WO2017111134A1 - Copolymère de polyimide et corps moulé l'utilisant - Google Patents

Copolymère de polyimide et corps moulé l'utilisant Download PDF

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Publication number
WO2017111134A1
WO2017111134A1 PCT/JP2016/088575 JP2016088575W WO2017111134A1 WO 2017111134 A1 WO2017111134 A1 WO 2017111134A1 JP 2016088575 W JP2016088575 W JP 2016088575W WO 2017111134 A1 WO2017111134 A1 WO 2017111134A1
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polyimide copolymer
diamine
dianhydride
polyimide
bis
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PCT/JP2016/088575
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English (en)
Japanese (ja)
Inventor
奈央 渡邉
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ソマール株式会社
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Priority to KR1020187017215A priority Critical patent/KR102390851B1/ko
Priority to CN201680075543.7A priority patent/CN108431087A/zh
Publication of WO2017111134A1 publication Critical patent/WO2017111134A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • plastic substrates such as substrate glass and cover glass
  • plastic substrates are strongly demanded for portable information terminals such as mobile phones, smartphones, and tablet PCs.
  • resin materials that have excellent heat resistance, mechanical properties, and transparency suitable for the above-described applications and that can suppress yellowing due to exposure to heat and light have been studied.
  • Polyimide is widely used as a heat-resistant insulating material in the electric and electronic industry because it has excellent heat resistance, mechanical properties, chemical resistance, and electrical insulation.
  • conventional polyimides starting from aromatic compounds are colored yellow-brown in the steady state due to intramolecular conjugation and charge transfer complex formation, so they are not suitable as a substitute for glass that requires transparency. .
  • an aromatic compound is not used as a polyimide constituent unit, and all are composed of aliphatic and / or alicyclic compounds. All aliphatic polyimides have been proposed.
  • aliphatic and / or alicyclic compounds are inferior in heat resistance as compared to conventionally used aromatic compounds and have low polymerization reactivity, so that the heat resistance and mechanical strength of the resulting polyimide are reduced.
  • yellowing due to oxidation in the heat treatment process becomes a problem.
  • the problem of heat resistance can be improved by introducing rigid aromatic raw materials into the polyimide resin structure, but this reduces the transparency and solubility of the polyimide.
  • an object of the present invention is to provide a polyimide copolymer having higher transparency and elastic modulus while maintaining excellent solubility, and a molded body using the same.
  • the present inventors have maintained excellent solubility in a polyimide copolymer obtained by copolymerizing an alicyclic acid dianhydride having a specific structure and a diamine having a hydroxyl group.
  • the polyimide copolymer of the present invention is derived from 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,4: 3 ′, 4′-dianhydride.
  • a structural unit derived from a diamine having a unit and a hydroxyl group is contained.
  • the diamine having a hydroxyl group is preferably a diamine represented by the following general formula (1).
  • R 21 is —SO 2 —, —C (CF 3 ) 2 —, —CO— or a direct bond.
  • the diamine having a hydroxyl group at least one of 2,2-bis (3-amino-4-hydroxyphenol) hexafluoropropane and bis (3-amino-4-hydroxyphenyl-3-amino-4-hydroxyphenyl) sulfone is used. It is preferable to include.
  • polyimide copolymer of the present invention is characterized by having a structural unit represented by the following general formula (2).
  • R 21 is —SO 2 —, —C (CF 3 ) 2 —, —CO— or a direct bond.
  • R 1 is preferably a divalent organic group derived from a diamine compound represented by the following formula (3) or formula (4).
  • the molded article of the present invention is characterized by containing any of the above polyimide copolymers.
  • the transparency and elastic modulus can be further improved while maintaining the solubility of the polyimide copolymer.
  • the polyimide copolymer of the present invention and a molded body using the same are obtained by copolymerizing an alicyclic acid dianhydride component having a specific structure and a diamine component having a hydroxyl group.
  • alicyclic acid dianhydride is used as a raw material, the problem of coloration of polyimide resin due to intramolecular conjugation and formation of a charge transfer complex is solved.
  • the polyimide copolymer of the present invention is obtained by copolymerizing (A) an alicyclic acid dianhydride having the structure of formula (5) and (B) a diamine having a hydroxyl group.
  • the polyimide copolymer of the present invention has an alicyclic acid anhydride (1,1′-bicyclohexane) represented by the formula (5) as an acid dianhydride component.
  • -3,3 ', 4,4'-tetracarboxylic acid-3,4: 3', 4'-dianhydride is used as a constituent.
  • 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,4: 3 ′, 4′-dianhydride is described, for example, in JP-A No. 2014-151559. Although it can synthesize
  • acid dianhydrides represented by the formula (5) can be used as a constituent component as long as the effects of the present invention are not affected.
  • acid dianhydrides include 3,3′4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 4,4′-oxydiphthalic dianhydride, 1,2 , 3,4-pentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 5- (2, 5-dioxotetrahydrofurfuryl) -3-cyclohexene-1,2-dicarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bistrimellitic dianhydride, 2,2 ′, 3,3 ′ -Biphenyltetracarbox
  • the polyimide copolymer of this invention uses the diamine which has a hydroxyl group as a structural component.
  • the diamine having a hydroxyl group is not particularly limited, and a diamine represented by the following general formula (1) is used.
  • R 21 is —SO 2 —, —C (CF 3 ) 2 —, —CO—, or a direct bond
  • R 21 is preferably —SO 2 —, —C (CF 3 ) 2 —, or a direct bond, —SO 2 —, —C (CF 3 ) 2.
  • R 21 in the formula is more preferably —C (CF 3 ) 2 —.
  • diamine examples include 2,2-bis (3-amino-4-hydroxyphenol) hexafluoropropane (BisAPAF) represented by the formula (3) and bis (3 -Amino-4-hydroxyphenyl) sulfone (SO2-HOAB) and the like.
  • BisAPAF containing fluorine is more preferable from the viewpoint of improving the solubility of the polyimide copolymer and suppressing the increase in water absorption due to the introduction of hydroxyl groups into the polyimide copolymer structure.
  • the hydroxyl group is formed by copolymerizing the 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,4: 3 ′, 4′-dianhydride and a diamine having a hydroxyl group.
  • the polyimide copolymer which has is obtained.
  • a hydrogen bond arises between the hydroxyl groups of a polyimide copolymer molecule, or between a hydroxyl group and another functional group.
  • a dense network structure is formed between the polyimide copolymers, and the elastic modulus of the obtained polyimide resin is improved by the intermolecular cohesive force of hydrogen bonds. For this reason, in this invention, the elasticity modulus of a polyimide resin can be improved effectively, maintaining transparency and solubility.
  • a diamine other than a diamine having a hydroxyl group can be used as a constituent component as long as the effect of the present invention is not affected.
  • diamines are not particularly limited, and specific examples of diamine compounds include 9,9-bis (4-aminophenyl) fluorene, 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, Phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (4-a
  • 4,4′-diaminodiphenyl ether 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (4-aminophenoxy) phenyl) sulfone, 4,4′-methylenebis (cyclohexylamine), 2,7-fluorenediamine, 2,2′-bis (trifluoromethyl) -4,4′-biphenyldiamine 9,9-bis (4-aminophenyl) fluorene and the like are preferable.
  • a sterically bulky cardo structure or a fluorine-containing diamine is used. It is preferable to use it. From the viewpoint of improving the heat resistance and film quality of the molded article of the present invention, 9,9-bis (4-aminophenyl) fluorene, 2,2′-bis (trifluoromethyl) -4,4′-biphenyldiamine Is more preferable.
  • the polyimide copolymer of the present invention can be dissolved in an organic solvent.
  • organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, N, N-dimethylformamide, N, N-diethylacetamide, gamma-butyrolactone, alkylene glycol monoalkyl ether, alkylene Glycol dialkyl ether, alkyl carbitol acetate, benzoate and the like can be used.
  • These organic solvents may be used alone or in combination of two or more.
  • the method for producing a polyimide copolymer of the present invention includes a step of (A) copolymerizing an alicyclic acid dianhydride having a specific structure and (B) a diamine having a hydroxyl group to produce a polyimide copolymer. .
  • an acid dianhydride other than the component (A) and / or a diamine other than the component (B) can be added as desired.
  • These components are preferably polymerized in an organic solvent at 150 to 200 ° C. in the presence of a catalyst.
  • the polymerization method is not particularly limited, and a known method can be used.
  • a method may be used in which the acid dianhydride and the diamine are all put into an organic solvent at a time for polymerization.
  • the above-mentioned total amount of the acid dianhydride is put in an organic solvent, and then a method of polymerizing by adding a diamine in an organic solvent in which the acid dianhydride is dissolved or suspended,
  • a method may be employed in which an acid dianhydride is added and polymerized in an organic solvent in which the diamine is dissolved after being put in a solvent.
  • a sequential addition method can also be used.
  • the polymerization method by the sequential addition method is also not particularly limited.
  • (A ) Component acid dianhydride and / or (B) component diamine may be additionally added.
  • acid dianhydride other than (A) component and / or ( A diamine other than the component B) can be additionally added.
  • the acid dianhydride of (A) component and / or ( B) Component diamine can be additionally added.
  • the organic solvent used for producing the polyimide copolymer of the present invention is not particularly limited.
  • N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, N, N-dimethylformamide, N, N-diethylacetamide, etc., gamma-butyrolactone, alkylene glycol dialkyl ether, alkyl carbitol acetate, benzoic acid Esters can be suitably used.
  • These organic solvents may be used alone or in combination of two or more.
  • the polymerization temperature is preferably 150 to 200 ° C. If the polymerization temperature is less than 150 ° C., imidization may not proceed or may not be completed. On the other hand, when the temperature exceeds 200 ° C., the resin concentration increases due to oxidation of the solvent and unreacted raw materials and volatilization of the solvent.
  • the polymerization temperature is more preferably 160 to 195 ° C.
  • the catalyst used for the production of the polyimide copolymer of the present invention is not particularly limited, and a known imidization catalyst can be used.
  • a known imidization catalyst can be used.
  • pyridine can usually be used.
  • a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound of a nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxy group, or an aromatic heterocyclic compound A cyclic compound is mentioned.
  • lower alkyl imidazoles such as 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, N-benzyl Imidazole derivatives such as -2-methylimidazole, substituted pyridines such as isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n-propylpyridine, etc. , P-toluenesulfonic acid and the like can be preferably used.
  • the amount of the imidization catalyst used is preferably 0.01 to 2 equivalents, more preferably 0.02 to 1 equivalents, based on the amic acid unit of the polyamic acid.
  • an azeotropic solvent can be added to the organic solvent in order to efficiently remove the water generated by the imidization reaction.
  • aromatic hydrocarbons such as toluene, xylene and solvent naphtha
  • alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and dimethylcyclohexane can be used.
  • the amount added is preferably about 1 to 30% by mass, more preferably 5 to 20% by mass, based on the total amount of organic solvent.
  • ⁇ Chemical imidization method> When the polyimide copolymer of the present invention is produced by a chemical imidization method, the acid dianhydride and / or the component (B) other than the component (A), the component (B), and the component (A) used as desired. Copolymerize with other diamines. In this copolymer production process, a dehydrating agent such as acetic anhydride and a catalyst such as triethylamine, pyridine, picoline, or quinoline are added to the polyamic acid solution. In the chemical imidization method, the imidization reaction is usually carried out by heating at 60 ° C. to 120 ° C., but the reaction may be completed at room temperature.
  • the reaction time is preferably 1 to 200 hours.
  • unreacted dehydrating agent such as acetic anhydride
  • by-products such as carboxylic acid (such as acetic acid and amine salt of acetic acid) are removed to purify the polyimide copolymer.
  • the purification method is not particularly limited, and a known method can be used.
  • the reaction solution may be dropped into a poor solvent such as water or alcohol while stirring to precipitate a polyimide copolymer, followed by washing and drying under reduced pressure.
  • the same imidization catalyst and organic solvent as in the thermal imidization method can be used.
  • Examples of methods for forming a film, film or sheet from the polyimide copolymer of the present invention include known methods such as spin coating, dipping, spraying and casting.
  • a coating, film or sheet is obtained by applying the polyimide copolymer to the surface of the substrate by a selected method according to the viscosity or the like and then drying.
  • any material may be used according to the use of the final product.
  • textile products such as cloth, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polycarbonate, triacetylcellulose, cellophane, polyimide, polyamide, polyphenylene sulfide, polyetherimide, polyethersulfone, aromatic polyamide, or polysulfone.
  • the substrate may be transparent, or may be colored by blending various pigments and dyes with the material constituting the substrate, and the surface may be processed into a mat shape.
  • an ordinary heating and drying furnace may be used for drying the coated polyimide copolymer of the present invention.
  • the atmosphere in the drying furnace include air, inert gas (nitrogen, argon), and vacuum.
  • the drying temperature can be appropriately selected depending on the boiling point of the solvent in which the polyimide copolymer of the present invention is dissolved, but is usually 80 to 350 ° C., preferably 100 to 320 ° C., particularly preferably 120 to 250 ° C. Good.
  • the drying time may be appropriately selected depending on the thickness, concentration, and type of solvent, and can be about 1 second to 360 minutes.
  • a product having the polyimide copolymer of the present invention as a film can be obtained, or a film can be obtained by separating the film from the substrate.
  • a molded body is obtained using a mold, a predetermined amount of the polyimide copolymer of the present invention is injected into the mold (especially a rotating mold is preferable), and then the same temperature as the molding conditions of the film, A molded body can be obtained by drying over time.
  • fillers such as silica, alumina, mica, carbon powder, pigments, dyes, polymerization inhibitors, thickeners, thixotropic agents, precipitation inhibitors, Antioxidants, dispersants, pH adjusters, surfactants, various organic solvents, various resins, and the like can be added.
  • the polyimide resin of the present invention is an optical fiber, optical waveguide, optical filter, lens, optical filter, adhesive sheet, interphase insulating film, semiconductor insulating protective film, TFT liquid crystal insulating film, liquid crystal alignment film, protective film for solar cell, flexible It is suitably used as an electronic material such as a display substrate, a circuit board, a lithium ion battery negative electrode member, or the like.
  • Example 1 1,1'-bicyclohexane-3,3 ', 4,4'-tetracarboxylic acid-into a 500 mL separable four-necked flask equipped with a stainless steel vertical stirrer, nitrogen inlet tube, and Dean-Stark apparatus 3,4: 3 ′, 4′-dianhydride (H-BPDA) 46.24 g, 2,2-bis (3-amino-4-hydroxyphenol) hexafluoropropane (BisAPAF) 54.94 g, gamma-butyrolactone (GBL) 177.86 g, 2.37 g of pyridine and 50 g of toluene were charged and the reaction system was purged with nitrogen, and then reacted at 180 ° C.
  • H-BPDA 2,2-bis (3-amino-4-hydroxyphenol) hexafluoropropane
  • BisAPAF 2,2-bis (3-amino-4-hydroxyphenol) hexafluoropropane
  • Example 2 Same as Example 1, except that 49.30 g of H-BPDA was used as the acid dianhydride and 29.30 g and 22.42 g of BisAPAF and SO2-HOAB were used as the diamine in the same apparatus as in Example 1, respectively. Thus, a polyimide copolymer solution having a concentration of 25% by mass was obtained. Table 2 shows the composition ratio (mass) of (A) acid dianhydride and (B) diamine used in the reaction.
  • Example 3 The same method as in Example 1 except that 61.64 g of H-BPDA was used as the acid dianhydride and 36.63 g and 32.02 g of BisAPAF and TFMB were used as the diamine in the same apparatus as in Example 1. Thus, a polyimide copolymer solution having a concentration of 35% by mass was obtained.
  • Table 2 shows the composition ratio (mass) of (A) acid dianhydride and (B) diamine used in the reaction.
  • Example 4 The same method as in Example 1, except that 49.32 g of H-BPDA and 29.30 g and 27.88 g of BisAPAF and FDA as diamines were used as the acid dianhydride in the same apparatus as in Example 1, respectively. Thus, a polyimide copolymer solution having a concentration of 35% by mass was obtained. Table 2 shows the composition ratio (mass) of (A) acid dianhydride and (B) diamine used in the reaction.
  • Example 5 In the same apparatus as in Example 1, 21.76 g and 32.57 g of H-BPDA and ODPA were used as the acid dianhydride, respectively, and 29.43 g and 24.39 g of SO2-HOAB and FDA were used as the diamine, respectively. In the same manner as in Example 1, a 30% by mass concentration polyimide copolymer solution was obtained. Table 2 shows the composition ratio (mass) of (A) acid dianhydride and (B) diamine used in the reaction.
  • the solubility, tensile elastic modulus and total light transmittance of the polyimide copolymers of Examples 1 to 5, Comparative Example 1 and Reference Example 1 were evaluated by the following methods. Further, the breaking strength, elongation and glass transition temperature of the polyimide copolymers of Examples 1 to 5 were measured by the following methods.
  • the measurement film was prepared by the following method. Using the polyimide copolymer solution obtained in each example, comparative example, and reference example, it was applied onto a silicon wafer by a spin coat method, and temporarily dried on a hot plate at 120 ° C. for 10 minutes. The temporarily dried film was peeled from the silicon wafer, fixed to a stainless steel frame, dried at 180 ° C. for 30 minutes, and then at 250 ° C. for 1 hour to obtain a measurement film. This film was cut into 100 mm ⁇ 10 mm and measured. For the measurement, a small desktop testing machine Ez-Test (EZ-LX manufactured by Shimadzu Corporation) was used. Each measurement was performed five times, and data showing the maximum stress at break was used. The distance between chucks was 50 mm, and the pulling speed was 100 mm / min. The obtained results are shown in Tables 1 and 2.
  • Such an improvement in the elastic modulus is considered to be due to the fact that the copolymer of Example 1 has a hydroxyl group derived from a diamine, so that a dense cross-linked structure is formed by hydrogen bonding between copolymer molecules. It is done.
  • the polyimide copolymer of the present invention uses a cohesive force between molecules due to hydrogen bonding, so that a significant improvement in elastic modulus is realized while maintaining transparency.
  • an aromatic dianhydride and a diamine having a hydroxyl group are copolymerized, it is possible to increase the elastic modulus, but there is a limit to improving the transparency.
  • H-PMDA 1,2,4,5-cyclohexanetetracarboxylic acid 1,2: 4,5-dianhydride
  • H-BPDA 1,2,4,5-cyclohexanetetracarboxylic acid 1,2: 4,5-dianhydride
  • Example 2 As shown in Table 2, even in the composition of Example 1, the polyimide copolymer of Example 2 in which SO2-HOAB was further added as a diamine and the polyimide copolymer of Example 3 in which TFMB was added were also capable of transmitting all light. It was found that excellent transparency exceeding 90% and an elastic modulus higher by 40% or more than Reference Example 1 were obtained. Moreover, in the polyimide copolymer of Example 3 to which TFMB was added, since the breaking strength and the elongation were greatly improved, the improvement of the film quality of the polyimide copolymer is expected.
  • Example 4 in which FDA is further added as a diamine to the composition of Example 1, the total light transmittance and the elastic modulus are lower than those of the polyimide copolymer of Example 1, but the breaking strength. A significant improvement was observed.
  • Example 5 in which aromatic ODPA was added to H-BPDA as an acid dianhydride and FDA was added to SO2-HOAB as a diamine, the transparency and elastic modulus were lower than in Example 1, but the glass transition temperature. A significant improvement in the breaking strength was observed.
  • the third component and the fourth component various properties can be controlled while maintaining excellent solvent solubility and transparency, and high elastic modulus. Can do. For this reason, it is thought that optimal material design is possible according to the use for which a polyimide copolymer is used.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
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Abstract

Le problème à résoudre par la présente invention consiste à préparer un copolymère de polyimide qui fait preuve d'excellentes solubilité et transparence ainsi que d'un module d'élasticité élevé, et un corps moulé utilisant le copolymère de polyimide. La solution selon l'invention est un copolymère de polyimide produit en copolymérisant du 1,1'-bicyclohexane-3,3',4,4'-(acide tétracarboxylique)-3,4:3',4'-dianhydride et une diamine contenant un groupe hydroxyle. La diamine contenant un groupe hydroxyle peut être au moins l'un du 2,2-bis(3-amino-4-hydroxyphénol)hexafluoropropane et de la bis(3-amino-4-hydroxyphényl3-amino-4-hydroxyphényl)sulfone.
PCT/JP2016/088575 2015-12-25 2016-12-22 Copolymère de polyimide et corps moulé l'utilisant WO2017111134A1 (fr)

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CN108431087A (zh) 2018-08-21
JP6718678B2 (ja) 2020-07-08
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