KR19990062029A - Siloxane polyimide precursor composition and preparation method thereof - Google Patents

Abstract

The present invention produces a polyamic acid by reacting an organic solvent with an aliphatic siloxane diamine of the following structural formula (I), an aromatic tetracarboxylic dianhydride of the following structural formula (II), and an aromatic diamine of the following structural formula (III), wherein the polya A siloxane polyimide precursor composition produced by adding a photosensitizer and a crosslinking aid to a mixed acid and a method of preparing the same:

[Formula I]

[Structure Formula II]

[Structure Formula III]

R ₁ in the formula (III) is two aliphatic substituents.

A photoinitiator, a sensitizer, a polymerization inhibitor, and / or a colloidal inorganic additive may be further added to the polyimide precursor composition to improve light sensitivity, thermal stability, and hardness of the film.

Description

[Name of invention]

Siloxane polyimide precursor composition and preparation method thereof

Detailed description of the invention

[Field of Invention]

The present invention relates to siloxane polyimide precursor compositions and methods for their preparation. More specifically, the present invention relates to a siloxane polyimide precursor composition having improved heat resistance, mechanical properties, and adhesion, comprising a siloxane diamine monomer, a tetracarboxylic dianhydride, an aromatic diamine, a photosensitizer, and a crosslinking aid, and a method for producing the same.

[Summary of invention]

Recently, in the semiconductor device field mainly on semiconductors and liquid crystal display devices, as the movement of high integration, high density, high reliability, and high speed of electronic devices are rapidly spreading, there is an attempt to take advantage of the advantages of organic materials that are easy to process and high purity. Research is actively underway. However, in order for organic polymers to be used in these fields, there must be thermal stability in a process requiring 200 ° C. or more during device manufacturing.

In addition to excellent electrical properties such as high heat resistance, excellent mechanical strength, low dielectric constant, and high insulation, polyimide resins have good planarization characteristics of the coating surface, very low content of impurities which degrade the reliability of the device, and can easily form fine shapes. There is a resin most suitable for the above purpose. The general method for synthesizing polyimide is a two-stage condensation polymerization, in which a diamine component and an acid dianhydride are polymerized in a polar organic solvent such as NMP (N-methyl-2-pyrrolidone), DMAc (demethylacetamide) or DMF (dimethyl-formamide). The mid precursor solution is obtained, coated on a silicon wafer or glass, and then cured by heat treatment to obtain a polyimide film.

Commercially available polyimide products for electronic materials are supplied in the form of polyimide precursor solutions or polyimide films, mainly in the form of polyimide precursor solutions or polyimide films in the field of semiconductor devices, and mainly in the state of polyimide precursor solutions in the field of semiconductor devices. Is supplied. In resin-encapsulated LSIs, cracks or damage to metal wiring may occur due to the thermal shrinkage of the resin after encapsulation and thermal stress caused by the difference in the coefficient of thermal expansion between the chip and the resin. .

This problem is solved by using a polyimide between the chip and the encapsulant as a buffer layer, and a polyimide film thickness of 10 μm or more plays a buffer role. The thicker the coating film is, the better the buffering effect is, which improves the yield of semiconductor products. You can. Polyimides require the formation of via holes, such as inter-electrode connections and wire-vonding pads. In order to form a fine pattern of polyimide, a method of coating a photoresist on an existing polyimide and etching is widely used, but recently, application of a photosensitive polyimide having a photosensitive function to the polyimide has been attempted.

Conventional non-photosensitive polyimide requires an etching process to process holes using a separate photoresist for wire-bonding and metal wire connection. If it is possible to omit some of the processes can greatly increase the productivity.

Practical photosensitive polyimide was developed by Rubner et al. Of Siemen (US-A-3957512). This is a form in which the photosensitive group is bonded to the polyamic acid as a polyimide precursor through an ester bond. When the photosensitive polyimide precursor solution is coated on a substrate to form a film and exposed to ultraviolet light, overpolymerization occurs in the exposed portion to form a crosslinked structure. In this state, the unexposed portion is removed during development with the organic solvent, and the final heat treatment causes the ester-bonded photosensitive component to be decomposed and removed at the same time as the imidization reaction to obtain a desired pattern of polyimide. However, the patterning of the thick polyimide precursor film has a disadvantage of poor resolution.

Toray Corp., on the other hand, developed photosensitive polyimides in which a compound having a photosensitive group and an imino component in polyamic acid was ion-bonded (US-A-4243743). Such photosensitive polyimide has advantages in that it is easy to manufacture and generates less harmful by-products than conventional photosensitive polyimide. The adhesion between polyimide, lead on chip (LOC) tape, polyimide and passivation film is one of the most important factors in securing the reliability of semiconductors in the production of photosensitive polyimide in the above examples. . When the adhesion of the polyimide is poor, impurities such as moisture penetrate and cause defects such as cracks. To impart adhesion to polyimides, siloxane-based diamines having the following structure are generally used, as shown in US Pat. No. 3,740,305.

Wherein x is an integer between 1 and 20.

However, when the aliphatic siloxane-based diamine in which the siloxane groups are included in the main chain, the thermal decomposition temperature of the polyimide is greatly decreased, and furthermore, when applied to the photosensitive polyimide, it is easily denatured and decomposed by the decomposition by-product of the photosensitive compound having low heat resistance. There is a disadvantage that the film properties of the polyimide film are greatly reduced. When the film characteristics of the polyimide film are deteriorated, problems such as the occurrence of cracks increase in later processes, such as a LOC tape bonding process and an epoxy encapsulation material molding process, lower the reliability of semiconductor products.

Accordingly, the present inventors have developed a polyimide precursor composition having improved heat resistance and adhesion by using an aliphatic siloxane-based diamine having a siloxane group included in a side chain to solve the above problems.

[Purpose of invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide an siloxane polyimide precursor composition having improved adhesion using a aliphatic siloxane-based diamine and a method for producing the same.

Another object of the present invention is to provide a siloxane polyimide precursor composition having improved heat resistance and mechanical properties by using an aliphatic siloxane-based diamine and a method of preparing the same.

The above and other objects of the present invention can be achieved by the present invention described below.

[Summary of invention]

The present invention provides a polyamic acid by reacting an organic solvent with an aliphatic siloxane-based diamine of the following structural formula (I), an aromatic tetracarboxylic dianhydride of the following structural formula (II), and an aromatic diamine of the following structural formula (III), wherein the polyamic acid is prepared. A siloxane polyimide precursor composition produced by adding a photosensitizer and a crosslinking aid to a mixed acid and a method of preparing the same:

[Formula I]

[Structure Formula II]

[Structure Formula III]

R ₁ in the above formula (III) is two aliphatic substituents.

Detailed Description of the Invention

The present invention provides a polyamic acid by reacting an organic solvent with an aliphatic siloxane-based diamine of the following structural formula (I), an aromatic tetracarboxylic dianhydride of the following structural formula (II), and an aromatic diamine of the following structural formula (III), wherein the polyamic acid is prepared. The present invention relates to a siloxane polyimide precursor composition produced by adding a photosensitizer and a crosslinking aid to a mixed acid and a method for producing the same.

[Formula I]

[Structure Formula II]

[Structure Formula III]

R ₁ in the above formula (III) is two aliphatic substituents.

Instead of the aromatic tetracarboxylic dianhydride of formula (II), one may be pretreated with alcohol, in which case a portion of the aromatic tetracarboxylic dianhydride of formula (II) is replaced by the compound of formula (IV):

[Formula IV]

R ₂ in the formula (IV) is a saturated aliphatic or unsaturated fatty acid group.

The alcohol compound used for the pretreatment is represented by the structural formula R ₂ OH, which includes methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol and allyl alcohol and 2-hydroxy ethyl acrylate or 2-hydroxy There are alcohols having a photosensitive group such as ethyl methacrylate.

The present invention may further include a photopolymerization initiator, a sensitizer and a thermal polymerization inhibitor according to the purpose.

The polyamic acid solution according to the siloxane polyimide precursor composition of the present invention can maintain the solution viscosity as low as 2,000-15,000 centipoise even at 20% by weight of solid content, and the coating film thickness may be 10 to 50 depending on the rotation speed by a spin coater or the like. Thick films exceeding the micrometer range can be easily formed.

The polyamic acid resin is also produced by the reaction of tetracarboxylic dianhydride as an acid component and diamine as an amine component in an organic solvent. Tetracarboxylic dianhydrides are broadly classified into aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.

The tetracarboxylic dianhydride may include butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, and cyclopentane tetracarboxylic. Acid dianhydride (cyclopentanetetracarboxylic dianhydride), bicyclolpentanetetracarboxylic dianhydride, cyclopropanetetracarboxylic dianhydride, methylcyclohexanetetracarboxylic dianhydride, methylcyclohexanetetracarboxlic dianhydride, 3 , 3 ', 4,4'-benzophenonetetracarboxylic dianhydride (3,3', 4,4'-benzophenonetetracarboxylic dianhydride), pyromellitic acid dianhydride, 3,4,9,10 Perylenetetracarboxylic dianhydride (3,4,9,10-perylenetertacaboxylic dianhydride), 4,4-sulfonyldiphthalic acid Anhydride (4,4-sulfonyldiphthalic dianhydride), 3,3'4,4'-biphenyl tetracarboxylic dianhydride (3,3'4,4'-biphenyltetracarboxylic dianhydride), 1,2,5,6-naphthalene Tetracarboxylic dianhydride (1,2,5,6-naphthalenetetracaboxylic dianhydride), 2,3,6,7-naphthalenetetracarboxylic dianhydride (2,3,6,7-naphthalenetetracaboxylic dianhydride), 1,4 , 5,8-naphthalenetetracarboxylic dianhydride (1,4,5,8-naphthalentetracaboxylic dianhydride), 2,3,5,6-pyridinetetracarboxylic dianhydride (2,3,5,6-pyridinetetracaboxylic dianhydride), m-terphenyl-3,4 ', 4,4', tetracarboxylic dianhydride (m-terphenyl-3,3 ', 4,4',-tetracaboxylic dianhydride), p-terphenyl- 3,3 ', 4,4', tetracarboxylic dianhydride (p-terphenyl-3,3 ', 4,4',-tetracaboxylic dianhydride), 4,4-oxydiphthalic dianhydride (4,4 -oxydiphthalic dianhydride), 1,1,1,3,3,3, -hexafluoro-2,2-bis (2,3 or 3,4-dicarboxyphenoxy) phenylpropane dianhydride (1,1, 1,3,3,3, -hexafluoro-2, 2-bis (2,3 or 3,4-dicarboxyphenoxy) phenylpropane dianhydride), 2,2-bis [4- (2,3 or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride (2,2- bis [4- (2,3 or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride), and 1,1,1,3,3,3, -hexafluoro-2,2-bis [4- (2, 3 or 3,4-dicarboxyphenoxy) phenol] propane dianhydride (1,1,1,3,3,3, -hexafluoro-2,2-bis [4- (2,3 or 3,4-dicarboxyphenoxy ) phenyl] propane dianhydride).

Aromatic diamines that can be used in the present invention include m-phenylene diamine, p-phenylenediamine, m-xylylenediamine, 1,5-diamino Naphthalene (1,5-diaminonaphthalene), 3,3'-dimethylbenzidine, 4,4- (or 3,4'-, 3,3'-, 2,4'- or 2 , 2 '-) diaminodiphenylmethane (4,4- (or 3,4'-, 3,3'-, 2,4'- or 2,2'-) diaminodiphenylmethane), 4,4- (or 3,4'-, 3,3'-, 2,4'- or 2,2 '-) diaminodiphenylether (4,4- (or 3,4'-, 3,3'-, 2, 4'- or 2,2 '-) diaminodiphenylether), 4,4- (or 3,4'-, 3,3'-, 2,4'- or 2,2'-) diaminodiphenylsulfide ( 4,4- (or 3,4'-, 3,3'-, 2,4'- or 2,2 '-) diaminodiphenylsufide), 4,4- (or 3,4'-, 3,3'- , 2,4'- or 2,2 '-) diaminodiphenylsulfide (4,4- (or 3,4'-, 3,3 '-, 2,4'- or 2,2'-) diaminodiphenylsulfide), 1,1,1,3,3,3, -hexafluoro-2,2-bis (4-aminophenyl) propane ((1,1,1,3,3,3, -hexafluoro-2 , 2-bis (4-aminophenyl) prpane), 2,2-bis (4- (4-amino Phenoxy) phenyl) propane (2,2-bis (4- (4-aminophenoxy) phenyl propane), 4,4-benzophenonediamine, 4,4'-di- (4-amino Phenoxy) phenylsulone (4,4'-di- (4-aminophenoxy) phenylsulfone), 3,3-dimethyl-4,4-diaminodiphenylmethane, 4,4'-di- (3-aminophenoxy) phenylsulfone (4,4'-di- (3-aminophenoxy) phenylsulfone), 2,4-diaminotoluene, 2,5 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 0-tolidine, 4,4'-diaminoter Phenyl (4,4'-diaminoterphenyl), 2,5-diaminopyridine, 4,4'-bis (p-aminophenoxy) biphenyl (4,4'-bis (p- aminophenoxy) biphenyl), and hexahydro-4,7-methanoindanylene dimethylene diamine.

The siloxane-based diamine used in the present invention serves to improve the mechanical strength and heat resistance as well as the adhesion of the polyimide precursor composition including the siloxane group in the side chain. The siloxane-based diamine is 1 to 30 mol%, preferably 2 to 5 mol% based on the total diamine used. If the amount of the siloxane-based diamine is less than 1 mol%, the adhesive strength is lowered, and using more than 30 mol% does not need to use too much amount because of the high manufacturing cost.

Organic solvents used in the preparation of the polyamic acid include N-methyl-2-pyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, gamma-butyrolactone And common organic solvents.

Examples of the compound having a photoreactive carbon-carbon unsaturated group added to the polyamic acid include N-methylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-diethyl acrylamide, N-acryl oil morpholine, N-vinylpyrrolidone, etc. are mentioned. There is no restriction on the compound including the carbon-carbon unsaturated group used in the present invention. However, when the unsaturated group is bonded to an amino group, the carboxyl group of the polyamic acid is bonded in the form of a salt, and the photoreactivity is superior to that of the photoreactive compound containing no amino group. Examples of the compound including both the carbon-carbon unsaturated group and the amino group having photoreactivity include N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N , N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, and the like, and instead of acrylate, 2-vinylpyridine, 4-vinylpyridine, arylamine, 2-methylarylamine, diarylamine, and the like.

Photoinitiators that can be used in the present invention include 2,6-di- (p-azidobenzal) -4-methylcyclohexanone (2,6-di- (p-azidobenzal) -4-methylcyclohexanone), and 2 Bisazide compounds, such as 6-di- (p-azidobenzal) -cyclohexanone, benzophenone, methyl 0-benzoylbenzoate, 4,4'-bis (dimethylaminobenzophenone), 4 , 4-bis (diethylaminobenzophenone), 4,4-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, florenone, 2,2'-diethoxyacephenone , 1-phenyl-1,2-butanedione-2- (o-ethoxycarbonyl) oxime (1-phenyl-butandione-2- (o-ethoxycarbonyl) oxime), 1,3-diphenyl-propanedione- 2- (o-ethoxycarbonyl) oxime (1,3-diphenyl-propandione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanedione-2- (o-benzyl) oxime ( 1-phenyl-3-ethoxy-propandione-2 (o-benzyl) oxime), miharazketone, N-phenylglycidine, 3-phenyl-5-isoxazolone, 1-hydroxycyclohexylphenylketone, 2 -Methyl- (4- (methylthio) phene Nil) -2-morpholino-1-propanone, naphthalenesulfonylchloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4'-azobisisobutyronitrile, diphenyldisulfide, Benzthiazole disulfide, triphenylpolspin, campolquinone, carbon tetrabromide, tribrophenylsulfone, benzoyl peroxide, etc. The photopolymerization initiator may be used alone or in combination of two or more.

The quantity of the photoinitiator contained in the siloxane polyimide precursor of this invention is 0.1-30 weight% based on a polyamic acid resin, and 2-15 weight% is preferable. If the amount of the photoinitiator is 0.1 wt% or less, the photosensitivity of the composition is lowered, and if it is 30 wt% or more, the film thickness is decreased during the final curing of the film.

In the present invention, a sensitizer may be used to improve light sensitivity. Such sensitizers include 2,5-bis (4'-diethylaminobenzal) cyclopentanone, 2,6-bis (4'-dimethylaminobenzal) cyclohexanone, miharazketone, 4,4'-bis ( Diethylamino) benzophenone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinyl Ene) -isonnaphthothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylamino Benzal) acetone, 3,3'-carbonyl-bis- (7-diethylaminocumalin), N-phenyldiethanoldiamine, N-tolyldiethanolamine, N-phenylethanoldiamine, dimethyaminobenzoic acid isoamyl , 3-phenyl-5isooxazolone, 1, -phenyl-5-benzoylthio-tetrazole, 1-5-ethoxycarbonylthio-tetrazole and the like.

One or more sensitizers may be used, and 0.1 to 30% by weight based on the polyamic acid is preferably 0.5 to 15% by weight. If the added amount of the sensitizer is 30% by weight or more, the thickness of the film decreases and the mechanical properties deteriorate during curing of the film. If the amount is less than 0.1% by weight, the photosensitivity of the composition is lowered.

When preserving the siloxane polyimide precursor of the present invention, a thermal polymerization inhibitor may be added to improve thermal stability. As the thermal polymerization inhibitor, a thermal polymerization inhibitor may also be added to improve thermal stability upon storage of the siloxane polyimide precursor. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, phenoxyazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p-methylphenol, charonanyl And pyrogallol.

In order to improve the hardness of the formed polyimide film, colloidal inorganic fine particles may be added. The inorganic fine particles include silica sol, titania sol, zirconia sol and the like. The amount of the colloidal inorganic fine particles used is 1 to 50% by weight based on the polyamic acid, preferably 2 to 30% by weight.

When mixing all the components constituting the siloxane polyimide precursor composition or when mixing the additives in the composition it can be prepared as a coating solution by adding colloidal inorganic fine particles and the like. Most of these photosensitive compounds added to the polyimide precursor solution are removed at a final curing temperature of 350 ° C. or higher, leaving only the fully cured polyimide.

Existing aliphatic siloxane-based diamine compound tends to easily decompose the aliphatic group in the photosensitive compound that is thermally decomposed, thereby deteriorating the film properties of the final film and reducing heat resistance, but polyimide using the siloxane-based diamine according to the present invention has a poor heat resistance. By reducing the length of the excellent heat resistance and mechanical properties can be obtained.

The present invention will be further illustrated by the following examples, which are only described for the purpose of illustrating the present invention and are not intended to limit the protection scope of the present invention.

EXAMPLE

[Synthesis of siloxane-based diamine monomer]

150 ml of tetrahydrofuran (THE) and 5,2 g of 2,2-bis (bromomethyl) -1,3-propanediol were added to a 500 ml three-necked flask under nitrogen stream, and dichlorodiethoxy silane dissolved in 150 ml 3.9 g was charged to the reactor over 60 minutes. After stirring the reaction mixture at room temperature for 24 hours, the solvent was removed by distillation under reduced pressure and recrystallized from diethyl ether to obtain about 4g (53%) of white crystals. 7.6 g of this white crystal and 1.6 g of sodium azide were dissolved in 200 ml of diethylene glycol and reacted at 150 ° C. for 24 hours. The reaction mixture was poured into 300 ml of water, extracted with 300 ml of ether, dried over magnesium sulfate and reduced to about 20% by solvent distillation to form a clear solid. 2 g of lithium aluminum hydride and 20 ml of tetrahydrofuran were put into a 100 ml three-necked flask, and the solid synthesized in the previous step was dissolved in 20 ml of tetrahydrofuran, charged into the reactor over 1 hour, and refluxed for 6 hours. After completion of the reaction, 4 ml of 8% aqueous sodium hydroxide solution was added thereto, followed by extraction for 24 hours using a Soxhlet apparatus to obtain a siloxane diamine monomer having 1.5 g of siloxane groups in the side chain.

Example 1

[Preparation of polyimide precursor composition with siloxane diamine, 3,3'4,4'-benzophenone tetracarboxylic dianhydride and oxy dianiline]

161.1 g (0.5 mol) of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2.43 g (0.025 mol) of siloxane-based diamine of formula (I), 95 g (0.475 mol) of oxydianiline and N 980 g of -methyl-2-pyrrolidone was placed in a polymerization tank and stirred at 15 DEG C for 5 hours under a nitrogen stream to obtain a polyamic acid solution as a polymer having a viscosity of 12,000 centipoise at room temperature. To 20 g of the polyamic acid prepared above, 3.2 g of dimethylaminoethyl methacrylate, 0.01 g of 2,6-di- (p-azidobenzal) -4-methylcyclohexanone and 1-phenyl-1,2-butadione- 0.05 g of 2- (0-methoxycarbonyl) oxime was mixed and stirred for 30 minutes to obtain a siloxane polyimide precursor composition having a viscosity of 13,500 centipoise. The obtained polyimide precursor composition was coated on a silicon wafer for 30 seconds at a rotational speed of 2500 rpm, and then cured at 120 ° C. for 4 minutes to form a film of polyimide precursor having a coating having a thickness of 15 μm. A photomask was put thereon and the resolution was 10 µm or more when developed by N-methylpyrrolidone after UV irradiation. Thereafter, the film thickness of the polyimide after curing at 200 ° C. for 30 minutes and at 350 ° C. for 30 minutes in a nitrogen gas distributor was 8 μm, thereby forming a very thick coating film. The adhesion characteristics of the polyimide were evaluated by scotch tape after preliminary storage of the polyimide film on the wafer for 100 hours under PCT (Pressure Cooking Test). The heat resistance of the obtained polyimide film was evaluated under a nitrogen atmosphere using TGA, and showed a very good heat resistance property with a 5% weight reduction temperature of 490 ° C. The mechanical strength of the film was measured by Instron, and a good value of tensile strength of 110 MPa and elongation of 30% or more was obtained.

Example 2

[Preparation of polyimide precursor composition with siloxane-based diamine, pretreated 3,3, '4,4'-benzophenone tetracarboxylic dianhydride and oxydianiline]

To a 250 ml three-necked round flask was added 116 g (1.17 mol) of N-2-methyl pyrrolidone under nitrogen stream and 23.64 g (0.7335 mol) of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride. 1.91 g (0.01467 mol) of 2-hydroxyethyl methacrylate was added thereto, and 12.5 g (0.06235 mol) of 4,4'-diaminodiphenyl ether and 1,3-bis (4-diamino-phenoxy)-were added. 2.1 g (0.00735 mol) of 2,2-dimethylpropane diamine and 0.451 g (0.0036675 mol) of siloxane-based diamines were sequentially added, and it reacted at 15 degrees or less for 8 hours or more. It was 8,000 cps when this reaction liquid confirmed the viscosity using the Brookfield viscometer. 1.6 g of 2- (N, N-dimethyl amino) ethyl methacrylate and 2,6- (di-4'-azidebenzyl) -4-methylcyclohexa to 2 g of the siloxane polyamic acid thus prepared (based on solids) After mixing 0.2 g of paddy and filtering with a 5 micron pressure filter was used as a photosensitive composition. The obtained siloxane polyimide precursor composition was coated on a silicon wafer for 30 seconds at a rotational speed of 2500 rpm and then cured at 120 ° C. for 4 minutes to form a film of polyimide precursor having a coating having a thickness of 15 μm. A photomask was put thereon to show a resolution of 10 µm or more when developed by N-methylpyrrolidone solution after ultraviolet irradiation. Thereafter, the film thickness of the polyimide after curing at 200 ° C. for 30 minutes and at 350 ° C. for 30 minutes in nitrogen gas was 8 μm, thereby forming a very thick coating film. The adhesion properties of the polyimide were evaluated by scotch tape after preliminary storage of the polyimide film cured on the wafer for 100 hours in PCT (Pressure Cooking Test), and showed good adhesive properties without any release parts. The heat resistance of the obtained polyimide film was evaluated under a nitrogen atmosphere using TGA, and showed a very good heat resistance property with a 5% weight reduction temperature of 490 ° C. The mechanical strength of the film was measured by Instron, and a good value of tensile strength of 120 MPa and elongation of 35% or more was obtained.

Comparative Example 1

[Preparation of polyimide precursor composition with siloxane diamine, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and oxy dianiline]

Except for using the conventional gamma aminopropyldiamine 3.25g (0.025mol) instead of the siloxane-based diamine monomer prepared in the above Example was carried out in the same manner as in Example 1, and the results were evaluated. The heat resistance of the obtained polyimide film was considerably good as the 5% weight reduction temperature of 480 ° C., but was significantly reduced compared to Example 1. The mechanical strength of the film was somewhat insufficient as the tensile strength of 100MPa, elongation of 28%.

Comparative Example 2

[Preparation of polyimide precursor composition by siloxane-based diamine, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, siloxane-based diamine, oxydianiline]

Except for using the conventional gamma amino propyldiamine 0.9114g (0.0036675 mol) instead of the siloxane-based diamine monomer prepared in Example 2 was carried out in the same manner as in Example 2, and the results were evaluated. The heat resistance of the obtained polyimide flim was good at 5% weight reduction temperature as 450 ° C., but was significantly reduced compared to Example 2. Mechanical strength of the film was somewhat insufficient as the tensile strength of 100MPa, elongation 20%.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (3)

A siloxane polyimide precursor composition produced by reacting an organic solvent with an aliphatic siloxane diamine of the following structural formula (I), an aromatic tetracarboxylic dianhydride of the following structural formula (II), and an aromatic diamine of the following structural formula (III): [Formula I] [Structure Formula II] [Structure Formula III] R ₁ in formula (III) is a divalent aliphatic substituent. The siloxane according to claim 1, wherein a part of the aromatic tetracarboxylic dianhydride is converted to a compound of the following structural formula (IV) by pretreating the aromatic tetracarboxylic dianhydride of the structural formula (II) to the organic solvent. Polyimide precursor composition: [Formula IV] R ₂ in the formula (IV) is a saturated aliphatic or unsaturated fatty acid group. The method of claim 2, wherein the alcohol is a photosensitive group such as methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, allyl alcohol and 2-hydroxy ethyl acrylate or 2-hydroxy ethyl methacrylate. A method for producing a siloxane polyimide precursor composition, characterized in that it is selected from the group consisting of alcohols having.