TW438861B - Copolymerized polyimide, copolymerized polyimide resin molded articles and the method of preparation thereof - Google Patents

Abstract

The invention provided a copolymerized polyimide copolymerized polyimide molded articles and a method of preparation thereof, having a high elasticity, low heat expansibility such as the metal, low water absorption. A block component of the polyimide is made up of the rigid consitution of the aromatic diamine compounds and of the rigid constitution of the aromitic diamine compounds and aromatic tetra carboxylic acid compounds, a random component of the copolymerized polyimide are made up of the flexible constitution of the aromatic diamine compounds and at least two of the aromatic tetra carboxylic acid compounds and taken in the molecular linkage to be made the copolymerized polyimides.

Description

4388 6 1 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (1) 1 1 [Technical Fields Invented by the Invention] 1 1 The present invention relates to a kind of metal with low thermal expansion and high elasticity1 i Low water-absorptive copolymerization polyimide »Copolymerization of α-polyimide resin, please first 1 and its manufacturing method 0 Read the back I [unknown technology] 1 I by pyromellitic anhydride and 4, 4'-Diamino dibenzyl ether condensation polymerization attention 1 1 Polyramimine 9 obtained because of excellent heat resistance and electrical insulation, can be used as an item 1 and 1 electrical used at high temperatures The order 1 is made of the polyimide film. Fill in this 1. The dimensional stability of the product can be used as a page for flexible printed circuit boards. — ^ 1 I Applications. In recent years, due to the requirements of high processability and high Precision Therefore, it is necessary to install 1 1 1C »LSI for TAB (Tape A ut 〇m at ed B ο η d Ϊ ng). The film is used as a base i I film, and its characteristics as polyimide also require high elasticity. For various reviews, order metal-like low thermal expansion and low water absorption. Example 1: JP Sho 60-2 1 06 2 9, JP Sho 64- 16832, JP Sho 1 I 64 -16833 »JP Sho 64 -16834 > JP Hei 1-131241, JP Hei 1 I 1- Publication No. 1 3 1 2 4 2 describes an example of using polyphenyleneimine in combination with 3 components made of p-benzene 1 diamine to increase the elastic modulus. Furthermore, 3, 3'-4, 4 1-bis-benzyl ί | tetracarboxylic dianhydride is added to the above-mentioned three-component system to improve the elastic modulus of the thread I. For example, kaikai 59 -164328 1 1 ΠχΗ Announcement 1 JP 6 1 -1 1 1 3 5 9 discloses an example of a 4-component oligomer 1 1 醯 imine 〇 Others are JP-A 5- 2 5 273 Revealed that alfalfa 1 tried to improve the physical properties by controlling the cis 1 1 order of the monomers added during the polymerization with 4 components of polyimide. 0 1 I [Problems to be solved by the invention] J 1 -3 1 1 1 1 This paper The standard is applicable to Chinese National Standard (CNS) A4 (210X 297 mm). It is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 4388 6 1 A7 B7. 5. Description of the invention (2) As mentioned above, when it is used for TAB purposes, there are High elastic modulus, metal-like low thermal expansion and low water absorption are required. The three-component polymer obtained in JP-A-Sho 60-210629, JP-A-Sho 64-16832, JP-A-Sho 64-16833, JP-A-Sho 64-16834, JP-A-HEI 1-131241, and JP-A- Hei 1-131242 Imine, compared with polypyrimide obtained from pyromellitic anhydride and 4, 4'-diamine bisphenyl ether, although the elasticity can be improved for TAB use, its elasticity is not sufficient. The 4-component polyimide obtained from JP-A-Sho 59-164328 and JP-A-Sho 61-111359 is also required. If you want to obtain sufficient elasticity for TAB applications, it is necessary to increase the amount of p-phenylenediamine. As a result, there is a problem that the thermal expansion coefficient is lower than that of the metal. Others, such as the 4-component polyimide obtained in Japanese Patent Application Laid-Open No. 5-2 5 2 7 3, have sufficient elasticity and thermal expansion properties to meet their applications, but the problem of water absorption is still a major problem. Therefore, an object of the present invention is to provide a copolymerized polyimide resin having a high elasticity, a metal-like thermal expansion coefficient, a low water absorption, a copolymerized polyimide resin molded body, and a method for producing the same. [Means required for solving the problem] The present invention for solving the above problems is a block component of polyimide formed by an aromatic diamine compound and an aromatic tetracarboxylic acid compound having a rigid structure and an aromatic structure having a flexible structure. Forming a copolymerized polyimide or a copolymerized polyimide resin composed of a random copolymer of polyamidoimide formed from a group of diamine compounds and at least two kinds of aromatic tetracarboxylic acid compounds. Body, or a rigid structure of the aromatic diamine compound and the aromatic tetracarboxylic acid compound to react the aromatic tetracarboxylic acid -4- This paper size applies to China's "standard car (CNS M4 now grid (210X297 mm) --------: --- button ------ ΪΤ ------ r cable (Please read the precautions on the back before filling this page) 4388 6 1 A7 B7 V. Description of the invention (5) The carboxyl reactant, the four anti-family M, fragrant I, aromatic amine, amine, amine, and amine, and fragrant, Αΐ 芳 —. 耳 之 （Α 摩 造物 〇 构 10 性 性, flexible Adding acid M, adding carboxyl X .. Four ears family Mo Hexiang 90 mixed aromatic as an indirect addition • I points (B into the amine compound diamine group fragrant acid aromatic compounds and the four acid carboxyl group four aromatic compounds are all about the mixing room, it is necessary to reverse the polymerization method and polymerize the solution to make a co-solvent. The amine body of the acid is dissolved and depolymerized to form a compound alicyclic polytree. A co-amine is applied with a sub-liquid. K is dissolved to form a polyacid-form amine or a polyacrylamide copolymer. The chemical structure of the sub-ring that is applied to the material is divided into amines, polyamines, polyamines, and polyamines, which are composed of acid-based carboxylic four-family fragrant polyaromatics in 11 species, 1 _ Aminated imines with sub-products _ dimer compound fragrance and re-fragrance to obtain the structure of the substance just compounded (please read the precautions on the back before filling out this page)-Pack. 1 of the first The seed of Μ has 2 less than what it has so far. It is synthesized by chemical compounds, and the two types of anti-fragrant compounds are combined with acidic carboxylic acids. High elasticity and non-elasticity Incorporating the structure of the amines into a common segment, together with the A, B, agglomerates, the Central Standards Bureau of the Ministry of Economic Affairs, the employee consumer cooperatives printed examples of real compound. Chemical amines. Low sex of water-absorbing structure> H ΒΒΙ, 0 (sexually swelled by swollen swollen by heat generation by low-enclosed Η Ν #-Η Ν-line.

The oxoalkane-lower alkane-lower sulfonyl halogen halide of X is based on the structure of the fb amine family in the epigenetic system. The substitution of the rigid radical is priced} T1 1 --- M The size of the selected paper is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) 438861 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) 1 1 The modulus of elasticity 1 is preferably 1 1 i in which X is hydrogen. Among them, p-phenylenediamine is preferred. 0 i [Examples of aromatic diamine compounds having a flexible structure. Nickel is represented by the following 谙 1 formula (Π) Compound 〇 First read 1 NH NHj • (Π) Back 1 1 X Υ i 1 (X t Υ represents hydrogen, halogen group t carboxyl group> lower alkyl 9 lower alkoxy matters 1 I then 1 I choose one Monovalent substituent »X 1 Y may be the same substituent or is Fill in this 1 with different substituents 0 and »A represents -0 I — S- t -C0- 9 -S 0- Page 1 | -SO 2-1 -CH 2-etc. 2-valent linking group 0 ) 1 1 An aromatic diamine compound having a flexible structure represented by the formula (I). If 1 i is to improve the moldability of the obtained molded body, it is preferably as represented by the following formula (nr): 1 Aromatic diamine compounds of the substituent 〇1 1 ΝΗ 普 nh2 (III) 1 1 1 (A series' represents from -0-S- -C0- 9 -so- I -so; _ 1 -CH? ~ 1 The divalent linking group selected by J) Line 1 Of which 4, 4, -diamino bisphenyl ether is particularly preferred < 1 I Ratio of aromatic diamine compound used 1 to fully aromatic diamine Ingredient 1 1 Uses a rigid structure aromatic diamine 1 12 with a molar structure of 30 mols and less than 12 mol% Μ Compound I 70 with a flexible structure of 88 mol% and less Group 1 diamine compound 0 For example, the use of aromatic diamine compounds with a rigid structure is smaller than that of I 1 and the ratio of M is small. The use of aromatic diamines with flexible structure is too large when 1 I is used. 9 The elasticity of the polymer polyimide shaped body 1 1 -6 ί 1 1 1 This paper size is applicable to the Chinese National Standard (CNS), see the grid (2IOX 297 mm) 4388 6 1 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Bag 5. Description of the invention (5) 1 1 will be reduced and the thermal expansion coefficient will increase, which is not suitable for application I. For example, if the flexible structure 1 1 is made of aromatic --- the use of amine compounds is reduced by 9 and it will be copolymerized with 1 1 m The water absorption of the imine formed body will increase and the coefficient of thermal expansion will be too high! Please reduce it, the elasticity will be too high and the moldability will be lost. It is not suitable for reading. Read 1 The aromatic tetracarboxylic acid compound m used should be good 1 is selected from pyromellitic acid t back 1 | 1 3, 3 ', 4 1 4' -bisphenyltetracarboxylic acid and 3,3 1 4, 4 Seed M. Item 1 I and I Aromatic tetracarboxylic acid compounds used> Including kk Pyromellitic acid or its filled-in 1 A-dianhydride as pyromellitic acid 1 With 3, 3 ', 4, 4 1 bisbenzene Tetracarboxylic acid »Page, _ / II or its dianhydride as 3, 3, 4, 4, 4« Biphenyltetracarboxylic acid hydrazone 3, 3 ', 4 1 1 1 4' -benzobenone tetracarboxylic acid Acid or its dianhydride as 3,3 > 4, 4'-bisphenyl tetral I carboxylic acid 〇1 The ratio of the aromatic tetracarboxylic acid compound to be used is 50 to the total aromatic tetral carboxylic acid component More than Molar% 80 Molar% 之 Pyromellitic acid 1 | acids, 20 mol M 50 mol 3, 3 ', 4,4 t bisphenyl 1 1 tetracarboxylic acid and / or 3 , 3 ', 4, 4 4 bisphenyltetracarboxylic acids such as 3, 3-* t 1 4, 4'-bisphenyltetracarboxylic acids and / or 3, 3 t 4, 4 1 -bisphenyltetracarboxylic acids When the proportion of the carboxylic acid line I is less than the above ratio »the copolymerized polyfluorene obtained The elasticity of the imine formed body will decrease t, and the water absorption rate will increase, so it is not suitable for I 1, and »such as 3, 3, 4, 4 1 bisphenyltetracarboxylic acids and / or 3, 3 1 y 1 When the use ratio of I 4, 4 ′ -benzophenone tetracarboxylic acids is greater than the ratio Μ on M, the gas permeability of the copolymerized polyimide obtained will deteriorate j 1 1 on the surface of the formed body The occurrence of air bubbles * leads to a decrease in the adhesion of the formed body. As for 3,3 ', 4,4'-dibenzyltetracarboxylic acids * 3, 3 1, 4, 4 * benzene 1 1 -7 1 1 1 f This paper size is applicable to Chinese national standards (CNS > A4 now available) (2〗 0X297 mm), 438861 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) 1 Benzophenone tetracarboxylic acids can be used individually or in combination. 01 1 Second »Η A description of the method for preparing the copolymerized polyimide of the present invention 1 1 0 First, the first stage of the polymerization used to form the polyfluorene imine block component is to be used firstly. Above 90 Molar X > Read the ratio at 100 Molar% Μ to the reaction components in a non-reverse trtif Desired 1¾ 1 I in 1 Solvent 9 Mix 1 aromatic tetracarboxylic acid over 1 hour ί 1 Next added to form a copolymerized polyimide without The ingredients are used as an aromatic amine compound for the flexible structure of the 2nd stage of polymer boxing 1 and I > add Renfang to fill in this 1 and add the aromatic tetracarboxylic acid (A) and mix for 1 hour and 1 again Add aromatic tetra-1 | carboxylic acid (B Α Φ B) to make the total aromatic tetracarboxylic acid component and the wholly aromatic 1 1 diamine component approximately equal to the molar amount f, then m and stir for 1 hour. I. Precursor of copolymerized poly (amino acid) solution obtained through a series of polymerizations. 〇 This total polymer poly (amino acid) solution is obtained through cyclization and desolvation to obtain copolymerized poly (polyimide). 〔1st at the time of polymerization. In stage 2 and stage 2, block polymerization polyamines 1 formed from each white are obtained by successively performing 1 under the excess amine component 1 |. The I component is combined with the M-copolymerized polyamine component M molecule. Of 1 1 Combine the polyphosphonic acid solution and pass this polyglycolic acid solution through the cyclization desolvation line | agent to obtain the desired copolymerized polyethylenimine 0 1 I Although the polymerization in the first stage of the manufacturing method can be used alone as Aromatic pyromellitic acids of the Group 1 1 tetracarboxylic acids 3, 3 ', 4, 4 1 Biphenyltetracarboxylic acids i I 3, 3', 4, 4 1 — Benzobenzene tetracarboxylic acids of any ♦ Only when 1 1 pyromellitic acid is used * Because the copolymerized polyimide obtained at the end can be converted into fluorene 1 1 MM m, it is most suitable for use. 0 Aromatic diamine components should use i I rigidity Structured aromatic diamine compound 〇I 1 -8 1 1 I i This paper size is applicable to Chinese National Standard (CNS) A4 standard (2IOx: N7 mm) 4 3 88 6 1 A7 B7 Staff Consumption of Central Standards Bureau, Ministry of Economic Affairs Cooperatives, Indo-Fifth, Invention Description (7) 1 1 Convergence in Phase 2 » It is best to use more than 1 type of white homobenzyltetracarboxylic acid »3, 1 1 3, 4, 4, 4 dibenzyltetracarboxylic acid and 3, 3 4, 4 1 _ Benzophenonetetracarboxylic acid 1 Compounds are used as aromatic tetracarboxylic acids f. If you want to increase the localization rate of the copolymerized polyimide (mm) after forming the first one, it is best to read the combination of pyromellitic acid and 3, 3 · , 4, 4 1 _ Biphenyltetracarboxylic acids 0 and 1 I on the back It is suitable to use an aromatic diamine compound with a flexible structure as the aromatic diamine. Note 1 Hua i points 0 item] I used in the production method Solvent t includes dimethylimide 1 Η, Η- fill in this \ dimethyl ethenamine t N, N '-diethyl acetamide, Η, Ν, Ν, dimethyl formamide S_, 1 I amine IN, N-diethylmethylpro mt N-methyl-2pyrrolidine and dimethyl 1 m 1 and the like may be used alone or combined temperature is eligible for use by the square of the production method to obtain co-polymerization of poly 1 I with an amine-based acid Μ 10 30% by weight Jiang [mu] plus modulation ratio in the solvent. 1 Order the copolymerized polylinamic acid and M obtained according to the manufacturing method to be cyclized to form a copolymer. 1 When polyimide is to be synthesized, t can be dehydrated with a lambda dehydrating agent and a catalyst. Any of the thermal closed-loop methods — a method> However, the chemical conversion of the copolymerized polyimide obtained by the closed-loop method ft has a higher elastic modulus of 19 and a lower thermal expansion coefficient, which can be used to spare TAB. Necessary chemical line | Etching and suitable for application. The dehydrating agent used in the chemical ring closure method includes I 1 aliphatic acid anhydrides with acetic anhydride, etc. > aromatic acids such as terephthalic anhydride 1 1 anhydride i may It can be used alone or in combination. As for the catalyst, it includes pyrimyl 1 1 pyridine »polycyclic tertiary amines such as triphenylamine 1 aliphatic third amines such as triethylamine 1 N, N-dimethylaniline Aromatic 3rd Amines etc. »Can 1 1 Use alone or mixed 〇1 i [Ranunculus Example] I 1 -9 1 1 1 1 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 43 88 6 1 A7 B7 V. Description of the invention ( 8) The present invention will be specifically described by examples of cells under M. The PPD in the case examples represents p-phenylenediamine, and 〇1 ^ is 4,4'-diaminobis-benzyl ether. 》 11 ^ is homo-tetracarboxylic dianhydride, BPD Α is 3, 3 ', 4, 4'-bis-benzyltetracarboxylic dianhydride, BTDA is 3,3', 4,4'-benzobenzo_tetra Carboxylic dianhydride, DMAC is N, N ~ dimethylacetamide. Quality Example 1 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives 1 (Please read the precautions on the back before filling out this page) Put 2 39.1 g of DMAC in a detachable flask of 5 0 hi 1 And put 1.870 grams (0.0173 moles) of PPD and 3.659 grams (0.0168 moles) of PMDA, and react at room temperature and pressure for 1 hour. Next, add 25.398 grams (0.1268 moles) of 01 ^ and stir until homogeneous, then add 8.48 grams (0.0288 moles) of BPD and react for 1 hour. Then, 21.491 g (0.0985 mol) of PMDA was added and reacted for 1 hour to obtain a polyamic acid solution. The molar ratio of each raw material added during polymerization was implemented according to the ratio shown in Table-1, and the total weight of solids was adjusted to 60.9 g. 15 grams of the polyamic acid solution was taken out and placed on a polyester film having a thickness of 125 wm, and then the 1H-3 60S spin coater M2500 "Pm made by Megasa was rotated at a rotation speed of 1 minute. Next, After being immersed in a mixed solution of acetic anhydride and / 9-methylpyridine for 10 minutes, the polyimide film was peeled from the polyester film, and the colloidal film was fixed on a supporting frame. It was then heated to 300 ° C for 20 minutes, and then heated to 40010 for 5 minutes. After that, the polyimide film with a thickness of about 25wni was taken out from the above support frame. Various characteristics of this film were evaluated. The results are shown in Table- As shown in Figure 1. As for the various properties are evaluated by the following methods plus M. —1 0-This paper size applies Chinese National Standard (CNS) A4 ^ (210 × 297 mm) 4 3 88 6 1 A7 B7 Central Standard of the Ministry of Economic Affairs Printed by the staff of the Bureau. Cooperative cooperatives. V. Description of the invention (9) (Evaluation method) ① Elasticity machine: RTM-250 Pulling speed: 1 0 0 in m / mi η Load: 10kg © Thermal expansion coefficient machine: TMA-50 Measurement Temperature range: 50 ~ 200Ό Heating speed: 10 it / min ③ The water absorption rate was left to stand in a desiccator at 9 8 S: R Η for 2 days, and the weight added to the original weight was evaluated. Examples 2 to 10 The same sequence as in Example 1, the aroma shown in Table 1 After obtaining the respective polyamino acid solution ratios of the triamine diamine component and the aromatic tetracarboxylic acid component, the polyimide film was obtained by the same operation as in Example 1 and its characteristics were evaluated by adding K. The results are shown in Table 1. Example 1 1 The same operation as in Example 1 was performed except that BM BPD A was used instead of BDTA, and the proportion of the raw material addition shown in Table 1 was obtained. After obtaining a polyamic acid solution, the same operation was performed as in Example 1. A polyimide film was obtained and its physical properties were evaluated. The results are shown in Table 1. 筲 例 1 2

Put 239.1 grams of DMAC in a 500ml detachable flask and put it into PPD 1-1 1-This paper is approved for China National Standard Soap (CNS) A4 specifications (2 丨 OX297 mm) I -------- --Shiyi ----- 1T ------ _ (Please read the precautions on the back before filling in this page) 43 88 6 1 A7 B7 Shellfish Consumer Cooperation, Central Standards Bureau, Ministry of Economic Affairs Description of the invention (10) 1 1 reacts with BPDA for 1 hour at room temperature and temperature. Then add 0DA m and mix until 1 1 is homogeneous. Add B PDA. Make it b * = l should be 1 hour. 0 then add PMDA was further reacted for 1 hour to obtain a polyglutamic acid solution. After the polymerization, each of the raw materials was added in advance. The total weight of the solid content was adjusted according to the ratio shown in Table 1 to read 60.9. After gram-like blistering, Example 1 The same operation was performed to obtain a polyaldimine film from a solution of polyimide dissolved τδ 1 |. Items shown in Table 1 1 I then 1 I Comparative Example 1 Fill in a 5 00 m 1 detachable tin bottle, put 239.1 g of DMAC, and put 0 DA pages w 1 1 and PHD A. The reaction was carried out under pressure for 1 hour to obtain a polyamine solution. The ratio of 0DA to PHDA was approximately 1; 1) It was adjusted to a solid weight 1 | The amount was 66.9 g. The same as in Example 1. Obtain 1 from polyacrylic acid solution. Order polyimide film 9 and evaluate the physical properties of this polyimide film. 1 * The results are shown in Table 2. 0 i | Comparative Example 2 1 I at 500m 1 The separable flask is filled with 2 39.1 g of DMC and put in 1 PPD and PMDA to reverse the UtE at room temperature and pressure. The UtE should be 1 hour 0 Next, put the line 1 into the 0DA. After the homogeneity »Add PMDA reaction 1 Hours to obtain polyamine 1 I acid solution. As for the amount of each raw material added during polymerization), it is performed according to the ratio 1 f example shown in Table 2, and the total weight of the solid content is 60.9 g. 0. Then imitate Zen m. Example 1 1 1 The solution obtained a polyimide film t and evaluated the physical properties of the 1 r polyimide f # film. The results are shown in Table 2. cf 1 Comparative Example 3 1 I was placed in a 500 ml separable flask in a 239 ' 1 gram of DMAC, followed by 1 1 -12- 1 1 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (21 Ox 297 mm) 4 3 88 6 1 A7 B7 V. Description of the invention (11) Add PPD ODA, BPDA, PMDA, and react at room temperature and pressure for 2 hours. Table imitation followed by »〇 量 克 丨 9 Plus-Add 60 for the original weight of each weight, and then it is solidified to adjust to the system. 〇 * Liquid dissolve into acid. Ammonium is obtained by polymerization than 7S polymerization. 2 0 C is thinner than amine. 2 It is polymerized to get fruit solution. Soluble acid amines are polymerized from the film as thin amine. Subordinate 1 Assess Γ--t, 1 Biography is applied, please read the notes on the back before filling out this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, this paper is applicable in China. ) Eight 4 rules _ grid (210 X 297 mm) -4 3 88 6 1 A7 B7 V. Description of the invention (12) ife it-B-^ * Drawing tt. Zhongxingshu U) (PP said / d) si ## (kg / ms.) (泚 crutt) · at 菡 render SS7J < tree (%) 静 quite ¾ smoke (ppm / rf) ss ^ (kg / mnri 鞔 Mirsbb window (* 4nltb) * 2.5 17.0 tn co CT > -〇D3 〇-U -σ Τ ~~ * ~ ζ7 rg * ~ T3? Ο Ο 3 »Ο ϋ: 3 =-> > οι ro -ο to ro on 〇〇π cn -J 〇〇2.2 7 210 〇〇σ > τ? Co ο " τ3 -σ 3 :: -σ ο 3 :: ο ο 3 > ο Ό a »f〇〇〇— 〇〇ο ro ^ σι 2.1 16,5 520 PPD 25 PMDA 24,3 ODAs BPDA 25 PHDA 5P7 8 2.0 ΓΟ ο ο σ >

Τ3 〇3 ο -α -σ 3:: σ ο 3 =: " 〇 ο σ > ϋ σ > > > CJ1 f 〇〇ι ~ k 1 00 〇00 1-4 ACT --- ------ < —.— ^-(Please read the notes on the back before filling in this page) 〔Thank 1〕 ΓΌ 2.6 12 / en -T ^ cc 0 -T7 -g 3! ^ DC? > ◦ ϋ 3 = > > > m ro to co 〇〇〇CO 〇ς〇►—4 ς〇-v4

CO T7 CO 0 -D 3T TJ ϋ 3: -T7 O O: t > port σ ό〇 o 00-ro C7 >

GO

IT 2'1 13 · 〇1 cn -σ σ5 ο -〇-t? -T3 X " T7 σ 3: C ^? C ~? ^ E »d? ≫: t * > co-^ 4 ro o〇0 0 0 CD 0 ^ Two I— · to to CJ1 I—k 05 " -〇σο Ο Π3 " 〇3S ^ T? 0 3C: " T3 ο ο s > ο σ S > 3 » tjl 00 1—1 t—I 〇〇o 00 — ro 2k 16 / s Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1.9 18 ^

05 CO PPD 25 PMDA 24.3 ODAs BPDA 25 PMDA 5P7

PPD PMDA ODA BPDA iA CT5 -ν] γο ro σί to οι οι -ο Οο 11 2.4

Is.4 ς〇ro to ο ^ 3Τ " Τί Ο S: ο c? Σ σ 3 > 5 »α > Γ〇〇〇ro ro ο ο ο ο ο ατ ro οο 100.0 545 PPD 20 SDA 20 ODA000 BPDA s iA s 6 This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm > 4 3 88 6 1 A7 B7 V. Description of the invention (13) [Table 2] Example 1 2 3 Adding order inverse proportion 0DA 100 PPD 12 PPD 25 (Molar ratio Γ PHDA 100 PMDA 11.6 PHDA 75 0DA 88 0DA 25 PMDA 88.4 PMDA 75 Elasticity (kg / mm 2 261 392 354 Thermal expansion coefficient 30.7 21.6 27.9 Water absorption (¾) 2.7 2,8 2.3 I. I --«^ 1 1—Hi-Hi-1. ~ i I-I— I-Im-n. N :: Γ (Please read the precautions on the back before filling out this page) Employees of Zhongli Standard Bureau, Ministry of Economic Affairs The mol ratio in the table printed by the consumer cooperative indicates the value of mol in the full aromatic diamine component and the mol in the full aromatic tetracarboxylic acid component. -15-Does this paper apply Chinese national standard? M CNS) Λ4 present case (210X297 mm) 4 3 88 Si A7 B7 V. Description of the invention (I4) [Effect of the invention] The copolymerization obtained by the present invention The imine series is a block copolymerized polyfluorene imine component produced from a rigid structured aromatic diamine compound and an aromatic tetrasolic acid compound through a two-stage polymerization, and a flexible structured aromatic diamine compound and The copolymerized polyfluorene imine component formed by at least two kinds of aromatic tetracarboxylic acid fluorene compounds is composed of a combination of molecules. Its resin molding effect has high elastic modulus, low thermal expansion, and low water absorption, so it can As a basic film that requires high processability and high accuracy of TAB, it can fully meet its functional requirements. I ^^^ 1 tft- · n ^ i ▼-—J · ^ — tn ^^^ 1 ^^^ 1 ^^^ 1 VJ 0 ^ -a '(Please read the notes on the back before filling in this page) The paper size printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 (210X29? Mm)

Claims (1)

ABCD 438861, patent application range No. 86102012 "copolymerized polyimide, copolymerized polyfluorene; amine tree dish conformation and its production method" patent (amended on August 11, 89) 6. Scope of patent application: a kind of Polymerized polyfluorene imide, which is a block component of polyfluorene imide formed by a rigid structured aromatic diamine compound and an aromatic tetracarboxylic acid compound, and a flexible structured aromatic diamine compound and at least two kinds The random component of the copolymerized polyfluorene imide formed by the aromatic tetracarboxylic acid compounds is composed of molecular bonds; among them, the aromatic diamine compound having a rigid structure accounts for 12 mol of the total aromatic diamine component. / β to 30 mol% 'and the aromatic diamine compound having a flexible structure accounts for 70 mol% to 88 mol% of the wholly aromatic diamine component. 2 'If the copolymerized polyfluorene imine in item i of the patent application scope, wherein the rigid structured aromatic diamine compound is a diamine represented by the following formula (I): (Please read the precautions on the back before filling in this Page) Order NH • NH: X ⑴-printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Of) (X represents a monovalent substituent selected from hydrogen, halogen, carboxy, low alkyl, and low oxygen.) 3. Such as The copolymerized polyfluorene imine of item 2 of the patent application, wherein X of the formula (Engineering) is hydrogen. 4. The copolymerized polyfluorene imine according to item 1 of the patent application scope, wherein the aromatic diamine compound having a rigid structure is p-phenylenediamine. This paper uses the national standard (CNS) A4 specification (210X29 * 7 mm) 4388 6 1 A8 B8 C8 D8. The scope of patent application is s. For example, the copolymerized polyimide of item 1 in the scope of patent application, where The aromatic diamine compound of a sexual structure is a diamine represented by the formula (π): XY (II) (x represents a monovalent substituent selected from hydrogen, a prime group, a carboxyl group, a lower alkyl group, and a lower alkoxy group. , X and Υ may be the same or different substituents, and A represents a divalent linking group selected from -0-, -S-, -CO-, -SO -'- S〇2-, -CH2- .) 6. If the copolymerized polyfluorene imine of item 5 of the patent application scope, wherein the flexible structure of the aromatic diamine compound is a diamine represented by the following formula (melon): (Please read the note on the back first Please fill in this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs • · · · * (III) so- '-S0Z-, -CHj- of (A represents selected from -〇-, -S- bivalent link Group.) 7. The copolymerized polyfluorene imine according to item 6 of the patent application scope, wherein the aromatic diamine compound having a flammable structure is 4,4'-diaminobisphenyl charm. 8. The copolymerized polyfluorene ggamine according to item 1 of the application, wherein the aromatic tetracarboxylic acid compound is selected from pyromellitic acid, 3,3 ,, 4,4, -bisphenyltetracarboxylic acid and 3 -3 ', 4,4'-benzophenone tetracarboxylic acid-more than one compound. 9. The copolymerized polyfluorene imine according to item 8 of the scope of patent application, in which pyromellitic acid accounts for 50 mol% to 80 mol of CO of aromatic tetracarboxylic acids. The paper size is applicable to the Chinese national standard ( CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 438861 ㈤ C8 D8 6. The scope of patent application is%, and 3,3 ', 4,4'-bisphenyltetracarboxylic acid and / or 3,3 ', 4,4'-benzophenone tetracarboxylic acid accounts for 20 mol% to 50 mol% of the wholly aromatic tetracarboxylic acid components = 10. A method for preparing copolymerized polyimide, It is characterized by: ① Aromatic diamine compounds and aromatic tetracarboxylic acid compounds with a rigid structure are reacted in a non-reactive organic solvent. The ratio of Molar% to 100 Molar% is mixed according to the time required for the reaction. ② An aromatic diamine compound with a flexible structure is added, followed by an aromatic tetracarboxylic acid compound (A), and then aromatic. Tetracarboxylic compounds (B; A Yin B) are fully aromatic tetracarboxylic The acid component and the wholly aromatic diamine component form about equal molar amounts, and are mixed for the time required for the reaction. ③ The obtained copolymerized polyamino acid solution is cyclized and desolvated. U_ As in the method for preparing the copolymerized polyfluorene imine under item 10 of the patent application scope, wherein the cyclization is a chemical cyclization using a cyclization catalyst and a dehydrating agent. 12_ —A copolymerized polyfluorene amine resin molded body, which is a block component of polyfluorene imide formed by an aromatic diamine compound having a rigid structure and an aromatic tetracarboxylic acid compound, and an aromatic diamine having a flexible structure. The random component of the copolymerized polyfluorene imide formed by an amine compound and at least two kinds of aromatic tetracarboxylic acid compounds is a copolymer composed of molecular bonds. -3- This paper applies the Chinese National Standard (CNS) A4 · (210X 297mm) (Please read the precautions on the back before filling in this page) Thread 4388 6 1 C8 D8 6. The scope of the patent application is that of polyimide to be formed. 13. The copolymerized polyfluorene imide resin molded article as claimed in claim 12, wherein the molded article is a film. 14. A method for producing a copolymerized polyfluorene imide resin molded article, which has the following features: ① A rigid structure of an aromatic diamine compound and an aromatic tetracarboxylic acid compound; the reaction component is in a non-reactive organic solvent, and the structure is rigid. After the aromatic diamine compound is mixed with the aromatic tetracarboxylic acid compound at a ratio of 90 mol% to 100 mol% according to the time required for the reaction, ② an aromatic diamine compound with a flexible structure is added, and then The aromatic tetracarboxylic acid compound (A) is added, and then the aromatic tetracarboxylic acid compound (B; A #B) is added in an amount equivalent to that of the fully aromatic tetracarboxylic acid component and the wholly aromatic diamine component. The time required for the reaction is mixed. ③ After forming the copolymerized polyamidic acid solution, it is cyclized and desolvated. 15. For example, a method for preparing a copolymerized polyfluorene imine resin molded article according to item 14 of the application, wherein the molded article is a film. 16. For example, a method for manufacturing a copolymerized polyimide resin molded article according to item 14 of the application, wherein the cyclization is a chemical cyclization using a cyclization catalyst and a dehydrating agent. -4- This paper scale is applicable to Chinese national standards (CNS > A4 size (210X 297 mm) (Please read the precautions on the back before filling out this page). Order the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs. DuPont 4 ι Η 1 1 r% Application Date Case No. 86102012 Category (The above blocks are filled out by the Bureau) Xinnong Chinese invention new name English name Nationality = Invention 1 'Creator's residence and residence name (name) 971-3683T Patent Specification Copolymerized Polyimide and Its Preparation Method Copolymerized Polyimide Resin Molded Body (Amended on August 11, 89) COPOLYMERIZED POLYIMIDE, COPOLYMERIZED POLYIMIDE RESIN MOLDED ARTICLES AND THE METHOD OF PREPARATION THEREOF Tazawa Hisamatsu 12 3 1-3 are all in Japan S3 1 7 8 Tome Fanding 8 2 έ 1 1tl Moutai Fanding on 3 also) 9 Ί × 丘 区区 丁 寮 寮 绿 寮 II 丘 市 6 新 西. 屋 屋 30 City, City, Ancient J-Tinto, 2 homes, prefectures, prefectures, prefectures, prefectures, prefectures, prefectures, prefectures, and counties. 3 Toray, DuPont Co., Ltd. (East B. Shovel > Co., Ltd.) Central Ministry of Binding Standards Bureau Shellfish Consumer Cooperatives India Benben Line Nationality Japanese Applicant's Residence and Domicile (Office) Representative Name 1 Nippon Hashimotocho, Chuo-ku, Tokyo No. 6 Yoshida Takamoto Paper Standards Used Chinese National Standards (CNS > A4 specification (210X297 mm) ABCD 438861, patent application range No. 86102012 "copolymerized polyimide, copolymerized polyfluorene; amine tree dish conformation and its manufacturing method" patent case (August 89, 1 1st amendment) 6. Scope of patent application: A copolymerized polyimide, which is a block component of polyimide formed by a rigid structure of an aromatic diamine compound and an aromatic tetracarboxylic acid compound. The random component of the copolymerized polyfluorene imide formed by an aromatic diamine compound of at least two kinds of aromatic tetracarboxylic acid compounds and formed by molecular bonding; among them, the aromatic diamine compound of rigid structure is 12 mol./β to 30 mol% of the total aromatic diamine component and the aromatic diamine compound having a flexible structure accounts for 70 mol% to 88 mol% of the total aromatic diamine component. 2 'If the copolymerized polyfluorene imine of item i of the patent application scope, wherein the rigid structure of the aromatic diamine compound is the diamine represented by the following formula (I): (Please read the precautions on the back before filling this page ) Order NH • NH: X ⑴-printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Of) (X represents a monovalent substituent selected from hydrogen, halogen, carboxy, low alkyl, and low oxygen.) 3. Such as The copolymerized polyfluorene imine of item 2 of the patent application, wherein X of the formula (Engineering) is hydrogen. 4. The copolymerized polyfluorene imine according to item 1 of the patent application scope, wherein the aromatic diamine compound having a rigid structure is p-phenylenediamine. This paper uses the national standard (CNS) A4 size (210X29 * 7mm)