JP5948538B2 - Method for manufacturing silicon wafer having insulating film - Google Patents

Description

  The present invention relates to a method for producing a silicon wafer having an insulating film and a silicon wafer obtained by the method.

  Conventionally, as a material such as an interlayer insulating film used for a semiconductor element of an electronic device, a polyimide resin or a polybenzoxazole resin that is excellent in heat resistance, mechanical characteristics, and the like has been widely used. Various studies have been made on the use of photosensitive polyimide or photosensitive polybenzoxazole-based resins imparted with photosensitivity in order to improve productivity and film formation accuracy.

  In recent years, a silicon wafer has been required to be enlarged from the viewpoint of improving productivity. However, when an insulating film is formed on a large silicon wafer, the shrinkage / insulation during curing of the insulating film is required. The generation of residual stress due to the difference in coefficient of linear expansion between the film and the silicon wafer and the warpage of the silicon wafer associated therewith have become a major problem, and improvements in reducing residual stress and warpage have been demanded.

  Under such circumstances, various photosensitive resin compositions capable of improving the occurrence of residual stress in the cured product have been proposed. For example, Patent Document 1 discloses a photosensitive property whose residual stress in a film is 15 MPa / μm or less. A resin composition is disclosed. Patent Document 2 discloses that a photosensitive resin composition containing an aromatic polyimide precursor has a light transmittance of 1% or more at a wavelength of 365 nm in a 10 μm thick layer of the aromatic polyimide precursor. And the photosensitive resin composition whose residual stress of the polyimide film with a film thickness of 10 micrometers deposited from the said resin composition on the silicon wafer by the imidization ring closure reaction is 25 Mpa or less is disclosed. Furthermore, Patent Document 3 states that at a film thickness of 20 μm, the transmittance of i-line (wavelength is 365 nm) is 20% or more, and the residual stress of the polyimide film obtained by curing this is 30 MPa or less. A characteristic photosensitive resin composition is disclosed.

  On the other hand, a large silicon wafer having an insulating film characterized by containing a resin having a phenolic hydroxyl group is disclosed (Patent Document 4). It is disclosed that these systems have a small wafer residual stress (30 MPa or less) and a small amount of warpage (300 μm or less) when the wafer diameter is 8 inches or more.

Japanese Patent No. 4368472 Japanese Patent No. 3475924 Japanese Patent No. 4207420 Japanese Patent No. 4765951

  In Patent Documents 1 to 3, the decrease in residual stress has been demonstrated only for small silicon wafers of about 5 inches. Document 4 discloses that a large-sized wafer of 8 inches or more has a small residual stress and warpage, but the wafer thickness is only 712 μm.

  In order to cope with the lighter and thinner semiconductor devices in recent years, thinner silicon wafers have been used. As a method of thinning the silicon wafer, a process of grinding the back surface of the silicon wafer to reduce the thickness of the silicon wafer is performed. In this wafer back grinding process, a back grind tape is first applied to the surface of a silicon wafer having an insulating film, the back surface of the silicon wafer is ground until the silicon wafer thickness is about 20 to 600 μm, and UV light is applied to the back grind tape. Irradiate and peel back grind tape. With the thinning of the silicon wafer, the problem that the amount of warpage of the silicon wafer becomes more prominent and the toughness of the insulating film formed on the silicon wafer is low. There existed a subject that a crack generate | occur | produces or an insulating film peels.

  Therefore, according to the present invention, when an insulating film is formed on a large and thin silicon wafer, the amount of warpage of the silicon wafer on which the insulating film is formed is small, and no crack is generated in the insulating film in the wafer back grinding process. It is an object to provide a method for producing a silicon wafer and a silicon wafer obtained by the method.

  The present invention is as follows.

｛式（１）中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ₁は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基から成る群から選ばれる少なくとも１つの１価の置換基を表し、ｂが２〜３である場合には、複数のＲ₁は、それぞれ同一であるか、又は異なっていてよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（８）：

（式（８）中、ｐは、１〜１０の整数であり、そしてｑは、１〜２０の整数である。）で表されるアルキレンオキシド基、及び芳香族基を有する２価の有機基から成る群から選ばれる少なくとも１つの２価の有機基を表す。｝
で表され、かつ水酸基当量が２５０ｇ／ｅｑ以下である繰り返し単位を有するフェノール樹脂：１００質量部；
（Ｂ）感光剤：０．１質量部〜１００質量部；
（Ｃ）架橋剤：１質量部〜５０質量部；及び
（Ｄ）溶剤：１０質量部〜１０００質量部；
を含む感光性樹脂組成物を、直径が８インチ以上であり、かつ厚さが２００μｍ〜８００μｍであるシリコンウエハに塗布する工程、
（ｉｉ）該感光性樹脂組成物が塗布されたシリコンウエハを加熱することにより溶剤を揮発させて、塗膜を有するシリコンウエハを得る工程、
（ｉｉｉ）該塗膜を有するシリコンウエハを露光する工程、
（ｉｖ）該塗膜を有するシリコンウエハをアルカリ現像液により現像する工程、
（ｖ）該塗膜を有するシリコンウエハを１００℃以上４００℃以下の温度で加熱することにより該塗膜を硬化して、絶縁膜を有するシリコンウエハを得る工程、並びに
（ｖｉ）該絶縁膜を有するシリコンウエハを、該シリコンウエハの厚さが２０μｍ〜６００μｍになるまでバックグラインドする工程、
を含む、絶縁膜を有するシリコンウエハの製造方法。 [1] (i) The following components:
(A) The following general formula (1):

{Wherein (1), a is an integer of 1 to 3, b is an integer of 0 to 3, a 1 ≦ (a + b) ≦ 4, R 1 is 1 1 to 20 carbon atoms Represents at least one monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 to 3, a plurality of R _{1 s} are the same. X may be or may be different, and X represents a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, General formula (8):

(In formula (8), p is an integer of 1 to 10 and q is an integer of 1 to 20) and a divalent organic group having an aromatic group Represents at least one divalent organic group selected from the group consisting of }
And a phenolic resin having a repeating unit having a hydroxyl group equivalent of 250 g / eq or less: 100 parts by mass;
(B) Photosensitizer: 0.1 to 100 parts by mass;
(C) Crosslinking agent: 1 part by mass to 50 parts by mass; and (D) Solvent: 10 parts by mass to 1000 parts by mass;
A step of applying a photosensitive resin composition comprising a silicon wafer having a diameter of 8 inches or more and a thickness of 200 μm to 800 μm;
(Ii) a step of obtaining a silicon wafer having a coating film by volatilizing the solvent by heating the silicon wafer coated with the photosensitive resin composition;
(Iii) exposing a silicon wafer having the coating film;
(Iv) developing a silicon wafer having the coating film with an alkali developer;
(V) a step of curing the coating film by heating the silicon wafer having the coating film at a temperature of 100 ° C. or more and 400 ° C. or less to obtain a silicon wafer having an insulating film; and (vi) the insulating film Back grinding a silicon wafer having a thickness of 20 μm to 600 μm,
A method for manufacturing a silicon wafer having an insulating film, comprising:

  [2] The production method according to [1], wherein in the general formula (1), a is an integer of 2 or 3, and b is an integer of 0 to 2.

｛式（２）中、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基、炭素数３〜２０の脂環式基、又は炭素数６〜２０の芳香族基を表し、そしてＲ_５は、不飽和結合を有していてもよい炭素数１〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、又は炭素数６〜２０の２価の芳香族基を表す。｝
で表される基から成る群から選ばれる少なくとも１つの１価の置換基である、［１］又は［２］に記載の製造方法。 [3] In the general formula (1), R ₁ is a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or a carbon atom having 3 to 20 carbon atoms. An alicyclic group, an aromatic group having 6 to 20 carbon atoms, and the following general formula (2):

{In Formula (2), R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or 3 to 20 carbon atoms. Represents an alicyclic group or an aromatic group having 6 to 20 carbon atoms, and R ₅ represents a divalent aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, and 3 to 3 carbon atoms. 20 bivalent alicyclic group or a C6-C20 bivalent aromatic group is represented. }
The production method according to [1] or [2], which is at least one monovalent substituent selected from the group consisting of groups represented by:

｛式（３）中、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０は、それぞれ独立に、水素原子、又はフッ素原子で置換されていてもよい炭素数１〜１０の脂肪族基を表す。｝

｛式（４）中、Ｒ_１１、Ｒ_１２、Ｒ_１３及びＲ_１４は、それぞれ独立に、水素原子、又はフッ素原子で置換されていてもよい炭素数１〜１０の脂肪族基を表し、そしてＺは、単結合、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族基、フッ素原子で置換されていてもよい炭素数３〜２０の脂環式基、下記一般式（８）：

（式（８）中、ｐは、１〜１０の整数であり、そしてｑは、１〜２０の整数である。）で表されるアルキレンオキシド基、及び下記式（５）：

で表される２価の基から成る群から選ばれる少なくとも１つの２価の有機基である。｝
で表される２価の有機基である、［１］〜［３］のいずれか一項に記載の製造方法。 [4] In the general formula (1), X represents the following general formula (3) or (4):

{In Formula (3), R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom or an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom. }

{In Formula (4), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and Z represents a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, the following general formula (8 ):

(In the formula (8), p is an integer of 1 to 10, and q is an integer of 1 to 20), and the following formula (5):

And at least one divalent organic group selected from the group consisting of divalent groups represented by: }
The manufacturing method as described in any one of [1]-[3] which is a bivalent organic group represented by these.

で表される２価の有機基である、［１］〜［４］のいずれか一項に記載の製造方法。 [5] In the general formula (1), X represents the following general formula (6):

The manufacturing method as described in any one of [1]-[4] which is a bivalent organic group represented by these.

で表される２価の有機基である、［１］〜［５］のいずれか一項に記載の製造方法。 [6] In the general formula (1), X represents the following general formula (7):

The manufacturing method as described in any one of [1]-[5] which is a bivalent organic group represented by these.

  [7] A silicon wafer having an insulating film, obtained by the manufacturing method according to any one of [1] to [6].

  According to the present invention, when an insulating film is formed on a large and thin silicon wafer, the amount of warpage of the silicon wafer on which the insulating film is formed is small, and the insulating film is not cracked in the wafer back grinding process. A method for producing a silicon wafer and a silicon wafer obtained by the method can be provided.

  Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “this embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

｛式（１）中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ₁は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基から成る群から選ばれる少なくとも１つの１価の置換基を表し、ｂが２〜３である場合には、複数のＲ₁は、それぞれ同一であるか、又は異なっていてよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（８）：

（式（８）中、ｐは、１〜１０の整数であり、そしてｑは、１〜２０の整数である。）で表されるアルキレンオキシド基、及び芳香族基を有する２価の有機基から成る群から選ばれる少なくとも１つの２価の有機基を表す。｝
以下、（Ａ）〜（Ｄ）の各成分を順に説明する。 In the present embodiment, a method for producing a silicon wafer having an insulating film includes: (A) a phenol resin represented by the following general formula (1) and having a repeating unit having a hydroxyl group equivalent of 250 g / eq or less: 100 parts by mass; (B) Photosensitive agent: 0.1 parts by mass to 100 parts by mass, (C) Crosslinker: 1 part by mass to 50 parts by mass, and (D) Solvent: 10 parts by mass to 1000 parts by mass (I) is applied to a silicon wafer having a diameter of 8 inches or more.

{Wherein (1), a is an integer of 1 to 3, b is an integer of 0 to 3, a 1 ≦ (a + b) ≦ 4, R 1 is 1 1 to 20 carbon atoms Represents at least one monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 to 3, a plurality of R _{1 s} are the same. X may be or may be different, and X represents a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, General formula (8):

(In formula (8), p is an integer of 1 to 10 and q is an integer of 1 to 20) and a divalent organic group having an aromatic group Represents at least one divalent organic group selected from the group consisting of }
Hereinafter, each component of (A)-(D) is demonstrated in order.

(A) Phenol resin In this embodiment, the phenol resin (A) has a repeating unit represented by the general formula (1) and having a hydroxyl group equivalent of 250 g / eq or less.

In this embodiment, the hydroxyl equivalent means a value that can be obtained from the following formula.
Hydroxyl equivalent (g / eq) = molecular weight per unit structure of resin / number of hydroxyl groups per unit structure of resin

  In the present embodiment, the hydroxyl group equivalent per repeating unit contained in the phenol resin (A) is not limited as long as it is 250 g / eq or less, but from the viewpoint of the warpage amount of the silicon wafer, alkali solubility, etc., 25 g / eq or more and 200 g. / eq or less, more preferably 25 g / eq or more and 175 g / eq or less.

｛式（２）中、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基、炭素数３〜２０の脂環式基、又は炭素数６〜２０の芳香族基を表し、そしてＲ_５は、不飽和結合を有していてもよい炭素数１〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、又は炭素数６〜２０の２価の芳香族基を表す。｝ In the present embodiment, the phenol resin (A) has a repeating unit represented by the general formula (1). In the general formula (1), R ₁ represents at least one 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. More specifically, R ₁ is, from the viewpoint of alkali solubility, a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms that may have an unsaturated bond, or 3 to 20 carbon atoms. Are preferably at least one monovalent substituent selected from the group consisting of a group represented by general formula (2):

{In Formula (2), R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or 3 to 20 carbon atoms. Represents an alicyclic group or an aromatic group having 6 to 20 carbon atoms, and R ₅ represents a divalent aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, and 3 to 3 carbon atoms. 20 bivalent alicyclic group or a C6-C20 bivalent aromatic group is represented. }

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

In the present embodiment, in the general formula (1), b is not limited as long as it is an integer of 0 to 3, but is an integer of 0 to 2 from the viewpoint of alkali solubility, the amount of warpage of the silicon wafer, and the elongation. Preferably there is. Moreover, when b is an integer of 2-3, several R < ₁ > may be the same or may differ.

  Furthermore, in the present embodiment, in the general formula (1), a and b satisfy the relationship 1 ≦ (a + b) ≦ 4.

｛式（３）中、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０は、それぞれ独立に、水素原子、又はフッ素原子で置換されていてもよい炭素数１〜１０の脂肪族基を表す。｝

｛式（４）中、Ｒ_１１、Ｒ_１２、Ｒ_１３及びＲ_１４は、それぞれ独立に、水素原子、又はフッ素原子で置換されていてもよい炭素数１〜１０の脂肪族基を表し、そしてＺは、単結合、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族基、フッ素原子で置換されていてもよい炭素数３〜２０の脂環式基、下記一般式（８）：

（式（８）中、ｐは、１〜１０の整数であり、そしてｑは、１〜２０の整数である。）で表されるアルキレンオキシド基、及び下記式（５）：

で表される２価の基から成る群から選ばれる少なくとも１つの２価の有機基である。｝ In this embodiment, in the said General formula (1), X is a C2-C10 bivalent aliphatic group which may have an unsaturated bond, A C3-C20 bivalent alicyclic ring. It may be at least one divalent organic group selected from the group consisting of a formula group, an alkylene oxide group represented by the general formula (8), and a divalent organic group having an aromatic group. Among these divalent organic groups, X is preferably a divalent organic group represented by the following general formula (3) or (4) from the viewpoint of the toughness of the cured film.

{In Formula (3), R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom or an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom. }

{In Formula (4), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and Z represents a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, the following general formula (8 ):

(In the formula (8), p is an integer of 1 to 10, and q is an integer of 1 to 20), and the following formula (5):

And at least one divalent organic group selected from the group consisting of divalent groups represented by: }

In the present embodiment, in the general formula (1), X is preferably a divalent organic group represented by the general formula (4), and the divalent group represented by the general formula (4). From the viewpoint of the elongation of the insulating film, the organic group is more preferably a divalent organic group represented by the following general formula (6), and further a divalent organic group represented by the following general formula (7). Particularly preferred is an organic group.

  In the present embodiment, the weight average molecular weight of the phenol resin (A) is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. is there. The weight average molecular weight is preferably 700 or more from the viewpoint of elongation, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

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

  The phenol resin (A) is an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, or a haloalkyl with respect to phenol and / or a phenol derivative (hereinafter also referred to as “phenol compound”) as shown below. It can be obtained by polymerizing a copolymer component such as a compound. From the viewpoint of reaction control and the stability of the obtained phenolic resin and phenolic resin composition, the charged molar ratio of the phenolic compound and the copolymerization component is preferably 5: 1 to 1.01: 1. More preferably, it is 2.5: 1 to 1.1: 1.

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

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

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

  Examples of the methylol compound include 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-di Methanol, 5-norbornene-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis (hydroxymethyl) durene, 2-nitro- p-xylylene glycol, 1,10-dihydroxydecane, 1,12-dihydro Siddecane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexene, 1,6-bis (hydroxymethyl) adamantane, 1,4-benzenedimethanol, 1,3-benzenedimethanol 2,6-bis (hydroxymethyl) -p-cresol, 2,6-bis (hydroxymethyl) -1,4-dimethoxybenzene, 2,3-bis (hydroxymethyl) naphthalene, 2,6-bis (hydroxy Methyl) naphthalene, 1,8-bis (hydroxymethyl) anthracene, 2,2′-bis (hydroxymethyl) diphenyl ether, 4,4′-bis (hydroxymethyl) diphenyl ether, 4,4′-bis (hydroxymethyl) diphenyl Thioether, 4,4'-bis (hydroxymethyl) ben Phenone, 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, Examples include 2-bis (4-hydroxymethylphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.

  Examples of the alkoxymethyl compound include 1,3-bis (methoxymethyl) urea, 2,2-bis (methoxymethyl) butyric acid, 2,2-bis (methoxymethyl) -5-norbornene, and 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 (methoxymethyl) benzene, 2,6-bis (methoxymethyl) -p-cresol, 2,6-bis (methoxymethyl) -1,4-dimethoxybenzene, 2,3-bis (Methoxymethyl) naphthalene, 2,6-bis (methoxymethyl) naphthalene, 1,8-bis (methoxymethyl) anthracene 2,2′-bis (methoxymethyl) diphenyl ether, 4,4′-bis (methoxymethyl) diphenyl ether, 4,4′-bis (methoxymethyl) diphenylthioether, 4,4′-bis (methoxymethyl) benzophenone, 4 -Methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylanilide, 4,4'-bis (methoxymethyl) phenylurea, 4,4'-bis (methoxymethyl) Phenylurethane, 1,8-bis (methoxymethyl) anthracene, 4,4′-bis (methoxymethyl) biphenyl, 2,2′-dimethyl-4,4′-bis (methoxymethyl) biphenyl, 2,2-bis (4-methoxymethylphenyl) propane, ethylene glycol dimethyl ether, di Chi 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.

  Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrylate, 2,4-hexadien-1-ol, and methyl. Cyclohexadiene, cyclopentadiene, cyclohexadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2, 5-norbornadiene, tetrahydroindene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl cyanurate, diallyl isocyanurate, triisocyanurate Lil, diallyl propyl etc. isocyanuric acid.

  Examples of the haloalkyl compound include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, Examples include 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 dehydrating or dealcoholizing the above-mentioned phenol compound and copolymer component, or by polymerizing while cleaving the unsaturated bond, but a catalyst may be used during the polymerization. . Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1. Examples include '-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex, and the like. On the other hand, examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, 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, hexamethylenetetramine and the like can be mentioned.

  In this embodiment, the amount of the catalyst used for obtaining the phenol resin (A) is 0.01 with respect to the number of moles of the aldehyde compound, ketone compound, methylol compound, alkoxymethyl compound, diene compound or haloalkyl compound. The range is preferably from mol% to 100 mol%.

  When performing the synthesis reaction of a phenol resin (A), an organic solvent can be used as needed. Specific examples of organic solvents that can be used include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, Examples include toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, but are not limited thereto. The amount of these organic solvents to be used is usually 10 parts by mass to 1000 parts by mass, preferably 20 parts by mass to 500 parts by mass, when the total mass of the charged raw materials is 100 parts by mass. In the synthesis reaction of the phenol resin (A), the reaction temperature is usually preferably 40 ° C. to 250 ° C., more preferably 100 ° C. to 200 ° C., and the reaction time is approximately 1 hour. 10 hours is preferable.

  The phenol resin (A) may be a copolymer of a plurality of components. In this case, as the copolymer component, a compound having no phenolic hydroxyl group may be used in addition to phenol and / or a phenol derivative. Here, the compound which does not have a phenolic hydroxyl group can be contained in the range which does not exert a bad influence on the effect of this invention, and it is preferable that content is 50 mass parts or less.

(B) Photosensitive agent In this embodiment, by selecting the type of the photosensitive agent (B) to be contained in the photosensitive resin composition, the photosensitive resin composition is made positive (the irradiated portion is eluted by development). It can also be of a negative type (the unirradiated part is eluted by development). When making the photosensitive resin composition positive, a photoacid generator can be selected as the photosensitive agent. As the photoacid generator, for example, a compound having a quinonediazide structure (hereinafter also referred to as “NQD compound”), an onium salt, a halogen-containing compound, and the like can be used, but from the viewpoint of solvent solubility and storage stability. NQD compounds are preferred.

  Examples of the onium salt include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, and the like. In particular, an onium selected from the group consisting of diaryl iodonium salts, triaryl sulfonium salts, and trialkyl sulfonium salts. Salts are preferred.

  Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound, and trichloromethyltriazine is preferable from the viewpoint of increasing sensitivity.

  Examples of the compound having a quinonediazide structure include a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure (hereinafter, also referred to as an NQD compound). No. 972, US Pat. No. 2,797,213, US Pat. No. 3,669,658, and the like. The compound having a 1,2-naphthoquinonediazide structure includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide of the polyhydroxy compound. At least one NQD compound selected from the group consisting of -5-sulfonic acid esters.

  The NQD compound is obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method, and subjecting the resulting naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound. For example, a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, tetrahydrofuran, etc. The NQD compound can be obtained by reacting in the presence of a basic catalyst for esterification, and washing the resulting product with water and drying.

｛式中、Ｑは、水素原子、又は下記式群（１０）：

のいずれかで表されるナフトキノンジアジドスルホン酸エステル基であるが、全てのＱが同時に水素原子であることはない。｝ Preferable NQD compounds include, for example, those represented by the following general formula group (9).

{In the formula, Q is a hydrogen atom, or the following formula group (10):

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

  In this embodiment, as the NQD compound, a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound. And a 5-naphthoquinonediazide sulfonyl ester compound may be used in combination.

  In this embodiment, when the photosensitive resin composition is a positive type, the blending amount of the photosensitive agent (B) with respect to 100 parts by mass of the phenol resin (A) is 0.1 parts by mass to 100 parts by mass. It is more preferable that it is 5-30 mass parts. When the blending amount of the photosensitive agent (B) is 1 part by mass or more, the patterning property is good. On the other hand, when the blending amount is 50 parts by mass or less, the tensile elongation of the film after curing is high. It is good and there is little development residue (scum) in the exposed area.

  In the present embodiment, when the photosensitive resin composition is a negative type, a compound that generates an acid upon irradiation with actinic rays is used as the photosensitive agent (B), and this is a crosslinking agent (D) described later. It can be used as a negative type by combining with. Examples of compounds that generate an acid upon irradiation with actinic rays include, for example, a) trichloromethyl-s-triazines, i) diaryliodoniums, u) triarylsulfoniums, e) diazoketone compounds, o) sulfone compounds, and ca). Examples thereof include sulfonic acid compounds, x) sulfonimide compounds, c) oxime ester compounds, and k) diazomethane compounds.

A) Trichloromethyl-s-triazines a) Trichloromethyl-s-triazines include, for example, tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloro) Methyl) -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-trichloro Methyl) -s-triazine, 2- (3-methylthiophenyl) bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- ( 2-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-tri Roromechiru) -s-triazine, 2- (2-methylthio -β- styryl) - bis (4,6-trichloromethyl) -s-triazine.

B) Diaryl iodonium i) Diaryl iodonium includes, for example, diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrafluorophosphate, diphenyl iodonium tetrafluoroarsenate, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium trifluoroacetate, diphenyl iodonium- p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4- Methoxyphenylpheny Ruiodonium 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, and the like.

C) Triarylsulfonium c) Examples of triarylsulfonium include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium tri Fluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium Methanesulfonate, 4-methoxyphenyldiph Enylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, Examples include 4-phenylthiophenyl diphenyl trifluoromethane sulfonate, 4-phenyl thiophenyl diphenyl trifluoroacetate, 4-phenyl thiophenyl diphenyl-p-toluene sulfonate, and the like.

  Among these compounds, trichloromethyl-s-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -bis (4, 6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, and the like as diaryl iodonium, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluor Lomethanesulfonate, 4-methoxyphenylphenyliodonium trifluorometa Sulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, etc., and triarylsulfonium, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyl Suitable examples include diphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, and the like.

D) Diazoketone compounds d) Diazoketone compounds include, for example, 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds and the like, and specific examples include 1,2-naphthoquinone diazides of phenols. A -4-sulfonic acid ester compound can be mentioned.

E) Sulfone compounds O) Sulfone compounds include, for example, β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesi Examples thereof include tilphenacyl sulfone and bis (phenacylsulfonyl) methane.

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

X) Sulfonimide compounds Specific examples of x) sulfonimide compounds include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenyl. Menimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned. .

C) Oxime ester compound c) Examples of the oxime ester compound include 2- [2- (4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl). ) Acetonitrile (trade name “Irgacure PAG121” by Ciba Specialty Chemicals), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (eg, Ciba Specialty) Chemicals trade name “Irgacure PAG103”), [2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (eg, Ciba Specialty Chemicals product) Name `` Irga Cure PAG108 "), α- (n-octanesulfonyloxyimino) -4-methoxybenzyl cyanide (for example, trade name“ CGI725 ”manufactured by Ciba Specialty Chemicals) and the like.

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

  Among these, oxime ester compounds, diaryl iodonium compounds, triaryl sulfonium compounds and sulfone compounds are preferable from the viewpoint of sensitivity, and oxime ester compounds are particularly preferable from the viewpoint of sensitivity.

  When the phenol resin composition of the present invention is a negative type, the blending amount of the photosensitive agent (B) with respect to 100 parts by mass of the phenol resin (A) is preferably 0.1 parts by mass to 100 parts by mass, It is more preferable that it is 1-40 mass parts. If the blending amount is 0.1 parts by mass or more, the effect of improving the sensitivity can be obtained favorably. On the other hand, if the blending amount is 100 parts by mass or less, the mechanical properties of the insulating film are good. preferable.

(C) Crosslinking agent In the present embodiment, the crosslinking agent (C) is a compound that generates acid upon irradiation with light, or the phenol generated by the action of the generated acid or heat. It is a compound that can react with the resin (A).

When the coating film is heat-cured by the crosslinking agent (C), film properties such as mechanical properties, heat resistance and chemical resistance can be enhanced. The crosslinking agent (C) is an epoxy group, an oxetane group, and a (CH ₂ —OR) group (wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) from the viewpoint of mechanical properties and heat resistance. . }, A compound having at least two groups selected from the group consisting of:

In the present embodiment, examples of the compound having two or more (CH ₂ —OR) groups for the crosslinking agent (C) include a compound bonded to a nitrogen atom and a compound bonded to a carbon atom. Examples of the compound bonded to the nitrogen atom include melamine resin and urea resin in which the nitrogen atom is substituted with a methylol group or an alkoxymethyl group. Specifically, for example, melamine resin, benzoguanamine resin, glycoluril resin, hydroxyethylene urea resin, urea resin, glycol urea resin, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, alkoxymethyl And urea-containing resins. Among these, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, and alkoxymethylated urea resin are known methylolated melamine resin, methylolated benzoguanamine resin, and methylol of methylolated urea resin, respectively. It is obtained by converting the group into an alkoxymethyl group.

  Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group and the like, but commercially available Cymel 300, 301, 303, 370, 325. 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cytec Co., Ltd.), Nicarax MX-270, -280, -290, Nicarak MS-11, Nicarak MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used. These compounds can be used alone or in combination.

  Examples of the compound bonded to the carbon atom include 1,4-bis (methoxymethyl) benzene, 4,4′-biphenyldimethanol, 4,4′-bis (methoxymethyl) biphenyl, commercially available 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A (Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML- PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, ML-Bis25X-PCHP, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymer-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) and the like. These compounds can be used alone or in combination.

  Regarding the molecular structure of the crosslinking agent (C), those having two or more epoxy groups or oxetane groups include, for example, 1,1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol tris. Glycidyl ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, isocyanuric acid triglycidyl, Denacol EX-201, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-731, EX-810, EX-911, EM-150 (trade names) , Nagase Chemtech Epoxy compounds GMBH, Ltd.), xylylene bisoxetane, 3-ethyl-3 {[(3-ethyloxetane - yl) methoxy] methyl} oxetane compound oxetane, and the like. These compounds can be used alone or in combination.

  The addition amount of the crosslinking agent (C) is 1 part by mass to 50 parts by mass, preferably 3 parts by mass to 50 parts by mass with respect to 100 parts by mass of the phenol resin (A). When the amount added is 1 part by mass or more, crosslinking sufficiently proceeds, so that an effect of enhancing film physical properties can be obtained. On the other hand, an amount of 50 parts by mass or less is preferable because the elongation is maintained.

  In this embodiment, as the crosslinking agent (C), in addition to the above-mentioned compounds, for example, 2,2′-bis (2-oxazoline), 2,2′-isopropylidenebis (4-phenyl-2-oxazoline) 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, Epocross K-2010E, K-2020E, K-2030E, Oxazoline compounds such as WS-500, WS-700, RPS-1005 (trade name, manufactured by Nippon Shokubai Co., Ltd.), carbodilite SV-02, V-01, V-02, V-03, V-04, V-05, Carbodiimide compounds such as V-07, V-09, E-01, E-02, LA-1 (trade name, manufactured by Nisshinbo Chemical Co., Ltd.), formaldehyde, glutaraldehyde, hexamethyl Aldehydes and modified aldehydes such as pentamine, trioxane, glyoxal, malondialdehyde, succindialdehyde, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4 ′ -Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate 500, 600, Cosmonate NBDI, ND (trade name, manufactured by Mitsui Chemicals) Duranate 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T ( (Trade name, manufactured by Asahi Kasei Chemical Co., Ltd.) isocyanate crosslinking agents, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetate Nchromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone nickel (II) salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, trifluoroacetylacetone Metal chelating agents such as magnesium (II) salt and trifluoroacetylacetone nickel (II) salt, vinyl acetate, trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitic acid, tetramellitic pyromellitic acid Esters, pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane Examples include tetraacrylate, BANI-M, and BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd.).

(D) Solvent In this embodiment, examples of the solvent (D) include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and the like. . More specifically, as the solvent (D), N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopenta Non, 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, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroether Emissions, 1,4-dichloro butane, chlorobenzene, o- dichlorobenzene, anisole, hexane, may be used heptane, benzene, toluene, xylene, mesitylene and the like.

  In this embodiment, the addition amount of a solvent (D) is 10 mass parts-1000 mass parts with respect to 100 mass parts of phenol resin (A), Preferably it is 120 mass parts-700 mass parts, Composition varnish From the viewpoint of controlling the viscosity and the coating film thickness, the range of 150 parts by mass to 500 parts by mass is more preferable.

(E) Other additives In this embodiment, if necessary, a photosensitive resin composition containing a dye, a surfactant, an adhesion aid for enhancing adhesion to the substrate, a dissolution accelerator, a crosslinking accelerator, and the like. Can be added.

｛式中、ｎは、１〜２０の整数である。｝

｛式中、ｍ’及びｎは、それぞれ独立に、１〜２０の整数である。｝ In the present embodiment, the photosensitive resin composition can further contain a thermal base generator from the viewpoint of improving the physical properties of the insulating film. In particular, when the crosslinking agent (C) contains an epoxy group or an oxetane group, the thermal base generator promotes the crosslinking reaction between the crosslinking agent (C) and the phenol resin (A) during thermosetting. In addition, since the film physical properties of the cured product composed of the photosensitive resin composition can be further enhanced, the photosensitive resin composition preferably further contains a thermal base generator. In this embodiment, the thermal decomposition temperature of the thermal base generator added to the photosensitive resin composition is 50 ° C. or higher, preferably 70 ° C. or higher, more preferably 90 ° C. or higher. Specific examples of the thermal base generator include compounds represented by the following formulas (11) and (12).

{Wherein n is an integer of 1-20. }

{In formula, m 'and n are the integers of 1-20 each independently. }

Particularly preferably, the thermal base generator is a compound represented by the following formula (13):

  In this embodiment, the addition amount of the thermal base generator to the photosensitive resin composition is preferably 0.1 to 40 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the phenol resin (A). 0.5 parts by mass to 30 parts by mass. This addition amount is preferably 0.1 parts by mass or more from the viewpoint of sufficiently promoting the crosslinking and obtaining an effect of enhancing film physical properties, and is preferably 40 parts by mass or less from the viewpoint of elongation.

  Examples of the adhesion assistant include alkyl imidazolines, butyric acid, alkyl acids, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymers, and various alkoxysilanes.

  Preferred examples of alkoxysilane include tetraalkoxysilane, bis (trialkoxysilyl) methane, bis (trialkoxysilyl) ethane, bis (trialkoxysilyl) ethylene, bis (trialkoxysilyl) hexane, and bis (trialkoxysilyl). Octane, bis (trialkoxysilyl) octadiene, bis [3- (trialkoxysilyl) propyl] disulfide, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) ) Pyridine, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, vinyltrialkoxysilane, 3-ureidopropyltrialkoxysilane, 3- Socyanate propyltrialkoxysilane, 3- (trialkoxysilyl) propyl succinic anhydride, N- (3-trialkoxysilylpropyl) -4,5-dihydroimidazole, 2- (3,4-epoxycyclohexyl) ethyltri Alkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxyalkylsilane and 3-aminopropyl dialkoxyalkylsilane and acid anhydrides or acid dianhydrides. Examples include reactants, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane in which the amino group is converted to a urethane group or a urea group.

  Examples of the alkyl group in the alkoxysilane compound include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the acid anhydride include maleic anhydride, phthalic anhydride, and 5 -Norbornene-2,3-dicarboxylic acid anhydride and the like, and examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride and the like are mentioned, t-butoxycarbonylamino group and the like are mentioned as urethane group, and phenylaminocarbonylamino group and the like are mentioned as urea group.

  In this embodiment, it is preferable that the compounding quantity of adhesion | attachment adjuvant is 0.1 mass part-30 mass parts with respect to 100 mass parts of phenol resin (A).

  Examples of the dye include methyl violet, crystal violet, and malachite green. It is preferable that the compounding quantity of dye is 0.1 mass part-30 mass parts with respect to 100 mass parts of phenol resin (A).

  As the surfactant, for example, in addition to nonionic surfactants composed of polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether or derivatives thereof, for example, Florard (registered trademark, trade name, manufactured by Sumitomo 3M) ), Mega-Fac (registered trademark, trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Lumiflon (registered trademark, trade name, manufactured by Asahi Glass Co., Ltd.), and the like, for example, KP341 (trade name, Shin-Etsu Chemical Co., Ltd.). Manufactured), DBE (trade name, manufactured by Chisso Corporation), granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

  It is preferable that the compounding quantity of surfactant is 0.01 mass part-10 mass parts with respect to 100 mass parts of phenol resin (A).

  As the dissolution accelerator, a compound having a hydroxyl group or a carboxyl group is preferable. Examples of the compound having a hydroxyl group include ballast agents, paracumylphenol, bisphenols, resorcinols, and linear phenolic compounds such as MtrisPC and MtetraPC, TrisP-HAP, TrisP used in the above-mentioned naphthoquinonediazide compounds. -Non-linear phenolic compounds such as PHBA and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2 to 5 phenol substitutes of diphenylmethane, 1 to 5 phenol substitutes of 3,3-diphenylpropane, A compound obtained by reacting 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane with 5-norbornene-2,3-dicarboxylic anhydride in a molar ratio of 1: 2, bis- ( 3-amino-4-hydroxyphenyl) sulfone and 1,2-cyclohexane Compounds obtained by reacting sildicarboxylic anhydride with a molar ratio of 1: 2, N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxy 5-norbornene-2,3-dicarboxylic imide, etc. Can be mentioned.

  As for the dissolution accelerator, examples of the compound having a carboxyl group include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandel. Acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid, and the like.

  It is preferable that the compounding quantity of a solubility promoter is 0.1 mass part-50 mass parts with respect to 100 mass parts of phenol resin (A).

  As the crosslinking accelerator, those that generate radicals by heat or light are preferable. Examples of those that generate radicals by heat or light include alkylphenones such as Irgacure 651, 184, 2959, 127, 907, 369, 379 (trade name, manufactured by BASF Japan), Irgacure 819 (trade name, BASF Japan). Acylphosphine oxide such as Irgacure 784 (trade name, manufactured by BASF Japan), and oxime esters such as Irgacure OXE01, 02 (trade name, manufactured by BASF Japan).

[Manufacture of silicon wafer having insulating film]
In the present embodiment, a method for manufacturing a silicon wafer having an insulating film includes the following steps (i) to (vi).
(I) A step of applying the photosensitive resin composition described above to a silicon wafer having a diameter of 8 inches or more,
(Ii) a step of obtaining a silicon wafer having a coating film by volatilizing the solvent (D) by heating the silicon wafer coated with the photosensitive resin composition;
(Iii) exposing a silicon wafer having the coating film;
(Iv) developing a silicon wafer having the coating film with an alkali developer;
(V) a step of curing the coating film by heating the silicon wafer having the coating film at a temperature of 100 ° C. or more and 400 ° C. or less to obtain a silicon wafer having an insulating film; and (vi) the insulating film Backgrinding a silicon wafer having a thickness of 20 μm to 600 μm.

Hereinafter, each process is demonstrated in order.
(I) The process of apply | coating the photosensitive resin composition mentioned above to the silicon wafer whose diameter is 8 inches or more (application | coating process).
The silicon wafer that can be used in the present embodiment is a so-called large silicon wafer having a diameter of about 8 inches (about 203.2 mm) or more and a thickness of 200 μm to 800 μm. A silicon wafer having a diameter of about 8 inches or about 12 inches (about 304.8 mm) is preferably used as such a silicon wafer. Such a silicon wafer may be a silicon wafer alone, a silicon wafer subjected to various surface treatments, a silicon wafer provided with a metal sputtered film, or a silicon wafer on which a circuit is formed.

  Examples of the method for applying the photosensitive resin composition on the silicon wafer include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. The thickness of the coating can be appropriately controlled by adjusting the coating means, the solid content concentration or the viscosity of the composition solution.

(Ii) Step of obtaining a silicon wafer having a coating film by volatilizing the solvent by heating the silicon wafer coated with the photosensitive resin composition (drying step)
Although it does not specifically limit as a drying process, For example, the method of heating about 1 minute-60 minutes at the temperature of about 50 to 150 degreeC using a hotplate, oven, an infrared furnace, etc. is mentioned. Can do.

(Iii) Step of exposing a silicon wafer having a coating film (exposure step)
As the exposure process, actinic radiation can be irradiated using an exposure apparatus such as a contact aligner, mirror projection, or stepper. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, and those having a wavelength of 200 nm to 500 nm are particularly preferable. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably g-line, h-line or i-line of a mercury lamp, and may be used alone or in combination. As the exposure apparatus, a contact aligner, mirror projection, or stepper is particularly preferable.

  The exposure process can be performed through a mask pattern as desired, whereby an insulating film on which a desired pattern is formed can be formed. When a uniform insulating film is formed on the entire surface, such as when the insulating film to be formed is a passivation film (interlayer insulating film), the mask pattern may not be used.

  In the present embodiment, the method for producing a silicon wafer having an insulating film may include a step (iii-2) of heating the silicon wafer having a coating film before being subjected to the development step after the exposure step. .

  As said process (iii-2), according to the mixing | blending or film thickness of a photosensitive resin composition, for example, using a hotplate, oven, an infrared furnace, etc., for example, 50 to 150 degreeC, Preferably it is 80. A method of heating at a temperature of about 1 to 60 ° C. for about 1 to 60 minutes can be mentioned.

(Iv) A step of developing a silicon wafer having a coating film with an alkali developer (development step)
In the development step, the exposed film on the silicon wafer is brought into contact with an alkaline developer according to the positive type or negative type of the photosensitive resin composition, and the exposed or unexposed part is dissolved and removed. Examples of the development method in this case include a shower development method, a spray development method, an immersion development method, a paddle development method, and the development conditions are, for example, usually from 20 ° C. to 40 ° C. for 1 minute to About 10 minutes. Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium An aqueous solution of a quaternary ammonium salt such as hydroxide, or an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added as required can be used. In particular, an aqueous tetramethylammonium hydroxide solution is preferable, and the concentration thereof is preferably 0.5% by mass to 10% by mass, and more preferably 1.0% by mass to 5% by mass. After development, the pattern film can be obtained by washing with a rinse solution and removing the developer. As a rinse liquid, distilled water, methanol, ethanol, isopropanol etc. can be used individually or in combination, for example.

(V) A step of curing a coating film by heating a silicon wafer having a coating film at a temperature of 100 ° C. or more and 400 ° C. or less to obtain a silicon wafer having an insulating film (curing step).
In the curing step, the coating film can be sufficiently cured by performing a heat treatment in order to sufficiently develop the characteristics as an insulating film after development. The curing condition in the curing step is not particularly limited as long as it is a temperature of 100 ° C. or higher and 400 ° C. or lower. The coating film can be cured. As a heat treatment apparatus for performing the curing process, for example, a hot plate, an oven, a temperature rising oven capable of setting a temperature program, or the like can be used. Further, air may be used as the atmospheric gas when the heat treatment is performed, and an inert gas such as nitrogen or argon may be used. Further, when it is necessary to perform heat treatment at a lower temperature, heating may be performed under reduced pressure using a vacuum pump or the like.

  If desired, a wet or dry cleaning step, a bump electrode forming step, and the like can be incorporated after the coating is cured.

(Vi) Step of back grinding a silicon wafer having an insulating film until the thickness of the silicon wafer becomes 20 μm to 600 μm (back grinding step)
In the back grinding process, in order to cope with the recent thinning of the semiconductor device, the surface on which the insulating film is not formed (wafer back surface) is ground to make the silicon wafer thinner. Here, in the semiconductor process, when a wafer having a small thickness is used from the beginning, the warpage of the wafer is likely to occur due to the influence of the material formed on the wafer. When the warpage occurs, it causes a conveyance trouble in the semiconductor process, and the manufacturing yield decreases. Therefore, the process of back grinding the wafer is generally performed at the end of the wafer processing (that is, before the wafer dicing process), and a wafer having a large thickness is generally used for the previous processes.

  In the back grinding process, first, a back grinding tape is applied to the surface having the insulating film (silicon wafer surface). The back grind tape may be either with or without a support. Next, the silicon wafer with the back grind tape is set on the platen of the wafer grinder, and the back surface of the silicon wafer is ground. Polishing can be performed until the thickness of the silicon wafer reaches 20 μm to 600 μm.

  The amount of warpage of the silicon wafer on which the insulating film obtained by the back grinding process is formed is such that the wafer diameter is 8 inches and the thickness is about 300 μm so as not to cause alignment errors, wafer transfer troubles, etc. Is preferably 400 μm or less, and more preferably 300 μm or less.

  A silicon wafer having an insulating film obtained by the manufacturing method described above has a small amount of warpage. Further, no cracks are generated in the insulating film after the wafer back grinding.

  Further, the elongation of the insulating film formed by the above-described manufacturing method is preferably 10% or more and 15% or more in order not to cause cracks in the insulating film after wafer back grinding in the semiconductor manufacturing process. It is more preferable.

  In the present embodiment, a silicon wafer having an insulating film manufactured by the above-described manufacturing method can also be provided.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following examples and comparative examples, “parts” are used in the meaning of parts by mass unless otherwise specified.
Moreover, about each characteristic of hardened | cured material, it evaluated in the following way.

Warpage amount:
The photosensitive resin composition of the example was applied by spin coating on a silicon wafer having a diameter of 8 inches and a thickness of 725 μm, and heated at 120 ° C. for 180 seconds using a hot plate. Thereafter, curing was carried out in a convection oven at 220 ° C. for 60 minutes in a nitrogen atmosphere to obtain a silicon wafer having a cured product having a thickness of about 10 μm after curing. A back grind tape (E-8000 manufactured by Lintec Corporation) was bonded to the wafer surface using a substrate bonding machine, and the wafer was ground by a back grinder (DAG 810 manufactured by Disco Corporation) until the wafer thickness became 300 μm. Next, the back grind tape was peeled by manual operation by irradiating the back grind tape with ultraviolet rays (UV) from a substrate peeling machine (BR-100, manufactured by JCM Co., Ltd.). Then, the amount of warpage of the silicon wafer on which the insulating film after back grinding was formed was measured with a thin film stress measuring device KLA-Tencor FLX-2320.

Elongation:
A sample for measuring elongation according to the present invention was produced by the following method.
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 6-inch silicon wafer substrate provided with an aluminum vapor deposition layer on the outermost surface, and a nitrogen atmosphere in a convection oven under a nitrogen atmosphere at 220 ° C. Curing was performed for 60 minutes to obtain an insulating film having a thickness of about 10 μm after curing. The obtained insulating film was cut to a width of 3 mm with a dicing saw, and then peeled off from the wafer with a dilute hydrochloric acid aqueous solution. After 20 samples were left in an atmosphere at a temperature of 23 ° C. and a humidity of 50% for 24 hours or more, The elongation was measured with a tensile tester (manufactured by A & D, Tensilon UTM-II-20), and the average value was used. The measurement conditions were as follows.
Temperature: 23 ° C
Humidity: 50%
Initial sample length: 50 mm
Test speed: 40 mm / min
Load cell rating: 2kgf (19.61N)

Cracks after wafer back grinding:
The resin composition was spin-coated on a silicon wafer having a diameter of 8 inches and a thickness of 725 μm, and heated at 120 ° C. for 180 seconds using a hot plate to produce a uniform coating film having a thickness of about 13 μm. Thereafter, using a stepper (Nikon, NSR2005i8A), UV light from a high-pressure mercury lamp was exposed through a pattern mask so that the exposure amount at a wavelength of 350 nm was 500 mJ / cm ² . Subsequently, it was immersed and developed at 23 ° C. using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. After washing with ultrapure water for 60 seconds and air-drying with air, curing is performed at 220 ° C. for 60 minutes under a nitrogen atmosphere in a convection oven under a nitrogen atmosphere, and the cured film has a thickness of about 10 μm after curing. Got. And it observed using the microscope, and it confirmed that abnormality, such as a crack, did not generate | occur | produce in the pattern (before back grinding).

  A back grind tape (E-8000 manufactured by Lintec Corporation) was bonded to the wafer surface using a substrate bonding machine, and the wafer was ground by a back grinder (DAG 810 manufactured by Disco Corporation) until the wafer thickness became 300 μm. Next, the back grind tape was irradiated with UV, and the back grind tape was peeled off manually using a substrate peeling machine (manufactured by DSI, SRM-12B). It was confirmed whether there were any abnormalities such as cracks (after back grinding).

The determination of cracks in Table 2 is as follows.
○: No cracks were observed during the back grinding process. ×: Cracks were observed during the back grinding process.

[Example 1]
Pyrogallol 88.3 g (0.7 mol), 4,4′-bis (methoxymethyl) biphenyl 121.2 g (0.5 mol), diethyl sulfate in a separable flask with a Dean-Stark device of 0.5 liter capacity 3.9 g (0.025 mol) and DMDG 140 g were mixed and stirred at 70 ° C. to dissolve the solid matter.

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

を有するビフェニルジイル／ピロガロール共重合体（Ａ−１）を収率７０％で得た。 Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluted solution is dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, and this is recovered, appropriately washed with water and dehydrated, and then vacuum-dried, and the structure represented by the following formula (14):

A biphenyldiyl / pyrogallol copolymer (A-1) having a yield of 70% was obtained.

  Thereafter, as shown in Table 1, 100 parts by mass of the obtained phenolic resin (A-1), 12 parts by mass of the photosensitive agent (B-1), and 6 parts by mass of the adhesion assistant (E-1) were mixed with a solvent (D- 1) It dissolved in 114 mass parts, and filtered with a 0.1 micrometer filter, and prepared the positive photosensitive resin composition. An insulating film was prepared using this composition, and the characteristics of the insulating film were measured according to the evaluation method. The obtained results are shown in Table 2.

を有するビフェニルジイル／フロログルシノール共重合体（Ａ−２）を収率６８％で得た。 [Example 2]
Synthesis was carried out in the same manner as in Example 1 using 100.9 g (0.8 mol) of phloroglucinol instead of pyrogallol in Example 1, and the structure represented by the following formula (15):

Biphenyldiyl / phloroglucinol copolymer (A-2) having a yield of 68% was obtained.

  A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1, and the characteristics of the insulating film were measured. The obtained results are shown in Table 2.

を有するビフェニルジイル／３，５-ジヒドロキシ安息香酸メチル共重合体（Ａ−３）を収率６５％で得た。 [Example 3]
Synthesis was carried out in the same manner as in Example 1 using 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate instead of pyrogallol in Example 1, and the structure represented by the following formula (16):

Biphenyldiyl / 3,5-dihydroxymethyl benzoate copolymer (A-3) having a yield of 65% was obtained.

  A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1, and the characteristics of the insulating film were measured. The obtained results are shown in Table 2.

を有するビフェニルジイル／レゾルシノール共重合体（Ａ−４）を収率６０％で得た。 [Example 4]
Synthesis was carried out in the same manner as in Example 1 except that 82.6 g (0.75 mol) of resorcinol was used instead of pyrogallol in Example 1, and the structure represented by the following formula (17):

A biphenyldiyl / resorcinol copolymer (A-4) having a yield of 60% was obtained.

  A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1, and the characteristics of the insulating film were measured. The obtained results are shown in Table 2.

[Example 5]
Phenol 141.2 g (1.5 mol) was placed in a 1 L separable flask, heated to 80 ° C. in an oil bath while stirring under a nitrogen stream, and boron trifluoride / phenol complex 3.0 g was added, Furthermore, it heated up at 130 degreeC and 132.2 g (1.0 mol) of dicyclopentadiene was dripped over 2 hours. After completion of dropping, the mixture was further stirred at 130 ° C. for 5 hours.

を有するジシクロペンタジエン／フェノール共重合体（Ａ−５）２０３ｇを得た。表１に示した成分から成る組成物を実施例１と同様に調製し、その絶縁膜の特性を測定した。得られた結果を表２に示す。 After the completion of the reaction, the acid catalyst is neutralized with calcium hydroxide, and then distilled under reduced pressure to remove unreacted phenol by distillation to obtain a structure represented by the following formula (18):

As a result, 203 g of a dicyclopentadiene / phenol copolymer (A-5) was obtained. A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1, and the characteristics of the insulating film were measured. The obtained results are shown in Table 2.

を有するフェニルジイル／フェノール共重合体（Ａ−６）、（明和化成（株）製、ＭＥＨ−７８００）を用いた。 [Example 6]
Instead of the biphenyldiyl / pyrogallol copolymer of Example 1, a structure represented by the following formula (19):

A phenyldiyl / phenol copolymer (A-6) (made by Meiwa Kasei Co., Ltd., MEH-7800) was used.

  A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1, and the characteristics of the insulating film were measured. The obtained results are shown in Table 2.

[Comparative Examples 1-3]
A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1, and the characteristics of the composition and its insulating film were measured. The obtained results are shown in Table 2.

In the said Example and comparative example, each component used is as follows.
Phenolic resin (A);
A-1: Biphenyldiyl / pyrogallol copolymer, polystyrene equivalent weight average molecular weight (Mw) = 13,000
A-2: Biphenyldiyl / phloroglucinol copolymer, polystyrene equivalent weight average molecular weight (Mw) = 15,000
A-3: Biphenyldiyl / 3,5-dihydroxybenzoic acid methyl copolymer, polystyrene equivalent weight average molecular weight (Mw) = 21,000
A-4: Biphenyldiyl / resorcinol copolymer, polystyrene equivalent weight average molecular weight (Mw) = 10,000
A-5: Dicyclopentadiene / phenol copolymer, polystyrene equivalent weight average molecular weight (Mw) = 10,200
A-6: Phenyldiyl / phenol copolymer (Maywa Kasei Co., Ltd., MEH-7800), polystyrene equivalent weight average molecular weight (Mw) = 5,000
A-7: Biphenyldiyl / phenol copolymer (Maywa Kasei Co., Ltd., MEH-7851), polystyrene equivalent weight average molecular weight (Mw) = 2,000
A-8: Cresol novolac (Asahi Organic Materials Co., Ltd., EP4020G), polystyrene equivalent weight average molecular weight (Mw) = 18,000
A-9: Poly p-hydroxystyrene (manufactured by Maruzen Petrochemical Co., Ltd., Markalinker M, S-4), polystyrene equivalent weight average molecular weight (Mw) = 10,000

｛式中、Ｑの内８３％が下記式（２１）の構造：

であり、残余が水素原子である。｝ Photosensitizer (B);
B-1: NQD compound having the structure of the following formula (20)

{In the formula, 83% of Q is a structure of the following formula (21):

And the remainder is a hydrogen atom. }

Cross-linking agent (C);
C-1: Tetramethoxymethylated glycoluril (manufactured by Sanwa Chemical Co., Ltd., Nicalak MX-270)

Solvent (D);
D-1: Gamma butyrolactone

Adhesion aid (E);
E-1: Silicon-based coupling agent having the structure of the following formula (22);

＊１：ウエハの直径８インチ、厚さ３００μｍ

* 1: Wafer diameter 8 inches, thickness 300μm

  The method for manufacturing a silicon wafer having an insulating film according to the present invention is used for manufacturing a large and thin silicon wafer having an insulating film such as a passivation film, an interlayer insulating film, a stress relaxation layer, a planarizing film, and a protective film. Can.

Claims (6)

(I) The following ingredients:
(A) The following general formula (1):

{Wherein (1), a is an integer of 1 to 3, b is an integer of 0 to 3, a 1 ≦ (a + b) ≦ 4, R 1 is 1 1 to 20 carbon atoms Represents at least one monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 to 3, a plurality of R _{1 s} are the same. there or may be different, X is a divalent carbon number 3-20 alicyclic group,及 beauty aromatic group divalent least one divalent selected from the group consisting of organic group having Represents an organic group. }
And a phenolic resin having a repeating unit having a hydroxyl group equivalent of 250 g / eq or less: 100 parts by mass;
(B) Photosensitizer: 0.1 to 100 parts by mass;
(C) Crosslinking agent: 1 part by mass to 50 parts by mass; and (D) Solvent: 10 parts by mass to 1000 parts by mass;
A step of applying a photosensitive resin composition comprising a silicon wafer having a diameter of 8 inches or more and a thickness of 200 μm to 800 μm;
(Ii) a step of obtaining a silicon wafer having a coating film by volatilizing the solvent by heating the silicon wafer coated with the photosensitive resin composition;
(Iii) exposing a silicon wafer having the coating film;
(Iv) developing a silicon wafer having the coating film with an alkali developer;
(V) a step of curing the coating film by heating the silicon wafer having the coating film at a temperature of 100 ° C. or more and 400 ° C. or less to obtain a silicon wafer having an insulating film; and (vi) the insulating film Back grinding a silicon wafer having a thickness of 20 μm to 600 μm,
A method for manufacturing a silicon wafer having an insulating film, comprising:   In the said General formula (1), a is an integer of 2 or 3, and b is an integer of 0-2, The manufacturing method of Claim 1. In the general formula (1), R ₁ is a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or an alicyclic group having 3 to 20 carbon atoms. Group, an aromatic group having 6 to 20 carbon atoms, and the following general formula (2):

{In Formula (2), R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or 3 to 20 carbon atoms. Represents an alicyclic group or an aromatic group having 6 to 20 carbon atoms, and R ₅ represents a divalent aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, and 3 to 3 carbon atoms. 20 bivalent alicyclic group or a C6-C20 bivalent aromatic group is represented. }
The manufacturing method of Claim 1 or 2 which is at least 1 monovalent substituent chosen from the group which consists of group represented by these. In the general formula (1), X represents the following general formula (3) or (4):

{In Formula (3), R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom or an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom. }

{In Formula (4), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and Z represents a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, the following general formula (8 ):

(In the formula (8), p is an integer of 1 to 10, and q is an integer of 1 to 20), and the following formula (5):

And at least one divalent organic group selected from the group consisting of divalent groups represented by: }
The manufacturing method as described in any one of Claims 1-3 which is a bivalent organic group represented by these. In the general formula (1), X represents the following general formula (6):

The manufacturing method as described in any one of Claims 1-4 which is a bivalent organic group represented by these. In the general formula (1), X represents the following general formula (7):

The manufacturing method as described in any one of Claims 1-5 which is a bivalent organic group represented by these.