JPH0138802B2 - - Google Patents
Info
- Publication number
- JPH0138802B2 JPH0138802B2 JP5229786A JP5229786A JPH0138802B2 JP H0138802 B2 JPH0138802 B2 JP H0138802B2 JP 5229786 A JP5229786 A JP 5229786A JP 5229786 A JP5229786 A JP 5229786A JP H0138802 B2 JPH0138802 B2 JP H0138802B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- vinylidene fluoride
- maleic anhydride
- mol
- analysis
- 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
- 229920001577 copolymer Polymers 0.000 claims description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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】
〔産業上の利用分野〕
本発明は、フツ化ビニリデン系含フツ素共重合
体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a vinylidene fluoride-based fluorine-containing copolymer.
従来、フツ化ビニリデン重合体は、耐候性塗料
材料、成形材料などとして使用されている。フツ
化ビニリデン重合体を塗料材料として用いるばあ
い、フツ化ビニリデン重合体は、汎用の有機溶媒
に溶解または分散させ難いので、イソホロンなど
の特別な有機溶媒を使つて、オルガノゾルにして
いる（特公昭43−10363号公報参照）。フツ化ビニ
リデンと炭化水素系の単量体を共重合させること
ができれば、比較的有機溶媒に溶解し易いフツ化
ビニリデン系重合体をうることができると考えら
れるが、フツ化ビニリデンと共重合させることが
できる炭化水素系の単量体は、ほとんど知られて
いないのが現状である。
Conventionally, vinylidene fluoride polymers have been used as weather-resistant paint materials, molding materials, and the like. When vinylidene fluoride polymer is used as a paint material, it is difficult to dissolve or disperse it in general-purpose organic solvents, so special organic solvents such as isophorone are used to make it into an organosol (Tokuko Showa). 43-10363). If vinylidene fluoride and a hydrocarbon monomer can be copolymerized, it is thought that a vinylidene fluoride polymer that is relatively easily soluble in organic solvents can be obtained. At present, very little is known about the hydrocarbon monomers that can do this.
本発明者らは、フツ化ビニリデンと共重合させ
ることができる炭化水素系の単量体を探したとこ
ろ、無水マレイン酸がフツ化ビニリデンとの共重
合性に優れていることを見出し、本発明に到達し
た。
The present inventors searched for a hydrocarbon monomer that can be copolymerized with vinylidene fluoride, and found that maleic anhydride has excellent copolymerizability with vinylidene fluoride. reached.
本発明の目的は、新規フツ化ビニリデン系共重
合体を提供することである。 An object of the present invention is to provide a new vinylidene fluoride copolymer.
本発明は、
式(1)：
―CH2―CF2― (1)
で表わされる構造単位40〜95モル％および式(2)：
で表わされる構造単位５〜60モル％
（ただし、構造単位(1)および(2)の合計は100モル
％である）からなる共重合体であつて、分子量
1000〜100000の含フツ素共重合体に関する。
The present invention comprises 40 to 95 mol% of the structural unit represented by formula (1): —CH 2 —CF 2 — (1) and formula (2): A copolymer consisting of 5 to 60 mol% of the structural unit represented by (however, the total of structural units (1) and (2) is 100 mol%), with a molecular weight of
1000 to 100000 fluorine-containing copolymer.
前記構造単位(1)は、主として塗料の耐候性を良
好にする機能を有し、構造単位(2)は、主として塗
料の基材への密着性を良好にする機能を有してい
る。 The structural unit (1) mainly has the function of improving the weather resistance of the paint, and the structural unit (2) mainly has the function of improving the adhesion of the paint to the base material.
本発明の共重合体における構造単位(1)および(2)
の含有量は、それぞれ40〜95モル％、好ましくは
50〜80モル％および５〜60モル％、好ましくは20
〜50モル％である。 Structural units (1) and (2) in the copolymer of the present invention
The content of each is 40 to 95 mol%, preferably
50-80 mol% and 5-60 mol%, preferably 20
~50 mol%.
本発明の共重合体の分子量は、ゲルパーミエー
シヨン法で測定して1000〜100000である。本発明
の共重合体を塗料として使用するばあい、その分
子量は5000〜50000の範囲が好ましい。 The molecular weight of the copolymer of the present invention is 1,000 to 100,000 as measured by gel permeation method. When the copolymer of the present invention is used as a paint, its molecular weight is preferably in the range of 5,000 to 50,000.
本発明の共重合体は、フツ化ビニリデンと無水
マレイン酸とをラジカル重合で共重合して構造単
位(1)と(2)を有する共重合体を調製することにより
うることができる。 The copolymer of the present invention can be obtained by copolymerizing vinylidene fluoride and maleic anhydride by radical polymerization to prepare a copolymer having structural units (1) and (2).
フツ化ビニリデンと無水マレイン酸を共重合す
る際、共重合体の特性を損わない範囲で他の単量
体を共重合してもよい。このような他の単量体と
しては、たとえばクロロトリフルオロエチレン、
テトラフルオロエチレン、フツ化ビニルなどがあ
げられる。 When copolymerizing vinylidene fluoride and maleic anhydride, other monomers may be copolymerized within a range that does not impair the properties of the copolymer. Examples of such other monomers include chlorotrifluoroethylene,
Examples include tetrafluoroethylene and vinyl fluoride.
ラジカル重合法としては、よく知られている塊
状、溶液、懸濁などいずれの方法も採用可能であ
る。 As the radical polymerization method, any of the well-known methods such as bulk, solution, and suspension methods can be employed.
ラジカル開始剤としては、たとえばアゾビスイ
ソブチロニトリルなどのアゾ系開始剤、ベンゾイ
ルパーオキサイド、ジイソプロピルパーオキシカ
ーボネートなどの有機過酸化物などがあげられ
る。 Examples of the radical initiator include azo initiators such as azobisisobutyronitrile, and organic peroxides such as benzoyl peroxide and diisopropyl peroxycarbonate.
溶液重合または懸濁重合で使用することができ
る媒体としては、たとえば１，１，２―トリクロ
ロ―１，２，２―トリフルオロエタン、１，２―
ジクロロ―１，１，２，２―テトラフルオロエタ
ン、酢酸エチル、酢酸ブチル、メチルエチルケト
ンなどがあげられる。水、アルコールなど無水マ
レイン酸の官能基と反応する溶媒類は避けたほう
がよい。重合温度および重合圧力は、前記いずれ
の重合法でもそれぞれ０〜150℃、好ましくは20
〜80℃および０〜100Kg/cm2Ｇ、好ましくは２〜40
Kg／cm2Ｇである。使用する単量体は、初めに全量
仕込んでもよいし、重合途中に連続的あるいは間
歇的に加えてもよい。 Examples of media that can be used in solution or suspension polymerization include 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-
Examples include dichloro-1,1,2,2-tetrafluoroethane, ethyl acetate, butyl acetate, and methyl ethyl ketone. It is better to avoid solvents that react with the functional groups of maleic anhydride, such as water and alcohol. In any of the above polymerization methods, the polymerization temperature and pressure are 0 to 150°C, preferably 20°C.
~80℃ and 0-100Kg/ cm2G , preferably 2-40
Kg/cm 2 G. The monomers used may be added in their entirety at the beginning, or may be added continuously or intermittently during the polymerization.
調製例 １
（フツ化ビニリデンと無水マレイン酸との共重
合体）
撹拌機を備えた250c.c.のオートクレーブに酢酸
エチル50ｇ、ジイソプロピルパーオキシジカーボ
ネート0.3ｇおよび無水マレイン酸25ｇを入れ、
窒素で空間部を三回置換し、フツ化ビニリデン
17.1ｇを仕込んだ。そののち、該オートクレーブ
を40℃の恒温槽に48時間浸漬して重合させ、赤色
の粘稠液をえた。
Preparation Example 1 (Copolymer of vinylidene fluoride and maleic anhydride) Put 50 g of ethyl acetate, 0.3 g of diisopropyl peroxydicarbonate, and 25 g of maleic anhydride into a 250 c.c. autoclave equipped with a stirrer.
By replacing the space with nitrogen three times, vinylidene fluoride
17.1g was charged. Thereafter, the autoclave was immersed in a constant temperature bath at 40° C. for 48 hours to polymerize, yielding a red viscous liquid.
前記粘稠液をクロロホルム中に滴下したとこ
ろ、桃色の固体が沈澱した。この固体を酢酸エチ
ルに溶解し、再度クロロホルム中に滴下して再沈
澱させて、白色共重合体31ｇをえた。 When the viscous liquid was dropped into chloroform, a pink solid precipitated. This solid was dissolved in ethyl acetate and dropped into chloroform again for reprecipitation to obtain 31 g of a white copolymer.
えられた共重合体について、単分散ポリスチレ
ンをスタンダードとしてゲルパーミエーシヨン分
析（GPC分析）を行つたところ、5000〜20000の
分子量分布を有していた。また、熱分解温度
（Td）は200℃であつた。トリフルオロ酢酸を外
部標準として 19F―NMR分析を行つたところ、
CF2のシグナルがδ＝16〜27ppmに観測され、テ
トラメチルシランを内部標準として、 1H―
NMR分析を行つたところ、＝CH―と―CH2―の
シグナルが各々δ＝4.1ppmと3.2ppmに観測され
た。また、赤外吸収分析によれば、酸無水物に基
づく吸収が1860cm-1と1790cm-1に、CF結合に基
づく吸収帯が1120〜1280cm-1に観測された。元素
分析によると、炭素45.0％、水素2.5％およびフ
ツ素23.5％が含有されていた。 When the resulting copolymer was subjected to gel permeation analysis (GPC analysis) using monodisperse polystyrene as a standard, it was found to have a molecular weight distribution of 5,000 to 20,000. Moreover, the thermal decomposition temperature (Td) was 200°C. 19F -NMR analysis using trifluoroacetic acid as an external standard revealed that
A CF 2 signal was observed at δ = 16 to 27 ppm, and using tetramethylsilane as an internal standard, 1 H-
When NMR analysis was performed, =CH- and -CH 2 - signals were observed at δ = 4.1 ppm and 3.2 ppm, respectively. Furthermore, according to infrared absorption analysis, absorption bands based on acid anhydrides were observed at 1860 cm -1 and 1790 cm -1 and absorption bands based on CF bonds were observed at 1120 to 1280 cm -1 . According to elemental analysis, it contained 45.0% carbon, 2.5% hydrogen and 23.5% fluorine.
前記元素分析およびNMR分析の結果より、え
られた共重合体は、フツ化ビニリデン／無水マレ
イン酸＝１／１（モル比）からなるものであるこ
とがわかつた。 From the results of the elemental analysis and NMR analysis, it was found that the obtained copolymer was composed of vinylidene fluoride/maleic anhydride=1/1 (mole ratio).
調製例 ２
（フツ化ビニリデンと無水マレイン酸との共重
合体）
フツ化ビニリデンの使用量を32.3ｇ、無水マレ
イン酸の使用量を5.1ｇ、重合時間を24時間に変
更した他は調製例１と同様の手順で共重合体を調
製した。Preparation Example 2 (Copolymer of vinylidene fluoride and maleic anhydride) Preparation Example 1 except that the amount of vinylidene fluoride used was changed to 32.3 g, the amount of maleic anhydride used was changed to 5.1 g, and the polymerization time was changed to 24 hours. A copolymer was prepared using a similar procedure.
GPC分析で求めた重量平均分子量は40000であ
つた。元素分析およびNMR分析の結果から、え
られた共重合体は、フツ化ビニリデン／無水マレ
イン酸＝91／９（モル比）からなるものであるこ
とがわかつた。 The weight average molecular weight determined by GPC analysis was 40,000. From the results of elemental analysis and NMR analysis, it was found that the obtained copolymer consisted of vinylidene fluoride/maleic anhydride=91/9 (molar ratio).
調製例 ３
（フツ化ビニリデンと無水マレイン酸との共重
合体）
調製例１と同じオートクレーブに酢酸エチル30
ｇ、ジイソプロピルパーオキシジカーボネート
0.6ｇおよび無水マレイン酸7.5ｇを入れ、窒素で
空間部を三回置換し、フツ化ビニリデン20.9ｇを
仕込んだ。該オートクレーブを40℃の恒温槽に20
時間浸漬した。そののち、20ｇの酢酸エチルに溶
解させた7.5ｇの無水マレイン酸をオートクレー
ブに圧入し、さらに24時間重合を継続し、共重合
体29ｇをえた。Preparation Example 3 (Copolymer of vinylidene fluoride and maleic anhydride) Add 30% ethyl acetate to the same autoclave as Preparation Example 1.
g, diisopropyl peroxydicarbonate
0.6 g of maleic anhydride and 7.5 g of maleic anhydride were added, the space was purged with nitrogen three times, and 20.9 g of vinylidene fluoride was charged. Place the autoclave in a constant temperature bath at 40℃ for 20 minutes.
Soaked for an hour. Thereafter, 7.5 g of maleic anhydride dissolved in 20 g of ethyl acetate was pressurized into the autoclave, and polymerization was continued for an additional 24 hours to obtain 29 g of a copolymer.
GPC分析で求めた重量平均分子量は20000であ
つた。元素分析およびNMR分析の結果から、え
られた共重合体はフツ化ビニリデン／無水マレイ
ン酸＝62／38（モル比）からなるものであること
がわかつた。 The weight average molecular weight determined by GPC analysis was 20,000. From the results of elemental analysis and NMR analysis, it was found that the obtained copolymer consisted of vinylidene fluoride/maleic anhydride = 62/38 (mole ratio).
フツ化ビニリデンと無水マレイン酸とを主成分
とする本発明の共重合体は、従来からあるフツ化
ビニリデン重合体に比べ、有機溶媒に対する溶解
性がよい。
The copolymer of the present invention containing vinylidene fluoride and maleic anhydride as main components has better solubility in organic solvents than conventional vinylidene fluoride polymers.
Claims (1)
％である）からなる共重合体であつて、分子量
1000〜100000の含フツ素共重合体。[Claims] 1 Formula (1): 40 to 95 mol% of structural units represented by -CH 2 -CF 2 - (1) and formula (2): A copolymer consisting of 5 to 60 mol% of the structural unit represented by (however, the total of structural units (1) and (2) is 100 mol%), with a molecular weight of
1000 to 100000 fluorine-containing copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5229786A JPS62260806A (en) | 1986-03-10 | 1986-03-10 | Fluorine-containing copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5229786A JPS62260806A (en) | 1986-03-10 | 1986-03-10 | Fluorine-containing copolymer |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33514388A Division JPH02604A (en) | 1988-12-28 | 1988-12-28 | Fluorinated copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62260806A JPS62260806A (en) | 1987-11-13 |
| JPH0138802B2 true JPH0138802B2 (en) | 1989-08-16 |
Family
ID=12910860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5229786A Granted JPS62260806A (en) | 1986-03-10 | 1986-03-10 | Fluorine-containing copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62260806A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02604A (en) * | 1988-12-28 | 1990-01-05 | Daikin Ind Ltd | Fluorinated copolymer |
| US5154881A (en) * | 1992-02-14 | 1992-10-13 | Hoeganaes Corporation | Method of making a sintered metal component |
| US5368630A (en) * | 1993-04-13 | 1994-11-29 | Hoeganaes Corporation | Metal powder compositions containing binding agents for elevated temperature compaction |
| JP3700736B2 (en) * | 1996-11-27 | 2005-09-28 | 株式会社ユアサコーポレーション | Manufacturing method of thin lithium battery |
| KR100371954B1 (en) * | 1997-07-24 | 2003-02-14 | 구레하 가가쿠 고교 가부시키가이샤 | Vinylidene fluoride copolymer for gel-form solid electrolyte formation, solid electrolyte, and battery |
| EP1498435B1 (en) * | 1997-10-15 | 2012-05-02 | E.I. Du Pont De Nemours And Company | Copolymers of maleic anhydride or acid and fluorinated olefins |
| DE69835649T2 (en) * | 1997-10-15 | 2007-09-13 | E.I. Dupont De Nemours And Co., Wilmington | Copolymers of maleic acid or its anhydride and fluorinated olefins |
| JP4513175B2 (en) | 2000-06-16 | 2010-07-28 | ソニー株式会社 | Gel electrolyte and non-aqueous electrolyte battery |
| EP2226338B1 (en) | 2007-12-27 | 2012-08-15 | Kureha Corporation | Adhesive vinylidene fluoride resin sheet |
-
1986
- 1986-03-10 JP JP5229786A patent/JPS62260806A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62260806A (en) | 1987-11-13 |
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