KR100560109B1 - Method for the preparation of polyamic acid and polyimide - Google Patents

Abstract

The present invention relates to a method for producing polyamic acid and polyimide having a three-dimensional structure that exhibits excellent properties as a material for high temperature adhesives or as a material for heat resistant films by improving flowability at high temperatures while maintaining the heat resistance and mechanical properties of the polymer. .

The present invention is a diamine comprising a siloxane structure represented by the formula (I) in addition to tetracarboxylic dianhydride and aromatic diamine, which are generally used for the production of polyimide, and is represented by the formula (II) or (III) The polyamino compound is reacted to produce polyamic acid, and the polyamic acid is produced by thermal imidization or chemical imidization.

Description

Method for preparing polyamic acid and polyimide {Method for the preparation of polyamic acid and polyimide}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the preparation of novel polyamic acids, which are precursors of polyimides having excellent heat resistance or high temperature adhesion properties, and polyimides using the same, and in particular, polyamic acids and polyimides, which are three dimensional network molecular structures, It relates to a manufacturing method of.

Reaction of tetracarboxylic dianhydride and diamine with an organic solvent to obtain polyamic acid as a polyimide precursor, followed by thermal or chemical imidization are known as common methods for producing polyimides.

Polyimide resins are excellent in heat resistance, chemical resistance, electrical insulation, mechanical properties, and the like, and are used in various applications such as electronic materials, adhesives, coatings, composite materials, fibers, and film materials.

In general, the polyimide has not only the rigid structure of the imide ring itself but also the linear structure of the main chain, so that the packing density between the chains is large and thus has excellent heat resistance characteristics.

In particular, the structure of the polyimide used for excellent heat resistance, such as film is dependent on the filling density between the chains according to the linear structure of the main chain, the heat resistance characteristics, commercially used polyimide films Kapton (Kapton), The case of Upilex films shows an example of such a structure. In the case of Kapton, it is obtained from monomers of pyromellitic dianhydride (PMDA) and oxygen dianiline (ODA). From monomers.

However, in terms of heat resistance, the linear structure as described above is difficult to expect the heat resistance characteristics of the conventional polyimide film, and even if the molecular weight is increased to increase heat resistance, mechanical properties such as flexibility are deteriorated.

In JP-63 254131, a polyimide of linear structure was used to increase the heat resistance by partially adding PPD to PMDA and ODA used in Kapton-type polyimide to increase the heat resistance. Since the strength is lowered, there is a limit to the increase in the PPD content, there is also a limit to increase only the heat resistance while maintaining mechanical properties.

In USP 5231162, in order to compensate for the shortcomings of the polyimide having a linear structure, tri or tetraamine was introduced into the existing aromatic diamine, and the thermal structure and the mechanical properties were simultaneously improved as a three-dimensional structure by gelling the linear structure. However, since only aromatic tetracarboxylic dianhydride and aromatic diamine are used, the flexibility of the film is insufficient, and the processing characteristics due to the decrease in the solubility of the polyamic acid and the polyimide due to gelation are lowered.

In addition, in the case of polyamic acid and polyimide used as an adhesive, in order to obtain adhesiveness at a high temperature, acer group or the like is introduced into the main chain of the polymer to lower the glass transition temperature to increase the flowability at a high temperature and thereby to promote high temperature adhesiveness. Although many methods are used for improving, in this case, there is a problem that the heat resistance is lowered and the reliability is poor in terms of processability at high temperature.

In USP 4847349, USP 5406124, etc., thermoplastic polyimide adhesives are prepared by using diamines having two or more isomers introduced between three or four phenyl rings, thereby improving high temperature flowability. have.

The present invention has been made to solve the above problems, while maintaining the heat resistance and mechanical properties of the polymer to improve the flowability at high temperatures to the polyamide acid having a three-dimensional structure suitable for the use of high temperature adhesive or heat-resistant film And polyimide.

The present invention is one method for achieving the object of the invention,

At least one or more tetracarboxylic dianhydrides and at least one or more aromatic diamines; At least one or more of diamines containing a siloxane structure represented by the following general formula (I); And a method for producing a polyamic acid and a polyimide characterized by reacting at least one or more of the polyamino compounds represented by the following formula (II) or formula (III).

[Formula I]

(In the formula (I), R4 is an alkylene group having 1 to 20 carbon atoms, n 'is an integer of 1 to 20)

[Formula II]

[Formula III]

(In the above formula (II) and formula (III), A1 is selected from the following structures,

A2 is selected from the following structures,

n1 is an integer from 0 to 4, n2 is an integer from 0 to 3, x represents an acid, q represents the number of bases of the acid, in the structural formula of A1 or A2, R is -O-, -CH _2- , -CO-, or -SO _2- , where n3 represents 0 or 1.

Hereinafter, the present invention will be described in detail.

In the present invention, polyfunctional polyimide having a linear molecular structure generally has a polyfunctional such as diamine having a siloxane structure and tri or tetra together with an aromatic diamine which is generally used to improve the properties (heat resistance, mechanical properties, adhesive properties, etc.) of the polyimide. Using a compound having an amino group, a polyamic acid or polyimide having a three-dimensional molecular structure was produced, and thus a polymer meeting the required properties can be obtained according to the content of the polyfunctional amino group.

As a typical example of the tetracarboxylic dianhydride used in the present invention, a compound represented by the following general formula (IV) may be mentioned.

[Formula IV]

Wherein R 1 is —O—, —CO—, SO ₂ —, —C (CF ₃ ) ₂ —, alkylene group, alkylene bicarbonyl group, phenylene group, phenylene alkylene group, phenylene dialkyl A rene group and the like, n4 represents 0 or 1, n5 represents 0 or 1, n6 represents 1 or 2, and n5 + n6 represents 2.

Specific examples of the aromatic tetracarboxylic anhydride having the structure of formula (IV) include pyromellitic dianhydride, 3,3, ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 '4,4'-biphenyltetracarboxylic dianhydride, 2,3,3'4'-biphenyltetracarboxylic dianhydride, 2,2', 6,6'-biphenyltetracarboxylic Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4- Dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) dianhydride, 3,4,9,10-phenylenetetra Carboxylic acid dianhydride, naphthalene-1,2,4,5-tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarbox Carboxylic acid dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), and the like. These compounds may be used alone or in combination of two or more thereof. .

In addition to the above aromatic tetracarboxylic dianhydrides, tetracarboxylic acids of aliphatic or alicyclic structure can also be used within the range of not lowering the heat resistance of the polyimide to be synthesized.

Examples of tetracarboxylic acids having aliphatic or alicyclic structure include 5- (2,5-diosotetrahydro) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride. , 4- (2,5-Diotetrahydrofuran-3-yl) -tetraline-1,2-dicarboxylic anhydride, buttcyclo (2,2,2) -7-ene-2 , 3,5,6-tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, and the like, and these compounds may be used alone or in combination of two or more thereof.

Specific examples of the aromatic diamine used in the present invention include 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminodi Phenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2- (3,3'-diaminodiphenyl) propane, 2,2- (3,4 '-Diaminodiphenyl) propane, 2,2- (4,4'-diaminodiphenyl) propane, 2,2- (3,3'-diaminodiphenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2- (4,4'diaminodiphenyl) hexafluoropropane, 3,3'-oxydianiline, 3,4'-jade Cydianiline, 4,4'-oxydianiline, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3, 3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 1,3-bis [1- (3-aminophenyl) -1-methylamine ) Benzene, 1,3-bis [1- (4-aminophenyl) -1-methylamine) benzene 1,4-bis [1- (3-amino Nil) -1-methylamine) benzene, 1,4-bis [1- (4-aminophenyl) -1-methylamine) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3'-bis (3-aminophenoxy) diphenylether , 3,3'-bis (4-aminophenoxy) diphenyl ether, 3,4'-bis (3-aminophenoxy) diphenyl ether, 3,4'-bis (4-aminophenoxy) diphenyl ether, 4 , 4'-bis (3-aminophenoxy) diphenylether, 4,4'-bis (4-aminophenoxy) diphenylether, 3,3'-bis (3-aminophenoxy) biphenyl, 3,3 ' -Bis (4-aminophenoxy) biphenyl, 3,4'-bis (3-aminophenoxy) biphenyl, 3,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3- Aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4- Aminophenoxy) phenyl] sulfone, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (4-a Minophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [ 3- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (4- Aminophenyl) fluorene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) benzidine, 1,2-phenylenediamine, 1,3-phenyl Rendiamine, 1,4-phenylenediamine, etc., These compounds can be used individually or in mixture of 2 or more types.

As the multifunctional polyamino compound represented by the formulas (II) and (III) used in the present invention, 3,3 ', 4,4'-tetraaminodiphenyl isomer, 3,3', 4,4'-tetra Aminodiphenylmethane, 3,3 ', 4,4'-tetraaminobenzophenone, 3,3', 4,4'-tetraaminodiphenyl sulfone, 3,3 ', 4,4'-tetraaminobiphenyl , 1,2,4,5-tetraaminobenzene, 3,3 ', 4-triaminodiphenyl, 3,3', 4-triaminodiphenylmethane, 3,3 ', 4-triaminobenzophenone, 3,3 ', 4-triaminodiphenylsulfone, 3,3', 4-triaminodibiphenyl, 1,2,4-triaminobenzene and the like, mono-, di-, tri- or tetra-acids of the above compounds Salt, 3,3 ', 4,4'-tetraaminodiphenyl istetetrahydrochloride, 3,3', 4,4'-tetraaminodiphenylmethane tetrahydrochloride, 3,3 ', 4, 4'-tetraaminobenzophenone tetrahydrochloride, 3,3 ', 4,4'-tetraaminodiphenyl sulfone tetrahydrochloride, 3,3', 4, 4'-tetraaminobiphenyl tetrahydrochloride, 1,2,4,5-tetraaminobenzene tetrahydrochloride, 3,3'4-triaminodiphenyl trihydrochloride, 3,3'4-triaminodiphenyl Methane trihydrochloride, 3,3'4-triaminobenzophenone trihydrochloride, 3,3'4-triaminodiphenylsulfone trihydrochloride, 3,3'4-triaminodibiphenyl trihydrochloride, 1, 2,4-triaminobenzene dihydrochloride, etc., These can be used 1 type or in mixture of 2 or more types.

Specific examples of the diamines containing the siloxane structure represented by the formula (I) in the present invention include bis (γ-aminopropyl) tetramethyldisiloxane (GAPD, n = 1), bis (γ-aminopropyl) polydimethyl Disiloxane (PSX-4, n = 4), bis ((gamma) -aminopropyl) polydimethyldisiloxane (PSX-8, n = 8), etc., These can be used together 1 type (s) or 2 or more types.

Diamine containing a siloxane structure gives flexibility to the rigid structure of the polyimide to compensate for the lack of flexibility of the polymer according to the three-dimensional network molecular structure due to gelation to prevent the mechanical properties of the three-dimensional polyimide It serves to increase the solvent solubility, it is possible to increase the content of the reactant to the organic solvent during the polymerization of the polyamic acid.

In addition, when used as an adhesive, it can play a role of increasing adhesion to various substrates. In particular, when applied to electronic materials, etc., there is an effect of improving adhesion characteristics with substrates such as silicon chips, chip insulating films, and lead frames.

When polymerizing polyimide using aromatic tetracarboxylic -2- anhydride and diamine, N-methyl-2-pyrrolidone (NMP), NN-dimethyl formamide (DMF), and NN-dimethylacetate are used as solvents. Aprotic polar solvents such as amide (DMAc), dimethyl sulfoxide (DMSO), sulfolane, hexamethyl phosphate triamide, 1,3-dimethyl-2-imidazolidone, phenol, cresol, xylphenol, p- Phenolic solvents, such as chlorophenol, are used. If necessary, ether solvents such as diethylene glycol and dimethyl ether, aromatic solvents such as benzene, toluene and xylene, etc. may be used. In addition, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, Diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, trichloroethylene, nitrobenzene, etc. are used, and these can be used individually or in mixture of 2 or more types.

In the case of the thermal imidization method, which is a general polymerization method of polyimide, first, the polyamic acid as a precursor is polymerized, and then the solution is coated and then thermally imidized by heating. The first step of the polymerization is a polyamic acid as a precursor of the polyimide. At least one or more of the tetracarboxylic dianhydride and the aromatic diamine of the formula (III) in the temperature range of -10 ℃ ~ 100 ℃ in accordance with the appropriate molecular weight and relative viscosity of the polyamic acid in the process of preparing, At least one or more of the diamines containing the siloxane structure of IV) and at least one or more tri or tetraamines of the above formulas (I) and (II) are added and reacted at 100 ° C. or lower with vigorous stirring in a nitrogen atmosphere in a solvent. To prepare a polyamic acid as a precursor of the polyimide. At this time, the reaction time is preferably 10 hours or less (more preferably 5 hours or less).

In order to convert polyamic acid to polyimide, it is imidized by applying or coating polyamic acid, and then applying heat to 250 to 500 ° C. in polyamic acid dissolved in a solvent to promote imidization during the drying process. Tertiary amines such as pyridine, triethylamine, tributylamine, isoquinoline, acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, and a ring closure catalyst for dehydration ringing may be added.

When polyimide is soluble in a solvent In the case of a preferable chemical imidation method, when tetracarboxylic -2- anhydride and diamine are used first, these are tributylamine and triethylamine in an organic solvent as needed. 100 ° C. or more in the presence of a catalyst such as triphenyl phosphite, isoquinoline, pyridine or the like (up to 25 parts by weight of the total reactant) or dehydration catalyst such as p-toluenesulfonic acid (up to 25 parts by weight of the total reactant) Preferably to obtain a polyimide directly by heating to 180 ° C. or higher), and then a tetraamic acid-2-anhydride and diamine are reacted at 100 ° C. or lower in an organic solvent to obtain polyamic acid as a precursor of the polyimide. And dehydration ring closing agents such as acid anhydrides such as acetic anhydride, propionic anhydride, benzoic anhydride, and carbodiimide compounds such as dicyclohexylcarbodiimide, and, if necessary, Closing ring catalysts such as pyridine, isoquinoline, imidazole, and triethylamine (dehydrating ring closure and ring closure catalyst are 2 to 10 times molar of tetracarboxylic acid-2- anhydride) and are added at relatively low temperatures (room temperature to 100 ° C). There is a method of ring closing.

In the present invention, the preferred amount of each component participating in the reaction in the polyimide reaction is 10-100 moles (more preferably 60-100 moles) of aromatic diamine, and a siloxane structure, based on 100 moles of tetracarboxylic dianhydride. 0.1 to 90 moles (more preferably 0.1-40 moles) of diamine compounds and 0.01-20 moles (more preferably 0.01-7 moles) of polyamino compounds.

In this case, the ratio of the equivalent of tetracarboxylic dianhydride and the total equivalent of the amine compounds to participate in the reaction is preferably reacted within the following range.

0.95 ≦ tetracarboxylic dianhydride equivalent / amine equivalent ≦ 1.05

As described above, the polyimide obtained according to the present invention has excellent electrical insulation and heat resistance, and has excellent characteristics in application to tapes for electronic components capable of hot melt bonding under high temperature taping conditions.

In general, adhesive tapes for electronic components are mainly used for bonding between components around a lead frame constituting a semiconductor device, for example, lead pins, semiconductor mounting substrates, heat sinks, and semiconductor chips themselves. Also included are adhesive tapes having increased adhesion to copper foil suitable for FPC (Flexible Printed Circuit) originals and two-layer tape automated bonding (TAB) adhesive tapes.

Tapes for electronic components include adhesive tapes for fixing leadframes, adhesive tapes for leadframe-semiconductor chips, and adhesive tapes for leadframe die pads. Process stability and product reliability are required.

In particular, even in the semiconductor assembly process, even if the adhesive properties in the high temperature taping process, thermal stability is required in high temperature processes such as wire bonding and epoxy molding. In general, polyimide lowers the glass transition temperature and melting temperature in order to increase the flowability and adhesive properties of the high temperature taping process, resulting in loss of heat resistance, and even though high temperature adhesive properties can be secured, high temperature such as wire bonding and epoxy molding processes Although there is a problem in that the heat resistance in the process is not secured, in the case of the polyimide of the three-dimensional network molecular structure, it is possible to increase the high temperature flowability without lowering the glass transition temperature, so that the high temperature adhesive properties, wire bonding, epoxy molding process, etc. It also has the advantage of ensuring reliability during high temperature processes.

The polyimide adhesive tape produced using the polyimide obtained according to the present invention is coated with the above liquid adhesive on one or both sides of the base film and dried to obtain a polyimide adhesive of 1 to 150 µm (more preferably 5 to 50). It can also be produced from adhesive tapes laminated at a thickness of mu m). The base film used at this time is a heat resistant film, for example, a heat resistant resin film such as polyimide, polyvinylene sulfide, polyether, polyethylene terephthalate, fluorine resin, epoxy resin-glass cloth, epoxy resin-polyimide-glass cloth, etc. Although a composite heat resistant film etc. can be mentioned, Especially a polyimide film is preferable. The thickness of the heat resistant film is suitably in the range of 5 to 150 μm, and in particular, in the case of the adhesive tape for LOC, a polyimide film having a thickness of 25 μm or 50 μm is mainly used. Moreover, in order to improve the adhesive force between a base film and a polyimide adhesive, you may use the film which carried out the chemical treatment, such as plasma, corona, or silane treatment, on the surface of a base film. And a peelable film having a thickness of approximately 1 to 200 µm may be used, which is released by a silicone-based release agent on the surface of the base film for the purpose of manufacturing an adhesive sheet composed of only a polyimide adhesive.

On the other hand, since the polyamic acid or polyimide obtained by the present invention is excellent in heat resistance and mechanical strength, it can also be used as a material of a heat resistant film.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

<Example 1>

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, first, 1,4-bis (4-aminophenoxy) biphenyl 7.01 g (0.024 mol) as biamine, bis (3-aminopropyl) tetramethyldisiloxane 1.45 g (0.00585 mole) and 0.03 g (0.00015 mole) of 3,3 ', 4,4'-tetraaminodiphenyl are added to 173.07 g of N-methyl-2-pyrrolidone (NMP) solvent at 15 ° C. After dissolving these, 10.74 g (0.03 mol) of 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride was added thereto, followed by vigorous stirring in a nitrogen atmosphere for 5 hours to synthesize polyamic acid.

<Example 2>

In a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet, 10.37 g (0.024 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone as a diamine and bis (3-aminopropyl) 1.45 g (0.00585 mole) of tetramethyldisiloxane and 0.03 g (0.00015 mole) of 3,3 ', 4,4'-tetraaminodiphenyl methane are added to 193.59 g of N-methyl-2-pyrrolidone (NMP) solvent. And dissolve them at 15 ° C., and then add 9.66 g (0.03 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, and stir vigorously for 5 hours in a nitrogen atmosphere. Was synthesized.

Comparative Example 1

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 8.76 g (0.03 mol) of 1,3-bis (4-aminophenoxy) biphenyl was first substituted with N-methyl-2-pyrrolidone (NMP). Into a 175.5g solvent to dissolve them at 15 ℃, 10.74g (0.03 mol) of 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride was added and vigorously in a nitrogen atmosphere for 5 hours. Stirring synthesized polyamic acid.

Comparative Example 2

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 12.96 g (0.03 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone is first added with diamine. It is placed in a solvent of 199.62 g of ralidone (NMP) and dissolved at 15 ° C., followed by 6.76 g (0.021 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and ethylene glycol bis (anhydrotri) Mellitate) 2.46 g (0.009 mol) was added thereto, and vigorously stirred in a nitrogen atmosphere for 5 hours to synthesize polyamic acid.

The relative viscosity of the polyamic acids obtained in Examples 1 and 2 and Comparative Examples 1 and 2 (diluted polyamic acid to 0.05% by weight in N, N-dimethylacetamide) is shown in Table 1 below.

The polyamic acid solutions synthesized in Examples 1 and 2 and Comparative Examples 1 and 2 were respectively coated on a glass plate using a knife coater, and then dried in a vacuum dryer at 80 ° C. for 60 minutes to remove the solvent, and then the film was plated. After peeling off from the above, 5 minutes at 150 ° C. and 5 minutes at 200 ° C. were respectively dried and finally thermally imidized at 300 ° C. for 1 hour to prepare 50 μm thick polyimide films. Infrared absorption spectra of the obtained polyimides were measured, and the absorption of typical imides was recognized at 1718 cm ^-1 and 1783 cm ^-1 .

And 5% pyrolysis temperature was measured to evaluate the heat resistance of the polyimide film, and the glass transition temperature and the elastic modulus value was measured using DMTA (Dynamic Mechanical Thermal Analysis), respectively.

In addition, the polyamic acid solutions synthesized in Examples 1 and 2 and Comparative Examples 1 and 2 were respectively coated on a Upilex-S polyimide film using a knife coater, followed by 80 ° C. × 10 minutes and 110 ° C. × 10 minutes. , 150 ° C. × 10 min, 200 ° C. × 10 min, respectively, was dried and finally thermally imidized at 300 ° C. for 1 hour to prepare adhesive tapes having a thickness of 20 μm of a polyimide adhesive layer. The tapes were adhered onto copper plate, nickel iron alloy plate, and PIK-3000 solution (Hitachi Chemical) coated plate at 400 ℃ under pressure of 5㎏ / ㎠, and then T-Peel tested at a speed of 50mm / min at room temperature. The evaluated adhesion is shown in Table 1 below.

<Example 3>

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 7.01 g (0.024 mol) of 1,4-bis (4-aminophenoxy) benzene as a diamine and bis (3-aminopropyl) tetramethyldisiloxane 1.45 g (0.00585 mol) and 0.03 g (0.00015 mol) of 3,3 ', 4,4'-tetraaminodiphenyl are added to a solvent of 196.38 g of N-methyl-2-pyrrolidone (NMP) and dissolved at 15 ° C. Next, 13.33 g (0.03 mol) of (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added thereto, followed by vigorous stirring for 5 hours in a nitrogen atmosphere to synthesize polyamic acid.

50 ml of toluene and 3.0 g of p-toluenesulfonic acid were added to the obtained polyamic acid, and it heated at 190 degreeC, and the imidation reaction was performed for 6 hours, separating water with progress of reaction. Thereafter, the obtained polyimide was obtained by injecting a polyimide polymer solution into methanol to separate, pulverize, wash and dry the precipitate, thereby obtaining a powdered polyimide, and measuring the infrared absorption spectrum of the obtained polyimide. typical was already recognized as the absorption of de ㎝ ^-1 and 1783㎝ ^-1.

<Example 4>

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 9.84 g (0.024 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine, bis (3-aminopropyl) 1.45 g (0.00585 mole) of tetramethyldisiloxane and 0.03 g (0.00015 mole) of 3,3 ', 4,4'-tetraaminodiphenyl are added to a solvent of 221.85 g of N-methyl-2-pyrrolidone (NMP). After dissolving them at 15 ° C., 13.33 g (0.03 mol) of (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added thereto, followed by vigorous stirring in a nitrogen atmosphere for 5 hours to synthesize polyamic acid.

50 ml of toluene and 3.0 g of p-toluenesulfonic acid were added to the obtained polyamic acid, and it heated at 190 degreeC, and the imidation reaction was performed for 6 hours, separating water with progress of reaction. Then, a polyimide in a powder state was obtained by subjecting the precipitate obtained by injecting the polyimide polymer solution into methanol to separate, pulverize, wash, and dry, and the infrared absorption spectrum of the obtained polyimide was measured. Absorption of typical imides was recognized at ^-1 and 1783 cm ^-1 .

<Example 5>

In a reaction vessel equipped with a stirrer, a reflux cooler, and a nitrogen inlet, 2.59 g (0.024) of paraphenylenediamine as diamine, 1.45 g (0.000858 mol) of bis (3-aminopropyl) tetramethyldisiloxane, and 3, 0.03 g (0.00015 mole) of 3 ', 4,4'-tetraaminodiphenyl is added to 147.33 g of N-methyl-2-pyrrolidone (NMP) and dissolved at 15 ° C., followed by ethylene glycol bis (anhydro 12.3 g (0.03 mol) of trimellitate was added thereto, followed by vigorous stirring in a nitrogen atmosphere for 5 hours to synthesize polyamic acid.

50 ml of toluene and 3.0 g of p-toluenesulfonic acid were added to the obtained polyamic acid, and it heated at 190 degreeC, and the imidation reaction was performed for 6 hours, separating water with progress of reaction. Then, a polyimide in a powder state was obtained by subjecting the precipitate obtained by injecting the polyimide polymer solution into methanol to separate, pulverize, wash, and dry, and the infrared absorption spectrum of the obtained polyimide was measured. The absorption of typical imides was recognized at ^-1 and 1783 cm ^-1 .

Comparative Example 3

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 8.76 g (0.03 mol) of 1,3-bis (4-aminophenoxy) benzene as diamine is first substituted with N-methyl-2-pyrrolidone (NMP). 198.81 g of solvent was dissolved at 15 ° C., and then, 13.33 g (0.03 mol) of (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added thereto, followed by vigorous stirring for 5 hours in a nitrogen atmosphere. Was synthesized.

50 ml of toluene and 3.0 g of p-toluenesulfonic acid were added to the obtained polyamic acid, and the mixture was heated to 190 ° C, and imidization reaction was performed for 6 hours while separating water as the reaction proceeded. Then, a polyimide in a powder state was obtained by subjecting the precipitate obtained by injecting the polyimide polymer solution into methanol to separate, pulverize, wash, and dry, and the infrared absorption spectrum of the obtained polyimide was measured. The absorption of typical imides was recognized at ^-1 and 1783 cm ^-1 .

Comparative Example 4

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 12.3 g (0.03 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as diamine is first substituted with N-methyl-2-pi. It was added to 216.81 g of a solvent of Ralidone (NMP) and dissolved at 15 DEG C, followed by 9.33 g (0.021 mol) of (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate) 2.46 g (0.009 mol) was added thereto, followed by vigorous stirring for 5 hours in a nitrogen atmosphere to synthesize polyamic acid.

50 ml of toluene and 3.0 g of p-toluenesulfonic acid were added to the obtained polyamic acid, and it heated at 190 degreeC, and the imidation reaction was performed for 6 hours, separating water with progress of reaction. Then, a polyimide in a powder state was obtained by subjecting the precipitate obtained by injecting the polyimide polymer solution into methanol to separate, pulverize, wash, and dry, and the infrared absorption spectrum of the obtained polyimide was measured. Absorption of typical imides was recognized at ^-1 and 1783 cm ^-1 .

Comparative Example 5

In a reaction vessel equipped with a stirrer, a reflux cooler, and a nitrogen inlet, 2.59 g (0.024 mol) of paraphenylenediamine and 2.21 g (0.006 mol) of 4,4-bis (4-aminophenoxy) biphenyl are first used as diamines. N-methyl-2-pyrrolidone (NMP) was added to a solvent of 156.69 g and dissolved at 15 ° C., followed by 4.00 g (0.009 mol) of (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, ethylene glycol bis (Anhydro trimellitate) 8.61 g (0.021 mol) was added thereto, followed by vigorous stirring for 5 hours in a nitrogen atmosphere to synthesize polyamic acid.

50 ml of toluene and 3.0 g of p-toluenesulfonic acid were added to the obtained polyamic acid, and it heated at 190 degreeC, and the imidation reaction was performed for 6 hours, separating water with progress of reaction. Then, a polyimide in a powder state was obtained by subjecting the precipitate obtained by injecting the polyimide polymer solution into methanol to separate, pulverize, wash, and dry, and the infrared absorption spectrum of the obtained polyimide was measured. Absorption of typical imides was recognized at ^-1 and 1783 cm ^-1 .

The relative viscosity of the polyamic acids obtained in Examples 3 to 5 and Comparative Examples 3 to 5 (diluted polyamic acid to 0.05% by weight in N, N-dimethylacetamide) is shown in Table 2, respectively.

After dissolving the polyimide obtained in Examples 3 to 5 and Comparative Examples 3 to 5 in a solid content of 15% by weight in NMP, the polyimide solutions were applied using a knife coater, respectively, and then 80 ° C. × 60 minutes in a vacuum dryer. After drying to remove the solvent, the film was removed from the glass plate, and then dried again for 150 ° C. × 5 minutes, 200 ° C. × 5 minutes, and 300 ° C. × 10 minutes to prepare 50 μm thick polyimide films.

In order to evaluate the heat resistance of the polyimide films, the 5% pyrolysis temperature was measured and shown in Table 2, respectively. The glass transition temperature and the elastic modulus were measured using DMTA (Dynamic Mechanical Thermal Analysis), and the results are shown in Table 2, respectively.

Polyimide solutions were applied on a 50 μm thick Upilex-SGA polyimide film using a knife coater, and then dried at 100 ° C. for 5 minutes, 130 ° C. for 5 minutes, 150 ° C. for 5 minutes, and 200 ° C. for 5 minutes, respectively. After removing the solvent, and finally dried at 300 ℃ for 10 minutes to prepare an adhesive tape of a thickness 20㎛ polyimide adhesive layer. The tapes were adhered onto copper plate, nickel iron alloy plate, and PIK-3000 solution (Hitachi Chemical) coated plate at 400 ℃ under pressure of 5㎏ / ㎠, and then T-Peel tested at a speed of 50mm / min at room temperature. The evaluated adhesive strength is shown in Table 2 below.

As confirmed in the above examples and comparative examples, the polyamic acid and the polyimide according to the present invention have excellent adhesive strength and high temperature stability while maintaining heat resistance and mechanical properties, and are very useful when used for high temperature adhesive adhesives such as semiconductor assembly. Do.

Claims (5)

Diamine comprising at least one or more tetracarboxylic dianhydrides, at least one or more aromatic diamines, and at least one or more siloxane structures represented by the following general formula (I); A method for producing a polyamic acid, which is prepared by reacting a polyamino compound represented by the formula (III). [Formula I]

(In the formula (I), R4 is an alkylene group having 1 to 20 carbon atoms, n 'is an integer of 1 to 20) [Formula II]

[Formula III]

(In the above formula (II) and formula (III), A1 is selected from the following structures,

A2 is selected from the following structures,

n1 is an integer from 0 to 4, n2 is an integer from 0 to 3, x represents an acid, q represents the number of bases of the acid, in the structural formula of A1 or A2, R is -O-, -CH _2- , -CO-, or -SO _2- , where n3 represents 0 or 1. Diamine comprising at least one or more tetracarboxylic dianhydrides, at least one or more aromatic diamines, and at least one or more siloxane structures represented by formula (I), and at least one or more formulas (II) Or a polyamic acid produced by reacting a polyamino compound represented by the formula (III) by thermal imidization or chemical imidization. [Formula I]

(In the formula (I), R4 is an alkylene group having 1 to 20 carbon atoms, n 'is an integer of 1 to 20) [Formula II]

[Formula III]

(In the above formula (II) and formula (III), A1 is selected from the following structures,

A2 is selected from the following structures,

n1 is an integer from 0 to 4, n2 is an integer from 0 to 3, x represents an acid, q represents the number of bases of the acid, in the structural formula of A1 or A2, R is -O-, -CH _2- , -CO-, or -SO _2- , where n3 represents 0 or 1. The method of producing polyimide according to claim 2, wherein the thermal imidation is performed at a high temperature of 250 to 500 ° C. The diamine compound according to claim 1, wherein each component participating in the polyamic acid production reaction comprises a siloxane structure represented by 10-100 moles of an aromatic diamine and a siloxane structure represented by formula (I) with respect to 100 moles of tetracarboxylic dianhydride. A process for producing a polyamic acid characterized in that it is used in the range of -90 moles and 0.01-20 moles of the polyamino compound represented by formula (II) or formula (III). 3. The diamine compound according to claim 2, wherein each component participating in the polyimide production reaction comprises 10-100 moles of an aromatic diamine with respect to 100 moles of tetracarboxylic dianhydride and a siloxane structure represented by the formula (I). A process for producing a polyimide characterized in that it is used in 90 moles and 0.01-20 moles of a polyamino compound represented by formula (II) or formula (III).