JPH031322B2 - - Google Patents
Info
- Publication number
- JPH031322B2 JPH031322B2 JP9466983A JP9466983A JPH031322B2 JP H031322 B2 JPH031322 B2 JP H031322B2 JP 9466983 A JP9466983 A JP 9466983A JP 9466983 A JP9466983 A JP 9466983A JP H031322 B2 JPH031322 B2 JP H031322B2
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- sulfoxide
- alcohol polymer
- vinyl
- reaction
- 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
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 65
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 25
- -1 alkyl vinyl sulfoxide Chemical compound 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000005360 alkyl sulfoxide group Chemical group 0.000 claims description 11
- 238000007127 saponification reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 31
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- UDDBCWCQRQREBI-UHFFFAOYSA-N 1-methylsulfinylethene Chemical compound CS(=O)C=C UDDBCWCQRQREBI-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229920001567 vinyl ester resin Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-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
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HNXMKNMCALMEPP-UHFFFAOYSA-N 1-ethenylsulfinylethane Chemical compound CCS(=O)C=C HNXMKNMCALMEPP-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 210000003491 skin Anatomy 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KLWAGMFJBPADPJ-UHFFFAOYSA-N 1-ethenylsulfinylbutane Chemical compound CCCCS(=O)C=C KLWAGMFJBPADPJ-UHFFFAOYSA-N 0.000 description 1
- HQSMEHLVLOGBCK-UHFFFAOYSA-N 1-ethenylsulfinylethene Chemical group C=CS(=O)C=C HQSMEHLVLOGBCK-UHFFFAOYSA-N 0.000 description 1
- HIOVAKRDECQPSR-UHFFFAOYSA-N 2-ethenylsulfinylpropane Chemical compound CC(C)S(=O)C=C HIOVAKRDECQPSR-UHFFFAOYSA-N 0.000 description 1
- WFJXYIUAMJAURQ-UHFFFAOYSA-N 2-propan-2-ylsulfinylpropane Chemical group CC(C)S(=O)C(C)C WFJXYIUAMJAURQ-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- SKSGINUILMRTET-UHFFFAOYSA-N ethenylsulfinylcyclohexane Chemical compound C=CS(=O)C1CCCCC1 SKSGINUILMRTET-UHFFFAOYSA-N 0.000 description 1
- SMWJPJLZIVEXKQ-UHFFFAOYSA-N ethenylsulfinylmethylbenzene Chemical compound C=CS(=O)CC1=CC=CC=C1 SMWJPJLZIVEXKQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は変性ポリビニルアルコール系重合体の
製法に関する。更に詳しくはポリビニルアルコー
ル系重合体の水酸基に対してアルキルビニルスル
ホキシドを反応させることによりアルキルスルホ
キシドの導入された、無機物質との接着性の優れ
た変性ポリビニルアルコール系重合体の製法に関
する。
ビニルエステル、とりわけ酢酸ビニルの単独ま
たは共重合体をけん化してえられるポリビニルア
ルコールまたはビニルアルコール共重合体等のポ
リビニルアルコール系重合体は繊維、フイルム、
シートなどの成形物の他、その強靭な皮膜形成能
および接着性能を生かし、水溶性の接着剤、バイ
ンダー被覆剤、紙加工剤、繊維糊剤など広く使用
されている。
このようにポリビニルアルコールは広範囲な材
料に対し良好な接着能を有しているが、接着力は
必ずしも高くない場合がある。例えばガラス、石
綿、コンクリート等の無機材料に対する接着力は
十分でなく、より接着力の高い材料が望まれてい
る。
本発明はこれらの背景のもとになされたもの
で、ポリビニルアルコール系重合体にアルキルビ
ニルスルホキシドを反応させて、アルキルスルホ
キシド基を導入することにより、接着力の高い、
とくに無機材料に対する接着力の高い材料がえら
れることを見出し、本発明に到達したものであ
る。
本発明の特徴は上述のごとく無機物、とくにガ
ラスとの接着性に優れた変性ポリビニルアルコー
ル系重合体がえられることにある。アルキルスル
ホキシド基の導入されたポリビニルアルコール系
重合体をえる方法としては本発明者らが、先に出
願（特願昭58−29956号）したアルキルビニルス
ルホキシドを酢酸ビニル等のビニルエステルと共
重合し、次いでけん化する方法があるが、この方
法はアルキルビニルスルホキシドの共重合性が良
くないため、アルキルビニルスルホキシド単位の
含量の高い共重合体をえようとして、アルキルビ
ニルスルホキシドを多量に共存させ、酢酸ビニル
と共重合し、けん化する場合、重合速度、重合度
の低下が大きく、効率よく高変性度、高重合度の
変性ポリビニルアルコール系重合体をえることが
難しい点がある。これに対し本発明の方法は高重
合度のポリビニルアルコール系重合体を多量のア
ルキルビニルスルホキシドを用いて反応すること
により容易に反応し、アルキルスルホキシド基含
量の高い高変性ポリビニルアルコール系重合体を
えることができる利点のあることである。
また本発明は工業的に大量に生産販売されてい
るポリビニルアルコール系重合体を利用して後反
応により、容易に新しい特性の付与された付加価
値の高い材料にすることができる。例えばポリビ
ニルアルコール系重合体の繊維、フイルム、成型
物等の成形物にその形態を保つた状態でアルキル
ビニルスルホキシドを反応させ、これらの表面に
アルキルビニルスルホキシド基を導入することに
より、表面特性の改良された成形物材料または成
形物を得ることができる利点がある。
本発明の方法により得られた多量のアルキルス
ルホキシド基の導入された変性ポリビニルアルコ
ール系重合体は特にアルキルスルホキシド基の親
水性と親油性を兼備する特性により、極性物質の
吸着能が増大すること、さらにたとえばこれを農
薬分散剤に用いた場合には農薬の昆虫皮膚への滲
透性が増大するなどの特異な効果が発揮され、す
ぐれた性能を有する。
以下本発明を具体的に説明する。
本発明で用いるポリビニルアルコール系重合体
とは
The present invention relates to a method for producing a modified polyvinyl alcohol polymer. More specifically, the present invention relates to a method for producing a modified polyvinyl alcohol polymer having excellent adhesion to inorganic substances, into which an alkyl sulfoxide is introduced by reacting the hydroxyl groups of the polyvinyl alcohol polymer with an alkyl vinyl sulfoxide. Polyvinyl alcohol-based polymers such as polyvinyl alcohol or vinyl alcohol copolymers obtained by saponifying vinyl esters, especially vinyl acetate alone or copolymers, can be used for fibers, films,
In addition to molded products such as sheets, it is widely used as water-soluble adhesives, binder coatings, paper processing agents, and fiber glues due to its strong film-forming and adhesive properties. As described above, polyvinyl alcohol has good adhesion ability to a wide range of materials, but the adhesion strength may not always be high. For example, adhesive strength to inorganic materials such as glass, asbestos, and concrete is insufficient, and materials with higher adhesive strength are desired. The present invention was made against these backgrounds, and by reacting an alkyl vinyl sulfoxide to a polyvinyl alcohol-based polymer and introducing an alkyl sulfoxide group, it is possible to create a polyvinyl alcohol-based polymer with high adhesive strength.
The present invention was achieved by discovering that a material with particularly high adhesion to inorganic materials can be obtained. As mentioned above, the feature of the present invention is that a modified polyvinyl alcohol polymer can be obtained which has excellent adhesion to inorganic materials, especially glass. As a method for obtaining a polyvinyl alcohol polymer into which an alkyl sulfoxide group has been introduced, the present inventors have previously applied (Japanese Patent Application No. 58-29956) by copolymerizing alkyl vinyl sulfoxide with a vinyl ester such as vinyl acetate. Then, there is a method of saponification, but since this method does not have good copolymerizability of alkyl vinyl sulfoxide, in order to obtain a copolymer with a high content of alkyl vinyl sulfoxide units, a large amount of alkyl vinyl sulfoxide is coexisted, and acetic acid When copolymerizing with vinyl and saponifying it, the polymerization rate and degree of polymerization decrease significantly, making it difficult to efficiently obtain a modified polyvinyl alcohol polymer with a high degree of modification and high degree of polymerization. In contrast, in the method of the present invention, a polyvinyl alcohol polymer with a high polymerization degree is easily reacted with a large amount of alkyl vinyl sulfoxide, and a highly modified polyvinyl alcohol polymer with a high content of alkyl sulfoxide groups can be obtained. This is an advantageous thing that can be done. Furthermore, the present invention can easily produce a high value-added material with new properties through a post-reaction using polyvinyl alcohol polymers that are industrially produced and sold in large quantities. For example, surface properties can be improved by reacting alkyl vinyl sulfoxide with polyvinyl alcohol polymer fibers, films, molded articles, etc. while maintaining their shape, and introducing alkyl vinyl sulfoxide groups onto their surfaces. This has the advantage that molded material or molded articles can be obtained. The modified polyvinyl alcohol polymer into which a large amount of alkyl sulfoxide groups have been introduced, which is obtained by the method of the present invention, has an increased ability to adsorb polar substances, especially due to the property of having both hydrophilicity and lipophilicity of the alkyl sulfoxide groups. Furthermore, when this is used as a dispersant for agricultural chemicals, for example, it exhibits unique effects such as increasing the permeability of agricultural chemicals into insect skin, and has excellent performance. The present invention will be specifically explained below. What is the polyvinyl alcohol polymer used in the present invention?
【式】（ＲはＨまたはメチル基
で、Ｈが好ましい。）単位を有する重合体で、単
独重合体、通常の共重合体、ブロツク共重合体、
グラフト重合体、ホルマール、ブチラール化等の
後反応重合体等すべての重合体を包含するもので
ある。これらのうち酢酸ビニル等のビニルエステ
ルを重合、けん化してえられるポリビニルアルコ
ール、あるいは酢酸ビニル等のビニルエステルを
コモノマー、例えばエチレン、アルキルビニルエ
ーテル、アクリル酸メチル、イタコン酸、無水マ
レイン酸等と共重合し、けん化してえられるポリ
ビニルアルコール系重合体が好ましい。ポリビニ
ルアルコール系重合体の未けん化の残存ビニルエ
ステル単位はアルキルビニルエステルとの反応時
に使用される触媒のアルカリ化合物を消費するの
で、ビニルエステル単位のけん化度は高いことが
好ましく、80モル％以上が望ましい。またこれら
のポリビニルアルコールあるいはポリビニルアル
コール系共重合体の重合度はとくに限定されるも
のでないが、10〜10000好ましくは200以上であ
る。該重合体のアルキルビニルスルホキシドとの
反応時の形態は特に制限はなく、溶液状、溶融
状、粉末、フイルム、繊維、発泡体等どのような
ものでもよい。
アルキルビニルスルキシドとしては、メチルビ
ニルスルホキシド、エチルビニルスルホキシド、
ブチルビニルスルホキシド、シクロヘキシルビニ
ルスルホキシド、ベンジルビニルスルホキシドな
どの炭素数１〜10のアルキル基を有するアルキル
ビニルスルホキシドなどが好適なものとして挙げ
られるが、なかでもメチル、エチル、ブチルなど
の炭素数１〜４の低級アルキルビニルスルホキシ
ドが反応性がよく好ましい。ポリビニルアルコー
ル系重合体とアルキルビニルスルホキシドとの反
応は両物質が接触反応できる方式であればどのよ
うなものでもよく、特に制限はない。しかし通常
ポリビニルアルコール系重合体の水溶液中でアル
キルビニルスルホキシドと反応させる溶液法、ポ
リビニルアルコール系重合体が水不溶性の場合は
該重合体をアルキルビニルスルホキシド含有水該
液中に浸漬接触させ、反応する方法など、水系の
反応が反応速度も大きく好ましい。他にジオキサ
ン、テトラヒドロフラン、ジエチルエーテル、ア
セトン、ジメチルスルホキシド、ジメチルホルム
アミド、ホルムアミド等の極性溶媒も用いること
ができる。また反応を阻害しない程度ならば他の
溶媒を用いることもできる。
ポリビニルアルコール系重合体とアルキルビニ
ルスルホキシドとの反応は反応触媒としてアルカ
リ、通常アルカリ金属の水酸化物が使用され、特
に水酸化ナトリウム、水酸化カリウムが好まし
い。またアルカリ濃度はポリビニルアルコール系
重合体の水酸基に対してモル比で0.005〜５が、
望ましくは0.01〜３が好ましい。モル比0.005以
下では反応速度が小さく、またアルカリ量が多す
ぎると、ポリマーが分解したり、着色したりする
などの副反応が著しくおこり、好ましくない。ア
ルキルビニルスルホキシドの使用量はポリビニル
アルコール系重合体の水酸基に対しモル比で
0.001以上、好ましくは0.01以上である。アルキ
ルビニルスルホキシドの使用量の上限は特に制限
はないが、必要以上に多量に用いても、水酸基の
すべてを反応することは困難であり、通常モル比
で100以下で実施される。
反応温度および時間は目的とする反応率、反応
物質の形態保持性等を考慮して、適宜決められる
が、適当な反応速度と重合体の分解着色等の副反
応の観点から反応温度は20〜100℃、好ましくは
30〜85℃、反応時間は１分〜10時間、好ましくは
30分〜５時間である。反応後は通常未反応のアル
キルビニルスルホキシド、触媒等を洗浄等により
分離精製した後、乾燥することにより後処理され
る。
アルキルスルホキシド基の導入量は上述した反
応条件を調節することにより制御することができ
る。アルキルスルホキシド基の導入量はポリビニ
ルアルコール系重合体の水酸基の0.1モル％以上、
好ましくは１モル％以上、最高には５モル％以上
である。上限はとくに限定されないが、約80モル
％である。またポリビニルアルコール系重合体の
成形物の表面のみにアルキルスルホキシド基を導
入したい場合は成形物表面の水酸基に対して前記
と同様の量導入すればよい。
このようにして得られた変性ポリビニルアルコ
ール系重合体はガラスなどの無機物との接着性が
優れているので、これらの特性を生かした用途に
使用することができる。たとえば石膏ボード、ガ
ラス材料、ガラス繊維、ロツクウール、セラミツ
クスなどの無機物のバインダー、接着剤、被覆剤
として、さらにはセメントやモルタルの添加剤あ
るいは表面仕上剤として有効に使用できる。また
その他繊維用糊剤、繊維加工剤、紙の表面サイジ
ング剤、顔料コーテイング用のバインダー、抄紙
用内添剤、アミノ樹脂接着剤の改良剤、エマルジ
ヨンの保護コロイド、感光性樹脂、成形物（フイ
ルム、シート、パイプ、チユーブ、繊維など）、
木材、紙、アルミニウム箔、プラスチツクスなど
の接着剤、不織布用バインダーなどの用途にも使
用することができる。
また本発明の変性ポリビニルアルコール系重合
体は動物、植物の皮膚、表皮等への親和性、滲透
性にすぐれ、例えば透析膜等の医療材料や農薬の
展着剤あるいはバインダーとして有効であり、ま
た薬効成分を本発明の変性ポリビニルアルコール
系重合体と結合することにより、いわゆるポリマ
ードラツグとしても使用することができる。さら
にまた本発明の変性ポリビニルアルコール系重合
体は、ガス分離膜として好適に使用できるもので
あり、とりわけSO2ガスの選択透過性にすぐれ、
例えばSO2ガスとN2ガスの混合ガス中よりのSO2
ガスの選択分離性に極めてすぐれたものである。
以下実施例により本発明を具体的に説明する
が、本発明はこれに限定されるものではない。な
お部は特に指定しないかぎり重量部を示す。
実施例 １
撹拌器、温度計を付した反応容器中に重合度＝
1750、けん化度98.2モル％のポリビニルアルコー
ルの5.2％水溶液845部を入れ、撹拌下、60℃に昇
温した。これに10％水酸化ナトリウム水溶液400
部を加え（ポリビニルアルコールの水酸基に対し
水酸化ナトリウムモル比は1.0）、さらにメチルビ
ニルスルホキシド90部を添加した後、60℃で５時
間、撹拌下に反応させた。反応容器を外部より冷
却し、反応液を25℃に冷却した後、反応液を大量
のメタノール中に投入し、沈殿した変性重合体を
別した。該重合体をさらにメタノールで十分洗
浄することにより触媒および未反応のメチルビニ
ルスルホキシドを除去した後、70℃で５時間乾燥
した。えられた重合体の重量は55部であり、この
重合体の赤外吸収スペクトルには1010cm-1にスル
ホキシドに基づく吸収が認められ、また1100cm-1
にビニルアルコールの第２級アルコールに基づく
吸収が認められ、この重合体がメチルビニルスル
ホキシドで変性された変性ポリビニルアルコール
であることがわかつた。さらに該重合体を重水中
に溶解して、ブロトン核磁気共鳴スペクトル分析
したところ、ビニルアルコールの水酸基が減少
し、メチルスルホキシドのメチルプルトンの吸収
が2.5ppmに認められ、かつメチルビニルスルホ
キシドのビニル基のブロトンシグナルが認められ
ないことから反応は水酸基にメチルビニルスルホ
キシドのビニル基が付加反応してメチルスルホキ
シド基の導入された変性ポリビニルアルコールが
えられていることがわかつた。Ｓ元素分析の結果
からメチルスルホキシド単位の変性量は14.3モル
％（ビニルアルコール単位の変性モル％）である
ことがわかつた。
実施例 ２〜６
重合度1700、けん化度99.2モル％のポリビニル
アルコールの4.5％水溶液600部と５％の水酸化ナ
トリウム水溶液400部を反応容器に入れ、混合後、
60℃でメチルビニルスルホキシド量をポリビニル
アルコールの水酸基に対しモル比で0.5、1.0、
1.5、2.0、3.0と変えて反応したところ、表１に示
す変性量（導入量）の変性ポリビニルアルコール
がえられた。えられた変性ポリビニルアルコール
の５％水溶液を調整し、ガラス板上に乾燥後の皮
膜厚みが50μになるように流延し、室温で乾燥し
た。その後、20℃×65％RHで、７日以上調湿し
た後、皮膜にセロテープを張りつけ、補強した
後、巾２cmに切断し、ヘツドスピード100mm／分
で、90℃剥離し、その剥離応力を接着力として
ｇ／cm単位で測定した。表１に反応時のメチルビ
ニルスルホキシドの使用量（モル比）とメチルス
ルホキシド変性量およびガラス面に対する接着力
を示した。なお比較のために反応原料の未変性の
ポリビニルアルコールの接着力を対照例として示
した。この結果からメチルスルホキシドが導入変
性された変性ポリビニルアルコールはガラスに対
する接着力が大ですぐれていることがわかる。[Formula] (R is H or a methyl group, preferably H) unit, including homopolymers, ordinary copolymers, block copolymers,
It includes all polymers such as graft polymers, formals, and post-reacted polymers such as butyralized polymers. Among these, polyvinyl alcohol obtained by polymerizing and saponifying vinyl esters such as vinyl acetate, or copolymerizing vinyl esters such as vinyl acetate with comonomers such as ethylene, alkyl vinyl ether, methyl acrylate, itaconic acid, maleic anhydride, etc. However, polyvinyl alcohol polymers obtained by saponification are preferred. Since the unsaponified residual vinyl ester units of the polyvinyl alcohol polymer consume the alkali compound of the catalyst used in the reaction with the alkyl vinyl ester, it is preferable that the degree of saponification of the vinyl ester units is high, and 80 mol% or more. desirable. The degree of polymerization of these polyvinyl alcohols or polyvinyl alcohol copolymers is not particularly limited, but is 10 to 10,000, preferably 200 or more. The form of the polymer upon reaction with the alkyl vinyl sulfoxide is not particularly limited, and may be in any form such as a solution, melt, powder, film, fiber, or foam. Examples of alkyl vinyl sulfoxide include methyl vinyl sulfoxide, ethyl vinyl sulfoxide,
Suitable examples include alkyl vinyl sulfoxides having an alkyl group having 1 to 10 carbon atoms, such as butyl vinyl sulfoxide, cyclohexyl vinyl sulfoxide, and benzyl vinyl sulfoxide, among which 1 to 4 carbon atoms, such as methyl, ethyl, and butyl. Lower alkyl vinyl sulfoxides have good reactivity and are preferred. The reaction between the polyvinyl alcohol polymer and the alkyl vinyl sulfoxide is not particularly limited and may be carried out in any manner as long as both substances can undergo a catalytic reaction. However, usually, the solution method involves reacting a polyvinyl alcohol polymer with an alkyl vinyl sulfoxide in an aqueous solution, or when the polyvinyl alcohol polymer is water-insoluble, the polymer is immersed in contact with an alkyl vinyl sulfoxide-containing solution to react. Regarding the method, a water-based reaction is preferable because the reaction rate is high. In addition, polar solvents such as dioxane, tetrahydrofuran, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, and formamide can also be used. Other solvents can also be used as long as they do not inhibit the reaction. In the reaction between a polyvinyl alcohol polymer and an alkyl vinyl sulfoxide, an alkali, usually an alkali metal hydroxide, is used as a reaction catalyst, and sodium hydroxide and potassium hydroxide are particularly preferred. In addition, the alkali concentration is 0.005 to 5 in molar ratio to the hydroxyl group of the polyvinyl alcohol polymer.
It is preferably 0.01 to 3. If the molar ratio is less than 0.005, the reaction rate will be low, and if the amount of alkali is too large, side reactions such as polymer decomposition or coloring will occur, which is not preferable. The amount of alkyl vinyl sulfoxide used is the molar ratio to the hydroxyl group of the polyvinyl alcohol polymer.
It is 0.001 or more, preferably 0.01 or more. There is no particular upper limit to the amount of alkyl vinyl sulfoxide used, but even if it is used in an unnecessarily large amount, it is difficult to react all of the hydroxyl groups, and the reaction is usually carried out at a molar ratio of 100 or less. The reaction temperature and time are determined as appropriate, taking into consideration the desired reaction rate, shape retention of the reactants, etc., but from the viewpoint of an appropriate reaction rate and side reactions such as decomposition and coloring of the polymer, the reaction temperature should be set at 20 - 20°C. 100℃, preferably
30~85℃, reaction time 1 minute~10 hours, preferably
The duration is 30 minutes to 5 hours. After the reaction, the unreacted alkyl vinyl sulfoxide, catalyst, etc. are usually separated and purified by washing, etc., and then post-treated by drying. The amount of alkyl sulfoxide groups introduced can be controlled by adjusting the reaction conditions described above. The amount of alkyl sulfoxide groups introduced is 0.1 mol% or more of the hydroxyl groups of the polyvinyl alcohol polymer,
Preferably it is 1 mol% or more, and the maximum is 5 mol% or more. The upper limit is not particularly limited, but is about 80 mol%. If it is desired to introduce alkyl sulfoxide groups only onto the surface of a molded product of polyvinyl alcohol polymer, the same amount as above may be introduced to the hydroxyl groups on the surface of the molded product. The modified polyvinyl alcohol polymer thus obtained has excellent adhesion to inorganic materials such as glass, so it can be used in applications that take advantage of these properties. For example, it can be effectively used as a binder, adhesive, or coating agent for inorganic materials such as gypsum boards, glass materials, glass fibers, rock wool, and ceramics, and as an additive or surface finishing agent for cement and mortar. In addition, other fiber glues, fiber processing agents, surface sizing agents for paper, binders for pigment coating, internal additives for paper making, improvers for amino resin adhesives, protective colloids for emulsions, photosensitive resins, molded products (films, etc.) , sheets, pipes, tubes, fibers, etc.),
It can also be used as an adhesive for wood, paper, aluminum foil, plastics, etc., and as a binder for nonwoven fabrics. Furthermore, the modified polyvinyl alcohol polymer of the present invention has excellent affinity and permeability to the skin and epidermis of animals and plants, and is effective as a spreading agent or binder for medical materials such as dialysis membranes and agricultural chemicals. By combining a medicinal ingredient with the modified polyvinyl alcohol polymer of the present invention, it can also be used as a so-called polymer drug. Furthermore, the modified polyvinyl alcohol polymer of the present invention can be suitably used as a gas separation membrane, and has particularly excellent selective permeability for SO 2 gas,
For example, SO 2 from a mixed gas of SO 2 gas and N 2 gas
It has extremely excellent selective separation of gases. The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. Note that parts are by weight unless otherwise specified. Example 1 Polymerization degree =
1750, and 845 parts of a 5.2% aqueous solution of polyvinyl alcohol with a saponification degree of 98.2 mol% were added, and the temperature was raised to 60°C while stirring. Add to this 10% sodium hydroxide aqueous solution 400
After adding 90 parts of methyl vinyl sulfoxide (molar ratio of sodium hydroxide to hydroxyl group of polyvinyl alcohol: 1.0), the mixture was reacted at 60° C. for 5 hours with stirring. After the reaction vessel was cooled from the outside and the reaction solution was cooled to 25° C., the reaction solution was poured into a large amount of methanol, and the precipitated modified polymer was separated. The polymer was further thoroughly washed with methanol to remove the catalyst and unreacted methyl vinyl sulfoxide, and then dried at 70°C for 5 hours. The weight of the obtained polymer was 55 parts, and the infrared absorption spectrum of this polymer showed absorption based on sulfoxide at 1010 cm -1 and 1100 cm -1
Absorption based on the secondary alcohol of vinyl alcohol was observed, and it was found that this polymer was modified polyvinyl alcohol modified with methyl vinyl sulfoxide. Furthermore, when the polymer was dissolved in heavy water and subjected to broton nuclear magnetic resonance spectroscopy, it was found that the hydroxyl group of vinyl alcohol decreased, the absorption of methyl pluton of methyl sulfoxide was observed at 2.5 ppm, and the vinyl group of methyl vinyl sulfoxide Since no broton signal was observed, it was found that the reaction was an addition reaction of the vinyl group of methylvinyl sulfoxide to the hydroxyl group, yielding modified polyvinyl alcohol into which a methyl sulfoxide group was introduced. From the results of S elemental analysis, it was found that the amount of modification of methyl sulfoxide units was 14.3 mol % (mol % of modification of vinyl alcohol units). Examples 2 to 6 600 parts of a 4.5% aqueous solution of polyvinyl alcohol with a degree of polymerization of 1700 and a degree of saponification of 99.2 mol% and 400 parts of a 5% aqueous sodium hydroxide solution were placed in a reaction vessel, and after mixing,
At 60℃, the molar ratio of methyl vinyl sulfoxide to the hydroxyl group of polyvinyl alcohol was 0.5, 1.0,
When the reaction was carried out with different amounts of 1.5, 2.0, and 3.0, modified polyvinyl alcohols having the modified amounts (introduced amounts) shown in Table 1 were obtained. A 5% aqueous solution of the obtained modified polyvinyl alcohol was prepared and cast onto a glass plate so that the film thickness after drying was 50 μm, and dried at room temperature. Then, after conditioning the humidity at 20°C x 65% RH for more than 7 days, the film was reinforced with cellophane tape, cut into 2cm wide pieces, and peeled at 90°C at a head speed of 100mm/min to reduce the peeling stress. Adhesive strength was measured in units of g/cm. Table 1 shows the amount (mole ratio) of methyl vinyl sulfoxide used during the reaction, the amount of methyl sulfoxide modified, and the adhesive strength to the glass surface. For comparison, the adhesive strength of unmodified polyvinyl alcohol as a reaction raw material is shown as a control example. This result shows that modified polyvinyl alcohol, which has been modified by introducing methyl sulfoxide, has a large and excellent adhesive force to glass.
【表】
実施例 ７
実施例１のポリビニルアルコールの代りに、重
合度550、けん化度97.5モル％のポリビニルアル
コールを用いる以外は実施例１と同様の条件で、
メチルビニルスルホキシドを反応させたところ、
メチルスルホキシドの変性量が13.5モル％の変性
ポリビニルアルコールがえられた。
実施例８および９
実施例１の水酸化ナトリウムの使用量を水酸基
に対するモル比0.5（実施例８）および0.1（実施例
９）にする以外は実施例１と同じ条件で反応した
ところ、メチルスルホキシドの変性量が12.5モル
％（実施例８）および7.7モル％（実施例９）の
変性ポリビニルアルコールをえた。
実施例10および11
実施例１の反応温度を30℃（実施例10）および
75℃（実施例11）にする以外は実施例１と同様の
条件で反応し、メチルスルホキシドの変性量6.1
モル％（実施例10）、14.5モル％（実施例11）の
変性ポリビニルアルコールをえた。
実施例 12
エチレン含量50モル％、重合度800のエチレン
−ビニルアルコール共重合体フイルム５部を水酸
化カリウム２部、イソプロピルビニルスルホキシ
ド12部を含む水溶液50部中に浸漬し、50℃で１時
間加熱反応した。フイルムを反応終了後、取り出
し、メタノールで十分に洗浄、乾燥した後、全反
射赤外分析法により表面部分のイソプロピルスル
ホキシド単位変性量をもとめたところ12モル％で
あつた。
実施例 13
反応容器に重合度50、ケン化度92モル％のポリ
ビニルアルコールの30％水溶液150部に５％水酸
化ナトリウム水溶液800部を加え、その上にエチ
ルビニルスルホキシド200部を加え、60℃で１時
間反応した。実施例１と同様の後処理をして、エ
チルスルホキシドの変性量12モル％の変性ポリビ
ニルアルコールをえた。
実施例 14
実施例１のポリビニルアルコールの代りにイタ
コン酸含有量が２モル％のイタコン酸−ビニルア
ルコール共重合体（重合度1700、けん化度98.5モ
ル％）を用いる以外は実施例１と同様の条件で反
応を行ない、メチルスルホキシドの変性量が12.5
モル％の変性ポリビニルアルコール共重合体をえ
た。[Table] Example 7 The same conditions as in Example 1 were used except that polyvinyl alcohol with a degree of polymerization of 550 and a degree of saponification of 97.5 mol% was used instead of the polyvinyl alcohol of Example 1.
When methyl vinyl sulfoxide was reacted,
A modified polyvinyl alcohol with a modified amount of methyl sulfoxide of 13.5 mol% was obtained. Examples 8 and 9 When the reaction was carried out under the same conditions as in Example 1 except that the molar ratio of sodium hydroxide to the hydroxyl group was 0.5 (Example 8) and 0.1 (Example 9), methyl sulfoxide Modified polyvinyl alcohols with a modified amount of 12.5 mol% (Example 8) and 7.7 mol% (Example 9) were obtained. Examples 10 and 11 The reaction temperature in Example 1 was changed to 30°C (Example 10) and
The reaction was carried out under the same conditions as in Example 1 except that the temperature was 75°C (Example 11), and the amount of modification of methyl sulfoxide was 6.1.
Modified polyvinyl alcohol of 14.5 mol% (Example 11) and 14.5 mol% (Example 11) were obtained. Example 12 5 parts of an ethylene-vinyl alcohol copolymer film with an ethylene content of 50 mol% and a degree of polymerization of 800 was immersed in 50 parts of an aqueous solution containing 2 parts of potassium hydroxide and 12 parts of isopropyl vinyl sulfoxide, and the mixture was heated at 50°C for 1 hour. A heating reaction occurred. After the reaction was completed, the film was taken out, thoroughly washed with methanol, and dried.The amount of modification of isopropylsulfoxide units on the surface was determined by total reflection infrared analysis, and it was found to be 12 mol%. Example 13 800 parts of a 5% aqueous sodium hydroxide solution was added to 150 parts of a 30% aqueous solution of polyvinyl alcohol with a degree of polymerization of 50 and a degree of saponification of 92 mol% in a reaction vessel, and 200 parts of ethyl vinyl sulfoxide was added thereto, and the mixture was heated at 60°C. It reacted for 1 hour. The same post-treatment as in Example 1 was carried out to obtain a modified polyvinyl alcohol having a modified amount of ethyl sulfoxide of 12 mol%. Example 14 Same as Example 1 except that itaconic acid-vinyl alcohol copolymer with an itaconic acid content of 2 mol% (degree of polymerization 1700, degree of saponification 98.5 mol%) was used instead of the polyvinyl alcohol of Example 1. The reaction was carried out under the following conditions, and the amount of modification of methyl sulfoxide was 12.5
Mol% of modified polyvinyl alcohol copolymer was obtained.
Claims (1)
ニルスルホキシドを反応させることを特徴とする
アルキルスルホキシド基の導入された変性ポリビ
ニルアルコール系重合体の製法。 ２ アルキルビニルスルホキシドが炭素数１〜10
のアルキルビニルスルホキシドである特許請求の
範囲第１項記載の変性ポリビニルアルコール系重
合体の製法。 ３ アルキルビニルスルホキシドが炭素数１〜４
の低級アルキルビニルスルホキシドである特許請
求の範囲第１項記載の変性ポリビニルアルコール
系重合体の製法。 ４ 変性ポリビニルアルコール系重合体のアルキ
ルスルホキシド基の導入量が変性ポリビニルアル
コール系重合体の水酸基に対し0.1モル％以上で
ある特許請求の範囲第１項〜第３項記載の変性ポ
リビニルアルコール系重合体の製法。 ５ ポリビニルアルコール系重合体が、けん化度
80モル％以上のポリビニルアルコールである特許
請求の範囲第１項〜第４項記載の変性ポリビニル
アルコール系重合体の製法。 ６ ポリビニルアルコール系重合体が酢酸ビニル
−エチレン共重合体けん化物である特許請求の範
囲第１項〜第４項記載の変性ポリビニルアルコー
ル系重合体の製法。[Scope of Claims] 1. A method for producing a modified polyvinyl alcohol polymer into which an alkyl sulfoxide group has been introduced, which comprises reacting a polyvinyl alcohol polymer with an alkyl vinyl sulfoxide. 2 Alkyl vinyl sulfoxide has 1 to 10 carbon atoms
A method for producing a modified polyvinyl alcohol polymer according to claim 1, which is an alkyl vinyl sulfoxide. 3 Alkyl vinyl sulfoxide has 1 to 4 carbon atoms
A method for producing a modified polyvinyl alcohol polymer according to claim 1, which is a lower alkyl vinyl sulfoxide. 4. The modified polyvinyl alcohol polymer according to claims 1 to 3, wherein the amount of alkyl sulfoxide groups introduced into the modified polyvinyl alcohol polymer is 0.1 mol% or more based on the hydroxyl groups of the modified polyvinyl alcohol polymer. manufacturing method. 5 The degree of saponification of the polyvinyl alcohol polymer
A method for producing a modified polyvinyl alcohol polymer according to claims 1 to 4, wherein the polyvinyl alcohol contains 80 mol% or more. 6. The method for producing a modified polyvinyl alcohol polymer according to claims 1 to 4, wherein the polyvinyl alcohol polymer is a saponified vinyl acetate-ethylene copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9466983A JPS59219308A (en) | 1983-05-27 | 1983-05-27 | Production of modified polyvinyl alcohol polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9466983A JPS59219308A (en) | 1983-05-27 | 1983-05-27 | Production of modified polyvinyl alcohol polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59219308A JPS59219308A (en) | 1984-12-10 |
| JPH031322B2 true JPH031322B2 (en) | 1991-01-10 |
Family
ID=14116642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9466983A Granted JPS59219308A (en) | 1983-05-27 | 1983-05-27 | Production of modified polyvinyl alcohol polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59219308A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02102204A (en) * | 1988-10-11 | 1990-04-13 | Kuraray Co Ltd | Manufacture of sulfoxide group-containing polymer |
| JP3006112B2 (en) * | 1991-02-18 | 2000-02-07 | 日本ゼオン株式会社 | Magnetic recording medium, binder for magnetic powder used therefor, and method for producing binder resin for magnetic powder |
-
1983
- 1983-05-27 JP JP9466983A patent/JPS59219308A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59219308A (en) | 1984-12-10 |
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