JPS63170420A - Molded article of colorless transparent polyimide and production thereof - Google Patents
Molded article of colorless transparent polyimide and production thereofInfo
- Publication number
- JPS63170420A JPS63170420A JP212587A JP212587A JPS63170420A JP S63170420 A JPS63170420 A JP S63170420A JP 212587 A JP212587 A JP 212587A JP 212587 A JP212587 A JP 212587A JP S63170420 A JPS63170420 A JP S63170420A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- polyamic acid
- molded article
- film
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims description 53
- 239000004642 Polyimide Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 33
- 125000003118 aryl group Chemical group 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 29
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 7
- 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 abstract description 14
- 125000003277 amino group Chemical group 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 8
- 150000004984 aromatic diamines Chemical class 0.000 abstract description 6
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical group C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000005357 flat glass Substances 0.000 abstract 1
- 238000006358 imidation reaction Methods 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 20
- 150000004985 diamines Chemical class 0.000 description 10
- 239000002798 polar solvent Substances 0.000 description 10
- -1 4-chloro-m-phenylenediamine 3.5-diaminobenzoic acid 5-nitro-m-phenylenediamine Chemical compound 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical group CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 description 1
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- DCSSXQMBIGEQGN-UHFFFAOYSA-N 4,6-dimethylbenzene-1,3-diamine Chemical group CC1=CC(C)=C(N)C=C1N DCSSXQMBIGEQGN-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- DFWXYHZQNLIBLY-UHFFFAOYSA-N 5-nitrobenzene-1,3-diamine Chemical compound NC1=CC(N)=CC([N+]([O-])=O)=C1 DFWXYHZQNLIBLY-UHFFFAOYSA-N 0.000 description 1
- 102100022117 Abnormal spindle-like microcephaly-associated protein Human genes 0.000 description 1
- 241000288673 Chiroptera Species 0.000 description 1
- 101000900939 Homo sapiens Abnormal spindle-like microcephaly-associated protein Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZPCCSZFPOXBNDL-ZSTSFXQOSA-N [(4r,5s,6s,7r,9r,10r,11e,13e,16r)-6-[(2s,3r,4r,5s,6r)-5-[(2s,4r,5s,6s)-4,5-dihydroxy-4,6-dimethyloxan-2-yl]oxy-4-(dimethylamino)-3-hydroxy-6-methyloxan-2-yl]oxy-10-[(2r,5s,6r)-5-(dimethylamino)-6-methyloxan-2-yl]oxy-5-methoxy-9,16-dimethyl-2-oxo-7-(2-oxoe Chemical compound O([C@H]1/C=C/C=C/C[C@@H](C)OC(=O)C[C@H]([C@@H]([C@H]([C@@H](CC=O)C[C@H]1C)O[C@H]1[C@@H]([C@H]([C@H](O[C@@H]2O[C@@H](C)[C@H](O)[C@](C)(O)C2)[C@@H](C)O1)N(C)C)O)OC)OC(C)=O)[C@H]1CC[C@H](N(C)C)[C@@H](C)O1 ZPCCSZFPOXBNDL-ZSTSFXQOSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- XFAIQVVTPAQNKL-UHFFFAOYSA-N benzene-1,3-diamine;4-methylbenzene-1,3-diamine Chemical compound NC1=CC=CC(N)=C1.CC1=CC=C(N)C=C1N XFAIQVVTPAQNKL-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000007767 bonding agent Substances 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
- 239000002131 composite material Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、液晶配向膜等に用いられる無色透明ポリイミ
ド成形体およびその製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a colorless and transparent polyimide molded body used for liquid crystal alignment films and the like, and a method for producing the same.
液晶配向膜は、透明性に富み、かつ電気２機械特性に優
れていることが要求されており、そのような特性を有す
るポリイミド膜が上記液晶配向膜として賞用されている
。ところで、芳香族系ポリイミドは、通常、不溶、不融
のため、その前駆体であるポリアミド酸の有機極性溶媒
（Ｎ−メチル−２−ピロリドン）溶液の状態で基板に塗
布され、高温加熱により脱水閉環イミド化して硬化する
ものであり、上記ポリイミド膜もこのようにして形成さ
れている。しかしながら、このようにして形成されたポ
リイミド膜は、透明性は有しているものの、生成に到る
までの苛酷な熱履歴により褐色に着色しており、これが
視野を暗くしてコントラストを悪くし、表示素子の機能
を損なうため、高品質の液晶表示素子の要求に応えてい
ないのが実情である。そのため従来から、上記着色を除
くことを目的として各種のポリイミドが提案されており
、そのなかでも着色度が小さく透明度が高いポリイミド
配向膜として特開昭５８−９１４３０に開示されている
、一般式（Ｖ）
で表される繰返し単位を有する芳香族ポリイミド重合体
からなるものが優れている。しかしながら、上記のポリ
イミド配向膜は透明性には優れているもののやはり膜自
体が黄色に着色しているため、液晶配向膜としていまひ
とつ満足しうるものではない。The liquid crystal alignment film is required to be highly transparent and have excellent electrical and mechanical properties, and polyimide films having such properties are used as the liquid crystal alignment film. By the way, aromatic polyimide is usually insoluble and infusible, so it is applied to a substrate in the form of a solution of its precursor, polyamic acid, in an organic polar solvent (N-methyl-2-pyrrolidone), and then dehydrated by high-temperature heating. It is cured by ring-closing imidization, and the above-mentioned polyimide film is also formed in this way. However, although the polyimide film formed in this way is transparent, it is colored brown due to the severe thermal history leading up to its formation, which darkens the field of view and worsens the contrast. The reality is that this method does not meet the demand for high-quality liquid crystal display devices because it impairs the functionality of the display device. Therefore, various polyimides have been proposed for the purpose of eliminating the above-mentioned coloring, and among them, a polyimide alignment film with a general formula ( V) Those made of aromatic polyimide polymers having repeating units represented by the following are excellent. However, although the above-mentioned polyimide alignment film has excellent transparency, the film itself is colored yellow, so it is not very satisfactory as a liquid crystal alignment film.
本発明は、上記のような色付きの透明性を備えているも
のではなく、無色透明なポリイミド成形体およびその製
法の提供をその目的とするものである。The purpose of the present invention is to provide a colorless and transparent polyimide molded product and a method for producing the same, rather than having the colored transparency described above.
上記の目的を達成するため、本発明は、下記の一般式（
ＩＩＩ）で表される繰返し単位および下記の一般式（ｎ
）で表される繰返し単位を主成分とすることを特徴とす
る無色透明なポリイミド成形体を第１の要旨とし、
下記の一般式（ＩＩＩ）で表される繰返し単位および下
記の一般式（Ｉ’／）で表される繰返し単位を主成分と
する芳香族ポリアミド酸のＮ、’Ｎ−ジメチルアセトア
ミド溶液を準備する工程と、上記溶液の溶媒除去および
芳香族ポリアミド酸の脱水閉環工程を備えることを特徴
とする無色透明ポリイミド成形体の製法。In order to achieve the above object, the present invention provides the following general formula (
III) and the following general formula (n
) The first gist is a colorless and transparent polyimide molded product characterized by containing as a main component a repeating unit represented by the following general formula (III) and a repeating unit represented by the following general formula (III) and the following general formula (I A step of preparing an N,'N-dimethylacetamide solution of an aromatic polyamic acid whose main component is a repeating unit represented by '/), and a step of removing the solvent from the solution and dehydrating and ring-closing the aromatic polyamic acid. A method for producing a colorless and transparent polyimide molded body characterized by:
すなわち、本発明者らは、ポリイミド膜の着色の原因に
ついて一連の研究を重ねた結果、ポリイミドの出発物質
である芳香族テトラカルボン酸二無水物とジアミノ化合
物の組み合わせが着色に大きく影響することを見いだし
、特に芳香族テトラカルボン酸二無水物として２．２−
ビス（３，４−ジカルボキシフェニル）へキサフルオロ
プロパンニ無水物を用い、これとジアミノ化合物として
メタ位置にアミノ基を有する芳咎族ジアミンとを組合わ
せると、無色透明なポリイミド成形体を形成でき、この
際、特に使用溶媒としてＮ−メチル−２−ピロリドンに
代えてＮ、Ｎ−ジメチルアセトアミド等のアミド系有機
溶媒を用いると好結果が得られることを見いだし本発明
に到達した。In other words, as a result of a series of studies on the causes of coloration of polyimide films, the present inventors have found that the combination of aromatic tetracarboxylic dianhydride and diamino compound, which are the starting materials for polyimide, greatly affects coloration. Found, especially as aromatic tetracarboxylic dianhydride 2.2-
By using bis(3,4-dicarboxyphenyl)hexafluoropropanihydride and combining it with an aromatic diamine having an amino group at the meta position as a diamino compound, a colorless and transparent polyimide molded body is formed. In this case, it has been found that good results can be obtained especially when an amide organic solvent such as N,N-dimethylacetamide is used instead of N-methyl-2-pyrrolidone as the solvent, and the present invention has been achieved.
本発明の無色透明なポリイミド成形体は、下記の一般式
（ＶＩ）
で表される２、２−ビス（３，４−ジカルボキシフェニ
ル）へキサフルオロプロパンニ無水ｔ１を用い、これに
下記の一般式（■）で表される芳香族ジアミノ化合物と
下記の一般式（■）で表される芳香族ジアミノ化合物と
を前者１００〜５０モル％に対して後者０〜５０モル％
の割合で用い、このジアミノ化合物と上記一般式（ＶＩ
）で表される酸二無水物とを反応させることによって得
られる。The colorless and transparent polyimide molded article of the present invention uses 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropanihydride t1 represented by the following general formula (VI), and the following The aromatic diamino compound represented by the general formula (■) and the aromatic diamino compound represented by the following general formula (■) are 100 to 50 mol% of the former and 0 to 50 mol% of the latter.
This diamino compound and the above general formula (VI
) can be obtained by reacting with the acid dianhydride represented by
１１□Ｎ −Ｘ ｒ Ｎ Ｈｔ ・・・・・・（■
）上記メタ位置にアミノ基を有する芳香族ジアミノ化合
物のうち、一般式（■）で表される芳香族ジアミノ化合
物の代表例としては下記のものがあげられる。11□N −X r N Ht ・・・・・・(■
) Among the aromatic diamino compounds having an amino group at the meta position, the following are representative examples of the aromatic diamino compounds represented by the general formula (■).
Ｌ ＣＦ。L C.F.
上記芳香族４核体ジアミンはそれぞれ単独で用いてもよ
いし、適宜組゛み合わせて用いてもよい。The above aromatic tetranuclear diamines may be used alone or in appropriate combinations.
また、一般式（■）で表される芳香族ジアミノ化合物の
代表例としては下記のものがあげられる。Further, the following are representative examples of the aromatic diamino compound represented by the general formula (■).
Ｈ２Ｎ−◎−０−ｏ−Ｏ−ｏ−ＮＨ２
１，３−ビス（３−アミノフェノキシ）ベンゼン’”
ＮＱ ＯＱ ＮＨ”
３．３゛−ジアミノジフェニルエーテルＨｔＮ−ｏ”０
１ンＮＨ。H2N-◎-0-o-O-o-NH2 1,3-bis(3-aminophenoxy)benzene'”
NQ OQ NH” 3.3゛-diaminodiphenyl ether HtN-o”0
1nNH.
３．３’−ジアミノジフェニルスルホンＨ２Ｎ−ｏ−３
−ｏ−ＮＨ２
３，３゛−ジアミノジフェニルスルフィドＨ，Ｎ會ＣＨ
正◎−ＮＨ２
３，３゛−ジアミノジフェニルメタン
（以下余白）
ＨｚＮ＊Ｃ−〇−Ｎ）（
３，３゛−ジアミノベンゾフェノン
ｍ−フェニレンジアミン
２．４− トルエンジアミン
４．６−ジメチル−ｍ−フェニレンジアミン２．４−ジ
アミノメシチレン
（余 白 ）
４−クロル−ｍ−フェニレンジアミン
３．５−ジアミノ安息香酸
５−ニトロ−ｍ−フェニレンジアミン
上記芳香族１〜３核体ジアミンはそれぞれ単独で用いて
もよいし、適宜組み合わせて用いてもよい。3.3'-diaminodiphenylsulfone H2N-o-3
-o-NH2 3,3゛-diaminodiphenyl sulfide H,N-CH
Positive ◎-NH2 3,3゛-diaminodiphenylmethane (blank below) HzN*C-〇-N) (3,3゛-diaminobenzophenone m-phenylenediamine 2.4-toluenediamine 4.6-dimethyl-m-phenylene Diamine 2.4-diaminomesitylene (margin) 4-chloro-m-phenylenediamine 3.5-diaminobenzoic acid 5-nitro-m-phenylenediamine Each of the above aromatic mono- to trinuclear diamines may be used alone. They may be used in appropriate combinations.
本発明においては、前記の芳香族４核体ジアミンを１０
０〜５０モル％使用し、残る０〜５０モル％に上記芳香
族１〜３核体ジアミンを用い、これらジアミンと前記一
般式（Ｖｌ）で表される酸二無水物とを反応させること
により前記一般式（■）で表される繰返し単位１００〜
５０モル％、前記一般式（ＩＶ）で表される繰返し単位
を０〜５０モル％を主成分とする芳香族ポリアミド酸を
合成する。そして、この芳香族ポリアミド酸をＮ、 Ｎ
−ジメチルアセトアミド溶液にし、溶媒除去、芳香族ポ
リアミド酸の脱水閉環工程を経由させることにより、前
記一般式（Ｉ）および一般式（ＩＩ）で表される繰返し
単位がｍ／ｎモル比で１００１０〜５０１５０の割合に
なっている無色透明ポリイミド成形体を合成するもので
ある。In the present invention, the aromatic tetranuclear diamine is
By using 0 to 50 mol%, using the above aromatic mono- to trinuclear diamine for the remaining 0 to 50 mol%, and reacting these diamines with the acid dianhydride represented by the general formula (Vl). Repeating unit 100~ represented by the above general formula (■)
An aromatic polyamic acid containing 50 mol% and 0 to 50 mol% of repeating units represented by the general formula (IV) as a main component is synthesized. Then, this aromatic polyamic acid was mixed with N, N
- By converting into a dimethylacetamide solution, removing the solvent, and dehydrating and ring-closing the aromatic polyamic acid, the repeating units represented by the general formula (I) and the general formula (II) can be converted to a m/n molar ratio of 10,010 to 10,010. A colorless and transparent polyimide molded body having a ratio of 50,150 is synthesized.
ここで、主成分とするとは全体が主成分のみからなる場
合も含める趣旨である。Here, the term "main component" is intended to include cases where the entire component consists only of the main component.
この場合において、無色透明なポリイミド成形体の主成
分となる前記一般式（Ｉ）および一般式（Ｉｆ）で表さ
れる繰返し単位の含有量が多いほど得られるポリイミド
成形体の無色透明性が高まる、しかしながら、前記一般
式（１）および一般式（Ｉｆ）で表される繰返し単位が
全体の７０モル％以上含有されていれば少なくとも本発
明で求める無色透明性が確保されるのでその範囲内にお
いて、上記２．２−ビス（３，４−ジカルボキシフエニ
ル）へキサフルオロブロバンニ無水物以外のその他の芳
香族テトラカルボン酸二無水物および上記メタ位置にア
ミノ基を有する芳香族ジアミン以外のその他のジアミノ
化合物を用いることができる。しかしながら、その他の
芳香族テトラカルボン酸および／またはその他のジアミ
ノ化合物の含有量の好ましい範囲は３０モル％以下であ
り、最も好ましい範囲は５モル％以下である。In this case, the greater the content of the repeating units represented by the general formula (I) and general formula (If), which are the main components of the colorless and transparent polyimide molded product, the higher the colorless transparency of the obtained polyimide molded product. However, if the repeating units represented by the general formulas (1) and (If) are contained in an amount of 70 mol% or more of the total, at least the colorless transparency required in the present invention is ensured, so within that range. , other aromatic tetracarboxylic dianhydrides other than the above-mentioned 2,2-bis(3,4-dicarboxyphenyl)hexafluorobrobannianhydride and aromatic diamines other than the above-mentioned aromatic diamines having an amino group at the meta position. Other diamino compounds can be used. However, the preferred range of the content of other aromatic tetracarboxylic acids and/or other diamino compounds is 30 mol% or less, and the most preferred range is 5 mol% or less.
上記その他の芳香族テトラカルボン酸二無水物としては
、ピロメリット酸二無水物、３．３’ 。Examples of the other aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride and 3.3'.
４．４゛ −ビフェニルテトラカルボン酸二無水物、２
．３．３’ 、４″ −ビフェニルテトラカルボン酸二
無水物、３．３’、４．４° −ベンゾフェノンテトラ
カルボン酸二無水物、４．４゛ −オキシシフタル酸二
無水物、４，４“−ビス（３，４−ジカルボキシフェノ
キシ）ジフエ゛ニルスルホン二無水物、２．３．６．７
−ナフタレンテトラカルボン酸二無水物、１．２，５．
６−ナフタレンテトラカルボン酸二無水物、１，４．５
．８−ナフタレンテトラカルボン酸二無水物があげられ
、これらは単独でまたは併せて用いることができる。4.4゛-Biphenyltetracarboxylic dianhydride, 2
．． 3.3′, 4″-biphenyltetracarboxylic dianhydride, 3.3′, 4.4°-benzophenonetetracarboxylic dianhydride, 4.4′-oxycyphthalic dianhydride, 4,4″- Bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 2.3.6.7
-naphthalenetetracarboxylic dianhydride, 1.2,5.
6-naphthalenetetracarboxylic dianhydride, 1,4.5
．． Examples include 8-naphthalenetetracarboxylic dianhydride, which can be used alone or in combination.
また、その他のジアミノ化合物としては、４゜４゛−ビ
ス（４−アミノフェノキシ）ジフェニルスルホン、４．
４゛−ビス（４−アミノフェノキシ）ビフェニル、２，
２−ビス（４−（４−アミノフェノキシ）フェニル〕プ
ロパン、２，２−ビス（４−（４−アミノフェノキし）
フェニル〕へキサフルオロプロパン、４，４゛ −ジア
ミノジフェニルエーテル、３．４’ −ジアミノジフ
ェニルエーテル、 ４． ４’ −ジアミノジフェ
ニルスルホン、４，４゛−ジアミノジフェニルメタン、
４゜４°−ジアミノベンゾフェノン、２．２−ビス（４
−アミノフェニル）プロパン、ベンジジン、３．３゛−
ジメチルベンジジン、４，４″ −ジアミノジフェニル
チオエーテル、３，３゛ −ジメトキシ−４，４’−ジ
アミノジフェニルメタン、３゜３゛−ジメチル−４，４
゛ −ジアミノジフェニルメタン、ｐ−フェニレンジ
アミン等があげられ、単独でもしくは併せて用いること
ができる。Other diamino compounds include 4゜4゛-bis(4-aminophenoxy)diphenylsulfone, 4.
4-bis(4-aminophenoxy)biphenyl, 2,
2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)
phenyl]hexafluoropropane, 4,4'-diaminodiphenyl ether, 3.4'-diaminodiphenyl ether, 4. 4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane,
4°4°-diaminobenzophenone, 2,2-bis(4
-aminophenyl)propane, benzidine, 3.3゛-
Dimethylbenzidine, 4,4''-diaminodiphenylthioether, 3,3゛-dimethoxy-4,4'-diaminodiphenylmethane, 3゜3゛-dimethyl-4,4
Examples include -diaminodiphenylmethane and p-phenylenediamine, which can be used alone or in combination.
また、本発明の無色透明なポリイミドをガラス板、ステ
ンレス板等の基板上に形成し、そのような複合体の形で
使用するような場合にはポリイミドと基板の接着力が重
要となる。このような用途に応用する場合には下記の一
般式（ＩＸ）で表されるジアミノシロキサン
を前記メタ位置にアミノ基を有する芳香族ジアミンの一
部に置き換えて使用してもよい。上記ジアミノシロキサ
ンの使用量の好ましい範囲は１０モル％以下であり、最
も好ましい範囲は５％以下である。Further, when the colorless and transparent polyimide of the present invention is formed on a substrate such as a glass plate or a stainless steel plate and used in the form of such a composite, the adhesive strength between the polyimide and the substrate becomes important. When applied to such uses, a diaminosiloxane represented by the following general formula (IX) may be used in place of a part of the aromatic diamine having an amino group at the meta position. The preferred range of the amount of the diaminosiloxane used is 10 mol% or less, and the most preferred range is 5% or less.
上記ジアミノシロキサンの代表例としては、下記のもの
があげられる。Representative examples of the above diaminosiloxane include the following.
（余 白 ） ＣＨ３Ｃ８゜ Ｉ Ｈ３ＣＨ３ ＣｂＨｓ ＱＣ）ｌｉ Ｃ６１１５ｌＩ Ｃ６Ｈｓ ０ＣＨ３Ｃ６Ｈ。(Left white) CH3C8゜ I H3CH3 CbHs QC)li C6115lI C6Hs 0CH3C6H.
上記ジアミノシロキサンはそれぞれ単独で用いてもよい
し、適宜組み合わせて用いてもよい。The above diaminosiloxanes may be used alone or in appropriate combinations.
本発明の無色透明なポリイミド成形体は、先に述べたよ
うに、上記の芳香族テトラカルボン酸二無水物およびジ
アミノ化合物を有機極性溶媒中において、８０℃以下の
温度で重合させることによりポリアミド酸溶液をつくり
、このポリアミド酸溶液を用いて所望の形状の賦形体を
形成し、この賦形体を空気中または不活性ガス中におい
て、温度：５０〜３５０℃、圧力；常圧もしくは減圧の
条件下で有機極性溶媒を蒸発除去すると同時にポリアミ
ド酸を脱水閉環してポリイミドにすること等により得ら
れる。また、上記ポリアミド酸をピリジンと無水酢酸の
ベンゼン溶液等を用い、脱溶媒とイミド化を行いポリイ
ミドにすること等化学的イミド化方法によっても得るこ
とができる。As mentioned above, the colorless and transparent polyimide molded article of the present invention can be produced by polymerizing the above-mentioned aromatic tetracarboxylic dianhydride and diamino compound in an organic polar solvent at a temperature of 80°C or lower. A solution is prepared, a molded body of a desired shape is formed using this polyamic acid solution, and the molded body is placed in air or an inert gas under conditions of a temperature of 50 to 350°C and a pressure of normal pressure or reduced pressure. It can be obtained by evaporating the organic polar solvent and simultaneously dehydrating and ring-closing the polyamic acid to form a polyimide. It can also be obtained by a chemical imidization method, such as by removing the solvent and imidizing the polyamic acid with a benzene solution of pyridine and acetic anhydride to form a polyimide.
上記有機極性溶媒としては、Ｎ、Ｎ−ジメチルホルムア
ミド、Ｎ、Ｎ−ジメチルアセトアミドのようなアミド系
有機極性溶媒が好適である。特に、Ｎ、Ｎ−ジメチルア
セトアミドのような沸点１７０℃以下のものが好ましい
。これらの有機極性溶媒は単独で用いてもよいし、２種
以上を混合して用いても支障はない。ただし、上記有機
極性溶媒としてＮ−メチル−２−ピロリドンを用いるこ
とは避けることが好ましい。Ｎ−メチル−２−ピロリド
ンは、ポリアミド酸溶液の賦形体を加熱し、脱水閉環し
てポリイミド化する際の加熱によって一部分解し、その
分解物が残存して黒褐色を呈するようになり、これが生
成ポリイミド成形体を黄褐色に着色する傾向が見られる
からである。有機極性溶媒として、上記に例示したＮ、
Ｎ−ジメチルアセトアミド等の各溶媒は、沸点が低いた
め、上記の加熱によって分解する前に揮散してしまい、
Ｎ−メチル−２−ピロリドンのようにポリイミド成形体
に対する着色を生じない。しかしながら、重合溶媒とし
てＮ−メチル−２−ピロリドンを用い、ポリアミド酸合
成後、溶媒置換により、上記例示の好適な溶媒に生成ポ
リアミド酸を溶解するようにすれば、Ｎ−メチル−２−
ピロリドンの上記弊害を排除しうる。この場合、上記例
示の好適な溶媒は希釈溶媒となる。上記ポリアミド成形
体の製造に際しては、このように、重合溶媒と希釈溶媒
とを別種のものにし、溶媒置換によって生成ポリアミド
酸を希釈溶媒に溶解するようにしてもよいのである。As the organic polar solvent, amide-based organic polar solvents such as N,N-dimethylformamide and N,N-dimethylacetamide are suitable. Particularly preferred are those having a boiling point of 170° C. or lower, such as N,N-dimethylacetamide. These organic polar solvents may be used alone or in combination of two or more without any problem. However, it is preferable to avoid using N-methyl-2-pyrrolidone as the organic polar solvent. N-Methyl-2-pyrrolidone is partially decomposed by heating the excipient of the polyamic acid solution and dehydrated and ring-closed to form polyimidation, and the decomposed product remains and becomes blackish brown. This is because there is a tendency to color the polyimide molded body yellowish brown. As the organic polar solvent, N exemplified above,
Solvents such as N-dimethylacetamide have low boiling points, so they volatilize before being decomposed by the heating described above.
Unlike N-methyl-2-pyrrolidone, it does not cause coloring of polyimide molded articles. However, if N-methyl-2-pyrrolidone is used as a polymerization solvent and the resulting polyamic acid is dissolved in a suitable solvent as exemplified above by solvent substitution after polyamic acid synthesis, N-methyl-2-pyrrolidone can be used as a polymerization solvent.
The above-mentioned adverse effects of pyrrolidone can be eliminated. In this case, the suitable solvent exemplified above is a diluting solvent. In producing the above polyamide molded article, the polymerization solvent and the diluting solvent may be of different types as described above, and the produced polyamic acid may be dissolved in the diluting solvent by solvent substitution.
なお、上記に例示した好適な有機極性溶媒を使用する際
に、上記溶媒に、エタノール、トルエン、ベンゼン、キ
シレン、ジオキサン、テトラヒドロフラン、ニトロベン
ゼン等の、透明性を損なわない貧溶媒または良溶媒を、
溶解性を損なわない範囲内において一種もしくは二種以
上適宜混合して用いてもよい。ただし、これらの溶媒は
、多量に使用すると、生成ポリアミド酸の溶解性に悪影
響を及ぼすようになる。したがって、その使用量は溶媒
全体の５０重量％未満に制限することが妥当であり、最
も好ましいのは３０重量％までにとどめることである。In addition, when using the suitable organic polar solvent exemplified above, a poor solvent or a good solvent that does not impair transparency, such as ethanol, toluene, benzene, xylene, dioxane, tetrahydrofuran, nitrobenzene, etc., is added to the solvent.
One type or two or more types may be appropriately mixed and used within a range that does not impair solubility. However, if these solvents are used in large amounts, they will adversely affect the solubility of the polyamic acid produced. Therefore, it is appropriate to limit the amount used to less than 50% by weight of the total solvent, and most preferably to 30% by weight.
上記のようにして、無色透明なポリイミド成形体を製造
する際に、ポリアミド酸溶液の固有粘度は０．３〜５．
０の範囲にあることが好ましい。より好適なのは０．４
〜２．０である。上記固有粘度は、Ｎ−メチル−２−ピ
ロリドン中０．５ｇ／１００ｍ１の濃度で測定した値で
ある。この固有粘度が低すぎると、得られるポリイミド
成形体の機械的強度が低くなるため好ましくない。また
、固有粘度が高すぎると、ポリアミド酸溶液を適当な形
状に賦形する際に流延させにく（作業が困難となるため
好ましくない。また、ポリアミド酸溶液の濃度も、作業
性等の見地から、５〜３０重量％、好ましくは１５〜２
５重量％に設定することが好ましいのである。When producing a colorless and transparent polyimide molded article as described above, the intrinsic viscosity of the polyamic acid solution is 0.3 to 5.
It is preferably in the range of 0. 0.4 is more suitable
~2.0. The above intrinsic viscosity is a value measured at a concentration of 0.5 g/100 ml in N-methyl-2-pyrrolidone. If the intrinsic viscosity is too low, the resulting polyimide molded article will have low mechanical strength, which is not preferable. In addition, if the intrinsic viscosity is too high, it will be difficult to cast the polyamic acid solution into an appropriate shape (this is not preferable as it will make the work difficult).In addition, the concentration of the polyamic acid solution will also affect workability, etc. From the standpoint of 5 to 30% by weight, preferably 15 to 2
It is preferable to set the content to 5% by weight.
なお、上記固有粘度はつぎの式で計算されるものであり
、式中の粘度は毛細管粘度計により測定されるものであ
る。The above-mentioned intrinsic viscosity is calculated by the following formula, and the viscosity in the formula is measured by a capillary viscometer.
ポリアミド酸溶液を用いての賦形の方法は、目的とする
成形体の形状により異なるが、例えばポリイミドフイル
ムを得る場合にはガラス板、ステンレス板等の鏡面に上
記ポリアミド酸溶液を一定の厚みになるように流延し、
１００〜３５０℃の温度で徐々に加熱して脱水閉環させ
、ポリアミド酸をイミド化することが行われる。ポリア
ミド酸溶液からのフィルム形成における有機極性溶媒の
除去およびポリアミド酸のイミド化のための加熱は、連
続して行ってもよく、またこれらの工程を減圧下もしく
は不活性ガス雰囲気中で行ってもよい。さらに短時間で
あれば４００℃前後まで最終的に加熱することにより生
成ポリイミドフィルムの特性を向上させることができる
。また、ポリイミドフィルム形成の他の方法は、上記ポ
リアミド酸溶液をガラス板上等に流延して１００〜１５
０℃で３０〜１２０分加熱乾燥して皮膜を形成し、この
皮膜をピリジンと無水酢酸のベンゼン溶液等に浸漬して
脱溶剤とイミド化反応を行い、上記皮膜をポリイミドフ
ィルムとする方法であり、この方法によってもポリイミ
ドフィルムを得ることができる。The shaping method using a polyamic acid solution varies depending on the shape of the desired molded product, but for example, when obtaining a polyimide film, the polyamic acid solution is applied to a mirror surface of a glass plate, stainless steel plate, etc. to a certain thickness. spread to become
The polyamic acid is imidized by gradually heating at a temperature of 100 to 350°C to cause dehydration and ring closure. In forming a film from a polyamic acid solution, the removal of the organic polar solvent and the heating for imidization of the polyamic acid may be performed continuously, or these steps may be performed under reduced pressure or in an inert gas atmosphere. good. Furthermore, the properties of the resulting polyimide film can be improved by finally heating it to around 400° C. for a short time. Another method for forming a polyimide film is to cast the above polyamic acid solution onto a glass plate, etc.
This is a method in which a film is formed by heating and drying at 0°C for 30 to 120 minutes, and this film is immersed in a benzene solution of pyridine and acetic anhydride to remove the solvent and perform an imidization reaction, thereby converting the film into a polyimide film. , a polyimide film can also be obtained by this method.
このようにして得られるポリイミドフィルムは、無色透
明であって従来のように黄色ないしは黄褐色に着色され
ていないため、厚膜であっても極めて透明性が良好であ
る。The polyimide film thus obtained is colorless and transparent and is not colored yellow or yellowish brown as in conventional films, so it has extremely good transparency even if it is a thick film.
なお、上記ポリアミド酸溶液を用いての賦形は、上記の
ようなポリイミドフィルムの形成に限るものではなく、
プラスチックレンズ等、他の成形体の形成にも適用でき
るものであり、その場合におけるポリアミド酸のイミド
化も前記のような加熱イミド化および化学イミド化のい
ずれかを適宜に選択しうるものである。Note that shaping using the above polyamic acid solution is not limited to the formation of a polyimide film as described above;
It can also be applied to the formation of other molded objects such as plastic lenses, and in that case, the imidization of polyamic acid can be appropriately selected from either the above-mentioned thermal imidization or chemical imidization. .
以上のようにして、ポリアミド酸溶液をイミド化してポ
リイミドとする場合において、生成ポリイミドは、特性
の点から固有粘度（９７％硫酸中０．５ｇ／ａの濃度で
３０℃のもとて測定）を０．３〜４．０の範囲内に設定
することが好ましい。最も好ましいのは０．４以上であ
る。When polyamic acid solution is imidized to form polyimide as described above, the produced polyimide has an intrinsic viscosity (measured at 30°C at a concentration of 0.5 g/a in 97% sulfuric acid) from the viewpoint of properties. is preferably set within the range of 0.3 to 4.0. The most preferable value is 0.4 or more.
このようにして得られたポリイミド成形体は、従来のも
のとは全く異なり、無色透明であって極めて透明度が高
いものである。なお、本発明において、無色透明とは、
膜厚５０±５μｍのポリイミドフィルムに対する可視光
線（５００ｎ＊）透過率が７０％以上であって黄色度（
イエローネスインデックス）が４０以下のもののことを
いう、なお、上記透過率はＡＳＰＭ Ｄ １００３に準
じて測定でき、黄色度はＪＩＳ Ｋ ７１０３に準じて
測定できる。特に、透明度が優れているのは一般式（■
）で示される芳香族４核体ジアミンにおいて、ＸｌがＳ
Ｏ３であるものを用いたものである。このものを用いて
得られたポリイミド成形体は、透明度が極めて優れてい
るばかりでなく耐熱性にも著しく優れているのである。The polyimide molded product thus obtained is completely different from conventional molded products, and is colorless and transparent, and has extremely high transparency. In addition, in the present invention, colorless and transparent means
The visible light (500n*) transmittance for a polyimide film with a film thickness of 50±5μm is 70% or more, and the yellowness (
The transmittance can be measured according to ASPM D 1003, and the yellowness can be measured according to JIS K 7103. In particular, the general formula (■
), in which Xl is S
O3 was used. The polyimide molded product obtained using this product not only has extremely high transparency but also extremely high heat resistance.
以上のように、本発明のポリイミド成形体は、前記特定
の酸二無水物と、メタ位置にアミノ基を有する特殊な芳
香族ジアミンとを組み合わせて得られたものであって、
これまでのもののように黄色ないし黄褐色に着色されて
なく、無色透明であるため極めて高い透明度を有してい
る。特に、上記ポリイミド成形体の製造に際し、ポリア
ミド酸溶液として、Ｎ、Ｎ−ジメチルアセトアミドを使
用すると、ポリアミド酸を脱水閉環してポリイミド化す
る際の加熱時に、上記溶媒が分解する前に揮散してしま
うため、Ｎ−メチル−２−ピロリドンを用いるときのよ
うな、ポリイミド化時の加熱によって分解しその生成黒
褐色分解物によってポリイミド成形体が着色されるとい
う不都合が全く生じず、完全な無色透明のポリイミド成
形体を製造しうるようになる。このように本発明のポリ
イミド成形体は、着色されてなく、無色透明であるため
、厚膜の液晶配向膜を形成することができ、また、それ
以外に太陽電池のベースフィルム基材、偏向膜基材、ソ
ーラーセルや熱制御システム等の特別な航空宇宙用コン
ポーネントのコーテイング材、耐熱性の必要とされてい
る光学的用途およびそのコーテイング材に好適に使用す
ることができる。また、屈折率が１．７以上とポリマー
中で１番大きいためプラスチックレンズまたはレンズの
コーテイング材としても有用である。このようなポリイ
ミド成形体の具体的用途を例示するとっぎのとおりであ
る。As described above, the polyimide molded article of the present invention is obtained by combining the specific acid dianhydride and a specific aromatic diamine having an amino group at the meta position,
Unlike conventional products, it is not colored yellow or tan, but is colorless and transparent, so it has extremely high transparency. In particular, when N,N-dimethylacetamide is used as the polyamic acid solution during the production of the polyimide molded article, the solvent evaporates before it decomposes during heating when the polyamic acid is dehydrated and ring-closed to form polyimide. Therefore, unlike when N-methyl-2-pyrrolidone is used, there is no inconvenience that the polyimide molded product is colored by the black-brown decomposition product produced by decomposition due to heating during polyimidation, and it is completely colorless and transparent. It becomes possible to produce polyimide molded bodies. As described above, the polyimide molded product of the present invention is not colored and is colorless and transparent, so it can be used to form a thick liquid crystal alignment film, and can also be used as a base film substrate for solar cells, a polarizing film, etc. It can be suitably used for substrates, coating materials for special aerospace components such as solar cells and thermal control systems, and optical applications and coating materials that require heat resistance. Furthermore, since it has the highest refractive index of 1.7 or more among polymers, it is useful as a coating material for plastic lenses or lenses. The following is an example of a specific use of such a polyimide molded article.
フレキシブル印刷回路基板（ＦＰＣ）、モーター絶縁、
ケーブル被覆、磁気記録媒体用ベースフィルム、耐熱粘
着テープ、光フアイバー結束、テープキャリア、フィル
ムキャリア、太陽電池、多層板、マトリックスレジン、
コイル含浸、エナメルフェス、液晶配向膜、半導体層間
絶縁膜、α線プロテクト膜、パッシベーション膜、グイ
ボンディング剤、摺動部材、耐熱部材、耐熱放射線部材
、耐ガス放出性部材、航空機内装部材
つぎに、実施例について比較例と併せて説明する。Flexible printed circuit board (FPC), motor insulation,
Cable coatings, base films for magnetic recording media, heat-resistant adhesive tapes, optical fiber bundles, tape carriers, film carriers, solar cells, multilayer plates, matrix resins,
Coil impregnation, enamel face, liquid crystal alignment film, semiconductor interlayer insulation film, alpha ray protection film, passivation film, Gui bonding agent, sliding member, heat resistant member, heat radiation resistant member, gas release resistant member, aircraft interior member Examples will be described together with comparative examples.
なお、後記の表において、ＨＦＤＡは２，２−ビス（３
，４−ジカルボキシフェニル）へキサフルオロプロパン
二ｍ水’１７Ｊ、ＢＰＤＡは３．３’ 。In addition, in the table below, HFDA is 2,2-bis(3
, 4-dicarboxyphenyl) hexafluoropropane dim water '17J, BPDA is 3.3'.
４．４゛ −ビフェニルテトラカルボン酸二無水物、Ｐ
ＭＤＡはピロメリット酸二無水物、３，３゛−ＢＡＰＳ
は４，４゛−ビス（３−アミノフェノキシ）ジフェニル
スルホン、３，３° −ＢＡＰＰは２，２−ビス（４−
（３−アミノフェノキシ）フェニル〕プロパン、３，３
” −ＢＡＰＦは２゜２−ビス（４−（３−アミノフェ
ノキシ）フェニル〕へキサフルオロプロパン、１，４．
３−ＢＡＰＢは１．４−ビス（３−アミノフェノキシ）
ベンゼン、１．３．３−ＢＡＰＢは１，３−ビス（３−
アミノフェノキシ）ベンゼン、３，３” −ＤＤＥは３
，３° −ジアミノジフェニルエーテル、３．３’−Ｄ
ＤＳは３，３゛ −ジアミノジフェニルスルホン、３，
３” −ＤＤＭは３，３° −ジアミノジフェニルメタ
ン、３，３° −ＤＳＰは３゜３°−ジアミノジフェニ
ルチオエーテル、３．３’−ＤＢＰは３，３° −ジア
ミノベンゾフェノン、ｍ−ＰＤＡはｍ−フェニレンジア
ミン、２，４−ＴＤＡは２．４−トルエンジアミン、２
．４−ＤＭＸは４．６−ジメチル−ｍ−フェニレンジア
ミン、ＤＭＡ５は２，４−ジアミノメシチレン、ＣＰＤ
Ａは４−クロル−ｍ−フェニレンジアミン、３．５−Ｄ
ＡＢＡは３，５−ジアミノ安息香酸、ＮＰＤＡは５−ニ
トロ−ｍ−フェニレンジアミン、ＢＡＴＳはビス（３−
アミノプロピル）テトラメチルジシロキサン、ｐ−ＰＤ
Ａはｐ−フェニレンジアミン、４，４°−ＤＤＥは４，
４° −ジアミノジフェニルエーテル、４．４’ −Ｂ
ＡＰＳは４，４′−ビス（４−アミノフェノキシ）ジフ
ェニルスルホン、ＤＭＡｃはＮ、Ｎ−ジメチルアセトア
ミド、ＤＭＦはＮ、Ｎ−ジメチルホルムアミド、ＮＭＰ
はＮ−メチル−２−ピロリドンを示す。4.4゛-Biphenyltetracarboxylic dianhydride, P
MDA is pyromellitic dianhydride, 3,3゛-BAPS
is 4,4゛-bis(3-aminophenoxy)diphenylsulfone, and 3,3°-BAPP is 2,2-bis(4-
(3-aminophenoxy)phenyl]propane, 3,3
” -BAPF is 2°2-bis(4-(3-aminophenoxy)phenyl]hexafluoropropane, 1,4.
3-BAPB is 1,4-bis(3-aminophenoxy)
Benzene, 1.3.3-BAPB is 1,3-bis(3-
aminophenoxy)benzene, 3,3”-DDE is 3
, 3°-diaminodiphenyl ether, 3.3'-D
DS is 3,3゛-diaminodiphenylsulfone, 3,
3''-DDM is 3,3°-diaminodiphenylmethane, 3,3°-DSP is 3°3°-diaminodiphenylthioether, 3,3'-DBP is 3,3°-diaminobenzophenone, and m-PDA is m- phenylene diamine, 2,4-TDA is 2,4-toluenediamine, 2
．． 4-DMX is 4,6-dimethyl-m-phenylenediamine, DMA5 is 2,4-diaminomesitylene, CPD
A is 4-chloro-m-phenylenediamine, 3.5-D
ABA is 3,5-diaminobenzoic acid, NPDA is 5-nitro-m-phenylenediamine, and BATS is bis(3-
aminopropyl)tetramethyldisiloxane, p-PD
A is p-phenylenediamine, 4,4°-DDE is 4,
4°-diaminodiphenyl ether, 4.4′-B
APS is 4,4'-bis(4-aminophenoxy)diphenylsulfone, DMAc is N,N-dimethylacetamide, DMF is N,N-dimethylformamide, NMP
represents N-methyl-2-pyrrolidone.
〔実施例１〜２４．比較例１〜３〕
１１のセパラブルフラスコに後記の表に示す溶媒とジア
ミノ化合物を入れてジアミノ化合物が完全に溶解するま
で室温でよく混合した。この場合、上記溶媒の使用量は
、上記ジアミノ化合物および後記の表に示す芳香族テト
ラカルボン酸二無水物の七ツマー仕込み濃度が２０重重
量となるように設定した。つぎに、上記フラスコ中に同
表に示す芳香族テトラカルボン酸二無水物を、発熱によ
る温度の上昇を抑制しながら徐々に添加した。ついで、
室温で４時間攪拌しながら反応させ、後記の表に示す固
有粘度をもつポリアミド酸の溶液を得た。[Examples 1 to 24. Comparative Examples 1 to 3] The solvents shown in the table below and the diamino compound were placed in a No. 11 separable flask and mixed well at room temperature until the diamino compound was completely dissolved. In this case, the amount of the solvent used was set so that the concentration of the diamino compound and the aromatic tetracarboxylic dianhydride shown in the table below was 20% by weight. Next, the aromatic tetracarboxylic dianhydride shown in the same table was gradually added to the flask while suppressing the temperature rise due to heat generation. Then,
The reaction was allowed to proceed at room temperature for 4 hours with stirring to obtain a polyamic acid solution having an intrinsic viscosity shown in the table below.
上記のようにして得られたポリアミド酸の溶液をガラス
板上に流延して皮膜を形成し、この皮膜を熱風乾燥機中
１２０℃で６０分間、さらに１８０℃で６０分間、つい
で２５０℃で６時間加熱してイミド化させることにより
厚み５０±５μｍのポリイミドフィルムをつくった。な
お、上記フィルムについて赤外線吸収スペクトルを測定
したところ、アミド酸の特有の吸収はみられず、１７８
Ｑ ｃｘ −’付近にイミド基の特性吸収がみられた。The polyamic acid solution obtained as above was cast onto a glass plate to form a film, and this film was heated in a hot air dryer at 120°C for 60 minutes, then at 180°C for 60 minutes, and then at 250°C. A polyimide film having a thickness of 50±5 μm was produced by heating for 6 hours to imidize. In addition, when the infrared absorption spectrum of the above film was measured, no absorption peculiar to amic acid was observed, and 178
A characteristic absorption of the imide group was observed near Q cx −'.
つぎに、上記のようにして得られたポリイミドフィルム
について、イエローネスインデックスを測定するととも
に、可視光線（５００ｎａ＋）における透過率を測定し
、後記の表に併せて示した。Next, the yellowness index of the polyimide film obtained as described above was measured, and the transmittance in visible light (500 na+) was also measured, and the results are also shown in the table below.
（以下余白）
表において、実施例１〜３はメタ位置にアミノ基を有す
るジアミノ化合物として芳香族４核体ジアミンのみを使
用した例を示しており、実施例４〜１９は上記ジアミノ
化合物として５０モル％以上の芳香族４核体ジアミンと
５０モル％以下の芳香族１核体ないし３核体ジアミンの
１種以上を併用した例を示している。また、実施例２０
〜２３はその他のジアミノ化合物またはその他の酸二無
水物を併用した例を示している。さらに、実施例２４は
芳香族４核体ジアミンとジアミノシロキサンを併用した
例を示している。(Leaving space below) In the table, Examples 1 to 3 show examples in which only aromatic tetranuclear diamines were used as diamino compounds having an amino group at the meta position, and Examples 4 to 19 show examples in which only aromatic tetranuclear diamines were used as diamino compounds having an amino group at the meta position. An example is shown in which mol % or more of aromatic tetranuclear diamine and 50 mol % or less of aromatic mononuclear to trinuclear diamine are used in combination. Also, Example 20
-23 show examples in which other diamino compounds or other acid dianhydrides were used in combination. Furthermore, Example 24 shows an example in which aromatic tetranuclear diamine and diaminosiloxane were used in combination.
表から明らかなように、実施例１〜２４のポリイミドフ
ィルムは、いずれもイエローネスインデックスが４０以
下であり、かつ透過率が７０％以上であって無色透明で
あることがわかる。As is clear from the table, the polyimide films of Examples 1 to 24 all have a yellowness index of 40 or less, a transmittance of 70% or more, and are colorless and transparent.
これに対して、比較例１．２では、ジアミノ化合物とし
てメタ位置にアミノ基を有するものではなく、パラ位置
にアミノ基を有するものを用いているため、イエローネ
スインデックスおよび透過率が実施例のものより劣って
おり、特にイエローネスインデックスの値が悪く、黄色
に着色していることがわかる。さらに比較例３では溶媒
としてＮ−メチル−２−ピロリドンを用いているため、
メタ位置にアミノ基を有するジアミノ化合物を使用して
いるにも係わらず着色の強いフィルムであった。On the other hand, in Comparative Example 1.2, a diamino compound having an amino group at the para position rather than one having an amino group at the meta position is used, so the yellowness index and transmittance are lower than those of the example. It can be seen that the yellowness index value is particularly poor, and the color is yellow. Furthermore, since N-methyl-2-pyrrolidone was used as the solvent in Comparative Example 3,
Despite using a diamino compound having an amino group at the meta position, the film was strongly colored.
Claims (2)
び下記の一般式（II）で表される繰返し単位を主成分と
することを特徴とする無色透明なポリイミド成形体。 ▲数式、化学式、表等があります▼・・・・・・（ I
） ▲数式、化学式、表等があります▼・・・・・・（II） 〔式（ I ）、（II）において、Ｘ＿１はＳＯ＿２、Ｃ
（ＣＨ＿３）＿２、Ｘ＿２はメタ置換の芳香族１〜３核
体残基であり、ｍ／ｎモル比は１００／０〜５０／５０
である。〕(1) A colorless and transparent polyimide molded article characterized by containing as main components a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) [In formulas (I) and (II), X_1 is SO_2, C
(CH_3)_2, X_2 are meta-substituted aromatic mono- to trinuclear residues, m/n molar ratio is 100/0 to 50/50
It is. ]
び下記の一般式（IV）で表される繰返し単位を主成分と
する芳香族ポリアミド酸のＮ，Ｎ−ジメチルアセトアミ
ド溶液を準備する工程と、上記溶液の溶媒除去および芳
香族ポリアミド酸の脱水閉環工程を備えることを特徴と
する無色透明ポリイミド成形体の製法。 ▲数式、化学式、表等があります▼・・・・・・（III
） ▲数式、化学式、表等があります▼・・・・・・（IV） 式（III）、（IV）において、Ｘ＿１はＳＯ＿２、Ｃ（
ＣＨ＿３）＿２またはＣ（ＣＦ＿３）＿２、Ｘ＿２はメ
タ置換の芳香族１〜３核体残基であり、ｍ／ｎモル比は
１００／０〜５０／５０である。(2) Prepare an N,N-dimethylacetamide solution of an aromatic polyamic acid whose main components are a repeating unit represented by the following general formula (III) and a repeating unit represented by the following general formula (IV). 1. A method for producing a colorless and transparent polyimide molded article, which comprises the following steps: removing the solvent from the solution and dehydrating and ring-closing the aromatic polyamic acid. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV) In formulas (III) and (IV), X_1 is SO_2, C(
CH_3)_2 or C(CF_3)_2, X_2 is a meta-substituted aromatic mono- to trinuclear residue, and the m/n molar ratio is from 100/0 to 50/50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62002125A JP2519228B2 (en) | 1987-01-08 | 1987-01-08 | Colorless and transparent polyimide molding and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62002125A JP2519228B2 (en) | 1987-01-08 | 1987-01-08 | Colorless and transparent polyimide molding and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63170420A true JPS63170420A (en) | 1988-07-14 |
| JP2519228B2 JP2519228B2 (en) | 1996-07-31 |
Family
ID=11520622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62002125A Expired - Lifetime JP2519228B2 (en) | 1987-01-08 | 1987-01-08 | Colorless and transparent polyimide molding and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2519228B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01118527A (en) * | 1987-07-15 | 1989-05-11 | Usa Government | Production of low dielectric polyimide |
| JPH04325523A (en) * | 1991-01-24 | 1992-11-13 | Cheil Synthetics Inc | Manufacture of siloxane-modified polyimide resin |
| US5470943A (en) * | 1994-01-07 | 1995-11-28 | Mitsui Toatsu Chemicals, Inc. | Polyimide |
| JP2010538103A (en) * | 2007-08-27 | 2010-12-09 | コーロン インダストリーズ，インコーポレイテッド | Polyimide film |
| JP2014501301A (en) * | 2010-12-31 | 2014-01-20 | コーロン インダストリーズ インク | Transparent polyimide film and method for producing the same |
| WO2018230495A1 (en) * | 2017-06-16 | 2018-12-20 | 大日本印刷株式会社 | Layered body, surface material for displays, touch panel member, liquid crystal display device, and organic electroluminescence display device |
| KR20190039180A (en) | 2016-08-10 | 2019-04-10 | 다이니폰 인사츠 가부시키가이샤 | Polyimide film, laminate and surface material for display |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58157190A (en) * | 1982-03-12 | 1983-09-19 | 日立化成工業株式会社 | Method of producing substrate for flexible printed circuit |
| JPS58180530A (en) * | 1982-04-19 | 1983-10-22 | Hitachi Ltd | Novel fluorine-containing polyamide and polyimide |
| JPS5976451A (en) * | 1982-10-26 | 1984-05-01 | Hitachi Ltd | Semiconductor device |
| JPS62127827A (en) * | 1985-11-29 | 1987-06-10 | Hitachi Chem Co Ltd | Composition for oriented film for liquid crystal |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01118527A (en) * | 1987-07-15 | 1989-05-11 | Usa Government | Production of low dielectric polyimide |
| JPH04325523A (en) * | 1991-01-24 | 1992-11-13 | Cheil Synthetics Inc | Manufacture of siloxane-modified polyimide resin |
| US5470943A (en) * | 1994-01-07 | 1995-11-28 | Mitsui Toatsu Chemicals, Inc. | Polyimide |
| JP2010538103A (en) * | 2007-08-27 | 2010-12-09 | コーロン インダストリーズ，インコーポレイテッド | Polyimide film |
| JP2014501301A (en) * | 2010-12-31 | 2014-01-20 | コーロン インダストリーズ インク | Transparent polyimide film and method for producing the same |
| KR20190039180A (en) | 2016-08-10 | 2019-04-10 | 다이니폰 인사츠 가부시키가이샤 | Polyimide film, laminate and surface material for display |
| US11566108B2 (en) | 2016-08-10 | 2023-01-31 | Dai Nippon Printing Co., Ltd. | Polyimide film, laminate and surface material for display |
| WO2018230495A1 (en) * | 2017-06-16 | 2018-12-20 | 大日本印刷株式会社 | Layered body, surface material for displays, touch panel member, liquid crystal display device, and organic electroluminescence display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2519228B2 (en) | 1996-07-31 |
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