JP7247867B2 - Photosensitive polyimide resin composition, pattern forming method, and semiconductor device manufacturing method - Google Patents

Description

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

Conventionally, photosensitive polyimide-based materials include materials using polyamic acid, which is a polyimide precursor, such as those in which a photosensitive group is introduced into the carboxyl group of polyamic acid through an ester bond (Patent Documents 1 and 2), A material including a polyamic acid and an amine compound having a photosensitive group (Patent Document 3) has been proposed. However, these materials require imidation treatment at high temperatures exceeding 300° C. in order to obtain the desired polyimide film after forming a patterned film. There were problems such as restrictions on the base material and oxidization of the copper of the wiring.

As an improvement to this, photosensitive polyimides using already imidized solvent-soluble resins have been proposed for the purpose of lowering the curing temperature (Patent Documents 4 to 6). However, all of them use a (meth)acrylic group to impart photosensitivity to the resin, and due to the photocuring mechanism, they are susceptible to oxygen inhibition and film thinning during development. However, it has not been possible to obtain a material that satisfies all the required properties.

On the other hand, positive materials have been proposed in which diazonaphthoquinone is combined with polyimide (Patent Document 7) or polyamide (Patent Documents 8 and 9) having a phenolic hydroxy group. For these, it is difficult to form a thick film exceeding 20 μm from the viewpoint of light transmission of the composition. is added in a large amount relative to the resin, there is a problem that it is difficult to obtain the original curing characteristics of the resin.

JP-A-49-115541 JP-A-55-45746 JP-A-54-145794 JP-A-10-274850 JP-A-10-265571 JP-A-2001-335619 JP-A-3-209478 Japanese Patent Publication No. 1-46862 JP-A-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, by heat treatment at a relatively low temperature of about 200 ° C., the film properties and as a protective film can be improved. It is an object of the present invention to provide a photosensitive polyimide resin composition capable of providing a highly reliable film, a pattern forming method, and a method for manufacturing a semiconductor device.

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

Furthermore, the photosensitive polyimide resin composition containing the polyimide mixture and a photoacid generator can be exposed to light with high sensitivity and a wide range of wavelengths, and it is possible to form a fine pattern by a pattern forming method described later. The inventors have found that this photosensitive polyimide resin composition and a 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。 Accordingly, the present invention provides the following photosensitive polyimide resin composition, pattern forming method, and semiconductor device manufacturing method.
1. (A) a primary alcoholic alcohol 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 comprising (C) a photoacid generator and (D) a cross-linking agent, wherein the content of component (B) is 1 to 10 parts by mass per 100 parts by mass of 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 each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. R ⁷ and R ⁸ are each independently a single bond or a 2 is a valent hydrocarbon group, R ⁹ and R ¹⁰ are each independently a trivalent organic group, m is an integer of 0 to 120, and the dashed line is a bond.)
X ² is a tetravalent group selected from groups represented by the following formulae.

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

(wherein A ¹ to A ³ are each independently a 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 each independently a hydroxy group or an alcoholic hydroxy group-containing group, but at least one is a primary alcoholic hydroxy group-containing group, R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 10, b and c are , each independently 0 or 1. d to g are each independently 0, 1 or 2. The dashed line is a bond.)
p is a positive integer and q is a positive integer. ]
2. 1. The photosensitive polyimide resin composition of 1, wherein the polyimide as 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 formula (4) and the group represented by formula (5). r and s are each independently 0 or a positive integer.

(wherein B ¹ to B ³ are each independently a 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 each independently an alkyl group having 1 to 4 carbon atoms, a' is 0 is an integer of ~ 10. b' and c' are each independently 0 or 1. d' to g' are each independently 0, 1 or 2. A broken line is a bond .)

(Wherein, R ³¹ to R ³⁴ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. n is an integer of 1 to 80. The dashed line indicates a bond.)]
3. Furthermore, (E) one or two photosensitive polyimide resin compositions containing a solvent.
4. (C) The photosensitive polyimide resin composition of any one of 1 to 3, wherein the photoacid generator is imido-yl-sulfonates, iminosulfonates or oximesulfonates.
5. 4. The photosensitive polyimide resin composition according to any one of 1 to 4, further comprising a basic compound.
6. A pattern forming method comprising the steps of applying the photosensitive polyimide resin composition according to any one of 1 to 5 onto a substrate to form a resist layer, exposing the resist layer, and developing it.
7. A method of manufacturing a semiconductor device having a patterned polyimide resin film, including the pattern forming method of 6.

By using the photosensitive polyimide resin composition of the present invention, it is possible to expose to light of a wide range of wavelengths and easily form a thin film without being affected by oxygen damage. In addition, it is possible to form a pattern with excellent resolution, and the cured film obtained from this composition has excellent adhesion to substrates, heat resistance, and electrical insulation, and is used for electrical, electronic parts, and semiconductor devices. It is preferably used as a protective film such as

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) a 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 component (B) is 1 to 10 parts by mass per 100 parts by mass of component (A).

[(A) Component]
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 200,000. It is a polyimide containing a higher alcoholic hydroxyl group.

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

In formula (2), R ¹ to R ⁶ are each independently a monovalent hydrocarbon group 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; aryl groups such as phenyl group; aralkyl groups such as benzyl group and phenethyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group and butenyl group. A methyl group, an ethyl group, a phenyl group, and a vinyl group are preferable from the viewpoint of availability of raw materials.

In formula (2), R ⁷ and R ⁸ are each independently a single bond or a divalent hydrocarbon group 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, a propane- 1,3-diyl group, butane-1,4-diyl group, benzene-1,4-diyl group, biphenyl-4,4'-diyl group and the like. R ⁷ and R ⁸ are preferably a single bond, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group and benzene-1,4-diyl group.

In formula (2), ^R9 and ^R10 are each independently a trivalent organic group. The trivalent organic group preferably has 2 to 10 carbon atoms. Examples of the trivalent organic group include, but are not limited to, those represented by the following formulae.

In formula (2), m is an integer of 0-120, preferably an integer of 3-80, more preferably an integer of 5-50. 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 it contains two or more different types of siloxane units, the siloxane units may be randomly bonded or alternately bonded, and may include multiple 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 formula, m ¹ and m ² are each independently an integer of 0 or 1 or more, and m ¹ +m ² =m. ^{m 3} and m ⁴ are each independently an integer of 0 or 1 or more. and m ³ +m ⁴ =m, ^{m 5} and m ⁶ are each independently an integer of 0 or 1 or more, and m ⁵ +m ⁶ =m, where m is the same as described above. )

The group represented by X ¹ is an acid anhydride having an unsaturated group, such as succinic anhydride, norbornene dicarboxylic anhydride, propylnadic anhydride or phthalic anhydride, and an organohydrogenpolysiloxane. It can be derived from modified silicones obtained by reacting. The number of siloxane units in the resulting acid anhydride-modified polysiloxane is also distributed according to the distribution of the number of siloxane units in the organohydrogenpolysiloxane, and therefore m in formula (2) represents the average value.

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

(In the formula, the dashed line is a 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 formula (3) below.

(In the formula, the dashed line is a bond.)

In formula (3), A ¹ to A ³ each independently represent a 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 each independently a hydroxy group or an alcoholic hydroxy group-containing group, at least one of which is a primary alcoholic hydroxy group. Examples of the alcoholic hydroxy group-containing group include 2,3-dihydroxypropyl group and 1,3-dihydroxy-2-propyloxy group.

In formula (3), R ¹³ to R ¹⁶ are each independently an alkyl group 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, and the methyl group is preferred.

In formula (3), a is an integer of 0-10, preferably an integer of 1-10. b and c are each independently 0 or 1; d to g are each independently 0, 1 or 2, with 0 or 1 being preferred.

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

In formulas (1-1) and (1-2), p and q are each independently a positive integer, preferably an integer satisfying 1 ≤ p ≤ 500 and 1 ≤ q ≤ 500, more preferably is an integer satisfying 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, more preferably 0.2≦p/(p+q) ≦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 component (A) preferably contains only repeating units represented by formula (1-1) and repeating units represented by formula (1-2).

The polyimide of component (A) has a weight average molecular weight (Mw) of 5,000 to 200,000, preferably 8,000 to 100,000. Polyimides with an Mw of less than 5,000 give films of low strength. On the other hand, polyimides with Mw exceeding 200,000 have poor compatibility with solvents and are difficult to handle. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using dimethylformamide to which 10 mmol/L of lithium bromide is added as a solvent.

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

As a method for synthesizing the polyimide of 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. A polyamic acid is obtained by reacting a monofunctional amine as a terminal group according to the above.

Diamines having a phenolic hydroxyl 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- hydroxyphenyl)hexafluoropropane and the like.

Examples of the acid anhydride-modified silicone include compounds in which both ends of the group exemplified as the tetravalent organic group represented by X ¹ have an acid anhydride structure. Specific examples include the following. include but are not limited to:

（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.)

Acid dianhydrides include 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′ ,4-biphenyltetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5 -dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3' ,4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoropropylidenebisphthalic dianhydride, 2,2-bis(p-trimethoxyphenyl)propanoic dianhydride, 1, 3-tetramethyldisiloxanebisphthalic dianhydride, 4,4'-oxydiphthalic dianhydride and the like.

Diamines having no phenolic hydroxy group include 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone and 3,3'. -dimethyl-4,4'-diaminobiphenyl, 4,4'-(p-phenylenediisopropylidene)dianiline, 4,4'-(m-phenylenediisopropylidene)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 '-bis(4-aminophenoxy)biphenyl, 9,9'-bis(4-aminophenyl)fluorene and the like.

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, etc., but the molar ratio is preferably 0.95 to 1.05, more than It is preferably in the range of 0.98 to 1.02. In order to adjust the molecular weight of the polyimide, it is also possible to add monofunctional acid anhydrides such as phthalic anhydride and aniline, and amine compounds. 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.

Reaction of a diamine and an acid dianhydride is normally performed in a solvent. The solvent is not particularly limited as long as it dissolves the polyimide component (A). Specific examples of the solvent include ethers such as diglyme, triglyme, tetrahydrofuran and anisole; ketones such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone and acetophenone; butyl acetate and methyl benzoate. , gamma-butyrolactone; cellosolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate; , and xylene. Among these, diglyme, cyclohexanone, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N'-dimethylacetamide and N-methyl-2-pyrrolidone are preferred. These solvents may be used singly or in combination of two or more. The amount of the solvent to be used is usually adjusted in the range that the polyimide concentration is 10 to 40% by mass in consideration of the yield per batch, the solution 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 performed by heating the polyamic acid solution to a temperature range of usually 80 to 250° C., preferably 140 to 200° C., or adding an acetic anhydride/pyridine mixed solution to the polyamic acid solution, and then obtaining It can be carried out by heating the obtained solution to around 50°C. As a result, the acid amide portion of the polyamic acid undergoes a dehydration ring-closure reaction to form a polyimide.

Thereafter, at least part of the phenolic hydroxy groups contained in this polyimide are substituted with primary alcoholic hydroxy group-containing organic groups to obtain the polyimide of the component (A). Examples of the substitution method include a method of reacting compounds such as glycidol, 3-chloro-1,2-propanediol and 3-chloro-2,2-dimethyl-1-propanol under a base catalyst. The proportion of the hydrogen atoms of the phenolic hydroxy group into which the hydroxy group-containing organic group is introduced is preferably 10 to 90 mol %, more preferably 30 to 60 mol %.

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

(A) component can be used individually by 1 type or in combination of 2 or more types.

[(B) Component]
The polyimide of component (B) is characterized by containing phenolic hydroxy groups and having an Mw of 2,000 or less.

Polyimide as 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 above. Y ² is at least one selected from the group represented by formula (4) and the group represented by formula (5).

(wherein B ¹ to B ³ are each independently a 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 each independently an alkyl group having 1 to 4 carbon atoms, a' is 0 is an integer of ~ 10. b' and c' are each independently 0 or 1. d' to g' are each independently 0, 1 or 2. A broken line is a bond .)

(In the formula, R ³¹ to R ³⁴ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. n is an integer of 1 to 80. A broken line indicates a bond.)

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

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

In formulas (1-3) and (1-4), r and s are each independently 0 or a positive integer, preferably an integer satisfying 0 ≤ r ≤ 500 and 0 ≤ s ≤ 500, More preferably, it is an integer satisfying 0≦r≦300 and 0≦s≦300.

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

The polyimide of the component (B) can be synthesized by controlling the amounts of amine, diamine and acid anhydride in the method for synthesizing the polyimide of the component (A), and by not reacting the hydroxy groups.

The content of component (B) is preferably 1 to 10 parts by mass per 100 parts by mass of component (A). If the content of component (B) is less than 1 part by mass, the effect of improving the solubility in the developer may not be obtained, and if it exceeds 10 parts by mass, the physical properties of the cured film may deteriorate. (B) Polyimide of a component can be used individually by 1 type or in combination of 2 or more types.

[(C) component]
The photoacid generator of component (C) is not particularly limited as long as it is decomposed by light irradiation to generate an acid, but it is preferable to generate an acid by irradiation with light having a wavelength of 240 to 500 nm. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonic acid ester derivatives, imido-yl-sulfonate derivatives, oximesulfonate derivatives, iminosulfonate derivatives. etc.

Examples of the onium salts include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, and (p-tert-butoxyphenyl)phenyl p-toluenesulfonate. Iodonium, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert) trifluoromethanesulfonate -butoxyphenyl)sulfonium, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, p- tris(p-tert-butoxyphenyl)sulfonium toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexyl trifluoromethanesulfonate methyl(2-oxocyclohexyl)sulfonium, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, p dicyclohexylphenylsulfonium-toluenesulfonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate and the like.

Examples of the diazomethane derivatives 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- 1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane and the like.

Examples of the glyoxime derivative include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime , bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclo xylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis- o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime oxime, 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- dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime and the like.

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 nitrobenzylsulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

Examples of the sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy ) benzene and the like.

Examples of the imido-yl-sulfonate derivatives include phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboxy imido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate, N-trifluoromethylsulfonyloxynaphthylimide and the like.

Examples of the oximesulfonate derivatives include α-(benzenesulfoniumoxyimino)-4-methylphenylacetonitrile.

Examples of the iminosulfonate derivatives include [5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene]-(2-methylphenyl)acetonitrile, [5-(4-(4-methylphenylsulfonyloxy ) phenylsulfonyloxyimino)-5H-thiophen-2-ylidene]-(2-methylphenyl)-acetonitrile and the like.

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

Among these, imido-yl-sulfonate derivatives, iminosulfonate derivatives, oximesulfonate derivatives and the like are preferably used.

The content of component (C) is preferably 0.03 to 20 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of component (A). If the content of component (C) is within the above range, sufficient contrast (difference in dissolution rate in developer between exposed and unexposed areas) can be obtained, and resolution is good. (C) component can be used individually by 1 type or in combination of 2 or more types.

[(D) component]
The cross-linking agent of component (D) acts on the phenolic hydroxy groups and/or primary alcoholic hydroxy groups in the polyimide of component (A) to cause cross-linking and curing, or condensation or addition between 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-based compounds, glycoluril-based compounds, urea-based compounds, epoxy-based compounds, and phenol compounds containing two or more methylol derivatives in one molecule.

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

Examples of the glycoluril-based compounds include tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, and the like.

Examples of the urea-based compounds include tetramethoxymethylurea, dimethoxymethylethyleneurea, and dimethoxymethylpropyleneurea.

Examples of the epoxy-based compounds include phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol A type epoxy resins such as diglycidyl bisphenol A, bisphenol F type epoxy resins such as diglycidyl bisphenol F, and triphenylolpropane triglycidyl ether. cycloaliphatic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; glycidyl esters such as diglycidyl phthalate, diglycidyl hexahydrophthalate, and dimethylglycidyl phthalate; glycidylamine-based resins such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, diglycidyltoluidine, and tetraglycidylbisaminomethylcyclohexane.

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, 6-hydroxy-5-methyl -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, trifunctional types such as 2-hydroxy-1,3,5-benzenetrimethanol, 3,5-dimethyl-2,4,6-trihydroxymethylphenol, etc. 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′-Tetrakis(methoxymethyl)[(1,1′-biphenyl)-4,4′-diol], 4,4′,4″-methyl lysine tris(2,6-dihydroxymethylphenol), 4,4',4''-ethylidine tris(2,6-dihydroxymethylphenol) and the like.

The content of component (D) is preferably 0.1 to 50 parts by mass, more preferably 2 to 40 parts by mass, per 100 parts by mass of component (A). If the content is within the above range, sufficient cross-linking density is obtained, and transparency and storage stability are good. (D) Component can be used individually by 1 type or in combination of 2 or more types.

[(E) component]
The solvent for component (E) is not particularly limited as long as it has sufficient solubility for each of the components described above and other components described later and provides good coating properties.

Such solvents include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; 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 include esters such as γ-butyrolactone.

Among these, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and γ-butyrolactone, which have the highest solubility of components (A), (B), (C) and (D). and mixed solvents thereof are preferred.

The solvent content of component (E) is preferably 20 to 1,200 parts by mass, more preferably 70 to 500 parts by mass, per 100 parts by mass of components (A) to (D). When the content is within the above range, there is no possibility that the compatibility of each component will be insufficient, and the resulting composition will have good applicability. (E) component can be used individually by 1 type or in mixture of 2 or more types.

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

Addition of a basic compound can improve environmental stability, pattern shape, or stability over time. Said basic compounds include amines, especially secondary or tertiary aliphatic amines. Examples of this secondary or tertiary amine include diethylamine, di-n-propylamine, diethanolamine, trimethylamine, triethylamine, tri-n-propylamine, triethanolamine, tripropanolamine, 1-adamantanamine and the like. mentioned.

The content of the basic compound is preferably 0.1 to 10 parts by weight per 100 parts by weight of component (A). The basic compounds may be used singly or in combination of two or more.

Also, the coating property can be improved by adding a surfactant. As the surfactant, a nonionic one is preferable. For example, fluorine-based surfactants, specifically perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, fluorine-containing organosiloxane-based compounds and the like.

Commercially available surfactants can be used, 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.), Megafac (registered trademark) F-8151 (manufactured by DIC Corporation), X-70-093 ( manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Among these, FLUORAD FC-4430 and X-70-093 are preferred.

The content of the surfactant is preferably 0.01 to 15 parts by weight per 100 parts by weight of component (A). The said surfactant can be used individually by 1 type or in mixture of 2 or more types.

[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 technique such as a dipping method, a spin coating method, or a roll coating method to form a resist layer, and if necessary, a heating device such as a hot plate or oven. to pre-bake the resist layer.

As the substrate, for example, a silicon wafer, plastic, ceramic circuit board, or the like is used. Moreover, 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.

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

After exposure or PEB, the film is developed using a developer. As the developer, a known alkaline developer such as an aqueous solution of tetramethylammonium hydroxide (TMAH) is used. Development can be carried out by a usual method, for example, by immersing the patterned product. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a desired pattern.

Here, the primary alcoholic hydroxy groups in the polyimide of the component (A) react with the cross-linking agent in the exposed portions by the action of the acid generated from the photoacid generator upon exposure, and are cured. On the other hand, the polyimide of the component (A) and the polyimide of the component (B) are soluble in an alkaline developer due to their phenolic hydroxy groups. It is formed. The polyimide of the component (B) does not have a cross-linking group, has only a group that enables dissolution, and is easy to dissolve because it has a low molecular weight, therefore promoting the solubility of the entire composition, when forming a pattern. This is effective in improving the pattern shape and contrast because the residue derived from the undissolved portion of the unexposed portion is less likely to occur.

After development, if necessary, the obtained pattern may be post-heated at 100 to 250° C. for about 10 minutes to 10 hours using an oven or a hot plate. The post-heat treatment increases the crosslink density, removes the remaining volatile components, and forms a cured film excellent in heat resistance, transparency, low dielectric constant properties, and solvent resistance.

Thus, the cured film obtained from the photosensitive polyimide resin composition of the present invention has excellent adhesion to substrates, heat resistance, electrical insulation, and mechanical properties, and can be used for electrical, electronic parts, semiconductor elements, and the like. In addition to being suitably used as a protective film, fine patterns can be formed, and the formed film has excellent adhesion to substrates, electrical properties, mechanical properties, etc., and is a protective film for semiconductor elements, a protective film for wiring, It is suitably used for coverlay films, solder resists, MEMS applications, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In addition, Mw was measured using TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a column, a flow rate of 0.6 mL/min, an elution solvent of dimethylformamide in which lithium bromide was dissolved at a concentration of 10 mmol/L, and a column temperature of It was measured by GPC using monodisperse polystyrene as a standard under analysis conditions of 40°C.

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

[1] Synthesis of polyimide resin [Synthesis Example 1]
455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A and 127 mol of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. .7 g (0.35 mol), 1,3-bis(3-aminophenoxy)benzene 27.2 g (0.10 mol), 4,4'-oxydiphthalic 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 stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution.

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

[Synthesis Example 2]
455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A and 98.1 g of 2,2-bis(3-amino-4-hydroxyphenyl)sulfone were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. (0.35 mol), 27.2 g (0.10 mol) of 1,3-bis(3-aminophenoxy)benzene, 57.7 g (0.19 mol) of 4,4'-oxydiphthalic dianhydride 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 stirring at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed 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 were added thereto and heated at 140° C. for 5 hours. , reacted. After completion of the reaction, the reaction solution was poured into water, and the deposited precipitate was filtered and dried to obtain polyimide resin A2. As a result of GPC analysis, the Mw of polyimide resin A2 was 15,100.

[Synthesis Example 3]
455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A and 127 mol of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. .7 g (0.35 mol), 9,9-bis(4-aminophenyl)fluorene 34.8 g (0.10 mol), 4,4'-oxydiphthalic 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 stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed 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 were added thereto and heated at 140° C. for 5 hours. , reacted. After completion of the reaction, the reaction solution was poured into water, and the deposited precipitate was filtered and dried to obtain polyimide resin A3. As a result of GPC analysis, the Mw of polyimide resin A3 was 12,200.

[Synthesis Example 4]
455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A and 127 mol of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. .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 dianhydride 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 stirring was performed at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution.

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

[Synthesis Example 5]
455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A and 127 mol of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. .7 g (0.35 mol), 1,3-bis(3-aminophenoxy)benzene 27.2 g (0.10 mol), 4,4'-oxydiphthalic 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 stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution.

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

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

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

[Synthesis Example 7]
295.6 g (0.28 mol) of acid anhydride-modified polysiloxane B and 127 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. .7 g (0.35 mol), 1,3-bis(3-aminophenoxy)benzene 27.2 g (0.10 mol), 4,4'-oxydiphthalic 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 stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution.

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

[Synthesis Example 8]
455.0 g (0.28 mol) of acid anhydride-modified polysiloxane A and 127 mol of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. .7 g (0.35 mol), 1,3-bis(3-aminophenoxy)benzene 29.9 g (0.11 mol), 4,4'-oxydiphthalic 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 stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed 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 heated at 140° C. for 5 hours to react. After completion of the reaction, the reaction solution was poured into water, and the deposited precipitate was filtered and dried to obtain polyimide resin A8. As a result of GPC analysis, the Mw of polyimide resin A8 was 65,100.

[Synthesis Example 9]
273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 76 g of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. 0.6 g (0.21 mol), 16.3 g (0.06 mol) of 1,3-bis(3-aminophenoxy)benzene, 34.6 g (0.11 mol) of 4,4'-oxydiphthalic dianhydride , 44.0 g (0.40 mol) of p-aminophenol and 2,200 g of γ-butyrolactone were added and stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, and the deposited precipitate was filtered and dried to obtain polyimide resin B1. As a result of GPC analysis, the Mw of polyimide resin B1 was 1,800.

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

[Synthesis Example 11]
273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 76 g of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. .6 g (0.21 mol), 9,9-bis(4-aminophenyl)fluorene 20.9 g (0.06 mol), 4,4'-oxydiphthalic dianhydride 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 stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, and the deposited precipitate was filtered and dried to obtain polyimide resin B3. As a result of GPC analysis, the Mw of polyimide resin B3 was 1,700.

[Synthesis Example 12]
273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 76 g of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. 0.6 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 dianhydride, p-amino 44.0 g (0.40 mol) of phenol and 2,200 g of γ-butyrolactone were added and stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, and the deposited precipitate was filtered and dried to obtain polyimide resin B4. As a result of GPC analysis, the Mw of polyimide resin B4 was 1,500.

[Synthesis Example 13]
273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 76 g of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. 0.6 g (0.21 mol), 16.3 g (0.06 mol) of 1,3-bis(3-aminophenoxy)benzene, 34.6 g (0.11 mol) of 4,4'-oxydiphthalic dianhydride , 49.6 g (0.40 mol) of p-aminoanisole and 2,200 g of γ-butyrolactone were added and stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, and the deposited precipitate was filtered and dried to obtain polyimide resin B5. As a result of GPC analysis, the Mw of polyimide resin B5 was 1,600.

[Synthesis Example 14]
273.0 g (0.17 mol) of acid anhydride-modified polysiloxane A, 76 g of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. 0.6 g (0.21 mol), 16.3 g (0.06 mol) of 1,3-bis(3-aminophenoxy)benzene, 34.6 g (0.11 mol) of 4,4'-oxydiphthalic dianhydride , 43.2 g (0.40 mol) of m-toluidine and 2,200 g of γ-butyrolactone were added and stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, and the deposited precipitate was filtered and dried to obtain polyimide resin B6. As a result of GPC analysis, the Mw of polyimide resin B6 was 1,600.

[Synthesis Example 15]
177.4 g (0.17 mol) of acid anhydride-modified polysiloxane B and 76 g of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane were placed in a flask equipped with a stirrer, thermometer and nitrogen purge device. 0.6 g (0.21 mol), 16.3 g (0.06 mol) of 1,3-bis(3-aminophenoxy)benzene, 34.6 g (0.11 mol) of 4,4'-oxydiphthalic dianhydride , 44.0 g (0.40 mol) of p-aminophenol and 2,200 g of γ-butyrolactone were added and stirred at room temperature for 14 hours. After stirring, a reflux condenser with a moisture receiver was attached to the flask, 100 mL of xylene was added, and the mixture was refluxed at 190° C. for 10 hours to obtain a brown solution. The brown solution was poured into water, and the deposited precipitate was filtered and dried to obtain polyimide resin B7. As a result of GPC analysis, the Mw of polyimide resin B7 was 1,300.

[2] Preparation of a photosensitive polyimide resin composition and its evaluation [Examples 1 to 17, Comparative Examples 1 to 5]
Polyimide resins A1 to A8 and polyimide resins B1 to B7 are mixed so as to have the compositions shown in Tables 1 to 3 below, and then photoacid generator P1, crosslinkers C1 and C2 and basic compound N1, After N2 was added and dissolved, the mixture was filtered using a glass filter with 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-ylidene]-(2-methylphenyl)-acetonitrile C1: 2,4,6-tris[bis (Methoxymethyl)amino]-1,3,5-triazine C2: 1,3,4,6-tetrakis(methoxymethyl)glycoluril 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 with a thickness of about 10.0 μm. A film was formed. Further, patterning exposure is performed using an i-line stepper (NSR-1755i7A manufactured by Nikon Corporation), puddle development is performed for 250 seconds using a 2.38% by mass TMAH aqueous solution as a developer, rinsing with pure water, and then using an oven. Heated at 180° C. for 2 hours under a nitrogen atmosphere.
The obtained samples were subjected to film physical properties, sensitivity evaluation, and resolution evaluation using SEM (S-4100) manufactured by Hitachi High-Technologies Corporation. The physical properties of the film were evaluated by observing the state in the vicinity of the pattern with a microscope and evaluating the number of defects (voids, peeling, and cracks) out of 10 locations. Sensitivity evaluation was carried out by changing the exposure amount, and the point with the smallest exposure amount among the portions where the composition remained after development was taken as the minimum exposure amount. The smaller the minimum exposure dose, the higher the sensitivity, which leads to a reduction in the process time when manufacturing chips and the like. For evaluation of resolution, a line and space pattern of 1.0 to 10.0 μm was formed and then observed. Results are shown in Tables 4 and 5.

As a result, the compositions of Examples 1 to 17 can form a line & space pattern with an aspect ratio of about 2, exhibit good resolution and film physical properties, and exhibit sufficient properties as photosensitive materials. It could be confirmed. From this feature, it can be said that when the resin composition of the present invention is used as a resist composition for semiconductors, fine patterns can be formed with high sensitivity, and abnormalities such as cracks and voids are less likely to occur.

Claims (6)

(A) a primary alcoholic alcohol 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 repeating unit represented by the following formula (1-3) and a repeating unit represented by the following formula (1-4), containing a phenolic hydroxy group, and having a weight average molecular weight of 2,000 or less ,
A photosensitive polyimide resin composition comprising (C) a photoacid generator and (D) a cross-linking agent, wherein the content of component (B) is 1 to 10 parts by mass per 100 parts by mass of 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 each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. R ⁷ and R ⁸ are each independently a single bond or a 2 is a valent hydrocarbon group, R ⁹ and R ¹⁰ are each independently a trivalent organic group, m is an integer of 0 to 120, and the dashed line is a bond.)
X ² is a tetravalent group selected from groups represented by the following formulae.

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

(wherein A ¹ to A ³ are each independently a 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 each independently a hydroxy group or an alcoholic hydroxy group-containing group, but at least one is a primary alcoholic hydroxy group-containing group, R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 10, b and c are , each independently 0 or 1. d to g are each independently 0, 1 or 2. The dashed line is a bond.)
p is a positive integer and q is a positive integer. ]

[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 formula (4) and the group represented by formula (5). r and s are each independently 0 or a positive integer.

(wherein B ¹ to B ³ are each independently a 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 each independently an alkyl group having 1 to 4 carbon atoms, a' is 0 is an integer of ~ 10. b' and c' are each independently 0 or 1. d' to g' are each independently 0, 1 or 2. A broken line is a bond .)

(Wherein, R ³¹ to R ³⁴ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. n is an integer of 1 to 80. The dashed line indicates a bond.)] 2. The photosensitive polyimide resin composition according to claim 1 , further comprising (E) a solvent. 3. The photosensitive polyimide resin composition according to claim 1, wherein (C) the photoacid generator is imido-yl-sulfonates, iminosulfonates or oximesulfonates. 4. The photosensitive polyimide resin composition according to any one of claims 1 to 3 , further comprising a basic compound. Coating the photosensitive polyimide resin composition according to any one of claims 1 to 4 on a substrate, comprising the steps of forming a resist layer, exposing the resist layer, and developing a pattern. Forming method. 6. A method for manufacturing a semiconductor device having a patterned polyimide resin film, comprising the pattern forming method according to claim 5 .