyclohexanone, and 2,6'-di (4'-diazidobenzal) cyclohexanone; 2- (O-methoxycarbonyl) oxime, 1-phenylpropanedione-2- ( (O-ethoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-benzoyl) oxime, Oximes such as 3-ethoxypropanetri-on-2- (O-benzoyl) oxime; N-aryl glycines such as N-phenylglycine; Peroxides such as benzoyl peroxide; Aromatic biimidazoles; And titanocenes are used. Of these, oximes are preferred from the viewpoint of photosensitivity.

The amount of the photoinitiator to be added is preferably from 1 to 40 parts by mass, more preferably from 2 to 20 parts by mass, per 100 parts by mass of the polyamide acid ester (A). When the photoinitiator is added in an amount of 1 part by mass or more based on 100 parts by mass of the polyamide acid ester (A), the photosensitivity is excellent. Also, the addition of 40 parts by mass or less of the photoinitiator is excellent in the thick film curability.

(B2)

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 ray exposure portion, and the solubility of the exposed portion in an aqueous alkali solution is increased. As a result, the resin can be used as the positive photosensitive resin composition.

Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like. Among them, a quinone diazide compound is preferably used from the viewpoint of exhibiting an excellent dissolution inhibiting effect and obtaining a positive-working positive photosensitive resin composition. Two or more kinds of photoacid generators may be contained.

(C) Solvent

(C) The solvent is the same as the solvent described in the item [photosensitive resin composition containing phenol resin]. The kind and amount of the desired solvent are also the same as those described in the item [photosensitive resin composition containing phenol resin].

<Polyimide>

The structure of the cured relief pattern formed of the polyimide precursor composition is represented by the following general formula (1):

(46)

(In the formula (1), X ¹ , Y ¹ , and m may be the same as X ¹ , Y ¹ , and m defined in the formula (11), and for example, X ¹ is a tetravalent organic group , Y ¹ is a divalent organic group, and m is an integer of 1 or more.

Respectively.

Preferred X ¹ , Y ¹ , and m in the general formula (11) are also preferable for the polyimide represented by the general formula (1) for the same reason as described for the general formula (11).

In the case of an alkali-soluble polyimide, the terminal of the polyimide may be substituted with a hydroxyl group.

[Photosensitive resin composition containing polybenzoxazole precursor]

(A) a polybenzoxazole precursor

As the photosensitive resin used in the polybenzoxazole precursor composition, a compound represented by the following general formula (14):

(47)

(In the formula (14), U and V are each independently a divalent organic group.)

(O-hydroxyamide) containing a repeating unit represented by the following formula (1) can be used.

From the viewpoint of heat melting property, U in the formula (14) is preferably a divalent organic group having 1 to 30 carbon atoms, more preferably a chain alkylene group having 1 to 15 carbon atoms, provided that the hydrogen atom of the chain alkylene is substituted with a halogen atom More preferably a chained alkylene group having 1 to 8 carbon atoms and partially or wholly substituted with a fluorine atom.

From the viewpoint of heat melting property, V in the formula (14) is preferably a divalent organic group containing an aromatic group, more preferably a group represented by any one of the following formulas (6) to (8):

(48)

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

(49)

(In the formula (7), R ₁₄ to R ₂₁ are each a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 5 carbon atoms, and may be the same or different.}

(50)

(In the formula (8), R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different.}

Lt; 2 &gt;

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 represented by the following general formula (9):

(51)

Is particularly preferably a divalent organic group containing a structure represented by the formula

From the viewpoint of heat melting property, 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, particularly preferably a divalent chain aliphatic group having 1 to 20 carbon atoms .

The polybenzoxazole precursor can be generally synthesized from a dicarboxylic acid derivative and a hydroxyl group-containing diamine. Specifically, a polybenzoxazole precursor can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then carrying out a reaction 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, and the like which are used in the acid chloride-forming reaction of a common carboxylic acid can be used.

As a method of synthesizing a dichloride derivative, there are a method of reacting a dicarboxylic acid derivative with the halogenating agent in a solvent, a method of reacting in an excess of a halogenating agent, followed by distilling off an excess portion.

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-hexafluoro Propane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxy diphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis -Carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6- Ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-methylglutaric acid, 3-ethylglutaric acid, 3-methylglutaric acid, Adipic acid, octafluoro Adipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuveric acid, azelaic acid, But are not limited to, acid, hexadecafluorosevac acid, 1,9-nonanedic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, There may be mentioned acetic acid, acetic acid, hexanoic acid, hexanoic acid, hexanoic acid, hexanoic acid, heptanoic acid, heptanoic acid, heptanoic acid, heptanoic acid, Dodecanedioic acid, diglycolic acid, and the like. These may be mixed and used.

Examples of the hydroxyl group-containing diamine include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, 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. These may be mixed and used.

(B2)

The photoacid generator has a function of increasing the solubility of the alkali aqueous solution in the light irradiation portion. Examples of the photoacid generator include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like. Among them, diazonaphthoquinone compounds are preferable because of their high sensitivity.

(C) Solvent

(C) The solvent is the same as the solvent described in the item [photosensitive resin composition containing phenol resin]. The kind and amount of the desired solvent are also the same as those described in the item [photosensitive resin composition containing phenol resin].

<Polybenzoxazole>

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

(52)

(In the formula (10), U and V are the same as U and V defined in the general formula (14).

Respectively. Preferred U and V in the general formula (14) are also preferable for 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 contain at least one selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and may contain a phenol resin .

&Lt; Second Embodiment: Low-melt viscosity photosensitive layer roll &gt;

In the photosensitive layer roll according to the second embodiment of the present invention,

A support film,

A photosensitive layer containing the photosensitive resin composition formed on the support film

Wherein the photosensitive resin composition comprises 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.

Since the conventional photosensitive layer roll has a high melt viscosity of the photosensitive layer, cracks tend to occur even when slits are formed by heating the teeth of the slitter at the time of slitting.

In order to solve the above problems, the photosensitive layer roll according to the second embodiment is characterized in that the photosensitive layer is a layer having a temperature point at which the melt viscosity is 500 Pa · s or less.

The photosensitive layer related 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 at which the melt viscosity is 450 Pa · s or less, preferably a layer having a temperature point at which the melt viscosity is 400 Pa · s or less, and has a temperature point at 350 Pa · s or less Layer is preferably a layer having a temperature point of 300 Pa · s or less, preferably a layer having a temperature point of 250 Pa · s or less, and a layer having a temperature point of 200 Pa · s or less desirable. By lowering the melt viscosity of the photosensitive layer, it is possible to suppress the occurrence of cracks when the slits, particularly the teeth of the slitter, are slit by heating.

The photosensitive layer of the present 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 more preferably 350 Pa · s or less And is preferably 300 Pa · s or less, more preferably 250 Pa · s or less, more preferably 200 Pa · s or less, preferably 150 Pa · s or less, and preferably 100 Pa · s or less.

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

If a cover film is provided, a cover film is not provided or a cover film having a high softening temperature is preferably used because slits may be formed when the slits are heated and slit, particularly when the slits are heated Do.

The softening point temperature of the cover film is preferably 90 占 폚 or higher, more preferably 100 占 폚 or higher, 110 占 폚 or higher, 120 占 폚 or higher, and 130 占 폚 or higher. The material of the cover film is not particularly limited as long as it meets 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. The details will be described later. The other points are the same as those described in the above item <First embodiment: two-layer photosensitive layer roll>.

&Lt; Preparation and use of photosensitive layer roll &gt;

A method of manufacturing the photosensitive film according to this embodiment will be described.

The photosensitive layer can be formed by applying the above photosensitive resin composition as a liquid photosensitive resin composition on a support film.

Examples of the application 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 carried out, for example, by heating. From the viewpoint of the residual amount of the organic solvent in the photosensitive layer, the heating temperature is preferably about 70 to 150 占 폚, more preferably 100 to 140 占 폚, and / or the heating time is preferably Is about 1 minute to 30 minutes, more preferably about 3 minutes to 20 minutes, and more preferably about 4 minutes to 10 minutes.

The thickness of the photosensitive layer differs depending on the use, but it is preferable that the thickness after removal of the solvent is about 1 to 30 占 퐉. The photosensitive film may further include an intermediate layer or a cover film such as a cushion layer, an adhesive layer, a light absorbing layer, or a gas barrier layer between the support film and the photosensitive layer.

The photosensitive film can be stored in the form of a roll as a photosensitive layer roll, for example, by winding it on a core having a shape such as a cylindrical shape. The core is not particularly limited as long as it is conventionally used and examples of the core 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 to be the outermost side. It is preferable that a cross-section separator is provided on the end face of the photosensitive film (photosensitive film roll) rolled up in a rolled manner from the viewpoint of the cross-sectional protection, and it is preferable to provide the cross- Do. When wrapping the photosensitive film or the photosensitive layer roll, it is preferable to wrap the photosensitive film or the photosensitive layer roll in a black sheet having low moisture permeability.

<Slit of photosensitive layer roll>

The slit photosensitive layer roll can be produced by slitting the produced photosensitive layer roll with a desired width by a slitter.

From the viewpoint of suppressing wrinkles or cracks at the cut surface of the slitter, the teeth of the slitter are preferably heated. The heating temperature of the teeth of the slitter may be 80 ° C or higher, 90 ° C or higher, 100 ° C or higher, 110 ° C or higher, 120 ° C or 130 ° C or higher.

When the photosensitive layer roll is provided with a cover film, wrinkles may occur in the cover film at the time of slitting. In particular, when slits are formed by heating the teeth of the slitter, large wrinkles may occur in the cover film. From the viewpoint of suppressing the wrinkles of the cover film that occurs at the time of slitting, the method of manufacturing the slit photosensitive layer roll includes the following steps:

Peeling the cover film when the photosensitive layer roll has a cover film on the side opposite to the side of the photosensitive layer on which the support film is formed,

A step of slitting the photosensitive layer roll having no cover film with a slitter,

A step of attaching the peeled cover film or a cover film different from the peeled cover film to the slit sensitive layer roll

.

&Lt; Lamination of Photosensitive Layer on Substrate &gt;

As a method for laminating the photosensitive layer of the slit photosensitive layer roll on the substrate, a method of laminating the substrate with a pressure of about 0.1 to 1 MPa (i.e., about 1 to 10 kgf / cm 2) to the substrate while heating the photosensitive layer to about 70 to 130 캜 And a method of pressing them by using a press. The lamination step may be carried out 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 is likely to be stuck to the support film (there is a fear of blocking). On the other hand, when the tackiness of the photosensitive layer is lowered, there is a fear that the photosensitive layer is not closely contacted when the photosensitive layer is laminated on a substrate. That is, it is preferable that the two-layer photosensitive layer roll according to the first embodiment exhibits low adhesiveness at room temperature in a storage state and exhibits high adhesiveness at the time of heating when laminated on a substrate.

The amount of the residual organic solvent in the photosensitive layer is preferably from 0.1 mass% to 15 mass% with respect to the total amount of the photosensitive layer, more preferably from 0.3 mass% By mass to 15% by mass or more, more preferably 0.5% by mass or more and 15% by mass or less, more preferably 0.8% by mass or more and 15% Is preferably 14 mass% or less, more preferably 3 mass% or more and 13 mass% or less, and still more preferably 5 mass% or more and 13 mass% or less. When the amount of the residual organic solvent in the photosensitive layer is in the above range, the photosensitive layer is less likely to adhere to the support film when the photosensitive layer roll is manufactured because the adhesiveness at room temperature is low, and when the photosensitive layer is laminated on the substrate, And exhibits high adhesiveness.

The organic solvent remaining in the photosensitive layer may be the above-described solvent (C), and from the viewpoints of the solubility of the resin, the stability of the resin composition, the adhesion to the substrate, the heat melting property, the storage stability, Butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol are preferable. Of these, Lactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethylsulfoxide are particularly preferable.

Similarly, the low-melt viscosity photosensitive layer roll according to the second embodiment has a high melt viscosity at room temperature, low adhesiveness to the photosensitive layer, and low slit, particularly when the slits are heated and slit, It is desired to have a melt viscosity and hardly cause a crack. The amount of the residual organic solvent in the preferable photosensitive layer is the same as the above range. The melt viscosity of the photosensitive layer can be adjusted by the amount of the organic solvent contained in the photosensitive layer. The higher the amount of the organic solvent contained in the photosensitive layer, the lower the melt viscosity of the photosensitive layer. The amount of the organic solvent in the photosensitive layer can be controlled by adjusting the heating temperature and / or the heating time for removing the organic solvent. In addition, it is also possible to adjust the melt viscosity of the photosensitive layer by a method of lowering the molecular weight of the polymer, a method of increasing a low molecular weight component such as a plasticizer that does not harden, and the like.

In this manner, the photosensitive layer laminated on the substrate is irradiated with actinic ray through the negative or positive mask pattern to form an exposed portion. At this time, when the support existing on the photosensitive layer is transparent to the active ray, it is possible to irradiate the active ray through the support. If the support shows a light shielding property to the active ray, The active ray is irradiated.

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

Next, the development can be carried out by a method such as a dipping method, a puddle method, and a spray method using a developing solution. By the development, a relief pattern can be obtained by eluting and removing the exposed portion (in the case of the positive type) or the unexposed portion (in the case of the negative type) from the applied photosensitive resin layer.

Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, organic amines such as tetramethylammonium hydroxide, tetrabutylammonium Quaternary ammonium salts such as hydroxides and hydroxides, and if necessary, a water-soluble organic solvent such as methanol and ethanol, or an aqueous solution containing an appropriate amount of a surfactant. Among these, tetramethylammonium hydroxide aqueous solution is preferable. The concentration of tetramethylammonium hydroxide is preferably 0.5 to 10 mass%, more preferably 1 to 5 mass%.

After development, the substrate is cleaned with a rinsing liquid to remove the developer, thereby obtaining a substrate having a relief pattern formed thereon. As the rinsing liquid, for example, distilled water, methanol, ethanol, isopropanol and the like can be used, and they can be used alone or in combination of two or more kinds.

Finally, the cured relief pattern can be obtained by heating the thus obtained relief pattern. The heating temperature is preferably 150 占 폚 or higher and 300 占 폚 or lower, and more preferably 250 占 폚 or lower.

A method of manufacturing a cured relief pattern using the photosensitive layer roll according to the first or second embodiment is applicable to a semiconductor device, a display body device, a surface protective film of a light emitting device, an interlayer insulating film, an insulating film for rewiring, A protective film for a flip chip device, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper clad, a solder resist film, a liquid crystal alignment film and the like Lt; / RTI &gt;

The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments. The present invention can be modified in various ways without departing from the gist of the invention.

Example

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

[Synthesis Example 1]

&Lt; Synthesis of phenol resin (A-1) &gt;

(0.8 mol) of fluoroglucinol and 4,4'-bis (methoxymethyl) biphenyl (hereinafter also referred to as &quot; BMMB &quot;) were added in a separable flask equipped with a dean- g (0.5 mol), 3.9 g (0.025 mol) of diethylsulfuric acid, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70 DEG C to dissolve the solids.

The mixed solution was heated to 140 DEG C by an oil bath, the generation of methanol was confirmed from the reaction solution, and the reaction solution was stirred at 140 DEG C for 2 hours.

Next, the reaction vessel was cooled in the atmosphere, and another 100 g of tetrahydrofuran was added thereto and stirred. The reaction dilution was added dropwise to 4 L of water under high-speed stirring, and the resin was dispersed and precipitated. The resin was recovered, washed with water and dewatered appropriately, and vacuum dried to obtain a copolymer (phenol resin A-1)) was obtained in a yield of 70%.

[Synthesis Example 2]

&Lt; Synthesis of phenol resin (A-2) &gt;

Synthesis was carried out in the same manner as in Synthesis Example 1 except that 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate was used instead of the fluoroglucinol in Synthesis Example 1 to obtain methyl 3,5-dihydroxybenzoate / A copolymer (phenol resin (A-2)) comprising BMMB was obtained in a yield of 65%.

[Synthesis Example 3]

&Lt; Synthesis of phenol resin (A-3) &gt;

A separable flask equipped with a 1.0 L dean-stark apparatus was purged with nitrogen. Then, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB and 3.81 g (0.02 mol) and propylene glycol monomethyl ether (hereinafter also referred to as "PGME") (116 g) were mixed and stirred at 50 ° C to dissolve the solids.

The mixed solution was heated to 120 DEG C by an oil bath, the generation of methanol was confirmed from the reaction solution, and the reaction solution was stirred at 120 DEG C for 3 hours.

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 dissolved homogeneously, And the mixture was added dropwise to the separable flask over one hour. After dropwise addition, the mixture was further stirred for 2 hours.

After completion of the reaction, the same treatment as in Synthesis Example 1 was carried out to obtain a copolymer (phenol resin (A-3)) consisting of resorcinol / BMMB / 2,6-bis (hydroxymethyl) %.

[Synthesis Example 4]

&Lt; Synthesis of polyimide precursor (A-5) &gt;

In a separable flask having a capacity of 2 L, 87.2 g (0.4 mol) of pyromellitic dianhydride, 59.3 g (0.8 mol) of isobutyl alcohol and 320 g of? -Butyrolactone (hereinafter also referred to as "GBL" (25 占 폚), dissolved, and 63.3 g (0.8 mol) of pyridine was added thereto while stirring under ice-cooling. After exothermic heating, the mixture was cooled to room temperature and allowed to stand for 16 hours.

Next, a solution of 165 g (0.8 mol) of dicyclohexylcarbodiimide in 120 g of GBL was added to the separable flask for 40 minutes while stirring under ice-cooling. Subsequently, a suspension in which 74.5 g (0.37 mol) of 4,4'-diaminodiphenyl ether was suspended in 150 g of GBL was added to the separable flask for 60 minutes with stirring under ice-cooling. After stirring for 2 hours at room temperature, 30 ml of ethyl alcohol was added to the separable flask and stirred for 1 hour. Further, 250 ml of dimethylacetamide (hereinafter referred to as "DMAc") and 400 ml of tetrahydrofuran (THF) After the addition, the precipitate was removed by suction filtration to obtain a reaction solution. The obtained reaction solution was added to 15 L of ethyl alcohol, and the resulting precipitate was separated by filtration, followed by vacuum drying to obtain a polyimide precursor (A-5).

[Synthesis Example 5]

&Lt; Synthesis of polybenzoxazole precursor (A-6) &gt;

197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75.9 g (0.96 mol) of pyridine and 692 g of DMAc were added to a separable flask having a capacity of 2 L The mixture was stirred and dissolved at room temperature (25 DEG C).

A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride in 88 g of a separate dimethyldiglycol (hereinafter also referred to as "DMDG") was added to the obtained mixed solution from a dropping funnel . The time required for the dropping was 40 minutes, and the reaction temperature was 28 ° C at the maximum.

After the addition was completed, the reaction mixture by heating to 50 ℃ tangyok and, after stirring for 18 hours, subjected to the measurement of IR spectrum of the reaction solution, a characteristic absorption of deugi already in 1385 cm ^-1 and 1772 cm ^-1 indicated Respectively.

Next, the reaction solution was cooled to 8 캜 by 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 this reaction solution, Was added dropwise from a dropping funnel. The time required for the dropping was 80 minutes, and the reaction temperature was 12 ° C at the maximum.

After 3 hours from the completion of the dropwise addition, the reaction solution was added dropwise to 12 L of water under high-speed stirring to disperse and precipitate the polymer. The polymer was recovered, washed with water appropriately and dehydrated and vacuum dried to obtain polybenzoxazole precursor A-6).

&Lt; Resins (A) and (A ') &gt;

A-1: Copolymer composed of fluoroglucinol / BMMB, polystyrene reduced weight average molecular weight (Mw) = 15,000

A-2: Copolymer of methyl 3,5-dihydroxybenzoate / BMMB, weight average molecular weight (Mw) in terms of polystyrene = 21,000

A-3: Copolymer composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol, weight average molecular weight (Mw) in terms of polystyrene = 9,900

A-4: Novolak resin, weight average molecular weight (Mw) in terms of polystyrene = 10,600 (product name: EP-4080G,

A-5: Polyimide precursor

A-6: polybenzoxazole precursor

&Lt; Photo acid generator (B) &gt;

B-1: photoacid generator represented by the following formula:

(53)

{Wherein, 83% of Q is:

(54)

And the remainder is a hydrogen atom.

&Lt; Solvent (C) &gt;

C-1:? -Butyrolactone (GBL)

C-2: methyl ethyl ketone

C-3: Acetone

C-4: N, N-dimethylformamide

&Lt; Surfactant (D) &gt;

D-1: silicone type surfactant DBE821 (trade name, manufactured by Gelest)

D-2: silicone type surfactant DBE224 (trade name, manufactured by Gelest)

<Cross-linking agent (E)>

E-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (NIKARAK MX-270, manufactured by Sanwa Chemical Co., Ltd.)

[Preparation of Photosensitive Resin Composition]

The resin (A), the photoacid generator (B), the surfactant (D) and the crosslinking agent (E) were dissolved in the solvent (C) and filtered with a filter of 0.1 탆, Thereby preparing a positive photosensitive resin composition.

[Support film]

As a support film, a PET film &quot; PET25X &quot; (manufactured by LINTEC CORPORATION, width 290 mm, thickness 25 mu m) subjected to release treatment with a silicone compound was prepared.

[Production of Photosensitive Film]

(Example 1)

As the support film, a solution of the photosensitive resin composition having the composition shown in Table 1 was applied on the releasably treated surface by using &quot; PET25X &quot; Subsequently, the PET film coated with the solution of the photosensitive resin composition was dried by hot air at 120 캜 for 5 minutes to form a photosensitive layer. At that time, the thickness of the photosensitive layer after heating was made to be 10 占 퐉. A photosensitive film having a width of 300 mm in the above composition was applied to a cylindrical plastic tube having an outer diameter of 3.5 inches and a pressure roll placed parallel to the crimp width direction so as to apply a linear pressure to the plastic tube, To obtain a photosensitive film roll.

(Examples 2 to 13)

Each of the photosensitive film rolls was produced in the same manner as in Example 1, except that the components, composition, and drying conditions shown in Table 1 were used.

(Comparative Examples 1 to 3)

Except that the components, the composition and the drying conditions shown in Table 1 were used, and a cover film having a softening temperature of 90 ° C was formed on the photosensitive layer at the time of obtaining the photosensitive film roll, A film roll was produced.

<Amount of residual solvent>

The photosensitive film was taken out from the photosensitive film roll prepared in each of Examples and Comparative Examples, and the photosensitive layer was peeled off from the support film. The peeled photosensitive layer was analyzed by gas chromatography (trade name &quot; 6890N &quot;, manufactured by Agilent Technologies Inc.) , 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 taken out from the photosensitive film roll prepared in each of Examples and Comparative Examples, the photosensitive layer was peeled from the support film, and the peeled photosensitive layer was measured with a melt viscosity measuring apparatus (trade name &quot; &Quot; DHR-2 &quot;). Table 1 shows the melt viscosity at a temperature of 100 캜.

· Sample shape

   Film thickness: 0.5 mmt

   Diameter: 25 mm Disc

·Measuring conditions

   Starting temperature: 50 ° C

   Heating rate: 5 ° C / min

   End temperature: 220 ℃

   Variation: 0.1%

   Frequency: 1 Hz

   Load: 0.5 N (± 0.1 N)

<Storage stability>

After each of the photosensitive film rolls prepared in Examples and Comparative Examples was stored at room temperature (25 DEG C) for 1 month or more, the rolls were visually observed and evaluated according to the following criteria.

S (remarkably good): Even if stored at room temperature for one month or longer in the form of a roll, the photosensitive layer does not adhere to the back surface of the support film.

A (good): When stored at room temperature for one month in the form of a roll, a part of the photosensitive layer adheres to the back surface of the support film.

<Peelability of Support Film>

A photosensitive film was taken out from the photosensitive film roll prepared in each of Examples and Comparative Examples, and the photosensitive layer was laminated on a glass plate while being heated to 130 캜 to transfer a photosensitive layer. Then, 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 can be removed without attaching the photosensitive layer to the support film.

A (good): In a part of the photosensitive layer, the photosensitive film is peeled off with the photosensitive layer adhered to the support film.

B (defective): The photosensitive layer is peeled from the entire surface of the photosensitive layer with the photosensitive layer adhered to the support film.

<Crack at slit>

The photosensitive film roll prepared in each of Examples and Comparative Examples was slit with a slitter heated to 100 ° C. The occurrence of cracks at the time of slitting and the aesthetics of the cut surfaces were visually evaluated.

S (remarkably good): No cracks occur and the cut surface is smooth.

A (good): There is no crack, but the cut surface is slightly irregular.

B (poor): Cracks occurred.

<Wrinkles of cover film>

The photosensitive film roll produced in the comparative example was slit with a slitter having teeth heated to 100 DEG C and wrinkles generated in the cover film were visually evaluated.

A (Good): No wrinkles occur in the cover film.

B (poor): The cover film was wrinkled.

&Lt; Evaluation result &gt;

For each of the examples and comparative examples, the evaluation results of the respective characteristics are shown in Table 1 above.

Industrial availability

The photosensitive layer roll of the present invention can be applied to a semiconductor device, a display body device, and a surface protective film of a light emitting device, an interlayer insulating film, an insulating film for rewiring, a rewiring layer for a wafer level package, a protective film for a flip chip device, An interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad, a solder resist film, a liquid crystal alignment film, and the like.

Claims (40)

A support film,
A photosensitive layer formed on the support film and including a photosensitive resin composition,
As a photosensitive layer roll,
Wherein the photosensitive resin composition contains at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and the photosensitive layer has a melt viscosity of 500 Pa s or less The photosensitive layer being a layer having a temperature point at which the photosensitive layer is exposed. The method according to claim 1,
Wherein the photosensitive layer is a layer having a temperature point at which a melt viscosity is 350 Pa · s or less. 3. The method according to claim 1 or 2,
Wherein the photosensitive layer has a melt viscosity at 100 캜 of 500 Pa s or less. The method of claim 3,
Wherein the photosensitive layer has a melt viscosity at 100 캜 of 350 Pa s or less. 5. The method according to any one of claims 1 to 4,
Wherein the cover film has a cover film on the side opposite to the side where the support film is formed of the photosensitive layer and the softening temperature of the cover film is 90 DEG C or more. 6. The method of claim 5,
Wherein the softening temperature of the cover film is 110 DEG C or higher. 7. The method according to any one of claims 1 to 6,
Wherein the amount of the organic solvent contained in the photosensitive layer is 0.1% by mass or more and 15% by mass or less based on the total amount of the photosensitive layer. 8. The method of claim 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 method according to claim 7 or 8,
Wherein the organic solvent is at least one selected from the group consisting of? -Butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethylsulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol And at least one selected from the group consisting of the following. 10. The method of claim 9,
Wherein the organic solvent comprises at least one selected from the group consisting of? -Butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethylsulfoxide. 11. The method according to any one of claims 1 to 10,
Wherein the photosensitive resin composition comprises the polyimide precursor. 11. The method according to any one of claims 1 to 10,
Wherein the photosensitive resin composition comprises the polybenzoxazole precursor. 11. The method according to any one of claims 1 to 10,
Wherein the photosensitive resin composition comprises the soluble polyimide. 11. The method according to any one of claims 1 to 10,
Wherein the photosensitive resin composition comprises the phenolic resin. 15. The method of claim 14,
Wherein the phenol resin is represented by the following general formula (1):

(1) wherein a is an integer of 1 to 3, b is an integer of 0 to 3, 1? (A + b)? 4, and R ₁ is a monovalent organic group having 1 to 20 carbon atoms A halogen atom, a nitro group and a cyano group, and a plurality of R _{1 s} when b is 2 or 3 may be the same or different and X is an unsaturated bond A bivalent aliphatic group having 2 to 10 carbon atoms and a bivalent alicyclic group having 3 to 20 carbon atoms,

A divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula (2) wherein p is an integer of 1 to 10, and a divalent organic group having an aromatic ring.
As a repeating unit. 16. The method of claim 15,
Wherein X in the general formula (1) is a group represented by the following general formula (3):

(In the 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 carbon number formed by substituting a part or all of hydrogen atoms with a fluorine atom and 1-10 aliphatic monovalent, n1 is an integer of 0 ~ 4, n1 is the case of 1 to 4 integer, R ₆ is a halogen atom, a hydroxyl group, or a monovalent organic group, at least one R ₆ is A plurality of R &lt; ₆ &gt; s may be the same or different when n1 is an integer of 2 to 4,
And a divalent group represented by the following general formula (4):

Wherein 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 carbon number of a hydrogen atom partially or entirely substituted with a fluorine atom W represents a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, a monovalent aliphatic group having 1 to 10 carbon atoms, (2) :

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

Is a divalent organic group selected from the group consisting of a divalent group represented by the formula:
Is a divalent organic group selected from the group consisting of a divalent group represented by the following formula: 17. The method according to claim 15 or 16,
Wherein X in the general formula (1) is a group represented by the following formula (6):

Is a divalent organic group represented by the following formula (1). 18. The method of claim 17,
Wherein X in the general formula (1) is a group represented by the following formula (7):

Is a divalent organic group represented by the following formula (1). 19. The method according to any one of claims 15 to 18,
Wherein the phenolic resin is represented by the following general formula (8):

(In the 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, n3 is an integer of 0 to 2, m1 . is an integer of 1 ~ 500, 2 ≤ (n2 + n3) ≤ 4 , and, R ₁₁ may be the same in each case of n3 is 2 and or different} repeat shown in units, and the following general formula (9):

(In the 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, n 4 is an integer of 1 to 3, is an integer of 2, n6 is an integer of 0 ~ 3, m2 is an integer of 1 ~ 500, 2 ≤ (n4 + n5) ≤ 4 , and, R ₁₂ in the case where n5 is 2 and may be the or different in the same respectively , and R &lt; ₁₃ &gt; when n6 is 2 or 3 may be the same or different.
Is contained in the same resin skeleton. A support film,
A photosensitive layer formed on the support film and including a photosensitive resin composition,
As a photosensitive layer roll,
Wherein the photosensitive resin composition comprises at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and both surfaces of the support film are in contact with the photosensitive layer , Photosensitive layer roll. 21. The method of claim 20,
Wherein the amount of the organic solvent contained in the photosensitive layer is 0.1% by mass or more and 15% by mass or less based on the total amount of the photosensitive layer. 22. The method of claim 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 method of claim 21 or 22,
Wherein the photosensitive resin composition comprises the phenolic resin. 24. The method according to any one of claims 21 to 23,
Wherein the organic solvent is at least one selected from the group consisting of? -Butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethylsulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol And at least one selected from the group consisting of the following. 25. The method of claim 24,
Wherein the organic solvent comprises at least one selected from the group consisting of? -Butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethylsulfoxide. 26. The method according to any one of claims 20 to 25,
Wherein the photosensitive resin composition comprises the polyimide precursor. 26. The method according to any one of claims 20 to 25,
Wherein the photosensitive resin composition comprises the polybenzoxazole precursor. 26. The method according to any one of claims 20 to 25,
Wherein the photosensitive resin composition comprises the soluble polyimide. 26. The method according to any one of claims 20 to 25,
Wherein the photosensitive resin composition comprises a phenol resin. 30. The method of claim 29,
Wherein the phenol resin is represented by the following general formula (1):

(1) wherein a is an integer of 1 to 3, b is an integer of 0 to 3, 1? (A + b)? 4, and R ₁ is a monovalent organic group having 1 to 20 carbon atoms A halogen atom, a nitro group and a cyano group, and a plurality of R _{1 s} when b is 2 or 3 may be the same or different and X is an unsaturated bond A bivalent aliphatic group having 2 to 10 carbon atoms and a bivalent alicyclic group having 3 to 20 carbon atoms,

A divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula (2) wherein p is an integer of 1 to 10, and a divalent organic group having an aromatic ring.
As a repeating unit. 31. The method of claim 30,
Wherein X in the general formula (1) is a group represented by the following general formula (3):

(In the 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 carbon number formed by substituting a part or all of hydrogen atoms with a fluorine atom and 1-10 aliphatic monovalent, n1 is an integer of 0 ~ 4, n1 is the case of 1 to 4 integer, R ₆ is a halogen atom, a hydroxyl group, or a monovalent organic group, at least one R ₆ is A plurality of R &lt; ₆ &gt; s may be the same or different when n1 is an integer of 2 to 4,
And a divalent group represented by the following general formula (4):

Wherein 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 carbon number of a hydrogen atom partially or entirely substituted with a fluorine atom W represents a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, a monovalent aliphatic group having 1 to 10 carbon atoms, (2) :

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

Is a divalent organic group selected from the group consisting of a divalent group represented by the formula:
Is a divalent organic group selected from the group consisting of a divalent group represented by the following formula: 32. The method according to claim 30 or 31,
Wherein X in the general formula (1) is a group represented by the following formula (6):

Is a divalent organic group represented by the following formula (1). 32. The method of claim 32, wherein
Wherein X in the general formula (1) is a group represented by the following formula (7):

Is a divalent organic group represented by the following formula (1). 34. The method according to any one of claims 30 to 33,
Wherein the phenolic resin is represented by the following general formula (8):

(In the 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, n3 is an integer of 0 to 2, m1 is an integer from 1 to 500, and 2 ≤ (n2 + n3) ≤ 4 , is R ₁₁ may be the same or is different from each of the case where n3 is 2.}
And a repeating unit represented by the following general formula (9):

(In the 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, n 4 is an integer of 1 to 3, is an integer of 2, n6 is an integer of 0 ~ 3, m2 is an integer of 1 ~ 500, 2 ≤ (n4 + n5) ≤ 4 , and, R ₁₂ in the case where n5 is 2 and may be the or different in the same respectively , and R &lt; ₁₃ &gt; when n6 is 2 or 3 may be the same or different, both of which are within the same resin skeleton. A process for producing a slit photosensitive layer roll, wherein the photosensitive layer roll according to any one of claims 1 to 34 is slit into a slit to produce a slit photosensitive layer roll. 36. The method of claim 35,
Wherein the teeth of the slitter are heated. 37. The method of claim 36,
Wherein the teeth of the slitter are heated to 100 DEG C or higher. The following steps:
34. A process for producing a photosensitive film comprising the steps of peeling the cover film when the photosensitive layer roll according to any one of claims 1 to 34 has a cover film on the side opposite to the side on which the support film is formed of the photosensitive layer,
A step of slitting the photosensitive layer roll having no cover film with a slitter,
A step of attaching the peeled cover film or a cover film different from the peeled cover film to the slit photosensitive layer roll
Wherein the slit photosensitive layer roll is formed by a method comprising the steps of: 39. The method of claim 38,
Wherein the teeth of the slitter are heated. 40. The method of claim 39,
Wherein the teeth of the slitter are heated to 100 DEG C or higher.