KR100418545B1 - Polyimide high temperature adhesive and adhesive tape using the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide adhesive having excellent heat resistance and high temperature adhesive properties, and an adhesive tape using the same. In particular, the present invention has excellent physical properties such as high temperature stability and adhesive strength, and thus is applied as an adhesive tape for semiconductor peripheral materials such as lead frames and semiconductor chips. This relates to possible high heat resistant adhesives and adhesive tapes.

The present invention discloses a polyimide high heat-resistant adhesive containing a polyamic acid represented by the formula (1) or a polyimide represented by the formula (6), and an adhesive tape in which an adhesive layer is formed on a base film using the adhesive. It has excellent flowability, heat resistance, and high temperature adhesive properties, so that it is possible to improve the reliability when used in semiconductor packages and the like during high temperature processes.

Description

Polyimide high temperature adhesive and adhesive tape using the same

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide adhesive and an adhesive tape having excellent heat resistance and high temperature adhesive properties. In particular, the present invention is excellent in high temperature stability, adhesive strength, and electrical insulation properties, and is applied as an adhesive tape for semiconductor peripheral materials such as lead frames and semiconductor chips. This relates to possible adhesives and adhesive tapes.

Polyimides obtained from tetracarboxylic dianhydrides and diamines have been widely used in fields requiring excellent high temperature stability due to their excellent heat resistance. In particular, it is excellent in mechanical properties, dimensional stability, electrical insulation, chemical resistance, etc. as well as heat resistance properties, and is widely used in electrical and electronic materials, aerospace, transportation machinery, etc. have.

While general polyimide is excellent in heat resistance, high temperature flowability is not good for high temperature adhesive applications, and heat resistance generally falls when increasing high temperature flowability.

In particular, the structure of the polyimide used for excellent heat resistance such as film depends on the packing density between the chains according to the linear structure of the main chain, and the heat resistance property is determined. In the case of commercially used Kapton and Upilex films, An example of a structure is shown. However, these polyimides have the same high temperature stability as thermosetting resins and thus lack the high temperature flowability required for adhesive applications.

On the other hand, meltable polyimides for adhesive applications have a lower glass transition temperature and lower heat resistance than conventional polyimides. Therefore, polyimide of melt flow characteristics is low in high temperature stability and shows high coefficient of thermal expansion.

In general, polyimide adhesives having high-temperature melting and adhesive properties are thermoplastic polyimides, and dianhydrides or diamines have two or more phenyl rings, and acer groups or the like are introduced between the phenyl rings to lower heat resistance, thereby reducing molecular movement at high temperatures. By having a high temperature flow property to have a high temperature adhesive properties. However, the glass transition temperature is lowered, the heat resistance is lowered, the high temperature stability is not secured, in particular, there is a problem in that it is not secured in the high temperature process of semiconductor assembly applications.

Polyimide adhesives and adhesive tapes for semiconductor package applications require melt flow during high temperature processes and wettability characteristics during adhesion processes on substrates such as semiconductor chips, protective films on semiconductor chips, or leadframes. In addition, after the bonding process, not only excellent adhesion properties but also high temperature stability for semiconductor package reliability during high temperature processes such as wire bonding and epoxy molding are required.

In general, the insulating adhesive tape is also bonded under high temperature processing conditions of 500 ° C. or less and 10 seconds or less, and should have adhesion with various semiconductor package materials. In addition, the insulating adhesive tape should not contaminate the surface on the leadframe and the semiconductor chip during the wire bonding process. The adhesive insulating tape should have heat resistance during the wire bonding process so that slight movement of the lead does not occur. When the lead moves, the wire adhesive force is lowered and electrical reliability cannot be secured.

The present invention has been made to solve the above problems, that is, the polyimide adhesive which can improve the reliability in the semiconductor package during high temperature process, such as excellent melt flow resistance, heat resistance and high temperature adhesive properties and this It is to provide an adhesive tape used.

The present invention relates to a high heat resistant adhesive containing a polyamic acid having a structure such as the following formula (1) which is a precursor of polyimide.

[Formula 1]

In the formula, R3 has the following structure.

In the above formula, R represents a tetravalent organic group, R1 represents a divalent organic group, and R2 represents a trivalent or tetravalent organic group. R3 represents a divalent organic group containing a siloxane structure, R4 is an alkylene group having 0 to 20 carbon atoms, and n 'represents a repeating unit number; And l, m, and n represent the number of moles of the repeating unit. l / (m + n) is a value between 99.985 / 0.0151 and 80/15 mole fraction, and m / (l + n) is a value between 1/2000 and 1/500 mole fraction.

The present invention also includes a polyamic acid ester in which the carboxylic group of the polyamic acid is esterified, and a polyimide obtained by condensation of the polyamic acid or polyamic acid ester of Formula 1 to remove water or alcoholol. .

The polyamic acid of Chemical Formula 1 of the present invention is obtained by reacting an amino group including tri or tetraamine with dianhydride in an organic solvent.

Polyamic acid, the polyimide precursor of the present invention, is obtained from the following chemicals.

(Iii) dianhydride of the formula (2) structure;

[Formula 2]

Wherein R is an aliphatic radical consisting of two or more carbons, a cyclo aliphatic radical, a monoaromatic radical, a radical consisting of two or more condensed aromatics, two or more uncondensed aromatics in which aromatic radicals are linked or bonded by crosslinking It is a tetravalent radical selected from the group, such as a radical consisting of. Examples of the tetravalent radical group R include those having the following structure.

(Ii) diamines of the following formula (3) structure;

[Formula 3]

Wherein R 1 is an aliphatic radical consisting of two or more carbons, a cyclo aliphatic radical, a monoaromatic radical, a radical consisting of two or more condensed aromatics, or two or more uncondensed aromatics in which aromatic radicals are linked or bonded by crosslinking Bivalent radicals selected from the group consisting of radicals and the like. Examples of the divalent radical group R1 include those having the following structure.

(Iii) triamine or tetraamine having the following formula (4) structure;

[Formula 4]

Wherein R 2 is an aliphatic radical consisting of two or more carbons, a cyclo aliphatic radical, a monoaromatic radical, a radical consisting of two or more condensed aromatics, two or more uncondensed aromatics in which aromatic radicals are linked or bonded by crosslinking Trivalent or tetravalent radical selected from the group such as a radical consisting of. Examples of the trivalent or tetravalent radical group R2 include those having the following structure.

(Iii) a siloxane compound having the structure of Formula 5 below;

[Formula 5]

In the formula, R4 represents an alkylene group having 0 to 20 carbon atoms, and n 'represents the number of repeating units.

Examples that can be used as anhydrides in the present invention are pyromellitic dianhydrides, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl Acid dianhydride, 2,3,3'4'-biphenyltetracarboxylic dianhydride, 2,2 ', 6,6'-biphenyltetracarboxylic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic 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) dian hydride, 3,4,9,10-perylenetetracarboxylic dianhydride, naphthalene-1,2 , 4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracar Acid dianhydride, ethylene glycol bis (anhydro trimellitate) and the like, and these compounds may be used alone or in combination of at least 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 tenercarboxylic acid dianhydride and the like, and these compounds may be used alone or in combination of two or more thereof.

As diamines used by this invention, the following are mentioned specifically ,.

3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 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) hexa Fluoropropane, 2,2- (4,4'-diaminodiphenyl) hexafluoropropane, 3,3'-oxydianiline, 3,4'-oxydianiline, 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-aminophenyl) -1-methylamine) benzene, 1,4-bis [1- (4-aminophenyl) -1-methyl-ace ) 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) diphenylether, 3,4'-bis (3-aminophenoxy) di Phenyl ether, 3,4'-bis (4-aminophenoxy) diphenyl ether, 4,4'-bis (3-aminophenoxy) diphenyl ether, 4,4'-bis (4-aminophenoxy) diphenyl ether , 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-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] Ropane, 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] hexa Fluoropropane, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2 , 2'-bis (trifluoromethyl) benzidine, 2,2-bis [4- (4-amino-2-trifluoro-phenoxy) phenyl] hexafluoropropane, 1,2-phenylenediamine , 1,3-phenylenediamine, 1,4-phenylenediamine, and the like, and these compounds may be used alone or in combination of two or more kinds.

As trivalent or tetravalent aminos used by this invention, specifically,

3,3 ', 4,4'-tetraaminodiphenyl iscer, 3,3', 4,4'-tetraaminodiphenylmethane, 3,3 ', 4,4'-tetraaminobenzophenone, 3,3 ', 4,4'-tetraaminodiphenyl sulfone, 3,3', 4,4'-tetraaminobiphenyl, 1,2,4,5-tetraaminobenzene, 3,3 ', 4-triaminodi Phenyl, 3,3 ', 4-triaminodiphenylmethane, 3,3', 4-triaminobenzophenone, 3,3 ', 4-triaminodiphenylsulfone, 3,3', 4-triaminodibi 3,3 ', 4,4'-tetraaminodiphenyl iscer tetrahydrochloride which is a mono-, di-, tri- or tetra-acid salt of the above compounds with phenyl, 1,2,4-triaminobenzene and the like , 3,3 ', 4,4'-tetraaminodiphenylmethane tetrahydrochloride, 3,3', 4,4'-tetraaminobenzophenone tetrahydrochloride, 3,3 ', 4,4'-tetraamino Diphenyl sulfone tetrahydrochloride, 3,3 ', 4,4'-tetraaminobiphenyl tetrahydrochloride, 1,2,4,5-tetraaminobenzene te Lahydrochloride, 3,3 ', 4-thiaminoaminodiphenyl trihydrochloride, 3,3', 4-triaminodiphenylmethane trihydrochloride, 3,3 ', 4-triaminobenzophenone trihydrochloride, 3,3 ', 4-triaminodiphenylsulfone trihydrochloride, 3,3', 4-triaminodibiphenyl trihydrochloride, 1,2,4-triaminobenzene dihydrochloride, and the like. Polyamino compounds can be used 1 type or in mixture of 2 or more types.

In the case of using a compound of the above trivalent or tetravalent polyfunctional polyamino compound that is not in the form of a salt additive, the rate of gelation during the reaction is reduced, so that the rate of gelation is controlled when forming a three-dimensional network structure. The ratio can be adjusted with the compound containing the salt additive form.

As a diamine containing the siloxane group used by this invention, specifically,

Bis (γ-aminopropyl) tetramethyldisiloxane (GAPD, n = 1), bis (γ-aminopropyl) polydimethyldisiloxane (PSX-4, n = 4), bis (γ-aminopropyl) polydimethyldi Siloxane (PSX-8, n = 8), etc., The diamine containing these siloxane structures 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 shortcoming of the lack of flexibility of the polymer according to the three-dimensional network molecular structure due to gelation, thereby reducing the mechanical properties of the three-dimensional polyimide It serves to prevent, and can increase the content of the solvent solubility to increase the content of the reactant to the organic solvent during the polymerization of the polyamic acid, or is advantageous in providing the solvent soluble properties to the polyimide. In addition, it may serve to increase the adhesive strength with various substrates when used for the adhesive. In particular, when applied to electronic materials, etc., there is an effect of improving the adhesion characteristics with substrates such as silicon chips, chip insulating films, and lead frames.

Diamine, triamine, or tetraamine whose functional group is used as a raw material for the production of polyimide may be polymerized using an isocyanate compound in which the functional group is an isocyanate group instead of the functional amine. In tetraamines, what substituted "amine" with "isocyanate" is mentioned.

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- Phenol solvents such as chlorophenol and the like. If necessary, ether solvents such as diethylene glycol and dimethyl ether, aromatic solvents such as benzene, toluene, and xylene are used. In addition, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, Solvents such as diglyme, methylcellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, trichloroethylene, nitrobenzene and tertiary amines such as pyridine can also be used. It is also possible to use one or more of the above solvents simultaneously.

In the case of the thermal imidization method, which is a general polymerization method of polyimide, first, the polyamic acid, which is a precursor, is polymerized, and then the solution is coated and heated to thermally imidize. The first step of the polymerization is poly, which is a precursor of polyimide. A process for preparing amic acid according to the appropriate molecular weight and relative viscosity of the polyamic acid at least one or more of the tetracarboxylic dianhydride and diamine in the temperature range of -10 ℃ to 100 ℃ of the diamine containing a siloxane structure At least 1 sort (s) or more, tri or tetraamine is thrown in, and it reacts at 100 degrees C or less by vigorous stirring in a solvent in nitrogen atmosphere, and manufactures the polyamic acid which is a precursor of a polyimide. The reaction time is preferably 10 hours or less, particularly preferably 5 hours or less.

When using a triamine, the ratio of "mole number of triamine / mole number of dianhydride" which is mole ratio with respect to dianhydride of a triamine is preferable in the range of 0.7 / 1.5-1.3 / 1.5, and 1.0 / 1.5 is more preferable. When using tetraamine, the ratio of "mole number of tetraamine / mole number of dianhydride" which is a molar ratio with respect to dianhydride of tetraamine is preferable in the range of 0.7 / 2.0-1.3 / 2.0, and 1.0 / 2.0 is more preferable.

The present invention also relates to an adhesive in which a polyimide represented by the following formula (6) obtained by imidating a polyamic acid as a precursor of the polyimide represented by the formula (1) is dissolved in an organic solvent.

[Formula 6]

In Formula 6, R, R ₁ , R ₂ , R ₃ , L, m, and n are the same concept as described in Formula 1.

In Formula 1 and Formula 6, l, m and n represent the number of moles of the repeating unit, l / (m + n) is a mole fraction between 99.985 / 0.0151 and 80/15, and m / (ℓ + n) is the mole fraction. It is a value between 1/2000 and 1/500.

If the value of m / (l + n) is less than 0.005 / 99.985, the crosslinking effect of increasing the thermal stability and reducing the packing density between the polymer chains and increasing the melt flow cannot be obtained, and m / (l + n If the value of) is greater than 2/17, the crosslinking effect is too great, and application to adhesives is difficult.

The adhesive tape developed in the present invention can be obtained by two methods, namely, a polyimide solution (a solution in which polyimide soluble in an organic solvent in Formula 6 is dissolved in an organic solvent) on at least one side of the base film. Coating to dry the solvent at least 250 ℃ or more, or more preferably obtained by removing the residual solvent at least 300 ℃ or more, and a polyamic acid or polyamic acid ester solution which is a precursor of polyimide at least one side of the base film To a solvent to dry and thermally imidize the solvent at least 250 ° C. or more, or more preferably, to remove residual solvent and thermal imidization at least 300 ° C. or more to obtain an adhesive tape having the chemical structure of Chemical Formula 6 above. There is this.

As the insulating substrate film used in the present invention, a film having heat resistance properties capable of withstanding high temperature drying of 250 ° C. or more is used, and commercial films such as the following may be used.

That is, Regulus (product of Mitsui Toatsu Chemicals, Inc.), Kapton H, V, E, K, ZT (product of Dupont Co.), Upilex M, S, SGA, SPA (product of Ube Industries, Ltd., respectively) ), Apical AH, NPI, HP (manufactured by Kanegafuchi Chemical Industry Co., Ltd.), or Aramica (manufactured by Asahi Chemical Industry Co., Ltd.), among others such as Upilex S, SGA, Polyimide films with low coefficients of thermal expansion such as Kapton E, and Apical HP are advantageous.

The thickness of the base film is not particularly limited, but is used in the range of 1 to 200 μm, more preferably in the range of 3 to 75 μm. In addition, the thickness of the entire tape is not particularly limited, but a range of 5 to 200 m is used, more preferably 10 to 100 m.

In order to increase the adhesive force between the base film and the adhesive layer, it is preferable to perform plasma or corona treatment on the surface of the base film.

The adhesive of the present invention has a glass transition temperature in the range of 135 to 280 ° C, an elastic modulus of 1010 to 1011 dyne / cm2 at 25 ° C, and an elastic modulus of 102 to 109 dyne around 150 to 300 ° C near the wire bonding temperature. / cm2 range.

When the glass transition temperature is lower than 135 ° C. or the elastic modulus at the wire bonding temperature is lower than 102 dyne / cm 2, problems such as the internal lead moving during the wire bonding process occur.

If the glass transition temperature is higher than 280 ° C or the elastic modulus at the wire bonding temperature is higher than 1010 dyne / cm2, the adhesion temperature during the high temperature bonding process of the lead or chip is too high and the adhesion time is too long. Will occur.

1% or less of the residual solvent in an adhesive agent is preferable, and the state in which the imidation of an adhesive agent fully advanced is preferable. In the case where the residual solvent of the adhesive is 1% or more or the imidization is not sufficiently progressed, bubbles are generated by water or alcohols, which are condensates during residual solvent or imidization, in a high temperature bonding process of 270 ° C. or more. It can also lead to contamination of the leadframe and chip surface.

The ion impurity content of sodium, potassium, chlorine, sulfate, and the like of the polyimide adhesive of the present invention is about 1 µg / g when extracted in pure water at 121 ° C. for 24 hours, and the content of such an amount is ionic impurities in the tape. It does not cause corrosion of the electric circuit around the adhesive tape and does not cause a short circuit of the circuit due to the metal transition.

The adhesive layer composed of polyimide in the adhesive tape obtained by the present invention can be obtained by applying a polyimide solution, a polyamide acid solution or a polyamide acid ester solution, or a mixed solution of the above.

Before applying the above solutions onto the base film, the solution may be mixed with inorganic particles except for particles that emit radio waves such as uranium. At this time, the solid content of the particles of the adhesive layer should be at least 50% or more, preferably 75% or more, and more preferably 90% or more.

Although the thickness of an adhesive layer is not limited, The range of adhesive layer thickness is 1-100 micrometers (preferably 3-50 micrometers).

In the coating, a coma, reverse, or die coater may be used. In the form of a drying unit for drying and imidizing the polyimide adhesive solution after coating, in general, a roll carrier form in which a film is moved to a roll and the film is moved may be used to coat one or both sides of the film. In the case of coating on, a floating carrier form in which the film is conveyed without contacting a roll or the like may be used.

In general, the drying conditions vary depending on the thickness of the adhesive layer, the concentration of the adhesive solution, the drying method and the like. For example, when the solid content of the adhesive solution is 25% and the thickness of the adhesive layer after drying is 25μm, the drying step is a drying time of 2 to 30 minutes at 80 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃ can do. In this case, when the final drying temperature is further raised to 300 to 400 ° C., the drying time can be reduced by 10 minutes or more, and it is also advantageous in terms of removing residual solvent and complete imidization of the adhesive layer.

The following examples and comparative examples illustrate the invention in more detail.

<Example 1>

In a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet, 13.851 g (0.0376 mol) of 4,4'-bis (4-aminophenoxy) biphenyl as a diamine, 3,3 ', 4,4'- 0.057 g (0.00027 mol) of tetraaminobiphenyl, 0.497 g of bis (3-aminopropyl) tetramethyldisiloxane

(0.0020 mole) was added to 156.8 g of N, N-dimethylacetamide (DMAc) and dissolved at room temperature, followed by 4.296 g of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride.

(0.012 mole) and 8.686 g (0.028 mole) of 4,4'-oxydiphthalic anhydride were added thereto, and vigorously stirred at room temperature for 20 hours under a nitrogen atmosphere to synthesize polyamic acid. The relative viscosity measured by diluting to 0.05% by weight in, N-dimethylacetamide was 0.85 dl / g.

<Example 2>

In a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet, 13.851 g (0.0376 mol) of 4,4'-bis (4-aminophenoxy) biphenyl as a diamine, 3,3 ', 4,4'- 0.062 g (0.00027 mole) of tetraaminodiphenylsulfide and 0.497 g (0.0020 mole) of bis (3-aminopropyl) tetramethyldisiloxane were added to 158.9 g of N, N-dimethylacetamide (DMAc) and dissolved at room temperature. Into a nitrogen atmosphere, 4.296 g (0.012 mol) of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride and 8.686 g (0.028 mol) of 4,4'-oxydiphthalic anhydride were added thereto. The mixture was stirred vigorously at room temperature for 20 hours to synthesize polyamic acid, and the relative viscosity measured by diluting the polyamic acid to 0.05% by weight in N, N-dimethylacetamide was 0.80 dl / g.

<Example 3>

In a reaction vessel equipped with a stirrer, a reflux cooler, and a nitrogen inlet, 13.851 g (0.0376 mol) of 4,4'-bis (4-aminophenoxy) biphenyl as a diamine, 3,3 ', 4'-triamino 0.043 g (0.00027 mol) of diphenyl isomers and 0.497 g (0.0020 mol) of bis (3-aminopropyl) tetramethyldisiloxane were added to 155.9 g of N, N-dimethylacetamide (DMAc), and these were dissolved at room temperature. 4.296 g (0.012 mol) of 3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride and 8.686 g (0.028 mol) of 4,4'-oxydiphthalic anhydride were added thereto, and the mixture was cooled to room temperature under a nitrogen atmosphere. Polyamic acid was synthesized by vigorous stirring for 20 hours at, and the relative viscosity measured by diluting the polyamic acid to 0.05% by weight in N, N-dimethylacetamide was 0.90 dl / g.

Comparative Example 1

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 14.736 g (0.040 mol) of 4,4'-bis (4-aminophenoxy) biphenyl was first substituted with N, N-dimethylacetamide as a diamine.

(DMAc) was dissolved in 155.9 g and dissolved at room temperature, followed by 4.296 g (0.012 mol) of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride and 4,4'-oxydiphthalic anhydride. 8.686 g (0.028 mol) of lide was added thereto, followed by vigorous stirring at room temperature under a nitrogen atmosphere for 20 hours to synthesize polyamic acid. The polyamic acid was measured by diluting the polyamic acid to 0.05% by weight in N, N-dimethylacetamide. The relative viscosity was 0.70 dl / g.

Comparative Example 2

In a reaction vessel equipped with a stirrer, a reflux cooler, and a nitrogen inlet, 13.262 g (0.0360 mol) of 4,4'-bis (4-aminophenoxy) biphenyl as diamine is used, and 3,3 ', 4,4'- 0.857 g (0.0020 mole) of tetraaminobiphenyl was added to 156.8 g of N, N-dimethylacetamide (DMAc) and dissolved at room temperature, and then 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride. 4.296 g (0.012 mole) of lide and 8.686 g (0.028 mole) of 4,4'-oxydiphthalic anhydride were added thereto, and vigorously stirred at room temperature for 20 hours under a nitrogen atmosphere to synthesize polyamic acid. The relative viscosity measured by diluting the acid to 0.05% by weight in N, N-dimethylacetamide was 1.05 dl / g.

The five polyamic acids of Examples 1 to 3 and Comparative Examples 1 to 2 were coated on a glass plate and on an Upilex-S polyimide film, respectively, and then 80 ° C, 150 ° C and 200 ° C. And, and dried for 1 hour at 300 ℃ each to prepare a polyimide adhesive film and an adhesive tape coated with a polyimide adhesive layer on the Upilex-S. Storage Modulus values were measured according to the glass transition temperature and temperature of the polyimide adhesive film by extension method of Dynamic Mechanicl Thermal Analysis (DMTA), and 5% weight loss temperature was measured in air by TGA (Thermo- Gravimetric Analysis). The adhesive tape composed of polyimide adhesive and Upilex-S was adhered to copper foil, nickel-iron alloy plate and PIX-3000 (Hitachi Chemical Co.) coated plate for 1 second at 400 ℃ and 10Kg / cm2, respectively. , The adhesive force between the adhesive tape and the substrate was measured by a T-Peel evaluation of 50mm / min at room temperature, the results obtained in this manner are shown in Table 1 below.

TABLE 1

<Example 4>

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 13.925 g (0.0378 mol) of 4,4'-bis (4-aminophenoxy) biphenyl as a diamine, 3,3 ', 4,4'- 0.029 g (0.0001 mole) of tetraaminobiphenyl and 0.497 g (0.0020 mole) of bis (3-aminopropyl) tetramethyldisiloxane were added to 175.8 g of N-mething-2-pyrrolidone (NMP) and dissolved at room temperature. 3.867 g (0.012 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 12.439 g (0.028 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride ), And vigorously stirred at room temperature for 20 hours under nitrogen atmosphere to synthesize polyamic acid. The relative viscosity measured by diluting polyamic acid to 0.05% by weight in N, N-dimethylacetamide was 0.65dl / g.

Example 5

In a reaction vessel equipped with a stirrer, a reflux cooler, and a nitrogen inlet, 13.925 g (0.0378 mol) of 4,4'-bis (4-aminophenoxy) biphenyl as a diamine, 3,3 ', 4'-triamino 0.031 g (0.00015 mol) diphenylsulfide, 0.497 g bis (3-aminopropyl) tetramethyldisiloxane

(0.0020 mole) was added to 176.7 g of N-mething-2-pyrrolidone (NMP) and dissolved at room temperature, followed by 3.867 g (0.012 g) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride. Mole) and 12.439 g (0.028 mole) of 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride were added thereto, followed by vigorous stirring at room temperature for 20 hours under a nitrogen atmosphere to synthesize polyamic acid. The relative viscosity measured by diluting the polyamic acid to 0.05% by weight in N, N-dimethylacetamide was 0.85 dl / g.

<Example 6>

In a reaction vessel equipped with a stirrer, a reflux cooler, and a nitrogen inlet, 13.925 g (0.0378 mol) of 4,4'-bis (4-aminophenoxy) biphenyl as a diamine, 3,3 ', 4'-triamino 0.021 g (0.00015 mol) of diphenyl and 0.497 g (0.0020 mol) of bis (3-aminopropyl) tetramethyldisiloxane were added to 175.3 g of N-mething-2-pyrrolidone (NMP) and dissolved at room temperature. 3.867 g (0.012 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 12.439 g (0.028 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride Was added, and the mixture was stirred vigorously at room temperature for 20 hours under nitrogen atmosphere to synthesize polyamic acid. The relative viscosity measured by diluting the polyamic acid to 0.05% by weight in N, N-dimethylacetamide was 0.85dl / g. It was.

Comparative Example 3

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 14.736 g (0.04 mol) of 4,4'-bis (4-aminophenoxy) biphenyl was first substituted with N-methyl-2-pyrrolidone as a diamine. NMP) and dissolve them at room temperature in 175.8 g, and then 3.867 g (0.012 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 4,4'-(hexafluoroisopropylidene). 12.439 g (0.028 mol) of diphthalic anhydride was added thereto, followed by vigorous stirring at room temperature under nitrogen atmosphere for 20 hours to synthesize polyamic acid. 0.05% by weight of polyamic acid was added to N, N-dimethylacetamide. The relative viscosity measured by dilution with was 0.55 dl / g.

Comparative Example 4

In a reaction vessel equipped with a stirrer, a reflux cooler, and a nitrogen inlet, 13.262 g (0.0360 mol) of 4,4'-bis (4-aminophenoxy) biphenyl as diamine is used, and 3,3 ', 4,4'- 0.857 g (0.0020 mol) of tetraaminobiphenyl was added to 175.8 g of N-mething-2-pyrrolidone (NMP) and dissolved at room temperature, and then 3,3 ', 4,4'-benzophenonetetracarboxylic diane 3.867 g (0.012 mol) of hydride and 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride were added thereto, followed by vigorous stirring at room temperature for 20 hours under a nitrogen atmosphere. Amic acid was synthesized, and the relative viscosity measured by diluting the polyamic acid to 0.05% by weight in N, N-dimethylacetamide was 0.80 dl / g.

The five polyamic acids of Examples 4 to 6 and Comparative Examples 3 to 4 were coated on a glass plate and on an Upilex-S polyimide film, respectively, followed by 80 ° C, 150 ° C and 200 ° C. And, and dried for 1 hour at 300 ℃ each to prepare a polyimide adhesive film and an adhesive tape coated with a polyimide adhesive layer on the Upilex-S. Storage Modulus values were measured according to the glass transition temperature and temperature of the polyimide adhesive film by extension method of Dynamic Mechanicl Thermal Analysis (DMTA), and 5% weight loss temperature was measured in the air by TGA (Thermo Gravimetric Analysis). The adhesive tape composed of the adhesive and Upilex-S was adhered to copper foil, nickel-iron alloy plate, and PIX-3000 (Hitachi Chemical Co.) coated plate for 1 second at 400 ° C. and 10 Kg / cm 2, respectively. The adhesive force between the adhesive tape and the substrate was measured by T-Peel evaluation of 50mm / min at. The results obtained in this manner are shown in Table 2 below.

TABLE 2

<Example 7>

19.496 g (0.0376 mol), 2,3-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, first as a diamine in a reaction vessel equipped with a stirrer, a reflux cooler and a nitrogen inlet. ,4,

0.057 g (0.0002 mol) of 4'-tetraaminobiphenyl and 0.497 g (0.0020 mol) of bis (3-aminopropyl) tetramethyldisiloxane were added to 186.6 g of N-methyl-2-pyrrolidone (NMP) at room temperature. After dissolving, 7.398 g (0.028 mol) of 5- (2,5-dioxotetrahydro) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride and ethylene glycol bis (an 4.920 g (0.012 mol) of hydro-trimelliate was added thereto, heated to 50 ° C. under nitrogen atmosphere, and vigorously stirred for 3 hours. Then, 37.24 g (0.04 mol) of gamma-picolin was added to the polyamic acid solution. The mixture was stirred at 185 ° C. for 6 hours, and water, which was a condensate produced by imidization, was continuously removed during the reaction. After completion | finish of heating, after cooling a polymerization liquid to normal temperature over 2 hours, after stirring for further 3 hours at normal temperature, reaction was complete | finished. The relative viscosity measured by diluting the polyamide to 0.05% by weight in N, N-dimethylacetamide was 0.45 dl / g.

<Example 8>

19.496 g (0.0376 mol), 2,3-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, first as a diamine in a reaction vessel equipped with a stirrer, a reflux cooler and a nitrogen inlet. ,4,

0.062 g (0.00027 mol) of 4'-triaminophenylsulfide and 0.497 g (0.0020 mol) of bis (3-aminopropyl) tetramethyldisiloxane were added to 186.6 g of N-mething-2-pyrrolidone (NMP) at room temperature. After dissolving, 7.398 g (0.028 mol) of 5- (2,5-dioxotetrahydro) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride and ethylene glycol bis (an 4.920 g (0.012 mol) of hydro-trimelliate was added thereto, heated to 50 ° C. under nitrogen atmosphere, and vigorously stirred for 3 hours. Then, 37.24 g (0.04 mol) of gamma-picolin was added to the polyamic acid solution. The mixture was stirred at 185 ° C. for 6 hours, and water, which was a condensate produced by imidization, was continuously removed during the reaction. After completion | finish of heating, after cooling a polymerization liquid to normal temperature over 2 hours, after stirring for further 3 hours at normal temperature, reaction was complete | finished. The relative viscosity measured by diluting the polyamide to 0.05% by weight in N, N-dimethylacetamide was 0.55 dl / g.

Example 9

19.496 g (0.0376 mol), 2,3-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, first as a diamine in a reaction vessel equipped with a stirrer, a reflux cooler and a nitrogen inlet. ,4'

0.043 g (0.0002 mole) of triaminodiphenyl and 0.497 g (0.0020 mole) of bis (3-aminopropyl) tetramethyldisiloxane were added to 185.3 g of N-mething-2-pyrrolidone (NMP), and these were added at room temperature. After dissolving, 7.398 g (0.028 mol) of 5- (2,5-dioxotetrahydro) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride and ethylene glycol bis (anhydro 4.920 g (0.012 mol) of trimelliate was added thereto, heated to 50 ° C. under nitrogen atmosphere, and vigorously stirred for 3 hours. Then, 37.24 g (0.04 mol) of gamma-picolin was added to the polyamic acid solution. Stirred at 185 ° C. for 6 hours, and water, a condensate resulting from imidization, was continuously removed during the reaction. After completion | finish of heating, after cooling a polymerization liquid to normal temperature over 2 hours, after stirring for further 3 hours at normal temperature, reaction was complete | finished. The relative viscosity measured by diluting the polyamide to 0.05% by weight in N, N-dimethylacetamide was 0.45 dl / g.

Comparative Example 5

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 20.74 g (0.040 mol) of 2,3-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane was added as N-methyl- as a diamine. It was added to 186.6 g of 2-pyrrolidone (NMP) and dissolved at room temperature, followed by 5- (2,5-dioxotetrahydrol) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid. 7.398 g (0.028 mol) of hydride and 4.920 g (0.012 mol) of ethylene glycol bis (anhydro- trimelliate) were added thereto, heated to 50 ° C. under a nitrogen atmosphere, and stirred vigorously for 3 hours. 37.24 g (0.04 mol) of choline was added to the polyamic acid solution and stirred for 6 hours at 185 DEG C. The condensate resulting from the imidization was continuously removed during the reaction. After completion | finish of heating, after cooling a polymerization liquid to normal temperature over 2 hours, after stirring for further 3 hours at normal temperature, reaction was complete | finished. The relative viscosity measured by diluting the polyamide to 0.05% by weight in N, N-dimethylacetamide was 0.35 dl / g.

Comparative Example 6

In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet, 18.666 g (0.0360 mol) of 2,3-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane as a diamine is used. ,4,

0.857 g (0.0020 mol) of 4'-tetraaminodiphenyl was added to 185.3 g of N-methyl-2-pyrrolidone (NMP) and dissolved at room temperature, and then 5- (2,5-dioxotetrahydrol)- 7.398 g (0.028 mole) of 3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride and 4.920 g (0.012 mole) of ethylene glycol bis (anhydro-trimelliate) were added thereto, followed by nitrogen atmosphere. The mixture was heated to 50 ° C. under vigorous stirring for 3 hours, and then 37.24 g (0.04 mol) of gamma-picolin was added to the polyamic acid solution and stirred at 185 ° C. for 6 hours. Water continued to be removed during the reaction. After completion | finish of heating, after cooling a polymerization liquid to normal temperature over 2 hours, after stirring for further 3 hours at normal temperature, reaction was complete | finished. The relative viscosity measured by diluting the polyamide to 0.05% by weight in N, N-dimethylacetamide was 0.65 dl / g.

The five polyimide solutions of Examples 7 to 9 and Comparative Examples 5 to 6 were coated on a glass plate and on an Upilex-S polyimide film, respectively, followed by 80 ° C, 150 ° C and 200 ° C. And 40 minutes of drying at 300 ° C. to prepare a polyimide adhesive film and an adhesive tape coated with a polyimide adhesive layer on Upilex-S. Glass transition of a polyimide adhesive film by extension of DMTA (Dynamic Mechanicl Thermal Analysis) Storage Modulus values were measured according to temperature and temperature, and 5% weight loss temperature was measured in the air by TGA (Thermo Gravimetric Analysis). The adhesive tape composed of polyimide adhesive and Upilex-S was coated with copper foil, nickel-iron alloy plate, After bonding to PIX-3000 (Hitachi Chemical Co.) coated plate for 1 second at 400 ° C and 10Kg / cm2, the adhesive strength between the adhesive tape and the substrate was measured by T-Peel evaluation at 50mm / min at room temperature. Measured, The results thus obtained are shown in Table 3 below.

TABLE 3

As shown in the above examples and comparative examples, the polyimide high heat resistant adhesives and adhesive tapes according to the present invention are excellent in high temperature flowability, heat resistance, and high temperature adhesive properties, thereby improving reliability when used in semiconductor packages during high temperature processes. Usability, etc. can be obtained.

Claims (5)

A polyimide high heat resistant adhesive comprising polyimide represented by the following formula (6). [Formula 6] In the above formula R2 is selected from the following structure, R3 has the following structure, (Wherein R4 is an alkylene group having 1 to 10 carbon atoms and n 'is a repeating unit number of 1 to 20). R is selected from the following structures: R1 is selected from the following structures, l, m and n represent the moles of repeating units, where l / (m + n) is a mole fraction between 99.985 / 0.0151 and 80/15, and m / (l + n) is a mole fraction 1/2000 to 1 /. The value is between 500. 2. The polyimide high heat resistant adhesive according to claim 1, wherein the glass transition temperature of the adhesive is in the range of 135 to 280 캜. (delete) (delete) (delete)