JPS6342656B2 - - Google Patents
Info
- Publication number
- JPS6342656B2 JPS6342656B2 JP11894780A JP11894780A JPS6342656B2 JP S6342656 B2 JPS6342656 B2 JP S6342656B2 JP 11894780 A JP11894780 A JP 11894780A JP 11894780 A JP11894780 A JP 11894780A JP S6342656 B2 JPS6342656 B2 JP S6342656B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonamide
- sulfonamide
- compound
- silane
- dianhydride
- 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.)
- Expired
Links
- 229910000077 silane Inorganic materials 0.000 claims description 20
- -1 Diaminoamide compound Chemical class 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 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 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229920005575 poly(amic acid) Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920006026 co-polymeric resin Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 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
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000006798 ring closing metathesis 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- HFXFYWMYAYUJAA-UHFFFAOYSA-N 2,5-diaminobenzenesulfonamide Chemical compound NC1=CC=C(N)C(S(N)(=O)=O)=C1 HFXFYWMYAYUJAA-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 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 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- PYHOFAHZHOBVGV-UHFFFAOYSA-N triazane Chemical class NNN PYHOFAHZHOBVGV-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明はポリアミド酸シラン型中間体の製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyamic acid silane type intermediate.
本発明は、イミド環、イソインドロキナゾリン
ジオン環または、これらと同系統の環より構成さ
れた反覆単位及びシリコン原子を骨核中に含むこ
とにより、基板との接着性、耐湿性にすぐれた新
規ポリマーであるポリイミドイソインドロキナゾ
リンジオンシラン共重合体樹脂の前駆物質として
の、ポリアミド酸シラン型中間体の製造方法を提
供するものである。 The present invention provides excellent adhesion to a substrate and moisture resistance by containing a repeating unit composed of an imide ring, an isoindoroquinazolinedione ring, or a ring of the same type as these, and a silicon atom in the bone core. The present invention provides a method for producing a polyamic acid silane type intermediate as a precursor of a new polymer, polyimidoisoindoquinazolinedione silane copolymer resin.
本発明の製造方法によつて得られる中間体より
得られるポリイミドイソインドロキナゾリンジオ
ンシラン共重合体樹脂は熱に安定であり、接着
性、耐湿性にすぐれ、ポリ―イソインドロキナゾ
リンジオンの耐熱安定性、ポリイミドの延伸性、
強靭性、シランの接着性、耐湿性の有効な諸特性
を有し、成形製品、フイルム、接着性、注型体、
複合材料、ワニス、被覆、塗装組成物等の製造に
使用することができる。 The polyimidoisoindoloquinazolinedione silane copolymer resin obtained from the intermediate obtained by the production method of the present invention is stable to heat and has excellent adhesiveness and moisture resistance. stability, stretchability of polyimide,
It has effective properties such as toughness, silane adhesion, and moisture resistance, and is useful for molded products, films, adhesive properties, cast bodies,
It can be used in the production of composite materials, varnishes, coatings, coating compositions, etc.
本発明は、
(a) 一般式
（式中、Arは芳香族残基、ＹはSO2又はCOを
示し、１個のアミノ基とＹ―NH2基とは互い
にオルト位に位置する）
で示されるジアミノアミド化合物
(b) 一般式
（式中Ｒは２価の炭化水素基、R′は１価の炭
化水素基を示し、Ｒ、R′は同一でも異なつて
もよい）
で示されるシラン化合物
(c) 芳香族ジアミンおよび
(d) 芳香族テトラカルボン酸二無水物をジアミン
成分のうちジアミノアミド化合物を５〜30モル
％とし、シラン化合物を0.1〜50モル％として
反応させるポリアミド酸シラン型中間体の製造
方法に関する。 The present invention provides: (a) General formula (In the formula, Ar is an aromatic residue, Y is SO 2 or CO, and one amino group and Y--NH 2 group are located in the ortho position to each other.) Diaminoamide compound (b) General formula (In the formula, R represents a divalent hydrocarbon group, R' represents a monovalent hydrocarbon group, and R and R' may be the same or different.) A silane compound represented by (c) aromatic diamine and (d ) The present invention relates to a method for producing a polyamic acid silane type intermediate in which an aromatic tetracarboxylic dianhydride is reacted with a diaminoamide compound in a proportion of 5 to 30 mol% and a silane compound in a proportion of 0.1 to 50 mol%.
本発明に用いるジアミノアミド化合物とは、例
えば次の式
で示される化合物である。 The diaminoamide compound used in the present invention is, for example, the following formula: This is a compound represented by
（）〜（）式においてＹはSO2又はCOを
示しＸはＯ、CH2、SO2、Ｓ、COなどを示し、
１個のアミノ基とＹ―NH2とは互いにオルト位
に位置する。その具体例をあげれば、４，4′―ジ
アミノジフエニルエーテル―３―スルホンアミ
ド、３，4′―ジアミノジフエニルエーテル―４―
スルホンアミド、３，4′―ジアミノジフエニルエ
ーテル―3′―スルホンアミド、３，3′―ジアミノ
ジフエニルエーテル―４―スルホンアミド、４，
4′―ジアミノジフエニルメタン―３―スルホンア
ミド、３，4′―ジアミノジフエニルメタン―４―
スルホンアミド、３，4′―ジアミノジフエニルメ
タン―3′―スルホンアミド、３，3′―ジアミノジ
フエニルメタン―４―スルホンアミド、４，4′―
ジアミノジフエニルスルホン―３―スルホンアミ
ド、３，4′―ジアミノジフエニルスルホン―４―
スルホンアミド、３，4′―ジアミノジフエニルス
ルホン―3′―スルホンアミド、３，3′―ジアミノ
ジフエニルスルホン―４―スルホンアミド、４，
4′―ジアミノジフエニルサルフアイド―３―スル
ホンアミド、３，4′―ジアミノジフエニルサルフ
アイド―４―スルホンアミド、３，3′―ジアミノ
ジフエニルサルフアイド―４―スルホンアミド、
３，4′―ジアミノジフエニルサルフアイド―3′―
スルホンアミド、１，４―ジアミノベンゼン―２
―スルホンアミド、４，4′―ジアミノジフエニル
エーテル―３―カルボンアミド、３，4′―ジアミ
ノジフエニルエーテル―４―カルボンアミド、
３，4′―ジアミノジフエニルエーテル―3′―カル
ボンアミド、３，3′―ジアミノジフエニルエーテ
ル―４―カルボンアミド、４，4′―ジアミノジフ
エニルメタン―３―カルボンアミド、３，4′―ジ
アミノジフエニルメタン―４―カルボンアミド、
３，4′―ジアミノジフエニルメタン―3′―カルボ
ンアミド、３，3′―ジアミノジフエニルメタン―
４―カルボンアミド、４，4′―ジアミノジフエニ
ルスルホン―３―カルボンアミド、３，4′―ジア
ミノジフエニルスルホン―４―カルボンアミド、
３，4′―ジアミノジフエニルスルホン―3′―カル
ボンアミド、３，3′―ジアミノジフエニルスルホ
ン―４―カルボンアミド、４，4′―ジアミノジフ
エニルサルフアイド―３―カルボンアミド、３，
4′―ジアミノジフエニルサルフアイド―４―カル
ボンアミド、３，3′―ジアミノジフエニルサルフ
アイド―４―カルボンアミド、３，4′―ジアミノ
ジフエニルサルフアイド―3′―スルホンアミドあ
るいは１，４―ジアミノベンゼン―２―カルボン
アミドなどがある。 In formulas () to (), Y represents SO 2 or CO, and X represents O, CH 2 , SO 2 , S, CO, etc.
One amino group and Y—NH 2 are located at ortho positions to each other. Specific examples include 4,4'-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-4-
Sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-diaminodiphenyl ether-4-sulfonamide, 4,
4'-diaminodiphenylmethane-3-sulfonamide, 3,4'-diaminodiphenylmethane-4-
Sulfonamide, 3,4'-diaminodiphenylmethane-3'-sulfonamide, 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4'-
Diaminodiphenylsulfone-3-sulfonamide, 3,4'-diaminodiphenylsulfone-4-
Sulfonamide, 3,4'-diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfone-4-sulfonamide, 4,
4'-diaminodiphenylsulfide-3-sulfonamide, 3,4'-diaminodiphenylsulfide-4-sulfonamide, 3,3'-diaminodiphenylsulfide-4-sulfonamide,
3,4'-diaminodiphenyl sulfide-3'-
Sulfonamide, 1,4-diaminobenzene-2
-Sulfonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, 3,4'-diaminodiphenyl ether-4-carbonamide,
3,4'-diaminodiphenyl ether-3'-carbonamide, 3,3'-diaminodiphenyl ether-4-carbonamide, 4,4'-diaminodiphenylmethane-3-carbonamide, 3,4' -diaminodiphenylmethane-4-carbonamide,
3,4'-diaminodiphenylmethane-3'-carbonamide, 3,3'-diaminodiphenylmethane-
4-carbonamide, 4,4'-diaminodiphenylsulfone-3-carbonamide, 3,4'-diaminodiphenylsulfone-4-carbonamide,
3,4'-diaminodiphenylsulfone-3'-carbonamide, 3,3'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide-3-carbonamide, 3,
4'-diaminodiphenylsulfide-4-carbonamide, 3,3'-diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide or 1,4 -Diaminobenzene-2-carbonamide, etc.
これらのジアミノアミド化合物は、２種以上を
併用することもできる。 Two or more types of these diaminoamide compounds can also be used in combination.
本発明に用いられる一般式
（式中Ｒは２価の炭化水素基、R′は１価の炭化
水素基を示す、Ｒ、R′は同じでも異なつてもよ
い）で示されるシラン化合物の例としては、
などがあげられる（Meはメチル基、Phはフエニ
ル基を示す）。これらの化合物は、２種以上を併
用することもできる。 General formula used in the present invention Examples of the silane compound represented by the formula (wherein R is a divalent hydrocarbon group and R' is a monovalent hydrocarbon group; R and R' may be the same or different) include: (Me represents a methyl group and Ph represents a phenyl group). Two or more of these compounds can also be used in combination.
芳香族ジアミンとしては、例えば４，4′―ジア
ミノジフエニルエーテル、４，4′―ジアミノジフ
エニルメタン、４，4′―ジアミノジフエニルスル
ホン、４，4′―ジアミノジフエニルサルフアイ
ド、ベンジジン、メタフエニレンジアミン、パラ
フエニレンジアミン、１，５―ナフタレンジアミ
ンあるいは２，６―ナフタレンジアミンがあげら
れ、２種以上を併用することもできる。 Examples of aromatic diamines include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzidine, Examples include metaphenylene diamine, paraphenylene diamine, 1,5-naphthalene diamine, and 2,6-naphthalene diamine, and two or more types can also be used in combination.
芳香族テトラカルボン酸二無水物としては、例
えば、ピロメリツト酸二無水物、３，3′，４，
4′―ジフエニルテトラカルボン酸二無水物、３，
3′，４，4′―ベンゾフエノ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、２，３，６，７―ナフタレンテ
トラカルボン酸二無水物、２，３，５，６―ピリ
ジ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、３，
４，９，10―ベリレンテトラカルボン酸二無水物
あるいは４，4′―スルホニルジフタル酸二無水物
があげられ、これらの１種または、２種以上が用
いられる。 Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,
4'-diphenyltetracarboxylic dianhydride, 3,
3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8
- Naphthalenetetracarboxylic dianhydride, 3,
Examples include 4,9,10-pyrylenetetracarboxylic dianhydride and 4,4'-sulfonyldiphthalic dianhydride, and one or more of these may be used.
本発明においては、上記のジアミノアミド化合
物、シラン化合物および芳香族ジアミン（ジアミ
ン成分）の総量を芳香族テトラカルボン酸二無水
物とほぼ等モルとして反応される。ジアミン成分
のうちジアミノアミド化合物は５〜30モル％、シ
ラン化合物は0.1〜50モル％とされる。 In the present invention, the diaminoamide compound, silane compound, and aromatic diamine (diamine component) are reacted in a total amount approximately equimolar to the aromatic tetracarboxylic dianhydride. Among the diamine components, the diaminoamide compound is 5 to 30 mol%, and the silane compound is 0.1 to 50 mol%.
本発明を実施するに当つては、不活性溶媒が使
用される。この溶媒は、前記４種の単量体の総て
を溶解するものである必要はない。 In the practice of this invention, inert solvents are used. This solvent does not need to dissolve all of the four types of monomers.
特に好ましいものとしては、生成するポリアミ
ド酸シラン型中間体を溶解するものである。例え
ば、Ｎ―メチル―２―ピロリドン、Ｎ，Ｎ―ジメ
チルアセトアミド、Ｎ，Ｎ―ジメチルホルムアミ
ド、Ｎ，Ｎ―ジエチルホルムアミド、ジメチルス
ルホキシド、ヘキサメチルホスホルアミド、テト
ラメチレンスルホンなどの１種若しくは２種以上
が用いられる。 Particularly preferred is one that dissolves the polyamic acid silane type intermediate produced. For example, one or two of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, etc. The above is used.
本発明においては好ましくは先ず、上記のジア
ミノアミド化合物、シラン化合物、芳香族ジアミ
ン及び芳香族テトラカルボン酸二無水物を前記不
活性溶媒にできるだけよくとかし、この反応系を
好ましくは約80℃以下特に室温付近ないしそれ以
下の温度に保ちながら、撹拌する。これによつて
反応は、すみやかに進行し、かつ反応系の粘度は
次第に上昇し、ポリアミド酸シラン型中間体が生
成する。 In the present invention, preferably, first, the diaminoamide compound, silane compound, aromatic diamine, and aromatic tetracarboxylic dianhydride are dissolved in the inert solvent as well as possible, and the reaction system is preferably heated at a temperature below about 80°C, especially Stir while maintaining the temperature near or below room temperature. As a result, the reaction proceeds rapidly, the viscosity of the reaction system gradually increases, and a polyamic acid silane type intermediate is produced.
本発明によつて得られる中間体は次の構造単位
を有するものである。 The intermediate obtained by the present invention has the following structural unit.
上式においてAr、Ar′およびAr″は芳香族基を
示す。 In the above formula, Ar, Ar' and Ar'' represent aromatic groups.
この中間体を100〜350℃の温度で好ましくは30
分〜５時間熱処理すると、脱水、閉環し、ポリイ
ミドイソインドロキナゾリンジオンシラン共重合
体樹脂が得られる。この脱水、閉環反応は脱水剤
として無水酢酸、リン酸等を用いて行なつてもよ
い。上記の中間体をガラス板等上に流し塗りし、
乾燥してフイルムとし、脱水、閉環を行なつても
よい。 This intermediate is preferably heated at a temperature between 100 and 350 °C for 30
When heat-treated for minutes to 5 hours, dehydration and ring closure occur to obtain a polyimidoisoindoquinazolinedionesilane copolymer resin. This dehydration and ring closure reaction may be carried out using acetic anhydride, phosphoric acid, etc. as a dehydrating agent. Pour the above intermediate onto a glass plate, etc.,
It may be dried to form a film, followed by dehydration and ring closure.
本発明の製造方法によつて得られるポリアミド
酸シラン型中間体によつて、耐熱性および接着性
に優れたポリイミドイソインドロキナゾリンジオ
ンシラン共重合体樹脂が得られ、この樹脂は、特
にガラス等の基板に対する接着性に優れるため
に、これを液晶配向膜、半導体の表面保護膜等に
用いた場合には基板との剥離、基板界面への水分
の浸入等を効果的に防ぎ、信頼性の高い製品を得
ることができる。 By using the polyamic acid silane type intermediate obtained by the production method of the present invention, a polyimide isoindoquinazoline dione silane copolymer resin having excellent heat resistance and adhesiveness can be obtained. Because of its excellent adhesion to substrates, when used in liquid crystal alignment films, semiconductor surface protection films, etc., it effectively prevents peeling from the substrate and moisture intrusion into the substrate interface, improving reliability. You can get high quality products.
以下、本発明の実施例を説明する。 Examples of the present invention will be described below.
実施例 １
温度計、撹拌機、および塩化カルシウム管を備
えた500c.c.の３つ口フラスコに、４，4′―ジアミ
ノジフエニルエーテル16.0g、４，4′―ジアミノ
ジフエニルエーテル―３―カルボンアミド2.5g、
ジアミノプロポキシジフエニルシラン3.3g及びＮ
―メチル―２―ピロリドン300gを入れ、よく撹
拌した。これに４，4′―ベンゾフエノンテトラカ
ルボン酸二無水物32.2gを徐々に加えた。添加終
了後、５時間撹拌した。次にこの反応液（生成し
たポリアミド酸シラン型中間体の溶液）の一部を
採取し、水に投じて、沈殿させ、ηsp/cを測定した
ところ、0.80dl/g（溶媒ジメチルスルホキシド、
濃度0.1g／100c.c.溶液、温度25℃）であつた。Example 1 In a 500 c.c. three-necked flask equipped with a thermometer, a stirrer, and a calcium chloride tube, 16.0 g of 4,4'-diaminodiphenyl ether and 3,4,4'-diaminodiphenyl ether were added. -Carbonamide 2.5g,
Diaminopropoxydiphenylsilane 3.3g and N
-Methyl-2-pyrrolidone (300g) was added and stirred well. To this was gradually added 32.2 g of 4,4'-benzophenonetetracarboxylic dianhydride. After the addition was complete, the mixture was stirred for 5 hours. Next, a part of this reaction solution (a solution of the produced polyamic acid silane type intermediate) was collected, poured into water to precipitate it, and η sp/c was measured.
The concentration was 0.1 g/100 c.c. solution, temperature 25°C).
参考例 １
前記反応液を、ガラス板上に塗布し、かつ乾燥
してフイルムを作り、これを300℃で２時間処理
すると、ポリイミドイソインドロキナゾリンジオ
ンシラン共重合体樹脂が得られた。Reference Example 1 The reaction solution was applied onto a glass plate and dried to form a film, which was then treated at 300°C for 2 hours to obtain a polyimidoisoindoquinazolinedionesilane copolymer resin.
このフイルムは、ガラス基板との接着性が良
く、ガラス基板からはくりすることは、困難であ
つた。また鉛筆硬度法で6Hまで傷がつかず、優
れた接着性、耐摩耗性を示した。 This film had good adhesion to the glass substrate and was difficult to peel off from the glass substrate. It also showed excellent adhesion and abrasion resistance, with no scratches up to 6H measured by the pencil hardness method.
一方このフイルムは空気中で450℃まで重量減
少せず耐熱性もすぐれていた。 On the other hand, this film did not lose weight in air up to 450°C and had excellent heat resistance.
実施例 ２
実施例１と同様なフラスコに、４，4′―ジアミ
ノジフエニルメタン11.9g、４，4′―ジアミノジ
フエニルエーテル―３―カルボンアミド5.0g、ジ
アミノエトキシジフエニルシラン6.0g及びＮ，Ｎ
―ジメチルアセトアミド300gを入れ、よく撹拌
した。これにピロメリツト酸二無水物10.9g、４，
4′―ベンゾフエノンテトラカルボン酸二無水物
16.1gを徐々に加えた。添加終了後５時間撹拌を
続けた。次にこの反応液の一部を採取し、ηsp/cを
測定したところ0.79dl/g（実施例１と同一条件で
測定）であつた。Example 2 In a flask similar to Example 1, 11.9 g of 4,4'-diaminodiphenylmethane, 5.0 g of 4,4'-diaminodiphenyl ether-3-carbonamide, 6.0 g of diaminoethoxydiphenylsilane, and N ,N
-Add 300g of dimethylacetamide and stir well. Add to this 10.9 g of pyromellitic dianhydride, 4,
4′-Benzophenonetetracarboxylic dianhydride
16.1g was added gradually. Stirring was continued for 5 hours after the addition was complete. Next, a portion of this reaction solution was sampled and η sp/c was measured and found to be 0.79 dl/g (measured under the same conditions as in Example 1).
参考例 ２
前記反応液を用い、参考例１と同様にしてフイ
ルムを作り、かつこれを300℃で２時間処理し、
ポリイミドイソインドロキナゾリンジオンシラン
共重合体樹脂のフイルムを得た。Reference Example 2 Using the above reaction solution, a film was made in the same manner as in Reference Example 1, and this was treated at 300°C for 2 hours,
A film of polyimide isoindoquinazolinedione silane copolymer resin was obtained.
このフイルムは参考例１で得たフイルムと同様
に、すぐれた接着性、耐摩耗性、耐熱性を示し
た。 Similar to the film obtained in Reference Example 1, this film exhibited excellent adhesion, abrasion resistance, and heat resistance.
Claims (1)
示し、１個のアミノ基とＹ―NH2基とは互い
にオルト位に位置する） で示されるジアミノアミド化合物 (b) 一般式 （式中Ｒは２価の炭化水素基、R′は１価の炭
化水素基を示し、Ｒ、R′は同一でも異なつて
もよい）で示されるシラン化合物、 (c) 芳香族ジアミンおよび (d) 芳香族テトラカルボン酸二無水物をジアミン
成分のうちジアミノアミド化合物を５〜30モル
％とし、シラン化合物を0.1〜50モル％として
反応させることを特徴とするポリアミド酸シラ
ン型中間体の製造方法。[Claims] 1 (a) General formula (In the formula, Ar is an aromatic residue, Y is SO 2 or CO, and one amino group and Y--NH 2 group are located at the ortho position to each other.) Diaminoamide compound (b) General formula (In the formula, R is a divalent hydrocarbon group, R' is a monovalent hydrocarbon group, and R and R' may be the same or different), (c) an aromatic diamine, and ( d) Production of a polyamic acid silane type intermediate characterized by reacting an aromatic tetracarboxylic dianhydride with a diaminoamide compound in a proportion of 5 to 30 mol% and a silane compound in a proportion of 0.1 to 50 mol%. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11894780A JPS5742732A (en) | 1980-08-27 | 1980-08-27 | Production of polyamido acid silicone type intermediate and polyimidoisoindoloquinazolinedione/silicone copolymer resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11894780A JPS5742732A (en) | 1980-08-27 | 1980-08-27 | Production of polyamido acid silicone type intermediate and polyimidoisoindoloquinazolinedione/silicone copolymer resin |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP665788A Division JPS63213523A (en) | 1988-01-14 | 1988-01-14 | Production of polyimidoisoindoloquinazolinedionesilane copolymer resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5742732A JPS5742732A (en) | 1982-03-10 |
| JPS6342656B2 true JPS6342656B2 (en) | 1988-08-24 |
Family
ID=14749182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11894780A Granted JPS5742732A (en) | 1980-08-27 | 1980-08-27 | Production of polyamido acid silicone type intermediate and polyimidoisoindoloquinazolinedione/silicone copolymer resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5742732A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705799B (en) * | 2018-12-21 | 2022-03-18 | 东华大学 | YASI epoxy organic imide silica gel and preparation method thereof |
| CN109735294A (en) * | 2018-12-21 | 2019-05-10 | 东华大学 | A kind of BDADTBHQ type silicon-containing adhesive and preparation method thereof |
| CN109628054A (en) * | 2018-12-21 | 2019-04-16 | 东华大学 | A kind of BAHPFP type silicon-containing adhesive and preparation method thereof |
| CN109679571A (en) * | 2018-12-21 | 2019-04-26 | 东华大学 | A kind of DADHBP type silicon-containing adhesive and preparation method thereof |
| CN109722213A (en) * | 2018-12-21 | 2019-05-07 | 东华大学 | A kind of BAHPP type silicon-containing adhesive and preparation method thereof |
| CN109628055A (en) * | 2018-12-21 | 2019-04-16 | 东华大学 | A kind of BDADDE type silicon-containing adhesive and preparation method thereof |
| CN109679570A (en) * | 2018-12-21 | 2019-04-26 | 东华大学 | A kind of BDAPOFP type silicon-containing adhesive and preparation method thereof |
| CN109722214A (en) * | 2018-12-21 | 2019-05-07 | 东华大学 | A kind of DAHTM type silicon-containing adhesive and preparation method thereof |
| WO2023228613A1 (en) * | 2022-05-24 | 2023-11-30 | パナソニックＩｐマネジメント株式会社 | Polyimide, method for producing imide compound, and method for producing recycled polyimide |
-
1980
- 1980-08-27 JP JP11894780A patent/JPS5742732A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5742732A (en) | 1982-03-10 |
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