JP2021085977A - Photosensitive polyimide resin composition, pattern formation method, and method for manufacturing semiconductor device - Google Patents

Abstract

To provide a photosensitive polyimide resin composition capable of providing a film which enables formation of a fine pattern, and is excellent in film characteristics and reliability as a protective film with comparatively low heat treatment of substantially 200°C after pattern formation, a pattern formation method and a method for manufacturing a semiconductor device.SOLUTION: A photosensitive polyimide resin composition contains (A) primary alcoholic hydroxy group-containing polyimide that includes a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2), and has a weight average molecular weight of 5,000-200,000, (B) polyimide which contains a phenolic hydroxy group and a weight average molecular weight of 2,000 or less, (C) a photoacid generator, and (D) a crosslinking agent. A content of the component (B) is 1-10 pts.mass based on 100 pts.mass of the component (A).SELECTED DRAWING: None

Description

The present invention relates to a photosensitive polyimide resin composition, a pattern forming method, and a method for manufacturing a semiconductor device.

Conventionally, as a photosensitive polyimide-based material, a material using a polyamic acid which is a precursor of polyimide, for example, a material in which a photosensitive group is introduced into a carboxy group of a polyamic acid by an ester bond (Patent Documents 1 and 2). A material composed of a polyamic acid and an amine compound having a photosensitive group (Patent Document 3) and the like have been proposed. However, these materials require imidization treatment at a high temperature of more than 300 ° C. in order to obtain the desired polyimide film after forming a film on which a pattern is formed, and in order to withstand this high temperature, a base material is used. There was a problem that the base material was restricted and the copper of the wiring was oxidized.

As an improvement for this, a photosensitive polyimide using an already imidized solvent-soluble resin has been proposed for the purpose of lowering the curing temperature (Patent Documents 4 to 6). However, all of them use (meth) acrylic groups to impart photosensitivity to the resin, and because of the photocuring mechanism, they are susceptible to oxygen inhibition and film slippage during development is likely to occur, so the resolution is improved. It was difficult, and it could not be a material that satisfied all the required properties.

On the other hand, positive materials in which a polyimide having a phenolic hydroxy group (Patent Document 7) or a polyamide (Patent Documents 8 and 9) and diazonaphthoquinone are combined have been proposed. It is difficult to form a thick film of more than 20 μm from the viewpoint of light transmission of the composition, and the molecular weight of the resin is small in order to ensure developability, or diazonaphthoquinone, which is a photosensitizer, is used. There is a problem that it is difficult to obtain the original curing characteristics of the resin because the amount of the resin added is larger than that of the resin.

Japanese Unexamined Patent Publication No. 49-115541 JP-A-55-45746 Japanese Unexamined Patent Publication No. 54-145794 Japanese Unexamined Patent Publication No. 10-274850 Japanese Unexamined Patent Publication No. 10-265571 Japanese Unexamined Patent Publication No. 2001-335319 Japanese Unexamined Patent Publication No. 3-209478 Special Fair 1-46862 Gazette Japanese Unexamined Patent Publication No. 11-65107

The present invention has been made in view of the above circumstances, and it is possible to form a fine pattern, and after this pattern formation, a relatively low temperature heat treatment of about 200 ° C. is performed to obtain film characteristics and a protective film. An object of the present invention is to provide a photosensitive polyimide resin composition, a pattern forming method, and a method for manufacturing a semiconductor device, which can provide a highly reliable film.

As a result of diligent studies to achieve the above object, the present inventors have made a polyimide having a primary alcoholic hydroxy group in the molecule and having a weight average molecular weight of 5,000 to 200,000. We have found that it is useful to add polyimide with an average molecular weight of 2,000 or less.

Further, the photosensitive polyimide resin composition containing the polyimide mixture and the photoacid generator can be exposed to light having high sensitivity and a wide range of wavelengths, and a fine pattern can be formed by a pattern forming method described later. We have found that the photosensitive polyimide resin composition and the cured film obtained by heating after pattern formation are excellent in heat resistance and electrical insulation, and have completed the present invention.

［式中、Ｘ¹は、下記式（２）で表される４価の有機基である。

（式中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、炭素数１〜８の１価炭化水素基である。Ｒ⁷及びＲ⁸は、それぞれ独立に、単結合又は炭素数１〜１２の２価炭化水素基である。Ｒ⁹及びＲ¹⁰は、それぞれ独立に、３価の有機基である。ｍは、０〜１２０の整数である。破線は、結合手である。）
Ｘ²は、下記式で表される基から選ばれる４価の基である。

（式中、破線は、結合手である。）
Ｙ¹は、下記式（３）で表される２価の基である。

（式中、Ａ¹〜Ａ³は、それぞれ独立に、単結合、メチレン基、エーテル結合、スルホニル基、アミド結合、プロパン−２,２−ジイル基、１,１,１,３,３,３−ヘキサフルオロプロパン−２,２−ジイル基又はフルオレン−９,９−ジイル基である。Ｒ¹¹及びＲ¹²は、それぞれ独立に、ヒドロキシ基、又はアルコール性ヒドロキシ基含有基であるが、少なくとも１つは１級アルコール性ヒドロキシ基含有基である。Ｒ¹³〜Ｒ¹⁶は、それぞれ独立に、炭素数１〜４のアルキル基である。ａは、０〜１０の整数である。ｂ及びｃは、それぞれ独立に、０又は１である。ｄ〜ｇは、それぞれ独立に、０、１又は２である。破線は、結合手である。）
ｐは、正の整数であり、ｑは、正の整数である。］
２．（Ｂ）成分のポリイミドが、下記式（１−３）で表される繰り返し単位及び下記式（１−４）で表される繰り返し単位を含むものである１の感光性ポリイミド樹脂組成物。

［式中、Ｘ¹及びＸ²は、前記と同じ。Ｙ²は、式（４）で表される基及び式（５）で表される基から選ばれる少なくとも１種である。ｒ及びｓは、それぞれ独立に、０又は正の整数である。

（式中、Ｂ¹〜Ｂ³は、それぞれ独立に、単結合、メチレン基、エーテル結合、スルホニル基、アミド結合、プロパン−２,２−ジイル基、１,１,１,３,３,３−ヘキサフルオロプロパン−２,２−ジイル基又はフルオレン−９,９−ジイル基である。Ｒ²¹〜Ｒ²⁴は、それぞれ独立に、炭素数１〜４のアルキル基である。ａ'は、０〜１０の整数である。ｂ'及びｃ'は、それぞれ独立に、０又は１である。ｄ'〜ｇ'は、それぞれ独立に、０、１又は２である。破線は、結合手である。）

（式中、Ｒ³¹〜Ｒ³⁴は、それぞれ独立に、炭素数１〜８の１価炭化水素基である。ｎは、１〜８０の整数である。破線は、結合手である。）］
３．更に、（Ｅ）溶剤を含む１又は２の感光性ポリイミド樹脂組成物。
４．（Ｃ）光酸発生剤が、イミド−イル−スルホネート類、イミノスルホネート類又はオキシムスルホネート類である１〜３のいずれかの感光性ポリイミド樹脂組成物。
５．更に、塩基性化合物を含む１〜４のいずれかの感光性ポリイミド樹脂組成物。
６．１〜５のいずれかの感光性ポリイミド樹脂組成物を基板上に塗布し、レジスト層を形成する工程と、前記レジスト層を露光する工程と、現像する工程とを含む、パターン形成方法。
７．６のパターン形成方法を含む、パターンが形成されたポリイミド樹脂皮膜を備える半導体装置の製造方法。 Therefore, the present invention provides the following photosensitive polyimide resin composition, a pattern forming method, and a method for manufacturing a semiconductor device.
1. 1. (A) A primary alcoholic substance containing a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2) and having a weight average molecular weight of 5,000 to 200,000. Hydroxy group-containing polyimide,
(B) A polyimide containing a phenolic hydroxy group and having a weight average molecular weight of 2,000 or less.
A photosensitive polyimide resin composition containing (C) a photoacid generator and (D) a cross-linking agent, and the content of the component (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the component (A).

[In the formula, X ¹ is a tetravalent organic group represented by the following formula (2).

(In the formula, R ^{1 to} R ⁶ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. R ⁷ and R ⁸ are independently single-bonded or 2 having 1 to 12 carbon atoms, respectively. It is a valent hydrocarbon group. R ⁹ and R ¹⁰ are independently trivalent organic groups. M is an integer of 0 to 120. The broken line is a bond.)
X ² is a tetravalent group selected from the groups represented by the following formulas.

(In the formula, the broken line is the bond.)
Y ¹ is a divalent group represented by the following formula (3).

(In the formula, A ^{1 to} A ³ are independently single bond, methylene group, ether bond, sulfonyl group, amide bond, propane-2,2-diyl group, 1,1,1,3,3,3. -Hexafluoropropane-2,2-diyl group or fluorene-9,9-diyl group. R ¹¹ and R ¹² are independently hydroxy groups or alcoholic hydroxy group-containing groups, but at least one. One is a primary alcoholic hydroxy group-containing group. R ^{13 to} R ¹⁶ are independently alkyl groups having 1 to 4 carbon atoms. A is an integer of 0 to 10. B and c are integers of 0 to 10. , 0 or 1 independently. D to g are 0, 1 or 2, respectively. The dashed line is the bond.)
p is a positive integer and q is a positive integer. ]
2. The photosensitive polyimide resin composition of 1 in which the polyimide of the component (B) contains a repeating unit represented by the following formula (1-3) and a repeating unit represented by the following formula (1-4).

[In the formula, X ¹ and X ² are the same as above. Y ² is at least one selected from the group represented by the formula (4) and the group represented by the formula (5). r and s are independently 0 or positive integers, respectively.

(In the formula, B ^{1 to} B ³ are independent, single bond, methylene group, ether bond, sulfonyl group, amide bond, propane-2,2-diyl group, 1,1,1,3,3,3. -Hexafluoropropane-2,2-diyl group or fluorene-9,9-diyl group. R ^{21 to} R ²⁴ are independently alkyl groups having 1 to 4 carbon atoms. A'is 0. -10, b'and c'are independently 0 or 1. d'to g'are independently 0, 1 or 2. The dashed line is the bond. .)

(In the formula, R ^{31 to} R ³⁴ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. N is an integer of 1 to 80. The broken line is a bond.)]
3. 3. Further, (E) 1 or 2 photosensitive polyimide resin composition containing a solvent.
4. (C) The photosensitive polyimide resin composition according to any one of 1 to 3, wherein the photoacid generator is an imide-yl-sulfonate, an iminosulfonate, or an oxime sulfonate.
5. Further, any of 1 to 4 photosensitive polyimide resin compositions containing a basic compound.
A pattern forming method including a step of applying the photosensitive polyimide resin composition according to any one of 6.1 to 5 on a substrate to form a resist layer, a step of exposing the resist layer, and a step of developing the resist layer.
A method for manufacturing a semiconductor device including a polyimide resin film on which a pattern is formed, which comprises the pattern forming method of 7.6.

By using the photosensitive polyimide resin composition of the present invention, it is possible to expose with light of a wide range of wavelengths, and a thin film can be easily formed without being affected by oxygen damage. Further, it is possible to form a pattern having excellent resolving power, and the cured film obtained from this composition has excellent adhesion to a base material, heat resistance, and electrical insulation, and is used for electrical, electronic components, and semiconductor elements. It is preferably used as a protective film for the like.

The photosensitive polyimide resin composition of the present invention is
(A) A primary alcoholic hydroxy group-containing polyimide containing a predetermined repeating unit and having a weight average molecular weight of 5,000 to 200,000.
(B) Polyimide having a weight average molecular weight of 2,000 or less,
It contains (C) a photoacid generator and (D) a cross-linking agent, and the content of the component (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the component (A).

[(A) component]
The component (A) contains a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2), and has a weight average molecular weight of 5,000 to 200,0001. It is a class alcoholic hydroxy group-containing polyimide.

In the formula (1-1), X ¹ is a tetravalent organic group represented by the following formula (2).

In the formula (2), R ^{1 to} R ⁶ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. The monovalent hydrocarbon group may be linear, branched or cyclic, and specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; cyclopentyl. Cycloalkyl groups such as groups and cyclohexyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl group and phenethyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group and butenyl group can be mentioned. From the viewpoint of easy availability of raw materials, a methyl group, an ethyl group, a phenyl group and a vinyl group are preferable.

In formula (2), R ⁷ and R ⁸ are independently single-bonded or divalent hydrocarbon groups having 1 to 12 carbon atoms. The divalent hydrocarbon group may be linear, branched or cyclic, and specific examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group and a propane-. Examples thereof include a 1,3-diyl group, a butane-1,4-diyl group, a benzene-1,4-diyl group, and a biphenyl-4,4'-diyl group. As R ⁷ and R ⁸ , a single bond, a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, and a benzene-1,4-diyl group are preferable.

In formula (2), R ⁹ and R ¹⁰ are independently trivalent organic groups. The trivalent organic group preferably has 2 to 10 carbon atoms. Examples of the trivalent organic group include those represented by the following formulas, but are not limited thereto.

In the formula (2), m is an integer of 0 to 120, preferably an integer of 3 to 80, and more preferably an integer of 5 to 50. When m ≧ 2, that is, when there are two or more siloxane units, each siloxane unit may be the same or may contain two or more different siloxane units. When two or more different siloxane units are contained, the siloxane units may be randomly bonded or alternately bonded, or may contain a plurality of blocks of the same type of siloxane units.
Examples of the tetravalent organic group represented by X ¹ include, but are not limited to, those shown below.

（式中、ｍ¹及びｍ²は、それぞれ独立に、０又は１以上の整数であり、ｍ¹＋ｍ²＝ｍである。ｍ³及びｍ⁴は、それぞれ独立に、０又は１以上の整数であり、ｍ³＋ｍ⁴＝ｍである。ｍ⁵及びｍ⁶は、それぞれ独立に、０又は１以上の整数であり、ｍ⁵＋ｍ⁶＝ｍである。ｍは、前記と同じである。）

(In the equation, m ¹ and m ² are independently integers of 0 or 1 or more, and m ¹ + m ² = m. M ³ and m ⁴ are independently integers of 0 or 1 or more, respectively. ^{M 3} + m ⁴ = m. M ⁵ and m ⁶ are independently integers of 0 or 1 or more, and m ⁵ + m ⁶ = m. M is the same as described above. )

The ^{group represented by X 1} is an acid anhydride having an unsaturated group, for example, a succinic anhydride, a norbornenedicarboxylic acid anhydride, a propylnadic acid anhydride, a phthalic acid anhydride, or the like, and an organohydrogenpolysiloxane. It can be derived from the modified silicone obtained by the reaction. Depending on the distribution of the number of siloxane units in the organohydrogenpolysiloxane, the number of siloxane units of the obtained acid anhydride-modified polysiloxane is also distributed, and therefore m in the formula (2) represents the average value thereof.

（式中、破線は、結合手である。） In formula (1-2), X ² is a tetravalent group selected from the groups represented by the following formula.

(In the formula, the broken line is the bond.)

（式中、破線は、結合手である。） In formulas (1-1) and (1-2), Y ¹ is a divalent group represented by the following formula (3).

(In the formula, the broken line is the bond.)

In formula (3), A ^{1 to} A ³ are independently single bond, methylene group, ether bond, sulfonyl group, amide bond, propane-2,2-diyl group, 1,1,1,3,3. , 3-Hexafluoropropane-2,2-diyl group or fluorene-9,9-diyl group.

In formula (3), R ¹¹ and R ¹² are independently hydroxy groups or alcoholic hydroxy group-containing groups, but at least one is a primary alcoholic hydroxy group. Examples of the alcoholic hydroxy group-containing group include a 2,3-dihydroxypropyl group and a 1,3-dihydroxy-2-propyloxy group.

In formula (3), R ^{13 to} R ¹⁶ are independently alkyl groups having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group, but a methyl group is preferable.

In the formula (3), a is an integer of 0 to 10, but an integer of 1 to 10 is preferable. b and c are independently 0 or 1, respectively. d to g are 0, 1 or 2, respectively, but 0 or 1 is preferable.

Examples of the group represented by the formula (3) include, but are not limited to, those shown below. In the following formula, R is a hydrogen atom or an alcoholic hydroxy group-containing group.

In the formulas (1-1) and (1-2), p and q are independently positive integers, preferably integers satisfying 1 ≦ p ≦ 500 and 1 ≦ q ≦ 500, and more preferably. Is an integer that satisfies 3 ≦ p ≦ 300 and 3 ≦ q ≦ 300. Further, p / (p + q) satisfies 0.01 ≦ p / (p + q) <1, preferably 0.1 ≦ p / (p + q) <1, and more preferably 0.2 ≦ p / (p + q). It satisfies ≦ 0.95, more preferably 0.5 ≦ p / (p + q) ≦ 0.9. If p / (p + q) is less than 0.01, sufficient flexibility may not be obtained.

The polyimide of the component (A) preferably contains only the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2).

The polyimide component (A) has a weight average molecular weight (Mw) of 5,000 to 200,000, preferably 8,000 to 100,000. When the Mw is less than 5,000, the strength of the obtained film is low. On the other hand, a polyimide having an Mw of more than 200,000 has poor compatibility with a solvent and is difficult to handle. In the present invention, Mw is a polystyrene-equivalent measured value by gel permeation chromatography (GPC) using dimethylformamide to which lithium bromide is added at 10 mmol / L as a solvent.

The polyimide of the component (A) may be a random copolymer or a block copolymer.

As a method for synthesizing the polyimide of the component (A), first, a diamine having a phenolic hydroxy group, an acid anhydride-modified silicone, an acid dianhydride, and if necessary, a diamine having no phenolic hydroxy group are reacted, and it is necessary. A monofunctional amine is reacted as a terminal group according to the above to obtain a polyamic acid.

Diamines having a phenolic hydroxy group include 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,2'-diamino-4,4'-dihydroxybiphenyl, 2,2'-bis (4-amino). -3-Hydroxyphenyl) propane, 2,2'-bis (3-amino-4-hydroxyphenyl) propane, 9,9'-bis (3-amino-4-hydroxyphenyl) fluorene, 2,2'-methylenebis [6- (4-Amino-3,5-dimethylbenzyl) -4-methyl] phenol, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 2,2'-bis (3-amino-4-4-) Hydroxyphenyl) Hexafluoropropane and the like can be mentioned.

Examples of the acid anhydride-modified silicone include compounds having an acid anhydride structure at both ends of the group exemplified as a tetravalent organic group represented by ^{X 1, and specific examples thereof include those shown below.} However, it is not limited to these.

（式中、ｍ及びｍ¹〜ｍ⁶は、前記と同じ。）

(In the formula, m and m ^{1 to} m ⁶ are the same as above.)

As the acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3' , 4-biphenyltetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 4- (2,5) −Dioxo tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride 1,2,3,4-butanetetracarboxylic acid dianhydride 3,3' , 4,4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-hexafluoropropyridene bisphthalic acid dianhydride, 2,2-bis (p-trimethoxyphenyl) propanoic acid dianhydride, 1, Examples thereof include 3-tetramethyldisiloxane bisphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride and the like.

As a diamine having no phenolic hydroxy group, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3' -Dimethyl-4,4'-diaminobiphenyl, 4,4'-(p-phenylenediisopropyridene) dianiline, 4,4'-(m-phenylenediisopropyridene) dianiline, 1,3-bis (4-amino) Phenoxy) Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4 Examples thereof include'-bis (4-aminophenoxy) biphenyl and 9,9'-bis (4-aminophenyl) fluorene.

In the synthesis of polyamic acid, the ratio of the total diamine component to the total tetracarboxylic dianhydride component is appropriately determined according to the molecular weight of the polyimide and the like, but is preferably 0.95 to 1.05 in terms of molar ratio. It is preferably in the range of 0.98 to 1.02. It is also possible to add a monofunctional acid anhydride such as phthalic anhydride or aniline and an amine compound in order to adjust the molecular weight of the polyimide. The amount added at this time is preferably 10 mol% or less with respect to the total amount of the tetracarboxylic dianhydride component or the diamine component.

The reaction between the diamine and the acid dianhydride is usually carried out in a solvent. The solvent is not particularly limited as long as it dissolves the polyimide of the component (A). Specific examples of the solvent include ethers such as diglime, triglime, tetrahydrofuran and anisole; ketones such as cyclohexanone, 2-butanone, methylisobutylketone, 2-heptanone, 2-octanone and acetophenone; butyl acetate and methyl benzoate. , Esters such as γ-butyrolactone; Cellosolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate; Amides such as N, N-dimethylformamide, N, N'-dimethylacetamide and N-methyl-2-pyrrolidone and toluene , Aromatic hydrocarbons such as xylene. Of these, diglyme, cyclohexanone, γ-butyrolactone, propylene glycol monomethyl ether acetate, N, N'-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable. These solvents may be used alone or in combination of two or more. The amount of the solvent used is usually adjusted in a range where the concentration of polyimide is 10 to 40% by mass in consideration of the yield per batch, the dissolution viscosity and the like.

Next, a polyimide having a phenolic hydroxy group is obtained by a dehydration ring closure reaction of the obtained polyamic acid. The dehydration ring closure reaction is obtained by raising the temperature of the polyamic acid solution to a temperature range of usually 80 to 250 ° C., preferably 140 to 200 ° C., or adding a mixed solution of acetic acid / pyridine to the polyamic acid solution. This can be done by raising the temperature of the resulting solution to around 50 ° C. This makes it possible to carry out a dehydration ring closure reaction on the acid amide moiety of the polyamic acid to make it polyimide.

Then, by substituting at least a part of the phenolic hydroxy group contained in this polyimide with a primary alcoholic hydroxy group-containing organic group, the polyimide of the component (A) can be obtained. Examples of the substitution method include a method of reacting a compound such as glycidol, 3-chloro-1,2-propanediol, 3-chloro-2,2-dimethyl-1-propanol or the like under a base catalyst. The ratio of the hydroxy group-containing organic group introduced into the hydrogen atom of the phenolic hydroxy group is preferably 10 to 90 mol%, more preferably 30 to 60 mol%.

In the reaction when introducing a primary alcoholic hydroxy group, one kind of aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran, 1,4-dioxane, ethyl acetate, diglime, γ-butyrolactone is used alone as a solvent. , Or a mixture of two or more. As the base catalyst, potassium carbonate, sodium hydrogen carbonate, pyridine, 4- (N, N-dimethyl) aminopyridine, imidazole, 2-methylimidazole and the like can be used.

The component (A) can be used alone or in combination of two or more.

[(B) component]
The polyimide component (B) contains a phenolic hydroxy group and has an Mw of 2,000 or less.

The polyimide of the component (B) preferably contains a repeating unit represented by the following formula (1-3) and a repeating unit represented by the following formula (1-4).

（式中、Ｂ¹〜Ｂ³は、それぞれ独立に、単結合、メチレン基、エーテル結合、スルホニル基、アミド結合、プロパン−２,２−ジイル基、１,１,１,３,３,３−ヘキサフルオロプロパン−２,２−ジイル基又はフルオレン−９,９−ジイル基である。Ｒ²¹〜Ｒ²⁴は、それぞれ独立に、炭素数１〜４のアルキル基である。ａ'は、０〜１０の整数である。ｂ'及びｃ'は、それぞれ独立に、０又は１である。ｄ'〜ｇ'は、それぞれ独立に、０、１又は２である。破線は、結合手である。）

（式中、Ｒ³¹〜Ｒ³⁴は、それぞれ独立に、炭素数１〜８の１価炭化水素基である。ｎは、１〜８０の整数である。破線は、結合手である。） In formulas (1-3) and (1-4), X ¹ and X ² are the same as described above. Y ² is at least one selected from the group represented by the formula (4) and the group represented by the formula (5).

(In the formula, B ^{1 to} B ³ are independent, single bond, methylene group, ether bond, sulfonyl group, amide bond, propane-2,2-diyl group, 1,1,1,3,3,3. -Hexafluoropropane-2,2-diyl group or fluorene-9,9-diyl group. R ^{21 to} R ²⁴ are independently alkyl groups having 1 to 4 carbon atoms. A'is 0. -10, b'and c'are independently 0 or 1. d'to g'are independently 0, 1 or 2. The dashed line is the bond. .)

(In the formula, R ^{31 to} R ³⁴ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. N is an integer of 1 to 80. The broken line is a bond.)

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{21 to} R ²⁴ include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms represented by R ^{31 to} R ³⁴ include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group; a cyclopentyl group and a cyclohexyl group. Cycloalkyl group such as; aryl group such as phenyl group; aralkyl group such as benzyl group and phenethyl group; alkenyl group such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group and the like. Of these, a methyl group, an ethyl group, a phenyl group, and a vinyl group are preferable from the viewpoint of easy availability of raw materials. Further, n is an integer of 1 to 80, preferably an integer of 1 to 20.

Examples of the group represented by the formula (4) include, but are not limited to, those shown below.

In equations (1-3) and (1-4), r and s are independently 0 or positive integers, preferably integers satisfying 0 ≦ r ≦ 500 and 0 ≦ s ≦ 500, respectively. More preferably, it is an integer satisfying 0 ≦ r ≦ 300 and 0 ≦ s ≦ 300.

The polyimide of the component (B) has an Mw of 2,000 or less, but preferably 1,200 to 1,800.

The polyimide of the component (B) can be synthesized by controlling the amounts of amines, diamines, and acid anhydrides in the method for synthesizing the polyimide of the component (A), and by not carrying out a reaction with a hydroxy group.

The content of the component (B) is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (A). If the content of the component (B) is less than 1 part by mass, the effect of improving the solubility in a developing solution may not be obtained, and if it exceeds 10 parts by mass, the physical properties of the cured film may deteriorate. The polyimide component (B) can be used alone or in combination of two or more.

[Component (C)]
The photoacid generator of the component (C) is not particularly limited as long as it decomposes by light irradiation and generates an acid, but one that generates an acid by irradiating light having a wavelength of 240 to 500 nm is preferable. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonic acid ester derivatives, imide-yl-sulfonate derivatives, oxime sulfonate derivatives, and imino sulfonate derivatives. And so on.

Examples of the onium salt include diphenyliodonium trifluoromethanesulfonic acid, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, diphenyliodonium p-toluenesulfonate, and p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl. Iodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tristrifluoromethanesulfonate (p-tert) -Butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonate bis (p-tert-butoxyphenyl) phenylsulfonium, p- Tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutane sulfonate triphenyl sulfonium, butane sulfonate triphenyl sulfonium, trifluoromethane sulfonate trimethyl sulfonium, p-toluene sulfonate trimethyl sulfonium, trifluoromethane sulfonate cyclohexyl Methyl (2-oxocyclohexyl) sulfonium, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, p -Dicyclohexylphenyl sulfonium of toluene sulfonate, bis (4-tert-butyl phenyl) iodonium hexafluorophosphate, diphenyl (4-thiophenoxyphenyl) sulfonium hexafluoroantimonate and the like can be mentioned.

Examples of the diazomethane derivative include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, and bis (n-butylsulfonyl). Diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-pentylsulfonyl) Diazomethane, bis (isopentylsulfonyl) diazomethane, bis (sec-pentylsulfonyl) diazomethane, bis (tert-pentylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl- Examples thereof include 1- (tert-pentylsulfonyl) diazomethane and 1-tert-pentylsulfonyl-1- (tert-butylsulfonyl) diazomethane.

Examples of the glyoxime derivative include bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, and bis-o- (p-toluenesulfonyl). -Α-Dicyclohexyl glioxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione glioxime, bis- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glycim , To bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclo Xylglioxime, bis-o- (n-butanesulfonyl) -2,3-pentanedioneglycim, bis-o- (n-butanesulfonyl) -2-methyl-3,4-pentanedioneglycim, bis- o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime Oxim, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime , Bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) -α- Examples thereof include dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, and bis-o- (campersulfonyl) -α-dimethylglyoxime.

Examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.

Examples of the disulfone derivative include diphenyldisulfone and dicyclohexyldisulfone.

Examples of the nitrobenzyl sulfonate derivative include p-toluenesulfonic acid 2,6-dinitrobenzyl and p-toluenesulfonic acid 2,4-dinitrobenzyl.

Examples of the sulfonic acid ester derivative include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, and 1,2,3-tris (p-toluenesulfonyloxy). ) Benzene and the like.

Examples of the imide-yl-sulfonate derivative include phthalimide-yl-trifrate, phthalimide-yl-tosylate, 5-norbornene-2,3-dicarboxyimide-yl-trifrate, and 5-norbornene-2,3-dicarboxy. Examples thereof include imide-yl-tosylate, 5-norbornene-2,3-dicarboxyimide-yl-n-butylsulfonate, N-trifluoromethylsulfonyloxynaphthylimide and the like.

Examples of the oxime sulfonate derivative include α- (benzenesulfonium oxyimino) -4-methylphenylacetonitrile.

Examples of the iminosulfonate derivative include [5- (4-methylphenyl) sulfonyloxyimino-5H-thiophen-2-iriden]-(2-methylphenyl) acetonitrile and [5- (4- (4-methylphenylsulfonyloxy). ) Phenylsulfonyloxyimino) -5H-thiophene-2-ylidene]-(2-methylphenyl) -acetonitrile and the like.

Further, 2-methyl-2 [(4-methylphenyl) sulfonyl] -1-[(4-methylthio) phenyl] -1-propane and the like can also be preferably used.

Among these, an imide-yl-sulfonate derivative, an iminosulfonate derivative, an oxime sulfonate derivative and the like are preferably used.

The content of the component (C) is preferably 0.03 to 20 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the component (A). When the content of the component (C) is within the above range, a sufficient contrast (difference in dissolution rate between the exposed portion and the unexposed portion with respect to the developing solution) can be obtained, and the resolution is good. The component (C) can be used alone or in combination of two or more.

[(D) component]
The cross-linking agent of the component (D) acts on the phenolic hydroxy group and / or the primary alcoholic hydroxy group in the polyimide of the component (A) to cause cross-linking and cure, or condensation or addition between the cross-linking agents. It is not particularly limited as long as it causes cross-linking by reaction and cures. Examples of the cross-linking agent include melamine compounds, glycoluril compounds, urea compounds, epoxy compounds, and phenol compounds containing two or more methylol derivatives in one molecule.

Examples of the melamine-based compound include hexamethylol melamine hexamethyl ether, hexamethylol melamine hexabutyl ether, tetramethoxymethylbenzoguanamine, and tetrabutoxymethylbenzoguanamine.

Examples of the glycol uryl-based compound include tetramethoxymethyl glycol uryl and tetrabutoxymethyl glycol uryl.

Examples of the urea compound include tetramethoxymethylurea, dimethoxymethylethyleneurea, and dimethoxymethylpropylene urea.

Examples of the epoxy-based compound include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin such as diglycidyl bisphenol A, bisphenol F type epoxy resin such as diglycidyl bisphenol F, and triphenylol propane triglycidyl ether. Etc. Triphenylmethane type epoxy resin, cyclic aliphatic epoxy resin such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, glycidyl ester such as diglycidyl phthalate, diglycidyl hexahydrophthalate, dimethyl glycidyl phthalate, etc. Examples thereof include glycidyl amine resins such as tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyl aniline, diglycidyl toluidine, and tetraglycidyl bisaminomethylcyclohexane.

Examples of the methylol derivative include compounds containing two or more methylol derivatives such as a methylol group or an alkoxymethyl group in one molecule. Specific examples thereof include (2-hydroxy-5-methyl) -1,3-benzenedimethanol, 2,6-di (methoxymethyl) -4-methylphenol, and 6-hydroxy-5-methyl as bifunctional types. -1,3-benzenedimethanol, 2,4-di (hydroxymethyl) -6-cyclohexylphenol, 2,6-di (methoxymethyl) -4- (1,1'-dimethylethyl) phenol, 3,3 '-Methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4'-[1,4-phenylenebis (1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 2-hydroxy- 5-Ethyl-1,3-benzenedimethanol, 2-hydroxy-4,5-dimethyl-1,3-benzenedimethanol, 4- (1,1'-dimethylethyl) -2-hydroxy-1,3- Benzenedimethanol, 2-hydroxy-5-cyclohexyl-1,3-benzenedimethanol, 2-hydroxy-5- (1,1', 3,3'-tetramethylbutyl) -1,3-benzenedimethanol, 2-Hydroxy-5-fluoro-1,3-benzenedimethanol, 4,4'-methylenebis (2-methyl-6-hydroxymethylphenol), 2,6-bis [(2-hydroxy-3-hydroxymethyl-) 5-Methylphenyl) Methyl] -4-methylphenol, etc. As a trifunctional type, 2-hydroxy-1,3,5-benzenetrimethanol, 3,5-dimethyl-2,4,6-trihydroxymethylphenol, etc., As a tetrafunctional type, 3,3', 5,5'-tetrakis (hydroxymethyl) [(1,1'-biphenyl) -4,4'-diol], 2,3,5,6-tetra (hydroxymethyl) -1,4-benzenediol, 4,4'-methylenebis [2,6-bis (hydroxymethyl) phenol], 4,4'-(1-methylethylidene) bis [2,6-bis (hydroxymethyl) phenol] ], 3,3', 5,5'-tetrax (methoxymethyl) [(1,1'-biphenyl) -4,4'-diol], etc., 4,4', 4''-methi as a hexafunctional type Examples thereof include lysine tris (2,6-dihydroxymethylphenol), 4,4', 4''-ethylysintris (2,6-dihydroxymethylphenol) and the like.

The content of the component (D) is preferably 0.1 to 50 parts by mass, more preferably 2 to 40 parts by mass with respect to 100 parts by mass of the component (A). When the content is within the above range, a sufficient cross-linking density can be obtained, and transparency and storage stability are good. The component (D) can be used alone or in combination of two or more.

[(E) component]
The solvent of the component (E) can be used without particular limitation as long as it has sufficient solubility in each of the above-mentioned components and other components described later and gives good coating film properties.

Such solvents include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1- Alcohols such as ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, Examples thereof include esters such as γ-butylolactone.

Among these, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and γ-butyrolactone, which have the highest solubility of the components (A), (B), (C) and (D), are particularly excellent. And a mixed solvent of these is preferable.

The solvent content of the component (E) is preferably 20 to 1,200 parts by mass, more preferably 70 to 500 parts by mass, based on 100 parts by mass of the total of the components (A) to (D). When the content is within the above range, there is no possibility that the compatibility of each component becomes insufficient, and the coating property of the obtained composition is good. The component (E) can be used alone or in combination of two or more.

[Other ingredients]
In addition to the above-mentioned components, other components may be added to the photosensitive polyimide resin composition of the present invention. Examples of other components include basic compounds and surfactants.

By adding a basic compound, environmental stability, pattern shape or stability over time can be improved. Examples of the basic compound include amines, particularly secondary or tertiary aliphatic amines. Examples of the secondary or tertiary amines include diethylamine, di-n-propylamine, diethanolamine, trimethylamine, triethylamine, tri-n-propylamine, triethanolamine, tripropanolamine, 1-adamantanamine and the like. Can be mentioned.

The content of the basic compound is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). The basic compound may be used alone or in combination of two or more.

In addition, the coatability can be improved by adding a surfactant. The surfactant is preferably nonionic, and is, for example, a fluorine-based surfactant, specifically, a perfluoroalkyl polyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, or a fluorine-containing organosiloxane type. Examples include compounds.

Commercially available products can be used as the surfactant, for example, FLUORAD (registered trademark) FC-4430 (manufactured by 3M), Surflon (registered trademark) S-141 and S-145 (manufactured by AGC Seimi Chemical Co., Ltd.). ), Unidyne (registered trademark) DS-401, DS-4031 and DS-451 (manufactured by Daikin Industries, Ltd.), Megafuck (registered trademark) F-8151 (manufactured by DIC Co., Ltd.), X-70-093 ( (Made by Shin-Etsu Chemical Industry Co., Ltd.) and the like. Of these, FLUORAD FC-4430 and X-70-093 are preferred.

The content of the surfactant is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the component (A). The surfactant may be used alone or in combination of two or more.

[Pattern formation method]
A pattern forming method using the photosensitive polyimide resin composition of the present invention will be described. First, the photosensitive polyimide resin composition of the present invention is applied to a substrate by a known method such as a dip method, a spin coating method, a roll coating method, etc. to form a resist layer, and if necessary, a heating device such as a hot plate or an oven. Prebake the resist layer with.

As the substrate, for example, a silicon wafer, a plastic, a ceramic circuit board, or the like is used. The thickness of the resist layer is preferably 0.1 to 50 μm, more preferably 1 to 30 μm. Pre-baking can be performed, for example, at 40 to 140 ° C. for about 1 minute to 1 hour.

Next, using an exposure device such as a stepper or a mask aligner, the resist layer is subjected to light of various wavelengths, for example, light having a wavelength of 190 to 500 nm (preferably ultraviolet rays such as g-line and i-line) via a photomask. To expose. After the exposure, heat treatment (PEB) may be performed if necessary in order to further increase the development sensitivity. The PEB can be, for example, at 40-160 ° C. for 0.5-20 minutes.

After exposure or PEB, develop with a developer. As the developing solution, a known alkaline developing solution typified by an aqueous solution of tetramethylammonium hydroxide (TMAH) or the like is used. The development can be carried out by a usual method, for example, by immersing the pattern-forming product. Then, if necessary, washing, rinsing, drying and the like are performed to obtain a desired pattern.

Here, the primary alcoholic hydroxy group in the polyimide of the component (A) reacts with the cross-linking agent of the exposed portion by the action of the acid generated from the photoacid generator by the exposure and is cured. On the other hand, the polyimide of the component (A) and the polyimide of the component (B) are soluble in the alkaline developer due to the phenolic hydroxy group, whereby only the unexposed portion is dissolved in the alkaline developer, and a negative pattern is formed. It is formed. The polyimide component (B) does not have a cross-linking group, has only a group capable of dissolution, and has a low molecular weight, so that it is easily dissolved. Therefore, when the solubility of the entire composition is promoted and a pattern is formed. It is difficult for residues derived from the undissolved residue of the unexposed portion to be generated, which is effective in improving the pattern shape and contrast.

After development, if necessary, the obtained pattern may be further heat-treated at 100 to 250 ° C. for about 10 minutes to 10 hours using an oven or a hot plate. By performing the post-heat treatment, the crosslink density can be increased, the remaining volatile components can be removed, and a cured film having excellent heat resistance, transparency, low dielectric constant characteristics and solvent resistance can be formed.

In this way, the cured film obtained from the photosensitive polyimide resin composition of the present invention is excellent in adhesion to a substrate, heat resistance, electrical insulation, mechanical properties, and electric, electronic parts, semiconductor elements, etc. In addition to being suitably used as a protective film, it is possible to form a fine pattern, and the formed film is excellent in adhesiveness to a substrate, electrical properties, mechanical properties, etc., and is a protective film for semiconductor elements, a wiring protective film, etc. It is suitably used for coverlay films, solder resists, MEMS applications, and the like.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. For Mw, TSKgel Super HZM-H (manufactured by Toso Co., Ltd.) was used as the column, the flow rate was 0.6 mL / min, and the elution solvent was dimethylformamide in which lithium bromide was dissolved at a concentration of 10 mmol / L, and the column temperature. It was measured by GPC using monodisperse polystyrene as a standard under analytical conditions of 40 ° C.

The acid anhydride-modified polysiloxane A and the acid anhydride-modified polysiloxane B used in the following synthesis examples have average structures represented by the following formulas (A) and (B), respectively.

[1] Synthesis of polyimide resin [Synthesis example 1]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 127. .7 g (0.35 mol), 1,3-bis (3-aminophenoxy) benzene 27.2 g (0.10 mol), 4,4'-oxydiphthalic acid dianhydride 57.7 g (0.19 mol) And 2,600 g of γ-butyrolactone were added and stirred at room temperature for 6 hours, then 5.5 g (0.05 mol) of p-aminophenol was further added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution.

To the brown solution, 14.8 g (0.2 mol) of glycidol and 0.15 g (0.0018 mol) of 2-methylimidazole were added, and the mixture was heated at 140 ° C. for 5 hours to react. After completion of the reaction, the reaction solution was poured into water, the precipitated precipitate was filtered and dried to obtain a polyimide resin A1. As a result of GPC analysis, the Mw of the polyimide resin A1 was 14,200.

[Synthesis Example 2]
455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A, 98.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) sulfone in a flask equipped with a stirrer, a thermometer and a nitrogen substitution device. (0.35 mol), 1,3-bis (3-aminophenoxy) benzene 27.2 g (0.10 mol), 4,4'-oxydiphthalic anhydride 57.7 g (0.19 mol) and γ After adding 2,600 g of −butyrolactone and stirring at room temperature for 6 hours, 5.5 g (0.05 mol) of p-aminophenol was further added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution.

After cooling the brown solution to room temperature (25 ° C.), 14.8 g (0.2 mol) of glycidol and 0.15 g (0.0018 mol) of 2-methylimidazole are added thereto, and the mixture is heated at 140 ° C. for 5 hours. , Reacted. After completion of the reaction, the reaction solution was poured into water, the precipitated precipitate was filtered and dried to obtain a polyimide resin A2. As a result of GPC analysis, the Mw of the polyimide resin A2 was 15,100.

[Synthesis Example 3]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 127. .7 g (0.35 mol), 9,9-bis (4-aminophenyl) fluorene 34.8 g (0.10 mol), 4,4'-oxydiphthalic anhydride 57.7 g (0.19 mol) And 2,600 g of γ-butyrolactone were added and stirred at room temperature for 6 hours, then 5.5 g (0.05 mol) of p-aminophenol was further added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution.

After cooling the brown solution to room temperature (25 ° C.), 14.8 g (0.2 mol) of glycidol and 0.15 g (0.0018 mol) of 2-methylimidazole are added thereto, and the mixture is heated at 140 ° C. for 5 hours. , Reacted. After completion of the reaction, the reaction solution was poured into water, the precipitated precipitate was filtered and dried to obtain a polyimide resin A3. As a result of GPC analysis, the Mw of the polyimide resin A3 was 12,200.

[Synthesis Example 4]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 127. .7 g (0.35 mol), 24.8 g (0.10 mol) of bis (3-aminophenyl) sulfone, 57.7 g (0.19 mol) of 4,4'-oxydiphthalic anhydride and γ-butyrolactone After adding 2,600 g and stirring at room temperature for 6 hours, 5.5 g (0.05 mol) of p-aminophenol was further added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution.

To the brown solution, 14.8 g (0.2 mol) of glycidol and 0.15 g (0.0018 mol) of 2-methylimidazole were added, and the mixture was heated at 140 ° C. for 5 hours to react. After completion of the reaction, the reaction solution was poured into water, the precipitated precipitate was filtered and dried to obtain a polyimide resin A4. As a result of GPC analysis, the Mw of the polyimide resin A4 was 14,800.

[Synthesis Example 5]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 127. .7 g (0.35 mol), 1,3-bis (3-aminophenoxy) benzene 27.2 g (0.10 mol), 4,4'-oxydiphthalic acid dianhydride 57.7 g (0.19 mol) And 2,600 g of γ-butyrolactone were added and stirred at room temperature for 6 hours, then 6.2 g (0.05 mol) of p-aminoanisole was further added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution.

To the brown solution, 14.8 g (0.2 mol) of glycidol and 0.15 g (0.0018 mol) of 2-methylimidazole were added, and the mixture was heated at 140 ° C. for 5 hours to react. After completion of the reaction, the reaction solution was poured into water, the precipitated precipitate was filtered and dried to obtain a polyimide resin A5. As a result of GPC analysis, the Mw of the polyimide resin A5 was 13,300.

[Synthesis Example 6]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 127. .7 g (0.35 mol), 1,3-bis (3-aminophenoxy) benzene 27.2 g (0.10 mol), 4,4'-oxydiphthalic anhydride 57.7 g (0.19 mol) And 2,600 g of γ-butyrolactone were added and stirred at room temperature for 6 hours, then 5.4 g (0.05 mol) of m-toluidine was further added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution.

To the brown solution, 14.8 g (0.2 mol) of glycidol and 0.15 g (0.0018 mol) of 2-methylimidazole were added, and the mixture was heated at 140 ° C. for 5 hours to react. After completion of the reaction, the reaction solution was poured into water, the precipitated precipitate was filtered and dried to obtain a polyimide resin A6. As a result of GPC analysis, the Mw of the polyimide resin A6 was 16,500.

[Synthesis Example 7]
295.6 g (0.28 mol) of acid anhydride-modified polysiloxane B, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 127, in a flask equipped with a stirrer, a thermometer and a nitrogen substitution device. .7 g (0.35 mol), 1,3-bis (3-aminophenoxy) benzene 27.2 g (0.10 mol), 4,4'-oxydiphthalic acid dianhydride 57.7 g (0.19 mol) And 2,600 g of γ-butyrolactone were added and stirred at room temperature for 6 hours, then 5.5 g (0.05 mol) of p-aminophenol was further added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution.

To the brown solution, 14.8 g (0.2 mol) of glycidol and 0.15 g (0.0018 mol) of 2-methylimidazole were added, and the mixture was heated at 140 ° C. for 5 hours to react. After completion of the reaction, the reaction solution was poured into water, the precipitated precipitate was filtered and dried to obtain a polyimide resin A7. As a result of GPC analysis, the Mw of the polyimide resin A7 was 16,500.

[Synthesis Example 8]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 127. .7 g (0.35 mol), 1,3-bis (3-aminophenoxy) benzene 29.9 g (0.11 mol), 4,4'-oxydiphthalic acid dianhydride 57.7 g (0.19 mol) And 2,600 g of γ-butyrolactone were added and stirred at room temperature for 6 hours, then 1.1 g (0.01 mol) of p-aminophenol was further added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution.

13.3 g (0.18 mol) of glycidol and 0.15 g (0.0018 mol) of 2-methylimidazole were added to the brown solution, and the mixture was heated at 140 ° C. for 5 hours to react. After completion of the reaction, the reaction solution was poured into water, the precipitated precipitate was filtered and dried to obtain a polyimide resin A8. As a result of GPC analysis, the Mw of the polyimide resin A8 was 65,100.

[Synthesis Example 9]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 76. .6 g (0.21 mol), 1,3-bis (3-aminophenoxy) benzene 16.3 g (0.06 mol), 4,4'-oxydiphthalic anhydride 34.6 g (0.11 mol) , 44.0 g (0.40 mol) of p-aminophenol and 2,200 g of γ-butyrolactone were added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, the precipitated precipitate was filtered, and dried to obtain a polyimide resin B1. As a result of GPC analysis, the Mw of the polyimide resin B1 was 1,800.

[Synthesis Example 10]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 58.9 g of 2,2-bis (3-amino-4-hydroxyphenyl) sulfone. (0.21 mol), 1,3-bis (3-aminophenoxy) benzene 16.3 g (0.06 mol), 4,4'-oxydiphthalic anhydride 34.6 g (0.11 mol), p. 44.0 g (0.40 mol) of −aminophenol and 2,200 g of γ-butyrolactone were added, and the mixture was stirred at room temperature for 16 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, the precipitated precipitate was filtered, and dried to obtain a polyimide resin B2. As a result of GPC analysis, the Mw of the polyimide resin B2 was 1,500.

[Synthesis Example 11]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 76. .6 g (0.21 mol), 9,9-bis (4-aminophenyl) fluorene 20.9 g (0.06 mol), 4,4'-oxydiphthalic anhydride 34.6 g (0.11 mol) , 44.0 g (0.40 mol) of p-aminophenol and 2,200 g of γ-butyrolactone were added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, the precipitated precipitate was filtered, and dried to obtain a polyimide resin B3. As a result of GPC analysis, the Mw of the polyimide resin B3 was 1,700.

[Synthesis Example 12]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 76. .6 g (0.21 mol), 14.9 g (0.06 mol) of bis (3-aminophenyl) sulfone, 34.6 g (0.11 mol) of 4,4'-oxydiphthalic anhydride, p-amino 44.0 g (0.40 mol) of phenol and 2,200 g of γ-butyrolactone were added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, the precipitated precipitate was filtered, and dried to obtain a polyimide resin B4. As a result of GPC analysis, the Mw of the polyimide resin B4 was 1,500.

[Synthesis Example 13]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 76. .6 g (0.21 mol), 1,3-bis (3-aminophenoxy) benzene 16.3 g (0.06 mol), 4,4'-oxydiphthalic anhydride 34.6 g (0.11 mol) , 49.6 g (0.40 mol) of p-aminoanisol and 2,200 g of γ-butyrolactone were added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, the precipitated precipitate was filtered, and dried to obtain a polyimide resin B5. As a result of GPC analysis, the Mw of the polyimide resin B5 was 1,600.

[Synthesis Example 14]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 76. .6 g (0.21 mol), 1,3-bis (3-aminophenoxy) benzene 16.3 g (0.06 mol), 4,4'-oxydiphthalic acid dianhydride 34.6 g (0.11 mol) , M-toluidine 43.2 g (0.40 mol) and γ-butyrolactone 2,200 g were added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, the precipitated precipitate was filtered, and dried to obtain a polyimide resin B6. As a result of GPC analysis, the Mw of the polyimide resin B6 was 1,600.

[Synthesis Example 15]
In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 177.4 g (0.17 mol) of acid anhydride-modified polysiloxane B, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 76. .6 g (0.21 mol), 1,3-bis (3-aminophenoxy) benzene 16.3 g (0.06 mol), 4,4'-oxydiphthalic anhydride 34.6 g (0.11 mol) , 44.0 g (0.40 mol) of p-aminophenol and 2,200 g of γ-butyrolactone were added, and the mixture was stirred at room temperature for 14 hours. After completion of stirring, a reflux condenser with a water receptor was attached to the flask, 100 mL of xylene was added, and reflux was performed at 190 ° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, the precipitated precipitate was filtered, and dried to obtain a polyimide resin B7. As a result of GPC analysis, the Mw of the polyimide resin B7 was 1,300.

[2] Preparation of Photosensitive Polyimide Resin Composition and Evaluation thereof [Examples 1 to 17, Comparative Examples 1 to 5]
Each polyimide resin A1 to A8 and each polyimide resin B1 to B7 are mixed so as to have the compositions shown in Tables 1 to 3 below, and a photoacid generator P1, a cross-linking agent C1, C2 and a basic compound N1 are added thereto. N2 was added and dissolved, and then filtered using a glass filter having a pore size of 0.2 μm to prepare a photosensitive polyimide resin composition.

In Tables 1 to 3, P1, C1, C2, N1 and N2 are as follows.
P1: [5- (4- (4-Methylphenylsulfonyloxy) phenylsulfonyloxyimino) -5H-thiophen-2-iriden]-(2-methylphenyl) -acetonitrile C1: 2,4,6-tris [bis] (Methyl) Amino] -1,3,5-Triazine C2: 1,3,4,6-Tetrax (Methyl) Glycoluryl N1: Triethanolamine N2: 1-adamantanamine

The compositions of Examples 1 to 17 and the compositions of Comparative Examples 1 to 5 were each applied on an 8-inch silicon wafer with a spinner, prebaked on a hot plate at 90 ° C. for 120 seconds, and a resist having a thickness of about 10.0 μm. A film was formed. Further, patterning exposure was performed using an i-line stepper (NSR-1755i7A manufactured by Nikon Corporation), paddle-developed for 250 seconds using a 2.38 mass% TMAH aqueous solution as a developing solution, rinsed with pure water, and then used in an oven. It was heated at 180 ° C. for 2 hours in a nitrogen atmosphere.
The obtained sample was evaluated for film physical characteristics, sensitivity evaluation, and resolution using SEM (S-4100) manufactured by Hitachi High-Technologies Corporation. The physical properties of the film were evaluated by observing the state near the pattern with a microscope and measuring how many of the 10 points had defects (voids, peeling and cracks). The sensitivity was evaluated by changing the exposure amount, and the point where the exposure amount was the smallest among the places where the composition remained after development was set as the minimum exposure amount. The smaller the minimum exposure amount, the higher the sensitivity, which leads to a reduction in the process time when manufacturing chips and the like. In the resolution evaluation, after forming a 1.0 to 10.0 μm line & space pattern, it was observed, and the smallest one that could be formed without collapsing the pattern was defined as the minimum resolution dimension (line & space). The results are shown in Tables 4 and 5.

As a result of the above, the compositions of Examples 1 to 17 are capable of forming a line & space pattern having an aspect ratio of about 2, exhibiting good resolving power and physical characteristics of a film, and exhibiting sufficient properties as a photosensitive material. It could be confirmed. From this feature, when the resin composition of the present invention is used as a resist composition for a semiconductor, it can be said that fine patterns can be formed with high sensitivity and abnormalities such as cracks and voids are unlikely to occur.

Claims (7)

(A) A primary alcoholic substance containing a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2) and having a weight average molecular weight of 5,000 to 200,000. Hydroxy group-containing polyimide,
(B) A polyimide containing a phenolic hydroxy group and having a weight average molecular weight of 2,000 or less.
A photosensitive polyimide resin composition containing (C) a photoacid generator and (D) a cross-linking agent, and the content of the component (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the component (A).

[In the formula, X ¹ is a tetravalent organic group represented by the following formula (2).

(In the formula, R ^{1 to} R ⁶ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. R ⁷ and R ⁸ are independently single-bonded or 2 having 1 to 12 carbon atoms, respectively. It is a valent hydrocarbon group. R ⁹ and R ¹⁰ are independently trivalent organic groups. M is an integer of 0 to 120. The broken line is a bond.)
X ² is a tetravalent group selected from the groups represented by the following formulas.

(In the formula, the broken line is the bond.)
Y ¹ is a divalent group represented by the following formula (3).

(In the formula, A ^{1 to} A ³ are independently single bond, methylene group, ether bond, sulfonyl group, amide bond, propane-2,2-diyl group, 1,1,1,3,3,3. -Hexafluoropropane-2,2-diyl group or fluorene-9,9-diyl group. R ¹¹ and R ¹² are independently hydroxy groups or alcoholic hydroxy group-containing groups, but at least one. One is a primary alcoholic hydroxy group-containing group. R ^{13 to} R ¹⁶ are independently alkyl groups having 1 to 4 carbon atoms. A is an integer of 0 to 10. B and c are integers of 0 to 10. , 0 or 1 independently. D to g are 0, 1 or 2, respectively. The dashed line is the bond.)
p is a positive integer and q is a positive integer. ] The photosensitive polyimide resin composition according to claim 1, wherein the polyimide component (B) contains a repeating unit represented by the following formula (1-3) and a repeating unit represented by the following formula (1-4).

[In the formula, X ¹ and X ² are the same as above. Y ² is at least one selected from the group represented by the formula (4) and the group represented by the formula (5). r and s are independently 0 or positive integers, respectively.

(In the formula, B ^{1 to} B ³ are independent, single bond, methylene group, ether bond, sulfonyl group, amide bond, propane-2,2-diyl group, 1,1,1,3,3,3. -Hexafluoropropane-2,2-diyl group or fluorene-9,9-diyl group. R ^{21 to} R ²⁴ are independently alkyl groups having 1 to 4 carbon atoms. A'is 0. -10, b'and c'are independently 0 or 1. d'to g'are independently 0, 1 or 2. The dashed line is the bond. .)

(In the formula, R ^{31 to} R ³⁴ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. N is an integer of 1 to 80. The broken line is a bond.)] The photosensitive polyimide resin composition according to claim 1 or 2, further comprising (E) a solvent. (C) The photosensitive polyimide resin composition according to any one of claims 1 to 3, wherein the photoacid generator is an imide-yl-sulfonates, iminosulfonates or oxime sulfonates. The photosensitive polyimide resin composition according to any one of claims 1 to 4, further comprising a basic compound. A pattern including a step of applying the photosensitive polyimide resin composition according to any one of claims 1 to 5 onto a substrate to form a resist layer, a step of exposing the resist layer, and a step of developing the resist layer. Forming method. A method for manufacturing a semiconductor device including a polyimide resin film on which a pattern is formed, which comprises the pattern forming method according to claim 6.