KR102293963B1 - 2 layer photosensitive layer roll - Google Patents

Abstract

The photosensitive layer roll has a support film and a photosensitive layer comprising a photosensitive resin composition formed on the support film, wherein the photosensitive resin composition is a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide. At least one resin selected from, and the photosensitive layer is a layer having a temperature point at which a melt viscosity becomes 500 Pa·s or less.

Description

2 layer photosensitive layer roll

The present invention relates to a photosensitive layer roll.

BACKGROUND ART Conventionally, as an image forming method used for patterning a semiconductor device, a liquid crystal display element, a printed wiring board, or the like, a photolithography method has been generally known. In the photolithography method, usually a method of applying a solution of the photosensitive resin composition on a substrate such as a copper clad laminate and drying it, or a support, a layer made of the photosensitive resin composition (hereinafter also referred to as "photosensitive layer"), and Any of the methods of laminating|stacking the photosensitive resin laminated body (henceforth "dry film resist") which laminated|stacked the cover film sequentially as needed on a board|substrate is used. In manufacture of a printed wiring board, the latter is often used.

A dry film resist may be stored in the form of a roll (refer patent document 1). In Patent Document 1, in order to reduce the manufacturing cost by omitting the cover film from the roll of dry film resist, a photosensitive layer and a non-tacky outer layer having a thickness of one fifth or less of the thickness of the photosensitive layer are sequentially included in the photosensitivity A complex has been proposed.

From the viewpoint of handling of dry film resist, dry film resist has no tackiness at room temperature, and it is required to exhibit fluidity when the dry film resist is thermocompression-bonded to a substrate or the like (ie, during lamination) (see Patent Document 2). . Patent Document 2 proposes a photosensitive coverlay film that has no tackiness at a substrate temperature of 20°C and can be easily repositioned even if it is placed on a substrate.

Moreover, coexistence of low-temperature curability and the chemical-resistance of a cured film is confirmed by patent document 3 by using the phenol resin which has a specific structure in combination with a nonionic surfactant in the photosensitive resin composition.

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

Usually, the photosensitive resin laminate is manufactured in the form of a roll, and is slitted to a required width and used. 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, wrinkles or cracks when slit This generate|occur|produced, and there existed a problem that it was difficult to slit so that a cross section might become smooth.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by adjusting the melt viscosity of a photosensitive layer, or removing a cover film, and completed this invention. That is, the present invention is as follows.

[One]

a support film;

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

As a photosensitive layer roll having,

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

[2]

The photosensitive layer roll according to [1], wherein the photosensitive layer is a layer having a temperature point at which the melt viscosity is 350 Pa·s or less.

[3]

The photosensitive layer roll according to [1] or [2], wherein the photosensitive layer has a melt viscosity at 100°C of 500 Pa·s or less.

[4]

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

[5]

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 on which the support film is formed, and the cover film has a softening temperature of 90°C or higher.

[6]

The photosensitive layer roll as described in [5] whose softening temperature of the said cover film is 110 degreeC or more.

[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 mass% or more and 15 mass% or less with respect to 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 mass% or more and 15 mass% or less with respect to the total amount of the photosensitive layer.

[9]

the organic solvent is γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol. The photosensitive layer roll according to [7] or [8], comprising at least one selected from

[10]

The photosensitive layer according to [9], wherein the organic solvent contains at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethyl sulfoxide. role.

[11]

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

[12]

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

[13]

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

[14]

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

[15]

The phenol resin has the following general formula (1):

[Formula 1]

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

[Formula 2]

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

The photosensitive layer roll according to [14], having a structure represented by as a repeating unit.

[16]

X in the said general formula (1) is following general formula (3):

[Formula 3]

{In formula (3), R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon number in which some or all of the hydrogen atoms are substituted with fluorine atoms. is a monovalent aliphatic group of 1 to 10, n1 is an integer of 0 to 4, R ₆ when n1 is an integer of 1 to 4 is a halogen atom, a hydroxyl group, or a monovalent organic group, and at least one R ₆ is It is a hydroxyl group, and several R<_6> in case n1 is an integer of 2-4 may be same or different, respectively.}

A divalent group represented by, and the following general formula (4):

[Formula 4]

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

[Formula 5]

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

[Formula 6]

It is a divalent organic group selected from the group consisting of a divalent group represented by.}

The photosensitive layer roll according to [15], which is a divalent organic group selected from the group consisting of a divalent group represented by .

[17]

X in the said general formula (1) is following formula (6):

[Formula 7]

The photosensitive layer roll according to [15] or [16], which is a divalent organic group represented by

[18]

X in the said general formula (1) is following formula (7):

[Formula 8]

The photosensitive layer roll according to [17], which is a divalent organic group represented by .

[19]

The phenol resin has the following general formula (8):

[Formula 9]

{In formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n2 is an integer of 1 to 3, n3 is an integer of 0 to 2, m1 is an integer from 1 to 500, 2 ≤ (n2 + n3) ≤ 4, and R ₁₁ when n3 is 2 may be the same or different, respectively.}, and a repeating unit represented by the following general formula (9):

[Formula 10]

{In formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n4 is an integer of 1 to 3, n5 is 0 to is an integer of 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≤ (n4 + n5) ≤ 4, and R ₁₂ when n5 is 2 may be the same or different, respectively _{, R 13} when n6 is 2 or 3 may be the same or different, respectively.}

The photosensitive layer roll according to any one of [15] to [18], wherein both of the repeating units represented by are in the same resin skeleton.

[20]

a support film;

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

As a photosensitive layer roll having,

The photosensitive resin composition contains at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and both 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 mass% or more and 15 mass% or less with respect to the total amount of the photosensitive layer.

[22]

The photosensitive layer roll according to [21], wherein the amount of the organic solvent contained in the photosensitive layer is 1 mass% or more and 15 mass% or less with respect to the total amount of the photosensitive layer.

[23]

The photosensitive layer roll according to [21] or [22], wherein the photosensitive resin composition contains the phenol resin.

[24]

the organic solvent is γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol. The photosensitive layer roll according to any one of [21] to [23], comprising at least one selected from

[25]

The photosensitive layer according to [24], wherein the organic solvent contains at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethyl sulfoxide. role.

[26]

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

[27]

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

[28]

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

[29]

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

[30]

The phenol resin has the following general formula (1):

[Formula 11]

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

[Formula 12]

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

The photosensitive layer roll according to [29], having a structure represented by as a repeating unit.

[31]

X in the said general formula (1) is following general formula (3):

[Formula 13]

{In formula (3), R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon number in which some or all of the hydrogen atoms are substituted with fluorine atoms. is a monovalent aliphatic group of 1 to 10, n1 is an integer of 0 to 4, R ₆ when n1 is an integer of 1 to 4 is a halogen atom, a hydroxyl group, or a monovalent organic group, and at least one R ₆ is It is a hydroxyl group, and several R<_6> in case n1 is an integer of 2-4 may be same or different, respectively.}

A divalent group represented by, and the following general formula (4):

[Formula 14]

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

[Formula 15]

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

A divalent alkylene oxide group represented by, and the following formula (5):

[Formula 16]

It is a divalent organic group selected from the group consisting of a divalent group represented by.}

The photosensitive layer roll according to [30], which is a divalent organic group selected from the group consisting of a divalent group represented by .

[32]

X in the said general formula (1) is following formula (6):

[Formula 17]

The photosensitive layer roll according to [30] or [31], which is a divalent organic group represented by

[33]

X in the said general formula (1) is following formula (7):

[Formula 18]

The photosensitive layer roll according to [32], which is a divalent organic group represented by .

[34]

The phenol resin has the following general formula (8):

[Formula 19]

{In formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n2 is an integer of 1 to 3, n3 is an integer of 0 to 2, m1 is an integer from 1 to 500, 2 ≤ (n2 + n3) ≤ 4, and R ₁₁ when n3 is 2 may be the same or different, respectively.}

A repeating unit represented by, and the following general formula (9):

[Formula 20]

{In formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n4 is an integer of 1 to 3, n5 is 0 to is an integer of 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≤ (n4 + n5) ≤ 4, and R ₁₂ when n5 is 2 may be the same or different, respectively _{, R 13} when n6 is 2 or 3 may be the same or different, respectively.} The photosensitive layer roll according to any one of [30] to [33], having both repeating units in the same resin skeleton. .

[35]

[1] A method for producing a slit photosensitive layer roll, wherein the slit photosensitive layer roll is produced by slitting the photosensitive layer roll according to any one of [1] to [34] with a slitter.

[36]

The method for producing a slit photosensitive layer roll according to [35], wherein the teeth of the slitter are heated.

[37]

The method for producing a slit photosensitive layer roll according to [36], wherein the teeth of the slitter are heated to 100°C or higher.

[38]

The following process:

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

slitting the photosensitive layer roll not having the cover film with a slitter;

Step of attaching the peeled cover film or a cover film different from the peeled cover film to the slitted photosensitive layer roll

A method of manufacturing a slit photosensitive layer roll comprising a.

[39]

The method for manufacturing a slit photosensitive layer roll according to [38], wherein the teeth of the slitter are heated.

[40]

The method for producing a slit photosensitive layer roll according to [39], wherein the teeth of the slitter are heated to 100°C or higher.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the photosensitive layer roll which is hard to generate|occur|produce wrinkles or cracks at the time of slitting, and can slit so that a cross section may become smooth.

<First embodiment: two-layer photosensitive layer roll>

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

In this embodiment, the photosensitive layer roll does not contain a cover film. The photosensitive layer is laminated on one side of the support film, and the other side of the support film (that is, the back surface of the support or the surface on which the photosensitive layer is not laminated) is exposed, so that both surfaces of the support film are in contact with the photosensitive layer.

Hereinafter, the photosensitive layer roll in which both surfaces of a support film are in contact with a photosensitive layer without a cover film are demonstrated as a two-layer photosensitive layer roll.

Since the conventional photosensitive layer roll has a cover film, wrinkles are likely to occur in the cover film during slitting. there was

In order to solve the said subject, the two-layer photosensitive layer roll which concerns on 1st Embodiment is the point which does not contain a cover film, It is characterized by the above-mentioned.

<Support film>

The support film according to the present embodiment is not particularly limited as long as the surface is smooth. For example, polymer films such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. Among them, polyethylene terephthalate film ( Hereinafter, it is called "PET film") is preferable.

From a viewpoint of transferring a photosensitive layer to a base material from a two-layer photosensitive layer roll when performing a photolithographic method, it is preferable that the mold release process is given to at least one surface of a support body film. The release treatment in the present embodiment refers to a silicone-based compound such as a silicone-based surfactant and a silicone resin, a fluorine-containing compound such as a fluorine-based surfactant and a fluororesin, and a release agent such as an alkyd resin, a chemical treatment to thinly coat the surface of the support film, Or it refers to physical treatment, such as corona-treating a support film.

When coating a mold release agent to a support body film, it is preferable to coat thinly in the limit from which the effect of a mold release is acquired. After coating, the mold release agent may be fixed to the support film by heat or UV treatment. Before coating a mold release agent, it is more preferable to give an undercoating layer to a support body film.

<Photosensitive layer>

The photosensitive layer includes at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide on a support film, preferably on the release-treated side of the support film. It is formed by apply|coating the photosensitive resin composition.

Hereinafter, the component contained in the photosensitive resin composition is demonstrated.

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

Generally, a phenol resin is a thermosetting resin formed from a phenol compound and an aldehyde compound.

In this embodiment, from a viewpoint of the thermal meltability of a photosensitive layer, a phenol resin (A) is following General formula (1):

[Formula 21]

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

[Formula 22]

(in formula (2), p is an integer of 1 to 10.) represents a divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by and a divalent organic group having an aromatic ring.} It is preferable to have a structure as a repeating unit.

The phenol resin (A) having a repeating unit of the structure represented by the formula (1) can be cured at a low temperature as compared with polyimide resin and polybenzoxazole resin, for example, and formation of a cured film having good elongation This is possible and further contributes to the thermal meltability of the photosensitive layer.

A photosensitive layer excellent in heat melting property is preferable because cracks are less likely to occur in the cut surface during slitting, particularly when slitting by heating the teeth of the slitter, and the slit can be performed so that the cross section becomes smooth.

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

[Formula 23]

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

In this embodiment, in the said General formula (1), a is an integer of 1-3, and 2 is preferable from a viewpoint of alkali solubility and elongation. When a is 2, the substitution position of hydroxyl groups may be any of the ortho, meta, and para positions. When a is 3, the substitution position of the hydroxyl groups may be any, such as the 1,2,3-position, the 1,2,4-position, and the 1,3,5-position.

In this embodiment, in the said General formula (1), b is an integer of 0-3, and it is preferable that it is 0 or 1 from a viewpoint of alkali solubility and elongation. When b is 2 or 3, some R<_1> may be same or different.

In addition, in this embodiment, in the said General formula (1), a and b satisfy|fill the relationship of 1 ≤ (a + b) ≤ 4 .

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

[Formula 24]

{In formula (3), R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon number in which some or all of the hydrogen atoms are substituted with fluorine atoms. is a monovalent aliphatic group of 1 to 10, n1 is an integer of 0 to 4, R ₆ when n1 is an integer of 1 to 4 is a halogen atom, a hydroxyl group, or a monovalent organic group, and at least one R ₆ is _{a hydroxyl group, and a plurality of R 6} in the case where n1 is an integer of 2 to 4 may be the same or different from each other.}, and the following general formula (4):

[Formula 25]

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

[Formula 26]

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

[Formula 27]

It is a divalent organic group selected from the group which consists of a divalent group represented by.} It is preferable that it is an organic group selected from the group which consists of a divalent group represented by.

W in formula (4) is 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 and heat meltability of the cured film. A divalent organic group selected from the group consisting of is preferable.

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 formability of the resin composition, and the elongation and heat meltability of the cured film after curing, the following formula (6):

[Formula 28]

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

[Formula 29]

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

About the ratio of the site|part containing a phenolic hydroxyl group in General formula (1), and the site|part represented by X, especially from a viewpoint of elongation, the ratio of the site|part represented by X in the structure represented by General formula (1) is 20 mass % or more, and more preferably 30 mass% or more.

The said ratio becomes like this. From an alkali solubility viewpoint, Preferably it is 80 mass % or less, More preferably, it is 70 mass % or less. Moreover, from a viewpoint of the thermal meltability of a photosensitive layer, and alkali solubility, a phenol resin (A) is following General formula (8):

[Formula 30]

{In formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n2 is an integer of 1 to 3, n3 is an integer of 0 to 2, m1 is an integer from 1 to 500, 2 ≤ (n2 + n3) ≤ 4, and R ₁₁ when n3 is 2 may be the same or different, respectively.}

A repeating unit represented by, and the following general formula (9):

[Formula 31]

{In formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n4 is an integer of 1 to 3, n5 is 0 to is an integer of 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≤ (n4 + n5) ≤ 4, and R ₁₂ when n5 is 2 may be the same or different, respectively _{, R 13} when n6 is 2 or 3 may be the same or different, respectively.}

It is especially preferable to have both of the repeating units represented by in the same resin skeleton.

m1 of the general formula (8) and m2 of the general formula (9) represent the total number of each repeating unit in the main chain of the phenol resin (A). That is, in the phenol resin (A), the repeating unit in parentheses in the structure represented by the general formula (8) and the repeating unit in parentheses in the structure represented by the general formula (9) are random, block, or a combination thereof. may be arranged as m1 and m2 are each independently an integer of 1 to 500 from the viewpoint of alkali solubility and elongation of the cured product, the lower limit is preferably 2, more preferably 3, and the upper limit is preferably 450, more preferably preferably 400, more preferably 350. m1 and m2 are each independently preferably 2 or more from the viewpoint of toughness and heat meltability of the film after curing, and preferably 450 or less from the viewpoint of solubility in aqueous alkali solution.

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

The phenol resin (A) is typically a phenol compound and a copolymerization component, specifically, a compound having an aldehyde group (including a compound that decomposes like trioxane to produce an aldehyde compound), a compound having a ketone group, methyl containing at least one compound selected from the group consisting of a compound having two ol groups in a molecule, a compound having two alkoxymethyl groups in a molecule, and a compound having two haloalkyl groups in a molecule, more typically monomers thereof It can synthesize|combine a component by making it polymerize-react. For example, aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds, or halo compounds for phenols and/or phenol derivatives (hereinafter, collectively referred to as “phenol compounds”) as shown below. A phenol resin (A) can be obtained by superposing|polymerizing copolymerization components, such as an alkyl compound. In this case, in the general formula (1) _{, the portion represented by the structure in which the OH group and any R 1} groups are bonded to the aromatic ring is derived from the phenol compound, and the portion represented by X is derived from the copolymerization component. From the viewpoint of reaction control and stability of the obtained phenol resin (A) and the photosensitive resin composition, the injection molar ratio of the phenol compound and the copolymerization component (phenol compound: copolymerization component) is preferably 5:1 to 1.01:1, It is more preferable that it is 2.5:1 - 1.1:1. In this embodiment, the weight average molecular weights of a phenol resin (A) become like this. Preferably it is 700-100,000, More preferably, it is 1,500-80,000, More preferably, it is 2,000-50,000. It is preferable that a weight average molecular weight is 700 or more from a viewpoint of the elongation of a cured film, On the other hand, it is preferable that a weight average molecular weight is 100,000 or less from a viewpoint of alkali solubility of the photosensitive resin composition.

A weight average molecular weight is measurable by gel permeation chromatography (GPC), and can be computed with the analytical curve created using standard polystyrene.

In this embodiment, as a phenolic compound which can be used in order to obtain a phenol resin (A), for example, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, Nitrobenzylphenol, cyanobenzylphenol, adamantanephenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N-(hydroxyphenyl)-5-norbornene-2, 3-dicarboxyimide, N-(hydroxyphenyl)-5-methyl-5-norbornene-2,3-dicarboxyimide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, hydroxybenzoic acid Ethyl, hydroxybenzoate benzyl, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methylcatechol, ethylcatechol , hexyl catechol, benzyl catechol, nitrobenzyl catechol, methyl resorcinol, ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid , methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzoate Hydroxybenzophenone, dihydroxybenzonitrile, N-(dihydroxyphenyl)-5-norbornene-2,3-dicarboxyimide, N-(dihydroxyphenyl)-5-methyl-5-nor Bornene-2,3-dicarboxyimide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol , Bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl trihydroxybenzoate , butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzonitrile, etc. can hear all.

Examples of the aldehyde compound include acetaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutylaldehyde, benzaldehyde, gly oxylic acid, 5-norbornene-2-carboxyaldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde, etc. are mentioned.

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

Examples of the methylol compound include 2,6-bis(hydroxymethyl)-p-cresol, 2,6-bis(hydroxymethyl)-4-ethylphenol, and 2,6-bis(hydroxymethyl). )-4-propylphenol, 2,6-bis(hydroxymethyl)-4-n-butylphenol, 2,6-bis(hydroxymethyl)-4-t-butylphenol, 2,6-bis(hydride) Roxymethyl)-4-methoxyphenol, 2,6-bis(hydroxymethyl)-4-ethoxyphenol, 2,6-bis(hydroxymethyl)-4-propoxyphenol, 2,6-bis( Hydroxymethyl)-4-n-butoxyphenol, 2,6-bis(hydroxymethyl)-4-t-butoxyphenol, 1,3-bis(hydroxymethyl)urea, ribitol, arabitol, Allitol, 2,2-bis(hydroxymethyl)butyric acid, 2-benzyloxy-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3 -Propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol, penta Erythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis(hydroxymethyl)durene, 2-nitro-p-xylylene glycol, 1,10-dihydr Roxydecane, 1,12-dihydroxydodecane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxymethyl)cyclohexene, 1,6-bis(hydroxymethyl)a Dantan, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis(hydroxymethyl)-1,4-dimethoxybenzene, 2,3-bis(hydroxymethyl)naphthalene, 2,6-bis(hydroxymethyl)naphthalene, 1,8-bis(hydroxymethyl)anthracene, 2,2'-bis(hydroxymethyl)diphenyl ether, 4,4'-bis(hydroxymethyl) Diphenylether, 4,4'-bis(hydroxymethyl)diphenylthioether, 4,4'-bis(hydroxymethyl)benzophenone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl, 4- Hydroxymethylbenzoic acid-4'-hydroxymethylanilide, 4,4'-bis(hydroxymethyl)phenylurea, 4,4'-bis(hydroxymethyl)phenylurethane, 1,8-bis(hydroxymethyl) ) anthracene, 4,4'-bis(hydroxymethyl)biphenyl, 2,2'-dimethyl-4,4-'bis( Hydroxymethyl)biphenyl, 2,2-bis(4-hydroxymethylphenyl)propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and the like.

Examples of the alkoxymethyl compound include 2,6-bis(methoxymethyl)-p-cresol, 2,6-bis(methoxymethyl)-4-ethylphenol, and 2,6-bis(methoxymethyl). )-4-propylphenol, 2,6-bis(methoxymethyl)-4-n-butylphenol, 2,6-bis(methoxymethyl)-4-t-butylphenol, 2,6-bis(methyl) Toxymethyl)-4-methoxyphenol, 2,6-bis(methoxymethyl)-4-ethoxyphenol, 2,6-bis(methoxymethyl)-4-propoxyphenol, 2,6-bis( Methoxymethyl)-4-n-butoxyphenol, 2,6-bis(methoxymethyl)-4-t-butoxyphenol, 1,3-bis(methoxymethyl)urea, 2,2-bis( Methoxymethyl)butyric acid, 2,2-bis(methoxymethyl)-5-norbornene, 2,3-bis(methoxymethyl)-5-norbornene, 1,4-bis(methoxymethyl) Cyclohexane, 1,4-bis(methoxymethyl)cyclohexene, 1,6-bis(methoxymethyl)adamantane, 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) naphthalene, 1,8 -bis (methoxymethyl) anthracene, 2,2'-bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) Diphenylthioether, 4,4'-bis(methoxymethyl)benzophenone, 4-methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylanilide, 4, 4'-bis(methoxymethyl)phenylurea, 4,4'-bis(methoxymethyl)phenylurethane, 1,8-bis(methoxymethyl)anthracene, 4,4'-bis(methoxymethyl)bi Phenyl, 2,2'-dimethyl-4,4'-bis(methoxymethyl)biphenyl, 2,2-bis(4-methoxymethylphenyl)propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene Glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, etc. are mentioned.

Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrylate, and 2,4-hexadiene. -1-ol, methylcyclohexadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclo Pentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2,5-norbornadiene, tetrahydroindene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene Nene, triallyl cyanurate, diallyl isocyanurate, triallyl isocyanurate, diallylpropyl isocyanurate, etc. are mentioned.

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

A phenol resin (A) can be obtained by making the above-mentioned phenol compound and a copolymerization component condensate with dehydration, dehydrohalogenation, or dealcoholization, or by superposing|polymerizing, cleaving an unsaturated bond. You may use a catalyst at the time of superposition|polymerization of a phenol compound and a copolymerization component.

Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethylsulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1' -Diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride/phenol complex, boron trifluoride/ether complex, etc. are mentioned.

Examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N,N-dimethylaminopyridine, piperidine, piperazine, 1, 4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, ammonia, hexa Methylenetetramine etc. are mentioned.

In this embodiment, the quantity of the catalyst used in order to obtain a phenol resin (A) is the total number of moles of a copolymerization component, Preferably, the sum total of an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, and a haloalkyl compound. It is preferable that it is the range of 0.01 mol% - 100 mol% with respect to 100 mol% of moles.

When performing the synthesis reaction of a phenol resin (A), an organic solvent can be used as needed. 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, di ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, and the like. The usage-amount of these organic solvents is 10 mass parts - 1000 mass parts normally, when the total mass of the injection|pouring raw material makes 100 mass parts, Preferably they are 20 mass parts - 500 mass parts. Further, in the synthesis reaction of the phenol resin (A), the reaction temperature is preferably 40°C to 250°C, more preferably 100°C to 200°C, and the reaction time is approximately 1 hour to 10 It is preferably time.

Further, the phenol resin (A) is a phenol compound that does not become a raw material of the structure of the general formula (1) in the range that does not impair the effects of the present invention, for example, a raw material of the phenol resin (A) What was further used and superposed|polymerized in 30% or less of the total moles of a phenol compound may be sufficient.

In the present embodiment, when a is 1 in the general formula (1), in order to improve alkali solubility, a phenol resin selected from the group consisting of novolak resins and polyhydroxystyrene resins (hereinafter, phenol resins) (A')) can be mixed with the phenol resin (A).

It is preferable that the mixing ratio of a phenol resin (A) and a phenol resin (A') is the range of (A)/(A') =10/90-90/10 by mass ratio. It is preferable that this mixing ratio is (A)/(A') =10/90 - 90/10 from a viewpoint of the solubility in aqueous alkali solution, and the elongation of a cured film, (A)/(A') = 20/ It is more preferable that it is 80-80/20, and it is still more preferable that it is (A)/(A')=30/70-70/30.

The said novolak resin can be obtained by condensing phenols and formaldehyde in presence of an acidic catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butyl phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, ?-naphthol, ?-naphthol, etc. are mentioned. Specific examples of the novolak resin include phenol/formaldehyde condensed novolak resin, cresol/formaldehyde condensed novolak resin, and phenol-naphthol/formaldehyde condensed novolac resin.

As the polyhydroxystyrene resin, polyparavinylphenol is preferable. Polyparavinylphenol will not be specifically limited if it is a polymer containing paravinylphenol as a polymerization unit. Any compound copolymerizable with paravinylphenol may be sufficient as a polymeric unit other than paravinylphenol which can comprise polyparavinylphenol, unless it is contrary to the objective of this invention. The compound copolymerizable with paravinylphenol is, for example, 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 dimetha Acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2-di (p- Hydroxyphenyl)-propanedimethacrylate, triethyleneglycol diacrylate, polyoxyethyl-2-2-di(p-hydroxyphenyl)-propanedimethacrylate, triethyleneglycol dimethacrylate, poly Oxypropyltrimethylolpropane triacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol di Methacrylate, 1,2,4-butanetriol trimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate, 1-phenylethylene- Acrylic acid, such as 1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol dimethacrylate esters of ; styrene, and substituted styrenes such as, for example, 2-methylstyrene and vinyltoluene; vinyl esters such as vinyl acrylate and vinyl methacrylate; vinylphenols other than paravinylphenol such as orthovinylphenol and metavinylphenol; Although monomers, such as these, are mentioned, It is not limited to these.

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

In addition, the phenol resin selected from the group which consists of a novolak resin and polyhydroxystyrene resin may be used individually by 1 type, and may be used in mixture of 2 or more type.

[Mine generator (B)]

In the present embodiment, the photosensitive resin composition is a composition capable of forming a resin pattern in response to actinic rays (that is, radiation) typified by ultraviolet rays, electron beams, X-rays, and the like. The photosensitive resin composition may be either of a negative type (that is, the unirradiated portion eluted by development) or a positive type (that is, the irradiated portion eluted by development).

In the present embodiment, when the photosensitive resin composition is used as a negative photosensitive resin composition, the photoacid generator (B) is irradiated with radiation to generate an acid, and the generated acid undergoes a crosslinking reaction between the phenol resin (A) and the crosslinking agent. By raising it, a radiation irradiation part becomes insoluble in a developing solution. As the photoacid generator (B) which can be used in the negative type, for example, the following compounds are mentioned:

(i) trichloromethyl-s-triazines

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

(ii) diaryliodonium salts

Diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoroacetate Phenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodoniumtetrafluoroborate, 4-methoxyphenylphenyliodoniumhexafluorophosphonate, 4-methoxyphenylphenyliodoniumhexafluoroar Cenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, bis(4- tert-butylphenyl)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, etc.;

(iii) triarylsulfonium salts

Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfoniummethanesulfonate, triphenylsulfonium trifluoroacetate, triphenyl Sulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfoniumtetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoro Loarsenate, 4-methoxyphenyldiphenylsulfoniummethanesulfonate, 4-methoxyphenyldiphenylsulfoniumtrifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4- Phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfo nate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, and the like.

Among these compounds, trichloromethyl-s-triazines include 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine and 2-(4-chlorophenyl)-bis (4,6-trichloromethyl)-s-triazine, 2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxy-β -styryl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine, etc. are preferable. do.

Examples of the diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, and 4-methoxyphenylphenyliodine. nium trifluoroacetate etc. are preferable.

Examples of the triarylsulfonium salts include triphenylsulfoniummethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfoniummethanesulfonate, and 4-methoxyphenyldiphenylsulfoniumtrifluoro Acetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, etc. are preferable.

In addition to this, as a photo-acid generator (B), the compound shown below can also be used.

(1) diazoketone compounds

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

(2) sulfone compounds

Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples thereof include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis(phenacylsulfonyl)methane.

(3) sulfonic acid compounds

Examples of the sulfonic acid compound include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Specific examples of the sulfonic acid compound include benzointosylate, pyrogallol trifluoromethanesulfonate, o-nitrobenzyltrifluoromethanesulfonate, and o-nitrobenzyl-p-toluenesulfonate. .

(4) sulfonimide compounds

As the sulfonimide compound, 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)naphthyl imide and the like.

(5) oxime ester compound

As the oxime ester compound, specifically, 2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile (Ciba Specialty Chemicals, trade name "Irgacure PAG121"), [2-(propylsulfonyloxyimino)-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile (Ciba Specialty) Chemicals trade name "Irgacure PAG103"), [2-(n-octanesulfonyloxyimino)-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile (Ciba Specialty Chemicals company brand name "Irgacure PAG108"), α-(n-octanesulfonyloxyimino)-4-methoxybenzylcyanide (Ciba Specialty Chemicals company brand name "CGI725"), etc. are mentioned.

(6) diazomethane compounds

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

From a viewpoint of a sensitivity, especially the said (5) oxime ester compound is preferable.

In this embodiment, when the photosensitive resin composition is negative, it is preferable that the compounding quantity of the photo-acid generator (B) with respect to 100 mass parts of phenol resins (A) is 0.1-50 mass parts, and it is more that it is 1-40 mass parts desirable. If the compounding quantity is 0.1 mass part or more, the improvement effect of a sensitivity can be acquired favorably, and the mechanical property of a cured film is favorable that the compounding quantity is 50 mass parts or less.

In this embodiment, the photosensitive resin composition can also be used as a positive photosensitive resin composition. In this case, the photo-acid generator and/or quinonediazide compound represented by said (i)-(iii) and (1)-(6) are used. Among them, a quinonediazide compound is preferable from the viewpoint of physical properties after curing. This is because a quinonediazide compound thermally decomposes at the time of hardening, and the quantity which remains in the film|membrane after hardening is very low. Therefore, it is preferable that a positive photo-acid generator (B) is a quinonediazide compound.

As a quinonediazide compound, the compound which has a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure (The compound which has the latter structure is also called "NQD compound" hereafter.) is mentioned. can These compounds are described, for example, in US Pat. No. 2,772,972, US Pat. No. 2,797,213, US Pat. No. 3,669,658, and the like. The NQD compound is a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a compound having a plurality of phenolic hydroxyl groups described in detail below (hereinafter also referred to as a “polyhydroxy compound”), and a polyhydroxy It is at least 1 sort(s) of compound chosen from the group which consists of 1,2-naphthoquinonediazide-5-sulfonic acid ester of a compound.

The NQD compound is a naphthoquinonediazidesulfonyl chloride obtained by changing naphthoquinonediazidesulfonic acid to sulfonylchloride with chlorsulfonic acid or thionyl chloride or the like according to a conventional method, and a condensation reaction of a polyhydroxy compound with naphthoquinonediazidesulfonylchloride obtained by doing For example, a predetermined amount of a polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride, dioxane, acetone or in a solvent such as tetrahydrofuran in the presence of a basic catalyst such as triethylamine, esterification is performed, and the obtained product is washed with water and dried.

As an example of a preferable NQD compound from a viewpoint of cured film physical properties, such as a sensitivity and elongation, the following general formula group:

[Formula 32]

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

[Formula 33]

Although it is a naphthoquinone diazide sulfonic acid ester group represented by any of

can be shown as

Further, 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, and 4-naphthoquinone diazide sulfonyl group may be used. It is also possible to use a mixture of a zidsulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound.

The said NQD compound may be used independently and may be used in mixture of 2 or more types.

In this embodiment, as for the usage-amount of the photo-acid generator (B) in case the photosensitive resin composition is positive, with respect to 100 mass parts of phenol resins (A) of this composition, Preferably it is 0.1-70 mass parts, More preferably It is 1-40 mass parts, More preferably, it is 5-30 mass parts. If this usage-amount is 0.1 mass part or more, a favorable sensitivity will be acquired, and the mechanical property of a cured film is favorable in it being 70 mass parts or less.

[Solvent (C)]

Examples of the solvent (C) include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, for example, N-methyl-2-pyrroly Don, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate , butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, tert- Butyl alcohol, 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, γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-py from the viewpoint of solubility of the resin, stability of the resin composition, adhesion to a substrate, heat meltability, storage stability, and blocking properties. Rollidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol are preferable, and among these, γ-butyrolactone, acetone, methyl ethyl ketone, and N-methyl-2-pyrroly Don, and dimethylsulfoxide are particularly preferred.

[Silicone type surfactant (D)]

A silicone type surfactant is a surfactant which has a siloxane bond and a silicon-carbon bond in a molecule|numerator. For example, a dimethylsiloxane ethyleneoxy graft compound, a dimethylsiloxane propyleneoxy graft compound, (hydroxyethyleneoxypropyl)methylsiloxane- dimethylsiloxane compound, etc. are mentioned.

Specific examples of the silicone type surfactant include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (above, trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, trade names, manufactured by Toray Dow Corning Silicon Corporation), SILWET L-77, L-7001, FZ- 2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (above, trade name, manufactured by Nippon Unika Corporation), DBE-814, DBE-224, DBE-621, CMS-626, CMS- 222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (above, brand name, big Chemi Japan), granol (trade name, Kyoeisha Chemical company make), etc. are mentioned. Among these, a dimethylsiloxane ethyleneoxy graft compound and a dimethylsiloxane propyleneoxy graft compound are preferable from a viewpoint of the applicability|paintability of the composition varnish. These silicone type surfactants can be used individually by 1 type or in combination of 2 or more type.

It is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of phenol resin (A) from a viewpoint of the applicability|paintability to the support body of a composition varnish, and, as for the usage-amount of silicone type surfactant (D), it is more preferable that it is 0.02-10 mass parts. do. When the usage-amount of silicone type surfactant (D) is 30 mass parts or less, the residue and pattern floatation at the time of image development can be suppressed.

[Other Ingredients]

It is possible to make the photosensitive resin composition which concerns on this embodiment contain a crosslinking agent (E), a thermal acid generator, a silane coupling agent, dye, a dissolution promoter, etc. as needed.

A crosslinking agent (E) is a compound which can crosslink with a phenol resin (A), or crosslinking agent itself forms a crosslinking network, when heat-hardening the relief pattern formed using the photosensitive resin composition which concerns on this embodiment. A crosslinking agent (E) will not be limited if it is a compound which can crosslink heat. Generally, a crosslinking agent has two or more crosslinking groups in a molecule|numerator, and can further improve the thermal characteristic, mechanical characteristic, and chemical-resistance of the cured film formed from the photosensitive resin composition.

Examples of the crosslinking agent (E) include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, which is a compound containing a methylol group and/or an alkoxymethyl group; 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300, Mycoat 102, 105 (above, manufactured by Mitsui Cytec), Nikalac (registered trademark) MX-270, -280, -290, Nikalac MS-11, Nikalac MW-30, -100, -300, -390, -750 (above, manufactured by Sanwa Chemical), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DMLPCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM- BP, TMOM-BPA, TML-BPAF-MF (above, manufactured by Honshu Chemical Industry Co., Ltd.), benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl Ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylphenyl, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxy Methyl) cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylbenzoate methoxymethylphenyl, bis(methoxymethyl)biphenyl, Dimethylbis(methoxymethyl)biphenyl etc. are mentioned.

Moreover, as a crosslinking agent (E), a phenol novolak type epoxy resin which is an oxirane compound, a cresol novolak type epoxy resin, a bisphenol type epoxy resin, a trisphenol type epoxy resin, a tetraphenol type epoxy resin, a phenol-xylylene 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, orthosecondary butyl Phenylglycidyl ether, 1,6-bis(2,3-epoxypropoxy)naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF -2004 (above, trade name, manufactured by Shin-Nitetsu Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (above, trade name, Nippon Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315-75 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Flaxel G402, PUE101, PUE105 (above, trade name, manufactured by Daicel Chemical Industries, Ltd.), Epiclone (registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (above, trade name, manufactured by DIC), Denacol (registered trademark) EX-201, EX -251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711, EX-731 , EX-810, EX -911, EM-150 (above, trade name, manufactured by Nagase Chemtex), EPOLITE (registered trademark) 70P, EPOLITE 100MF (above, brand name, manufactured by Kyoeisha Chemical), etc. are mentioned.

Further, as the crosslinking agent (E), 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4'-, which are isocyanate group-containing compounds Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (above, trade name, manufactured by Mitsui Chemicals) Duranate (registered trademark) 17B-60PX , TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, a brand name, manufactured by Asahi Kasei Chemicals) etc. are mentioned.

Further, as the crosslinking agent (E), 4,4'-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, bisphenol A diphenyletherbismaleimide, 3, which are bismaleimide compounds; 3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2 ,2,4-trimethyl)hexane, 4,4'-diphenyl etherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1, 3-bis(4-maleimidephenoxy)benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI -6000 and BMI-8000 (above, a brand name, Owa Chemical Industry Co., Ltd. product) etc. are mentioned.

As a compounding quantity in the case of using a crosslinking agent (E), 0.1-40 mass parts is preferable with respect to 100 mass parts of phenol resins (A), and 1-30 mass parts is more preferable. If the compounding amount is 0.1 parts by mass or more, the thermal properties and mechanical strength of the thermosetting film are good, and if it is 40 parts by mass or less, the stability of the composition in the varnish state and the elongation of the thermosetting film are good.

It is preferable to mix|blend a thermal acid generator with a resin composition from a viewpoint of expressing favorable thermal and mechanical properties of hardened|cured material even if it is a case where hardening temperature is lowered|hung.

The thermal acid generator is not limited as long as it is a compound that generates an acid by heat, and for example, allyl chloroacetate, n-butyl chloroacetate, t-butyl chloroacetate, ethyl chloroacetate, methyl chloroacetate, benzyl chloroacetate, isochloroacetate Propyl, 2-methoxyethyl chloroacetate, methyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, 2-ethoxyethyl trichloroacetate, t-butyl cyanoacetate, t-butyl methacrylate, trifluoro Ethyl acetate, methyl trifluoroacetate, phenyl trifluoroacetate, vinyl trifluoroacetate, isopropyl trifluoroacetate, allyl trifluoroacetate, ethyl benzoate, methyl benzoate, t-butyl benzoate, methyl 2-chlorobenzoate , 2-chlorobenzoate ethyl, 4-chlorobenzoate ethyl, 2,5-dichlorobenzoate ethyl, 2,4-dichlorobenzoate methyl, p-fluorobenzoate ethyl, p-fluorobenzoate methyl, pentachlorophenylcarboxylic acid t -butyl, methyl pentafluoropropionate, ethyl pentafluoropropionate, and carboxylate esters such as t-butyl crotonic acid; cyclic carboxylic acid esters such as phenolphthalein and thymolphthalein; Ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, 2-isopropoxyethyl methanesulfonate, p-toluenesulfonate phenyl, p-toluenesulfonate ethyl, p-toluenesulfonate methyl, p-toluenesulfonate 2-phenyl Ethyl, p-toluenesulfonic acid n-propyl, p-toluenesulfonic acid n-butyl, p-toluenesulfonic acid t-butyl, p-toluenesulfonic acid n-hexyl, p-toluenesulfonic acid n-heptyl, p-toluenesulfonic acid n-octyl, 2-methoxyethyl p-toluenesulfonate, propargyl p-toluenesulfonate, 3-butynyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, ethyl perfluorobutanesulfonate, Methyl perfluorobutanesulfonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluorophosphate, trimethylsulfonium methyl sulfate, tri- sulfonic acid esters such as p-sulfonium trifluoromethanesulfonate, trimethylsulfonium trifluoromethanesulfonate, pyridinium-p-toluenesulfonate, and ethyl perfluorooctanesulfonate; cyclic sulfonic acid esters such as 1,4-butanesultone, 2,4-butanesultone, 1,3-propanesultone, phenol red, bromocresol green, and bromocresol purple; Aromatic carboxylic acid anhydrides, such as 2-sulfobenzoic acid anhydride, p-toluenesulfonic acid anhydride, and a phthalic anhydride, etc. are mentioned.

As a compounding quantity in the case of using a thermal acid generator, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) phenol resins, 0.5-10 mass parts is more preferable, 1-5 mass parts is still more preferable. When the compounding amount is 0.1 parts by mass or more, the effect of maintaining the pattern shape after thermosetting is good, while when the compounding amount is 30 parts by mass or less, there is no adverse effect on the lithography performance, and the stability of the composition is good.

As the silane coupling agent, for example, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Silaace S810), 3-mercaptopropyltriethoxysilane (Azu Manufactured by Max Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (Azmax) Manufactured by Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyl dimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane , 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropyl Methoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2 -Mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyl trime Toxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Corporation: Trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxy) Cydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N -(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydime Toxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3 -dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (Azmax) Manufactured by Co., Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1) aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 2-(tri Methoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine , (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra -i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-pro Poxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl) ) Methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl) Propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, bis(pentadionate) ) Titanium-O,O'-bis(oxyethyl)-aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n- butylphenylsilanediol, Sobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol , isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, Isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like. These may be used individually or in combination of two or more.

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

[Formula 34]

A compound represented by

As a compounding quantity in the case of using a silane coupling agent, 0.01-20 mass parts is preferable with respect to 100 mass parts of phenol resins (A).

As a dye, methyl violet, crystal violet, malachite green etc. are mentioned, for example. As a compounding quantity of dye, 0.1-30 mass parts is preferable with respect to 100 mass parts of phenol resins (A).

As a dissolution promoter, the compound which has a hydroxyl group or a carboxyl group is preferable. Examples of the compound having a hydroxyl group include the ballast agent used in the above-mentioned naphthoquinonediazide compound, paracumylphenol, bisphenol, resorcinol, and linear phenolic compounds such as MtrisPC and MtetraPC, TrisP-HAP , TrisP-PHBA, TrisP-PA, etc. non-linear phenolic compounds (all manufactured by Honshu Chemical Industries, Ltd.), 2 to 5 phenol substituted products for diphenylmethane, 1 to 5 phenolic substituted products for 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 to 2, bis-( A compound obtained by reacting 3-amino-4-hydroxyphenyl) sulfone with 1,2-cyclohexyldicarboxylic anhydride in a molar ratio of 1 to 2, N-hydroxysuccinimide, N-hydroxyphthalimide; N-hydroxy 5-norbornene-2,3-dicarboxylic acid imide etc. are mentioned. Examples of the compound having a carboxyl group include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2 -methoxy-2-(1-naphthyl)propionic acid, mandelic acid, atrolactic acid, ?-methoxyphenylacetic acid, O-acetylmandelic acid, itaconic acid, and the like.

As a compounding quantity in the case of using a dissolution accelerator, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) phenol resins.

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

(A) polyimide precursor

Polyamide, polyamic acid ester, etc. are mentioned as photosensitive resin used for a polyimide precursor composition. For example, as polyamic acid ester, the following general formula (11):

[Formula 35]

{in formula (11), R ¹ and R ² are each independently a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, a monovalent organic group having a carbon-carbon unsaturated double bond, or carbon-carbon unsaturated It is a monovalent ion having a 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. }

Polyamic acid ester containing a repeating unit represented by can be used.

^{When R 1} and R ² in the above general formula (11) exist as monovalent cations, O is negatively charged (ie, exists as -O-). Moreover, X<^1> and Y<^1> may contain the hydroxyl group.

^{R 1} and R ² in the general formula (11) are more preferably, the following general formula (12):

[Formula 36]

{In general formula (12), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m ₁ is an integer of 1 to 20.}

A monovalent organic group represented by, or the following general formula (13):

[Formula 37]

{In general formula (13), R ₆ , R _{7 ,} and R ₈ are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m ₂ is an integer of 1 to 20.}

It has a structure having an ammonium ion at the terminal of the monovalent organic group represented by .

You may mix two or more polyamic acid esters represented by General formula (11). Moreover, you may use the polyamic acid ester which copolymerized the polyamic acid esters represented by General formula (11).

^{It is preferable that X<1>} in Formula (11) is a tetravalent organic group containing an aromatic group from a heat-meltable viewpoint. Specifically, X ¹ is the following general formulas (2) to (4):

[Formula 38]

[Formula 39]

[Formula 40]

{In formula (4), R ₉ is any of an oxygen atom, a sulfur atom, and a divalent organic group.}

It is preferable that it is a tetravalent organic group containing at least 1 structure represented by.

_R<9> in General formula (4) is a C1-C40 divalent organic group or a halogen atom, for example. R ₉ may contain a hydroxyl group.

From the viewpoint of thermal meltability, X ¹ is the following general formula (5):

[Formula 41]

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

^{It is preferable that Y<1>} in Formula (11) is a divalent organic group containing an aromatic group from a viewpoint of the adhesiveness of an interlayer insulating film and a sealing material. Specifically, Y ¹ is represented by the following general formulas (6) to (8):

[Formula 42]

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

[Formula 43]

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

[Formula 44]

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

It is preferable that it is a divalent organic group containing at least 1 structure represented by.

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

From the viewpoint of thermal meltability, as Y ¹ , the following general formula (9):

[Formula 45]

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

Said polyamic acid ester WHEREIN: X<^1> in the repeating unit originates in the tetracarboxylic dianhydride ^{used as a raw material, Y<1>} originates in the diamine used as a raw material.

Although not limited as a tetracarboxylic dianhydride used as a raw material, For example, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone- 3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4' -tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis( 3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane and the like. Moreover, these may be used individually or in mixture of 2 or more types.

Examples of the diamine used as a raw material include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodi Phenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'- Diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3- Bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy) cy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl) Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy) Si)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidinesulfone, 9,9-bis(4-aminophenyl)fluorene, etc. are mentioned. Some of the hydrogen atoms on these benzene rings may be substituted. Moreover, these may be used individually or in mixture of 2 or more types.

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

The alcohols used in the esterification reaction of the tetracarboxylic dianhydride are alcohols having an olefinic double bond, and specifically, 2-hydroxyethyl methacrylate, 2-methacryloyloxyethyl alcohol, glycerin di Acrylate, glycerol dimethacrylate, etc. are mentioned, It is not limited to these. These alcohols can be used individually or in mixture of 2 or more types.

As for the specific synthesis method of the polyamic acid ester (A) used for this embodiment, a conventionally well-known method is employable. About the synthesis method, the method shown by the international publication 00/43439 pamphlet is mentioned, for example. That is, a tetracarboxylic acid diester is once converted into a tetracarboxylic acid diester diacid, and the tetracarboxylic acid diester diacid and diamine are subjected to a condensation reaction in the presence of a basic compound to obtain a polyamic acid ester (A) to manufacture Moreover, as a synthetic|combination method, the method of manufacturing polyamic-acid ester (A) by the method of using tetracarboxylic-acid diester and diamine to a condensation reaction in presence of an organic dehydrating agent is mentioned.

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

It is preferable that it is 6,000-150,000, as for the weight average molecular weight of polyamic acid ester (A) used for this embodiment, it is more preferable that it is 7,000-50,000, It is more preferable that it is 7,000-20,000.

(B1) photoinitiator

In the case of negative photosensitive resin, a photoinitiator is added to the resin composition. Examples of the photoinitiator 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-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; azides such as 2,6-di(4'-diadobenzal)-4-methylcyclohexanone and 2,6'-di(4'-diadobenzal)cyclohexanone; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-( O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl- oximes such as 3-ethoxypropanetrione-2-(O-benzoyl)oxime; N-arylglycines, such as N-phenylglycine; peroxides such as benzoyl peroxide; aromatic biimidazoles; And titanocenes and the like are used. Among these, the said oximes are preferable at the point of photosensitivity.

1-40 mass parts is preferable with respect to 100 mass parts of polyamic acid ester (A), and, as for the addition amount of a photoinitiator, 2-20 mass parts is more preferable. By adding 1 mass part or more of photoinitiators with respect to 100 mass parts of polyamic acid ester (A), it is excellent in photosensitivity. Moreover, it is excellent in thick-film sclerosis|hardenability by adding 40 mass parts or less of photoinitiators.

(B2) photoacid generator

In the case of positive photosensitive resin, a photo-acid generator is added to a resin composition. When a resin composition contains a photo-acid generator, an acid generate|occur|produces in an ultraviolet-ray exposure part, and the solubility with respect to the aqueous alkali solution of an exposure part increases. Thereby, resin can be used as a positive photosensitive resin composition.

As a photo-acid generator, a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, an iodonium salt, etc. are mentioned, for example. Among these, a quinonediazide compound is preferably used from a viewpoint that the outstanding dissolution inhibitory effect is expressed and a highly sensitive positive photosensitive resin composition can be obtained. Moreover, you may contain 2 or more types of photo-acid generators.

(C) solvent

(C) The solvent is the same as the solvent described in the above item [Photosensitive resin composition containing phenol resin]. Also about the kind and amount of preferable solvent, it is the same as that of the kind and amount demonstrated in the said item [Photosensitive resin composition containing a phenol resin].

<Polyimide>

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

[Formula 46]

{In formula (1), X ¹ , Y ^{1 , and m may be the same as X 1} , Y ¹ , and m defined in the general formula (11), 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.}

is represented by

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

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

[Photosensitive resin composition containing polybenzoxazole precursor]

(A) Polybenzoxazole precursor

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

[Formula 47]

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

Poly(o-hydroxyamide) including a repeating unit represented by can be used.

From the viewpoint of thermal meltability, U in the formula (14) is preferably a divalent organic group having 1 to 30 carbon atoms, and 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) ) is more preferable, and a chain alkylene group having 1 to 8 carbon atoms and in which some or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.

Moreover, it is preferable that V in Formula (14) is a divalent organic group containing an aromatic group from a viewpoint of thermal meltability, More preferably, the following general formulas (6)-(8):

[Formula 48]

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

[Formula 49]

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

[Formula 50]

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

It is a divalent organic group containing at least 1 structure represented by.

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

From the viewpoint of thermal meltability, V is represented by the following general formula (9):

[Formula 51]

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

From the viewpoint of thermal meltability, V is preferably a divalent organic group having 1 to 40 carbon atoms, more preferably a divalent chain aliphatic group having 1 to 40 carbon atoms, and particularly preferably a divalent chain aliphatic group having 1 to 20 carbon atoms. .

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

A dichloride derivative can be synthesize|combined by making a halogenating agent act on a dicarboxylic acid derivative. As a halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc. which are used for the acid chloride reaction of common carboxylic acid can be used.

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

Examples of the dicarboxylic acid used for the dicarboxylic acid derivative include isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoro Propane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p -Carboxyphenyl)propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, malonic acid, dimethylmalonic acid , ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, Hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, Adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid , azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanoic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecandioic acid, octadecanedioic acid , nonadecanic acid, icosane diacid, henic acid diacid, docosic acid diacid, trichoic acid diacid, tetracosan diacid, pentacoic acid diacid, hexacoic acid diacid, heptaconic acid diacid, octacoic acid diacid, nonaconic acid diacid, triacone tandioic acid, hentriacontandioic acid, dotriacontandioic acid, diglycolic acid, etc. are mentioned. You may mix and use these.

Examples of the hydroxyl group-containing diamine include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydr Roxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3 -hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane etc. are mentioned. You may mix and use these.

(B2) photoacid generator

A photo-acid generator has the function of increasing the solubility of the aqueous alkali solution of a light irradiation part. Examples of the photoacid generator include a diazonaphthoquinone compound, an aryldiazonium salt, a diaryliodonium salt, and a triarylsulfonium salt. Among these, the diazonaphthoquinone compound has high sensitivity and is preferable.

(C) solvent

(C) The solvent is the same as the solvent described in the above item [Photosensitive resin composition containing phenol resin]. Also about the kind and amount of preferable solvent, it is the same as that of the kind and amount demonstrated in the said item [Photosensitive resin composition containing a phenol resin].

<Polybenzoxazole>

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

[Formula 52]

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

is indicated by Preferred U and V in the general formula (14) are also preferable in the polybenzoxazole of the general formula (10) for the same reasons as those 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 a phenol resin from the viewpoint of thermal meltability. It is preferable to include

<Second Embodiment: Low Melting Viscosity Photosensitive Layer Roll>

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

a support film;

A photosensitive layer comprising a photosensitive resin composition formed on the support film

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· It is a layer having a temperature point below s.

Since the conventional photosensitive layer roll has a high melt viscosity of the photosensitive layer, there is a problem that cracks are easily generated even when the slit is slit by heating the teeth of the slitter during slitting.

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

The photosensitive layer according to the present embodiment is a layer having a temperature point at which the melt viscosity is 500 Pa·s or less. The photosensitive layer is preferably a layer having a temperature point at which the melt viscosity becomes 450 Pa·s or less, preferably a layer having a temperature point at which it becomes 400 Pa·s or less, and has a temperature point at which it becomes 350 Pa·s or less. It is preferably a layer, 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 becomes possible to suppress the occurrence of cracks in the slit, particularly in the case of heating and slitting the teeth of the slitter.

The photosensitive layer of this embodiment has a melt viscosity at 100°C of preferably 500 Pa·s or less, preferably 450 Pa·s or less, preferably 400 Pa·s or less, and 350 Pa·s or less. Preferably, it is preferably 300 Pa·s or less, preferably 250 Pa·s or less, preferably 200 Pa·s or less, preferably 150 Pa·s or less, and preferably 100 Pa·s or less.

The photosensitive layer roll which concerns on 2nd Embodiment may have a cover film on the opposite side to the side in which the said support body film of the photosensitive layer was formed.

If a cover film is provided, wrinkles may occur during slitting, particularly when slitting by heating the teeth of the slitter. do.

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

The melt viscosity of the photosensitive layer can be adjusted with the type and/or amount of the organic solvent contained in the photosensitive layer. The details will be described later. In other respects, it is the same as the structure described in the said item <1st Embodiment: Two-layer photosensitive layer roll>.

<Production and use of photosensitive layer roll>

The manufacturing method of the photosensitive film which concerns on this embodiment is demonstrated.

A photosensitive layer can be formed by apply|coating the said photosensitive resin composition on a support body film as a liquid photosensitive resin composition.

As a method of application|coating, methods, such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, are mentioned, for example. Moreover, removal of a solvent (C) can be performed by heating, for example. When removing the organic solvent from the viewpoint of the remaining amount of the organic solvent in the photosensitive layer, the heating temperature is preferably about 70 to 150°C, more preferably 100 to 140°C, and/or the heating time is preferably is from about 1 minute to 30 minutes, more preferably from about 3 minutes to 20 minutes, still more preferably from about 4 minutes to 10 minutes.

Moreover, although the thickness of a photosensitive layer changes with uses, it is preferable that the thickness after removing a solvent is about 1-30 micrometers. The photosensitive film may further be equipped with intermediate|middle layers, such as a cushion layer, a contact bonding layer, a light absorption layer, and a gas barrier layer, or a cover film between a support body film and a photosensitive layer.

The photosensitive film can be wound around a core having a cylindrical shape or the like, and stored as a photosensitive layer roll in a roll shape. The core is not particularly limited as long as it is conventionally used, and the material is, for example, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer). Plastics, such as these, are mentioned. At the time of storage, it is preferable to wind up so that a support film may become outermost. Moreover, on the end face of the photosensitive film (photosensitive film roll) wound up in roll shape, it is preferable to provide an end face separator from a viewpoint of end surface protection, and also from a viewpoint of internal fusion, it is preferable to provide a moisture-proof end surface separator. do. Moreover, when packing a photosensitive film or a photosensitive layer roll, it is preferable to wrap in the black sheet with low moisture permeability and to package.

<Slit of photosensitive layer roll>

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

From the viewpoint of suppressing wrinkles or cracks on the cut surface of the slitter, 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 higher, or 130 °C or higher.

When the photosensitive layer roll has a cover film, wrinkles may occur in the cover film at the time of slitting. In particular, when slitting by heating the teeth of the slitter, large wrinkles may occur in the cover film. From the viewpoint of suppressing wrinkling of the cover film that occurs during slitting, the method for 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 on which the support film is formed of the photosensitive layer;

slitting the photosensitive layer roll not having the cover film with a slitter;

Step of attaching the peeled cover film or a cover film different from the peeled cover film to the slitted photosensitive layer roll

It is preferable to include

<Lamination of photosensitive layer on substrate>

As a method of laminating the photosensitive layer of the slit photosensitive layer roll on the substrate, while the photosensitive layer is heated to about 70 to 130° C., the substrate is subjected to a pressure of about 0.1 to 1 MPa (that is, about 1 to 10 kgf/cm 2 ) using a laminator or the like. and a method of pressing using The lamination process may be performed under reduced pressure. The surface of the base material on which the photosensitive layer is laminated is not particularly limited.

In the case of the two-layer photosensitive layer roll which concerns on 1st Embodiment, since it does not have a cover film, there exists a possibility that a photosensitive layer may stick to a support body film (fear of blocking). On the other hand, when the adhesiveness of the photosensitive layer is made low, when the photosensitive layer is laminated on a base material, there is a possibility that the photosensitive layer may not adhere. That is, it is preferable that the two-layer photosensitive layer roll according to the first embodiment exhibits low adhesiveness under room temperature, which is a storage state, and exhibits high adhesiveness when heated when laminating on a substrate.

The amount of the organic solvent remaining in the photosensitive layer is preferably 0.1 mass % or more and 15 mass % or less with respect to the total amount of the photosensitive layer, from the viewpoint of achieving both adhesion at room temperature and formation of a photosensitive film that is easily melted by heat, and is 0.3 mass %. % or more and 15 mass% or less, preferably 0.5 mass% or more and 15 mass% or less, preferably 0.8 mass% or more and 15 mass% or less, preferably 1 mass% or more and 15 mass% or less, 3 mass% or more It is preferable that they are 14 mass % or less, It is preferable that they are 3 mass % or more and 13 mass % or less, and 5 mass % or more and 13 mass % or less are more preferable. If the amount of the organic solvent remaining in the photosensitive layer is within the above range, the tackiness is low at room temperature, and when the photosensitive layer roll is produced, the photosensitive layer is rarely adhered to the support film, and when the photosensitive layer is heated and laminated on the substrate, high meltability and exhibits high adhesiveness.

The organic solvent remaining in the photosensitive layer may be the solvent (C) described above, and from the viewpoint of solubility of the resin, stability of the resin composition, adhesion to the substrate, heat meltability, storage stability, and blocking properties, γ- Butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol are preferable, and among these, γ-buty Lolactone, acetone, methylethylketone, N-methyl-2-pyrrolidone and dimethylsulfoxide are particularly preferred.

Similarly, in the case of the low-melting-viscosity photosensitive layer roll according to the second embodiment, it has a high melt viscosity at room temperature, the adhesiveness of the photosensitive layer is low, and the slit, particularly, when slitting by heating the teeth of the slitter, is low. It is desired to have melt viscosity and to be difficult to crack. The amount of the organic solvent remaining in a preferable photosensitive layer is the same as the said range. The melt viscosity of the photosensitive layer can be adjusted by the amount of the organic solvent contained in the photosensitive layer. The greater the amount of 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 heating time for removing the organic solvent. In addition, it is possible to adjust the melt viscosity of the photosensitive layer by a method of lowering the molecular weight of the polymer or a method of increasing a low molecular weight component such as a plasticizer that is not thermally cured.

With respect to the photosensitive layer laminated on the substrate in this way, actinic light is irradiated as an image through a negative or positive mask pattern to form an exposed portion. At this time, when the support present on the photosensitive layer is transparent to actinic light, actinic light can be irradiated through the support. irradiate with actinic light.

As a light source of an actinic light, although X-ray, an electron beam, an ultraviolet-ray, a visible light, etc. can be used, the thing of a wavelength of 200-500 nm is preferable. It is preferable that the light source wavelength is the area|region of g line|wire, h line|wire, or i line|wire of a mercury lamp from the point of the resolution and handleability of a pattern, and may be independent, or two or more actinic rays may be mixed. As an exposure apparatus, an aligner, a parallel exposure machine, mirror projection, and a stepper are preferable. After exposure, you may heat a coating film at 80-140 degreeC again as needed.

Next, development can be performed by selecting from methods, such as an immersion method, a puddle method, and a spray method, using a developing solution. By development, an exposed part (in the case of a positive type) or an unexposed part (in the case of a negative type) can be eluted and removed from the apply|coated photosensitive resin layer, and a relief pattern can be obtained.

As a developing solution, For example, inorganic alkalis, such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines, such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium Aqueous solutions, such as quaternary ammonium salts, such as a hydroxide, and water-soluble organic solvents, such as methanol and ethanol, or the aqueous solution which added appropriate amount of surfactant as needed can be used. Among these, tetramethylammonium hydroxide aqueous solution is preferable. The density|concentration of tetramethylammonium hydroxide becomes like this. Preferably it is 0.5-10 mass %, More preferably, it is 1-5 mass %.

After development, the substrate with a relief pattern can be obtained by washing with a rinsing solution to remove the developing solution. As a rinse liquid, distilled water, methanol, ethanol, isopropanol, etc. can be used, for example, These can be used individually or in combination of 2 or more types.

Finally, a hardening relief pattern can be obtained by heating the relief pattern obtained in this way. 150 degrees C or more and 300 degrees C or less are preferable, and, as for heating temperature, 250 degrees C or less is more preferable.

A method for manufacturing a cured relief pattern using a photosensitive layer roll according to the first or second embodiment is a surface protective film, an interlayer insulating film, an insulating film for rewiring, a fan-out type wafer level package ( FOWLP), a protective film for flip-chip devices, a high-density substrate, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper clad plate, a solder resist film, and a liquid crystal alignment film. can be used

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to the said embodiment. Various modifications are possible in the present invention without departing from the gist thereof.

Example

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

[Synthesis Example 1]

<Synthesis of phenol resin (A-1)>

In a separable flask equipped with a Dean-Stark apparatus having a capacity of 0.5 liters, 100.9 g (0.8 mol) of phloroglucinol, 4,4'-bis(methoxymethyl)biphenyl (hereinafter also referred to as “BMMB”) 121.2 g (0.5 mol), 3.9 g (0.025 mol) of diethyl sulfuric acid, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70°C to dissolve the solid.

The mixed solution was heated to 140 degreeC with the oil bath, generation|occurrence|production of methanol was confirmed from the reaction liquid, and the reaction liquid was stirred at 140 degreeC as it was 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 diluent is added dropwise to 4 L of water under high-speed stirring, the resin is dispersed and precipitated, and this is recovered, washed with water and dehydrated appropriately, and then vacuum dried, and a copolymer composed of phloroglucinol/BMMB (phenol resin ( A-1)) was obtained in a yield of 70%.

[Synthesis Example 2]

<Synthesis of phenol resin (A-2)>

The synthesis was carried out in the same manner as in Synthesis Example 1 except that 128.3 g (0.76 mol) of 3,5-dihydroxybenzoate was used instead of phloroglucinol of Synthesis Example 1, and 3,5-dihydroxymethyl benzoate/ A copolymer (phenol resin (A-2)) composed of BMMB was obtained in a yield of 65%.

[Synthesis Example 3]

<Synthesis of phenol resin (A-3)>

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

The mixed solution was heated to 120 degreeC with the oil bath, generation|occurrence|production of methanol was confirmed from the reaction liquid, and the reaction liquid was stirred at 120 degreeC as it is 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 a uniformly dissolved solution was prepared using a dropping funnel, It was dripped at the separable flask over 1 hour, and it stirred after dripping for further 2 hours.

After completion of the reaction, the same treatment as in Synthesis Example 1 was performed to obtain a copolymer (phenol resin (A-3)) comprising resorcinol/BMMB/2,6-bis(hydroxymethyl)-p-cresol in a yield of 77 % was obtained.

[Synthesis Example 4]

<Synthesis of polyimide precursor (A-5)>

In a separable flask with a capacity of 2 L, 87.2 g (0.4 mol) of pyromellitic dianhydride, 59.3 g (0.8 mol) of isobutyl alcohol, and 320 g of γ-butyrolactone (hereinafter also referred to as “GBL”) were placed at room temperature. (25°C) was mixed and stirred, dissolved, and pyridine 63.3 g (0.8 mol) was added while stirring under ice cooling, and after completion of exotherm, it stood to cool to room temperature, and left to stand for 16 hours.

Next, the solution which melt|dissolved 165 g (0.8 mol) of dicyclohexylcarbodiimide in GBL 120g was added to the said separable flask in 40 minutes, stirring under ice cooling. Then, a suspension obtained by suspending 74.5 g (0.37 mol) of 4,4'-diaminodiphenyl ether in 150 g of GBL was added to the separable flask over 60 minutes while stirring under ice cooling. After stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added to the separable flask, stirred for 1 hour, and further 250 ml of dimethylacetamide (hereinafter referred to as "DMAc") and 400 ml of tetrahydrofuran (THF) After adding , the precipitate was removed by suction filtration to obtain a reaction solution. After adding the obtained reaction liquid to 15 L of ethyl alcohol and filtration-separating the produced|generated precipitation, it vacuum-dried and obtained the polyimide precursor (A-5).

[Synthesis Example 5]

<Synthesis of polybenzoxazole precursor (A-6)>

In a separable flask with a capacity of 2 L, 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 The mixture was stirred and dissolved at room temperature (25°C).

A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride in 88 g of dimethyldiglycol (hereinafter also referred to as “DMDG”) in the obtained mixed solution was separated from the dropping funnel. was dropped. The time required for dripping was 40 minutes, and the reaction liquid temperature was 28 degreeC at the maximum.

After completion of the dropwise addition, the reaction solution was heated to 50° C. by a hot water bath, stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to show characteristic absorption of imide groups at ^{1385 cm -1} and 1772 cm ^{-1 .} confirmed that.

Next, the reaction solution was cooled to 8°C with a water bath, and a solution in which 142.3 g (0.48 mol) of 4,4'-diphenyl ether dicarboxylic acid dichloride was dissolved in 398 g of DMDG was added to the reaction solution. It was dripped from the dropping funnel. The time required for dripping was 80 minutes, and the reaction liquid temperature was 12 degreeC at the maximum.

After 3 hours from the completion of the dropwise addition, the reaction solution is added dropwise to 12 L of water under high-speed stirring, the polymer is dispersed and precipitated, this is recovered, washed with water appropriately, dehydrated, then vacuum dried, and a polybenzoxazole precursor ( A-6) was obtained.

<Resin (A) and (A')>

A-1: Copolymer consisting of phloroglucinol/BMMB, polystyrene conversion weight average molecular weight (Mw) = 15,000

A-2: A copolymer comprising 3,5-dihydroxymethyl benzoate/BMMB, polystyrene conversion weight average molecular weight (Mw) = 21,000

A-3: a copolymer comprising resorcinol/BMMB/2,6-bis(hydroxymethyl)-p-cresol, polystyrene reduced weight average molecular weight (Mw) = 9,900

A-4: novolac resin, polystyrene equivalent weight average molecular weight (Mw) = 10,600 (manufactured by Asahi Organic Co., Ltd., product name EP-4080G)

A-5: polyimide precursor

A-6: polybenzoxazole precursor

<Mine generator (B)>

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

[Formula 53]

{wherein, 83% of Q is the following:

[Formula 54]

It is a structure represented by , and the remainder is a hydrogen atom.}

<Solvent (C)>

C-1: γ-butyrolactone (GBL)

C-2: methyl ethyl ketone

C-3: Acetone

C-4: N,N-dimethylformamide

<Surfactant (D)>

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

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

<Crosslinking agent (E)>

E-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical, trade name; Nikarac MX-270)

[Preparation of photosensitive resin composition]

According to the composition shown in Table 1 below, the resin (A), the photoacid generator (B), the surfactant (D), and the crosslinking agent (E) are dissolved in the solvent (C) and filtered with a 0.1 µm filter, A positive photosensitive resin composition was prepared.

[Support film]

As the support film, a PET film "PET25X" (manufactured by Lintec Co., Ltd., width 290 mm, thickness 25 µm) subjected to a release treatment with a silicone compound was prepared.

[Production of photosensitive film]

(Example 1)

As a support film, the solution of the photosensitive resin composition which has a composition shown in said Table 1 was apply|coated on the mold release process surface using "PET25X" which is a mold release process PET film. Then, the PET film to which the solution of the photosensitive resin composition was apply|coated was dried over 5 minutes by 120 degreeC hot air, and the photosensitive layer was formed. In that case, it was made so that the thickness of the photosensitive layer after heating was set to 10 micrometers. A photosensitive film of the composition having a width of 300 mm was applied to a cylindrical plastic tube having an outer diameter of 3.5 inches using a pressure roll arranged parallel to the crimp width direction in a linear manner against the plastic tube, and a tension of 7 kg was applied. It wound up 1000 m with this, and the photosensitive film roll was obtained.

(Examples 2-13)

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

(Comparative Examples 1 to 3)

In the same procedure as in Example 1, except that the components, compositions and 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 to obtain a photosensitive film roll, each photosensitive A film roll was made.

<Residual solvent>

The photosensitive film was unwound from the photosensitive film rolls prepared in Examples and Comparative Examples, respectively, the photosensitive layer was peeled from the support film, and the peeled photosensitive layer was analyzed by gas chromatography (manufactured by Agilent Technology Co., Ltd., trade name "6890N"). Thus, the amount of residual solvent (parts by mass) with respect to 100 parts by mass of the phenol resin was measured.

<Melt viscosity>

The photosensitive film was unwound from the photosensitive film roll produced in each of the 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 device (manufactured by TAA Instruments Japan Co., Ltd., product name " DHR-2"), and it measured under the following conditions. Table 1 shows the melt viscosity at a temperature of 100°C.

・Sample shape

Film thickness: 0.5 mmt

Diameter: 25 mm disc

·Measuring conditions

Start temperature: 50℃

Temperature increase rate: 5 ℃/min

End temperature: 220℃

Deformation: 0.1%

Frequency: 1 Hz

Load: 0.5 N (±0.1 N)

<Storage stability>

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

S (remarkably good): A photosensitive layer does not adhere to the back surface of a support body film even if it preserve|saves at room temperature for 1 month or more in roll form.

A (good): A part of a photosensitive layer adheres to the back surface of a support body film when it preserve|saves at room temperature for 1 month in roll form.

<Peelability of support film>

The photosensitive film was unwound from the photosensitive film rolls prepared in Examples and Comparative Examples, respectively, and the photosensitive layer was laminated on a glass plate while heating to 130 ° C., to prepare a sample for property evaluation in which the photosensitive layer was transferred. Next, the support film was peeled off from the sample for characteristic evaluation, and the transfer state of the photosensitive layer was visually evaluated.

S (remarkably good): Peeling and removal are possible without a photosensitive layer adhering to a support film.

A (good): In a part of the photosensitive layer, it peels in the state which the photosensitive layer adhered to the support film.

B (defective): Peeling in a state in which the photosensitive layer was adhered to the support film from the entire surface of the photosensitive layer.

<Crack at slit>

The photosensitive film rolls each produced in the Example and the comparative example were slitted with the slitter which heated the sawtooth at 100 degreeC. The occurrence of cracks upon slitting and the aesthetics of the cut surface were visually evaluated.

S (remarkably good): A crack does not generate|occur|produce and a cut surface is also smooth.

A (good): A crack is not generated, but there are some irregularities in the cut surface.

B (defective): A crack occurred.

<Wrinkles of the cover film>

The photosensitive film roll produced in the comparative example was slitted by the slitter which has a tooth|tooth heated to 100 degreeC, and the wrinkles which generate|occur|produced in the cover film were evaluated visually.

A (good): Wrinkles do not occur in the cover film.

B (defective): Wrinkles occurred in the cover film.

<Evaluation result>

For each Example and Comparative Example, each characteristic evaluation result is shown in Table 1 above.

Industrial Applicability

The photosensitive layer roll of the present invention is a semiconductor device, a surface protective film for a display device and a light emitting device, an interlayer insulating film, an insulating film for redistribution, a redistribution layer for a wafer level package, a protective film for a flip chip device, a high-density substrate, a device having a bump structure It can be used suitably as a protective film of , the interlayer insulating film of a multilayer circuit, the cover coat of a flexible copper clad board, a soldering resist film, a liquid crystal aligning film, etc.

Claims (40)

a support film;
A photosensitive layer comprising a photosensitive resin composition, formed on the support film
As a photosensitive layer roll having,
At least one surface of the support film is subjected to a release treatment,
The photosensitive layer is formed on the surface of the support film subjected to the release treatment,
The photosensitive resin composition contains at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and the photosensitive layer has a melt viscosity of 500 Pa·s or less It is a layer with a temperature point where
A cover film is provided on the side opposite to the side on which the support film is formed of the photosensitive layer, and the softening temperature of the cover film is 110° C. or higher;
The photosensitive layer roll, wherein the amount of the organic solvent contained in the photosensitive layer is 0.1 mass% or more and 15 mass% or less with respect to the total amount of the photosensitive layer. The method of claim 1,
The photosensitive layer is a layer having a temperature point at which the melt viscosity is 350 Pa·s or less. The method of claim 1,
The said photosensitive layer is a photosensitive layer roll whose melt viscosity in 100 degreeC is 500 Pa*s or less. 4. The method of claim 3,
The said photosensitive layer is a photosensitive layer roll whose melt viscosity in 100 degreeC is 350 Pa*s or less. The method of claim 1,
At least one of the resins included in the photosensitive resin composition has a weight average molecular weight of 10,600 to 21,000, the photosensitive layer roll. The method of claim 1,
The photosensitive layer roll of which the quantity of the organic solvent contained in the said photosensitive layer is 1 mass % or more and 15 mass % or less with respect to the total amount of the said photosensitive layer. The method of claim 1,
the organic solvent is γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol. At least one selected from, the photosensitive layer roll. 8. The method of claim 7,
The photosensitive layer roll, wherein the organic solvent contains at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethyl sulfoxide. The method of claim 1,
The photosensitive resin composition comprises the polyimide precursor, a photosensitive layer roll. The method of claim 1,
The photosensitive resin composition comprising the polybenzoxazole precursor, photosensitive layer roll. The method of claim 1,
A photosensitive layer roll, wherein the photosensitive resin composition comprises the soluble polyimide. The method of claim 1,
The photosensitive resin composition contains the said phenolic resin, photosensitive layer roll. 13. The method of claim 12,
The phenol resin has the following general formula (1):

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

(In formula (2), p is an integer of 1 to 10.) A divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by and a divalent organic group having an aromatic ring is shown.}
A photosensitive layer roll having a structure represented by , as a repeating unit. 14. The method of claim 13,
X in the said general formula (1) is following general formula (3):

{In formula (3), R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon number in which some or all of the hydrogen atoms are substituted with fluorine atoms. is a monovalent aliphatic group of 1 to 10, n1 is an integer of 0 to 4, R ₆ when n1 is an integer of 1 to 4 is a halogen atom, a hydroxyl group, or a monovalent organic group, and at least one R ₆ is It is a hydroxyl group, and several R<_6> in case n1 is an integer of 2-4 may be same or different, respectively.}
A divalent group represented by, and the following general formula (4):

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

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

It is a divalent organic group selected from the group consisting of a divalent group represented by.}
A photosensitive layer roll, which is a divalent organic group selected from the group consisting of a divalent group represented by . 14. The method of claim 13,
X in the said general formula (1) is following formula (6):

A photosensitive layer roll, which is a divalent organic group represented by . 16. The method of claim 15,
X in the said general formula (1) is following formula (7):

A photosensitive layer roll, which is a divalent organic group represented by . 14. The method of claim 13,
The phenol resin has the following general formula (8):

{In formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n2 is an integer of 1 to 3, n3 is an integer of 0 to 2, m1 is an integer from 1 to 500, 2 ≤ (n2 + n3) ≤ 4, and R ₁₁ when n3 is 2 may be the same or different, respectively.}, and a repeating unit represented by the following general formula (9):

{In formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n4 is an integer of 1 to 3, n5 is 0 to is an integer of 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≤ (n4 + n5) ≤ 4, and R ₁₂ when n5 is 2 may be the same or different, respectively _{, R 13} when n6 is 2 or 3 may be the same or different, respectively.}
A photosensitive layer roll having both of the repeating units represented by , in the same resin skeleton. The method of claim 1,
The photosensitive layer roll whose quantity of the organic solvent contained in the said photosensitive layer is 3 mass % or more and 14 mass % or less with respect to the total amount of the said photosensitive layer. a support film;
A photosensitive layer comprising a photosensitive resin composition, formed on the support film
As a photosensitive layer roll having,
At least one surface of the support film is subjected to a release treatment,
The photosensitive layer is formed on the surface of the support film subjected to the release treatment,
The photosensitive resin composition contains at least one resin selected from the group consisting of a phenol resin, a polyimide precursor, a polybenzoxazole precursor, and a soluble polyimide, and both surfaces of the support film are in contact with the photosensitive layer, ,
The photosensitive layer roll, wherein the amount of the organic solvent contained in the photosensitive layer is 0.1 mass% or more and 15 mass% or less with respect to the total amount of the photosensitive layer. 20. The method of claim 19,
At least one of the resins included in the photosensitive resin composition has a weight average molecular weight of 10,600 to 21,000, the photosensitive layer roll. 20. The method of claim 19,
The photosensitive layer roll of which the quantity of the organic solvent contained in the said photosensitive layer is 1 mass % or more and 15 mass % or less with respect to the total amount of the said photosensitive layer. delete 20. The method of claim 19,
the organic solvent is γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, tert-butyl alcohol and tetrahydrofurfuryl alcohol. At least one selected from, the photosensitive layer roll. 24. The method of claim 23,
The photosensitive layer roll, wherein the organic solvent contains at least one selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and dimethyl sulfoxide. 20. The method of claim 19,
The photosensitive resin composition comprises the polyimide precursor, a photosensitive layer roll. 20. The method of claim 19,
The photosensitive resin composition comprising the polybenzoxazole precursor, photosensitive layer roll. 20. The method of claim 19,
A photosensitive layer roll, wherein the photosensitive resin composition comprises the soluble polyimide. 20. The method of claim 19,
The photosensitive resin composition contains a phenol resin, the photosensitive layer roll. 29. The method of claim 28,
The phenol resin has the following general formula (1):

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

(In formula (2), p is an integer of 1 to 10.) A divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by and a divalent organic group having an aromatic ring is shown.}
A photosensitive layer roll having a structure represented by as a repeating unit. 30. The method of claim 29,
X in the said general formula (1) is following general formula (3):

{In formula (3), R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon number in which some or all of the hydrogen atoms are substituted with fluorine atoms. is a monovalent aliphatic group of 1 to 10, n1 is an integer of 0 to 4, R ₆ when n1 is an integer of 1 to 4 is a halogen atom, a hydroxyl group, or a monovalent organic group, and at least one R ₆ is It is a hydroxyl group, and several R<_6> in case n1 is an integer of 2-4 may be same or different, respectively.}
A divalent group represented by, and the following general formula (4):

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

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

It is a divalent organic group selected from the group consisting of a divalent group represented by.}
A photosensitive layer roll, which is a divalent organic group selected from the group consisting of a divalent group represented by . 30. The method of claim 29,
X in the said general formula (1) is following formula (6):

A photosensitive layer roll, which is a divalent organic group represented by . 32. The method of claim 31
X in the said general formula (1) is following formula (7):

A photosensitive layer roll, which is a divalent organic group represented by . 30. The method of claim 29,
The phenol resin has the following general formula (8):

{In formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n2 is an integer of 1 to 3, n3 is an integer of 0 to 2, m1 is an integer from 1 to 500, 2 ≤ (n2 + n3) ≤ 4, and R ₁₁ when n3 is 2 may be the same or different, respectively.}
A repeating unit represented by, and the following general formula (9):

{In formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n4 is an integer of 1 to 3, n5 is 0 to is an integer of 2, n6 is an integer of 0 to 3, m2 is an integer of 1 to 500, 2 ≤ (n4 + n5) ≤ 4, and R ₁₂ when n5 is 2 may be the same or different, respectively _{, R 13} in the case where n6 is 2 or 3 may be the same or different, respectively.} A photosensitive layer roll having both of the repeating units represented by } in the same resin skeleton. 20. The method of claim 19,
The photosensitive layer roll whose quantity of the organic solvent contained in the said photosensitive layer is 3 mass % or more and 14 mass % or less with respect to the total amount of the said photosensitive layer. A method for producing a slit photosensitive layer roll, wherein the slit photosensitive layer roll is manufactured by slitting the photosensitive layer roll according to any one of claims 1 to 21 and 23 to 34 with a slitter. 36. The method of claim 35,
A method for manufacturing a slit photosensitive layer roll, wherein the teeth of the slitter are being heated. 37. The method of claim 36,
A method for manufacturing a slit photosensitive layer roll, wherein the teeth of the slitter are heated to 100° C. or higher. The following process:
When the photosensitive layer roll of any one of Claims 1-21 and 23-34 has a cover film on the opposite side to the side on which the said support body film of the said photosensitive layer was formed, the said cover film a process of peeling the
slitting the photosensitive layer roll not having the cover film with a slitter;
Step of attaching the peeled cover film or a cover film different from the peeled cover film to the slitted photosensitive layer roll
A method of manufacturing a slit photosensitive layer roll comprising a. 39. The method of claim 38,
A method for manufacturing a slit photosensitive layer roll, wherein the teeth of the slitter are being heated. 40. The method of claim 39,
A method for manufacturing a slit photosensitive layer roll, wherein the teeth of the slitter are heated to 100° C. or higher.