TWI254058B - Method for the preparation of polyamic acid and polyimide - Google Patents

Abstract

Disclosed is a method for preparing polyamic acid and polyimide of three-dimensional molecular. The polymers are superior in adhesive strength and high-temperature stability while maintaining their inherent thermal resistance and mechanical properties, and thus can be effectively used as an adhesive material for high temperature adhesive tape suitable for semiconductor assembly. The polyamic acid is prepared by reacting at least one tetracarboxylic dianhydride, at least one aromatic diamine, at least one diamine with a siloxane structure, represented by the following general formula I, and at least one polyamino compound represented by the following general formula II or III.

Description

A7 1!) Ministry of Economic Affairs, Central Bureau of Standards, Staff Consumption 2, Co., Ltd. Printed 1254058 B7__ _ V. Inventive Note (/ ) 发明 Field of the Invention The present invention relates to the preparation of a poly-t-acid, ie, a precursor of poly-imine, which is excellent The high-temperature bonding property of high temperature resistance and the method for preparing polyimine from the polyamine, in particular, a method for preparing a tertiary molecular structure of poly-t-acid and poly-i-imine. BACKGROUND OF THE INVENTION - A general polyimide is a poly-t-acid obtained by reacting a dianhydride with a diamine in an organic solvent via thermal or chemical means, that is, an imine of a pre-polyamine imine. Prepared by chemical. Various types of polyimine resins are widely used in electrical and electronic products, adhesives, composite materials, fiber and film industries due to their excellent heat resistance, acid resistance, electrical insulation and mechanical properties. Polyimine, by virtue of its linear backbone structure, allows high-density encapsulation of the chemical chain, plus the rigidity of the quinone ring itself, which exhibits ultra-high heat resistance. In particular, it is used in applications where high temperature stability is required. For example, polyimine in the production of film has a linear backbone structure, which allows the polymer chain to have a high packing density. The heat resistance of the polyimide is largely dependent on this. structure. Commercially available polyimine films, such as Kaptoii and Upilex, generally show such structures. Kapton is known to be prepared using pyromellitic dianhydride (PMDA) and oxydiphenylamine (ODA) monomers, while UpUex can be used from 3,3M, 4'.carboxybiphenyl dianhydride (BPDA) and zhonglian Preparation of phenylenediamine (PPD) monomers. Regardless of how it is modified, the thermal resistance of the linear structures is still within the heat resistance range of conventional poly-synthesis films. Increasing the molecular weight of the poly-Simine film in order to improve the thermal properties deteriorates mechanical properties such as elasticity. The industry is trying to improve the thermal resistance of poly-imine. For example, Japanese Patent No. 63-254131 incorporates PPD into a polySimine structure such as Kapton prepared from PMDA and ODA. However, the content of ^PPD is higher, resulting in the result that the film is found to have poor mechanical strength. In addition, -3 paper sizes apply to the Chinese National Standard (CNS) A4 specification (210X297 mm)

1254058 A7 B7 Ministry of Economic Affairs Central Bureau of Standards staff consumption cooperation 衽 printing 5, invention description () /) also found that only increase the heat resistance while not damaging the mechanical properties. U.S. Patent No. 5,231,162 discloses another technique for overcoming the problems of polyimine structures in which triamines or tetraamines are introduced into aromatic diamines with the goal of converting linear structures into three dimensions by gelation. Molecular structure, thereby improving the properties of the Nobel and mechanical properties. When only an aromatic tetracarboxylic acid dianhydride and an aromatic diamine were used, the result was that insufficient elasticity was found in the film. In addition, gelation causes a decrease in the solubility of polyamic acid and polyamethylene, which deteriorates the processability of the resin. The needle is polyencephalic acid or polyimine which is used as a bonding material, and its viscous system at a high temperature adheres to the flowability at the temperatures. The introduction of diethyl ether into the main chain of the polymer lowers the glass transition temperature, so that the temperature can be improved, but the thermal resistance is lowered at the same time, and the reliability of the process using the adhesive is poor. The use of thermoplastic adhesives containing two or more ether groups introduced into three or four aniline rings is disclosed in U.S. Patent Nos. 4,847,349 and 5,406,124. These adhesives show an improvement in high temperature flowability, but have the disadvantage of lower thermal resistance. SUMMARY OF THE INVENTION It is an object of the present invention to overcome the aforementioned problems encountered in various prior art, and to provide a method for preparing a polyanthracene acid and a polylimine, both of which have a three-dimensional molecular structure. In order to greatly improve the high-temperature flowability and simultaneously generate the inherent thermal resistance and mechanical properties of the polymer, the polymers are suitable for use in heat-resistant adhesive films and high-temperature adhesives. According to the present invention, the foregoing object can be attained by providing a process for preparing a polyantamic acid and a polys-imine which consists of a reaction comprising a mixture of the following formulas, the mixture containing more than one tetracarboxylic acid. A mercapto dianhydride, one or more aromatic diamines, and one or more diamines having a oxime structure. [Molecular Formula] --4 (Please read the notes on the back and fill out this page)

This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1254058 A7 B7 V. Invention description (, 3) CH3 CH, I 3 I 3 -R4——Si—fO~Si-trr~R4-I I n CH, CH, (I) wherein R 4 is an alkene group having 0 to 20 carbon atoms; and M is a number of from 1 to 20 recurring individuals; and - or more is represented by the following formula or molecular formula Poly-amplifier compound H2N\ / A1 -NH2 n1/qX h2n (II) [Molecular formula] [Molecular formula] H2NN /NH2 A2 n2/qX / \ h2n nh2_ (III) Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs A1 is selected from a group containing the following formula

Χτ^Ό7

Xr(R)n3 Όχ (Please read the notes on the back and fill out this page)

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X mm) 1254058 A7 B7 V. Description of invention ($) VIII. It is selected from the group containing the following formula:

Xr(R)n3<X wherein R represents -0 -, -CH2 -, -CO - or -S〇2 - ; ni means an integer from 〇 to 4; X represents an acid and q represents the cardinality of the acid. DETAILED DESCRIPTION OF THE INVENTION For physical properties including thermal resistance, mechanical properties, adhesion properties, and the like, a oxime structure utilizing a diamine and an amine compound such as a tri- or tetra-amino amine are used together with the aromatic used. Diamine The advantages of preparing a polyimine linear molecular structure with a three-dimensional molecular structure of a polyanthracene and a polyamine. The desired poly-proline or polyggg amine properties can be obtained based on the content of the multifunctional amine group.

In the standard example, the compound E ^ acid dianhydride is referred to as the following general formula 肆 compound: 5 Printed by the Ministry of Economic Affairs, Central Bureau of Standards

[Molecular formula 肆] wherein R1 represents -〇-, - C0 ·, -S〇2 -C(CF3)2, monoalkenyl, mono-dicarboxyalkenyl, monophenylene '-tenphenylene or monoene Phenyl; in the case of n5+n6=2, Μ is 0 or 1; n5 is 0 or 1 and n6 is a tetracarboxylic acid dianhydride of a ruthenium or an aromatic group. A specific example of a general formula 包括 benzene dianhydride , 3,3M,4,-benzophenonetetracarboxylic dianhydride, 3,3M,4\biphenyltetracarboxylic dianhydride, 2,3,,3M,-biphenyltetracarboxylic dianhydride, 2,2,6 , 6'-biphenyltetracarboxylic dianhydride, -6 (please read the notes on the back and fill out this page)

Ping - Inspection 3⁄4 Gong 1254058 A7 B7 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Printing 5, invention description (5) 2,3,6,7-tetracarboxylic dianhydride, 1,2,5,6- ear benzene Carboxylic dianhydride, 2,2-bis(3,4-dicarboxybenzene) diethyl ether dianhydride, bis(3,4-dicarboxybenzene) stone dianhydride, bis(3,4-dicarboxyphenyl) diethyl ether dianhydride , 3,4,9,10-tetracarboxylic dianhydride, biphenyl-1,2,4,5-tetracarboxylic dianhydride, biphenyl-1,4,5,8-tetracarboxylic dianhydride, benzene-:1 2,3,4-tetracarboxylic dianhydride, and ethylene glycol bis(anhydrous-triphenylhexacarboxylate). These compounds can be used singly or in combination. In addition to the above-mentioned aromatic tetracarboxylic dianhydride, an aliphatic or alicyclic tetracarboxylic dianhydride structure may be used in the range in which the thermal resistance is not deteriorated in the synthesis of the polyamic acid or the poly-s-imine. . Examples of such aliphatic or alicyclic tetracarboxylic dianhydride structures include 5-(2,5-bisdioxytetrahydro)-3-methyl-3-cyclohexa-1,2-dicarboxylic dianhydride , 4-(2,5-dioxotetrahydropyran-311)-tetrachloro-1,2-dicarboxylic dianhydride, bicyclo(2,2,2)-7,-2,3,5,6-tetra The carboxylic dianhydride is 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and these compounds may be used singly or in combination. The aromatic diamines which can be used in the present invention include 3,3f-diaminodiphenyl, 3,4'-diaminodiphenyl, 4,4f-diaminodiphenyl, 3,3 diamine diphenyl. Methane, 3屮 diamine diphenylmethane, 4,4′-diamine diphenylmethane, 2,2-(3,3f-diamine diphenyl)propane, 2,2-(3,4匕Diamine diphenyl)propane, 2,2-(3,3'-diaminediphenyl)hexachloropropane, 2,2-(3,-diaminediphenyl)hexachloropropane, 2,2- (4,V-diaminediphenyl)hexachloropropane, 3,3f-oxydiphenylamine, 3,4)oxydiphenylamine, 4,f-oxydiphenylamine, 3,3Λ-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3~diaminomonophenylsulfide, 3,4,-diaminodiphenylsulfide, 4,4'-diaminobiphenylite, 1, 3-bis[Η3-aminophenylhydrazine-methylamine]benzene, 1, each bis[1-(4-aminophenyl)-1-methylamine]benzene, 1,4-bis[Η3-amine benzoquinone-methylamine Benzene, hydrazine-bis[Η4-aminophenylhydrazine-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)diphenylethyl ether, 3,3f- Bis(4-Aminephenoxy)diphenylethyl ether, 3屮-bis(3-aminophenoxy)]diphenylethyl ether, 3,4'-bis(4-aminobenzene Diphenylethyl ether, 4,4 bis(3-aminophenoxy)diphenylethyl ether, 4,4^bis(4-aminophenoxy)diphenylethyl ether, 3,3^bis(3-aminobenzene Oxy)diphenyl, 3,3f-bis(4-aminophenoxy)diphenyl, 3,4f-bis(3--7

This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1254058 C 1 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Print A7 B7 V. Inventions (b) Amine phenoxy) Diphenyl '3,4 ~Bis(4-Aminephenoxy)diphenyl, 4,4f-bis(3-aminophenoxy)diphenyl, 4,4f-bis(4-aminephenoxy)diphenyl, 2,2-double [4-(3-Aminephenoxy)benzene] stone, 2,2-bis[4-(4-aminophenoxy)benzene] stone, 2,2-bis[3-(aminophenoxy) Benzo)propane, 2,2-bis[4-(3-aminophenoxy)benzene]propane, 2,2-bis[4-(44-phenoxy)benzene]propane, 2,2-double [3-(3-Aminephenoxy)benzene] hexachloropropyl, 2,2-bis[4-(4-armenoxy)], /, H, 9,9-bis (3- Amine benzene) oxygen, 9,9-bis(4-aminophenyl)fluoro, 3,3'-dimethyl-4,4-diamine benzene, 2,2^ bis(trifluoromethyl-benzidine, l, 2 - phenylenediamine, U_phenylenediamine, and 1,4-phenylenediamine. The foregoing may be used singly or in combination of two or more. Examples of the multifunctional polyamine compound represented by the general formula 贰 and the reference are as follows; 3f A4f - tetraaminodiphenyl ether, 3,3M, 4'-tetraaminotoluene diethyl ether, 3,3M, f-tetraaminodiphenylmethane, 3,3M, f-tetramine Ketone, 3,3',4,4,-tetraaminobiphenyl wind, 3,3,4,4,-tetraaminodiphenyl, i,2,4,5-tetraaminobenzene, 3 , 3/4-triaminodiphenylmethane, 3,3,4-triaminobiphenylite, 3,3M-triaminodiphenyl, U4-triaminobenzene, and the above compounds Bis, tri- and tetra-acids such as 3,3,f 4,4f-tetraaminodiphenylether tetrahydrogen chloride, 3,3/4,4f-tetraaminodiphenylmethanetetrahydrochloride, 3,3/4 , 4^tetraaminobenzophenone tetrahydrogen chloride, 3,3/4,-tetraaminobiphenylite tetrahydrogen chloride, 3,3/4,4f-tetraaminodiphenyltetrahydrochloride, 1,2, 4,5-tetraaminobenzene tetrahydrogen chloride, 3,3M-triaminodiphenyltrihydrochloride, 3,3f,4-triaminodiphenylmethane trihydrogen, 3,3/4-triaminodiphenyl Ketone hydrogen trichloride, 3,3/4-triaminodiphenyl-trihydrogen chloride, 3,3/4-triaminodiphenyltrihydrogen chloride, and 1,2,4-triaminobenzene dihydrogen dichloride. These compounds They can be used singly or in combination with each other. The oxime structure represented by the general formula 壹 can be obtained by bis(□-aminopropyl)tetramethyl dioxin (GAPD, n=l), bis(□-aminopropyl) Polydimethyl dioxane (PSX-4, n=4) and bis(□-aminopropyl Polydimethyl dioxane (PSX-8, n=8) is exemplified, and these compounds can be used singly or in combination. In the present invention, it is used to complement the gel formation to form a polymethylene three-dimensional network. The elasticity of the molecular structure is not - 8 This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page)

1254058 A7 B7 Ministry of Economic Affairs, Central Bureau of Standards, Employees, Consumer Cooperation, Printing, Printing, V. Inventive Note (rj) / Foot Diamine oxime structure is to prevent the mechanical properties of the three-dimensional molecular structure of poly-II imine from deteriorating. In addition to the elasticity imparted to the rigid structure of the polyimine, the decane structure also helps the solvent to dissolve to increase the content of each reactant in the solvent. Where the polymer is used as a bonding material, the dioxane structure of the diamine can also simultaneously improve the bonding properties in different substrates, especially in the field of electronics, such as germanium wafers, insulating layers on wafers, lead pads. and many more. The solvent used for the synthesis of polydiimine from aromatic tetracarboxylic dianhydride and diamine is a polar solvent which is inert to protons, such as methyl group, 2-acridine (NMP), N,N-dimethyl group. Indoleamine (DMF), hydrazine, hydrazine-dimethylacetamide (DMAC), dimethyl (DMSO), tetrahydrofuran, hexamethylphosphonium, 1,3-dimethyl-2-imidazole Pyridine, with phenol solvents such as phenol, cresol, xylenol, and hydrazine-chlorophenol. If necessary, a solvent such as diethylene glycol or dimethyl ether can be used, and an aromatic solvent such as benzene, toluene or xylene can be used for the supply of the polyimine from the aromatic tetracarboxylic dianhydride. The diamine is used for synthesis. Further usable solvents are butanone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetone, methanol, ethanol, isopropyl Alcohol, methylene dichloride, chloroform, trichloroethylene and nitrogen benzene. These solvents can be used singly or as a mixture. The thermal S imine process, which is generally a synthesis of polystimine, consists of a poly-I1 acid solution coated with a precursor of SI imine, and the coating apparatus is composed of a heat treatment. To this end, the precursor poly-s-acid is prepared first. One or more tetracarboxylic dianhydrides of the general formula 、, one or more aromatic diamines, one or more diamine oxirane structures represented by the general formula 以及, and at least one of the three according to the general formula 贰 or 参Or the tetraamine is reacted in a nitrogen pressure at a temperature not exceeding 100 ° C to obtain a precursor polyanhydride. It is best to continue the reaction for ten hours'. It would be better if it could continue for another five hours. The conversion of the poly-t-acid to the acid imine can be accomplished by coating the poly-sialic acid and heating it to 250 ° C to 500 ° C. In order to enhance the imidization during the drying process, the tetrakisamine, trimethylamine and tetrabutylamine can be used as the acridine (please read the back of the page and fill out this page)

The book paper scale is applicable to China National Standard (CNS) A4 specification (2(1)X297 mm) 1254058 A7 B7 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Printing 5, invention description (厶) and isonitrogen, as acetic anhydride dianhydride, propionic acid An acidic dianhydride of dianhydride and phthalic anhydride, a dehydration and ring shut-off agent, and/or a ring-closing catalyst can be added to the polyamic acid solution. As previously mentioned, the poly-t-acid can be converted into The poly-imine completes the chemical SI imidization process. The polyamicimide obtained from the tetracarboxylic acid-2-dianhydride acid and the diamine is soluble in an organic solvent, and the polyamine solution obtained from the reactants is added to the selected from the group consisting of tributylamine. a catalyst selected from the group consisting of triethylamine, triphenyl phosphite, iso-nitrogen and acridine or a dehydration catalyst such as p-toluenesulfonic acid (addition amount is 25 by weight based on the total reaction weight) The river uses a temperature higher than 10 CTC, if necessary, more than 18 ° C straight 勧 to provide polyimine. The alternative is to put the tetracarboxylic acid-2- dianhydride and diamine in an organic solution at low The reaction is carried out at a lake [to provide a poly-t-acid, and then the poly-sialic acid is added from room temperature to 10 ° C, and an acid dianhydride, such as acetic anhydride dianhydride, The acid dianhydride and the acid dianhydride of phthalic anhydride, as well as the carbon di-imine compound, the dehydration ring closure agent of dicyclohexacarbodiamine, such as sputum, isoniazid, carnation forest and top three The ring-closing catalyst such as an amine receives a ring closure effect. The mole number of the dehydration ring closure agent and the ring closure catalyst is two to eight times that of the tetracarboxylic acid-2-dianhydride acid. In the synthesis of poly-i imine, better results can be obtained by using the appropriate amount of each component. For example, the aromatic diamine is preferably added in an amount of 10 to 100 moles based on 100 moles of the carboxylic acid dianhydride. Preferably, it is preferably between 60 and 100 moles 5. The diamine addition D having a decane structure is preferably between 0.1 and 90 moles, preferably between 0.1 and 40 moles. Between the ranges of the number, the polytamine compound is preferably added in an amount of from 0.01 to 2 moles, preferably from 0. 01 to 7 moles. Further, the tetracarboxylic acid used to participate in the reaction The dianhydride and the amine compound should meet the following equivalent conditions '· 0.95 □ TCDA equivalent / total amine equivalent □ 丄, 05 : 〇 (TCDA : tetracarboxylic dianhydride) — 10 This paper scale applies to the Chinese National Standard (CNS) A4 Specifications (2!0X297 mm)

1254058 The Central Bureau of Standards of the Ministry of Economic Affairs, the Consumer Cooperative, printed A7 B7. V. INSTRUCTION (q) Therefore, the polyimine prepared according to the present invention has excellent electrical insulation and thermal resistance, and can be applied to an adhesive tape for electronic parts. The tape can conduct electricity even at high temperatures because of its hot melt bonding force. Most of the tape used for electronic parts is formed by the semiconductor assembly along the lead frame and its surroundings, such as lead pins, semiconductor wafer device pads, heat sinks, semiconductor wafers, etc., and can also be used to require a thin The enamel film forms a high bond strength, such as a flexible printed circuit board (FPC) structural base layer and a double layer tape for automatic tape bonding (TAB). The tape used for the electronic parts has tape for fixing the lead frame, tape for bonding the lead frame to the semiconductor, and tape for use in the lead pad. Basically, these tapes must have good workability when pasting, and ensure good stability and semiconductor package reliability during subsequent semiconductor assembly processes after pasting. The polymethyleneimine adhesive can also be prepared by coating the polydiimine of the present invention on one or both sides of a base film. In this case, a solution using a polymethylene imide adhesive is applied to one or both sides of the base film, and the coating thickness is generally the dry film thickness of the final adhesive layer between 1 and 5 μm, preferably at 5 to Between 50μιπ. The base film should include a heat-resistant resin film, such as a polyimide film, a polyethylene film, a fluorine-based film and a comprehensive heat-resistant film, a blister glass cloth, and a photo-imide glass cloth, among which It is especially preferable to use a surface imine film. The thickness 5 of the heat resistant film is preferably between 5 and 150 μm. Especially for LOC special tapes, the thickness of polyimine is generally between 25 and dumb. In order to add minerals | the leg of the face will be the face of the face, will be on the dirty dirt, corona or chemical agents such as stone. At the same time, the base film can also be treated with a sulfhydryl release agent to produce a layer containing only a polymethyleneimine. Fiber vine, lit-feeding _ biliary brewing between 1 and 200 qing.面 Amino acid or surface imine prepared according to the present invention can be used as a material for a heat-resistant film by virtue of excellent heat resistance and mechanical strength. 11 11 paper scale applicable to China National Standard (CNS) A4 specification (210X 297 mm)

1254058 DAP Department of Central Bureau of Standards Staff Consumer Cooperatives printed f- A7 _______ B7 V. Inventions (f) The following examples can be used to understand the invention, but the examples are for illustrative purposes only. This constitutes a limitation on the practice of the invention. Example 1 - In a reaction tank equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 173.07 g of N-methyl-2-acridine (NMP) as a solvent, 7.01 g (0.024 mol) was first introduced. I,-bis(4-aminophenoxy)diphenyl, 1.45 g (0.00585 mol) of bis(3-aminepropanol)tetramethyldioxane and 〇.〇3 g (0.00015 mol) of 3, 3\4,4'-tetraaminediphenylethyl ether was dissolved at 15 Torr, followed by the addition of 74 g (0.03 mol) of 3,3/4,4, cardiobiphenite tetracarboxylic dianhydride. The resulting reaction solution was placed in a nitrogen atmosphere and vigorously stirred for five hours to obtain a polyamic acid. > Example 2 was first introduced into a reaction tank equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube containing 193.59 g of N-methyl-2-acridine (NMP) as a solvent. 〇24 moles of 2,2' bis(4-aminophenoxy)phenyl] stone, 1.45 g (0.00585 mol) of bis(3-aminepropanol)tetramethyldioxane and 〇.〇 3 g (0.00015 mol) of 3,3r,4,4f-tetraamine diphenyl ether and dissolved at 15 ° C, followed by the addition of 9.66 g (0.03 mol) of 3,3/4,4,-diphenyl 3 ketone tetracarboxylic dianhydride. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain a polyamide. Comparative Example 1 was equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 175.5 g of hydrazine methyl acridine (ΝΜΡ). In the reaction tank as a solvent, 8.76 g (〇·〇3 mol) of 1,3, bis(4-aminophenoxy)diphenyl was first introduced into the tank 3 and dissolved, and then 10.74 g (〇·〇) was added. 3 moles of 3,3/4,4, _diphenyl; g wind tetracarboxylic dianhydride. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain a polyanhydride. —12 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm)

1254058 A7 B7 C 1 Ministry of Economic Affairs, Central Bureau of Standards, Staff Consumer Cooperatives, Printing 5, Inventions (c) Comparative Example 2, equipped with a mixer, a reflux condenser, and a nitrogen inlet tube containing 199.62 g of N-methyl oxime In the reaction tank containing pyridine (NMP) as a solvent, 12.96 g (0.03 mol) of 2,2-bis[winter (4-aminophenoxy)phenyl: 1 stone wind was first introduced and dissolved at 15 ° C, followed by addition. 16.76 g (0.021 mol) of 3,3/4,4,-benzene-tetracarboxylic dianhydride and 246 g (0.009 mol) of ethylene glycol bis(anhydrous hexaphenylate). The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain polyamic acid. The relative viscosity measurements of the poly-proline acids prepared in Examples 1 and 2 and in Comparative Examples 1 and 2 (polyamic acid has been dissolved in NN-dimethylacetic acid at a concentration of 0.05 by weight). Amine), the results obtained are listed in Table 1 below. Using the coating knife, the four kinds of poly-anthraquinone lacquers obtained in the foregoing examples and comparative examples were separately coated on a glass plate, and dried in a vacuum dryer at 80 ° C for 60 minutes to produce glue. membrane. After peeling off the film from the glass plate, it was dried at 150 ° C for five minutes, dried at 200 ° C for five minutes, and finally placed at 300 ° C for one hour of hot polyimine to provide 50 μm thick poly駆5 amine film. The polyimine found in the IR spectrum read the adsorption peak of the typical imine group at 1718 cm·11783 cm·1. > Next, a 5% weight loss temperature was measured in the air to examine the thermal resistance of the polysimide films. The glass transition temperature and storage modulus of the polyacrylamide films were measured according to the Dynamic Mechanical Thermal Analysis (DMTA) extension method and the results are shown in Table 1 below. The above four kinds of polyglycolamine paints are applied to the Upilex-S film by a coating knife, and should be placed at 8 ° C, 110 ° C, 150 ° (: and 200 ° (: after drying for 10 minutes). Conductive imidization at 300 ° C for one hour to produce tape, each tape has a 2 _ thick] adhesive layer. After bonding at a pressure of 10 kg / cm 2 and 400 ° C to a coated copper plate, nickel-iron alloy After the board and a PIX-3000 (Hitachi Chemical Co., Ltd.), the T-peel strength test was carried out on the tape at a pull rate of 50 mm per minute at room temperature. 13 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm).

1254058 A7 B7 V. Description of invention (\ > ). The results are shown in Table 1 below. Table - an example relative Tg 5% weight f storage modulus activity intensity (kg / cm) Item number viscosity (C) ί shell temperature 25 ° C 230 〇 C copper nickel iron PIX-3000 1.21 255 501 L3xl 〇 10 l. OxlO10 1.30 1.40 1.35 _一Π5 249 502~ 1.3χ1〇10 9·〇χ109 1.35 1.50 1.45 Compare a 1.02 252 518 1·3χ1〇10 7.3 χΙΟ8 0.65 0.60 0.20 Compare two L03 251 490 — 1.3χ1〇10 4.3χ1〇8 0.60 0.554 0.40 (Please read the notes on the back and fill out this page)

Example 3 was first introduced into a reaction tank equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 38 g of N-methyl-2-acridine (NMP) as a solvent. , l,4-bis(4-aminophenoxy)benzene, gram (0.00585 moles) of bis(3-aminepropanol)tetramethyldioxane, and 〇·〇3 g (0.00015 mol) of 3 3,4,4'-tetraaminediphenylethyl ether was dissolved at 15 ° C, followed by the addition of 13.33 g (0.03 mol) of (3/k dicarboxybenzene) hexachloropropane dianhydride. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain a poly-t-acid. The polyamic acid was heated at 190 ° C by adding 50 ml of toluene and 3.0 g of p-toluenesulfonic acid. Then, the imidation was carried out for six hours while removing the humidity-dependent reaction process from the reaction. . The polystimrite solution was then added to methanol for precipitation. The formed precipitate was isolated, honed and dried to obtain a polyduramine powder. A typical imine group adsorption peak was read from 1718 cm1 and 1783 cm·1 in the IR spectrum of the polyunsenine. 4 The paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1 Ding Jingchu Central Bureau of Standards Member X Consumer Cooperative Printed 1254058 A7 B7 Printed by the Central Bureau of Standards of the Department of Consumers and Consumers Co., Ltd. (I).) Example 4: Introduce 9.84 g in a reaction tank equipped with a stirrer, a reflux condenser, and a gas-introducing tube containing 221.85 g of N-methyl-2-acridine (NMP) as a solvent. (0.024 mol) of Z2[4-(4-aminophenoxy)benzene]propane, 1.45 g (0.00585 mol) of bis(3-aminopropanol)tetramethyldioxane and 〇·〇3 g ( 0.00015 moles of > 3,3'4,4f-tetraaminediphenylethyl ether and dissolved at 15 ° C, followed by the addition of 13.33 g of Φ.03 moles of (3,4-dicarboxybenzene) hexachloropropane dianhydride . The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain a polyamic acid. The polyantamic acid was heated at 190 ° C by adding 50 ml of toluene and 3.0 g of p-toluenesulfonic acid, and then subjected to a six-hour diamine reaction while removing the humidity-dependent reaction process from the reaction. . The polyimide solution was then added to methanol for cleavage. The formed educts were isolated, honed and dried to obtain a polyimide powder. A typical imine group adsorption peak was read from the IR spectrum of the polyimine at 1783 cm·1. Example 5: In a reaction tank equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube containing M7.33 g of N-methyl-2-3 acridine (NMP) as a solvent, 2.59 g (先·对24Molecular p-phenylene diamine, 1.45 g (0.00585 mol) of bis(3-aminopropanol) tetramethyldioxaxan and 0.03 g (0.00015 mol) of 3,3f,4,4f-four Amine-phenylethyl ether and 丨5. (: Dissolved, followed by the addition of 12.3 g (0.03 mol) of ethylene glycol bis(anhydrous hexaphenylate). The reaction solution was placed in a nitrogen atmosphere and stirred vigorously. The polyglycolic acid is obtained in an hour after the addition of 5 ml of toluene and 3.00 p-toluenesulfonic acid, followed by heating in the (9) core, followed by shifting the reaction from the reaction during the wet-dependent reaction. The acid imine effect was simultaneously carried out for six hours, and then the polyimide solution was added to methanol for precipitation. The formed precipitate was isolated, honed and dried to obtain a polyimide powder. —15 (Please read the notes on the back and fill out this page.

Sold out This paper scale applies to China National Standard (CNS) Λ4 specification (210x 297 mm) 1254058 A7 B7 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Printed V. Invention Description "X) K spectra from these poly-imines A typical imine group adsorption peak was read at 17 and 1783 cm:i. Comparative Example 3 was first introduced into a reaction tank equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 198.81 g of N-methyl-2--, acridine (NMP) as a solvent. 0_03 moles of 1,3-bis(4-aminophenoxy)benzene was dissolved at 15 °C. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain a polyanhydride. The polyanhydride was heated at 190 ° C by adding 50 ml of toluene and 3.0 g of p-toluenesulfonic acid, followed by six hours of t-imine while removing the humidity-dependent reaction from the reaction. effect. The polyimide solution was then added to methanol for precipitation. The formed precipitate was isolated, honed and dried to obtain a polyimide powder. A typical imine group adsorption peak was read from the IR spectra of the polyIIimine at 1718 cm·1 and 17830^1. Comparative Example 4: 12.3 g (0.03 mol) was first introduced into a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 216.81 g of N-methyl-2-acridine (NMP) as a solvent. 2,2[4-(4-Aminophenoxy)phenyl]propane 5 and dissolved at 15 ° C, followed by the addition of 9.33 g (0.021 mol) of (3,4-dicarboxybenzene) hexachloropropane dianhydride 2.46 g (0.009 mol) of ethylene glycol bis(anhydrous hexaphenylate). The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain a poly-fluoric acid. The poly-SS acid was placed on wot:heated by adding 50 ml of toluene and 3.0 g of p-toluenesulfonic acid, followed by a six-hour g-imine effect while removing the humidity-dependent reaction from the reaction. The polyimide solution was then added to methanol for precipitation. The formed precipitate was isolated, honed and dried to obtain a polyimide powder. A typical imine group adsorption -16 was read from the IR spectra of these poly-imine at 1718 cm_1 and 1783 cm1 (please read the notes on the back and fill out this page)

_· ·- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1254058 Printed by the Central Bureau of Standards and Consumers of the Department of Drops A7 _____________ B7 V. Invention Description (丨/f) Peak. Comparative Example 5 First introduced into a reaction tank equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 156.69 g of N-methyl-2-acridine (NMP) as a solvent, first introduced 2.59 g (0,024 Mo If) The p-phenylenediamine and 2.21 g (α〇〇6 mol) of 4,4-bis(4-aminophenoxy)dibenzo were dissolved in I5t, followed by the addition of 4.00 g (0.0009 Moss (3,4) -dicarboxybenzene)hexachloropropane dianhydride and 8.61 g (0.021 mol) of ethylene glycol bis(anhydrous hexaphenylate). The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain polysamine. The poly-an acid was heated at 190 ° C by adding 50 ml of toluene and 3.0 g of p-toluenesulfonic acid, and then subjected to a six-hour acid acid while removing the humidity-dependent reaction process from the reaction. Amine action. The polyS |imine solution is then added to methanol for precipitation. The formed precipitate is isolated, honed and dried to obtain a polyimide powder. IR from the poly-imine Typical imine group adsorption peaks were read at 1718 cm'1 and 1783cn^ in the spectrum. For Examples 3 to 5 and in Comparative Examples 3 to 5 The relative viscosity measurement of the poly-an acid prepared in the test (polyrian acid has been dissolved in NN-dimethylacetic acid in a concentration of 0. 05 by weight, and the results are listed in the following table) Using a coating knife, the five kinds of polyamic acid enamel paints obtained in the foregoing examples and comparative examples were separately coated on a glass plate, and dried in a vacuum dryer at 80 ° C for sixty minutes. The film is produced. The film is peeled off the glass plate, and then placed on 15 (TC dry for five minutes, dried at 200 ° C for five minutes, and finally placed at 300 ° C - one hour of heat polymerization with both imines A 50 μm thick polyimine film was provided. The polyimine seen in the IR spectrum, 3 was read at 1718 OT 11783 (the adsorption peak of the typical imine group was read at ^1. Then it was measured in the air 5 % weight loss temperature to test the thermal resistance of the polyimide film. According to the dynamic machine - 17 I paper size is suitable for China National Standard (CNS) A4 specification (2ϋ_7 mm)

1254058 A7 B7 V. INTRODUCTION uw) Mechanical thermal analysis (DMTA) extension method, measuring the glass transition temperature and storage modulus of these polySiimine films and the results are shown in Table 2 below. The above five kinds of polyamidoxime paints are coated on Uph-S film by coating knife, and should be placed at KXTC, 1.30Ϊ:, 150°C and 20 respectively (TC is dried for 5 minutes and then placed at 300 °C for heat. Imine for ten minutes to produce tape, each tape has a 20μηι thick layer of adhesive. After bonding to a coated copper plate, nickel-iron alloy plate and a PIX-3000 at a pressure of 5kg/cm2 and 40 (TC) (Hitachi After the chemical company, the T-peel strength test was carried out on the tape at a pull rate of 50 mm per minute at room temperature. The results are shown in Table 2 below. (Please read the notes on the back and fill out this page.

Printed by the Central Bureau of Standards of the Ministry of Finance - Consumers' Cooperatives Example Relative Tg 5% by weight; Storage Modulus Active Strength (kg/cm) Item No. Viscosity ΓΟ Damage Temperature 25V 230. . Copper-nickel-iron PIX-3000 Three U3 245 501 1.3χ1010 LOxlO10 130 L40 1.35 Four 1.17 249 502 1.2χ1010 9.〇χ1010 1.35 1.50 L45 Five 1.33 252 495 1.2χ1010 Ι.ΟχΙΟ9 1.10 1.20 1.20 Comparison three 1.12 248 518 1.3 χΙΟ10 7.3 χ108 0.65 0.60 0.20 Comparative four 1.08 246 495 1.2χ1010 43 χ10δ 0.60 0.55 0.40 Comparative five 1.31 235 492 1.2χ1010 8·3χ108 0.50 0.4 0.10 In addition to the data obtained according to the foregoing examples and comparative examples, the polyfluorene prepared according to the present invention Amines Acids and poly-Simides have excellent bonding strength and high temperature stability, and can maintain their original thermal resistance and mechanical properties, so they can be effectively used as adhesive materials for high-temperature adhesive tapes for semiconductor assembly. —18 The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1254058 A7 B7 V. Inventive Note) The present invention has been described in the drawings, in which the proper nouns used are intended to comply with the description. It is not intended to limit the content of the invention. Many variations and modifications of the present invention are possible in light of the foregoing teachings. Therefore, the invention may be practiced otherwise than as specified in the scope of the appended claims. (Please read the notes on the back and fill out this page)

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Claims (1)

1254058 8 8 8 8 ABCD VI. Patent Application 1. A method for preparing poly-proline, which comprises reacting a mixture comprising: one or more tetracarboxylic acid dianhydrides having a structure such as a molecular formula Nothing N5 [Molecular formula 肆] wherein h represents -0---C0---S〇2-C(CF3)2, monoalkenyl, mono-dicarboxyalkenyl, monophenylene, monophenylene or a woman Diphenyl; under the condition of n5 + n6 = 2, n4 is 〇 or 丨: the heart is ^ or 丨 and "is ^ or more than one aromatic diamine; the above diamine having a monooxane structure The structure is as shown in the formula: CH3 I , -Si 9^3 -13 ιϋ· mi- -f «II iB3 ^s— -SC33 n uaedyi -I (please read the notes on the back and fill out this page) Ordered by the Ministry of Economic Affairs, Central Bureau of Standards, Staff Consumer Cooperatives, 0-f 十|^4—CH3 CH3n, [Molecular Formula] wherein R 4 is an olefin group containing 1 - 2 carbon precursors; and η, is a pull 1 to 20 0 number of recurring individuals; and more than one compound rich in the following formula: or "sub-parameters" of the poly-glyph g. This paper scale applies to the Chinese National Standard (CNS) Λ 4 specifications (210X29^^· 1254 〇58 κ, application patent scope ABCD Η?Ν A1—ΝΗ2 nl/qX η2ν [Molecular formula 贰] Η2Ν\ /ΝΗ2 A H2N NH2 n2/qX (Please read the notes on the back and fill in this 10 again? Printed by the Central Bureau of Standards and Staff Consumer Cooperatives of the Ministry of Economic Affairs [Molecular Formula Wherein A 1 is selected from the group consisting of the following formula: (R) n 3 -(R) n 3 2 is selected from the group consisting of the following formula: (Κ)η3~;::::^:ΧΝχν^ wherein the formula A The R in 1 and A 2 is selected from the following: 〇-, 2-, -co- or -s〇2-; n-system means an integer from 4 to 4; n2 means 〇 to 3 Integer; χ represents an acid and q represents the _, and based on 100 moles of tetracarboxylic acid dianhydride, the paper wave scale applies the Chinese National Standard (CNS) specification (210X297 mm) g 1254058 AS B8 C8 D8 patent application The aromatic diamine is used in an amount of 10 to 100 moles, and the diamine having the structure of the oxy-oxygen is represented by the general formula 壹, and the amount is from 0.1 to 90 moles. The amount of the polyamide compound represented by the formula is 〇·〇1 to 20 moles. One for preparing the polyimine. The method comprises the steps of reacting a mixture, the mixture comprising: 2. showing: more than one tetracarboxylic acid dianhydride having a structure such as a molecular formula of 0 || "? Ί II Λ V II II 0_ηβ J n5 in m amhjl n" 0α -RS (please read the note on the back and fill out this page) Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs [Molecular Formula] Its ": On behalf of '〇-, , -, -S〇2-C(CF3)2, alkenyl, mono-dicarboxyalkenyl, -phenylene|, one-supported or mono-diphenyl; under the condition of n5 + n6 = 2 14 Is 〇 or 1; n5 is _ and n (is 0 or 1. More than one aromatic diamine; the above diamine having a oxy-oxygen structure, the structure of which is as shown 壹 子 分 中 Λ Λ Λ s s s s s s s Λ 家 家 家 家 家 家 家 家 家 家 家 家 家 家 家 家 家 家 家 家 家 家 家 ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ η 订 -. 1254058 AS 38 C8 D8 The number of patents ranging from 1 to 20 recurring individuals; and more than one polyamine compound represented by the following formula 分子 or molecular formula: H ^ N a \ A1 - NH2 nl/qX [Molecular formula] H2N\ /NH2/\ H2N nh2 n2/qX [Molecular formula] wherein A1 is selected from the group consisting of the following formula: (R)n3 (Please read the back of the note first. ) 订 c , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , - 03⁄4 -, - C0 - or - S〇2 - one of them; nl means an integer from 0 to 4; n2 means an integer from 0 to 3; This paper scale applies to China National Standard (CNS) Λ4 specification (210x297 mm I# 1254058 cofferdam - t t' ABCD x represents an acid and q represents the base of the acid to provide the polyamic acid and is thermally or chemically The polyamic acid is imidized and is based on 1 mole of tetracarboxylic acid dianhydride. The aromatic diamine is used in an amount of 10 to 100 moles, which is represented by a general molecular formula φ. The diamine having a decane structure has an amount of from 1 to 90 moles, and the polyamine compound is used in an amount of from 0.01 to 20 mol% depending on the molecular formula or the reference. ·-1 m · 1 had HTfa 1—d 11 « (Please read the notes on the back and fill out this page.) 订 轻 轻 济 济 Η Η Η Η Η Η Η Η Η Η Η Η China National Standard (CNS) Α4 Specifications (210X297 mm) 5