JP6688906B2 - Polyamic acid composition to which alicyclic monomer is applied and transparent polyimide film using the same - Google Patents
Polyamic acid composition to which alicyclic monomer is applied and transparent polyimide film using the same Download PDFInfo
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- JP6688906B2 JP6688906B2 JP2018551729A JP2018551729A JP6688906B2 JP 6688906 B2 JP6688906 B2 JP 6688906B2 JP 2018551729 A JP2018551729 A JP 2018551729A JP 2018551729 A JP2018551729 A JP 2018551729A JP 6688906 B2 JP6688906 B2 JP 6688906B2
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- Prior art keywords
- dianhydride
- polyamic acid
- group
- acid composition
- polyimide resin
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims description 80
- 239000000203 mixture Substances 0.000 title claims description 72
- 229920005575 poly(amic acid) Polymers 0.000 title claims description 67
- 125000002723 alicyclic group Chemical group 0.000 title claims description 21
- 239000000178 monomer Substances 0.000 title description 32
- 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 claims description 94
- 150000004985 diamines Chemical class 0.000 claims description 44
- 239000009719 polyimide resin Substances 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 22
- 230000009477 glass transition Effects 0.000 claims description 18
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000002834 transmittance Methods 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 150000003457 sulfones Chemical class 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000004262 Ethyl gallate Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- WPWLFFMSSOAORQ-UHFFFAOYSA-N 5-bromo-4-chloro-3-indolyl acetate Chemical compound C1=C(Br)C(Cl)=C2C(OC(=O)C)=CNC2=C1 WPWLFFMSSOAORQ-UHFFFAOYSA-N 0.000 claims 1
- BZUNJUAMQZRJIP-UHFFFAOYSA-N CPDA Natural products OCCCCCCCCCCCCCCC(O)=O BZUNJUAMQZRJIP-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- GISJHCLTIVIGLX-UHFFFAOYSA-N n-[4-[(4-chlorophenyl)methoxy]pyridin-2-yl]-2-(2,6-difluorophenyl)acetamide Chemical compound FC1=CC=CC(F)=C1CC(=O)NC1=CC(OCC=2C=CC(Cl)=CC=2)=CC=N1 GISJHCLTIVIGLX-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 32
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 27
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 18
- 239000004642 Polyimide Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 125000005462 imide group Chemical group 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000007363 ring formation reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012769 display material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000006159 dianhydride group Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 2
- -1 phenoxy diphenyl sulfone Chemical compound 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PEMPMNYSHMRDEU-UHFFFAOYSA-N 1-phenoxypropylbenzene Chemical compound C=1C=CC=CC=1C(CC)OC1=CC=CC=C1 PEMPMNYSHMRDEU-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- RJIXOOWTCNNQQD-UHFFFAOYSA-N 2-[(2-carboxyphenyl)-dimethylsilyl]benzoic acid Chemical compound C=1C=CC=C(C(O)=O)C=1[Si](C)(C)C1=CC=CC=C1C(O)=O RJIXOOWTCNNQQD-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- RCHGVEYCLFLTGN-UHFFFAOYSA-N FC(C1=C(C=C(C=C1)N)C1=C(C=CC(=C1)N)C(F)(F)F)(F)F.FC(C1=C(C=C(C=C1)N)C1=C(C=CC(=C1)N)C(F)(F)F)(F)F Chemical group FC(C1=C(C=C(C=C1)N)C1=C(C=CC(=C1)N)C(F)(F)F)(F)F.FC(C1=C(C=C(C=C1)N)C1=C(C=CC(=C1)N)C(F)(F)F)(F)F RCHGVEYCLFLTGN-UHFFFAOYSA-N 0.000 description 1
- WULMVFVTDMHEBR-UHFFFAOYSA-N FC(C1=C(C=CC(=C1)N)C1=C(C(=CC=C1)N)C(F)(F)F)(F)F.FC(C1=C(C=CC(=C1)N)C1=C(C(=CC=C1)N)C(F)(F)F)(F)F Chemical group FC(C1=C(C=CC(=C1)N)C1=C(C(=CC=C1)N)C(F)(F)F)(F)F.FC(C1=C(C=CC(=C1)N)C1=C(C(=CC=C1)N)C(F)(F)F)(F)F WULMVFVTDMHEBR-UHFFFAOYSA-N 0.000 description 1
- 241001024304 Mino Species 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- BKDVBBSUAGJUBA-UHFFFAOYSA-N bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Chemical compound C1=CC2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O BKDVBBSUAGJUBA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 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 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical group NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、フレキシブルディスプレイ基板又は保護膜として適用可能な透明ポリイミド樹脂、及び、このようなポリイミド樹脂を製造するためのポリアミック酸組成物に関する。 The present invention relates to a transparent polyimide resin applicable as a flexible display substrate or a protective film, and a polyamic acid composition for producing such a polyimide resin.
一般に、ポリイミド（Ｐｏｌｙｉｍｉｄｅ、ＰＩ）樹脂とは、芳香族ジアンヒドリドと芳香族ジアミン又は芳香族ジイソシアネートとを溶液重合してポリアミック酸誘導体を製造した後、高温で閉環脱水によりイミド化して製造される高耐熱樹脂を指す。 Generally, a polyimide (PI) resin is a high-performance resin produced by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to produce a polyamic acid derivative, and then imidization by ring-closing dehydration at a high temperature. Refers to heat-resistant resin.
前記ポリイミド樹脂を製造するための芳香族ジアンヒドリド成分としては、ピロメリト酸二無水物（ＰＭＤＡ）又はビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）などが使用され、前記芳香族ジアミン成分としては、オキシジアニリン（ＯＤＡ）、ｐ−フェニレンジアミン（ｐ−ＰＤＡ）、ｍ−メチレンジアミン（ｍ−ＭＤＡ）、メチレンジアミン（ＭＤＡ）、ビスアミノフェニルヘキサフルオロプロパン（ＨＦＤＡ）などが主に使用されている。このようなポリイミド樹脂は、不溶又は不融の超高耐熱性樹脂であって、耐熱酸化性、耐熱特性、耐放射線性、低温特性、耐薬品性などに優れた特性を有するため、自動車材料、航空や宇宙船素材などの耐熱に優れた新素材、及び、絶縁コーティング剤、絶縁膜、半導体、ＬＣＤの電極保護膜などの電子材料として、広範な分野で使用されている。 As the aromatic dianhydride component for producing the polyimide resin, pyromellitic dianhydride (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) is used, and the aromatic diamine component is oxydiamine. Aniline (ODA), p-phenylenediamine (p-PDA), m-methylenediamine (m-MDA), methylenediamine (MDA), bisaminophenylhexafluoropropane (HFDA), etc. are mainly used. Such a polyimide resin is an insoluble or infusible ultrahigh heat resistant resin, and has excellent properties such as heat oxidation resistance, heat resistance characteristics, radiation resistance, low temperature characteristics, and chemical resistance. It is used in a wide range of fields as new materials with excellent heat resistance, such as aviation and spacecraft materials, and electronic materials such as insulating coating agents, insulating films, semiconductors, and electrode protective films for LCDs.
しかし、ポリイミド（ＰＩ）樹脂は、芳香族環の密度が高く、これにより、褐色又は黄色に着色され、可視光線領域において透過度が低くなるため、透明性が求められる分野に使用することが困難である。近年、無色透明なポリイミドフィルムが開発されつつあるが、この場合、既存のポリイミド樹脂に比べて、熱膨張係数（ＣＴＥ）が高く、耐溶剤性が低くなる。これにより、前記無色透明なポリイミドを、基板用、光学用のコート及びフィルムとして使用する場合、高い熱膨張係数による反りや捩れが生じ易いという問題点がある。これにより、上述の用途で使用される場合、ポリイミドフィルムの低い熱膨張係数が要求される。また、ディスプレイ材料として適用するためには、優れた光学的特性及び優れた耐熱特性を備える必要がある。 However, the polyimide (PI) resin has a high density of aromatic rings, which causes it to be colored brown or yellow and has a low transmittance in the visible light region, and thus is difficult to use in fields requiring transparency. Is. In recent years, colorless and transparent polyimide films have been developed, but in this case, they have a higher coefficient of thermal expansion (CTE) and lower solvent resistance than existing polyimide resins. As a result, when the colorless and transparent polyimide is used as a substrate and an optical coat and film, there is a problem that warpage or twisting due to a high coefficient of thermal expansion easily occurs. This requires a low coefficient of thermal expansion of the polyimide film when used in the above applications. Further, in order to be applied as a display material, it is necessary to have excellent optical characteristics and excellent heat resistance characteristics.
それで、ディスプレイ材料として適用するため、ガラス基板のような高透明性を示しかつ耐熱性に優れた、低い熱膨張係数を有する透明プラスチック基板を製造するためのポリアミック酸（Ｐｏｌｙａｍｉｃ ａｃｉｄ）組成物の開発が要望されている。 Therefore, for application as a display material, development of a polyamic acid composition for producing a transparent plastic substrate having a low coefficient of thermal expansion, which exhibits high transparency like a glass substrate and is excellent in heat resistance. Is required.
本発明は、上述の問題点を解決するためになされたものであって、特定の化学構造及び反応基を有するモノマーを導入することで、光学特性及び熱的特性が従来に比べて改善されることに着目したものである。 The present invention has been made to solve the above-mentioned problems, and by introducing a monomer having a specific chemical structure and a reactive group, the optical characteristics and the thermal characteristics are improved as compared with conventional ones. It focuses on that.
具体的に、本発明は、高透明性のポリイミド樹脂を得るためには、剛直な（Ｒｉｇｉｄ）化学構造を有するジアンヒドリドモノマーの導入が効果的であることを知見し、特定の化学構造を有するジアミン及びジアンヒドリドモノマーを採択し、これらの含有量を特定の範囲に調節することで、低いＹ．Ｉ（Ｙｅｌｌｏｗ Ｉｎｄｅｘ）、高い光透過度、及び高いガラス転移温度（Ｔｇ）などを同時に実現することができる、透明ポリアミック酸組成物を提供することを目的とする。 Specifically, the present invention has found that the introduction of a dianhydride monomer having a rigid (Rigid) chemical structure is effective for obtaining a highly transparent polyimide resin, and has a specific chemical structure. By adopting diamine and dianhydride monomers and adjusting their contents within a specific range, a low Y.V. An object of the present invention is to provide a transparent polyamic acid composition capable of simultaneously achieving I (Yellow Index), high light transmittance, and high glass transition temperature (T g ).
さらに、本発明の他の目的は、ＬＣＤ及びＯＬＥＤのフレキシブルディスプレイ用プラスチック透明基板、ＴＦＴ基板、フレキシブル印刷回路基板、フレキシブルＯＬＥＤ面照明基板、電子ペーパー用基板材料などに適用可能な透明ポリアミック酸組成物、及び、これで製造された透明ポリイミドフィルムを提供することにある。 Further, another object of the present invention is a transparent polyamic acid composition applicable to plastic transparent substrates for LCD and OLED flexible displays, TFT substrates, flexible printed circuit substrates, flexible OLED surface illumination substrates, substrate materials for electronic paper, and the like. And to provide a transparent polyimide film produced by the method.
上述の目的を達成するため、（ａ）ジアミン、（ｂ）フッ素化第１のジアンヒドリドと脂環族第２のジアンヒドリドとを含有するジアンヒドリド、及び、（ｃ）有機溶媒を含み、前記脂環族第２のジアンヒドリドは、全ジアンヒドリド１００モル％に対して、１０〜８０モル％の範囲で含まれることを特徴とするポリアミック酸組成物を提供する。 In order to achieve the above object, (a) diamine, (b) dianhydride containing a fluorinated first dianhydride and an alicyclic second dianhydride, and (c) an organic solvent, and An alicyclic second dianhydride is provided in the range of 10 to 80 mol% with respect to 100 mol% of the total dianhydride, to provide a polyamic acid composition.
本発明の好適な一例によれば、前記脂環族第２のジアンヒドリドは、下記の化１で示されるものであることができる。
本発明において、前記脂環族第２のジアンヒドリドは、シクロブタンテトラカルボン酸二無水物（ＣＢＤＡ）、１，２，３，４−シクロペンタンテトラカルボン酸二無水物（ＣＰＤＡ）及びビシクロ［２，２，２］−７−オクテン−２，３，５，６−テトラカルボン酸二無水物（ＢＣＤＡ）からなる群から選択される１種以上であることができる。 In the present invention, the alicyclic second dianhydride includes cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA) and bicyclo [2,2]. It can be one or more selected from the group consisting of 2,2] -7-octene-2,3,5,6-tetracarboxylic dianhydride (BCDA).
本発明において、前記フッ素化第１のジアンヒドリドの含有量は、全ジアンヒドリド１００モル％に対して、２０〜９０モル％であることができる。 In the present invention, the content of the fluorinated first dianhydride may be 20 to 90 mol% based on 100 mol% of the total dianhydride.
本発明において、前記ジアンヒドリドは、非フッ素化第３のジアンヒドリドをさらに含むことができる。 In the present invention, the dianhydride may further include a non-fluorinated third dianhydride.
本発明において、前記ジアミンは、フッ素化第１のジアミン及びスルホン系第２のジアミンからなる群から選択される１種以上を含むことができる。 In the present invention, the diamine may include at least one selected from the group consisting of a fluorinated first diamine and a sulfone-based second diamine.
本発明において、前記フッ素化第１のジアミンの含有量は、全ジアミン１００モル％に対して、５０〜１００モル％であることができ、前記スルホン系第２のジアミンの含有量は、全ジアミン１００モル％に対して、０〜５０モル％であることができる。 In the present invention, the content of the fluorinated first diamine may be 50 to 100 mol% with respect to 100 mol% of the total diamine, and the content of the sulfone-based second diamine may be the total diamine. It can be 0 to 50 mol% relative to 100 mol%.
本発明において、前記ジアミン（ａ）と前記ジアンヒドリド（ｂ）とのモル数比（ａ／ｂ）は、０．７〜１．３の範囲であることができる。 In the present invention, the molar ratio (a / b) of the diamine (a) and the dianhydride (b) may be in the range of 0.7 to 1.3.
また、本発明は、上述のポリアミック酸組成物をイミド化して製造される透明ポリイミド樹脂フィルムを提供する。 The present invention also provides a transparent polyimide resin film produced by imidizing the above polyamic acid composition.
本発明において、前記ポリイミド樹脂は、ガラス転移温度（Ｔｇ）が、３５０〜３９０℃の範囲であることができる。 In the present invention, the polyimide resin may have a glass transition temperature (T g ) in the range of 350 to 390 ° C.
本発明において、前記透明ポリイミド樹脂フィルムは、波長５５０ｎｍの光線透過率が９０％以上であり、ＡＳＴＭ Ｅ３１３規格による黄色度が３以下であり、次式で算出される厚さ方向の位相差（Ｒｔｈ）が、厚さ１０μｍ当たり、９０ｎｍ〜１００ｎｍであることができる。
位相差Ｒｔｈ（ｎｍ）＝［（ｎｙ−ｎｚ）×ｄ＋（ｎｘ−ｎｚ）×ｄ］／２
（ここで、ｎｘは、波長５５０ｎｍの光で測定されるポリイミド樹脂フィルムのｘ方向の屈折率であり、ｎｙは、波長５５０ｎｍの光で測定されるポリイミド樹脂フィルムのｙ方向の屈折率であり、ｎｚは、波長５５０ｎｍの光で測定されるポリイミド樹脂フィルムのｚ方向の屈折率であり、ｄは、ポリイミドフィルムの厚さである。）
In the present invention, the transparent polyimide resin film has a light transmittance of 90% or more at a wavelength of 550 nm, a yellowness degree of 3 or less according to the ASTM E313 standard, and a phase difference (R th ) can be 90 nm to 100 nm per 10 μm thickness.
Retardation R th (nm) = [( n y -n z) × d + (n x -n z) × d] / 2
(Here, n x is the refractive index in the x direction of the polyimide resin film measured with light having a wavelength of 550 nm, and n y is the refractive index in the y direction of the polyimide resin film measured with light having a wavelength of 550 nm. Yes, nz is the refractive index in the z direction of the polyimide resin film measured with light having a wavelength of 550 nm, and d is the thickness of the polyimide film.)
本発明において、前記透明ポリイミド樹脂フィルムは、フレキシブルディスプレイ用基板及び保護膜として使用することができる。 In the present invention, the transparent polyimide resin film can be used as a flexible display substrate and a protective film.
本発明によれば、特定の構造を有するジアミン及びジアンヒドリドモノマーを採択し、その組成を調節することにより、高いガラス転移温度（Ｔｇ）、低い黄色度、高い光透過度などを同時に有するポリアミック酸組成物を提供することができる。 According to the present invention, by adopting a diamine and a dianhydride monomer having a specific structure and adjusting the composition thereof, a polyamic acid having a high glass transition temperature (T g ), a low yellowness degree, a high light transmittance and the like at the same time. An acid composition can be provided.
また、本発明によれば、高い光透過度及び高いガラス転移温度を有する前記ポリアミック酸組成物を基板に適用することにより、優れた物性及び製品の信頼性を発揮するフレキシブルディスプレイ基板を提供することができる。 Further, according to the present invention, by applying the polyamic acid composition having a high light transmittance and a high glass transition temperature to the substrate, to provide a flexible display substrate exhibiting excellent physical properties and product reliability. You can
以下、本発明について詳述する。なお、下記のものは例示に過ぎず、本発明はこれらの例によって制限されるものではなく、後述の特許請求範囲によって定義される。 Hereinafter, the present invention will be described in detail. It should be noted that the following is merely an example, and the present invention is not limited by these examples, and is defined by the claims that will be described later.
＜ポリアミック酸組成物＞
本発明のポリアミック酸組成物は、透明ポリイミド樹脂フィルムを製造するためのものであって、（ａ）ジアミン、（ｂ）フッ素化第１のジアンヒドリドと脂環族第２のジアンヒドリドとを含有するジアンヒドリド及び（ｃ）有機溶媒を含み、この時、脂環族第２のジアンヒドリドを、特定範囲の含有量で含むように構成されることを特徴とする。
<Polyamic acid composition>
The polyamic acid composition of the present invention is for producing a transparent polyimide resin film, and comprises (a) a diamine, (b) a fluorinated first dianhydride and an alicyclic second dianhydride. And a (c) organic solvent, wherein the alicyclic second dianhydride is contained in a specific range of content.
前記脂環族第２のジアンヒドリドは、化学構造が剛直（Ｒｉｇｉｄ）であるため、熱や光による分解が発生することなく安定している。従って、これを含むポリアミック酸組成物の光学特性及び熱的特性を有意に改善することができる。 Since the alicyclic second dianhydride has a rigid chemical structure, it is stable without being decomposed by heat or light. Therefore, the optical characteristics and thermal characteristics of the polyamic acid composition containing the same can be significantly improved.
また、本発明では、ヒドロキシ基（−ＯＨ）又はスルホン基（−ＳＯ２−）が導入されるジアンヒドリド又はジアミンモノマーをさらに適用することで、優れた接着力特性及び光学的特性を発揮することが可能となる。 In the present invention, hydroxy groups (-OH) or a sulfone group (-SO 2 -) by further applying the dianhydride or diamine monomer are introduced, exhibits excellent adhesion and optical properties Is possible.
本発明の透明ポリアミック酸の製造に使用されるジアミン単量体（ａ）としては、当業界で周知のものを使用することができ、例えば、フッ素置換基が導入されたジアミン単量体を使用することができる。好ましくは、フッ素化第１のジアミン、スルホン系第２のジアミン又はこれらの混合物を使用する。 As the diamine monomer (a) used for producing the transparent polyamic acid of the present invention, those known in the art can be used, for example, a diamine monomer having a fluorine substituent introduced therein. can do. Preferably a fluorinated first diamine, a sulphonic second diamine or mixtures thereof are used.
使用可能なジアミン単量体（ａ）としては、例えば、オキシジアニリン（ＯＤＡ）、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）、２，２’−ビス（トリフルオロメチル）−４，３’−ジアミノビフェニル（２，２’−Ｂｉｓ（ｔｒｉｆｌｕｏｒｏｍｅｔｈｙｌ）−４，３’−Ｄｉａｍｉｎｏｂｉｐｈｅｎｙｌ）、２，２’−ビス（トリフルオロメチル）−５，５’−ジアミノビフェニル（２，２’−Ｂｉｓ（ｔｒｉｆｌｕｏｒｏｍｅｔｈｙｌ）−５，５’−Ｄｉａｍｉｎｏｂｉｐｈｅｎｙｌ）、ビスアミノヒドロキシフェニルヘキサフルオロプロパン（ＤＢＯＨ）、ビスアミノフェノキシフェニルヘキサフルオロプロパン（４ＢＤＡＦ）、ビスアミノフェノキシフェニルプロパン（６ＨＭＤＡ）、ビスアミノフェノキシジフェニルスルホン（ＤＢＳＤＡ）、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）、ビス（３−アミノフェニル）スルホン（３，３’−ＤＤＳ）、スルホニルジフタル酸無水物（ＳＯ２ＤＰＡ）、ビス（カルボキシフェニル）ジメチルシラン、又は、これらの１種又は２種以上の混合物を適用することができるが、これらに制限されない。 Examples of usable diamine monomers (a) include oxydianiline (ODA), 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFDB), 2,2'-bis (trifluoromethyl) -4,3'-diaminobiphenyl (2,2'-bis (trifluoromethyl) -4,3'-diaminobiphenyl), 2,2'-bis (trifluoromethyl)- 5,5′-diaminobiphenyl (2,2′-Bis (trifluoromethyl) -5,5′-diaminobiphenyl), bisaminohydroxyphenylhexafluoropropane (DBOH), bisaminophenoxyphenylhexafluoropropane (4BDAF), bisamino Phenoxyphenyl propane (6HMDA), bis Mino phenoxy diphenyl sulfone (DBSDA), bis (4-aminophenyl) sulfone (4,4'-DDS), bis (3-aminophenyl) sulfone (3,3'-DDS), sulfonyl di phthalic anhydride (SO 2 DPA), bis (carboxyphenyl) dimethylsilane, or one or a mixture of two or more thereof can be applied, but is not limited thereto.
本発明のジアミン単量体（ａ）において、前記フッ素化第１のジアミン及びスルホン系第２のジアミンは、それぞれ、化合物中、フッ素化構造及びスルホン系を含むジアミンモノマーであれば、特に限定されない。なお、高いガラス転移温度と光学特性を実現するため、フレキシブル構造を有するモノマーを選択して使用することが好ましい。 In the diamine monomer (a) of the present invention, the fluorinated first diamine and the sulfone-based second diamine are not particularly limited as long as they are diamine monomers containing a fluorinated structure and a sulfone-based compound in the compound. . It is preferable to select and use a monomer having a flexible structure in order to achieve a high glass transition temperature and optical characteristics.
高透明性、高いガラス転移温度及び低い黄色度を考慮して、前記フッ素化第１のジアミンとしては、直線状の高分子化を誘導し得る２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）を使用することが好ましい。また、前記スルホン系第２のジアミンは、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）を含むことが好ましい。 Considering high transparency, high glass transition temperature and low yellowness, the fluorinated first diamine may be 2,2′-bis (trifluoromethyl) -4 which can induce linear polymerization. , 4'-Diaminobiphenyl (2,2'-TFDB) is preferably used. The sulfone-based second diamine preferably contains bis (4-aminophenyl) sulfone (4,4'-DDS).
本発明において、前記フッ素化第１のジアミンの使用量は、特に限定されないが、例えば、全ジアミン１００モル％に対して、５０〜１００モル％であることができ、好ましくは、６０〜９０モル％の範囲である。 In the present invention, the amount of the fluorinated first diamine used is not particularly limited, but can be, for example, 50 to 100 mol%, and preferably 60 to 90 mol, based on 100 mol% of all the diamines. % Range.
また、本発明において、前記スルホン系第２のジアミンの使用量は、特に限定されないが、例えば、全ジアミン１００モル％に対して、０〜５０モル％の範囲であることができ、好ましくは、５〜４５モル％の範囲である。 Further, in the present invention, the amount of the sulfone-based second diamine used is not particularly limited, but may be, for example, in the range of 0 to 50 mol% based on 100 mol% of all the diamines, and preferably, It is in the range of 5 to 45 mol%.
本発明の透明ポリアミック酸の製造に使用されるジアンヒドリド（ｂ）単量体としては、当業界で周知のフッ素化第１のジアンヒドリドと、脂環族第２のジアンヒドリドを使用することができる。 As the dianhydride (b) monomer used for producing the transparent polyamic acid of the present invention, a fluorinated first dianhydride and an alicyclic second dianhydride known in the art may be used. it can.
前記フッ素化第１のジアンヒドリド単量体としては、フッ素置換基が導入された芳香族ジアンヒドリドであれば、特に限定されない。 The fluorinated first dianhydride monomer is not particularly limited as long as it is an aromatic dianhydride having a fluorine substituent introduced.
使用可能なフッ素化第１のジアンヒドリドとしては、例えば、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）、４−（トリフルオロメチル）ピロメリト酸二無水物（４−（ｔｒｉｆｌｕｏｒｏｍｅｔｈｙｌ）ｐｙｒｏｍｅｌｌｉｔｉｃ ｄｉａｎｈｙｄｒｉｄｅ、４−ＴＦＰＭＤＡ）などが挙げられる。これらは、単独で又は２種以上を混合して使用することができる。 Examples of the fluorinated first dianhydride that can be used include, for example, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride. , 6-FDA), 4- (trifluoromethyl) pyromellitic dianhydride (4- (trifluoromethyl) pyromellitic dianhydride, 4-TFPMDA) and the like. These may be used alone or in admixture of two or more.
フッ素化ジアンヒドリドの中の６−ＦＤＡは、分子鎖間及び分子鎖内の電荷移動錯体（ＣＴＣ：Ｃｈａｎｇｅ Ｔｒａｎｓｆｅｒ Ｃｏｍｐｌｅｘ）の形成を制限するという特性が非常に大きいので、透明化に非常に適している。従って、前記フッ素化第１のジアンヒドリドとしては、(２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）を使用することが好ましい。 6-FDA in the fluorinated dianhydride is very suitable for clarification because it has a very large property of restricting the formation of charge transfer complex (CTC) between and between molecular chains. There is. Therefore, as the fluorinated first dianhydride, (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, It is preferred to use 6-FDA).
本発明において、前記フッ素化第１のジアンヒドリドの使用量は、特に制限されないが、例えば、全ジアンヒドリド１００モル％に対して、２０〜９０モル％であり、好ましくは、３０〜８０モル％の範囲である。 In the present invention, the amount of the fluorinated first dianhydride used is not particularly limited, but is, for example, 20 to 90 mol% with respect to 100 mol% of the total dianhydride, and preferably 30 to 80 mol%. Is the range.
また、本発明において使用可能な脂環族第２のジアンヒドリドとしては、化合物の内、芳香族環でなく、脂環族環を有しかつ酸二無水物構造を有する化合物であれば、特に制限されない。 Further, as the alicyclic second dianhydride that can be used in the present invention, among the compounds, if it is a compound having an alicyclic ring and an acid dianhydride structure, not an aromatic ring, Not limited.
前記脂環族第２のジアンヒドリドは、下記の化１で示されるものであることが好ましい。
本発明の好適な一例によれば、前記Ｃｙは、
本発明において使用可能な脂環族第２のジアンヒドリドとしては、例えば、シクロブタンテトラカルボン酸二無水物（ＣＢＤＡ）、１，２，３，４−シクロペンタンテトラカルボン酸二無水物（ＣＰＤＡ）、ビシクロ［２，２，２］−７−オクテン−２，３，５，６−テトラカルボン酸二無水物（ＢＣＤＡ）、又は、これらの１種以上の混合物などが挙げられるが、これらに制限されない。 Examples of the alicyclic second dianhydride that can be used in the present invention include cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA), Examples include, but are not limited to, bicyclo [2,2,2] -7-octene-2,3,5,6-tetracarboxylic dianhydride (BCDA), or a mixture of one or more of these. .
本発明において、前記脂環族第２のジアンヒドリドの使用量は、特に制限されないが、例えば、全ジアンヒドリド１００モル％に対して、１０〜８０モル％の範囲であることができ、好ましくは、２０〜７０モル％の範囲である。 In the present invention, the amount of the alicyclic second dianhydride used is not particularly limited, but may be, for example, in the range of 10 to 80 mol% with respect to 100 mol% of the total dianhydride, and preferably It is in the range of 20 to 70 mol%.
本発明では、ジアンヒドリド成分として、フッ素置換基が導入されていない非フッ素化芳香族第３のジアンヒドリドをさらに含むことができる。 In the present invention, the dianhydride component may further include a non-fluorinated aromatic third dianhydride in which no fluorine substituent is introduced.
使用可能な非フッ素化第３のジアンヒドリド単量体として、例えば、ピロメリト酸二無水物（Ｐｙｒｏｍｅｌｌｉｔｉｃ Ｄｉａｎｈｙｄｒｉｄｅ、ＰＭＤＡ）、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（３，３’，４，４’−Ｂｉｐｈｅｎｙｌ ｔｅｔｒａｃａｒｂｏｘｙｌｉｃ ａｃｉｄ ｄｉａｎｈｙｄｒｉｄｅ、ＢＰＤＡ）などが挙げられるが、これらに制限されない。これらは、単独で使用又は２種以上を混用することができる。 Examples of usable non-fluorinated third dianhydride monomers include, for example, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (3,3). 3 ′, 4,4′-Biphenyl tetracarboxylic acid dianhydride (BPDA) and the like, but are not limited thereto. These may be used alone or in combination of two or more.
本発明において、前記非フッ素化第３のジアンヒドリドの使用量は、特に制限されないが、全ジアンヒドリド１００モル％に対して、５〜５０モル％の範囲であることができ、好ましくは、５〜４０モル％の範囲である。 In the present invention, the amount of the non-fluorinated third dianhydride used is not particularly limited, but may be in the range of 5 to 50 mol% based on 100 mol% of the total dianhydride, and preferably 5 Is in the range of up to 40 mol%.
本発明の透明ポリアミック酸組成物において、前記ジアミン成分（ａ）のモル数と前記ジアンヒドリド成分（ｂ）のモル数との比（Ａ／Ｂ）は、０．７〜１．３であることができ、好ましくは、０．８〜１．２、より好ましくは、０．９〜１．１の範囲である。 In the transparent polyamic acid composition of the present invention, the ratio (A / B) of the number of moles of the diamine component (a) and the number of moles of the dianhydride component (b) is 0.7 to 1.3. Can be achieved, preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.
本発明のポリアミック酸組成物に含まれる、上述の単量体の溶液重合反応を行うための溶媒（ｃ）としては、当業界で公知の有機溶媒を制約なく使用することができる。 As the solvent (c) contained in the polyamic acid composition of the present invention for carrying out the solution polymerization reaction of the above-mentioned monomers, organic solvents known in the art can be used without restriction.
使用可能な溶媒としては、例えば、ｍ−クレゾール、Ｎ−メチル−ピロリドン（ＮＭＰ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルスルホキシド（ＤＭＳＯ）、アセトン、ジエチルアセテート、及び、ジメチルフタレート（ＤＭＰ）からなる群から選択される１つ以上の極性溶媒を使用することができる。その他、テトラヒドロフラン（ＴＨＦ）、クロロホルムのような低沸点溶液又はγ−ブチロラクトンのような低吸収性溶媒を使用することができる。 Examples of usable solvents include m-cresol, N-methyl-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate, and dimethyl phthalate ( It is possible to use one or more polar solvents selected from the group consisting of DMP). In addition, a low boiling point solution such as tetrahydrofuran (THF) or chloroform or a low absorption solvent such as γ-butyrolactone can be used.
前記溶媒の含有量は、特に限定されないが、適正なポリアミック酸溶液の分子量及び粘度を得るために、重合用溶媒（第１の溶媒）の含有量は、ポリアミック酸組成物の全重量に対して、５０〜９５重量％の範囲であることができ、好ましくは、７０〜９０重量％、より好ましくは、７５〜８５重量％の範囲である。 The content of the solvent is not particularly limited, but in order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, the content of the polymerization solvent (first solvent) is based on the total weight of the polyamic acid composition. , 50 to 95% by weight, preferably 70 to 90% by weight, more preferably 75 to 85% by weight.
本発明では、上述の成分を有するジアンヒドリドとジアミンとを、前記有機溶媒に投入した後、反応させることで、ポリアミック酸組成物を製造する。例えば、フッ素系第１のジアミン、スルホン系第２のジアミン、フッ素系第１のジアンヒドリド、脂環族第２のジアンヒドリドなどの成分を、ガラス転移温度及び黄色度の改善を図るため、ジアミン（ａ）とジアンヒドリド（ｂ）とがおよそ１：１の当量比となるようにして透明ポリアミック酸組成物を形成する。 In the present invention, the polyamic acid composition is produced by introducing the dianhydride having the above-mentioned components and the diamine into the organic solvent and then reacting them. For example, in order to improve the glass transition temperature and the yellowness, components such as a fluorine-based first diamine, a sulfone-based second diamine, a fluorine-based first dianhydride, and an alicyclic second dianhydride are used as diamines. A transparent polyamic acid composition is formed such that (a) and dianhydride (b) have an equivalent ratio of about 1: 1.
前記ポリアミック酸組成物の組成は、特に制限されないが、例えば、ポリアミック酸組成物の全１００重量％に対して、酸二無水物２．５〜２５．５重量％、ジアミン２．５〜２５．５重量％、及び、残部の有機溶媒を含んで構成することができる。なお、本発明に係るポリアミック酸組成物の組成において、固形分１００重量％に対して、酸二無水物３０〜７０重量％、及び、ジアミン３０〜７０重量％の範囲であることができるが、これらに制限されない。 The composition of the polyamic acid composition is not particularly limited, but for example, 2.5 to 25.5% by weight of acid dianhydride and 2.5 to 25.% of diamine relative to 100% by weight of the total polyamic acid composition. It can be constituted by including 5% by weight and the balance of the organic solvent. In the composition of the polyamic acid composition according to the present invention, the amount of the acid dianhydride can be 30 to 70% by weight and the diamine can be 30 to 70% by weight with respect to 100% by weight of solid content, It is not limited to these.
このような本発明の透明ポリアミック酸組成物は、約１，０００〜５０，０００ｃｐｓ、好ましくは、約３，０００〜１５，０００ｃｐｓ範囲の粘度を有することができる。ポリアミック酸溶液の粘度が上述の範囲内であれば、ポリアミック酸溶液のコーティング時に、厚さの調節が容易で、均一なコーティング表面が得られる。 The transparent polyamic acid composition of the present invention may have a viscosity in the range of about 1,000 to 50,000 cps, preferably about 3,000 to 15,000 cps. When the viscosity of the polyamic acid solution is within the above range, it is possible to easily adjust the thickness when coating the polyamic acid solution and obtain a uniform coating surface.
また、本発明のポリアミック酸溶液は、必要に応じて、本発明の目的と効果を損なわない範囲で、可塑剤、酸化防止剤、難燃化剤、分散剤、粘度調節剤、レベリング剤などの添加剤を少量含むことができる。 Further, the polyamic acid solution of the present invention, if necessary, within a range that does not impair the purpose and effects of the present invention, such as a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, a leveling agent, etc. Small amounts of additives can be included.
本発明のポリアミック酸溶液は、フッ素化第１のジアンヒドリドと、脂環族第２のジアンヒドリドと、ジアミンと、必要に応じて非フッ素化第３のジアンヒドリドとを有機溶媒に投入した後、反応させることで製造することができる。 The polyamic acid solution of the present invention is prepared by adding the fluorinated first dianhydride, the second alicyclic dianhydride, the diamine, and optionally the non-fluorinated third dianhydride to the organic solvent. , Can be produced by reacting.
この時、反応条件は、特に限定されず、反応温度は、−２０〜８０℃が好ましく、重合時間は、１〜４８時間、好ましくは、２〜１２時間の範囲であることができる。また、アルゴンや窒素などの不活性雰囲気下で反応を行うことがより好ましい。上述の透明ポリアミック酸溶液を、発熱溶液の重合反応を行うことで、透明ポリアミック酸樹脂を合成することができる。 At this time, the reaction conditions are not particularly limited, the reaction temperature is preferably −20 to 80 ° C., and the polymerization time is 1 to 48 hours, preferably 2 to 12 hours. Further, it is more preferable to carry out the reaction under an inert atmosphere such as argon or nitrogen. A transparent polyamic acid resin can be synthesized by subjecting the above-mentioned transparent polyamic acid solution to a polymerization reaction of an exothermic solution.
＜ポリイミド樹脂フィルム＞
本発明は、上述のポリアミック酸溶液を高温でイミド化及び熱処理を行って製造されるポリイミド樹脂フィルムを提供する。
<Polyimide resin film>
The present invention provides a polyimide resin film produced by subjecting the above polyamic acid solution to imidization and heat treatment at high temperature.
前記ポリイミド樹脂は、イミド（ｉｍｉｄｅ）環を含む高分子物質であって、耐熱性、耐化学性、耐摩耗性及び電気的特性に優れている。なお、前記ポリイミド樹脂は、ランダム共重合体（Ｒａｎｄｏｍ ｃｏｐｏｌｙｍｅｒ）又はブロック共重合体（ｂｌｏｃｋ ｃｏｐｏｌｙｍｅｒ）の形態であることができる。 The polyimide resin is a polymer material containing an imide ring and is excellent in heat resistance, chemical resistance, abrasion resistance and electrical characteristics. In addition, the polyimide resin may be in the form of a random copolymer or a block copolymer.
本発明に係るポリイミド樹脂は、下記の化２又は化３で示される繰り返し単位を含むことができる。
Ｙは、ジアミンから誘導される炭素数６〜４０の２価有機基であって、脂肪族基、単環式脂肪族基、単環式芳香族基、縮合多環式芳香族基、又は、芳香族基が直接、又は、橋かけで互いに連結された非縮合多環式芳香族基である。
The polyimide resin according to the present invention may include a repeating unit represented by the following chemical formula 2 or chemical formula 3.
Y is a divalent organic group having 6 to 40 carbon atoms, which is derived from a diamine, and is an aliphatic group, a monocyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or An aromatic group is a non-condensed polycyclic aromatic group linked to each other directly or via a bridge.
本発明の好適な一例によれば、前記繰り返し単位において、Ｃｙは、
また、前記繰り返し単位において、Ｙは、
式中、Ｒ１〜Ｒ６は、互いに同一又は異なって、それぞれ独立に、水素、又はフッ素で置換又は非置換のＣ１〜Ｃ６のアルキル基であり、Ｒ７及びＲ８は、それぞれ独立に、水素又はヒドロキシ基である。 In the formula, R 1 to R 6 are the same or different from each other, each independently, are hydrogen or a C 1 to C 6 alkyl group substituted or unsubstituted with fluorine, and R 7 and R 8 are each independently. And hydrogen or a hydroxy group.
なお、ポリイミド樹脂フィルムは、フレキシブルディスプレイなどに適用するためには、基本的に、高透明性、低い熱膨張係数、高いガラス転移温度などの特徴を有する必要がある。より具体的に、膜厚さ１０μｍの場合、４００ｎｍの光透過率が７５％以上、５５０ｎｍの光透過率が９０％以上、５５０ｎｍでの黄色度の値が３以下、ガラス転移温度（Ｔｇ）が３００℃以上、などが要求される。 In addition, the polyimide resin film basically needs to have characteristics such as high transparency, a low thermal expansion coefficient, and a high glass transition temperature in order to be applied to a flexible display or the like. More specifically, when the film thickness is 10 μm, the light transmittance at 400 nm is 75% or more, the light transmittance at 550 nm is 90% or more, the yellowness value at 550 nm is 3 or less, and the glass transition temperature (T g ). Is required to be 300 ° C. or higher.
実際に、上述のポリアミック酸組成物をイミド化して製造される本発明のポリイミド樹脂フィルムは、繰り返し単位内に剛直な（Ｒｉｇｉｄ）化学構造を有することで、高透明性を示しながら、低い黄色度及び熱膨張係数、高いガラス転移温度（Ｔｇ）を有するようになる。より具体的に、（i）ガラス転移温度（Ｔｇ）は、３５０℃以上、好ましくは、３５０〜３９０℃の範囲であり、（ii）膜厚さ１０μｍで、５５０ｎｍの光線透過率が９０％以上であり、（iii）ＡＳＴＭ Ｅ３１３規格による５５０ｎｍでの黄色度（Ｙｅｌｌｏｗ Ｉｎｄｅｘ、Ｙ．Ｉ）が３以下（厚さ１０μｍ）であり、（iｖ）下記の式で算出される厚さ方向の複屈折位相差（Ｒｔｈ）が、厚さ１０μｍ当り、１００ｎｍ以下、好ましくは、９０ｎｍ〜１００ｎｍの範囲を有することができる。
位相差Ｒｔｈ（ｎｍ）＝［（ｎｙ−ｎｚ）×ｄ＋（ｎｘ−ｎｚ）×ｄ］／２
ここで、ｎｘは、波長５５０ｎｍの光で測定されるポリイミド樹脂フィルムのｘ方向の屈折率であり、ｎｙは、波長５５０ｎｍの光で測定されるポリイミド樹脂フィルムのｙ方向の屈折率であり、ｎｚは、波長５５０ｎｍの光で測定されるポリイミド樹脂フィルムのｚ方向の屈折率であり、ｄは、ポリイミドフィルムの厚さである。
In fact, the polyimide resin film of the present invention produced by imidizing the above-mentioned polyamic acid composition has a rigid (Rigid) chemical structure in the repeating unit, and thus exhibits high transparency and low yellowness. And have a high coefficient of thermal expansion, a high glass transition temperature (T g ). More specifically, (i) the glass transition temperature (T g ) is 350 ° C. or higher, preferably in the range of 350 to 390 ° C., (ii) the film thickness is 10 μm, and the light transmittance at 550 nm is 90%. And (iii) the yellowness index (Yellow Index, YI) at 550 nm according to the ASTM E313 standard is 3 or less (thickness 10 μm), and (iv) the compound in the thickness direction calculated by the following formula. The refraction retardation (R th ) can have a range of 100 nm or less, preferably 90 nm to 100 nm per 10 μm of thickness.
Retardation R th (nm) = [( n y -n z) × d + (n x -n z) × d] / 2
Here, n x is the refractive index in the x direction of the polyimide resin film measured with light having a wavelength of 550 nm, and n y is the refractive index in the y direction of the polyimide resin film measured with light having a wavelength of 550 nm. , Nz is the refractive index in the z direction of the polyimide resin film measured with light having a wavelength of 550 nm, and d is the thickness of the polyimide film.
本発明に係るポリイミド樹脂フィルムは、常法で製造することができ、例えば、前記透明ポリアミック酸組成物を、ガラス基板にコーティング（キャスティング）した後、３０〜３５０℃の範囲で徐々に昇温しながら、０．５〜８時間の間、イミド閉環反応（Ｉｍｉｄａｚａｔｉｏｎ）を誘導させることで製造することができる。 The polyimide resin film according to the present invention can be produced by a conventional method. For example, after coating (casting) the transparent polyamic acid composition on a glass substrate, the temperature is gradually raised in the range of 30 to 350 ° C. However, it can be manufactured by inducing an imide ring closure reaction (Imidazation) for 0.5 to 8 hours.
なお、前記コーティング方法は、当業界で周知の方法を制約なく使用することができ、例えば、スピンコーティング（ｓｐｉｎ ｃｏａｔｉｎｇ）法、ディップコーティング（ｄｉｐ ｃｏａｔｉｎｇ）法、ソルベントキャスティング（ｓｏｌｖｅｎｔ ｃａｓｔｉｎｇ）法、スロットダイコーティング（ｓｌｏｔ ｄｉｅ ｃｏａｔｉｎｇ）法及びスプレーコーティング法からなる群から選択される少なくとも１つの方法で行うことができる。前記無色透明なポリイミド層の厚さが、数百ｎｍ〜数十μｍとなるように、透明ポリアミック酸組成物のコーティングを１回以上行うことができる。 As the coating method, any method known in the art can be used without limitation, and examples thereof include a spin coating method, a dip coating method, a solvent casting method, and a slot die. It can be carried out by at least one method selected from the group consisting of a coating method and a spray coating method. The transparent polyamic acid composition can be coated one or more times so that the colorless and transparent polyimide layer has a thickness of several hundred nm to several tens of μm.
上述のように、透明ポリイミドフィルムは、種々の分野で使用することができ、特に、高透明性及び耐熱性が要求される、有機ＥＬ素子（ＯＬＥＤ）用ディスプレイ、液晶素子用ディスプレイ、ＴＦＴ基板、フレキシブル印刷回路基板、フレキシブルＯＬＥＤ面照明基板、電子ペーパー用基板素材のようなフレキシブルディスプレイ用基板及び保護膜として活用することができる。 As described above, the transparent polyimide film can be used in various fields, and in particular, high transparency and heat resistance are required, a display for an organic EL element (OLED), a display for a liquid crystal element, a TFT substrate, It can be used as a flexible printed circuit board, a flexible OLED surface lighting substrate, a flexible display substrate such as a substrate material for electronic paper, and a protective film.
以下、好適な実施例を挙げて本発明について詳述する。後述の実施例は、本発明の理解を助けるための例示に過ぎず、本発明の範囲は、これらの実施例によって限定されない。 Hereinafter, the present invention will be described in detail with reference to preferred examples. The examples described below are merely examples for facilitating the understanding of the present invention, and the scope of the present invention is not limited by these examples.
［実施例１］
１．透明ポリアミック酸組成物の製造
より具体的に、１００ｍｌの三口丸底フラスコに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）５８．５０４ｇ（８５．０ｗｔ％）を入れた後、反応器の温度を５０℃に昇温し、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）３ｇ（４．３ｗｔ％）を加え、３０分後、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）１．５５１ｇ（２．３ｗｔ％）を加えた。次に、当該モノマーを１時間攪拌し、２，２’−ＴＦＤＢ及び４，４’−ＤＤＳを完全に溶解させた。次に、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）及びシクロブタンテトラカルボン酸二無水物（ＣＢＤＡ）を、それぞれ順次に、４．８５５ｇ（７．１ｗｔ％）、０．９１９ｇ（１．３ｗｔ％）加えた後、３０℃に冷却して溶解させた。この時、固形分は１５％であった。次に、３時間攪拌した。モノマー反応終了後、自然冷却し、２５℃での溶液粘度６５ｐｏｉｓｅ（６５００ＣＰｓ）の透明ポリアミック酸組成物を得た。
[Example 1]
1. Preparation of transparent polyamic acid composition More specifically, after adding N.N-dimethylacetamide (DMAc) 58.504 g (85.0 wt%) to a 100 ml three-neck round bottom flask, the temperature of the reactor was 50 ° C. The temperature was raised to 2, 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-TFDB) 3 g (4.3 wt%) was added, and after 30 minutes, bis (4- Aminophenyl) sulfone (4,4′-DDS) (1.551 g, 2.3 wt%) was added. Next, the monomer was stirred for 1 hour to completely dissolve 2,2′-TFDB and 4,4′-DDS. Next, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA) and cyclobutanetetracarboxylic dianhydride. The compound (CBDA) was sequentially added to each of 4.855 g (7.1 wt%) and 0.919 g (1.3 wt%), and then cooled to 30 ° C. to be dissolved. At this time, the solid content was 15%. Then, the mixture was stirred for 3 hours. After completion of the monomer reaction, the mixture was naturally cooled to obtain a transparent polyamic acid composition having a solution viscosity of 65 poise (6500 CPs) at 25 ° C.
２．透明ポリイミドフィルムの製造
前記透明ポリアミック酸溶液をＬＣＤ用ガラスにスピンコーティングを行った後、窒素雰囲気のコンベクションオーブンで、８０℃で３０分間、１５０℃で３０分間、２００℃で１時間、段階的に徐々に昇温しながら乾燥及びイミド閉環反応（Ｉｍｉｄａｚａｔｉｏｎ）を行った。これにより、イミド化率が８５％以上である、膜厚さ１０μｍの透明ポリイミドフィルムを製造した。次に、フッ酸でガラスをエッチングし、ポリイミドフィルムを得た。
2. Preparation of transparent polyimide film After spin coating the glass for LCD with the transparent polyamic acid solution, in a convection oven in a nitrogen atmosphere, 80 ° C for 30 minutes, 150 ° C for 30 minutes, 200 ° C for 1 hour, stepwise. Drying and imide ring closure reaction (Imidazation) were performed while gradually raising the temperature. This produced a transparent polyimide film having a film thickness of 10 μm and an imidization ratio of 85% or more. Next, the glass was etched with hydrofluoric acid to obtain a polyimide film.
［実施例２］
１．透明ポリアミック酸組成物の製造
上述の実施例１と同様な条件で、丸底フラスコに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）５４．１１４ｇ（８５．０ｗｔ％）を入れた後、反応器の温度を５０℃に昇温し、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）３ｇ（４．７ｗｔ％）を加え、３０分後、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）１．５５１ｇ（２．４ｗｔ％）を加えた。次に、当該モノマーを１時間攪拌し、２，２’−ＴＦＤＢ及び４，４’−ＤＤＳを完全に溶解させた。次に、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）及びシクロブタンテトラカルボン酸二無水物（ＣＢＤＡ）を、それぞれ順次に、３．４６８ｇ（５．５ｗｔ％）、１．５３１ｇ（２．４ｗｔ％）加えた後、３０℃に冷却して溶解させた。この時、固形分は１５％であった。次に、３時間攪拌した。モノマー反応終了後、自然冷却し、２５℃での溶液粘度８０ｐｏｉｓｅ（８０００ＣＰｓ）の透明ポリアミック酸組成物を得た。
[Example 2]
1. Preparation of Transparent Polyamic Acid Composition Under the same conditions as in Example 1 above, 54.114 g (85.0 wt%) of N, N-dimethylacetamide (DMAc) was placed in a round bottom flask, and then the temperature of the reactor was changed. Was heated to 50 ° C., 3 g (4.7 wt%) of 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFDB) was added, and after 30 minutes, bis was added. 1.551 g (2.4 wt%) of (4-aminophenyl) sulfone (4,4′-DDS) was added. Next, the monomer was stirred for 1 hour to completely dissolve 2,2′-TFDB and 4,4′-DDS. Next, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA) and cyclobutanetetracarboxylic dianhydride. The compound (CBDA) was sequentially added in an amount of 3.468 g (5.5 wt%) and 1.531 g (2.4 wt%), and then cooled to 30 ° C. to be dissolved. At this time, the solid content was 15%. Then, the mixture was stirred for 3 hours. After completion of the monomer reaction, it was naturally cooled to obtain a transparent polyamic acid composition having a solution viscosity of 80 poise (8000 CPs) at 25 ° C.
２．透明ポリイミドフィルムの製造
無色透明なポリイミドフィルムの製造は、上述の実施例１と同様に行った。
2. Production of Transparent Polyimide Film Production of a colorless transparent polyimide film was performed in the same manner as in Example 1 described above.
［実施例３］
１．透明ポリアミック酸組成物の製造
上述の実施例１と同様な条件で、丸底フラスコに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）４４．８３３ｇ（８５．０ｗｔ％）を入れた後、反応器の温度を５０℃に昇温し、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）３ｇ（５．７ｗｔ％）を加え、３０分後、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）０．５８２ｇ（１．１ｗｔ％）を加えた。次に、当該モノマーを１時間攪拌し、２，２’−ＴＦＤＢ及び４，４’−ＤＤＳを完全に溶解させた。次に、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）及びシクロブタンテトラカルボン酸二無水物（ＣＢＤＡ）を、それぞれ順次に、３．６４１ｇ（６．９ｗｔ％）、０．６８９ｇ（１．３ｗｔ％）加えた後、３０℃に冷却して溶解させた。この時、固形分は１５％であった。次に、３時間攪拌した。モノマー反応終了後、自然冷却し、２５℃での溶液粘度５６ｐｏｉｓｅ（５６００ＣＰｓ）の透明ポリアミック酸組成物を得た。
[Example 3]
1. Production of Transparent Polyamic Acid Composition Under the same conditions as in Example 1 above, 44.833 g (85.0 wt%) of N, N-dimethylacetamide (DMAc) was placed in a round bottom flask, and then the temperature of the reactor was changed. Was heated to 50 ° C., 3 g (5.7 wt%) of 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFDB) was added, and after 30 minutes, bis was added. 0.582 g (1.1 wt%) of (4-aminophenyl) sulfone (4,4′-DDS) was added. Next, the monomer was stirred for 1 hour to completely dissolve 2,2′-TFDB and 4,4′-DDS. Next, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA) and cyclobutanetetracarboxylic dianhydride. The compound (CBDA) was sequentially added to each of 3.641 g (6.9 wt%) and 0.689 g (1.3 wt%), and then cooled to 30 ° C. to be dissolved. At this time, the solid content was 15%. Then, the mixture was stirred for 3 hours. After the completion of the monomer reaction, the mixture was naturally cooled to obtain a transparent polyamic acid composition having a solution viscosity of 56 poise (5600 CPs) at 25 ° C.
２．透明ポリイミドフィルムの製造
無色透明なポリイミドフィルムの製造は、上述の実施例１と同様に行った。
2. Production of Transparent Polyimide Film Production of a colorless transparent polyimide film was performed in the same manner as in Example 1 described above.
［実施例４］
１．透明ポリアミック酸組成物の製造
上述の実施例１と同様な条件で、丸底フラスコに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）４２．２７３ｇ（８５．０ｗｔ％）を入れた後、反応器の温度を５０℃に昇温し、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）３ｇ（４．２ｗｔ％）を加え、３０分後、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）１．５５１ｇ（２．２ｗｔ％）を加えた。次に、当該モノマーを１時間攪拌し、２，２’−ＴＦＤＢ及び４，４’−ＤＤＳを完全に溶解させた。次に、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）及びビシクロ［２，２，２］−オクテン−２，３，５，６−テトラカルボン酸二無水物（ＢＣＤＡ）を、それぞれ順次に、４．８５５ｇ（６．９ｗｔ％）、１．１６３ｇ（１．７ｗｔ％）加えた後、３０℃に冷却して溶解させた。この時、固形分は１５％であった。次に、３時間攪拌した。モノマー反応終了後、自然冷却し、２５℃での溶液粘度４７ｐｏｉｓｅ（４７００ＣＰｓ）の透明ポリアミック酸組成物を得た。
[Example 4]
1. Preparation of Transparent Polyamic Acid Composition Under the same conditions as in Example 1 above, 42.273 g (85.0 wt%) of N, N-dimethylacetamide (DMAc) was placed in a round bottom flask, and then the temperature of the reactor was changed. Is heated to 50 ° C., 3 g (4.2 wt%) of 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFDB) is added, and after 30 minutes, bis is added. 1.551 g (2.2 wt%) of (4-aminophenyl) sulfone (4,4′-DDS) was added. Next, the monomer was stirred for 1 hour to completely dissolve 2,2′-TFDB and 4,4′-DDS. Next, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA) and bicyclo [2,2,2,2]. 2] -octene-2,3,5,6-tetracarboxylic dianhydride (BCDA) was sequentially added to each of 4.855 g (6.9 wt%) and 1.163 g (1.7 wt%). The solution was cooled to 30 ° C and dissolved. At this time, the solid content was 15%. Then, the mixture was stirred for 3 hours. After completion of the monomer reaction, the mixture was naturally cooled to obtain a transparent polyamic acid composition having a solution viscosity of 47 poise (4700 CPs) at 25 ° C.
２．透明ポリイミドフィルムの製造
無色透明なポリイミドフィルムの製造は、上述の実施例１と同様に行った。
2. Production of Transparent Polyimide Film Production of a colorless transparent polyimide film was performed in the same manner as in Example 1 described above.
［実施例５］
１．透明ポリアミック酸組成物の製造
上述の実施例１と同様な条件で、丸底フラスコに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）４１．５６０ｇ（８５．０ｗｔ％）を入れた後、反応器の温度を５０℃に昇温し、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）３ｇ（４．３ｗｔ％）を加え、３０分後、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）１．５５１ｇ（２．２ｗｔ％）を加えた。次に、当該モノマーを１時間攪拌し、２，２’−ＴＦＤＢ及び４，４’−ＤＤＳを完全に溶解させた。次に、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）及び１，２，３，４−シクロペンタンテトラカルボン酸二無水物（ＣＰＤＡ）を、それぞれ順次に、４．８５５ｇ（７．０ｗｔ％）、０．９８４ｇ（１．５ｗｔ％）加えた後、３０℃に冷却して溶解させた。この時、固形分は１５％であった。次に、３時間攪拌した。モノマー反応終了後、自然冷却し、２５℃での溶液粘度５０ｐｏｉｓｅ（５０００ＣＰｓ）の透明ポリアミック酸組成物を得た。
[Example 5]
1. Production of transparent polyamic acid composition Under the same conditions as in Example 1 above, 41.560 g (85.0 wt%) of N, N-dimethylacetamide (DMAc) was placed in a round bottom flask, and then the temperature of the reactor was changed. Is heated to 50 ° C., 3 g (4.3 wt%) of 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFDB) is added, and after 30 minutes, bis is added. 1.551 g (2.2 wt%) of (4-aminophenyl) sulfone (4,4′-DDS) was added. Next, the monomer was stirred for 1 hour to completely dissolve 2,2′-TFDB and 4,4′-DDS. Next, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA) and 1,2,3,3. After adding 4.855 g (7.0 wt%) and 0.984 g (1.5 wt%) of 4-cyclopentanetetracarboxylic dianhydride (CPDA) in order, respectively, the mixture was cooled to 30 ° C. and dissolved. It was At this time, the solid content was 15%. Then, the mixture was stirred for 3 hours. After completion of the monomer reaction, the mixture was naturally cooled to obtain a transparent polyamic acid composition having a solution viscosity of 50 poise (5000 CPs) at 25 ° C.
２．透明ポリイミドフィルムの製造
無色透明なポリイミドフィルムの製造は、上述の実施例１と同様に行った。
2. Production of Transparent Polyimide Film Production of a colorless transparent polyimide film was performed in the same manner as in Example 1 described above.
［比較例１］
上述の実施例１と同様な条件下で、丸底フラスコに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）５３．１８０ｇ（８４．０ｗｔ％）を入れた後、反応器の温度を５０℃に昇温し、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）３ｇ（４．７ｗｔ％）を加え、３０分後、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）１．５５１ｇ（２．４ｗｔ％）を加えた。次に、当該モノマーを１時間攪拌し、２，２’−ＴＦＤＢ及び４，４’−ＤＤＳを完全に溶解させた。次に、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）及びピロメリト酸二無水物（ＰＭＤＡ）を、それぞれ順次に、４．８５５ｇ（７．６ｗｔ％）、１．０２２ｇ（１．３ｗｔ％）加えた後、３０℃に冷却して溶解させた。この時、固形分は１５％であった。次に、３時間攪拌した。モノマー反応終了後、自然冷却し、２５℃での溶液粘度４３ｐｏｉｓｅ（４３００ＣＰｓ）の透明ポリアミック酸組成物を得た。
[Comparative Example 1]
Under the same conditions as in Example 1 above, 53.180 g (84.0 wt%) of N, N-dimethylacetamide (DMAc) was placed in a round bottom flask, and then the temperature of the reactor was raised to 50 ° C. Then, 2 g of 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFDB) (4.7 wt%) was added, and after 30 minutes, bis (4-aminophenyl) was added. 1.551 g (2.4 wt%) of sulfone (4,4′-DDS) was added. Next, the monomer was stirred for 1 hour to completely dissolve 2,2′-TFDB and 4,4′-DDS. Next, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA) and pyromellitic dianhydride ( 4.855 g (7.6 wt%) and 1.022 g (1.3 wt%) of PMDA) were sequentially added, and then cooled to 30 ° C. to be dissolved. At this time, the solid content was 15%. Then, the mixture was stirred for 3 hours. After completion of the monomer reaction, the mixture was naturally cooled to obtain a transparent polyamic acid composition having a solution viscosity of 43 poise (4300 CPs) at 25 ° C.
２．透明ポリイミドフィルムの製造
前記ポリアミック酸溶液をＬＣＤ用ガラスにスピンコーティングを行った後、窒素雰囲気のコンベクションオーブンで、８０℃で３０分間、１５０℃で３０分間、２００℃で１時間、３００℃で１時間、段階的に徐々に昇温しながら乾燥及びイミド閉環反応（Ｉｍｉｄａｚａｔｉｏｎ）を行った。これにより、イミド化率が８５％以上である、膜厚さ１０μｍの透明ポリイミドフィルムを製造した。次に、フッ酸でガラスをエッチングし、ポリイミドフィルムを得た。
2. Preparation of Transparent Polyimide Film After spin-coating the polyamic acid solution on glass for LCD, it was heated in a convection oven in a nitrogen atmosphere at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, 200 ° C. for 1 hour, and 300 ° C. for 1 hour. Drying and imide ring closure reaction (Imidazation) were performed while gradually raising the temperature gradually over time. This produced a transparent polyimide film having a film thickness of 10 μm and an imidization ratio of 85% or more. Next, the glass was etched with hydrofluoric acid to obtain a polyimide film.
［比較例２］
１．透明ポリアミック酸組成物の製造
上述の実施例１と同様な条件で、丸底フラスコに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）５８．５８１ｇ（８４．０ｗｔ％）を入れた後、反応器の温度を５０℃に昇温し、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）３ｇ（４．３ｗｔ％）を加え、３０分後、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）１．５５１ｇ（２．２ｗｔ％）を加えた。次に、当該モノマーを１時間攪拌し、２，２’−ＴＦＤＢ及び４，４’−ＤＤＳを完全に溶解させた。次に、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）を６．９３６ｇ（９．５ｗｔ％）加えた後、３０℃に冷却して溶解させた。この時、固形分は１５％であった。次に、３時間攪拌した。モノマー反応終了後、自然冷却し、２５℃での溶液粘度２０ｐｏｉｓｅ（２０００ＣＰｓ）の透明ポリアミック酸組成物を得た。
[Comparative Example 2]
1. Preparation of transparent polyamic acid composition Under the same conditions as in Example 1 above, 58.581 g (84.0 wt%) of N, N-dimethylacetamide (DMAc) was placed in a round bottom flask, and then the temperature of the reactor was changed. Is heated to 50 ° C., 3 g (4.3 wt%) of 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFDB) is added, and after 30 minutes, bis is added. 1.551 g (2.2 wt%) of (4-aminophenyl) sulfone (4,4′-DDS) was added. Next, the monomer was stirred for 1 hour to completely dissolve 2,2′-TFDB and 4,4′-DDS. Next, 6.936 g (9.2 g) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA). 5 wt%), and then cooled to 30 ° C. to dissolve. At this time, the solid content was 15%. Then, the mixture was stirred for 3 hours. After completion of the monomer reaction, it was naturally cooled to obtain a transparent polyamic acid composition having a solution viscosity of 20 poise (2000 CPs) at 25 ° C.
２．透明ポリイミドフィルムの製造
前記ポリアミック酸溶液をＬＣＤ用ガラスにスピンコーティングを行った後、窒素雰囲気のコンベクションオーブンで、８０℃で３０分間、１５０℃で３０分間、２００℃で１時間、３００℃で１時間、段階的に徐々に昇温しながら乾燥及びイミド閉環反応（Ｉｍｉｄａｚａｔｉｏｎ）を行った。これにより、イミド化率が８５％以上である、膜厚さ１０μｍの透明ポリイミドフィルムを製造した。次に、フッ酸でガラスをエッチングし、ポリイミドフィルムを得た。
2. Preparation of Transparent Polyimide Film After spin-coating the polyamic acid solution on glass for LCD, it was heated in a convection oven in a nitrogen atmosphere at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, 200 ° C. for 1 hour, and 300 ° C. for 1 hour. Drying and imide ring closure reaction (Imidazation) were performed while gradually raising the temperature gradually over time. This produced a transparent polyimide film having a film thickness of 10 μm and an imidization ratio of 85% or more. Next, the glass was etched with hydrofluoric acid to obtain a polyimide film.
［比較例３］
１．透明ポリアミック酸組成物の製造
上述の実施例１と同様な条件で、丸底フラスコに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）４０．７４４ｇ（８４．０ｗｔ％）を入れた後、反応器の温度を５０℃に昇温し、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル（２，２’−ＴＦＤＢ）３ｇ（６．２ｗｔ％）を加え、３０分後、ビス（４−アミノフェニル）スルホン（４，４’−ＤＤＳ）１．５５１ｇ（１．２ｗｔ％）を加えた。次に、当該モノマーを１時間攪拌し、２，２’−ＴＦＤＢ及び４，４’−ＤＤＳを完全に溶解させた。次に、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（２，２−ｂｉｓ（３，４−ｄｉｃａｒｂｏｘｙｐｈｅｎｙｌ）ｈｅｘａｆｌｕｏｒｏｐｒｏｐａｎｅ ｄｉａｎｈｙｄｒｉｄｅ、６−ＦＤＡ）及びピロメリト酸二無水物（ＰＭＤＡ）を、それぞれ順次に、３．６４１ｇ（７．５ｗｔ％）、０．７６６ｇ（１．１ｗｔ％）加えた後、３０℃に冷却して溶解させた。この時、固形分は１５％であった。次に、３時間攪拌した。モノマー反応終了後、自然冷却し、２５℃での溶液粘度４３．２ｐｏｉｓｅ（４３２０ＣＰｓ）の透明ポリアミック酸組成物を得た。
[Comparative Example 3]
1. Preparation of Transparent Polyamic Acid Composition Under the same conditions as in Example 1 above, after charging 40.744 g (84.0 wt%) of N, N-dimethylacetamide (DMAc) in a round bottom flask, the temperature of the reactor was changed. Was heated to 50 ° C., 3 g (6.2 wt%) of 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFDB) was added, and after 30 minutes, bis was added. 1.551 g (1.2 wt%) of (4-aminophenyl) sulfone (4,4′-DDS) was added. Next, the monomer was stirred for 1 hour to completely dissolve 2,2′-TFDB and 4,4′-DDS. Next, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA) and pyromellitic dianhydride ( PMDA) was sequentially added to each of 3.641 g (7.5 wt%) and 0.766 g (1.1 wt%), and then cooled to 30 ° C. to be dissolved. At this time, the solid content was 15%. Then, the mixture was stirred for 3 hours. After the completion of the monomer reaction, the mixture was naturally cooled to obtain a transparent polyamic acid composition having a solution viscosity at 25 ° C. of 43.2 poise (4320 CPs).
２．透明ポリイミドフィルムの製造
前記ポリアミック酸溶液をＬＣＤ用ガラスにスピンコーティングを行った後、窒素雰囲気のコンベクションオーブンで、８０℃で３０分間、１５０℃で３０分間、２００℃で１時間、３００℃で１時間、段階的に徐々に昇温しながら乾燥及びイミド閉環反応（Ｉｍｉｄａｚａｔｉｏｎ）を行った。これにより、イミド化率が８５％以上である、膜厚さ１０μｍの透明ポリイミドフィルムを製造した。次に、フッ酸でガラスをエッチングし、ポリイミドフィルムを得た。
2. Preparation of Transparent Polyimide Film After spin-coating the polyamic acid solution on glass for LCD, it was heated in a convection oven in a nitrogen atmosphere at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, 200 ° C. for 1 hour, and 300 ° C. for 1 hour. Drying and imide ring closure reaction (Imidazation) were performed while gradually raising the temperature gradually over time. This produced a transparent polyimide film having a film thickness of 10 μm and an imidization ratio of 85% or more. Next, the glass was etched with hydrofluoric acid to obtain a polyimide film.
上述の実施例１〜５及び比較例１〜３で得られたポリアミック酸組成物の組成を下記の表１に示す。 The compositions of the polyamic acid compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1 below.
［物性評価］
実施例１〜５及び比較例１〜３で得られた透明ポリイミド樹脂フィルムの物性を、下記のような方法で評価し、その結果を下記の表２に示す。
[Evaluation of the physical properties]
The physical properties of the transparent polyimide resin films obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated by the following methods, and the results are shown in Table 2 below.
＜物性評価方法＞
１）光透過度の測定
４００ｎｍ及び５５０ｎｍの波長で、ＵＶ−Ｖｉｓ ＮＩＲ Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒを用いて、ＡＳＴＭ Ｅ３１３−７３規格であるＣ光源及び２°視野角で測定した。
<Physical property evaluation method>
1) Measurement of Light Transmittance Using a UV-Vis NIR Spectrophotometer at wavelengths of 400 nm and 550 nm, measurement was carried out with a C light source, which is an ASTM E313-73 standard, and a 2 ° viewing angle.
２）複屈折の測定
複屈折測定装置（Ｒｅｔａｒｄｅｒ、大塚社製、ＲＥＴｓ−１００）を用いて測定した。サンプルは、横５ｃｍ×縦５ｃｍの正方形の試験片をサンプルホルダーに装着し、モノクロメーターを用いて５５０ｎｍに固定し、厚さ方向複屈折（Ｒｔｈ）は、入射角４５°で測定した。
Ｒｔｈ＝［（ｎｙ−ｎｚ）×ｄ＋（ｎｘ−ｎｚ）×ｄ］／２
ここで、ｎｘは、ｘ方向の屈折率、ｎｙは、ｙ方向の屈折率、ｎｚは、ｚ方向の屈折率、ｄは、ポリイミドフィルムの厚さを１０μｍに換算して計算した値である。
2) Measurement of birefringence It was measured using a birefringence measuring device (Retarder, manufactured by Otsuka Co., Ltd. RETs-100). As a sample, a square test piece of 5 cm in width × 5 cm in length was mounted on a sample holder and fixed at 550 nm using a monochromator, and birefringence in the thickness direction (R th ) was measured at an incident angle of 45 °.
R th = [(n y -n z) × d + (n x -n z) × d] / 2
Here, n x is the refractive index in the x direction, n y is the refractive index in the y direction, nz is the refractive index in the z direction, and d is the value calculated by converting the thickness of the polyimide film into 10 μm. Is.
３）黄色度の測定
ＵＶ分光計（コニカミノルタＣＭ−３７００ｄ）を用いて、５５０ｎｍでの黄色度を、ＡＳＴＭ Ｅ３１３規格によって測定した。
3) Measurement of Yellowness Using a UV spectrometer (Konica Minolta CM-3700d), the yellowness at 550 nm was measured according to the ASTM E313 standard.
４）ガラス転移温度（Ｔｇ）の測定
示差走査熱量計（ＤＳＣ、ＴＡインスツルメント社製、Ｑ２００）を用いて、ガラス転移温度を測定した。
4) Measurement of glass transition temperature (T g ) The glass transition temperature was measured using a differential scanning calorimeter (DSC, TA Instruments Co., Q200).
５）厚さの測定
シリコンウェハに、透明ポリアミック酸樹脂を、膜厚さ２０μｍ以下となるようにコーティングを行った後、乾燥及びイミド閉環反応を行い、５５０ｎｍ波長での非接触式屈折率測定装置（Ｅｌｌｉｐｓｏ Ｔｅｃｈｎｏｌｏｇｙ社製、Ｅｌｌｉ−ＲＰ）を用いて、フィルムの厚さを測定した。
5) Thickness measurement A transparent polyamic acid resin is coated on a silicon wafer to a film thickness of 20 μm or less, followed by drying and imide ring closure reaction, and a non-contact type refractive index measuring device at a wavelength of 550 nm. (Elli-RP, manufactured by Ellipso Technology) was used to measure the thickness of the film.
６）接着力の測定（ＡＳＴＭ Ｄ３００２／Ｄ３３５９）
ガラス基板の上に、透明ポリアミック酸樹脂を、膜厚さ２０μｍ以下となるようにコーティングを行った後、乾燥及びイミド閉環反応を行い、形成されたポリイミド薄膜の表面を刃物でカットし、カットされた表面の上に接着力測定用テープを貼り付けた後、剥離し、ポリイミド接着面の剥離状態を確認した。
6) Measurement of adhesive strength (ASTM D3002 / D3359)
After coating a transparent polyamic acid resin on a glass substrate to a film thickness of 20 μm or less, drying and imide ring closure reaction are performed, and the surface of the formed polyimide thin film is cut with a knife and cut. A tape for measuring the adhesive strength was attached on the surface, and then peeled off to confirm the peeled state of the polyimide-bonded surface.
この時、５Ｂは、剥離されたポリイミドの百分率が０％、４Ｂは、剥離されたポリイミドの百分率が５％以下、３Ｂは、剥離されたポリイミドの百分率が５〜１５％、２Ｂは、剥離されたポリイミドの百分率が１５〜３５％、１Ｂは、剥離されたポリイミドの百分率が３５〜６５％、０Ｂは、剥離されたポリイミドの百分率が６５％超であることをそれぞれ示す。 At this time, 5B has a peeled polyimide percentage of 0%, 4B has a peeled polyimide percentage of 5% or less, 3B has a peeled polyimide percentage of 5 to 15%, and 2B has a peeled polyimide percentage. The polyimide percentage is 15 to 35%, 1B indicates that the peeled polyimide percentage is 35 to 65%, and 0B indicates that the peeled polyimide percentage is over 65%.
表１に示されるように、本発明の無色透明なポリイミドフィルムは、その特性値が、脂環族ジアンヒドリドであるＣＢＤＡの添加量が多くなるほどガラス転移温度（Ｔｇ）が高くなるという結果が得られ、ＣＢＤＡによるガラス転移温度の上昇効果が確認された。 As shown in Table 1, the colorless and transparent polyimide film of the present invention has the characteristic value that the glass transition temperature (Tg) becomes higher as the addition amount of CBDA which is an alicyclic dianhydride increases. As a result, the effect of increasing the glass transition temperature by CBDA was confirmed.
また、フレキシブルディスプレイ材料及び基板として適用するためには、５５０ｎｍ条件での透過度が９０％以上、厚さの複屈折が１００ｎｍ以下、黄色度が３以下であるという条件を満たす必要がある。前記表１の結果によれば、上述の条件をいずれも満たすことが確認された。 Further, in order to be applied as a flexible display material and a substrate, it is necessary to satisfy the conditions that the transmittance is 90% or more under the condition of 550 nm, the birefringence of the thickness is 100 nm or less, and the yellowness is 3 or less. According to the results shown in Table 1, it was confirmed that all the above conditions were satisfied.
さらに、基板のガラス転移温度（Ｔｇ）が３００℃〜４００℃の範囲である条件を満たす必要があるが、本発明では、ガラス転移温度（Ｔｇ）が３５０℃〜３９０℃の範囲であるため、フレキシブルディスプレイ材料として適用可能な条件を満たすことが確認された。 Further, the glass transition temperature (T g ) of the substrate needs to meet the condition of 300 ° C. to 400 ° C., but in the present invention, the glass transition temperature (T g ) is 350 ° C. to 390 ° C. Therefore, it was confirmed that the applicable condition as a flexible display material was satisfied.
上述のような結果から、本発明のポリアミック酸組成物は、フレキシブルディスプレイ用基板及び保護膜として適用可能であることが確認された。 From the above results, it was confirmed that the polyamic acid composition of the present invention can be applied as a flexible display substrate and a protective film.
Claims (12)
（ｂ）フッ素化第１のジアンヒドリドと脂環族第２のジアンヒドリドとを含有するジアンヒドリド、及び
（ｃ）有機溶媒；
を含み、
前記脂環族第２のジアンヒドリドは、全ジアンヒドリド１００モル％に対して、１０〜８０モル％の範囲で含まれており、
前記フッ素化第１のジアミンの使用量は、全ジアミン１００モル％に対して、６０〜９０モル％であることを特徴とするポリアミック酸組成物。 (A) a diamine consisting only of a fluorinated first diamine and a sulfone-based second diamine,
(B) a dianhydride containing a fluorinated first dianhydride and an alicyclic second dianhydride, and (c) an organic solvent;
Including,
The alicyclic second dianhydride is contained in the range of 10 to 80 mol% with respect to 100 mol% of the total dianhydride ,
The amount of the fluorinated first diamine, the total diamine 100 mol%, the polyamic acid composition according to claim 60 to 90 mol% der Rukoto.
Ｙは、ジアミンから誘導された炭素数６〜４０の２価有機基であり、脂肪族基、単環式脂肪族基、単環式芳香族基、縮合多環式芳香族基、又は、芳香族基が直接、又は、橋かけにより連結される非縮合多環式芳香族基である。） The transparent polyimide resin film according to claim 8 , wherein the polyimide resin includes a repeating unit represented by Chemical formula 2 or Chemical formula 3.
Y is a divalent organic group having 6 to 40 carbon atoms derived from diamine, and is an aliphatic group, a monocyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group. A non-fused polycyclic aromatic group in which the group group is directly or crosslinked. )
（ここで、Ｒ１〜Ｒ６は、互いに同一又は異なって、それぞれ独立に、水素、又はフッ素で置換又は非置換のＣ１〜Ｃ６のアルキル基であり、Ｒ７及びＲ８は、それぞれ独立に、水素又はヒドロキシ基である。） Y of the repeating unit is
(Here, R 1 to R 6 are the same or different from each other, each independently, are hydrogen or a fluorine-substituted or unsubstituted C 1 to C 6 alkyl group, and R 7 and R 8 are each Independently, it is a hydrogen or a hydroxy group.)
次式で算出される厚さ方向の複屈折位相差（Ｒｔｈ）が、厚さ１０μｍ当り、９０ｎｍ〜１００ｎｍであることを特徴とする請求項８に記載の透明ポリイミド樹脂フィルム。
位相差Ｒｔｈ（ｎｍ）＝［（ｎｙ−ｎｚ）×ｄ＋（ｎｘ−ｎｚ）×ｄ］／２
（ｎｘは、波長５５０ｎｍの光で測定されるポリイミド樹脂フィルムのｘ方向の屈折率であり、ｎｙは、波長５５０ｎｍの光で測定されるポリイミド樹脂フィルムのｙ方向の屈折率であり、ｎｚは、波長５５０ｎｍの光で測定されるポリイミド樹脂フィルムのｚ方向の屈折率であり、ｄは、ポリイミドフィルムの厚さである。） The light transmittance at a wavelength of 550 nm is 90% or more ,
The birefringence retardation (R th ) in the thickness direction calculated by the following formula is 90 nm to 100 nm per 10 μm thickness, and the transparent polyimide resin film according to claim 8 .
Retardation R th (nm) = [( n y -n z) × d + (n x -n z) × d] / 2
(N x is the refractive index in the x direction of the polyimide resin film measured with light having a wavelength of 550 nm, n y is the refractive index in the y direction of the polyimide resin film measured with light having a wavelength of 550 nm, and n (z is the refractive index in the z direction of the polyimide resin film measured with light having a wavelength of 550 nm, and d is the thickness of the polyimide film.)
The transparent polyimide resin film according to claim 8 , which is used as a substrate for a flexible display and a protective film.
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| KR1020150182872A KR102417428B1 (en) | 2015-12-21 | 2015-12-21 | Polyamic acid composition comprising alicyclic monomer and trasparent polyimide film using the same |
| KR10-2015-0182872 | 2015-12-21 | ||
| PCT/KR2016/012483 WO2017111289A1 (en) | 2015-12-21 | 2016-11-01 | Polyamic acid composition to which alicyclic monomers are applied and transparent polyimide film using same |
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| TW201920364A (en) * | 2017-08-11 | 2019-06-01 | 美商杜邦股份有限公司 | Low-color polymers for flexible substrates in electronic devices |
| US20200255596A1 (en) * | 2017-10-11 | 2020-08-13 | Kaneka Corporation | Polyimide resin and production method therefor, polyimide solution, and polyimide film and production method therefor |
| JP7039947B2 (en) * | 2017-11-17 | 2022-03-23 | 大日本印刷株式会社 | Polyimide film, polyimide precursor, method for manufacturing polyimide film, and display device members |
| KR102430152B1 (en) * | 2017-12-08 | 2022-08-08 | 주식회사 두산 | Polyamic acid solution, transparent polyimide film and transparent substrate using the same |
| KR102036227B1 (en) * | 2018-01-31 | 2019-10-24 | 에스케이씨 주식회사 | Polyamide-imide film and preparation method thereof |
| JP7298141B2 (en) * | 2018-11-30 | 2023-06-27 | 株式会社リコー | CUREABLE COMPOSITION, COMPOSITION CONTAINER, TWO-DIMENSIONAL OR THREE-DIMENSIONAL IMAGE FORMING METHOD AND FORMING APPARATUS, CURED PRODUCT, STRUCTURE, AND MOLDED PROCESSED PRODUCT |
| KR102152278B1 (en) * | 2018-11-30 | 2020-09-07 | 한국화학연구원 | BCDA-based semi-alicyclic polyimide membrane materials for gas separation and the preparation method thereof |
| KR102551047B1 (en) | 2019-02-01 | 2023-07-04 | 주식회사 엘지화학 | Polyimide film, flexible substrate using same and flexible display comprising flexible substrate |
| US11603440B2 (en) * | 2019-09-12 | 2023-03-14 | Dupont Electronics, Inc. | Polyimide films and electronic devices |
| CN112708131A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of alternating copolymerization polyamic acid solution |
| KR20210075610A (en) * | 2019-12-13 | 2021-06-23 | 주식회사 두산 | Polyimide film having excellent weather resistance |
| KR102485698B1 (en) * | 2021-02-05 | 2023-01-06 | 주식회사 두산 | Polyimide film having excellent optical property |
| CN113072702B (en) * | 2021-03-31 | 2023-03-10 | 上海大学(浙江·嘉兴)新兴产业研究院 | Colorless transparent copolymerized polyimide film and preparation method thereof |
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