TW508360B - Method for the preparation of polyamic acid and polyimide useful for adhesives - Google Patents

Abstract

Disclosed is a method for preparing polyamic acid and polyimide. Being suitable for use in adhesives or adhesive tapes for electronic parts, the polymers have such three-dimensional molecular structures that a significant improvement can be brought about in solvent solubilization, thermal resistance, mechanical properties, and adhesive properties onto various substrate. 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 bye the following general formula I, and at least one polyamino compound represented by the following general formula II or III. The polyamic acid is converted into polyimide through thermal or chemical imidization.

Description

508360 A7 B7 V. Description of the invention (丨) FIELD OF THE INVENTION The present invention refers to the preparation of a polystyrenic acid, that is, a precursor of polySimine, which has excellent high temperature resistance, and a polydrum made from the polyfxamine. The method of amine 'particularly refers to a method for preparing a three-dimensional polypirancid acid and a polycinimine molecular structure. 5 Background of the Invention In view of the fact that polyimide is a high temperature resistant resin, it is generally obtained by reacting a dianhydride with a diamine in an organic solvent, and then placing the resulting polyammonium acid, that is, the precursor of polyimide. Prepared by thermal or chemical imidization. All kinds of polyimide resins are widely used in electrical and electronic products, adhesives, synthetic materials, fiber and film industry due to their excellent heat resistance, acid and alkali resistance, electrical insulation and mechanical properties. LD polyimide, by virtue of its linear backbone structure nature, allows high-density encapsulation chemical chains' and the rigidity of the fluorene imine ring itself to exhibit ultra-high heat resistance. In particular, it is specially used in occasions requiring high temperature stability. With its linear backbone structure, imine allows high-density encapsulation of the chain, coupled with the rigidity of the imine ring itself, so that polyimide exhibits excellent heat resistance. However, these structural characteristics also make it difficult to dissolve the polyimide in a solvent, and it is also difficult to melt it with heat, making it inferior to other materials in terms of processability and adhesion. L5 is especially for polyimide specifically for applications requiring high temperature stability. For example, it is used in the production of film. It is printed by the staff consumption order of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out) (This page) There is a linear backbone that makes the packing density of the polymer chain very high, which mostly determines the thermal resistance of polyimide. 6 Commercially available polyimide films, such as Kapton and Upilex, for example. Demonstrate those structures. Kapton is known to be prepared using pyromellitic dianhydride (PMDA) and oxydiphenylamine (ODA) monomers, while Upilex can be prepared from 3Y, 4,4 ~ tetracarboxylic biphenyl dianhydride (BPDA) Preparation of phenylenediamine (PPD) monomer. It is also known that a polyIt imine resin with higher thermal resistance can be obtained from the combination of PMDA and PPD monomer 23. However, the excessive rigidity and chain packing density of these polyfluorene S amine resins will have a negative impact on their processability, fluidity, and adhesion properties at high temperatures. This paper size applies Chinese National Standard (CNS) A4 regulations (210X29 *? Public &) 508360 A7 B7 V. Description of the invention (^) In order to improve these problems, many attempts have been made, including the introduction of polar groups into the polymerization The backbone or side chain of the body, introduces a large number of link bases or side chains into the backbone and improves the elasticity of the polymer backbone °

Kurosaki and others, macromolecular amidines, 1994, 22, 1117, proposed improvements to the solubilization of polyimide resins, in which alicyclic acid dianhydride was used as a monomer to prepare a soluble dianhydride coating Loading solution. According to Qin Jin and 5 others, Polymer Chemistry 1993 1993 Edition, II, 2345-2351, which also uses a cyclic diamine to prepare a soluble polySimine. However, most of the soluble polydrumimines modified in these ways are difficult to practically use because they are significantly degraded in thermal stability and mechanical properties. In order to improve the solubilization and adhesion of polyimines, it has been proposed to introduce the diamine compound's siloxane structure into the polymer backbone, as described in US Patent Nos. 5,839,181, 5,942,592, and 5,094,919. . And, regardless of the improvement method described therein, the solubilization properties caused by the introduction of the diamine siloxane structure fall into the range of traditional polyimide film. In addition, the presence of a large number of siloxane structures in the polymer deteriorates the thermal resistance and mechanical properties of the polymer. It is also difficult to introduce a large amount of the siloxane structure into the polymer. Summary of the Invention Please read the 5th item on the back and then 15 the staff of the Central Bureau of Standards of the Ministry of Economic Affairs. Therefore, the purpose of the present invention is to overcome the problems encountered in the prior art and to provide a method for preparing polymer The method of stilbene acid and polyimide enables both to have a three-dimensional molecular structure to greatly improve the solvent solubilization, thermal resistance, mechanical properties and adhesion of various substrates14, making these polymers suitable for electron donors. Use special adhesive or tape for parts. .. According to the present invention, the aforementioned object can be achieved by providing a method for preparing polygallic acid and polyimine. The formulation is composed of a reaction containing a mixture of the following formula one, the mixture containing more than one Tetracarboxylic acid dianhydrides, one or more aromatic diamines, and one or more diamines having a silicon dioxide structure. The paper size of the press is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 508360 Μ B7 V. Description of the invention (3) -R4- CH. 占 丨 一 | CH〇 ~ t〇. 1 n CH0 CH0 -R4 -(I) [Molecular formula one] wherein R4 is a hydrocarbon storage group containing 1-20 carbon atoms; and V is the number of recurrent individuals from 1 to 20; and one or more of the following are represented by the following formula 贰 or formula parameters Alkyl or aromatic cyclohexene diphenylamine (CYCLOHEXYLEDENEDIANILINE):

R (II) (Please read the notes on the back before filling this page)

nh3 10 15 Printed by X Consumers, Central Bureau of Standards, Ministry of Economic Affairs 20 [Molecular Formula 贰] [Molecular Formula Parameters] where R represents or -Cft, -CftCa, -C (CH3MCH2aL), or phenyl. Detailed description of the invention: For the physical properties including thermal resistance, mechanical properties, adhesive properties, etc., the advantages of the linear molecular structure of polyimide can be used. By using the three-dimensional molecular structure of diamine and an alkyl or aromatic Cyclohexene diphenylamine compound, together with traditionally used diamines, is prepared with polyanthionic acid and polyS imine. In the standard example, the tetracarboxylic acid dianhydride that can be used in the present invention refers to compounds of the following general formulas ...

(R1) n4

-5- (IV) This paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 508360 A7 * B7 V. Description of the invention (y) [Liver-style] where R1 stands for --CO-,-S 〇2 '-C (CF3) 2' -alkenyl, a di-residual alkenyl, a phenylene, a phenylene or a diphenyl group; under the condition of n5 + n6 = 2, n4 is 0 Or 1; n5 is 0 or 1 and 116 is 1 or 2. Specific examples of the general formula of aromatic tetracarboxylic acid dianhydrides include benzene dianhydride, 3,3M, 4 ^ diphenyl 5 ketone tetracarboxylic dianhydride, 3,3M, 4 ^ biphenyl dianhydride, 2, 3Ύ V-biphenyltetracarboxylic dianhydride, 2,2 &lt; 6,6 ^ biphenyltetracarboxylic dianhydride, • 2,3,6,7-tetracarboxylic dianhydride, 1,2,5,6 Carboxydianhydride, 2,2-bis (3,4-dicarboxybenzene) ether dianhydride, bis (3,4-dicarboxybenzene) stone dianhydride, bis (3,4-diphenylbenzene) 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, fluorenetetracarboxylic dianhydride 'and ethylene glycol bis (anhydro-triphenylhexacarboxylate). The compounds can be used alone or in combination. In addition to the aforementioned aromatic tetracarboxylic dianhydride, an aliphatic or alicyclic tetracarboxylic dianhydride structure may be used within a range that does not degrade thermal resistance when synthesizing polyhexamic acid or polyimide. . Examples of such aliphatic or cycloaliphatic tetracarboxylic dianhydride structures include 5- (2,5-didioxytetrahydro) formamidine-3-cyclohexane-1,2-dicarboxylic dianhydride, 4 -(2,5-Dioxotetrahydro-3-yl) -tetrachloro-1,2-dicarboxylic dianhydride, bicyclic (2,2,2) -7-en-2,3,5tetracarboxylic The dianhydride is 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and these compounds can be used alone or in combination. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Specific examples of aromatic diamines that can be used in the present invention include 3Y-diamine diphenyl, 3,4, diamine Diphenylbenzene, 4, diaminodiphenyl, 3,3, diaminediphenylmethane, 3, diaminedi.pyridylmethane, 4,4f-diaminediphenylmethane, 2,2 <3, 3 diamine diphenyl) propane, 2,2- (3, -diamine diphenyl) propane, 2,2- (3,3, -diamine diphenyl) hexachloropropane, 2,2- (3,4, -diamine diphenyl) hexachloropropane, 2,2- (4,4 diamine diphenyl) hexachloropropane, 3,3 \ oxydiphenylamine, 2] 3,4,- Oxydiphenylamine, 4,4 ~ oxydiphenylamine, 3,3 ~ diaminodiphenylsulfide, 3,4 ~ diaminodiphenylsulfide, 4,4, -diaminodiphenylsulfide, 3,3 ^ Diaminodiphenylene wind '3, -diaminodiphenylene wind, 4,4, diaminodiphenylene wind, 1,3-bis [1- -6- · This paper size applies to Chinese national standards (〇 \ 5) 8 4 specifications (210, / 297 g) 508360 A7 B7 V. Description of the invention (f) (3-amine is called h methylamine] benzene, i, each bis [H4 · aminebenzene] small methylamine] benzene 1,4-bis [H3-amine is called 1-methylamine] benzene, 1, 'bis [H4 · amine benzyl ] Benzene, 1,3-bis (3-aminephenoxy) benzene ', 3-bis (4-aminephenoxy) benzene, 丨, 4 · bis (3-aminephenoxy) benzene, 1, 4-bis (4-aminephenoxy) benzene '3,3'-bis (3-aminephenoxy) diphenyl ether, 3,3, -bisamidophenoxy) diphenyl ether, 3,4 '-Bis (3-aminephenoxy) diphenyl ether, 3,4, · bis (4-aminephenoxy) diphenyl ether, 4,4, -bis (3-aminephenoxy) monophenylethyl _, 4,4 bis (4-aminophenoxy) diphenyl ether, 3,3, bis (3-aminephenoxy) diphenyl, 3,3, -bis (4-aminephenoxy) Monobenzene, 3,4'-bis (3-aminephenoxy) diphenyl, 3,4f-bis (4-aminephenoxy) diphenyl, 4,4, -bis (3-aminephenoxy) Diphenyl, 4,4'bis (dongaminephenoxy) diphenyl, 2,2-bis [4 · (3-aminephenoxy) benzene] Shifeng, 2,2-bis [4 Luaminephenoxy (Yl) benzene] Shi Feng, 2,2-bis (4-aminephenoxy group C, Yuan, 2,2-bis [4 · (3 · aminophenoxy) glucan, 2,2-bis [4 »(4« S 安 phenoxy) 本] Bingyuan, 2,2-bis [4- (3-fl femalephenoxy) benzene] six episodes of propylene, 2,2_bis [4 »(4_ Aminephenoxy) benzene] Hexafluorene, 3,9- Please read the notice on the back before t

1D 15 Prospective employees of the central government of the Ministry of Economic Affairs, the company printed bis (3-aminebenzenelan, 9,9-bis (4aminephenyl) fluorine, 3,3'-dimethyl-4,4, -diaminebenzene, 2,2, -bis (trifluoromethyl) benzidine, 1,2-phenylenediamine, 1,3-phenylenediamine, and fentanediamine. The foregoing can be used alone or in a mixture of two or more. By general The alkyl or aryl cyclohexene diphenylamine represented by the structural formula 参 or ginseng can be used to provide a large number of pendant groups for backbones after being introduced into the polymer to provide excellent thermal resistance and stomach #base layer. It is represented by the general molecular formula one The siloxane structure can be obtained by bis (γ-aminopropyl) tetramethyldisilazane (GApD, n = 1), bis (γ-aminopropyl) polydimethyldisilazane (psx- 4, n = 4) and bis (γ-aminopropyl) polydimethyldisilazane (PSX-8, n = 8), and these compounds can be used alone or in a mixture ^ Silane is provided by Elasticity gives the rigid structure of polyimide, and plays an important role in improving polymer acids and helping to increase the content of various reactants in organic solvents by solubilizing in solvents. In addition, where polymers are used as Where bonding material is used, diamine silicon The alkane structure can also improve the adhesion properties of different base layers at the same time, especially in the electronics field, such as silicon wafers, insulating layers on wafers, lead holders, etc. It can be used for poly-age 5 amines from aromatic tetracarboxylic dianhydrides. The solvent used for synthesizing with diamine is extremely inert to protons. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 508360 ΑΊ _ B7 The employees of the Central Bureau of Standards of the Ministry of Economic Affairs consume Ar. Explanation of the invention (G) Solvents such as N-methylmorphidine (NMP), n, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), Dimethylmethylene (DMSO), tetrahydrofuran, hexamethylphosphamide, 1,3-dimethyl-2-imidazolidine, and phenol solvents, such as phenol, cresol, ligol, and p-chlorophenol .If necessary, you can use flavor solvents such as diethylene glycol, and dimethyl ether, and aromatic solvents such as benzene'toluene, and xylene can be used for the Anhydride and diamine are used for synthesis. In addition, available solvents include methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, and monoglyme Diethylene glycol dimethyl ether, methyl cellosolve, cellosolve acetone'methanol, ethanol, isopropanol, methylene monochloride, chloroform, trichloroethane and nitrogen benzene. Generally synthesized by poly fximine The hot-imine embedding process consists of coating a polyuretamic acid solution of the imine-precursor and coating it. For this purpose, the pre-curing polyphosphonic acid is prepared first. The amine composition] mixture is placed in a solvent, and the reaction is carried out under a nitrogen pressure of 40 to 10 CTC and vigorously stirred to obtain the precursor polyan acid. It is best to continue the reaction for ten hours. It lasts for more than five hours. By coating the polymandelic acid and heating it to 250. (: To 500 ° C can complete the conversion of polyammonium acid to 5 amines. In order to enhance the imidization during the drying of the coating, tetraylamine, trimethylamine, tetrabutyl Base amines and isonitrogens, such as acetic dianhydride, propanoic acid dianhydride and benzoic anhydride, acid dianhydride, 7JC and ring-blocking agent, and / or a ring-blocking catalyst can be added to the polyhydrazine solution. The premise is that the chemical imidization process can be completed by converting polyphosphinoic acid into polyS imine. The polyimide system obtained from tetracarboxylic dianhydride acid and diamine can be dissolved in a bending machine solvent In the case, the polyfluorene solution obtained from these reactants is added to a catalyst selected from the group consisting of tributylamine, triethylamine, triphenylphosphite, isonitrogen, and pyridine, or the like In the case of methylbenzenesulfonic acid dehydration catalyst (addition amount is 25 parts by weight based on the total reaction weight), a temperature higher than 100 ° C can be used, and if necessary, it should be directly heated above 180 ° C to provide polyimide. ◊ The alternative is to place tetramethylene acid-2-dianhydride acid and diamine in an organic solution at a level below 100 (please read the back first Please note this page before filling in this page) Bing Qing · •---· This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 508360 ΑΊ B7 V. Description of the invention (7). Provide polyanionic acid, and then add the polyamic acid at a temperature from room temperature to 100 ° C to add an acidic dianhydride selected from acid dianhydrides, such as acetic dianhydride, propionic dianhydride and benzoic anhydride. And dehydration ring closure agents such as carbodiimide compounds and dicyclohexahexadicarbodiimide, together with ring closure catalysts such as pyridine, isonitrogen, glycoxaline, and trimethylamine, etc., undergo ring closure. 5 Synthesis For polySimine, better results can be obtained by using the appropriate amount of components. The amount of the diamine compound in the general molecular formula is preferably from 0.1 to 50 moles of the total amount of diamine used. Hundreds of percents. For example, when the amount of diamine used is less than 0.1 mole percent, the solubilization and adhesion properties obtained are poor. On the other hand, if the amount of diamine used exceeds 50 Mole percentage, acid can improve adhesion, but it is difficult to increase polymerization Ίο As for the alkyl or aryl ring 3 ene diphenylamine represented by the general molecular formula 贰 or ginseng, its usage range should preferably be between 0.01 and 40 mole percent of the total amount of diamine used. If it is an alkyl or If the amount of aromatic cyclohexene diphenylamine is less than 0.01 mole percent, the thermal resistance of the polymer can be improved, but the solubilizing effect becomes poor. On the other hand, alkyl or aromatic cyclohexene If the amount of diphenylamine exceeds 40 mole percent, it will lead to an improvement in solubilization, but the thermal resistance of the polymer will be deteriorated and the production cost will be increased. The lead socket and its surroundings, for example, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) pins, semiconductor wafer device pads, heat sinks, semiconductor wafers, etc. At the same time, it can also be used in places where high adhesive strength with thin copper film is required, such as the base layer for flexible printed p-board (FPC) structure and the double-adhesive tape (TAB). Layer of tape. Examples of tapes for use in electronic parts include tapes for fixing lead bases, tapes for bonding lead bases to semiconductors, and tapes for use in lead base mold pads. Basically, all of these tapes must have good workability at the time of bonding, and can ensure good stability during the subsequent semiconductor assembly process after «% bonding, and reliability of semiconductor packaging. This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X297). 508360 Α7 Β7 V. Description of the invention (Please read the notes on the back before filling this page} Especially for semiconductor assembly, adhesive The glue must have a high degree of adhesion during the high-temperature bonding process, and high-temperature stability is required in subsequent processes such as wire bonding and resin molding. Generally, in order to enhance its fluidity and adhesion during the high-temperature bonding process Properties, all made of polyimide will reduce its glass transition temperature and melting temperature. However, the reduction of thermal stability does not guarantee subsequent processes such as wire bonding and resin shaping. Conversely, according to this The three-dimensional molecular structure of the polyimide prepared by the invention shows excellent fluidity at high temperatures without reducing the fluidity at the glass transition temperature. Therefore, after bonding, the adhesiveness of the present invention still retains the adhesiveness. Excellent adhesive properties and thermal stability of the agent, even in subsequent subsequent processes such as wire bonding and resin molding, to ensure the reliability of semiconductor packaging The polyimide of the present invention can also be coated on one or both sides of a base adhesive film to prepare a polyimide adhesive. L] At this point, a solution using a polySS amine adhesive is applied to the base adhesive film. On one or both sides, the thickness of the dry film printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs as the final adhesive polymer layer is between 1 and 150 μm, preferably between 5 and 50 μm. The base film should be heat-resistant Adhesive film, including heat-resistant resin film, such as polyimide film, polyethylene film, fluorine-based film and comprehensive heat-resistant film, such as resin glass cloth, and resin imine glass cloth, etc. Polyamine 5 amine film is particularly preferred. The thickness of the heat-resistant film should be between 5 and 150 μm. Especially for LOC tapes, the thickness of poly 155 amine is generally between 15 and 50 μm. In order to strengthen the polyimide The adhesive strength between the adhesive and the base film will use a slurry, corona, or chemical agent such as Shi Guiyao on the base film. At the same time, the base film can be treated with a silicon-based release agent to produce a An adhesive sheet with a polyamine layer as the adhesive layer. The thickness of this releasable adhesive film is between 1 and 200 μιη. By virtue of excellent heat resistance and mechanical strength, the polyanthionic acid or polyimide prepared according to the present invention can be used as a heat resistant adhesive for 20 The material of the film is used to further understand the present invention through the description of the following examples, but these examples are for illustration only and do not constitute the application of the Chinese National Standard (CNS) A4 specification (210X297) for this paper size 508360 A7 B7 V. Explanation of the invention (?) The limitation of the present invention is limited to f. Example 1 is equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 173.07 g of N-methyl-2-pyridine (NMP) As a solvent, 2.8 g (0.014 mol) of oxydiphenylamine, 4.31 g (0.014 mol) of 5 trimethylcyclohexene diphenylamine, and 1.45 g (0.00585 mol) of bis (3- Aminopropanol) tetramethyldisilazane was dissolved at 15 ° C, followed by the addition of 10.74 g (0.03 moles) of 3,3 / 4, diphenylstone tetracarboxylic dianhydride. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain poly-pianthric acid. Poly-t-amino acid was added to 50 ml of toluene and 3.0 g of p-toluenic acid and heated at 90 ° C., followed by sub-drumming for six hours, and moisture was removed from the reaction solution according to the progress of the reaction. After that, the polyimine solution 3 was added to methanol to precipitate. The formed sinker is isolated, honed and dried to obtain a polydrum imine powder. These polyimines, which are seen in the IR spectrum, read the adsorption peak 値 of a typical imine group at ^ 1801 ^ 17830 ^ 1. Example 2 Consumption of Employees of the Central Standards Bureau of the Ministry of Economic Affairs #Printed by the cooperative (please read the precautions on the back before filling this page) It is equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 173.07 grams of N-A 2.8 g (0.014 mol) of oxydiphenylamine, 4.31 g (0.014 mol) of 5 trimethylcyclohexene diphenylamine, and 1.45 g (0.00585 moles of bis (3-aminepropanol) tetramethyldisilazane and dissolved at 15. ° C, then 6.45 g (0.3 mol) of pyromellitic dianhydride was added, and the resulting reaction solution was placed in a The reaction was stirred vigorously in a nitrogen atmosphere for five hours to obtain polyarsinic acid., Polyarsinic acid was added to 50 ml of toluene and 3.0 g of para-mellitic acid and heated at 190 ° C, followed by six hours of subacidization. And remove the moisture from the reaction solution according to the progress of the reaction. After that, the polyimide solution 0 was added to methanol Shen Wei. The formed precipitate was isolated, honed and dried to obtain polyimide. Powder. These polyimines seen in the IR spectrum can be read at 1718cm · 11783cm · 1. The adsorption peaks of the group. The national standard (CNS) M specifications of this paper (210X297), ~ 508360 A7 B7 V. Description of the invention (, Example 3 is equipped with a stirrer-reflux condenser 'and a A nitrogen introduction tube containing 173.07 g of N-methyl-2-pyridine (NMP) as a solvent was first introduced into 2.8 g (0.014 mol) of oxydiphenylamine and 4.31 g (0.014 mol) of trimethyl Cyclohexene diphenylamine and 1.45 g (0.00585 mol) of bis (3-aminopropanol) tetramethyldisoxaxane and dissolved in 15 process, then add 9.30 g φ · 03 friction of 3,3 / 4, -Oxydiphenylphosphonic dianhydride. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain polytamine. Polydotamic acid was added to 50 ml of toluene and 3.0 g of paratoluene fengfeng acid. And placed at 190 ° C for heating, followed by six hours of sub-dark dagger, and the moisture was removed from the reaction solution according to the progress of the reaction. After that, the polySIimine solution was added to the methanol. The polyimide powder is obtained after the exciter is isolated, honed and dried. The polyimide powders seen in the IR light ψ spectrum, An adsorption peak 値 of a typical imine group was read at 1718〇1 ^ 1783 〇. Example 4 15 A 173.07 g of N-methyl-2- 喏 was equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube. Into a reaction tank in which pyridine (NMP) was used as a solvent, 2.8 g (0.014 mol) of oxydiphenylamine, 4.31 g of ⑽14 mol) of trimethylhexene diphenylamine, and 1.45 g of bis (3) -Aminopropanol) tetramethyldisilazane and dissolved at 15 ° C 'followed by the addition of 10.74 g (0.03 mol) of 3,3,' 4,4'-diphenyltetracarboxylic dianhydride . The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain poly-anionic acid. Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 23 (Please read the precautions on the back before filling out this page) Add polysamine to 50 ml of toluene and 3.0 g of p-toluene succinic acid and heat it, then Perform sub-darkening for / hours, and remove moisture from the reaction solution according to the progress of the reaction. After that, the imine solution was added to the methanol to sink the temple. The formed precipitate was isolated, honed and dried to obtain polyimide powder. These polyimines seen in the Han spectrum were read at 1718cn ^ 1783cm-1 for the adsorption peaks of typical imine groups. Example 5: 2 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) 508360 A7 B7 5. Description of the invention (\ \) One is equipped with a mixer, a reflux condenser, and a A nitrogen introduction tube containing 173.07 g of N-methyl-2-pyridine (NMP) as a solvent was first introduced into 2.8 g (0.014 mol) of oxydiphenylamine and 4.31 g (0.014 mol) of trimethylcyclohexane Diphenylaniline and 1.45 g (0.00585 mol) of bis (3-aminopropanol) tetramethyldisilanes and dissolve at 15 ° C, then 8.82 g (0.03 mol) of 3,3 / 4, -hexa Fluorotetracarboxylic di-field. The resulting reaction solution was placed in a nitrogen atmosphere to vigorously agitate the reaction for five hours to obtain polytyrosine. Polypeng 5 acid was added to 50 ml of toluene and 3.0 g of p-toluene 5-feng acid and heated at 190 ° C, followed by sub-fxization for six hours, and moisture was removed from the reaction solution according to the progress of the reaction. After that, the polyfluorene solution was added to methanol and poured. The formed precipitate is isolated, honed and dried to obtain polyimide powder. In the IR spectra of these polyimines, adsorption peaks 値 of typical imine groups were read at 171801 ^ 17830 ^.六 Example 6 15 In a reaction tank equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 173.07 g of N-methylpyridine (NMP) as a solvent, first introduce 2 · 8 g (0.014 mol) of Oxydiphenylamine, 4.31 g (0.014 mol) of trimethylcyclohexene diphenylamine and 1.45 g (0.00585 mol) of bis (3-aminopropanol) tetramethyldisilazane and dissolve at 15 ° C Then, 0.74 g (<0.03 mole) of 3,3 / 4,4 benzophenone tetracarboxylic dianhydride was added. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain polyacrylic acid. Employees of the Central Bureau of Standards of the Ministry of Economic Affairs, printed by the company (please read the precautions on the back before filling out this page). Add polypentanic acid to 50ml of toluene and 3.0g of paratoluene fengfeng acid and place on i9 It was heated at 0 ° C, followed by six hours of hyposulfite, and the moisture was removed from the reaction solution according to the progress of the reaction. Afterwards, the polyimide solution was added to the source in methanol. The formed antiseptic is isolated, honed and dried to obtain polyimide powder. These polyimines seen in the Han spectrum were read at 1718 cm · 11783 cm · 1 for the typical imine group adsorption peak 値. ^ Example 7: Equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 73.07 g] Sl · methyl-2- This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) ) 508360 A7 B7 V. Description of the invention u &gt;) Introduce 2.8 g (0.014 mol) of oxydiphenylamine, 3.91 g (0.014 mol) of 4 into the reaction tank containing NMP as a solvent. -Methylcyclohexene diphenylamine and 1.45 g (0,0585 mol) of bis (3-aminepropanol) tetramethyldisilazane and dissolved at 15 ° C, followed by the addition of 6.45 g (0.03 mol) of pyromellitic acid Dianhydride. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain polyjiananic acid. Polypentanoic acid was added to 50 ml of toluene and 3.0 g of p-toluene rheinic acid and heated at 190 ° C, followed by six hours of sub-sacrifice, and moisture was removed from the reaction solution according to the progress of the reaction. After that, the polydrum solution was precipitated in methanol. The formed precipitate is isolated, honed and dried to obtain a polyimide powder. These polyimides, which are seen in the spectroscopic spectrum, read the absorption peaks of typical imine groups at 1718 cm · 11783 cm · 1. Example 8 In a reaction tank equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 173.07 g of N-methyl-2-pyridine (NMP) as a solvent, 2.8 g (0.014 mol) of oxygen was first introduced. Diphenylamine, 4.31 g (0.014 mol) of 4-methylcyclohexene diphenylamine and L45 g (0.00585 mol) of bis (3-aminopropanol) tetramethyldisilazane and dissolve at 15 ° C Then, 9-30 grams (0.03 moles) of 3,3 / 4,4 dioxydiphenylphosphoric dianhydride was added. The resulting reaction solution was placed under a nitrogen atmosphere and stirred vigorously for five hours to obtain polyamic acid. Add poly_an acid to 50 ml of toluene and 3.0 g of p-toluene delta wind acid and heat at 190 ° C, then enter 1 * printed by the consumer cooperation of the Central Sample Rate Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) Fill out this page again) for six hours of sub-drumming, and remove moisture from the reaction solution according to the progress of the reaction. After that, the polyimine solution was added to methanol and poured. The formed precipitate is isolated, honed and dried to obtain polyimide powder. In the IR spectrum of these polyfluorene imines, adsorption peaks of typical imine groups were read at 1718 cm · 11783 cm · 1. Comparative Example 1 In a reaction tank equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube containing 157.59 g of N-methyl-2 "pyridine (NMP) as a solvent, 6 β0 g of 3 mol was first introduced. ) Oxydiphenylamine and dissolve at 156C, the size of this paper applies the Chinese National Standard (CNS) A4 specifications (210X297 mm) 508360 A7 B7 V. Description of the invention (d) 10.74 grams (〇.〇mol) ) 3,3 / 4, -benzophenone quaternary dianhydride. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain polycinnamic acid. Comparative Example Two One is equipped with a stirrer, one A reflux condenser, and a nitrogen introduction tube containing 157.59 g of stilbylmethyl-2- (5) -min) were used as a solvent, and 6.0 g (0.03 mol) of oxydiphenylamine was first introduced and dissolved at 15 ° C. Next, 6.54 g (0.33 gm of pyromellitic dianhydride was added. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain polyisocyanic acid. Comparative Example 3 was equipped with a stirrer , A reflux condenser, and a nitrogen introduction tube containing 173.07 g of N-methyl-2-3 Steep (NMP) was used as a solvent to introduce 6.16 g (0.02 mol of trimethylcyclohexene diphenylamine) and 2.92 g (0.01 mol) of ι, 3 · bis (4-aminephenoxy) benzene. And dissolved at 15t, and then 8.58 g (0.03 mole) of 4,4f-oxydiphenylphosphonic dianhydride was added. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain poly-benzoic acid. Add 50ml of toluene and 3.0g of p-toluene rhetoic acid and heat at 190 ° C, then proceed to L5 for six hours of hyposulfite, and remove the moisture from the reaction solution according to the progress of the reaction. After that, it will be printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the Polyimide Solution (please read the precautions on the back before filling this page) and add it to the methanol. Isolate the formed precipitate and grind it The polyimide powder was obtained after drying. The polyimide powders seen in the IR spectrum were recorded at 1718cm · 11783cm · 1 of the adsorption peaks of typical imine groups. Comparative Example 4: One equipped with a Stirrer, a reflux condenser, and a nitrogen introduction tube containing 173.07 g of N-methyl 2-23 Steep (NMP) was used as a solvent to introduce 5.84 g (0.02 mol) of 1,3-bis (4-aminephenoxy) benzene and 2.48 g (0.01 mol) of bis (3-amine propane). Alcohol) Tetramethyldisiloxane and dissolve at 15 ° C, and then add 10.74 g (0.03 mol) of this paper. The standard of this paper is applicable to China National Standard (CNS) A4 (210X 297 cm) 360 360 Central Ministry of Economic Affairs Consumption of employees of the Bureau of Standards and Standards 4 for the printing company A7 B7 V. Description of the invention (\ ψ) 3,3, M, 4 ^ benzophenone tetracarboxylic dianhydride. The resulting reaction solution was placed in a nitrogen atmosphere and stirred vigorously for five hours to obtain poly-anthroic acid. Polyanisoleic acid was added to 50 ml of toluene and 3.0 g of p-toluene pentanoic acid and placed at 190. (: Heating, followed by six hours of sub-i, and the moisture is removed from the reaction solution according to the progress of the reaction. After that, the polyimide solution was added to methanol to precipitate. The formed precipitate was isolated, After honing and drying, polyimide powder was obtained. The polyimide powders seen in the spectrum of melon read the adsorption peaks of typical imine groups at 171801 ^ 17830 ^ 1. Examples 1 to 8 And the relative viscosity measurements of the polypyrrolamic acids prepared in Comparative Example 1 to Comparative Example 4 (Polyvaleric acid has been dissolved in NN-dimethylethene in a concentration of 0.05 by weight. ), The results are listed in the table below ... Using a painting knife, apply the four types of polyurethane paints obtained in the previous example and the comparative example to glass plates and dry them at 80 ° C under vacuum. Dry in the device for 60 minutes to produce a glue film. After tearing off the rubber sheet, place it at 150 ° C for 5 minutes, dry at 200 ° C for 5 minutes, and finally heat it at 300 ° C for one hour. Polyfluorene 5amine acts to provide a 50um thick polydrumimide film. Seen in the IR spectrum The polyimide obtained here read the adsorption peaks of typical imine groups at 1718cm · 11783cm · 1. • In order to check the thermal properties of the obtained film, use a hot liquid density meter to measure the equivalent 5%. Weight loss temperature, while using a differential scanning calorimeter to measure the glass transfer temperature. For the mechanical strength test, the amount of elastic film at room temperature of these rubber molds and the tensile strength results at break are shown in Table 1. It is as follows: Table 1 IS relative viscosity 5 minutes volume loss brewing ~ Ti tensile strength ~ impeachment amount—item (dl / g) (° C) (Kgf / mm2) (Kgf / mm2)

I 135 l73 &quot; &quot; &quot; '305 108 500 This paper size is applicable to China National Standard (CNS) A4 specifications (21 OX 297 mm) (Please read the precautions on the back before filling out this page) Order 508360 A7 B7 5. Description of the invention (丨 f) Example 2 2.52 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 2.13 2.40 1.84 1.73 168 2.27 1.55 L92 L74 1.24 568 564 582 560 531 574 581 593 557 557 485 342 290 283 310 276 265 245 269 249 246 247 13.5 1L5 10.9 12.6 11.9 10.3 123 13.4 15.3 10.1 5.4 400 480 440 430 425 395 340 540 430 320 173 (Please read the notes on the back before filling in this Page) Central Standards of the Ministry of Economic Affairs% Polyimide solutions obtained in Examples 1 to 8 and Comparative Examples 3 and 4 and the polyamidoacids obtained in Comparative Examples 1 and 2 (these are passed through polytamine Polyimide obtained by acid imidization is insoluble in solvents)) is coated on Upilex-S film by a coating knife. The polyimide solutions were dried at 230 ° C for 30 minutes, and the polyacrylic acid was dried at 80 ° C, 110 ° C, 150 ° C, and 200 ° C for ten minutes, and then heated at 300 ° C. One hour of amination produced tapes, each tape having a 20 μm thick adhesive layer. After bonding to a coated copper plate, nickel-iron alloy plate, and a PIX-3000 (Hitachi Chemical Co., Ltd.) under a pressure of 10 kg / cm2 and 400 ° C, the tape was pulled at a rate of 50 mm per minute at room temperature. T-peel strength test. The results are shown in Table 2 below. Digested, printed by the agency 10 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 508360 A7 B7 V. Description of the invention (/ 厶) Example item number Soluble active strength (kg / cm) NMP DMAc DMF DMSO Cu NiFe PIX-3000 Example 1 ◎ ◎ ◎ 1.30 L40 1.35 Example 2 ◎ ◎ ◎ ◎ 1.35 1.50 1.45 Example 3 ◎ ◎ ◎ ◎ 'no 1.24 1.20 Example 4 ◎ ◎ ◎ no 1,54 1.15 Example 5 ◎ ◎ ◎ 1.50 L21 1.24 Example 6 ◎ ◎ ◎ ◎ 1J0 1.12 1.34 Example 7 ◎ ◎ ◎ ◎ 1.97 1.78 1.49 Example 8 ◎ ◎ ◎ ◎ 2.12 1.79 1.49 Comparative Example 1 XXXX 0.25 0.30 0.20 Comparative Example 2 XXX * X 0.47 0.57 0.40 Comparative Example Three ◎ ◎ ◎ ◎ 042 0.29 0.27 Comparative Example 4 ◎ XX 1.94 1.75 1.49 N-methyl-2-pyridine (NMP), N, N-dishenylformamide (DMFr ^^ sz_ (DMAQ, two ¥ Gia (DMSO), ®: Completely soluble, X: Completely insoluble · (Please read the notes on the back before filling this page) Remarks · Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs In addition to the data obtained in the examples and comparative examples, the polyacrylic acid and imine prepared according to the present invention have excellent adhesion strength and qualitative properties, and can maintain their original thermal resistance mechanical properties, so they can Effectively used as an adhesive material for semiconductor assembly special high-temperature tapes. This turn has been @ 国 ， 其 巾 臓 励 萌 编 __ To meet the non-restrictive limit of the round surface ----__ i6 This paper size ϋ China Standard (CNS) A4 Specification (210 Father 297 Gong Chu 1 &quot; 1-508360 A7 B7 V. Invention Description (丨 7) makes the content of the invention. In view of the foregoing teachings, many changes and improvements to the invention are likely to occur. Therefore Within the scope of the proposed patent claim, the present invention can still be implemented in ways other than the specified description. ---------- · --I ---, 玎 ---------- (Please Please read the notes on the back before filling this page) 2 ___ 5- 2, printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 9 i This paper size applies to the Chinese National Standard (〇, 5) 8.4 (210/297 mm)

Claims (1)

8rο 5 0_ Proclamation ABCD Year 8, 2 2, VI. Application for patent scope 1. A method for preparing polyamic acid for producing adhesive, comprising the step of reacting a mixture, the hybrid comprising: at least one tetracarboxylic acid 3: Anhydrides at least one aromatic 1: amine; at least one diamine having a siloxane structure, the siloxane structure is represented by the following molecular formula one: CH〇CHq R4— (-0- R4- 1 CH, CMa ο 1 Printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs of the cooperative [5 ^ 合作 一一] where R4 is an olefin group containing 1-2 (K0 carbon atoms; and Y is the number of repeating structural units between 1 and 20; And at least one alkyl or aromatic cyclohexene diphenylamine, the aromatic cyclohexene diphenylamine is represented by the following molecular formula 贰 or molecular formula parameter ... -NH, 〇 CH3 [rapid ginseng] wherein R represents -Cft, -CBCHb, CXCftMCftCft), or a phenyl group. 2. —A method for preparing poly (beta) amine for manufacturing adhesives, which comprises the steps of reacting a hybrid to produce poly (p-aminoacid), the compound containing this paper is applicable to Chinese National Standard (CNS) Λ4 Specifications (210X29 * 7mm) 508360 A8 B8 C8 D8 6. The scope of patent application is at least one tetracarboxylic acid dihexyl; at least one aromatic diamine; at least one diamine with a siloxane structure, the siloxane structure It is expressed by the following molecular formula one: ch3 ch3 one R4—έί (-0—έί-^-Γ-Η4— CH〇CH〇 [liver formula one] where R4 is an olefin group containing i-20f @ carbon atom; and Y Is the number of repeating structural units between 1 and 20; and ο 1 at least one polyurethane, which is represented by the following formula or parameter: R 5 1 Printed by the Central Bureau of Standards of the Ministry of Economy g £ 2 Consumer cooperatives [liver type [] [liver type ginseng] where R represents-CHb,-CBCB,-QCHsMCHCft), or a phenyl group; and thermally or chemically Polyammonium 5® is first aminated. 3. The preparation method as described in item 2 of the scope of patent application, wherein the thermal amidation first amination step is performed in a temperature range of 250 ° C to 500 ° C. 4. The preparation method according to item 1 of the scope of patent application, wherein the thermal amidation step is performed at a temperature ranging from room temperature to 100 ° C with the addition of a dehydrating cyclizing agent. 2 The scale of this paper is applicable to the Chinese National Standard (CNS) Λ4 specification (21 × 297 mm) 508360 A8 B8 C8 _ D8 ^ --- one &quot; '*-~~ --------- VI 2. The scope of patent application 5. The preparation method described in item 4 of the scope of patent application, wherein the dehydration ring sealant is selected from the group consisting of acetic dianhydride, propionic dianhydride, benzoic dianhydride, and dicyclohexylcarbodiimide The basis of composition. 6. The preparation method as described in item 1 or item 2 of the scope of patent application, wherein the diamine having a siloxane structure having a structure as shown in Formula One is used in an amount of 0.1 to 50 of the total amount of diamines Number of moles. 7 • The preparation method described in item 1 or 2 of the scope of patent application, wherein the amount of the academy or cyclohexene diphenylamine is from 0.01 to 40 mole percent of the total amount of diamine. (Please read the precautions on the reverse side before filling out this page) Printed by the Consumers' Cooperatives of the Bureau of Standards and Loss Standards of the Ministry of Economic Affairs, 3 countries, China, i-scale, paper, paper, grid, A4 Ns, public 7 9 2