JP2009086147A - Positive-type photosensitive polyimide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive-type photosensitive polyimide composition which enables processing of a fine pattern, can form a coating film having excellent heat resistance and a linear expansion coefficient proximal to that of a substrate, and does not need imidization at a high temperature. <P>SOLUTION: The positive-type photosensitive polyimide resin composition comprises: a polyimide resin that has a specific skeleton and is soluble in an organic solvent; and a compound (b) that can generate an acid by being irradiated with an active ray. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a positive photosensitive polyimide resin composition used as an electrical and electronic insulating material in the manufacture of semiconductor devices and the like.

Conventionally, polyimide resins having excellent heat resistance, electrical properties, mechanical properties, and the like have been used for surface protection films, interlayer insulating films, and buffer coats of semiconductor elements. However, in recent years, as semiconductor elements have been highly integrated and increased in size, there has been a demand for thinner and smaller sealing resin packages, and LOC (lead-on-chip) and surface mounting methods such as solder reflow have been adopted. Therefore, a polyimide resin excellent in mechanical properties, heat resistance and the like has been required more than ever.
Furthermore, in recent years, circuit boards and semiconductor mounting parts used in electronic devices have been rapidly miniaturized in order to achieve both weight reduction and high integration / density. In this trend, the difference in coefficient of linear expansion between substrates and component materials, which has not been emphasized so far, is beginning to have a significant impact on product quality and reliability. There is a strong demand for polyimide films with excellent dimensional stability that solve this problem.

On the other hand, photosensitive polyimide having a photosensitive property imparted to the polyimide resin itself has been used. However, when this is used, the pattern production process can be simplified, and complicated manufacturing processes can be shortened. In the negative type, a method in which a methacryloyl group is introduced into a polyimide precursor (amic acid) via an ester bond, an ionic bond or an amide bond, an IPN type, or the like (for example, see Patent Documents 1 to 5), soluble having a photopolymerized olefin Polyimide (see, for example, Patent Document 6), self-sensitized polyimide using a hydrogen abstraction reaction having an benzophenol skeleton and an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (for example, Patent Document 7, 8), soluble polyimide having a furan structure utilizing a photo-oxidation-induced polymerization reaction (for example, see Patent Document 9).
The positive heat-resistant resin composition in which the exposed portion is dissolved by development includes those obtained by adding naphthoquinone diazide to polyamic acid (for example, see Patent Document 10), and those obtained by adding naphthoquinone diazide to a polyamic acid having a hydroxyl group. (See, for example, Patent Document 11), a polyimide precursor having an acid / base decomposable group added with a photoacid generator (PAG) / photobase generator (PBG) (see, for example, Patent Documents 12 and 13), What introduced O-nitrobenzyl group into the polyimide precursor (for example, refer patent document 14).
In the case of using a polyimide precursor, any of the above methods needs to carry out imide ring closure by heat treatment after photoprocessing, and at that time, the film shrinks due to volume shrinkage due to dehydration accompanying imide ring closure and volatilization of the crosslinking group component. Thickness loss and reduced dimensional stability are unavoidable drawbacks. Furthermore, the heat treatment process at a high temperature may cause deterioration of other electronic components or organic materials. Although the thing which sensitized the organic solvent soluble polyimide itself which does not require the cyclization process itself is proposed (for example, refer patent documents 15-18 regarding positive type), these are photosensitive characteristics, heat resistance, mechanical characteristics, and There is a drawback inferior to any of the dimensional stability.
Therefore, in reality, none of them is yet sufficient for practical use.
Japanese Patent Laid-Open No. 54-145794 JP-A-55-030207 JP-A-61-118424 Japanese Patent Laid-Open No. 57-168942 Japanese Patent Laid-Open No. 03-170547 JP 59-108031 A Japanese Patent Application Laid-Open No. 61-145794 JP 2003-076017 A JP 2000-338668 A JP 52-013315 A Japanese Patent Laid-Open No. 04-204945 Japanese Patent Laid-Open No. 04-120171 Japanese Patent Laid-Open No. 10-186664 Japanese Patent Laid-Open No. 60-037550 JP 63-013032 A Japanese Patent Laid-Open No. 04-046345 JP 2000-199957 A JP 2001-249454 A

The present invention is associated with the reduction of problems involving the prior art such as lowering of adhesion to the substrate and warping of the substrate due to the large thermal expansion coefficient of the conventional positive photosensitive resin, and accompanying heating in imidization. It is intended to solve the problems that have a great influence on products such as semiconductor devices during the formation of surface protection film and interlayer insulation film due to high temperature and water generated from imidization reaction, and has a small thermal expansion coefficient, For this reason, lowering of adhesion to the substrate and warping of the substrate are alleviated, and the semiconductor device is formed during the formation of the surface protective film or interlayer insulating film by the high temperature accompanying heating in imidization and water generated from the imidization reaction The purpose of the present invention is to provide a positive photosensitive polyimide composition capable of providing a heat-resistant resin film that has a great influence on products such as the above and does not deteriorate electrical characteristics and resolution. It is.
Moreover, this invention provides the manufacturing method of the pattern from which the pattern of the favorable shape which is excellent in heat resistance, a mechanical characteristic, and thermal dimensional stability is obtained by use of the said composition. In addition, the present invention provides a highly reliable electronic component by having a pattern having a good shape and characteristics.

As a result of continuing intensive studies in view of such circumstances, the present inventors have reached the next invention. That is, the present invention has the following configuration.
The positive photosensitive polyimide composition of the present invention comprises an organic solvent-soluble polyimide (a) having a specific bulky skeleton in the main chain and a benzazole skeleton, particularly preferably a benzoxazole skeleton, and an acid upon irradiation with actinic rays. And the above-mentioned object is achieved thereby, and the present invention has the following constitution.
1. (A) At least one selected from the following general formulas (Chemical Formula 1) and (Chemical Formula 2) (wherein R ¹ is any ^one of phenyl, 3-biphenyl, 4-biphenyl, 1-naphthyl, and 2-naphthyl) Az represents a divalent aromatic organic group.) It contains an organic solvent-soluble polyimide resin containing a repeating unit, and (b) a compound that generates an acid upon irradiation with actinic rays. Positive photosensitive polyimide resin composition.

２．前記式（化１）または（化２）のＡｚがベンズアゾール構造を有する２価の有機基である請求項１記載のポジ型感光性ポリイミド樹脂組成物。
３．前記式（化１）または（化２）のＡｚがベンズオキサゾール構造を有する２価の有機基である請求項１〜２いずれかに記載のポジ型感光性ポリイミド樹脂組成物。
４．前記式（化１）または（化２）のＡｚが下記の一般式（化３）〜（化１６）のいずれかの１種以上のＡｚである請求項１〜３いずれかに記載のポジ型感光性ポリイミド樹脂組成物。

2. 2. The positive photosensitive polyimide resin composition according to claim 1, wherein Az in the formula (Chemical Formula 1) or (Chemical Formula 2) is a divalent organic group having a benzazole structure.
3. The positive photosensitive polyimide resin composition according to claim 1, wherein Az in the formula (Chemical Formula 1) or (Chemical Formula 2) is a divalent organic group having a benzoxazole structure.
4). The positive type according to any one of claims 1 to 3, wherein Az in the formula (Chemical Formula 1) or (Chemical Formula 2) is one or more Az in any one of the following general formulas (Chemical Formula 3) to (Chemical Formula 16). Photosensitive polyimide resin composition.

５．活性光線照射により酸を発生する化合物がエステル化したキノンジアジド化合物である請求項１〜４いずれかに記載のポジ型感光性樹脂組成物。

5). The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the compound that generates an acid upon irradiation with actinic rays is an esterified quinonediazide compound.

  The polyimide from the positive photosensitive polyimide resin composition of the present invention has a small coefficient of thermal expansion, and a resin film such as an insulating film can be formed on a substrate having a low coefficient of thermal expansion such as a silicon wafer only by coating and drying. , Without imidization, the difference in thermal expansion coefficient is small, the adhesion with the substrate is good, the warp etc. can be reduced, and developability, photosensitivity, etc. can be maintained well. As a result, a good pattern is obtained, which is extremely effective as an electrical and electronic insulating material in the manufacture of semiconductor devices and the like.

  Hereinafter, embodiments of the present invention will be described.

The polyimide in the present invention is soluble in an organic solvent (solvent), and if it is insoluble in an organic solvent, it is necessary to form a polyimide layer through a dehydration ring-closing reaction using a polyimide precursor. Since a high temperature process is required, the semiconductor device may be thermally deteriorated. Here, organic solvent soluble means that at least 1% by mass of polyimide is dissolved (at 30 ° C.) in at least one organic solvent selected from the following organic solvents.
Examples of these organic solvents include those having a boiling point of 350 ° C. or less, preferred examples include those having a boiling point of 300 ° C. or less, and more preferred examples include those having a boiling point of 250 ° C. or less. Specific examples include phenol solvents such as p-chlorophenol and m-cresol, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, and the like.
In the present invention, the polyimide resin is at least the general formula (Chemical Formula 1) or (Chemical Formula 2) (wherein R ¹ is any ^one of phenyl, 3-biphenyl, 4-biphenyl, 1-naphthyl, and 2-naphthyl). And Az represents a divalent organic group having a benzazole structure.

  The Az component in the polyimide resin structure represented by the above formula (Chemical Formula 1) or (Chemical Formula 2) is not particularly limited as long as it is a divalent organic group having a benzazole structure. In order to further reduce the rate, a divalent organic group having a benzoxazole structure is preferable. Further, in order to further improve the heat resistance or to further reduce the linear expansion coefficient, A structure represented by 3) to (Chemical Formula 16) is more preferable, and a structure represented by (Chemical Formula 3) or (Chemical Formula 4) is particularly preferable.

The polyimide in the present invention refers to aromatic tetracarboxylic acid anhydrides (referring to acids, acid anhydrides, polyimide-binding derivatives, etc.) and aromatic diamines (referring to diamines, polyimide-binding derivatives, etc.). It is preferable to obtain a reaction from
As the aromatic tetracarboxylic acid anhydrides, aromatic tetracarboxylic acid anhydrides represented by the following formula (Chemical Formula 17) or (Chemical Formula 18) are preferably used. It is preferably at least mol%, more preferably at least 85 mol%. Without being limited to these chemical formulas 3 and 4, aromatic tetracarboxylic acids other than (Chemical formula 3) or (Chemical formula 4) can be used at less than 30 mol%, preferably less than 15 mol%. Examples of aromatic tetracarboxylic acids other than (Chemical Formula 17) or (Chemical Formula 18) include pyromellitic anhydride, biphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, and benzophenone-3. , 4,3 ′, 4′-tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenylsulfone-3,4,3 ′, 4′-tetracarboxylic dianhydride, 4,4 ′-(2, 2-hexafluoroisopropylidene) diphthalic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutanetetracarboxylic Acid dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3 5, 6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- ( 1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1 -Ethylcyclohexane-1- (1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3 -Dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride, bicyclo [2 2.1] Heptane-2,3,5,6-tetracarbo Acid dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2, 3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid Dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6 -Tetracarboxylic acid dianhydride and the like can be mentioned, but in order to maintain a low linear expansion coefficient, it is preferable to use pyromellitic anhydride or biphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride . These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

（式中、Ｒ^１はフェニル、３−ビフェニル、４−ビフェニル、１−ナフチル、２−ナフチルのいずれかの基を示す。）

(In the formula, R ¹ represents any group of phenyl, 3-biphenyl, 4-biphenyl, 1-naphthyl, and 2-naphthyl.)

（式中、Ｒ^１はフェニル、３−ビフェニル、４−ビフェニル、１−ナフチル、２−ナフチルのいずれかの基を示す。）

(In the formula, R ¹ represents any group of phenyl, 3-biphenyl, 4-biphenyl, 1-naphthyl, and 2-naphthyl.)

As the aromatic diamine, it is preferable to use an aromatic diamine having a benzazole structure. Examples of aromatic diamines having a benzazole structure include, for example, the following formulas (Chemical Formula 19) to (Chemical Formula 26) (wherein X is an oxygen atom, sulfur atom or NR ⁷ (wherein R ⁷ is a hydrogen atom or phenyl). R ² , R ⁵ , and R ⁶ each independently represent an aromatic ring group or a heterocyclic group composed of a single ring or a plurality of rings, and R ³ and R ⁴ each represent Independently, it represents an aromatic ring group, a heterocyclic group or an aliphatic ring group composed of a single ring or a plurality of rings.) And a diamine having a structure represented by: Among these, it is preferable to use aromatic diamines having a benzoxazole structure, and it is particularly preferable to use diamines having a skeleton structure represented by the above (Chemical Formula 3) to (Chemical Formula 16). The amount of aromatic diamines having a benzazole structure and / or aromatic diamines having a benzoxazole structure in the total diamine is preferably 70 mol% or more, and more preferably 85 mol% or more.

  Examples of diamines having no benzazole structure include 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, and bis [4- (3-aminophenoxy). ) Phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) ) Phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3 '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether 3,3′-diaminodiphenylsulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-diaminodiphenylsulfone, 3,4 ′ -Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane.

    3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1, 2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] Propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-amino) Phenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane Emissions, 2,2-bis [4- (4-Aminofenoshi) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane.

  2- [4- (4-Aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3- Methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4 -Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,4 -Bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) bif Nyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4 -Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [(3- Aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [ -(3-aminophenoxy) phenyl] propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Fluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl ] Ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) ) Benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4 ′ Bis [4- (4-amino-.alpha., alpha-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone.

1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluorophenoxy) -α , Α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6) -Cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-diphenoxybenzophenone, 3, , 4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone 3,4′-diamino-5′-phenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 4,4′-diamino-5,5′-dibiphenoxybenzophenone, 3,4 ′ -Diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone 3,4′-diamino-5′-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybe Zoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-) Phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino) -5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzo Part or all of the hydrogen atoms on the aromatic ring in the nitrile and the aromatic diamine are halogen atoms, alkyl groups having 1 to 3 carbon atoms, or alkoxyl , A cyano group, an alkyl group or an alkoxyl group, or a part or all of hydrogen atoms substituted with a halogen atom, a C 1-3 halogenated alkyl group or an aromatic diamine substituted with an alkoxyl group. In order to maintain a low linear expansion coefficient, p-phenylenediamine is preferably used. These diamines may be used alone or in combination of two or more.
When these are used in combination with aromatic diamines having a benzazole structure and / or aromatic diamines having a benzoxazole structure, the total diamine is preferably less than 30 mol%, more preferably less than 15 mol%.

The monomer mixing ratio (molar ratio) in synthesizing the polyimide resin of the present invention is a notation method of tetracarboxylic acid (acid anhydride) / diamine, and preferably 0.800 to 1.200 / 1.200 to 0.00. 800, more preferably 0.900 to 1.100 / 1.100 to 0.900, and still more preferably 0.950 to 1.150 / 1.150 to 0.950.
Moreover, terminal blockers, such as a dicarboxylic acid anhydride, a tricarboxylic acid anhydride, and an aniline derivative, can be used for the molecular terminal blockage of the present invention. Preferred for use in the present invention are phthalic anhydride, maleic anhydride, and ethynylaniline, and the use of maleic anhydride is more preferred. The usage-amount of terminal blocker is 0.001-1.0 molar ratio per mol of monomer components.

  The organic solvent used when synthesizing the polyimide resin of the present invention is not particularly limited as long as it dissolves both the raw material monomer and the polyamic acid which is an intermediate product, and the polyimide resin which is a product. o-cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl Examples thereof include sulfoxide, γ-butyrolactone, sulfolane, halogenated phenols, and the like. These solvents can be used alone or in combination. The amount of the polar organic solvent used may be an amount sufficient to dissolve the charged monomer, and is usually 1 to 50% by mass, preferably 5 to 30% by mass.

The polymerization reaction is continued for 10 minutes to 30 hours in a temperature range of 0 to 80 ° C. while stirring and / or mixing in an organic solvent, and further in a temperature range of 100 to 300 ° C. for 10 minutes to 30 hours. Although the process proceeds continuously, the polymerization reaction may be divided or the temperature may be increased or decreased as necessary. In this case, the order of addition of both reactants is not particularly limited, but it is preferable to add aromatic tetracarboxylic anhydrides to the solution of aromatic diamines.
In the present invention, a ring-closing catalyst may be used. Specific examples of the ring-closing catalyst used in the present invention include aromatic carboxylic acids such as benzoic acid, o-benzoic acid, m-benzoic acid, and p-benzoic acid, aliphatic tertiary amines such as trimethylamine and triethylamine, Examples include heterocyclic tertiary amines such as isoquinoline, pyridine, and betapicoline. At least one amine selected from heterocyclic tertiary amines is preferably used. The content of the ring-closing catalyst is preferably in a range in which the content (mol) of the ring-closing catalyst (mol) / the content (mol) of the precursor polyamic acid is 0.01 to 10.00.

In the present invention, a dehydrating agent may be used. Examples thereof include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. It is not limited. The content of the dehydrating agent is preferably in a range where the content of dehydrating agent (mole) / polyamic acid content (mole) is 0.01 to 10.00.
In the present invention, a co-solvent may be used to azeotrope water. For example, toluene, xylene and the like can be mentioned, but not limited to these as long as water can be efficiently azeotroped.

In the present invention, an additive may be added for the purpose of improving the performance of the polyimide resin. These additives vary depending on the purpose and are not particularly limited.
Further, the addition method and the addition time are not particularly limited. Examples of the additive include known organic and inorganic fillers such as metal oxides such as silicon oxide, titanium oxide, and aluminum oxide, and phosphates such as calcium phosphate, calcium hydrogen phosphate, and calcium pyrophosphate.

  In the present invention, the polyimide resin obtained by the reaction may be reprecipitated from the reaction solution using an appropriate poor solvent. Examples of the poor solvent include acetone, methanol, ethanol, water, and the like. However, the poor solvent is not particularly limited as long as it can be efficiently re-precipitated. Moreover, although it does not specifically limit about the solvent which removes the residual reaction solvent after reprecipitation, It is preferable to use the solvent used at the time of reprecipitation.

  In the present invention, the reaction solution may be used as it is as a polyimide resin solution, or the polyimide resin reprecipitated from the reaction solution by the above method may be dissolved again in a solvent to obtain a polyimide resin solution. In the latter case, the polyimide resin is not particularly limited as long as it efficiently dissolves the polyimide resin. For example, o-cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, N- Examples thereof include organic solvents such as acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, sulfolane, and halogenated phenols.

In the present invention, the means for mixing the polyimide resin and the organic solvent is not particularly limited. For example, a normal stirring blade, a method of mixing and stirring using a stirring blade for high viscosity, a multi-screw extruder, or a static Examples of the method include mixing and stirring using a method using a mixer or the like, and further using a method using a mixing and dispersing machine for high viscosity such as a roll mill.
As a composition of the polyimide resin in the polyimide resin solution obtained by this invention, Preferably it contains 1-50 mass%, More preferably, containing 5-30 mass% is mentioned. in this case. The viscosity is preferably 0.1 to 2000 Pa · S, preferably 1 to 1000 Pa · S, as measured with a Brookfield viscometer, because stable liquid feeding is possible.

The compound (b) used in the present invention, which generates an acid by light, is a photosensitizer and has a function of generating an acid and increasing the solubility of the light irradiated part in the developer. . Examples of the type include O-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like. Although there is no particular limitation, O-quinonediazide compounds are preferred because of their high sensitivity.
In addition, the amount of component (b) added is preferably 1 to 50 parts by weight with respect to 100 parts by weight of component (a) from the viewpoints of sensitivity and tolerance of development time.
The positive photosensitive polyimide resin composition of the present invention may further contain other additives, for example, additives such as a crosslinking agent, a plasticizer, a surfactant, a sensitizer, and an adhesion promoter.

The pattern forming method using the positive photosensitive polyimide resin composition of the present invention is performed by using the positive photosensitive polyimide resin composition of the present invention to form a polyimide film made of polyimide of the composition by photolithography. To form. In the pattern forming method of the present invention, first, a film using the positive photosensitive polyimide resin composition of the present invention is formed on the surface of a support substrate or the like.
In the pattern forming method using the positive photosensitive polyimide resin composition of the present invention, the surface of the support substrate is treated with an adhesion aid in advance in order to improve the adhesion between the polyimide coating and the support substrate. May be. The film made of polyimide is formed, for example, by forming a film of a positive photosensitive polyimide resin composition (hereinafter referred to as varnish) and then drying it. The thickness of the polyimide coating of the present invention is not particularly limited, but is suitable for forming a coating of about 2 μm to 50 μm, and further suitable for application to a thickness of 3 μm or more, particularly 25 μm.

Formation of a polyimide film using a positive photosensitive polyimide resin composition can be performed by spin coating using a spinner, immersion, spray printing, screen printing, etc., depending on the viscosity of the positive photosensitive polyimide resin composition. It is performed by means appropriately selected from the means. In addition, the film thickness of a film can be adjusted with coating conditions, solid content concentration of this composition, etc. Alternatively, the above-described coating film may be formed by peeling a coating film previously formed on the support substrate from the support and attaching a polyimide sheet to the surface of the support substrate.
Next, the formed film is irradiated with light (actinic rays such as ultraviolet rays) through a photomask having a predetermined pattern, and then the exposed portion is dissolved and removed with an organic solvent or a basic aqueous solution to obtain a desired relief. Get a pattern. At this time, the remaining film ratio after development is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. As the sensitivity is preferably 600 mJ / cm ² or less, more preferably 500 mJ / cm ² or less, it is a deliberately preferably 450 mJ / cm ² or less. Here, the sensitivity is the minimum exposure amount necessary to obtain a pattern with a high resolution of 10 μm or less.

Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. , Xylene, tetrahydrofuran, dioxane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, hexyl acetate, methyl cellosolve, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol mono-acetate n-butyl ether, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, sulfur Orchids, cyclohexanol, cyclohexanone, cyclohexane oxime, cyclohexane, 1,4-cyclohexane dimethanol, cyclohexyl acetate, cyclopentanol, cyclopentanone, cyclopentanone oxime, cyclopentane, and the like. You may use these individually or in combination of 2 or more types.
The basic aqueous solution is usually a solution in which a basic compound is dissolved in water. The concentration of the basic compound is preferably 0.1 to 50% by weight, more preferably 0.1 to 30% by weight from the viewpoint of influence on the support substrate and the like. In order to improve the solubility of polyimide, water-soluble organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like are further added. You may contain.

Examples of the basic compound include alkali metal, alkaline earth metal or ammonium ion hydroxides or carbonates, amine compounds, and the like.
When a conventional polyimide precursor is used, a stable high heat resistant polyimide pattern can be obtained by heating this pattern. At this time, the heating temperature is 300 to 500 ° C. If the heating temperature is less than 300 ° C., the mechanical properties and thermal properties of the polyimide film tend to deteriorate. Although there is a tendency to be inferior in properties and thermal properties, in the present invention, this high-temperature heating is not required and drying at a temperature of about 200 ° C. or removal of low-boiling substances is performed, resulting in heat resistance and low linear expansion. A polyimide coating such as a polyimide pattern of coefficients can be formed.
Thus, the positive photosensitive polyimide resin composition of the present invention can be used for a surface protective film for electronic parts such as a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like. Since the surface protective film (buffer coat film) using the positive photosensitive polyimide resin composition of the present invention has excellent adhesiveness and a low linear expansion coefficient, there is no warping of the base material or peeling from the base material. The semiconductor element using the interlayer insulating film and the surface protective film obtained from the positive photosensitive polyimide resin composition of the present invention is extremely excellent in reliability. The specific linear expansion coefficient (average linear expansion coefficient in the temperature range of 50 to 200 ° C.) of the film for obtaining such a highly reliable semiconductor element is preferably 0 to 40 ppm / ° C., and more Preferably it is 0.1-30 ppm / degrees C.
The positive photosensitive polyimide resin composition of the present invention is used not only as an interlayer insulating layer and a surface protective film layer but also as a material for a cover coat layer, a core, a color, an underfill, etc. because of its excellent characteristics. It ’s good.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In addition, each characteristic in an Example was measured with the following method except the above-mentioned method.
1. Linear thermal expansion coefficient (CTE) of polyimide
The polyimide to be measured is broken and peeled off, the stretch rate is measured under the following conditions, and the stretch rate / temperature at intervals of 50 ° C. to 65 ° C., 65 ° C. to 80 ° C. and 15 ° C. is measured, This measurement was performed up to 200 ° C., and the average value of all measured values was calculated as CTE.
Device name: TMA4000S manufactured by MAC Science
Sample length; 20mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rise end temperature; 250 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon

2. Calculation of remaining film ratio The film thickness after pre-baking treatment and the film thickness after development were measured, and the remaining film ratio was calculated by the following calculation method.
Residual film ratio (%) = {(film thickness after development) / (film thickness after pre-baking treatment)} × 100

3. Evaluation of Sensitivity The minimum exposure amount required to clearly form a pattern with a resolution of 10 μm was defined as sensitivity. Whether or not a pattern with a resolution of 10 μm was clearly formed was determined by observing a relief pattern after exposure and development with a microscope. The exposure amount was measured using an ultraviolet illuminance meter / light quantity system (UV-M03: manufactured by Oak Co., Ltd.).

4). Appearance Evaluation of Film The appearance after development and after heat treatment was observed visually and with a microscope. With respect to the appearance evaluation after development, it was evaluated as “good” if there was no undeveloped undeveloped residue and the pattern edge was smooth. Further, regarding the appearance evaluation after the heat treatment, it was evaluated as “good” if there was no film cracking, swelling, voids, peeling, wafer cracking or warping.

(Synthesis Example 1) The inside of a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, and then 10.00 g of 5-amino-2- (p-aminophenyl) benzoxazole and 2,2′-diphenoxy Charged 20.37 g of -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 0.50 g of isoquinoline. Subsequently, 270 g of m-cresol was added and completely dissolved, and then stirred at a reaction temperature of 25 ° C. for 20 hours to obtain a pale yellow polyamic acid solution. Thereafter, a Dean Turk trap was installed in the apparatus, and the mixture was stirred at a temperature of 200 ° C. for 6 hours under a N ₂ stream. After air cooling, reprecipitation was first performed with 2000 ml of acetone. The obtained solid was pulverized with a mixer, washed twice with stirring at 25 ° C. in 500 ml of acetone, and stirred and washed under reflux in 500 ml of acetone for 6 hours. Drying was performed under reduced pressure at 70 ° C. for 12 hours to obtain a pale yellow polyimide resin in a yield of 28.8 g. Next, 10 g of the obtained polyimide resin and 80 g of N-methyl-2-pyrrolidone were mixed and stirred at a temperature of 80 ° C. for 1 hour to obtain a polyimide resin solution. This polyimide resin solution is named Varnish-1.

Synthesis Example 2 Synthesis Example except that 27.10 g of 2,2′-bis (3-phenylphenoxy) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was used as the acid anhydride. 1 was used to obtain a corresponding polyimide resin solution. This polyimide resin solution is named Varnish-2.

Synthesis Example 3 Synthesis Example except that 27.10 g of 2,2′-bis (4-phenylphenoxy) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was used as the acid anhydride. 1 was used to obtain a corresponding polyimide resin solution. This polyimide resin solution is named Varnish-3.

Synthesis Example 4 Synthesis Example 1 except that 24.78 g of 2,2′-bis (1-naphthoxy) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was used as the acid anhydride. The corresponding polyimide resin solution was obtained by the same operation as. This polyimide resin solution is named Varnish-4.

Synthesis Example 5 Synthesis Example 1 except that 24.78 g of 2,2′-bis (2-naphthoxy) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was used as the acid anhydride. The corresponding polyimide resin solution was obtained by the same operation as. This polyimide resin solution is named Varnish-5.

(Synthesis Example 6) A corresponding polyimide resin solution was obtained in the same manner as in Synthesis Example 1 except that 10.00 g of 6-amino-2- (p-aminophenyl) benzoxazole was used as the diamine. This polyimide resin solution is named Varnish-6.

(Synthesis Example 7) A corresponding polyimide resin solution was obtained in the same manner as in Synthesis Example 1 except that 10.00 g of 5-amino-2- (p-aminophenyl) benzimidazole was used as the diamine. This polyimide resin solution is designated as varnish-7.

(Synthesis Example 8) A corresponding polyimide resin solution was obtained in the same manner as in Synthesis Example 1, except that 10.00 g of 5-amino-2- (p-aminophenyl) benzthiazole was used as the diamine. This polyimide resin solution is named Varnish-8.

(Synthesis Example 9) The same operation as in Synthesis Example 1 except that 18.92 g of 2,2′-diphenyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was used as the acid anhydride. A corresponding polyimide resin solution was obtained. This polyimide resin solution is named Varnish-9.

Synthesis Example 10 Synthesis Example 1 except that 25.68 g of 2,2′-bis (4-biphenyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was used as the acid anhydride. The corresponding polyimide resin solution was obtained by the same operation as. This polyimide resin solution is named Varnish-10.

(Synthesis Example 11) Synthesis Example 1 except that 23.36 g of 2,2'-bis (1-naphthyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was used as the acid anhydride. The corresponding polyimide resin solution was obtained by the same operation as. This polyimide resin solution is named Varnish-11.

(Synthesis Example 12) A corresponding polyimide resin solution was obtained in the same manner as in Synthesis Example 9 except that 10.00 g of 5-amino-2- (p-aminophenyl) benzimidazole was used as the diamine. This polyimide resin solution is designated as varnish-12.

Synthesis Example 13 For 15.07 g of 4,4′-di (m-aminophenoxy) diphenyl ether as diamine and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as acid anhydride A corresponding polyimide resin solution was obtained in the same manner as in Synthesis Example 1 except that This polyimide resin solution is named Varnish-13.

(Synthesis Example 14) Synthesis Example except that 5.00 g of p-phenylenediamine was used as the diamine and 19.67 g of 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride was used as the acid anhydride. 1 was used to obtain a corresponding polyimide resin solution. This polyimide resin solution is named Varnish-14.

Example 1
2.00 g of photosensitizer NT-200 (Toyo Gosei Co., Ltd.) was added to 90 g of varnish-1 to prepare a positive photosensitive polyimide resin composition. This positive photosensitive polyimide resin composition was spin-coated on a silicon wafer with a spin coater and dried at 100 ° C. for 10 minutes using a hot plate to obtain a 10 μm coating film. This coating film was irradiated with ultraviolet rays through a pattern mask using an ultra-high pressure mercury lamp through a mask (1-50 μm left pattern and blank pattern). Thereafter, development was performed. Development was performed using N-methyl-2-pyrrolidone. Next, it was rinsed with isopropanol and dried. As a result, a good pattern was formed by irradiation with an exposure amount of 300 mJ / cm ² , and the residual film ratio was 90%. The appearance after exposure was also good. Furthermore, heat treatment was performed at 120 ° C./15 minutes and 250 ° C./60 minutes in a nitrogen atmosphere to obtain a silicon wafer with a polyimide coating without warping, cracking or peeling. Moreover, it was 20 ppm / degrees C when the linear expansion coefficient of the polyimide membrane | film | coat was measured by the above-mentioned method.

(Examples 2 to 12)
A positive photosensitive polyimide resin composition was prepared in the same manner as in Example 1 except that varnishes 2 to 12 were used instead of varnish-1 used in Example 1, and the same as in Example 1. evaluated. The results are shown in Table 1.

(Comparative Examples 1-2)
A positive photosensitive polyimide resin composition was prepared in the same manner as in Example 1 except that varnish-13 to 14 was used instead of varnish-1 used in Example 1, and the same as in Example 1. evaluated. The results are shown in Table 1.

  The positive photosensitive polyimide composition of the present invention is used as an electrical and electronic insulating material in the manufacture of semiconductor devices and the like, and more specifically, used as a surface protective film and interlayer insulating film of semiconductor elements such as IC and LSI. It can be used for things that require pattern processing, does not generate water due to imidization, is not exposed to high temperatures, and has a low coefficient of linear expansion and linear expansion with a semiconductor wafer as a substrate. The coefficients are close to each other, and there is no warpage of the base material due to the difference or peeling of the coating film from the base material, which is extremely significant for these applications.

Claims (5)

(A) At least one selected from the following general formulas (Chemical Formula 1) and (Chemical Formula 2) (wherein R ¹ is any ^one of phenyl, 3-biphenyl, 4-biphenyl, 1-naphthyl, and 2-naphthyl) Az represents a divalent aromatic organic group.) It contains an organic solvent-soluble polyimide resin containing a repeating unit, and (b) a compound that generates an acid upon irradiation with actinic rays. Positive photosensitive polyimide resin composition.

  2. The positive photosensitive polyimide resin composition according to claim 1, wherein Az in the formula (Chemical Formula 1) or (Chemical Formula 2) is a divalent organic group having a benzazole structure.   The positive photosensitive polyimide resin composition according to claim 1, wherein Az in the formula (Chemical Formula 1) or (Chemical Formula 2) is a divalent organic group having a benzoxazole structure. 4. The positive electrode according to claim 1, wherein Az in the formula (Chemical Formula 1) or (Chemical Formula 2) is one or more types of Az in the following general formulas (Chemical Formula 3) to (Chemical Formula 16). Type photosensitive polyimide resin composition.

  The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the compound that generates an acid upon irradiation with actinic rays is an esterified quinonediazide compound.