WO2014034760A1 - ポリイミド及びその製造に用いる脂環式テトラカルボン酸二無水物 - Google Patents
ポリイミド及びその製造に用いる脂環式テトラカルボン酸二無水物 Download PDFInfo
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- WO2014034760A1 WO2014034760A1 PCT/JP2013/073104 JP2013073104W WO2014034760A1 WO 2014034760 A1 WO2014034760 A1 WO 2014034760A1 JP 2013073104 W JP2013073104 W JP 2013073104W WO 2014034760 A1 WO2014034760 A1 WO 2014034760A1
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- Prior art keywords
- general formula
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- spiro
- polyimide
- norbornane
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 222
- 239000004642 Polyimide Substances 0.000 title claims abstract description 211
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims description 241
- 125000002723 alicyclic group Chemical group 0.000 title claims description 123
- 238000004519 manufacturing process Methods 0.000 title claims description 40
- 150000000000 tetracarboxylic acids Chemical class 0.000 title description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 42
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 157
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 261
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 49
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- -1 dimethanol naphthalene-2,3,6,7-tetracarboxylic Chemical compound 0.000 description 46
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- 239000000178 monomer Substances 0.000 description 29
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 28
- 238000000926 separation method Methods 0.000 description 27
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- 238000002329 infrared spectrum Methods 0.000 description 22
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
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- 230000008022 sublimation Effects 0.000 description 9
- 230000004580 weight loss Effects 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
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- 239000012043 crude product Substances 0.000 description 8
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 8
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- 238000001914 filtration Methods 0.000 description 8
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- 238000006116 polymerization reaction Methods 0.000 description 7
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 6
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- 125000003710 aryl alkyl group Chemical group 0.000 description 6
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- 125000000753 cycloalkyl group Chemical group 0.000 description 6
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- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 5
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- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 5
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- RHRNYXVSZLSRRP-UHFFFAOYSA-N 3-(carboxymethyl)cyclopentane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CC1C(C(O)=O)CC(C(O)=O)C1C(O)=O RHRNYXVSZLSRRP-UHFFFAOYSA-N 0.000 description 2
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- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- JWHOQZUREKYPBY-UHFFFAOYSA-N rubonic acid Natural products CC1(C)CCC2(CCC3(C)C(=CCC4C5(C)CCC(=O)C(C)(C)C5CC(=O)C34C)C2C1)C(=O)O JWHOQZUREKYPBY-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/93—Spiro compounds
Definitions
- the present invention relates to a polyimide and an alicyclic tetracarboxylic dianhydride used for the production thereof.
- polyimide is attracting attention from the viewpoint of excellent heat resistance and dimensional stability.
- an aromatic polyimide “Kapton” which is a representative organic material developed in the 1960s by DuPont of the United States, is marketed as having the highest heat resistance among heat resistant polymers. It is known that such aromatic polyimide is a polymer material that can withstand a high temperature of about 300 ° C. and a severe space environment for a long period of time.
- wholly aromatic polyimides exhibit a brown color and require transparency because intramolecular charge transfer (CT) occurs between the aromatic tetracarboxylic dianhydride unit and the aromatic diamine unit.
- CT intramolecular charge transfer
- alicyclic polyimides examples include trans-1,4-cyclohexanediamine (t-CHDA) and pyromellitic anhydride (PMDA) or 3,3 ′, 4,4′-biphenyltetracarboxylic acid dicarboxylic acid.
- t-CHDA trans-1,4-cyclohexanediamine
- PMDA pyromellitic anhydride
- BPDA an anhydride
- An alicyclic polyimide combining such t-CHDA and PMDA or BPDA has an extremely low linear expansion coefficient (for example, 10 ppm / ° C. for t-CHDA / PMDA system, 10 ppm for t-CHDA / BPDA system).
- trans-1,4-cyclohexanediamine (t-CHDA) used in the production of such alicyclic polyimide is a monomer that forms a very strong salt in the early stage of polymerization with PMDA or BPDA. It is extremely difficult to polymerize by a conventional method, and such a polyimide is not necessarily sufficient in terms of polymerizability and is difficult to put into practical use.
- Patent Document 1 As another alicyclic polyimide, for example, in International Publication No. 2011/099518 (Patent Document 1), the following general formula:
- R a , R b , and R c each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and R d represents 6 carbon atoms.
- R d represents 6 carbon atoms.
- the polyimide which has a repeating unit represented by this is disclosed.
- Non-Patent Document 1 New Revised Polyimide: Basics and Applications, NTS Publishing, 2010, p. (Refer to Non-Patent Document 1)
- Such a polyimide described in Patent Document 1 can be produced under normal production conditions, and is sufficiently practical. Moreover, such a polyimide described in Patent Document 1 has high light transmittance and sufficiently high heat resistance. Moreover, when the present inventors confirmed the polyimide of the said patent document 1, in one Embodiment, the linear expansion coefficient is 19 ppm / degrees C (refer the comparative example 1 and Table 1 of this specification). It has also been confirmed that it has a sufficiently appropriate linear expansion coefficient for use in various applications such as printable electronics applications, flexible glass substitute applications, and semiconductor resist applications.
- an inorganic material having a small coefficient of linear expansion (CTE) employed during its use is used.
- CTE coefficient of linear expansion
- the emergence of a polyimide having a lower linear expansion coefficient that enables the thermal expansion to be suppressed at a higher level is desired.
- the present invention has been made in view of the above-mentioned problems of the prior art, and is excellent in light transmittance and heat resistance, and has a sufficiently low linear expansion coefficient, and an alicyclic tetracarboxylic acid dicarboxylic acid used in the production thereof.
- the object is to provide an anhydride.
- the present inventors have found that the repeating units represented by the following general formulas (1) and (2) having a unique structure are 90 mol% based on the total repeating units. Surprisingly, it has been found that the polyimide to be obtained is sufficiently excellent in light transmittance and heat resistance, and has a sufficiently low linear expansion coefficient, and the present invention is completed. It came to do.
- polyimide of the present invention has the following general formulas (1) and (2):
- R 1 , R 2 and R 3 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom.
- R 4 represents an aryl group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12.
- a polyimide containing at least one of the repeating units represented by formula (1) and wherein the total amount of the repeating units represented by the general formulas (1) and (2) is 90 mol% or more based on all repeating units. is there.
- R 4 in the general formulas (1) and (2) is represented by the following general formulas (3) to (6):
- R 5 represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group and a trifluoromethyl group
- Q is a formula: —O—, —S—, —CO—, —CONH—, —C 6 H 4 —, —COO—, —SO 2 —, —C (CF 3 ) 2 —, —C (CH 3 ) 2 —, —CH 2 —, —O—C 6 H 4 —C (CH 3 ) 2 —C 6 H 4 —O—, —O—C 6 H 4 —SO 2 —C 6 H 4 —O—, —C ( CH 3) 2 -C 6 H 4 -C (CH 3) 2 -, - from O-C 6 H 4 -C 6 H 4 -O- and -O-C 6 group represented by H 4 -O- 1 type
- the polyimide of the present invention has a linear expansion coefficient of 15 ppm / ° C. or less obtained by measuring a change in length in a temperature range of 50 ° C. to 200 ° C. under a nitrogen atmosphere under a temperature rising rate of 5 ° C./min. Are preferred.
- the total amount of the repeating units represented by the general formulas (1) and (2) is preferably 95 to 100 mol% with respect to all the repeating units.
- the alicyclic tetracarboxylic dianhydride of the present invention is an alicyclic tetracarboxylic dianhydride used for the production of the polyimide of the present invention, and has the following general formula (7):
- R 1, R 2, R 3, n are as defined R 1, R 2, R 3 , n in the general formula (1) and (2).
- R 1, R 2, R 3, n are as defined R 1, R 2, R 3 , n in the general formula (1) and (2).
- the total amount of the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) is 90 mol% or more.
- Carboxylic dianhydride is 90 mol% or more.
- the polyimide of the present invention has a sufficiently low linear expansion coefficient is not necessarily clear, but the present inventors speculate as follows. That is, in the polyimide of this invention, the repeating unit represented by the said General formula (1) and (2) is contained 90 mol% or more in total amount. By using the above repeating unit at such a content ratio, the main chain of the polymer has a so-called planar zigzag structure and forms a higher order structure.
- R 1 , R 2 , and R 3 are each a hydrogen atom
- R 4 is a group represented by the general formula (6)
- Q is a formula: —CONH—
- n is 2.
- molecular orbital calculation regarding the polymer main chain structure is performed by taking as an example a polyimide containing 100 mol% of the repeating unit represented by the above general formula (2), a higher order structure of such a polymer Has a planar zigzag structure as shown in FIGS.
- Such molecular orbital calculation can be performed using MOPAC software installed in Chem Bio3D Ultra10 using a FUJITSU FMV-B8200 type personal computer.
- the calculation method includes an alicyclic ring used as a monomer.
- a polyimide formed from a tetracarboxylic dianhydride of formula and an aromatic diamine can be depicted in Chem Bio3D Ultra10, MM2 calculated, then AM1 calculated, which can be used to calculate the stability of the polymer.
- the structure can be simulated.
- a polyimide is in-plane-oriented by the structure (planar zigzag structure as shown in FIG.1 and FIG.2) calculated
- the inventors infer that the orientation state of the film is such that the planar portion of the zigzag structure shown in FIG. 1 overlaps in the thickness direction (Z direction) of the film.
- the film in-plane direction (XY direction: the direction perpendicular to the film is the Z direction, and one direction perpendicular to the Z direction is the X direction, the Z direction and the X direction
- the linear expansion coefficient is low). Therefore, in the present invention, the present inventors infer that the linear expansion coefficient in the XY direction is sufficiently low, and for example, when a film is produced, the linear expansion coefficient is sufficiently low.
- the polyimide by containing 90 mol% or more of the repeating units represented by the above general formulas (1) and (2), the polyimide has a planar zigzag structure and has a sufficiently low linear expansion. The present inventors infer that the coefficient can be exhibited.
- the present inventors since the linear expansion coefficient in the in-plane direction is low, when the film expands under high heat conditions, the expansion of the film is expected to occur in the film thickness direction (Z direction).
- the present inventors infer that the stress applied to the materials in the X and Y directions is sufficiently reduced, and the occurrence of cracks and the like is sufficiently suppressed even when the inorganic layer is laminated under high heat conditions. Therefore, the present inventors speculate that the polyimide of the present invention can be suitably used for applications such as processing steps under high temperature conditions.
- the present invention it is possible to provide a polyimide having excellent light transmittance and heat resistance and having a sufficiently low linear expansion coefficient, and an alicyclic tetracarboxylic dianhydride used for the production thereof.
- FIG. 3 is a graph showing an HPLC spectrum of the compound obtained in Synthesis Example 1.
- 6 is a graph showing an IR spectrum of a compound obtained in Synthesis Example 2.
- 3 is a graph showing a 1 H-NMR (DMSO-d 6 ) spectrum of the compound obtained in Synthesis Example 2.
- FIG. 3 is a graph showing a 13 C-NMR (DMSO-d 6 ) spectrum of the compound obtained in Synthesis Example 2.
- FIG. 3 is a graph showing an HPLC spectrum of the compound obtained in Synthesis Example 2.
- 6 is a graph showing an IR spectrum of the compound obtained in Synthesis Example 3.
- 3 is a graph showing a 1 H-NMR (DMSO-d 6 ) spectrum of the compound obtained in Synthesis Example 3.
- FIG. 4 is a graph showing a 13 C-NMR (DMSO-d 6 ) spectrum of the compound obtained in Synthesis Example 3.
- 6 is a graph showing an HPLC spectrum of the compound obtained in Synthesis Example 3.
- 2 is a graph showing an HPLC spectrum of the first compound obtained in the monomer synthesis step employed in Example 1.
- FIG. 2 is a graph showing an IR spectrum of the first compound obtained in the monomer synthesis step employed in Example 1.
- FIG. 2 is a graph showing a 1 H-NMR (DMSO-d 6 ) spectrum of the first compound obtained in the monomer synthesis step employed in Example 1.
- FIG. 2 is a graph showing a 13 C-NMR (DMSO-d 6 ) spectrum of the first compound obtained in the monomer synthesis step employed in Example 1.
- FIG. 2 is a graph showing an IR spectrum of a second compound obtained in the monomer synthesis step employed in Example 1.
- FIG. 2 is a graph showing a 1 H-NMR (DMSO-d 6 ) spectrum of a second compound obtained in the monomer synthesis step employed in Example 1.
- FIG. 2 is a graph showing a 13 C-NMR (DMSO-d 6 ) spectrum of a second compound obtained in the monomer synthesis step employed in Example 1.
- FIG. 2 is a graph showing an HPLC spectrum of a second compound obtained in the monomer synthesis step employed in Example 1.
- FIG. 2 is a graph showing an IR spectrum of a compound (polyimide) obtained in the polyimide preparation step employed in Example 1.
- FIG. 2 is a graph showing an IR spectrum of a compound (polyimide) obtained in the polyimide preparation step employed in Example 2.
- FIG. 4 is a graph showing an IR spectrum of a compound (polyimide) obtained in the polyimide preparation step employed in Comparative Example 1.
- the polyimide of the present invention has the following general formulas (1) and (2):
- R 1 , R 2 and R 3 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom.
- R 4 represents an aryl group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12.
- a polyimide containing at least one of the repeating units represented by formula (1) and wherein the total amount of the repeating units represented by the general formulas (1) and (2) is 90 mol% or more based on all repeating units. is there.
- the alkyl group that can be selected as R 1 , R 2 , or R 3 in the general formulas (1) and (2) is an alkyl group having 1 to 10 carbon atoms.
- heat shock heat shock
- the glass transition temperature is lowered, and the film formed by the resulting polyimide is resistant to heat shock (heat shock) (the quality is sufficiently improved against ambient high temperature changes).
- heat shock resistance when it is necessary to adopt a process of laminating an inorganic layer under a high temperature condition of about 300 ° C. or higher, it is sufficient that peeling or cracking occurs even under such a temperature condition. In the following, such resistance is referred to as “thermal shock resistance”).
- the number of carbon atoms of the alkyl group that can be selected as R 1 , R 2 , or R 3 is preferably 1 to 6 and is preferably 1 to 5 from the viewpoint of easier purification. Is more preferably 1 to 4, particularly preferably 1 to 3. Further, such an alkyl group that can be selected as R 1 , R 2 , or R 3 may be linear or branched. Further, such an alkyl group is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification.
- R 1 , R 2 and R 3 in the general formulas (1) and (2) are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms from the viewpoint of obtaining higher heat resistance.
- each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. It is more preferable that it is a hydrogen atom or a methyl group.
- R ⁇ 1 >, R ⁇ 2 >, R ⁇ 3 > in such a formula is the same from viewpoints, such as easiness of refinement
- the aryl group that can be selected as R 4 in the general formulas (1) and (2) is an aryl group having 6 to 40 carbon atoms. Further, such a carbon number is preferably 6 to 30, and more preferably 12 to 20. When the number of carbons exceeds the upper limit, the glass transition temperature decreases and sufficient heat resistance cannot be obtained, and when a film is formed, sufficient thermal shock resistance tends to be not obtained, If it is less than the said minimum, the solubility with respect to the solvent of the obtained polyimide will fall, and it exists in the tendency for the moldability to a film etc. to fall.
- R 4 in the general formulas (1) and (2) has a sufficiently high glass transition temperature and a sufficiently low linear expansion coefficient, and can exhibit these characteristics in a more balanced manner. From the viewpoint of becoming, the following general formulas (3) to (6):
- R 5 represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group and a trifluoromethyl group
- Q is a formula: —O—, —S—, —CO—, —CONH—, —C 6 H 4 —, —COO—, —SO 2 —, —C (CF 3 ) 2 —, —C (CH 3 ) 2 —, —CH 2 —, —O—C 6 H 4 —C (CH 3 ) 2 —C 6 H 4 —O—, —O—C 6 H 4 —SO 2 —C 6 H 4 —O—, —C ( CH 3) 2 -C 6 H 4 -C (CH 3) 2 -, - from O-C 6 H 4 -C 6 H 4 -O- and -O-C 6 group represented by H 4 -O- 1 type
- the glass transition temperature and the linear expansion coefficient can be more balanced and higher in terms of hydrogen atom, fluorine atom.
- a methyl group or an ethyl group is more preferable, and a hydrogen atom is particularly preferable.
- Q in the general formula (6) is a formula: —O—, —S—, —CONH— from the viewpoint of achieving a higher balance between the glass transition temperature and the linear expansion coefficient.
- —COO—, —CO—, —C 6 H 4 —, —CH 2 —, —O—C 6 H 4 —O— are preferred.
- a group represented by —, —COO— or —CH 2 — is more preferred, and a group represented by the formula: —O— or —CONH— is particularly preferred.
- the glass transition temperature can be set to a sufficiently high temperature, and the linear expansion coefficient can be more sufficiently increased. From the viewpoint that the balance of these characteristics can be improved and higher thermal shock resistance can be obtained, the group represented by the general formula (5) or (6) is more preferable. preferable.
- R 4 is a group represented by the general formula (5), Or a group represented by the general formula (6) and Q is represented by —CONH—, —COO—, —CO—, —C 6 H 4 — (more preferably represented by —CONH— or —COO—). In particular, it is preferably a group that is at least one of the following groups, particularly preferably a group represented by —CONH—.
- R 4 is represented by the general formula (3) from the viewpoint that when a film is formed using the obtained polyimide, a high degree of flexibility (flexibility) can be imparted to the film.
- At least one of the groups represented by the general formula (6) and the Q is represented by —O—, —S—, —CH 2 —, —O—C 6 H 4 —O—. It is preferably a group that is a species (more preferably, one of groups represented by —O— or —CH 2 —, more preferably a group represented by —O—).
- n represents an integer of 0 to 12.
- the upper limit of the numerical value range of n in the general formulas (1) and (2) is more preferably 5 and particularly preferably 3 from the viewpoint of easier purification.
- the lower limit value of the numerical value range of n in the general formulas (1) and (2) is a monomer used for the production of polyimide (for example, tetramers represented by the following general formulas (7) and (8)). From the viewpoint of the stability of the raw material of carboxylic dianhydrides), 1 is more preferable, and 2 is particularly preferable.
- n in the general formulas (1) and (2) is particularly preferably an integer of 2 to 3.
- such a polyimide has a high level of balance between a sufficiently high glass transition temperature, a sufficiently low linear expansion coefficient, and a sufficient flexibility (flexibility) of the film when it is formed. From the viewpoint of exhibiting well, it is preferable to contain at least two types of repeating units among the repeating units represented by the general formulas (1) and (2) having different types of R 4 in the polyimide.
- R 4 is a group represented by the general formula (5); and wherein Q is -CONH -, - COO -, - A group represented by CO— or —C 6 H 4 — (more preferably a group represented by —CONH— or —COO—, particularly preferably a group represented by —CONH—).
- a repeating unit comprising at least one of the repeating units represented by the general formulas (1) and (2), which is one group selected from the group consisting of the group represented by the general formula (6).
- R 4 are groups represented by the general formula (3); and Q is represented by —O—, —S—, —CH 2 —, —O—C 6 H 4 —O—.
- Q is represented by —O—, —S—, —CH 2 —, —O—C 6 H 4 —O—.
- one more preferably -O among the groups -, - CH 2 - one of the groups represented by, yet good Or a group represented by the general formula (6) which is a group represented by —O—; and a group represented by the general formulas (1) and (2) which is one group selected from the group consisting of:
- a repeating unit (B) composed of at least one of the repeating units.
- R 4 is a group represented by the general formula (6) and the formula (6).
- Q is represented by —O—, —CH 2 —, —O—C 6 H 4 —O— (more preferably a group represented by —O—, —CH 2 —). Of these, more preferred is a group represented by —O—.
- the total amount of the repeating units represented by the general formulas (1) and (2) is 90 mol% or more based on all repeating units.
- the content ratio (total amount) of the repeating units represented by the general formulas (1) and (2) is more preferably 95 to 100 mol%, and 98 to 100 mol based on all repeating units. % Is more preferable, and 100 mol% is particularly preferable.
- limit especially as repeating units other than the repeating unit represented by the said General formula (1) and (2) According to a use etc., the other repeating unit derived from a well-known monomer is selected suitably. Can be used.
- the polyimide according to the present invention may contain at least one of the repeating units represented by the general formulas (1) and (2).
- the molar ratio ([formula (1)]: [formula (2)]) is 1: 2. It is preferably ⁇ 2: 1, more preferably 1: 1.85 to 1.85: 1, and even more preferably 1: 1.7-1 to 1.7: 1.
- the content ratio of the repeating unit represented by the general formula (1) is less than the lower limit, the film tends to be brittle. On the other hand, when the content exceeds the upper limit, the film tends to become brittle.
- the repeating units (A) and (B) are contained as the repeating units represented by the general formulas (1) and (2), these repeating units are combined.
- the total amount of the repeating units (A) and (B) is preferably 90 mol% or more, and 95 to 100 mol% with respect to all the repeating units. More preferably, it is more preferably 98 to 100 mol%, and particularly preferably 100 mol%.
- the content ratio of the repeating unit (A) to the repeating unit (B) is 9 in molar ratio ((A) :( B)).
- the glass transition temperature is preferably 350 ° C. to 450 ° C., more preferably 360 ° C. to 420 ° C., and further preferably 370 to 410 ° C.
- the heat resistance is not sufficient, and when the film is formed, the thermal shock resistance is not sufficient, for example, the manufacture of solar cells and liquid crystal display devices.
- the heating process in the process it tends to be difficult to sufficiently suppress the deterioration of the film quality (such as occurrence of cracks).
- the glass transition temperature of such a polyimide is measured by using a differential scanning calorimeter (for example, trade name “DSC7020” manufactured by SII Nano Technology Co., Ltd.) as a measuring device. : A value obtained by scanning between 30 ° C. and 440 ° C. under a nitrogen atmosphere under a condition of 30 ° C./min can be employed. In addition, about the polyimide which does not have a glass transition temperature between scanning temperature 30 degreeC to 440 degreeC, the above-mentioned scanning temperature is changed from 30 degreeC to 470 degreeC, and a glass transition temperature is measured.
- a differential scanning calorimeter for example, trade name “DSC7020” manufactured by SII Nano Technology Co., Ltd.
- a linear expansion coefficient is 15 ppm / degrees C or less, It is more preferable that it is 12 ppm / degrees C or less, It is further more preferable that it is 10 ppm / degrees C or less.
- a linear expansion coefficient exceeds the upper limit, sufficient thermal shock resistance cannot be obtained when a film is formed, and it is difficult to sufficiently suppress deterioration in quality due to cracking in the thin film.
- Tend to be. when a film is formed using polyimide having a linear expansion coefficient exceeding the upper limit, when the film is used for manufacturing a solar cell or a liquid crystal display device, the film is exposed to a high temperature in the manufacturing process and cracked in the film. Etc.
- a lower limit of a linear expansion coefficient although it changes with uses, it is preferable that it is 1 ppm / degreeC, and it is more preferable that it is 4 ppm / degreeC.
- the film is vacuum-dried (120 ° C. 1 hour), using a measurement sample obtained by heat treatment at 200 ° C.
- thermomechanical analyzer (trade name “TMA8310” manufactured by Rigaku) as a measurement device
- TMA8310 thermomechanical analyzer
- the change in the length of the sample in the longitudinal direction at 50 ° C. to 200 ° C. was measured using a tension mode (49 mN) and a heating rate of 5 ° C./min under a nitrogen atmosphere, and 50 ° C. to 200 ° C.
- the value obtained by calculating the average value of the change in length per 1 ° C. in the temperature range can be adopted.
- the glass transition temperature and the linear expansion coefficient of such a polyimide can be easily within the above numerical range by appropriately changing the types of R 1 to R 4 in the general formulas (1) and (2). Can be.
- the polyimide film is stretched (longitudinal stretching, lateral stretching, oblique stretching, press stretching, etc.), the polyamide acid film that is a polyimide precursor is stretched before heat treatment, or the polyamide acid film that is a polyimide precursor is stretched. Even if heat treatment is performed while fixing, the linear expansion coefficient can be finely adjusted within the numerical range.
- such a polyimide preferably has a 5% weight loss temperature of 450 ° C. or more, more preferably 460 to 550 ° C. If the 5% weight loss temperature is less than the lower limit, sufficient thermal shock resistance tends to be not obtained when a film is formed. On the other hand, if the upper limit is exceeded, a polyimide having such characteristics is produced. Tend to be difficult. Such 5% weight reduction temperature is obtained by gradually heating from room temperature (25 ° C.) while flowing nitrogen gas in a nitrogen gas atmosphere and measuring the temperature at which the weight of the used sample is reduced by 5%. Can be sought.
- the film after thermal imidization may be difficult to dissolve in a general-purpose organic solvent, so the molecular weight is evaluated using the intrinsic viscosity [ ⁇ ] of the polyamic acid that is the precursor.
- the intrinsic viscosity [ ⁇ ] of the polyamic acid is preferably from 0.1 to 8.0, more preferably from 0.1 to 6.0, and preferably from 0.1 to 3.0. Further preferred is 0.4 to 2.0.
- the intrinsic viscosity is less than the lower limit, sufficient thermal shock resistance tends to be difficult to achieve.
- the upper limit is exceeded, casting film formation (cast film formation) tends to be difficult.
- Such intrinsic viscosity [ ⁇ ] can be measured as follows.
- a measurement sample (solution) in which N, N-dimethylacetamide is used as a solvent and the polyamic acid is dissolved in the N, N-dimethylacetamide so as to have a concentration of 0.5 g / dL. obtain.
- the viscosity of the measurement sample is measured using a kinematic viscometer under a temperature condition of 30 ° C., and the obtained value is adopted as the intrinsic viscosity [ ⁇ ].
- an automatic viscosity measuring device (trade name “VMC-252”) manufactured by Koiso Co., Ltd. is used.
- such a polyimide has a higher order structure in which the polymer chain has a planar zigzag structure.
- the structure of the polymer chain of such a polyimide can be determined by calculating the molecular orbital of the polyimide based on the type of monomer used. By using MOPAC software, the formed polyimide is depicted in Chem Bio3D Ultra10, MM2 is calculated, and then AM1 is calculated to simulate the stable structure of the resulting polymer.
- Such a polymer chain structure can also be obtained by measuring the linear expansion coefficient in the Z direction of a polyimide thin film using an optical interference method and clarifying the relationship between the linear expansion coefficient and the molecular structure. .
- the form of such a polyimide is not particularly limited, and various forms (for example, a film shape, etc.) can be used depending on the application.
- the shape and size can be appropriately designed according to the application and the like, and the thickness of the film is 1 to 200 ⁇ m, although not particularly limited. It is preferably 5 to 100 ⁇ m. If the thickness of such a film is less than the above lower limit, the mechanical strength tends to be reduced and weakened when used for various applications, and on the other hand, if it exceeds the upper limit, film forming tends to be difficult. .
- the total light transmittance is 80% or more (more preferably 85% or more, particularly preferably 87% or more). ) Is more preferable.
- Such total light transmittance can be easily achieved by appropriately selecting the type of polyimide or the like.
- a value measured using a trade name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. can be used as a measuring device.
- such a polyimide preferably has a refractive index of 1.50 to 1.70, more preferably 1.55 to 1.65 when a film is formed.
- the refractive index is less than the lower limit, the difference in refractive index between polyimide and the conductive thin film becomes large when a laminate with the conductive thin film is formed and used for transparent applications, and the total light transmittance is
- it exceeds the upper limit the polyimide tends to be colored and the synthesis itself tends to be difficult.
- a refractive index a value measured under a temperature condition of 23 ° C. under a light source of 589 nm using a refractive index measuring device (trade name “NAR-1T SOLID” manufactured by Atago Co., Ltd.) is adopted. be able to.
- Such a polyimide of the present invention is colorless and transparent despite being an aliphatic polyimide obtained by using an aliphatic tetracarboxylic dianhydride, and the glass transition temperature (Tg) is an indicator.
- the heat resistance is sufficiently high, and it can have a sufficiently high Tg as compared with a polyimide made from a conventionally known aliphatic tetracarboxylic dianhydride.
- such a polyimide of the present invention can have a sufficiently high solubility in a solvent.
- such a polyimide of the present invention has a sufficiently low linear expansion coefficient due to containing 90 mol% or more of the repeating units represented by the above general formulas (1) and (2) in a total amount. It will have.
- the polyimide of the present invention includes polyimide for flexible wiring boards, polyimide for heat-resistant insulating tape, polyimide for wire enamel, polyimide for semiconductor protective coating, polyimide for liquid crystal alignment film, polyimide for printable electronics, ITO It is particularly useful as a polyimide for film, a polyimide for solar cell, a polyimide for organic EL, a polyimide for electronic paper, a polyimide for lithium ion battery, and the like.
- the alicyclic tetracarboxylic dianhydride of the present invention is an alicyclic tetracarboxylic dianhydride used for the production of the polyimide of the present invention, and has the following general formula (7):
- R 1, R 2, R 3, n are as defined R 1, R 2, R 3 , n in the general formula (1) and (2).
- R 1, R 2, R 3, n are as defined R 1, R 2, R 3 , n in the general formula (1) and (2).
- the total amount of the alicyclic tetracarboxylic dianhydrides represented by the general formulas (7) and (8) is 90 mol% or more.
- Trans, endo, endo-norbornane-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 represented by the general formula (7) '' -Tetracarboxylic dianhydride (hereinafter sometimes simply referred to as “alicyclic tetracarboxylic dianhydride represented by the general formula (7)”) is used to form the polyimide of the present invention.
- R 1, R 2, R 3, n alicyclic tetracarboxylic acid dianhydride in represented by the general formula (7) is, R 1, R 2 in formula (1) , R 3 and n have the same meaning (the preferred one is also the same). It should be noted that such an alicyclic tetracarboxylic dianhydride represented by the general formula (7) has two norbornane groups in a trans conformation, and a carbonyl of cycloalkanone with respect to each of the two norbornane groups.
- the cis, endo, endo-norbornane-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 represented by the above general formula (8) '' -Tetracarboxylic dianhydride (hereinafter sometimes simply referred to as “alicyclic tetracarboxylic dianhydride represented by the general formula (8)”) forms the polyimide of the present invention.
- R 1, R 2, R 3, n alicyclic tetracarboxylic acid dianhydride in represented by the general formula (8), R 1, R 2 in the general formula (2) , R 3 and n have the same meaning (the preferred one is also the same).
- the alicyclic tetracarboxylic dianhydride represented by the general formula (8) has two norbornane groups in cis conformation, and each of the two norbornane groups has a carbonyl of cycloalkanone.
- the total amount (content) of the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) is the total fat. It is 90 mol% or more with respect to cyclic tetracarboxylic dianhydride.
- the alicyclic tetracarboxylic dianhydride of the present invention is an alicyclic tetracarboxylic dianhydride represented by the above general formulas (7) and (8) having a purity of 90 mol% or more. It is a cyclic tetracarboxylic dianhydride.
- the total amount (content ratio) of the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) is less than the lower limit, and the polyimide is prepared using the alicyclic tetracarboxylic dianhydride.
- the planar zigzag structure of the main chain cannot be sufficiently formed in the manufactured polyimide, and a sufficiently low linear expansion coefficient cannot be obtained.
- the total amount (content ratio) of the alicyclic tetracarboxylic dianhydrides represented by the general formulas (7) and (8) is the total alicyclic tetracarboxylic dianhydrides.
- it is preferably 95 mol% or more, more preferably 98 to 100 mol%, and particularly preferably 100 mol%.
- the alicyclic tetracarboxylic dianhydride of this invention should just contain at least 1 sort (s) of the alicyclic tetracarboxylic dianhydride represented by the said General formula (7) and (8).
- a molar ratio ([formula (7)]: [Formula (8)]) is preferably 1: 2 to 2: 1, more preferably 1: 1.85 to 1.85: 1, and 1: 1.7 to 1.7: 1. More preferably. If such a molar ratio is less than the lower limit, the resulting polyimide film tends to be brittle, and on the other hand, even if the upper limit is exceeded, the resulting polyimide film tends to be brittle.
- the total amount (content) of the alicyclic tetracarboxylic dianhydride represented by the general formula (7) and the general formula (8) in the alicyclic tetracarboxylic dianhydride of the present invention is obtained, for example, by determining the area ratio of peaks based on each isomer based on a graph of a spectrum obtained by HPLC measurement, and using a calibration curve. It can be obtained by calculating.
- HPLC measurement uses the product name “1200 Series” manufactured by Agilent Technologies, Inc.
- DAD diode array detector
- the calibration curve can be obtained by obtaining an HPLC spectrum under the same measurement conditions using dicyclopentadiene or naphthalene as a standard sample. Moreover, in the graph of the HPLC spectrum, the peak area ratio based on each isomer can be directly determined by the above-described measuring apparatus.
- the total amount (content) of the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) is 90 mol%. What is necessary is just above, and other alicyclic tetracarboxylic dianhydrides may also be contained.
- alicyclic tetracarboxylic dianhydrides other than the alicyclic tetracarboxylic dianhydrides represented by the general formulas (7) and (8) include, for example, norbornane-2-spiro- ⁇ -Other isomers of cycloalkanone- ⁇ '-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride (general formulas (7) and (8) above) Isomers other than the isomers represented by the following formula: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5- Tetrahydrofur
- alicyclic tetracarboxylic dianhydride bicyclo [2,2,1] -heptane-2,3,5,6-tetracar Phosphate dianhydride, deca hydro dimethanol naphthalene-2,3,6,7-tetracarboxylic dianhydride, and the like.
- the method for producing such an alicyclic tetracarboxylic dianhydride of the present invention is not particularly limited, and for example, the following general formula (9):
- R 1, R 2, R 3, n are as defined R 1, R 2, R 3 , n in the general formula (7) and (8).
- 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes represented by the formula (hereinafter referred to simply as “compound represented by the general formula (9)”)
- the compound represented by the general formula (9) is then converted into a tetracarboxylic dianhydride, and the following general formula (10):
- R 1, R 2, R 3, n are as defined R 1, R 2, R 3 , n in the general formula (7) and (8).
- the tetracarboxylic dianhydride represented by the general formula (10) is used so that the purity becomes 90 mol% or more.
- the total amount of the alicyclic tetracarboxylic dianhydrides represented by the general formulas (7) and (8) is obtained by separating them out so as to be 90 mol% or more and converting them to tetracarboxylic dianhydrides.
- a method of obtaining the alicyclic tetracarboxylic dianhydride of the present invention by obtaining rubonic acid dianhydride (second method), preparing a compound represented by the general formula (9), The compound represented by the formula (9) is esterified (subsequently subjected to hydrolysis treatment or transesterification with a carboxylic acid to give a carboxylic acid), and then obtained from the resulting compound (ester or carboxylic acid).
- the endo-endo isomer and / or trans-endo-endo isomer is separated and removed so that the purity is 90 mol% or more, and this is converted into an acid dianhydride to give the above general formulas (7) and (8).
- the alicyclic tetracarboxylic dianhydride according to the present invention is obtained by obtaining an alicyclic tetracarboxylic dianhydride containing 90 mol% or more of the alicyclic tetracarboxylic dianhydride represented by obtain It can be utilized modulo (third method) as appropriate.
- a method for obtaining the alicyclic tetracarboxylic dianhydride of the present invention for example, a tetracarboxylic acid represented by the general formula (10) using the compound represented by the general formula (9) is used.
- the dianhydride is obtained, the cis-endo-endo isomer and / or trans-endo-endo isomer is separated and removed so that the purity is 90 mol% or more.
- a method (first method) for obtaining a cyclic tetracarboxylic dianhydride may be used, and at the stage where a compound represented by the general formula (9) is prepared as a material to be used, By separating and removing the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound represented by a purity of 90 mol% or more, and converting this to tetracarboxylic dianhydride ,Up
- the method (second method) for obtaining the alicyclic tetracarboxylic dianhydride of the present invention may be used, or obtained at the stage of esterifying the compound represented by the general formula (9).
- the compound represented by the general formula (9) (raw material compound) obtained by adopting a general production method has six isomers (cis-endo-endo isomer, cis-exo-endo isomer, Cis-exo-exo isomers, trans-endo-endo isomers, trans-exo-endo isomers, trans-exo-exo isomers).
- the dianhydrides consist of six isomers (cis-endo-endo isomer, cis-exo-endo isomer, cis-exo-exo isomer, trans-endo-endo isomer, trans Exo - endo isomer, trans - exo - a mixture comprising exo isomer). Therefore, when the alicyclic tetracarboxylic dianhydride of the present invention is produced using the method as described above, the raw material compound stage before the reaction is started (represented by the general formula (9)).
- reaction intermediate stage stage obtained by esterifying the compound represented by the general formula (9)
- compound stage obtained after the reaction tetracarboxylic acid represented by the general formula (10)
- any stage of (acid dianhydride) it is necessary to separate the cis-endo-endo isomer and / or trans-endo-endo isomer so that the purity is 90 mol% or more. Further, in the above-mentioned raw material compound stage and reaction intermediate stage stage, the purity of the cis-endo-endo isomer and / or trans-endo-endo isomer of these compounds is adjusted to 90 mol% or more.
- the total amount of the cis-endo-endo isomer and / or trans-endo-endo isomer of the final compound derived from the compound obtained after separation is 90 mol% or more. . Therefore, the alicyclic tetracarboxylic dianhydride of the present invention can be obtained even when any one of the above-described first to third methods is employed. In addition, it does not restrict
- the method for producing the alicyclic tetracarboxylic dianhydride of the present invention will be described by taking the first method as an example.
- Said 1st method for manufacturing alicyclic tetracarboxylic dianhydride of this invention prepares the compound represented by the said General formula (9), Then, it represents with the said General formula (9). To obtain a tetracarboxylic dianhydride represented by the general formula (10), and then from the tetracarboxylic dianhydride represented by the general formula (10). The alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) so as to have a purity of 90 mol% or more is separated and taken out, whereby the alicyclic of the present invention is obtained. This is a method for obtaining tetracarboxylic dianhydride.
- R 1, R 2, R 3, n is the general formula (7) and (8) R 1, R 2 , R 3, n and are as defined in (what its preferred And R represents a monovalent organic group capable of forming an amine independently (for example, a linear saturated hydrocarbon group having 1 to 20 carbon atoms), and X ⁇ represents an amine and ammonium.
- a monovalent ion capable of forming a salt for example, halogen ion, hydrogen sulfate ion, acetate ion, etc.
- Such a method represented by the reaction formula (I) includes a cycloalkanone represented by the general formula (I-1) (cyclopentanone, cyclohexanone, etc.) and 2 equivalents or more of the cycloalkanone.
- Ammonium salts of secondary amines eg hydrochlorides, sulfates, acetates, etc .: compounds represented by the formula: NHR 2 HX in reaction formula (I)), formaldehyde derivatives, acids (hydrochloric acid, sulfuric acid, acetic acid, etc.)
- the reaction solution is heated at 30 to 180 ° C. for 0.5 to 10 hours in an inert gas atmosphere, and active in the reaction solution on both sides of the carbonyl group.
- the Mannich reaction of ⁇ -hydrogen-containing cyclic ketones, formaldehydes and secondary amines proceeds to synthesize the Mannich base represented by the general formula (I-2), and then the obtained Mannich base is simply Without separation, the reaction solution may be an organic solvent (any organic solvent that can be used for Diels-Alder reaction, preferably tetrahydrofuran, methanol, ethanol, isopropanol, butanol, acetonitrile, methyl cellosolve, ethyl cellosolve).
- organic solvent any organic solvent that can be used for Diels-Alder reaction, preferably tetrahydrofuran, methanol, ethanol, isopropanol, butanol, acetonitrile, methyl cellosolve, ethyl cellosolve).
- An organic solvent such as ethylene glycol, propylene glycol monomethyl ether, and propylene glycol) and a cyclopentadiene (which may have a substituent similar to the group that can be selected as R 1 in the general formula (10) ( 2 equivalents or more with respect to the Mannich base) is added to make a mixture, and then a base is introduced into the mixture to make it neutral or basic, under conditions of 0 to 150 ° C. (preferably about 60 ° C.). The mixture is stirred into the mixture for 0.1 to 48 hours.
- the divinyl ketone represented by the general formula (I-3) is prepared. And a cyclopentadiene optionally having the above substituent (Diels-Alder reaction) to produce a compound represented by the general formula (9).
- formaldehyde derivative known formaldehyde derivatives used for the production of Mannich base can be used as appropriate, and for example, formalin, paraformaldehyde, trioxane, 1,3-dioxolane, etc. can be used as appropriate.
- the divinyl ketone is synthesized by desorbing an amine compound from the Mannich base during stirring of the mixture at 0 to 150 ° C.
- Examples of the cycloalkanone represented by the general formula (I-1) in the reaction formula (I) include cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone.
- Examples of the secondary amine ammonium salt include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-t-butylamine, Dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, di (2-ethylhexyl) amine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, di Pentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, dinonadecylamine, morpholine, diethanolamine, aziridine, azetidine, pyrrolidine, pipet
- X ⁇ is a so-called counter anion, for example, F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , C 6 H 5 SO 3 ⁇ , CH 3 C 6 H 4 SO 3 ⁇ , HOSO 3 ⁇ and H 2 PO 4 — and the like can be mentioned.
- the divinyl ketone is synthesized by desorbing an amine compound from the Mannich base during stirring of the mixture at 0 to 150 ° C.
- Examples of the compound represented by the general formula (9) thus obtained include 5-norbornene-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene ( Also known as “5-norbornene-2-spiro-2′-cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene”), methyl-5-norbornene-2-spiro- ⁇ -cyclopentanone— ⁇ '-spiro-2 ′′-(methyl-5 ′′ -norbornene), 5-norbornene-2-spiro- ⁇ -cyclohexanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene (also known as “5- Norbornene-2-spiro-2′-cyclohexanone-6′-spiro-2 ′′ -5 ′′ -norbornene ”), methyl-5-norbornene-2-spiro- ⁇ -
- the compound (raw material compound) represented by the general formula (9) thus obtained has six isomers (cis-endo-endo isomer, cis-exo-endo isomer, cis-exo-exo). Isomers, trans-endo-endo isomers, trans-exo-endo isomers, trans-exo-exo isomers).
- a suitable method for obtaining a tetracarboxylic dianhydride represented by the general formula (10) by converting the compound represented by the general formula (9) into a tetracarboxylic dianhydride there is no particular limitation, and a known method capable of dianhydrating tetracarboxylic acid can be used as appropriate.
- a known method capable of dianhydrating tetracarboxylic acid can be used as appropriate.
- the method described in Macromolecules (Vol. 27), page 1117, published in 1994 is adopted. May be. That is, as a method for making such a tetracarboxylic dianhydride, the compound represented by the above general formula (9) is converted into carbon monoxide and methanol in the presence of a Pd catalyst, copper (II) chloride and sodium acetate.
- tetraesterification with alcohol After tetraesterification with alcohol, the resulting tetramethyl ester was subjected to a transesterification reaction with formic acid in the presence of an acid catalyst such as p-toluenesulfonic acid to obtain a tetracarboxylic acid.
- an acid catalyst such as p-toluenesulfonic acid
- a method in which acetic anhydride is allowed to coexist and the tetracarboxylic acid is converted to tetracarboxylic dianhydride with acetic anhydride may be employed. You may employ
- a suitable method for obtaining a tetracarboxylic dianhydride represented by the above general formula (10) by converting the compound represented by the general formula (9) into a tetracarboxylic dianhydride For example, in the presence of a palladium catalyst and an oxidizing agent, the compound represented by the general formula (9) is reacted with alcohol and carbon monoxide, and the following general formula (11):
- R 1, R 2, R 3, n has the same meaning as R 1, R 2, R 3 , n in the general formula (7) and (8)
- R 6, R 7 , R 8 and R 9 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl having 6 to 20 carbon atoms.
- 1 represents a group selected from the group consisting of a group and an aralkyl group having 7 to 20 carbon atoms
- n represents an integer of 0 to 12.
- the alkyl group that can be selected as R 6 , R 7 , R 8 , R 9 in the general formula (11) is an alkyl group having 1 to 10 carbon atoms. When the carbon number of such an alkyl group exceeds 10, purification becomes difficult.
- the number of carbon atoms of the alkyl group that can be selected as R 6 , R 7 , R 8 , or R 9 is more preferably 1 to 5 from the viewpoint of easier purification. 3 is more preferable.
- such an alkyl group that can be selected as R 6 , R 7 , R 8 , and R 9 may be linear or branched.
- the cycloalkyl group that can be selected as R 6 , R 7 , R 8 , R 9 in the general formula (11) is a cycloalkyl group having 3 to 10 carbon atoms. If the number of carbon atoms in such a cycloalkyl group exceeds 10, purification becomes difficult.
- the number of carbon atoms of the cycloalkyl group that can be selected as R 6 , R 7 , R 8 , or R 9 is more preferably 3 to 8 from the viewpoint of easier purification. More preferably, it is .about.6.
- the alkenyl group that can be selected as R 6 , R 7 , R 8 , R 9 in the general formula (11) is an alkenyl group having 2 to 10 carbon atoms.
- the carbon number of such an alkenyl group exceeds 10, purification becomes difficult.
- the number of carbon atoms of the alkenyl group that can be selected as R 6 , R 7 , R 8 , R 9 is more preferably 2 to 5 from the viewpoint of easier purification. 3 is more preferable.
- the aryl group that can be selected as R 6 , R 7 , R 8 , R 9 in the general formula (11) is an aryl group having 6 to 20 carbon atoms. If the number of carbon atoms in such an aryl group exceeds 20, purification becomes difficult.
- the number of carbon atoms of the aryl group that can be selected as R 6 , R 7 , R 8 , or R 9 is more preferably 6 to 10 from the viewpoint of easier purification. More preferably, it is 8.
- the aralkyl group that can be selected as R 6 , R 7 , R 8 , R 9 in the general formula (11) is an aralkyl group having 7 to 20 carbon atoms. If the number of carbon atoms in such an aralkyl group exceeds 20, purification becomes difficult.
- the number of carbon atoms of the aralkyl group that can be selected as R 6 , R 7 , R 8 , R 9 is more preferably 7-10, from the viewpoint of easier purification. More preferably, it is 9.
- R 6 , R 7 , R 8 , and R 9 in the general formula (11) are each independently a hydrogen atom, a methyl group, an ethyl group, or n-propyl, from the viewpoint of easier purification.
- R 6 , R 7 , R 8 and R 9 may be the same or different, but from the viewpoint of synthesis, they may be the same. More preferred.
- Examples of the compound represented by the general formula (11) include norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 '' -Tetracarboxylic acid tetramethyl ester, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acid tetraethyl ester Norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic acid tetrapropyl ester, norbornane-2-spiro- ⁇ -Cyclopentanone- ⁇ '-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic
- R 10 is other than a hydrogen atom among atoms and groups that can be selected as R 6 , R 7 , R 8, or R 9 in General Formula (11).
- R 10 is alcohol represented by these. That is, as such an alcohol, an alkyl alcohol having 1 to 10 carbon atoms, a cycloalkyl alcohol having 3 to 10 carbon atoms, an alkenyl alcohol having 2 to 10 carbon atoms, an aryl alcohol having 6 to 20 carbon atoms, It is preferable to use aralkyl alcohol having 7 to 20 carbon atoms.
- Such alcohols include methanol, ethanol, butanol, allyl alcohol, cyclohexanol, benzyl alcohol, etc.
- methanol and ethanol are preferred from the viewpoint that purification of the resulting compound is easier. Is more preferable, and methanol is particularly preferable.
- Such alcohols may be used alone or in combination of two or more.
- ester group represented by the above formula (the ester group may have the same or different R 10 at each introduced position), and norbornane-2 represented by the general formula (11) -Spiro- ⁇ -cycloalkanone- ⁇ '-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -reaction to obtain tetracarboxylic acid esters (esterification reaction).
- the amount of alcohol used in the esterification reaction is not particularly limited as long as it is an amount capable of obtaining the compound represented by the general formula (11).
- the alcohol may be added to a theoretically necessary amount (theoretical amount) for obtaining the represented compound, and the excess alcohol may be used as a solvent as it is.
- the required amount of carbon monoxide can be supplied to the reaction system. Therefore, it is not necessary to use a high-purity gas of carbon monoxide as the gas for supplying the carbon monoxide, and a mixture in which a gas inert to the esterification reaction (for example, nitrogen) and carbon monoxide is mixed. Gas may be used, and further, synthesis gas, coal gas, or the like may be used. Further, the pressure of such carbon monoxide is not particularly limited, but is preferably normal pressure (about 0.1 MPa [1 atm]) or more and 10 MPa or less.
- the palladium catalyst used in the first step is not particularly limited, and a known catalyst containing palladium can be appropriately used.
- a known catalyst containing palladium can be appropriately used.
- Specific examples of such a palladium catalyst include palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, palladium acetate trimer, palladium propionate, palladium carbon, palladium alumina, palladium black, and Pd having various ligands. A complex etc. are mentioned.
- the amount of the palladium catalyst used is such that the molar amount of palladium in the palladium catalyst is 0.001 to 0.1 times the molar amount of the compound represented by the general formula (9). Is preferred.
- the Pd 0 can be oxidized to Pd 2+.
- Any material can be used without particular limitation, and examples thereof include copper compounds, iron compounds, oxygen, air, and hydrogen peroxide.
- Specific examples of such oxidizing agents include cupric chloride, cupric nitrate, cupric sulfate, cupric acetate, ferric chloride, ferric nitrate, ferric sulfate, and acetic acid ferrous. Examples include ferric iron, manganese dioxide, and manganese acetate.
- Such an oxidizing agent is used in an amount of 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene represented by the general formula (9). It is preferably 2 to 16 times mol (more preferably about 8 times mol).
- a solvent for the reaction (esterification reaction) of the compound represented by the general formula (9) with alcohol and carbon monoxide is not particularly limited, and examples thereof include hydrocarbon solvents such as n-hexane, cyclohexane, heptane, pentane, and toluene.
- a base may be added to remove the acid.
- fatty acid salts such as sodium acetate, sodium propionate, and sodium butyrate are preferable.
- the amount of such base used may be appropriately adjusted according to the amount of acid generated.
- the reaction temperature conditions for the esterification reaction are not particularly limited, but are preferably 0 ° C. to 100 ° C. (more preferably about room temperature (25 ° C.)). When the reaction temperature exceeds the upper limit, the yield tends to decrease, and when the reaction temperature is less than the lower limit, the reaction rate tends to decrease.
- the reaction time for the esterification reaction is not particularly limited, but is preferably about 30 minutes to 24 hours.
- R 6 , R 7 , R 8 or R 9 in the general formula (11) a hydrogen atom
- Decomposition treatment or transesterification with carboxylic acid may be performed.
- the method for such a reaction is not particularly limited, and a known method in which the group represented by the formula: —COOR 10 can be changed to the formula: —COOH can be appropriately employed.
- a purification step such as recrystallization may be appropriately performed in order to obtain a compound with higher purity.
- a purification method is not particularly limited, and a known method can be appropriately employed.
- the compound represented by the general formula (11) (norbornane-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′ ′, 6,6 ′′ -tetracarboxylic acid esters) can be obtained efficiently.
- the compound represented by the general formula (11) thus obtained in the first step is composed of six isomers (cis-endo-endo isomer, cis-exo-endo isomer, cis-exo isomer). -Exo isomers, trans-endo-endo isomers, trans-exo-endo isomers, trans-exo-exo isomers).
- the acid catalyst used in the second step is not particularly limited, but from the viewpoint of acid strength, p-toluenesulfonic acid, benzenesulfonic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, trifluoroacetic acid, Amberlist and amberlite are preferable, and p-toluenesulfonic acid is more preferable.
- the amount of the acid catalyst used in the second step is 0.01 to 2.0 times mol (more preferably 0.01 to 0.2 mol) relative to the compound represented by the general formula (11). Double moles). When the amount of the acid catalyst used is less than the lower limit, the reaction rate tends to decrease. On the other hand, when the amount exceeds the upper limit, the yield tends to decrease.
- the lower carboxylic acid used in the second step formic acid, acetic acid and propionic acid are preferable, and acetic acid and propionic acid are more preferable from the viewpoint of removability of lower carboxylic acid ester generated by transesterification and water generated by dehydration and ring closure.
- the amount of the lower carboxylic acid (for example, formic acid, acetic acid, propionic acid) used in the second step is not particularly limited, but is 4 to 1000 times mol with respect to the compound represented by the general formula (11). (More preferably, it is 4 to 100 times mol).
- the amount of acetic anhydride used in the second step is not particularly limited, but it is 4 to 1000 times mol (more preferably 4 to 100 times mol) with respect to the compound represented by the general formula (11). It is preferable.
- the amount of acetic anhydride used is less than the lower limit, the reaction rate tends to decrease, and when it exceeds the upper limit, the yield tends to decrease.
- the second step is not particularly limited, but preferably includes the following steps (2-a) to (2-c), for example. That is, as such a second step, a mixed solution of the compound represented by the general formula (11), a lower carboxylic acid (formic acid, acetic acid, propionic acid, etc.) and an acid catalyst is prepared, and the mixed solution is A step (2-a) of heating to reflux, a part of the liquid in the mixed solution was distilled off under reduced pressure to concentrate the mixed solution, and a lower carboxylic acid (formic acid or the like) was added again to the obtained concentrated solution.
- a mixed solution of the compound represented by the general formula (11), a lower carboxylic acid (formic acid, acetic acid, propionic acid, etc.) and an acid catalyst is prepared, and the mixed solution is A step (2-a) of heating to reflux, a part of the liquid in the mixed solution was distilled off under reduced pressure to concentrate the mixed solution, and a lower carboxylic acid (formic acid or the like) was added
- a part of the liquid in the obtained mixed liquid is distilled off under reduced pressure and concentrated again to obtain a concentrated liquid (2-b), and a lower carboxylic acid (formic acid, It is preferable to include a step (2-c) of adding a compound represented by the general formula (10) by adding acetic anhydride, acetic anhydride, and the like and heating to reflux.
- a step (2-c) of adding a compound represented by the general formula (10) by adding acetic anhydride, acetic anhydride, and the like and heating to reflux.
- the amount of the lower carboxylic acid (formic acid, acetic acid, propionic acid, etc.) used in preparing the mixed solution in the step (2-a) is 4 to 4 with respect to the compound represented by the general formula (11).
- the molar amount is preferably 1000 times (particularly preferably about 50 times mole).
- step (2-b) the step of adding and concentrating lower carboxylic acid such as formic acid, acetic acid, propionic acid, etc. to the concentrated solution is repeatedly carried out in step (2-b) (preferably 1 It is preferable to repeat the process 5 to 5 times or alternatively, in step (2-b), after the produced carboxylic acid ester and water are distilled off together with the lower carboxylic acid, the lower carboxylic acid is continuously added.
- step (2-b) R 6 and R 7 in the general formula (11) are repeatedly carried out by repeatedly adding and concentrating a lower carboxylic acid such as formic acid, acetic acid and propionic acid to the concentrated solution.
- the tetraester can be completely converted to a tetracarboxylic acid, and the step (2-c) to be carried out after that makes the above general formula (2-c) more efficient. It becomes possible to obtain the compound represented by 10). Furthermore, the amount of the lower carboxylic acid (formic acid, acetic acid, propionic acid, etc.) used in the production of the mixed solution in the step (2-a) is 50 times that of the compound represented by the general formula (11). It is preferable to be about a mole. In addition, the amount of the lower carboxylic acid (formic acid, etc.) added to the concentrate in the steps (2-b) and (2-c) is preferably about the same as the amount of the liquid distilled off during the concentration.
- the method for concentrating (depressurizing distillation) of the mixed solution in the step (2-b) is not particularly limited, and a known method can be appropriately employed.
- the temperature condition for heating and refluxing in the steps (2-a) to (2-c) is preferably 100 ° C. to 180 ° C., more preferably 100 ° C. to 140 ° C.
- the heating reflux temperature is less than the lower limit, the yield tends to decrease.
- the upper limit is exceeded, by-products increase and coloring tends to decrease and the transparency decreases.
- the heating and refluxing time is preferably about 30 minutes to 50 hours (more preferably about 30 minutes to 24 hours).
- R 1 , R 2 , R 3 and n in the formula (10) are represented by the above general formulas (7) and ( 8) (that is, the same as R 1 , R 2 , R 3 and n in the above general formulas (1) and (2)), and the preferred one is R 1 in the above general formula (1).
- R 2 , R 3 and n are the same as preferred.
- the tetracarboxylic dianhydride represented by the general formula (10) thus obtained includes, for example, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane- 5,5 ′′, 6,6 ′′ -tetracarboxylic dianhydride (also known as “norbornane-2-spiro-2′-cyclopentanone-5′-spiro-2 ′′ -norbornane-5,5 ′′ , 6,6 ′′ -tetracarboxylic dianhydride ”), methylnorbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′-(methylnorbornane) -5,5 ′′, 6 , 6 ′′ -tetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -cyclohexanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5
- R 1, R 2, R 3, n has the same meaning as R 1, R 2, R 3 , n in the general formula (7) and (8)
- R 6, R 7 , R 8 and R 9 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. It represents one selected from an aryl group, and the group consisting of an aralkyl group having a carbon number of 7 ⁇ 20, R 10 has the same meaning as R 10 in the general formula (12).
- the preferred method for obtaining the tetracarboxylic dianhydride represented by the general formula (10) is not limited to this method. .
- the compound represented by the general formula (11) is obtained by carrying out the first step. Then, the compound represented by the general formula (11) is hydrolyzed in the presence of an acid catalyst or a base catalyst to obtain norbornane-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′- Norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic acid was prepared, and then norbornane-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -norbornane-5 was obtained.
- tetracarboxylic acid can be dehydrated and closed by heating or by using a dehydrating agent to produce a tetracarboxylic dianhydride represented by the general formula (10). It is done.
- a compound represented by the general formula (11) by carrying out the first step After preparing a mixture of the compound represented by the general formula (11), a lower carboxylic acid (formic acid, acetic acid, propionic acid, etc.) and an acid catalyst, and heating and refluxing the mixture, You may employ
- the carboxylic acid ester and water that are produced are distilled off together with the lower carboxylic acid from the mixed solution that is being heated and refluxed, so that the amount of the lower carboxylic acid becomes constant. It is preferable to heat and reflux while adding.
- the amount of the lower carboxylic acid (formic acid, acetic acid, propionic acid, etc.) used in such a method is 4 to 1000 times the molar amount of the compound represented by the general formula (11) (particularly preferably 50 It is preferable to set it to about a double mole.
- the temperature condition for such heating and reflux is preferably 100 ° C. to 180 ° C., more preferably 100 ° C. to 140 ° C.
- the heating and refluxing time is preferably about 5 to 50 hours.
- the compound represented by the general formula (10) can be precipitated by leaving the mixed solution at room temperature (25 ° C.). it can.
- the tetracarboxylic dianhydride represented by the general formula (10) thus obtained includes the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8). 6 stereoisomers (cis-endo-endo isomer, cis-exo-endo isomer, cis-exo-exo isomer, trans-endo-endo isomer, trans-exo-endo isomer, trans-exo isomer) -Exo isomers).
- the general formula (10) By separating and removing the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) from the compound represented by (10) so that the purity is 90 mol% or more.
- the alicyclic tetracarboxylic dianhydride of the present invention is obtained.
- the method for separating and taking out the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) from the compound represented by the general formula (10) is particularly limited. It is possible to appropriately use a known method capable of separating a desired isomer from a compound group, for example, employing a recrystallization method (including a crystallization method) or an adsorption separation method. May be.
- the conditions for the recrystallization method may be appropriately set according to the type of the alicyclic tetracarboxylic dianhydride represented by the general formula (7) and / or (8).
- the compound represented by the general formula (10) is dissolved in a solvent under a temperature condition of ⁇ 40 ° C.
- Solvents that can be used in such a recrystallization method are not particularly limited.
- hydrocarbon solvents such as pentane, hexane, heptane, and petroleum ether
- aromatic solvents such as benzene, toluene, and xylene.
- Ester solvents such as ethyl acetate; ether solvents such as ethyl ether, isopropyl ether, THF and dioxane; nitrile solvents such as acetonitrile and propionitrile; polar solvents such as DMF, DMAc, NMP and DMSO; And halogen solvents such as chloroform and chlorobenzene; carboxylic acid solvents such as formic acid, acetic acid, propionic acid, and acetic anhydride;
- the temperature condition for dissolving the compound represented by the general formula (10) in such a solvent is preferably ⁇ 40 ° C. to 200 ° C., more preferably 0 to 150 ° C.
- the compound represented by the general formula (10) is decomposed by impurities such as moisture, alcohol, and amine, and the alicyclic ring represented by the general formulas (7) and (8).
- the alicyclic tetracarboxylic dianhydride tends not to be sufficiently dissolved in the solvent below the lower limit.
- the amount of the solvent used in the case of adopting such a recrystallization method is 0.5 to 500 times (V / V) based on the capacity with respect to the compound represented by the general formula (10). It is preferably 1 to 100 times (V / V). If the amount (magnification) of the solvent used is less than the lower limit, the alicyclic tetracarboxylic dianhydride tends not to be sufficiently dissolved in the solvent. Precipitation of the alicyclic tetracarboxylic dianhydride represented by 8) is insufficient and the yield tends to decrease.
- adsorption separation that can be employed to separate and remove the alicyclic tetracarboxylic dianhydrides represented by the general formulas (7) and (8) from the compound represented by the general formula (10).
- the compound represented by the general formula (10) is dissolved in a solvent.
- the above-mentioned general formula (7) is used by appropriately using a known adsorbent and employing a known adsorption separation means such as adsorbent addition, column chromatography, HPLC, filtration, solid-liquid extraction and the like. And the method etc.
- adsorbent examples include, but are not limited to, celite, silica gel, alumina, activated clay, silica alumina, zeolite, activated carbon, carbon nanotube, charcoal, ion exchange resin and the like.
- hydrocarbon solvents such as pentane, hexane, heptane and petroleum ether
- aromatic solvents such as benzene, toluene and xylene
- ester solvents such as ethyl acetate
- ethyl And ether solvents such as ether, isopropyl ether, THF and dioxane
- nitrile solvents such as acetonitrile and propionitrile
- halogen solvents such as methylene chloride, chloroform and chlorobenzene
- the separation means described above when the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) is selectively separated by the separation means described above, for example, the polarity of the solvent in the solution is changed.
- a method of desorption can be used, and the separation method is appropriately changed according to the type of the alicyclic tetracarboxylic dianhydride represented by the general formula (7) and / or (8) to be separated. Can do.
- the temperature condition for separating the compounds by such an adsorption separation method is preferably ⁇ 40 ° C. to 200 ° C., more preferably 0 to 100 ° C.
- the compound represented by the general formula (10) is decomposed by impurities such as moisture, alcohol, and amine, and the fat represented by the general formulas (7) and (8).
- impurities such as moisture, alcohol, and amine
- the fat represented by the general formulas (7) and (8) There is a tendency that cyclic tetracarboxylic dianhydride cannot be obtained.
- alicyclic tetracarboxylic dianhydride tends not to be sufficiently dissolved in the solvent.
- the amount of the solvent used in the case of employing such an adsorption separation method is 0.5 to 500 times (V / V) based on the capacity of the compound represented by the general formula (10). Is preferably 2 to 100 times (V / V). If the amount (magnification) of the solvent used is less than the lower limit, the alicyclic tetracarboxylic dianhydride tends not to be sufficiently dissolved in the solvent. It tends to be a dilute product solution, resulting in a decrease in work efficiency and recovery rate.
- the purity of the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) can be 90 mol% or more, whereby the fat of the present invention can be obtained. It is possible to obtain cyclic tetracarboxylic dianhydrides.
- the compound represented by the said General formula (9) As mentioned above, after manufacturing the compound represented by the said General formula (9) as a method for manufacturing the alicyclic tetracarboxylic dianhydride of this invention (the said General formula (9)
- the compound represented by this formula is converted into a tetracarboxylic dianhydride to obtain a tetracarboxylic dianhydride represented by the following general formula (10), and then the tetracarboxylic dianhydride represented by the general formula (10).
- the alicyclic tetracarboxylic dianhydride of the present invention is obtained by separating and removing the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) from the product) In the following, the second and third methods described above will be described.
- Said 2nd method for manufacturing the alicyclic tetracarboxylic dianhydride of this invention prepares the compound represented by the said General formula (9), The compound represented by the said General formula (9) The cis-endo-endo isomer and / or the trans-endo-endo isomer are separated and removed so as to have a purity of 90 mol% or more.
- the alicyclic tetracarboxylic dianhydride containing the alicyclic tetracarboxylic dianhydride represented by 7) and (8) in a total amount of 90 mol% or more is obtained, whereby the alicyclic tetracarboxylic acid of the present invention is obtained.
- a second method as a method of converting the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound represented by the general formula (9) to tetracarboxylic dianhydride, A method similar to the method of converting the compound represented by the general formula (9) described in the first method to tetracarboxylic dianhydride can be used.
- the method for separating and extracting the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound from the compound represented by the general formula (9) is not particularly limited, and is publicly known.
- the method can be appropriately used, and for example, a recrystallization method and an adsorption separation method can be appropriately employed.
- Such a recrystallization method is not particularly limited, and the conditions can be appropriately changed according to the compound represented by the general formula (9) and the kind of the target isomer.
- the compound represented by the general formula (9) is dissolved in a solvent under a temperature condition of ⁇ 40 ° C. to 120 ° C., and then recrystallized at a temperature lower than the dissolution temperature, whereby the general formula (9)
- a method of selectively separating the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound represented by 9) can be employed.
- a recrystallization method is used as a method for separating and extracting the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound represented by the general formula (9).
- the solvent that can be suitably used for the recrystallization method include alcohol solvents such as methanol, ethanol, and propanol; hydrocarbon solvents such as pentane, hexane, heptane, and petroleum ether.
- the temperature condition for dissolving the compound represented by the general formula (9) in such a solvent is preferably ⁇ 40 ° C. to 120 ° C., more preferably 0 to 100 ° C.
- a temperature exceeds the upper limit the compound represented by the general formula (9) is decomposed by the retro Diels-Alder reaction, and the alicyclic tetracarboxylic acid represented by the general formulas (7) and (8).
- the acid dianhydride tends to be unable to be obtained.
- the compound represented by the general formula (9) tends not to be sufficiently dissolved.
- the amount of the solvent used in the case of employing such a recrystallization method is 0.5 to 100 times (V / V) based on the capacity of the compound represented by the general formula (9). It is preferably 1 to 50 times (V / V).
- the amount of use (magnification) of such a solvent is less than the lower limit, the compound represented by the general formula (9) tends not to be sufficiently dissolved in the solvent. The yield of the compound tends to decrease due to insufficient precipitation of the compound.
- an adsorptive separation method is used as a method for separating and taking out the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound represented by the general formula (9)
- the method of the adsorptive separation method is not particularly limited, and the conditions can be appropriately changed according to the compound represented by the general formula (9) and the kind of the target isomer.
- the compound represented by the general formula (9) Is dissolved in a solvent to obtain a solution, and a known adsorption agent is appropriately used to adopt a known adsorption separation means such as adsorbent addition, column chromatography, HPLC, filtration, solid-liquid extraction, etc.
- a method of selectively separating the endo-endo isomer and / or the trans-endo-endo isomer can be employed.
- the compound represented by the general formula (9) is dissolved in a solvent to obtain a solution as described above, and then recrystallized to represent the general formula (9).
- a method may be employed in which after the cis-endo-endo isomer and / or trans-endo-endo isomer of the resulting compound is precipitated, the solvent-soluble portion thereof is filtered using an adsorbent.
- the adsorptive separation method when used as a method for separating and extracting the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound represented by the general formula (9) Basically, from the compound represented by the general formula (10), a compound represented by the above general formula (10) can be used except that the temperature conditions and the like are appropriately changed according to the kind of the cis-endo-endo isomer and / or the trans-endo-endo isomer.
- a method similar to the adsorption separation method that can be employed for separating and removing the alicyclic tetracarboxylic dianhydride represented by (7) and (8) can be employed.
- the temperature condition is preferably ⁇ 40 ° C. to 120 ° C., more preferably 0 to 100 ° C.
- the compound represented by the general formula (9) is decomposed by the retro Diels-Alder reaction, and the alicyclic tetramer represented by the general formulas (7) and (8).
- Carboxylic dianhydride tends to be unable to be obtained.
- the compound represented by the general formula (9) tends not to be sufficiently dissolved in the solvent.
- a method of obtaining an anhydride in carrying out such a method, as the method for obtaining the compound represented by the general formula (11), and the subsequent method for acid dianhydride conversion of the tetracarboxylic acid or ester, the first method described above is used. Can be used.
- the method for separating and extracting the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound from the compound represented by the general formula (11) is not particularly limited, and is publicly known.
- the method can be appropriately used, and a recrystallization method and an adsorption separation method can be appropriately employed.
- Such a recrystallization method is not particularly limited, and the conditions can be appropriately changed according to the compound represented by the general formula (11) and the kind of the target isomer.
- a recrystallization method for example, the compound represented by the general formula (11) is dissolved in a solvent under a temperature condition of ⁇ 40 ° C. to 200 ° C., and then the temperature is lower than the dissolved temperature.
- a method of selectively separating the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound represented by the general formula (11) by recrystallization can be employed.
- Solvents that can be suitably used in the method include alcohol solvents such as methanol, ethanol and propanol; hydrocarbon solvents such as pentane, hexane, heptane and petroleum ether; aromatic solvents such as benzene, toluene and xylene Solvent; Ester solvent such as ethyl acetate; Ether solvent such as ethyl ether, isopropyl ether, THF, dioxane; Nitrile solvent such as acetonitrile, propionitrile; Polar solvent such as DMF, DMAc, NMP, DMSO, methylene chloride , Halogen solvents such as chloroform and chlorobenzene It is.
- the temperature condition for dissolving the compound represented by the general formula (11) in such a solvent is preferably ⁇ 40 ° C. to 200 ° C., more preferably 0 to 150 ° C.
- the compound represented by the general formula (11) is decomposed by water, oxygen, etc., and the alicyclic tetracarboxylic acid represented by the general formulas (7) and (8)
- the dianhydride tends to be unable to be obtained.
- the compound represented by the general formula (11) tends not to be sufficiently dissolved in the solvent.
- the amount of the solvent used in the case of employing such a recrystallization method is 0.5 to 100 times (V / V) based on the capacity with respect to the compound represented by the general formula (11). It is preferably 1 to 50 times (V / V). If the amount (magnification) of the solvent used is less than the lower limit, the compound represented by the general formula (11) tends not to be sufficiently dissolved. On the other hand, if the amount exceeds the upper limit, the compound represented by the general formula (11) Precipitation is insufficient and the yield tends to decrease.
- an adsorptive separation method is used as a method for separating and extracting the cis-endo-endo isomer and / or trans-endo-endo isomer of the compound represented by the general formula (11), Basically, from the compound represented by the general formula (10), a compound represented by the general formula (7) is used except that the temperature condition and the like are appropriately changed according to the type of the endo-endo isomer and / or the trans-endo-endo isomer. ) And (8), the same method as the adsorption separation method that can be employed for separating and taking out the alicyclic tetracarboxylic dianhydride can be employed.
- the method for producing the polyimide of the present invention is not particularly limited.
- the alicyclic tetracarboxylic dianhydride of the present invention in the presence of an organic solvent, the alicyclic tetracarboxylic dianhydride of the present invention and the following general formula (14):
- R 4 represents an aryl group having 6 to 40 carbon atoms.
- the polyamic acid solution is prepared by preparing a polyamic acid containing at least one type of repeating unit represented by formula (II) and having a total amount of the repeating units represented by the general formulas (15) and (16) of 90 mol% or more. (Step (I)) to obtain A step of obtaining the polyimide of the present invention by imidizing the polyamic acid (step (II)); A method including can be suitably used.
- step (I) and step (II) will be described separately.
- step (I) a polyamic acid is prepared by reacting the alicyclic tetracarboxylic dianhydride of the present invention with the aromatic diamine represented by the general formula (14) in the presence of an organic solvent. And a step of obtaining a polyamic acid solution.
- the alicyclic tetracarboxylic dianhydride used in such step (I) is the alicyclic tetracarboxylic dianhydride of the present invention, which is represented by the general formula (7) and (8).
- the total amount of alicyclic tetracarboxylic dianhydride is 90 mol% or more.
- the alicyclic tetracarboxylic dianhydride of the present invention is represented by a plurality of general formulas (1) and (2) in which the types of R 1 , R 2 , R 3 and n are different.
- the properties of the resulting polyimide can be changed as appropriate by changing the type as appropriate. .
- Examples of the aromatic diamine represented by the general formula (14) include 4,4′-diaminodiphenylmethane, 4,4 ′′ -diamino-p-terphenyl, 3,3′-diaminodiphenylmethane, 4 , 4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2 , 2-bis (4-aminophenoxyphenyl) propane, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] Sulfone, bis [4- (3-aminophenoxy) phenyl] sul
- R 4 of the aromatic diamine represented by the general formula (14) is:
- the group represented by the general formula (5) or (6) is more preferable, and among them, the group represented by the general formula (5) and the group represented by the general formula (6) and Q is —CONH At least one group represented by —, —COO—, —CO—, —C 6 H 4 — (more preferably a group represented by —CONH—, —COO—, particularly preferably —CONH It is preferable that the group is a group represented by-.
- R 4 of the aromatic diamine represented by the general formula (14) is selected from the general formula (3) from the viewpoint of imparting higher flexibility.
- Q is one of the groups represented by —O—, —S—, —CH 2 —, —O—C 6 H 4 —O—
- the group represented by 6) is preferably one group selected from the group consisting of: From the viewpoint of easy availability, R 4 of the aromatic diamine represented by the general formula (14) is such that Q is —O—, —CH 2 —, —O—C 6 H 4 —O—.
- a group represented by the above general formula (one more preferably a group represented by —O— or —CH 2 —, and more preferably a group represented by —O—).
- the group represented by 6) is preferable.
- the glass transition temperature and the linear expansion coefficient of polyimide can be set within the ranges of the above preferable numerical values, and the glass transition temperature and the linear expansion can be obtained. From the viewpoint of more reliably preparing a polyimide that can exhibit a good balance between the coefficient and the flexibility when a film is formed, a plurality of different types of R 4 in the general formula (14) are used. It is preferable to use a combination of two or more aromatic diamines.
- R 4 is the general in the general formula (14) A group represented by formula (5); and at least one of the groups represented by Q is represented by —CONH—, —COO—, —CO—, —C 6 H 4 — (more preferably —CONH— A group represented by the general formula (6) which is a group represented by —COO—, particularly preferably a group represented by —CONH—.
- a group diamine and R 4 in the general formula (14) is a group represented by the general formula (3); and the Q is —O—, —S—, —CH 2 —, —O—C 6.
- organic solvent used in the step (I) it is possible to dissolve both the alicyclic tetracarboxylic dianhydride of the present invention and the aromatic diamine represented by the general formula (14). It is preferable that it is an organic solvent.
- organic solvents examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide N, N′-dimethylimidazole, dimethyl sulfoxide, ⁇ -butyrolactone, propylene carbonate, tetra Aprotic polar solvents such as methylurea, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, pyridine; phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol; tetrahydro And ether solvents such as furan, dioxane, cellosolve, and glyme; aromatic solvents such as benzene, toluene, xylene, and 2-chloro-4-hydroxytoluene. Such organic solvents may be used alone or in combination of two or more.
- step (I) the ratio of the alicyclic tetracarboxylic dianhydride of the present invention to the aromatic diamine represented by the general formula (14) is represented by the general formula (14).
- the acid anhydride group of the alicyclic tetracarboxylic dianhydride of the present invention is 0.2 to 2 equivalents relative to 1 equivalent of the amino group of the aromatic diamine to be used, More preferably, it is 1.2 equivalents. If the use ratio is less than the lower limit, the polymerization reaction does not proceed efficiently, and a high molecular weight polyamic acid tends not to be obtained. On the other hand, if the upper limit is exceeded, a high molecular weight polyamic acid is obtained as described above. There is no tendency.
- the molar ratio of the alicyclic tetracarboxylic dianhydride of the present invention and the aromatic diamine represented by the general formula (14) ([the alicyclic tetracarboxylic dianhydride of the present invention is used).
- Anhydride]: [diamine compound]) is 0.5: 1.0 to 1.0: 0.5 (more preferably 0.9: 1.0 to 1.0: 0.9) Is preferred. If the amount of the alicyclic tetracarboxylic dianhydride used in the present invention is less than the lower limit, the yield of the polyimide tends to decrease. On the other hand, even if the upper limit is exceeded, the yield of the polyimide tends to decrease. It is in.
- the total amount of the aromatic diamine represented by the said alicyclic tetracarboxylic dianhydride of this invention and the said General formula (14) is the reaction solution.
- the amount is preferably 0.1 to 50% by mass (more preferably 10 to 30% by mass) with respect to the total amount. If the amount of the organic solvent used is less than the lower limit, the polyamic acid tends not to be obtained efficiently. On the other hand, if it exceeds the upper limit, stirring tends to be difficult due to the increase in viscosity.
- a basic compound may be further added to the organic solvent.
- examples of such basic compounds include, but are not limited to, triethylamine, tetrabutylamine, tetrahexylamine, 1,8-diazabicyclo [5.4.0] -undecene-7, pyridine, isoquinoline, N-methylpiperidine, ⁇ -picoline and the like can be mentioned.
- the amount of such a base compound used is preferably 0.001 to 10 equivalents relative to 1 equivalent of the alicyclic tetracarboxylic dianhydride of the present invention, preferably 0.01 to 0.1 More preferably, it is equivalent. If the amount of such a basic compound used is less than the lower limit, the effect of addition tends to be lost. On the other hand, if it exceeds the upper limit, it tends to cause coloring or the like.
- the reaction temperature for reacting the alicyclic tetracarboxylic dianhydride of the present invention with the aromatic diamine represented by the general formula (14) is the reaction of these compounds.
- the temperature can be suitably adjusted to a temperature that can be adjusted, and is not particularly limited, but is preferably 80 ° C. or less, and preferably ⁇ 30 to 30 ° C.
- tetracarboxylic A method capable of performing a polymerization reaction of acid dianhydride and aromatic diamine can be appropriately used, and is not particularly limited.
- an inert diamine such as nitrogen, helium, or argon
- the aromatic diamine A method may be employed in which the compound is dissolved in a solvent, the alicyclic tetracarboxylic dianhydride of the present invention is added at the reaction temperature, and then reacted for 10 to 48 hours. If the reaction temperature or reaction time is less than the lower limit, it tends to be difficult to react sufficiently. On the other hand, if the upper limit is exceeded, the mixing probability of substances (such as oxygen) that degrade the polymer increases, and the molecular weight increases. It tends to decrease.
- the polyamic acid thus obtained may be isolated and then dissolved again in a solvent (for example, the organic solvent) to form a polyamic acid solution used in step (II), or A reaction obtained by reacting the alicyclic tetracarboxylic dianhydride of the present invention with the aromatic diamine represented by the general formula (14) in an organic solvent without isolating the polyamic acid.
- the solution (reaction solution containing the above polyamic acid) may be used as it is as the polyamic acid solution used in step (II).
- the isolation method is not particularly limited, and a known method capable of isolating the polyamic acid can be appropriately employed. For example, a method of isolating as a reprecipitate may be employed.
- R 1, R 2, R 3, n is, R 1 in the general formula (7) and (8), R 2, R 3, n synonymous in and, R 4 has the same meaning as R 4 in the general formula (14). That, R 1 in the general formula (15) and (16), R 2, R 3, R 1 R 4 and n are the general formula (1) and (2) in, R 2, R 3, R 4 and n are the same as those described above, and suitable ones thereof are also the same as R 1 , R 2 , R 3 , R 4 and n in the general formulas (1) and (2).
- the total amount of the repeating units represented by the general formulas (15) and (16) is 90 mol% or more.
- the total amount of such repeating units is the total amount of the alicyclic tetracarboxylic dianhydride represented by the general formulas (7) and (8) in the alicyclic tetracarboxylic dianhydride of the present invention.
- the preferred range of the total amount is the same as the preferred range of the total amount of the alicyclic tetracarboxylic dianhydrides represented by the general formulas (7) and (8). If the total amount of the repeating units represented by the general formulas (15) and (16) is less than 90 mol%, the polyimide of the present invention cannot be produced.
- the polyamic acid obtained in the step (I) preferably has an intrinsic viscosity [ ⁇ ] of 0.1 to 8.0 dL / g, preferably 0.1 to 6.0 dL / g. Is more preferably 0.1 to 3.0 dL / g, and particularly preferably 0.4 to 2.0 dL / g.
- the intrinsic viscosity [ ⁇ ] is smaller than 0.1 dL / g, when a film-like polyimide is produced using the intrinsic viscosity [ ⁇ ], the resulting film tends to become brittle, while 8.0 dL / g is reduced.
- Such intrinsic viscosity [ ⁇ ] can be measured as follows. Specifically, first, a measurement sample (solution) in which N, N-dimethylacetamide is used as a solvent and the polyamic acid is dissolved in the N, N-dimethylacetamide so as to have a concentration of 0.5 g / dL. obtain. Next, using the measurement sample, the viscosity of the measurement sample is measured using a kinematic viscometer under a temperature condition of 30 ° C., and the obtained value is adopted as the intrinsic viscosity [ ⁇ ]. In addition, as such a kinematic viscometer, an automatic viscosity measuring device (trade name “VMC-252”) manufactured by Koiso Co., Ltd. is used.
- VMC-252 automatic viscosity measuring device manufactured by Koiso Co., Ltd.
- repeating units other than the repeating units represented by the above general formulas (1) and (2) may be contained.
- other repeating units may be added to the alicyclic tetracarboxylic dianhydride of the present invention represented by the above general formulas (7) and (8). It may be formed by introducing another tetracarboxylic dianhydride other than tetracarboxylic dianhydride, and in the step (I), other monomers together with the alicyclic tetracarboxylic dianhydride of the present invention. It may be formed by using other diamine compounds together with the aromatic diamine represented by the general formula (14). Combination as appropriate It may be formed by adoption.
- alicyclics other than the alicyclic tetracarboxylic dianhydrides represented by the general formulas (7) and (8) that can be introduced into the alicyclic tetracarboxylic dianhydrides of the present invention.
- examples of other monomers that can be used together with the tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride of the present invention include alicyclic tetracarboxylic acids represented by the general formulas (7) and (8).
- the well-known diamine compound which can be used for manufacture of a polyimide or a polyamic acid can be used suitably, for example, aliphatic diamine, An alicyclic diamine or the like can be used as appropriate.
- aliphatic diamines include ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, and polyoxyalkylene diamine.
- Examples of the alicyclic diamine include 4,4′-diamino-dicyclohexylmethane, 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane, and 3,3′-diethyl-4,4′-.
- Step (II) is a step of obtaining the polyimide of the present invention by imidizing the polyamic acid obtained in step (I).
- the method for imidizing the polyamic acid obtained by such step (I) is not particularly limited as long as it is a method capable of imidizing polyamic acid, and a known method can be appropriately employed. It is preferable to employ a method of imidizing by performing a dehydration reaction by subjecting the polyamic acid to a heat treatment or a method of imidizing using a so-called “imidizing agent”.
- a temperature of 200 to 450 ° C. (preferably 250 to It is preferable to perform the heat treatment at a temperature of 440 ° C., more preferably 300 to 430 ° C., still more preferably 350 to 420 ° C., particularly preferably 360 ° C. to 410 ° C.
- reaction solution reaction solution containing the polyamic acid
- aromatic diamine represented by the general formula (14) as a solution of the polyamic acid for imidization as it is, It is preferable to employ a method of imidizing the polyamic acid solution (reaction solution) by subjecting it to a drying treatment to remove the solvent and then performing a heating treatment in the temperature range.
- the temperature condition in such a drying treatment method is preferably 0 to 100 ° C., more preferably 20 to 80 ° C. If the temperature condition in such a drying process is less than the lower limit, the solvent tends not to be dried. On the other hand, if the upper limit is exceeded, the solvent boils, and the resulting polyimide tends to contain bubbles and voids.
- the atmosphere in such a drying treatment method is preferably an inert gas atmosphere (for example, a nitrogen atmosphere).
- the pressure condition in such a drying process is preferably 1 to 200 mmHg.
- the organic solvent described in the step (I) can be preferably used. Therefore, in the case of adopting the imidization method using an imidizing agent, the alicyclic tetratetrafluoroethylene of the present invention is isolated in an organic solvent without isolating the polyamic acid obtained in the step (I).
- the reaction liquid reaction liquid containing the polyamic acid
- the aromatic diamine represented by the general formula (14) as it is. It is more preferable to employ a method in which an imidizing agent is added to the polyamic acid solution (reaction solution) and imidized.
- an imidizing agent a known imidizing agent can be appropriately used.
- acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride
- pyridine collidine
- lutidine triethylamine
- N -Tertiary amines such as methylpiperidine and ⁇ -picoline
- the imidation reaction temperature is preferably 0 to 180 ° C, more preferably 60 to 150 ° C.
- the reaction time is preferably 0.1 to 48 hours. If the reaction temperature or time is less than the lower limit, it tends to be difficult to sufficiently imidize. On the other hand, if the upper limit is exceeded, the mixing probability of a substance (such as oxygen) that degrades the polymer increases, and the molecular weight increases. It tends to decrease.
- the amount of the imidizing agent used is not particularly limited, and is from several millimoles to several mols per mol of the repeating unit represented by the general formulas (15) and (16) in the polyamic acid ( (Preferably about 0.05 to 1.0 mol).
- the polyamic acid contains at least one repeating unit represented by the general formulas (1) and (2) and is represented by the general formulas (1) and (2).
- a polyimide having a total amount of repeating units of 90 mol% or more based on all repeating units can be obtained.
- the form of such polyimide is not particularly limited, and may be a film shape.
- a method for obtaining such a film for example, after forming the polyamic acid coating film on a substrate, the coating film is subjected to a drying treatment to remove the solvent, and the polyamide as a dry coating film obtained is obtained.
- the method (a) for obtaining a film comprising the polyimide of the present invention by imidizing an acid and heat-curing may be employed, or obtained as a dry coating film on a substrate as described above.
- polyimide or a solution of polyimide imidized by adding an imidizing agent as described above this is added to a solvent with poor solubility of the polyimide, and appropriately subjected to filtration, washing, drying, etc.
- the polyimide of the present invention is isolated, the isolated polyimide is dissolved in an organic solvent to prepare a polyimide solution, the polyimide solution is applied to a substrate, and the coating film is dried. , And heat-curing the dried coating film of the polyimide, a method may be adopted (b) to obtain a film of polyimide of the present invention.
- the base material used in such methods (a) and (b) is not particularly limited, and from known materials that can be used for film formation, depending on the shape of the film made of the target polyimide.
- a base material for example, a glass plate or a metal plate
- the method for applying the polyamic acid solution or the like on the substrate is not particularly limited.
- spin coating, spray coating, dip coating, dropping, gravure printing, screen printing, letterpress Known methods such as a printing method, a die coating method, a curtain coating method, and an ink jet method can be appropriately employed.
- the thickness of the polyamic acid coating film formed on the substrate in the method (a) is preferably 1 to 200 ⁇ m after drying, and preferably 5 to 100 ⁇ m. More preferably. If such a thickness is less than the lower limit, the mechanical strength of the resulting film tends to decrease, and if it exceeds the upper limit, film forming tends to be difficult.
- the temperature condition when the coating film is dried in the method (a) is preferably 0 to 100 ° C., more preferably 20 to 80 ° C. If the temperature condition in such a drying process is less than the lower limit, the solvent tends not to be dried. On the other hand, if the temperature condition exceeds the upper limit, the solvent tends to boil and form a film containing bubbles and voids.
- the atmosphere in such a drying treatment method is preferably an inert gas atmosphere (for example, a nitrogen atmosphere).
- the pressure condition in such a drying process is preferably 1 to 200 mmHg.
- the method for heat curing the dried polyimide coating film is not particularly limited, but a temperature in the vicinity of the glass transition temperature of the polyimide (more preferably glass transition temperature ⁇ 40). It is preferable to employ a method of heating at 0.1 ° C., more preferably glass transition temperature ⁇ 20 ° C., particularly preferably glass transition temperature ⁇ 10 ° C. for 0.1 to 10 hours (preferably 0.5 to 2 hours). If the heating temperature and time are less than the lower limit, the solid phase polymerization reaction does not proceed sufficiently and the film tends to be brittle and weak. On the other hand, if the upper limit is exceeded, coloration or molecular weight reduction due to thermal decomposition may occur. It tends to happen.
- the atmosphere at the time of heat curing of such a dried coating film is preferably an inert gas atmosphere (for example, nitrogen atmosphere), and the pressure condition at the time of heat curing is 0.01 to 760 mmHg. It is preferable that it is 0.01 to 200 mmHg.
- the heat treatment for imidization and the heat treatment for subsequent heat curing may be performed simultaneously as a series of heat treatments. It is preferable that the heat treatment at the time of imidization is continuously performed at a constant temperature as a temperature within a temperature range employed in the heat curing.
- a film in the case of employing the method (a), a film can be obtained by curing a coating film as it is after imidization by a series of heat treatments (imidation and heat curing are one heat treatment). it can.
- a substrate for example, a glass plate
- a film made of polyimide can be produced by a simple method.
- the said method (b) although it does not restrict
- the solvent for the polyimide solution in the method (b) the same solvent as that for the polyamic acid solution described above can be used, and furthermore, the polyimide solution applied in the method (b) can be used.
- a method for drying the film a method similar to the method for drying the coating film of the polyamic acid solution described above can be employed.
- a film made of the polyimide of the present invention can be obtained.
- the polyimide film thus obtained has a sufficiently high heat resistance and a sufficiently low coefficient of linear expansion, and has a sufficiently high resistance to thermal shock (change in ambient temperature). It becomes.
- the transparent film made of the polyimide of the present invention has a sufficiently high transparency as well as a sufficiently high heat resistance and a very low coefficient of linear expansion. Since the film can be sufficiently suppressed from cracking or cracking at a high level even when exposed to high temperature in the alignment process of display devices, etc., for example, a substrate for laminating transparent electrodes for touch panels and solar cells.
- films and substrate films for laminating transparent electrodes of display devices organic EL display devices, liquid crystal display devices, etc.
- FPCs optical waveguides, image sensors, LED reflectors, LED lighting covers, skeleton FPCs, covers Ray film, chip-on-film, highly ductile composite substrate, liquid crystal alignment film, polyimide coating material (DRAM, flash memory) Li, buffer coat materials such as next-generation LSI), a semiconductor for resist, it is particularly useful as a film or the like for use in lithium-ion battery, and various of material applications.
- Identification of the molecular structure of the compound obtained in each synthesis example, each example, and the like is performed by infrared spectroscopy (manufactured by JASCO Corporation, FT / IR-460, FT / IR-4100, Thermo Fisher Scientific Co., Ltd.) The measurement was carried out by measuring IR and NMR spectra using a company-made, NICOLET 380FT-IR) and an NMR measuring device (VARIAN, trade name: UNITY INOVA-600 and JEOL Ltd. JNM-Lambda500).
- the detection wavelength of the diode array detector (DAD) was set to 210 nm, the temperature was set to 35 ° C., and each sample was prepared by adding 1 mg of each compound to 1.5 ml of the solvent.
- the total amount (content ratio: purity) of the trans-endo-endo isomer and cis-endo-endo isomer in the compounds obtained in each synthesis example and each example, and the trans-endo-endo isomer The molar ratio of cis-endo-endo isomer was determined by calculating from the HPLC area ratio using a calibration curve (the standard sample used is shown in the description of each synthesis example and each example). It was.
- the glass transition temperatures (Tg) of the compounds obtained in Examples 1 to 4 and Comparative Example 1 are 5 mm, 2 mm wide, and 50 ⁇ m thick film-shaped samples, placed in an aluminum sample pan.
- a differential scanning calorimeter (trade name “DSC7020” manufactured by SII NanoTechnology Co., Ltd.), under a nitrogen atmosphere under conditions of a heating rate of 10 ° C./min and a cooling rate of 30 ° C./min, The measurement was performed by scanning the range from °C to 440 °C.
- Intrinsic viscosity [ ⁇ ] of the polyamic acid obtained as an intermediate in the production of films and the like in Examples 1 to 4 and Comparative Example 1 is an automatic viscosity measuring apparatus (trade name “VMC-252”) manufactured by Koiso Co., Ltd. Was used to prepare a polyamic acid measurement sample having a concentration of 0.5 g / dL using N, N-dimethylacetamide as a solvent, and measurement was performed at a temperature of 30 ° C.
- the linear expansion coefficient was determined by forming 20 mm long, 5 mm wide, and 0.05 mm (50 ⁇ m) thick films from the polyimides obtained in Examples 1 to 4 and Comparative Example 1 (film-shaped polyimide).
- the film was vacuum-dried (120 ° C., 1 hour (Hr)), and each sample (dried film) obtained by heat treatment at 200 ° C. for 1 hour (Hr) in a nitrogen atmosphere was used as a measuring device.
- an analyzer trade name “TMA8310” manufactured by Rigaku
- Refractive index was measured for each of the 5 mm vertical, 5 mm wide, and 50 ⁇ m thick film-shaped samples formed from the polyimides obtained in Examples 1 to 4 and Comparative Example 1 (film-shaped polyimide).
- a refractive index measuring device (trade name “NAR-1T SOLID” manufactured by Atago Co., Ltd.) was used as an apparatus, and the measurement was performed under a temperature condition of 23 ° C. under a light source of 589 nm.
- the total light transmittance was obtained by forming film-shaped samples having a length of 20 mm, a width of 20 mm, and a thickness of 50 ⁇ m from the polyimides (film-shaped polyimide) obtained in Examples 1 to 4 and Comparative Example 1, and using these samples, This was determined by performing measurement in accordance with JIS K7361-1 using a trade name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. as a measuring device.
- the reaction solution in the three-necked flask was heated to 60 ° C., and while maintaining the temperature (60 ° C.), methanol (1000 ml) was added to the reaction solution to disperse the contents.
- the reaction liquid in which such contents were dispersed was cooled to 30 ° C., and then 4.28 g (47.5 mmol) of a 50 mass% dimethylamine aqueous solution and 61.0 g of cyclopentadiene were contained in the reaction liquid. (1.0 mol) was added to obtain a mixture.
- the atmosphere gas inside the three-necked flask is replaced again with nitrogen, the three-necked flask is submerged in an 80 ° C.
- the toluene extract was washed once with 5% by mass NaOH aqueous solution (100 ml) and then washed once with 5% by mass hydrochloric acid water (100 ml).
- the toluene extract after washing with the hydrochloric acid water was washed once with a saturated aqueous sodium bicarbonate solution (100 ml). Subsequently, the toluene extract thus washed was dehydrated and dried by toluene azeotropy.
- Synthesis Example 2 Preparation of norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic acid tetramethyl ester
- a container of 1000 ml glass autoclave (trade name “Hyperblaster TEM-V type” manufactured by pressure-resistant glass industry)
- 61.1 g (454 mmol) of methanol (600 ml) and CuCl 2 (II) were obtained in Synthesis Example 1.
- toluene (900 ml) and 5 mass% hydrochloric acid (900 ml) were added to the reaction product, and the mixture was vigorously stirred at 80 ° C. for 1 hour to obtain a reaction mixture.
- the aqueous layer was discarded from the reaction mixture to obtain a toluene extract, and then the toluene extract was washed with 5% by mass hydrochloric acid (450 ml) under a temperature condition of 80 ° C.
- the toluene extract thus washed with hydrochloric acid was washed twice with a saturated aqueous sodium hydrogen carbonate solution (450 ml) at a temperature of 80 ° C.
- the toluene extract thus obtained was dehydrated and dried by toluene azeotropy.
- the liquid obtained after dehydration and drying is filtered and then concentrated using an evaporator, and toluene is distilled off to obtain a product (norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′.
- '-Norbornane-5,5'',6,6''-tetracarboxylic acid tetramethyl ester was obtained (yield 49.8 g, yield 95.4%).
- FIG. 7 shows the IR spectrum of the compound thus obtained
- FIG. 8 shows the 1 H-NMR (DMSO-d 6 ) spectrum
- FIG. 9 shows the 13 C-NMR (DMSO-d 6 ) spectrum.
- the spectrum of the HPLC measurement is shown in FIG.
- the obtained compound has the following general formula (18):
- the peak at a position of about 3.2 minutes on the horizontal axis is a toluene peak.
- the content ratio of trans-endo-endo isomer and cis-endo-endo isomer was determined using a calibration curve (standard sample: dicyclopentadiene) from the HPLC area ratio. From the obtained results, it was confirmed to be 79 mol%.
- the obtained crude product (1.0 g) was put into a sublimation purification apparatus (product name “Glass Tube Oven GTO-350RD with sublimation purification apparatus” manufactured by Shibata Kagaku Co., Ltd.) and 250 to 290 ° C./0.1 mmHg.
- the compound (norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′- Tetracarboxylic dianhydride) was obtained (yield 0.89 g, yield 89%).
- trans-endo-endo isomer and cis-endo-endo isomer content ratios were determined from the HPLC area ratio using a calibration curve (standard sample: naphthalene). The result confirmed that it was 79 mol%.
- Example 1 ⁇ Monomer synthesis process> Norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetra obtained in Synthesis Example 2 in toluene (90 ml) After adding 17.8 g (37.4 mmol) of carboxylic acid tetramethyl ester, the solution was heated to 110 ° C. and dissolved to obtain a toluene solution.
- the toluene solution was cooled at a rate of temperature decrease of 2 ° C./min, cooled to room temperature (25 ° C.), and allowed to stand overnight (15 hours), whereby white crystals (norbornane-2- Spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2 "-norbornane-5,5", 6,6 "-trans-endo-endo isomers and cis-endo- of tetracarboxylic acid tetramethyl ester The crystals of endo isomers) were separated (recrystallization method). Next, the white crystals thus obtained were filtered and dried under vacuum to obtain the first compound (white crystals) (yield 8.9 g, yield 50%).
- the first compound (white crystals) thus obtained was subjected to HPLC measurement.
- the obtained result is shown in FIG.
- the result of the HPLC measurement shown in FIG. 15 has one peak (signal), and it was confirmed that the specific isomer was selectively separated by the recrystallization method.
- IR measurement and NMR ( 1 H-NMR and 13 C-NMR) measurements were performed to confirm the structure of the obtained first compound (white crystals).
- FIG. 16 shows the IR spectrum of the obtained first compound
- FIG. 17 shows the 1 H-NMR (DMSO-d 6 ) spectrum
- FIG. 18 shows the 13 C-NMR (DMSO-d 6 ) spectrum.
- the obtained crude product (1.0 g) was put into a sublimation purification apparatus (product name “Glass Tube Oven GTO-350RD with sublimation purification apparatus” manufactured by Shibata Kagaku Co., Ltd.) and 250 to 290 ° C./0.1 mmHg. Was purified by sublimation for 5 hours to obtain a second compound consisting of a white solid (yield 0.90 g, yield 90%).
- a sublimation purification apparatus product name “Glass Tube Oven GTO-350RD with sublimation purification apparatus” manufactured by Shibata Kagaku Co., Ltd.
- the content ratio (total amount) of the compounds represented by the general formulas (20) and (21) in the obtained second compound is determined using a calibration curve (standard sample: naphthalene) from the area ratio of HPLC.
- ⁇ Polyimide preparation process> First, a 30 ml three-necked flask was sufficiently dried by heating with a heat gun. Next, the atmosphere gas in the three-necked flask that was sufficiently dried was replaced with nitrogen, and the inside of the three-necked flask was changed to a nitrogen atmosphere. Next, after adding 0.2045 g (0.90 mmol: Tokyo Chemical Industry Co., Ltd .: DABAN) of 4,4′-diaminobenzanilide to the three-necked flask, 2.7 g of N, N-dimethylacetamide was further added. By adding and stirring, an aromatic diamine compound (4,4′-diaminobenzanilide (DABAN)) was dissolved in the N, N-dimethylacetamide to obtain a solution (partly dissolved in DABAN) ).
- DABAN aromatic diamine compound
- the second compound (compound represented by the general formula (20) and the general formula (21) obtained by the monomer synthesis step in a nitrogen atmosphere
- the mixture was stirred at room temperature (25 ° C.) for 12 hours under a nitrogen atmosphere to obtain a reaction solution.
- polyamic acid was formed in the reaction solution.
- a dimethylacetamide solution having a polyamic acid concentration of 0.5 g / dL was prepared by using a part of the reaction solution (polyamic acid dimethylacetamide solution), and the intrinsic viscosity of the polyamic acid as the reaction intermediate was prepared.
- the intrinsic viscosity [ ⁇ ] of the polyamic acid was 0.93.
- the reaction solution obtained as described above was cast on a glass plate (length: 200 mm, width 200 mm) so that the thickness of the coating film after heat curing was 50 ⁇ m, and the coating film was coated on the glass plate. Formed. Thereafter, the glass plate on which the coating film has been formed is put into a vacuum oven, heated under a temperature condition of 40 ° C. for 12 hours under a pressure of 100 mmHg, and further under a temperature condition of 400 ° C. under a pressure of 1 mmHg. The coating film was cured by heating for 1 hour to form a polyimide film on the glass plate. Next, the glass plate on which the film made of polyimide is formed is taken out from the vacuum oven, immersed in water at 25 ° C. for 12 hours, the film made of polyimide is recovered from the glass plate, the end is cut off, and the colorless plate made of polyimide is obtained. A transparent film (length 100 mm, width 100 mm, thickness 50 ⁇ m) was obtained.
- FIG. 23 shows the IR spectrum of the obtained compound.
- C ⁇ O stretching vibration of imide carbonyl was confirmed at 1696.8 cm ⁇ 1
- the obtained compound was confirmed to be polyimide.
- the polyimide which forms the obtained film is the monomer used (second compound (a mixture of the compound represented by the general formula (20) and the compound represented by the general formula (21)) and aromatic.
- second compound a mixture of the compound represented by the general formula (20) and the compound represented by the general formula (21)
- aromatic aromatic.
- 99 mol% of the repeating units represented by the general formulas (1) and (2) are based on the total repeating units.
- Example 2 ⁇ Monomer synthesis process> Norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetra obtained in Synthesis Example 2 in toluene (90 ml) Carboxylic acid tetramethyl ester (17.8 g, 37.4 mmol) was added, and then heated to 110 ° C. for dissolution to obtain a toluene solution.
- the obtained crude product (1.0 g) was put into a sublimation purification apparatus (product name “Glass Tube Oven GTO-350RD with sublimation purification apparatus” manufactured by Shibata Kagaku Co., Ltd.) and 250 to 290 ° C./0.1 mmHg. Was purified by sublimation over 5 hours to obtain a fourth compound consisting of a white solid (yield 0.89 g, yield 89%).
- a sublimation purification apparatus product name “Glass Tube Oven GTO-350RD with sublimation purification apparatus” manufactured by Shibata Kagaku Co., Ltd.
- the obtained fourth compound is a mixture of the compound represented by the general formula (20) and the compound represented by the general formula (21) (trans, endo, endo and cis, Endo, endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic dianhydride mixture) It was confirmed.
- the content ratio (total amount) of the compounds represented by the general formulas (20) and (21) in the obtained fourth compound was determined using a calibration curve (standard sample: naphthalene) from the HPLC area ratio. From the obtained results, it was confirmed that it was 99 mol%, and the molar ratio of the compound represented by the general formula (20) and the compound represented by the general formula (21) ([Formula (20)] : [Formula (21)]) was 64:36 from the result obtained from the area ratio of HPLC using a calibration curve (standard sample: naphthalene).
- ⁇ Polyimide preparation process> A colorless and transparent polyimide comprising the same method as the polyimide preparation step employed in Example 1 except that the fourth compound obtained in the monomer synthesis step was used instead of the second compound. Film (length 100 mm, width 100 mm, thickness 50 ⁇ m) was obtained. In addition, the intrinsic viscosity [ ⁇ ] of the polyamic acid, which is a reaction intermediate obtained when carrying out such a polyimide preparation step, was 0.94.
- FIG. 24 shows the IR spectrum of the obtained compound.
- C ⁇ O stretching vibration of imidecarbonyl was confirmed at 1696.5 cm ⁇ 1, and it was confirmed that the obtained compound was polyimide.
- the polyimide which forms the obtained film is the monomer used (fourth compound (a mixture of the compound represented by the general formula (20) and the compound represented by the general formula (21)) and aromatic.
- 99 mol% of the repeating units represented by the general formulas (1) and (2) are based on the total repeating units.
- Example 3 ⁇ Monomer preparation process> The second compound obtained in Example 1 (0.39 g, content in the fifth compound: 78% by mass) and norbornane-2-spiro- ⁇ -cyclopentanone obtained in Synthesis Example 3 ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic dianhydride (0.11 g, content in the fifth compound: 22% by mass) mixed ( And a fifth compound having a content ratio (total amount) of the compounds represented by the general formulas (20) and (21) of 95 mol% was prepared.
- ⁇ Polyimide preparation process> A colorless and transparent polyimide comprising the same method as the polyimide preparation step employed in Example 1 except that the fifth compound obtained in the monomer preparation step was used instead of the second compound. Film (length 100 mm, width 100 mm, thickness 50 ⁇ m) was obtained. As a result of evaluating the characteristics of the polyimide as described above by using the polyimide film thus obtained, the linear expansion coefficient of the polyimide is 12 ppm / ° C., the glass transition temperature is 370 ° C., 5% weight loss temperature: 482 ° C. The obtained results are shown in Table 1.
- Example 4 ⁇ Monomer preparation process> The second compound obtained in Example 1 (0.28 g, content in the sixth compound: 56% by mass) and norbornane-2-spiro- ⁇ -cyclopentanone obtained in Synthesis Example 3 ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic dianhydride (0.22 g, content in the sixth compound: 44 mass%) was mixed ( And a sixth compound having a content ratio (total amount) of the compounds represented by the general formulas (20) and (21) of 90 mol% was prepared.
- ⁇ Polyimide preparation process> A colorless and transparent polyimide comprising the same method as the polyimide preparation step employed in Example 1 except that the sixth compound obtained in the monomer preparation step was used instead of the second compound. Film (length 100 mm, width 100 mm, thickness 50 ⁇ m) was obtained. As a result of evaluating the characteristics of the polyimide as described above by using the polyimide film thus obtained, the linear expansion coefficient of the polyimide is 14 ppm / ° C, the glass transition temperature is 370 ° C, 5% weight loss temperature: 482 ° C. The obtained results are shown in Table 1.
- the IR spectrum of the compound constituting the film thus obtained was measured.
- the IR spectrum of the obtained compound is shown in FIG.
- C ⁇ O stretching vibration of imide carbonyl was confirmed at 1697.6 cm ⁇ 1
- the obtained compound was confirmed to be polyimide.
- the polyimide forming the obtained film was obtained by using the monomer (norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′ obtained in Synthesis Example 3).
- the polyimide of the present invention has sufficiently high heat resistance and a very low coefficient of linear expansion, for example, a material for forming a substrate film for laminating transparent electrodes of touch panels and solar cells, display
- a material for forming a substrate film for laminating transparent electrodes of devices organic EL display devices, liquid crystal display devices, etc.
- FPC optical waveguide, image sensor, LED reflector, LED illumination cover, skeleton type FPC , Cover lay film, chip on film, high ductility composite substrate, liquid crystal alignment film, polyimide coating material (buffer coating material for DRAM, flash memory, next generation LSI, etc.), resist for semiconductors, various electrical materials, etc.
- specially used as a material for film formation and various battery materials such as lithium-ion batteries. It is useful.
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Abstract
Description
で表される繰り返し単位を有するポリイミドが開示されている。
で表される繰り返し単位のうちの少なくとも1種を含有し且つ前記一般式(1)及び(2)で表される繰り返し単位の総量が全繰り返し単位に対して90モル%以上である、ポリイミドである。
で表される基のうちの1種であることが好ましい。
で表されるトランス、エンド、エンド-ノルボルナン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物及び下記一般式(8):
で表されるシス、エンド、エンド-ノルボルナン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物のうちの少なくとも1種を含有し、且つ、前記一般式(7)及び(8)で表される脂環式テトラカルボン酸二無水物の総量が90モル%以上である、脂環式テトラカルボン酸二無水物である。
で表される繰り返し単位のうちの少なくとも1種を含有し且つ前記一般式(1)及び(2)で表される繰り返し単位の総量が全繰り返し単位に対して90モル%以上である、ポリイミドである。
で表される基のうちの1種であることが好ましい。
で表されるトランス、エンド、エンド-ノルボルナン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物及び下記一般式(8):
で表されるシス、エンド、エンド-ノルボルナン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物のうちの少なくとも1種を含有し、且つ、前記一般式(7)及び(8)で表される脂環式テトラカルボン酸二無水物の総量が90モル%以上である、ものである。
で表される5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類(以下、場合により単に「一般式(9)で表される化合物」という。)を準備し、次いで、前記一般式(9)で表される化合物をテトラカルボン酸二無水物化して、下記一般式(10):
で表されるテトラカルボン酸二無水物を得た後、かかる一般式(10)で表されるテトラカルボン酸二無水物から、純度が90モル%以上となるようにして前記一般式(7)及び(8)で表される脂環式テトラカルボン酸二無水物を分離して取り出すこと(選別すること)により、上記本発明の脂環式テトラカルボン酸二無水物を得る方法(第一の方法)、前記一般式(9)で表される化合物を準備し、前記一般式(9)で表される化合物からシス-エンド-エンド異性体及び/又はトランス-エンド-エンド異性体を純度が90モル%以上となるようにして分離して取り出し、これをテトラカルボン酸二無水物化して、前記一般式(7)及び(8)で表される脂環式テトラカルボン酸二無水物を総量で90モル%以上含有する脂環式テトラカルボン酸二無水物を得ることにより、上記本発明の脂環式テトラカルボン酸二無水物を得る方法(第二の方法)、前記一般式(9)で表される化合物を準備し、前記一般式(9)で表される化合物をエステル化(次いで加水分解処理やカルボン酸とのエステル交換反応を施してカルボン酸としてもよい。)した後に、得られる化合物(エステル又はカルボン酸)からシス-エンド-エンド異性体及び/又はトランス-エンド-エンド異性体を純度が90モル%以上となるようにして分離して取り出し、これを酸二無水物化して前記一般式(7)及び(8)で表される脂環式テトラカルボン酸二無水物を総量で90モル%以上含有する脂環式テトラカルボン酸二無水物を得ることにより、上記本発明の脂環式テトラカルボン酸二無水物を得る方法(第三の方法)を適宜利用することができる。
で表されるような反応を利用することにより一般式(9)で表される化合物を製造する方法を採用することにより準備してもよい。
で表されるノルボルナン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸及びそのエステル類(以下、場合により単に「一般式(11)で表される化合物」という。)のうちの少なくとも1種の化合物を得る工程(第1工程)と、
低級カルボン酸(ギ酸、酢酸、プロピオン酸等)と、酸触媒と、無水酢酸とを用いて、前記化合物から上記一般式(10)で表されるテトラカルボン酸二無水物(ノルボルナン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物)を得る工程(第2工程)と、
を含む方法(以下、場合により「前記一般式(10)で表されるテトラカルボン酸二無水物の製造方法(i)」という。)を利用してもよい。なお、前記一般式(11)で表される化合物において、前記一般式(11)中のR1、R2、R3、nは前記一般式(7)及び(8)中のR1、R2、R3、nと同義である(好適なものも同様である)。
R10OH (12)
[式(12)中、R10は、前記一般式(11)中のR6、R7、R8又はR9として選択され得る原子及び基のうちの水素原子以外のものである。]
で表されるアルコールであることが好ましい。すなわち、このようなアルコールとしては、炭素数が1~10のアルキルアルコール、炭素数が3~10のシクロアルキルアルコール、炭素数が2~10のアルケニルアルコール、炭素数が6~20のアリールアルコール、炭素数が7~20のアラルキルアルコールを用いることが好ましい。このようなアルコールとしては、具体的には、メタノール、エタノール、ブタノール、アリルアルコール、シクロヘキサノール、ベンジルアルコール等が挙げられ、中でも、得られる化合物の精製がより容易となるという観点から、メタノール、エタノールがより好ましく、メタノールが特に好ましい。また、このようなアルコールは1種を単独であるいは2種以上を混合して用いてもよい。
-COOR10 (13)
[式(13)中、R10は前記一般式(11)中のR6、R7、R8又はR9として選択され得る原子及び基のうちの水素原子以外のものである。]
で表されるエステル基(かかるエステル基は導入される位置ごとにR10が同一であっても異なっていてもよい。)を導入して、前記一般式(11)で表されるノルボルナン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸エステル類を得る反応(エステル化反応)である。
で模式的に表されるような反応を利用する方法であるが、前記一般式(10)で示されるテトラカルボン酸二無水物を得るための好適な方法は、これに制限されるものではない。
で表される芳香族ジアミンとを反応させて、下記一般式(15)及び(16):
で表される繰り返し単位を少なくとも1種含有し且つ前記一般式(15)及び(16)で表される繰り返し単位の総量が90モル%以上のポリアミド酸を調製することにより、前記ポリアミド酸の溶液を得る工程(工程(I))と、
前記ポリアミド酸をイミド化することにより、本発明のポリイミドを得る工程(工程(II))と、
を含む方法を好適に利用することができる。以下、工程(I)と工程(II)を分けて説明する。
工程(I)は、有機溶媒の存在下、上記本発明の脂環式テトラカルボン酸二無水物と、上記一般式(14)で表される芳香族ジアミンとを反応させることによりポリアミド酸を調製し、ポリアミド酸の溶液を得る工程である。
次に、工程(II)について説明する。工程(II)は、工程(I)により得られた前記ポリアミド酸をイミド化することにより、本発明のポリイミドを得る工程である。
各合成例及び各実施例等で得られた化合物の分子構造の同定は、赤外分光分析装置(日本分光株式会社製、FT/IR-460、FT/IR-4100、サーモフィッシャーサイエンティフィック株式会社製、NICOLET380FT-IR)及びNMR測定機(VARIAN社製、商品名:UNITY INOVA-600及び日本電子株式会社製JNM-Lambda500)を用いて、IR及びNMRスペクトルを測定することにより行った。
各合成例及び各実施例等で得られた化合物の異性体の種類の同定はHPLC測定により行った。すなわち、各化合物に対するHPLC測定は、測定装置としてアジレントテクノロジー株式会社製の商品名「1200 Series」を用い、カラムはアジレントテクノロジー株式会社製の商品名「Eclipse XDB-C18(5μm、直径4.6mm、長さ150mm)」を用い、溶媒はアセトニトリルと蒸留水との混合物(アセトニトリル/蒸留水=70ml/30ml)を用い、溶媒の流速を1ml/min.とし、ダイオードアレイ検出器(DAD)の検出波長を210nmに設定し、温度を35℃とし、各化合物をそれぞれ溶媒1.5mlに対して1mgずつ添加した試料をそれぞれ調製して行った。また、各合成例及び各実施例等で得られた化合物中のトランス-エンド-エンド異性体及びシス-エンド-エンド異性体の総量(含有比率:純度)、及び、トランス-エンド-エンド異性体とシス-エンド-エンド異性体とのモル比は、HPLCの面積比より検量線(用いた標準試料については各合成例及び各実施例の記載中に示す。)を用いて算出することにより求めた。なお、5-ノルボルネン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-5’’-ノルボルネンについては、トランス-エンド-エンド異性体及びシス-エンド-エンド異性体の総量(純度)を1H-NMRの積分比より求めた。
実施例1~4及び比較例1で得られた化合物のガラス転移温度(Tg)は、それぞれ、縦2mm、横2mm、厚み50μmのフィルム形状の試料を5枚、アルミ製サンプルパンに入れて、示差走査熱量計(エスアイアイ・ナノテクノロジー株式会社製の商品名「DSC7020」)を使用して、昇温速度:10℃/分及び降温速度:30℃/分の条件で、窒素雰囲気下、30℃から440℃の範囲を走査することで測定を行なった。
実施例1~4及び比較例1で得られた化合物の5%重量減少温度は、それぞれ、縦2mm、横2mm、厚み50μmのフィルム形状の試料を5枚、アルミ製サンプルパンに入れ、測定装置としてTG/DTA7200熱重量分析装置(エスアイアイ・ナノテクノロジー株式会社製)を使用して、窒素ガスを流しながら、室温(25℃)から600℃の範囲で10℃/分の条件で加熱して、用いた試料の重量が5%減少する温度を測定することにより求めた。
実施例1~4及び比較例1でフィルム等を製造する際に中間体として得られたポリアミド酸の固有粘度[η]は、離合社製の自動粘度測定装置(商品名「VMC-252」)を用い、N,N-ジメチルアセトアミドを溶媒として、濃度0.5g/dLのポリアミド酸の測定試料を調整し、30℃の温度条件下において測定した。
線膨張係数は、実施例1~4及び比較例1で得られたポリイミド(フィルム形状のポリイミド)から縦20mm、横5mm、厚み0.05mm(50μm)の大きさのフィルムをそれぞれ形成した後に、そのフィルムを真空乾燥(120℃、1時間(Hr))し、窒素雰囲気下で200℃で1時間(Hr)熱処理して得られた試料(乾燥フィルム)をそれぞれ用い、測定装置として熱機械的分析装置(リガク製の商品名「TMA8310」)を利用して、窒素雰囲気下、引張りモード(49mN)、昇温速度5℃/分の条件を採用して、50℃~200℃における前記試料の長さの変化を測定して、50℃~200℃の温度範囲における1℃あたりの長さの変化の平均値を求めることにより測定した。
屈折率は、実施例1~4及び比較例1で得られたポリイミド(フィルム形状のポリイミド)から縦5mm、横5mm、厚み50μmのフィルム形状の試料をそれぞれ形成し、かかる試料に対して、測定装置として屈折率測定装置(株式会社アタゴ製の商品名「NAR-1T SOLID」)を用い、589nmの光源下、23℃の温度条件で測定を行うことにより求めた。
全光線透過率は、実施例1~4及び比較例1で得られたポリイミド(フィルム形状のポリイミド)から縦20mm、横20mm、厚み50μmのフィルム形状の試料をそれぞれ形成し、かかる試料を用い、測定装置として日本電色工業株式会社製の商品名「ヘーズメーターNDH-5000」を用いてJIS K7361-1に準拠した測定を行うことにより求めた。
先ず、2Lの三口フラスコにジメチルアミン塩酸塩を61.7g(0.757mol)、1,3-ジオキソランを182g(2.46mol)、シクロペンタノンを25.9g(0.308mol)、35%塩酸を4.0g(38mmol)添加した。次いで、前記三口フラスコに玉付きコンデンサーをセットした後、前記三口フラスコの内部の雰囲気ガスを窒素で置換した。その後、前記三口フラスコを90℃のオイルバスに沈め、5時間加熱攪拌を行なって、マンニッヒ塩基(上記反応式(I)に記載されている一般式(I-2)で表される化合物[一般式(I-2)中のnが2であり、R2及びR3がいずれも水素であり、Rがいずれもメチル基であり、且つX-が塩素イオンである化合物])を含有する反応液を得た。なお、このようにして得られた反応液に対してガスクロマトグラフィー分析(GC分析:検出器としてAgilent Technologies社製の商品名「6890N」を使用)を行った結果、シクロペンタノンの転化率は99.9%以上であることが確認された。
1000mlのガラス製のオートクレーブ(耐圧ガラス工業製の商品名「ハイパーグラスターTEM-V型」)の容器に、メタノール(600ml)、CuCl2(II)を61.1g(454mmol)、合成例1で得られた5-ノルボルネン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-5’’-ノルボルネンを26.0g(108mmol)及びPd(OAc)2を243mg(1.08mmol)添加して混合液を得た後、前記容器を密閉して内部の雰囲気ガスを窒素で置換した。次に、前記容器の内部に一酸化炭素を導入しながら、20℃、0.9MPaの条件下において、前記混合液を5時間攪拌し、反応液を得た。次いで、前記容器の内部から一酸化炭素を除き、前記反応液をエバポレーターで濃縮することにより前記反応液中からメタノールを除去して、反応生成物を得た。その後、前記反応生成物に対して、トルエン(900ml)及び5質量%の塩酸(900ml)を加えて、80℃の温度条件で1時間激しく攪拌することにより反応混合液を得た。次いで、前記反応混合液から水層を廃棄してトルエン抽出液を得た後、80℃の温度条件で、前記トルエン抽出液を5質量%の塩酸(450ml)で洗浄した。次いで、このようにして塩酸で洗浄した前記トルエン抽出液を、80℃の温度条件で、飽和炭酸水素ナトリウム水溶液(450ml)により2回洗浄した。次いで、このようにして得られたトルエン抽出液をトルエン共沸により脱水乾燥した。次に、脱水乾燥後に得られた液体をろ過した後にエバポレーターを用いて濃縮し、トルエンを留去して、生成物(ノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸テトラメチルエステル)を得た(収量49.8g、収率95.4%)。
蒸留装置付きの200ml三口フラスコに、合成例2で得られたノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸テトラメチルエステルを17.8g(37.4mmol)、酢酸を113g(1.88mol)、p-トルエンスルホン酸一水和物を1.78g(9.4mmol)添加して混合液を得た。次に、前記三口フラスコを135℃のオイルバスに沈めて、内温113~121℃の温度条件で前記混合液の加熱還流を20時間行った(還流工程)。なお、このような還流工程においては、生成された酢酸メチルと水を、酢酸と共に留去しながら還流を続けた。また、このような還流工程においては、フラスコ中の酢酸の量が一定になるように滴下ロートで酢酸を随時追加しながら還流を行った。このような環流工程を実施して前記混合液中において反応を進行せしめた後、室温(25℃)で一晩(15時間)放置し、灰色の固体を析出させた。次いで、得られた灰色固体をろ過した後、得られた灰色固体を酢酸(50ml)で2回洗浄し、次いで、トルエン(50ml)で1回洗浄した。このような洗浄後の灰色固体を真空乾燥機を用いて80℃、1mmHgの条件で一晩(15時間)乾燥させて、粗生成物を得た(収量13.8g、収率96%)。次いで、得られた粗生成物(1.0g)を昇華精製装置(柴田科学社製の製品名「ガラスチューブオーブンGTO-350RD 昇華精製装置付き」)に入れて、250~290℃/0.1mmHgで5時間かけて昇華精製して白色固体からなる化合物(ノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物)を得た(収量0.89g、収率89%)。
<モノマー合成工程>
トルエン(90ml)中に、合成例2で得られたノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸テトラメチルエステルを17.8g(37.4mmol)添加した後、110℃まで加熱して溶解させてトルエン溶液を得た。次いで、前記トルエン溶液を2℃/分の降温速度で冷却して室温(25℃)まで冷却し一晩(15時間)放置することにより、白色結晶(合成例2で得られたノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸テトラメチルエステルのトランス-エンド-エンド異性体及びシス-エンド-エンド異性体の結晶)を分離した(再結晶法)。次に、このようにして得られた白色結晶をろ過し、真空乾燥して、第一の化合物(白色結晶)を得た(収量8.9g、収率50%)。
先ず、30mlの三口フラスコをヒートガンで加熱して十分に乾燥させた。次に、十分に乾燥させた前記三口フラスコ内の雰囲気ガスを窒素で置換して、前記三口フラスコ内を窒素雰囲気とした。次いで、前記三口フラスコ内に、4,4’-ジアミノベンズアニリド0.2045g(0.90mmol:東京化成工業株式会社製:DABAN)を添加した後、更に、N,N-ジメチルアセトアミドを2.7g添加して、攪拌することにより、前記N,N-ジメチルアセトアミド中に芳香族ジアミン化合物(4,4’-ジアミノベンズアニリド(DABAN))を溶解させて溶解液を得た(DABANは一部溶解)。
<モノマー合成工程>
トルエン(90ml)中に、合成例2で得られたノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸テトラメチルエステル(17.8g、37.4mmol)を添加した後、110℃まで加熱して溶解させてトルエン溶液を得た。次いで、前記トルエン溶液を室温(25℃)まで冷却することにより前記トルエン溶液中に固形分を析出させた後、セライト濾過(セライト:和光純薬製スタンダードスーパーセル)を行なって固形分を濾別した(濾過工程:吸着分離法)。次いで、室温(25℃)条件下において、濾過工程後のセライトをトルエンで洗浄した後、ソックスレー抽出器を利用し、回収したセライトを用いて、トルエンを溶媒としたソックスレー抽出を行って、白色の結晶を得た。次に、このようにして得られた白色結晶をろ過し、真空乾燥して、第三の化合物(白色結晶)を得た(収量7.8g、収率44%)。
前記第二の化合物の代わりに、前記モノマー合成工程により得られた第四の化合物を用いた以外は、実施例1で採用したポリイミドの調製工程と同様の方法を採用してポリイミドからなる無色透明のフィルム(縦100mm、横100mm、厚み50μm)を得た。なお、このようなポリイミドの調製工程を実施する際に得られた反応中間体であるポリアミド酸の固有粘度[η]は0.94であった。
<モノマー調製工程>
実施例1で得られた第二の化合物(0.39g、第五の化合物中の含有割合:78質量%)と、合成例3で得られたノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物(0.11g、第五の化合物中の含有割合:22質量%)を混合(ブレンド)し、上記一般式(20)及び(21)で表される化合物の含有比率(総量)が95モル%になる第五の化合物を調製した。
前記第二の化合物の代わりに、前記モノマー調製工程により得られた第五の化合物を用いた以外は、実施例1で採用したポリイミドの調製工程と同様の方法を採用してポリイミドからなる無色透明のフィルム(縦100mm、横100mm、厚み50μm)を得た。このようにして得られたポリイミドからなるフィルムを利用して、前述のようにしてポリイミドの特性を評価した結果、ポリイミドの線膨張係数は12ppm/℃であり、ガラス転位温度は370℃であり、5%重量減少温度:482℃であった。得られた結果を表1に示す。
<モノマー調製工程>
実施例1で得られた第二の化合物(0.28g、第六の化合物中の含有割合:56質量%)と、合成例3で得られたノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物(0.22g、第六の化合物中の含有割合:44質量%)を混合(ブレンド)し、上記一般式(20)及び(21)で表される化合物の含有比率(総量)が90モル%になる第六の化合物を調製した。
前記第二の化合物の代わりに、前記モノマー調製工程により得られた第六の化合物を用いた以外は、実施例1で採用したポリイミドの調製工程と同様の方法を採用してポリイミドからなる無色透明のフィルム(縦100mm、横100mm、厚み50μm)を得た。このようにして得られたポリイミドからなるフィルムを利用して、前述のようにしてポリイミドの特性を評価した結果、ポリイミドの線膨張係数は14ppm/℃であり、ガラス転位温度は370℃であり、5%重量減少温度:482℃であった。得られた結果を表1に示す。
<ポリイミドの調製>
前記第二の化合物の代わりに、合成例3で得られたノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物(6種の異性体の混合物)をそのまま用いた以外は、実施例1で採用したポリイミドの調製工程と同様の方法を採用してポリイミドからなる無色透明のフィルム(縦100mm、横100mm、厚み50μm)を得た。なお、このようなポリイミドの調製工程を実施する際に得られた反応中間体であるポリアミド酸の固有粘度[η]は0.67であった。
Claims (5)
- 前記一般式(1)及び(2)中のR4が、下記一般式(3)~(6):
で表される基のうちの1種である、請求項1に記載のポリイミド。 - 前記ポリイミドが、窒素雰囲気下、昇温速度5℃/分の条件で50℃~200℃の温度範囲において長さの変化を測定して求められる線膨張係数が15ppm/℃以下のものである、請求項1又は2に記載のポリイミド。
- 前記一般式(1)及び(2)で表される繰り返し単位の総量が全繰り返し単位に対して95~100モル%である、請求項1~3のうちのいずれか一項に記載のポリイミド。
- 請求項1~4のうちのいずれか一項に記載のポリイミドの製造に用いる脂環式テトラカルボン酸二無水物であり、下記一般式(7):
で表されるトランス、エンド、エンド-ノルボルナン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物及び下記一般式(8):
で表されるシス、エンド、エンド-ノルボルナン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物のうちの少なくとも1種を含有し、且つ、前記一般式(7)及び(8)で表される脂環式テトラカルボン酸二無水物の総量が90モル%以上である、脂環式テトラカルボン酸二無水物。
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WO2016084777A1 (ja) * | 2014-11-27 | 2016-06-02 | Jx日鉱日石エネルギー株式会社 | ポリイミドフィルム、それを用いた基板、及び、ポリイミドフィルムの製造方法 |
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EP2891675A1 (en) | 2015-07-08 |
TW201418328A (zh) | 2014-05-16 |
EP2891675A4 (en) | 2016-04-13 |
US9399703B2 (en) | 2016-07-26 |
US20150218317A1 (en) | 2015-08-06 |
CN104583275B (zh) | 2016-09-07 |
JP6077550B2 (ja) | 2017-02-08 |
KR101686755B1 (ko) | 2016-12-14 |
CN104583275A (zh) | 2015-04-29 |
KR20150048825A (ko) | 2015-05-07 |
TWI586710B (zh) | 2017-06-11 |
JPWO2014034760A1 (ja) | 2016-08-08 |
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