JPS6150482B2 - - Google Patents
Info
- Publication number
- JPS6150482B2 JPS6150482B2 JP57017945A JP1794582A JPS6150482B2 JP S6150482 B2 JPS6150482 B2 JP S6150482B2 JP 57017945 A JP57017945 A JP 57017945A JP 1794582 A JP1794582 A JP 1794582A JP S6150482 B2 JPS6150482 B2 JP S6150482B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- weight
- hydrosol
- water
- particles
- 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 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 22
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- -1 hydroxyalkyl acrylates Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 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
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000008131 herbal destillate Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- LGHIWNMQZBIHOB-UHFFFAOYSA-N 2-prop-2-enoyloxy-1h-naphthalene-2-sulfonic acid Chemical compound C1=CC=C2C=CC(S(=O)(=O)O)(OC(=O)C=C)CC2=C1 LGHIWNMQZBIHOB-UHFFFAOYSA-N 0.000 description 1
- YVGWMNRYRLGBNQ-UHFFFAOYSA-N 2-prop-2-enoyloxybenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1OC(=O)C=C YVGWMNRYRLGBNQ-UHFFFAOYSA-N 0.000 description 1
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100172879 Caenorhabditis elegans sec-5 gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Description
この発明はヒドロゾルつまり粒子径0.01〜0.1
μｍの重合体粒子が水中に安定に分散された分散
体の新しい製造方法、とくに溶剤その他の媒体お
よび未反応物をほとんど含まない比較的高分子量
の重合体固形物をヒドロゾル化することを特徴と
する新規な製造方法に関する。
従来、ヒドロゾルの製造方法としては、たとえ
ば特公昭46―22343号公報、特開昭50―19842号公
報などにみられる如く、エマルジヨン重合法によ
り得たカルボキシル基を有する重合体粒子（粒径
約0.3〜0.7μｍ）を苛性カリ、苛性ソーダ、水酸
化アンモニウムなどのアルカリを用いて高速撹拌
下粒子表面を削り取り、粒径約0.01〜0.1μｍの
微細粒子にするという、いわゆるストリツパブル
の手法が一般的に採用されてきた。
ところが、上記従来法によると、ヒドロゾル中
に乳化剤が混入してくるため、これより得られる
塗膜その他の成形物の耐水性が悪くなる。また、
ヒドロゾル化しうる重合体の分子量に制限があ
り、一般に重量平均分子量が104（１万）以上に
なるとヒドロゾル化が難しくなる。このため、各
種用途への応用面で自ずと限界を生じ、主に塗料
分野や紙サイズ処理分野への応用展開しか計れな
かつた。
そこで、この発明者らは先に、無溶剤ないし少
量の溶剤の存在下で分子内に酸性基を有する共重
合体を合成し、これにアルカリと水とを加えてヒ
ドロゾルを得る方法を提案した。この方法によれ
ば、乳化剤を使用していないので得られる塗膜の
耐水性が優れるという利点がある。
この発明は、上記提案法をさらに改良してヒド
ロゾル化をより容易にしてかつ分散液の安定性を
いつそう高めたヒドロゾルの製造方法に係り、そ
の要旨とするところは、酸性基を有する不飽和単
量体２〜20重量％とこれと共重合可能な他の不飽
和単量体98〜80重量％とからなる重量平均分子量
104〜106の共重合体を合成した後、末反応物と溶
剤その他の媒体とを除去して実質的に末反応物お
よび媒体を含まぬ固形物を調製し、これにアルカ
リないしアルカリ水溶液を加えて上記共重合体分
子中の酸性基の一部または全部を中和、その後さ
らに水を加えて転相させることにより、上記共重
合体が平均粒子径0.01〜0.1μｍの範囲で安定に
分散されたヒドロゾルを得ることを特徴とするヒ
ドロゾルの製造方法にある。
すなわち、この発明者らは、バルク重合法、溶
液重合法、乳化重合法等の任意の公知重合法によ
つて酸性基を有する共重合体で比較的分子量が高
いものを得て、この共重合体より有機溶剤、水等
の媒体および末反応のモノマーを除去した固形物
から上記共重合体が水中に安定に分散されて乳化
剤や安定剤を含まないヒドロゾルを得ることに成
功したものである。
この発明法によれば、既述提案法による場合に
比較して公知の重合法を広く適用できるためヒド
ロゾル化がより容易で、また未反応物の除去によ
つてヒドロゾル化後の分散液が非常に安定し、粘
度も比較的低くなる。また、乳化剤を含まぬため
にこれを塗膜その他の成形物としたとき、従来法
に比べてはるかに改善された耐水性を示し、ま
た、重合体の分子量が比較的高いものであること
から各種物理特性も良好で、一般の有機溶剤溶液
から形成される塗膜などと変らないすぐれた性能
を発揮する。このため、従来のヒドロゾルよりも
応用範囲が広くなり、塗料や紙サイズ処理剤はも
ちろん、粘着剤、接着剤、オーバーコート剤、外
装材、内装材、包装材、フイルムなどの各種分野
に極めて有効に適用することができる。
この発明において、まず、溶液重合法、乳化重
合法、パール重合法、バルク重合法などの従来公
知の方法により、酸性基を有する不飽和単量体２
〜20重量％とこれに共重合可能な他の不飽和単量
体80〜98重量％とからなる重量平均分子量104〜
106の共重合体を合成する。その後、それぞれの
重合法に応じて使用した有機溶剤や水等の媒体お
よび未反応のモノマーを除去し、実質的に媒体と
未反応物を含まぬ固形物とする。すなわち、溶液
重合法、バルク重合法では蒸留などの手段によつ
て有機溶剤と未反応物を除き、乳化重合法では塩
析によつて凝固分離することによつて水分と未反
応物を除き、またパール重合法では粒状の共重合
体をろ取することによつて水分と未反応物から分
離する。なお、乳化重合法やパール重合法では重
合時に用いた乳化剤が重合体粒子の表面に一部付
着してくるが、この乳化剤は上記の除去操作時に
除かれ、また必要なら洗浄を行なつて除去すれば
よい。
単量体成分中とくに重要な酸性基を有する不飽
和単量体としては、たとえばアクリル酸、メタク
リル酸、クロトン酸、イタコン酸、マレイン酸、
フマル酸などの酸性基としてカルボキシル基を有
する不飽和カルボン酸、スチレンスルホン酸、ア
リルスルホン酸、スルホプロピルアクリレート、
２―アクリロイルオキシナフタレン―２―スルホ
ン酸、２―メタクリロイルオキシナフタレン―２
―スルホン酸、２―アクリルアミド―２―メチル
プロパンスルホン酸、２―アクリロイルオキシベ
ンゼンスルホン酸などの酸性基としてスルホン酸
を有する不飽和スルホン酸などを挙げることがで
き、またその他の酸性基を有するものであつても
よく、これらの１種もしくは２種以上を使用す
る。
上記不飽和単量体の使用量は、全単量体中２〜
20重量％とする必要があり、たとえば不飽和カル
ボン酸の場合とくに好適には５〜15重量％、ま
た、不飽和スルホン酸の場合とくに好適には３〜
10重量％である。この使用量が２重量％に満たな
いかあるいは20重量％を越えてしまうと、いずれ
もヒドロゾル化に好結果が得られない。
このような不飽和単量体と併用される共重合可
能な他の不飽和単量体としては、各種のエチレン
性不飽和単量体のなかから任意に選択できる。た
とえばアルキル基の炭素数１〜15、とくに好適に
は３〜10のアクリル酸エステルやメタクリル酸エ
ステル、その他ビニルエーテル、ビニルエステ
ル、アクリロニトリル、アクリルアミド、ヒドロ
キシアルキルアクリレート、スチレン、塩化ビニ
ル、エチレン、分子内にアミノ基の如き官能基を
有するエチレン性不飽和単量体などを挙げること
ができ、用途目的に応じてその１種または２種以
上を選択して使用する。
この発明において、種々の重合法によつて合成
される酸性基を有する共重合体はその重量平均分
子量が104〜106の範囲に設定されていることが必
要である。この理由はつぎのとおりであり、104
に満たない場合は、塗膜その他の成形物としたと
きの物性、たとえば凝集力や物理的強度などに劣
り、また106を越えるようでは高粘度となつてそ
のごのアルカリ処理に支障をきたし、ヒドロゾル
を生成しにくくなるからである。
この発明においては、つぎに、上述の如き分子
量を有してかつ媒体および未反応物を含まぬ固形
物とした共重合体に、必要ならばヒドロゾル化を
容易にするためにメタノール、エタノール、ｎ―
プロパノール、イソプロピルアルコール、sec―
ブタノールなどのアルコール系水溶性溶媒を添加
した後、撹拌下、アルカリないしアルカリ水溶液
を加えて中和処理する。このときの処理温度は共
重合体の種類、性状に応じて一定温度下に保たれ
るが、一般には40〜95℃である。中和処理に用い
るアルカリないしアルカリ水溶液としては、アン
モニア、アンモニア水、苛性ソーダ、苛性カリな
どの苛性アルカリの水溶液などがあり、通常共重
合体のカルボキシル基やスルホン基の如き酸性基
に対して約1/50〜２当量の割合で使用すればよ
い。
このように中和処理したのち、さらに撹拌を続
けてよく混合しながら、水を徐々に加えていく
と、一定時間ごにいわゆる転相現象がおこり、水
が連続層となりこのなかに共重合体粒子が分散さ
れたＯ／Ｗ型の分散体が生成する。この分散体生
成ご、さらに必要量の水を徐々に添加し、分散体
の粘度と固形分濃度を調節する。この粘度は一般
に25℃で30〜1000ポイズであり、また固形分濃度
は通常10〜60重量％である。
かくして得られる分散体は、分散粒子である共
重合体の平均粒子径が0.01〜0.1μｍとされ、こ
の共重合体粒子が水中に均一にかつ安定に分散さ
れたヒドロゾルであり、これを単独であるいは架
橋剤などを加えて担体上に流延し乾燥して塗膜化
したときに、またその他の成形物に硬化成形した
ときに、前述のとおりのすぐれた性能を発揮す
る。
以下に、この発明の実施例を記載する。なお、
以下において、部とあるは重量部を意味する。
実施例 １
メタクリル酸ｎ―ブチル 60ｇ
アクリル酸エチル 60ｇ
メタクリル酸 15ｇ
アゾビスイソブチロニトリル 0.15ｇ
ベンゼン 200ｇ
上記原料組成物を１のフラスコに仕込み、撹
拌しながら65℃で４時間反応させ、重量平均分子
量３×105（GPCによる）の共重合体を合成し
た。この重合反応物から減圧蒸留によつてトルエ
ンおよび未反応のモノマーを留去した。
つぎに、この共重合体のカルボキシル基に対し
て1/4当量の苛性ソーダ水溶液（20重量％）を加
えて80℃の温度下で中和処理し、その後さらに撹
拌しながら共重合体100部に対して250部の水を約
２時間要して徐々に滴下すると、55部の水を加え
た時点で連続相が水となる転相現象が生じ、最終
的に半透明のヒドロゾルが得られた。
このようにして得られたヒドロゾルは、その粘
度（25℃）が100ポイズ、固形分濃度が29重量％
で、平均粒子径が0.06μｍ（ナノサイザーによ
る）であつた。このヒドロゾルを、75μｍ厚のポ
リエステルフイルム上に流延し、110℃で10分間
加熱乾燥を行なつて、50μｍ厚の皮膜を形成し
た。この皮膜の耐水性およびその他の特性を調べ
た結果はつぎの第１表に示されるとおりであつ
た。
This invention is a hydrosol, that is, a particle size of 0.01 to 0.1.
A new method for producing a dispersion in which μm polymer particles are stably dispersed in water, in particular, it is characterized by hydrosolizing a relatively high-molecular-weight polymer solid containing almost no solvent or other medium and unreacted substances. This invention relates to a new manufacturing method. Conventionally, methods for producing hydrosols include polymer particles having carboxyl groups (particle size of approximately 0.3 The so-called strippable method is generally adopted, in which the surface of the particles (~0.7 μm) is scraped off under high-speed stirring using an alkali such as caustic potash, caustic soda, or ammonium hydroxide to form fine particles with a particle size of approximately 0.01 to 0.1 μm. It's here. However, according to the above conventional method, since the emulsifier is mixed into the hydrosol, the water resistance of coating films and other molded products obtained from the hydrosol becomes poor. Also,
There is a limit to the molecular weight of polymers that can be hydrosolized, and generally, when the weight average molecular weight is 10 4 (10,000) or more, hydrosolization becomes difficult. For this reason, there was a natural limit in terms of application to various uses, and applications could only be developed mainly in the paint field and paper size processing field. Therefore, the inventors first proposed a method to obtain a hydrosol by synthesizing a copolymer having an acidic group in the molecule without a solvent or in the presence of a small amount of solvent, and then adding an alkali and water to this copolymer. . This method has the advantage that the resulting coating film has excellent water resistance because no emulsifier is used. This invention relates to a method for producing a hydrosol that further improves the proposed method to facilitate hydrosolization and further improves the stability of the dispersion. Weight average molecular weight consisting of 2 to 20% by weight of monomer and 98 to 80% by weight of other unsaturated monomers copolymerizable with this monomer
After synthesizing the copolymer of 10 4 to 10 6 , the final reactant and the solvent or other medium are removed to prepare a solid material substantially free of the final reactant and the medium, and this is treated with an alkali or an alkaline aqueous solution. By adding water to neutralize some or all of the acidic groups in the copolymer molecules, and then further adding water for phase inversion, the copolymer becomes stable with an average particle size in the range of 0.01 to 0.1 μm. A method for producing a hydrosol, which is characterized by obtaining a dispersed hydrosol. That is, the inventors obtained a copolymer having a relatively high molecular weight with an acidic group by any known polymerization method such as a bulk polymerization method, a solution polymerization method, or an emulsion polymerization method. The above-mentioned copolymer was stably dispersed in water from the solid material from which the organic solvent, medium such as water, and terminally reacted monomers were removed from the coalescence, and a hydrosol containing no emulsifier or stabilizer was successfully obtained. According to the method of the present invention, known polymerization methods can be widely applied compared to the previously proposed method, making hydrosolization easier, and the dispersion after hydrosolization is much easier due to the removal of unreacted substances. stable and has a relatively low viscosity. In addition, since it does not contain an emulsifier, when it is used as a coating film or other molded product, it exhibits much improved water resistance compared to conventional methods, and because the polymer has a relatively high molecular weight, It also has good physical properties and exhibits the same excellent performance as coatings formed from general organic solvent solutions. Therefore, it has a wider range of applications than conventional hydrosols, and is extremely effective in various fields such as paints and paper sizing agents, as well as adhesives, adhesives, overcoating agents, exterior materials, interior materials, packaging materials, and films. It can be applied to In this invention, first, an unsaturated monomer 2 having an acidic group is prepared by a conventionally known method such as a solution polymerization method, an emulsion polymerization method, a pearl polymerization method, a bulk polymerization method, etc.
A weight average molecular weight of 104 to 20% by weight and 80 to 98% by weight of other unsaturated monomers that can be copolymerized therewith.
Synthesize a copolymer of 10 6 . Thereafter, a medium such as an organic solvent or water used according to each polymerization method and unreacted monomers are removed to obtain a solid material substantially free of medium and unreacted substances. That is, in the solution polymerization method and the bulk polymerization method, the organic solvent and unreacted materials are removed by means such as distillation, and in the emulsion polymerization method, water and unreacted materials are removed by solidifying and separating by salting out. In the pearl polymerization method, the particulate copolymer is separated from water and unreacted substances by filtering it. In addition, in the emulsion polymerization method and pearl polymerization method, the emulsifier used during polymerization partially adheres to the surface of the polymer particles, but this emulsifier is removed during the removal operation described above, and if necessary, it can be removed by washing. do it. Among the monomer components, unsaturated monomers having particularly important acidic groups include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid,
Unsaturated carboxylic acids having a carboxyl group as an acidic group such as fumaric acid, styrene sulfonic acid, allyl sulfonic acid, sulfopropyl acrylate,
2-acryloyloxynaphthalene-2-sulfonic acid, 2-methacryloyloxynaphthalene-2
Examples include unsaturated sulfonic acids having sulfonic acid as acidic groups, such as sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-acryloyloxybenzenesulfonic acid, and other acids having acidic groups. One or more of these may be used. The amount of the above unsaturated monomer used is 2 to 20% of the total monomers.
For example, in the case of unsaturated carboxylic acids, it is particularly preferably 5 to 15% by weight, and in the case of unsaturated sulfonic acids, it is particularly preferably 3 to 15% by weight.
It is 10% by weight. If the amount used is less than 2% by weight or more than 20% by weight, good results cannot be obtained in hydrosolization. Other copolymerizable unsaturated monomers used in combination with such unsaturated monomers can be arbitrarily selected from various ethylenically unsaturated monomers. For example, an alkyl group having 1 to 15 carbon atoms, preferably 3 to 10 carbon atoms, acrylic esters and methacrylic esters, other vinyl ethers, vinyl esters, acrylonitrile, acrylamide, hydroxyalkyl acrylates, styrene, vinyl chloride, ethylene, etc. Examples include ethylenically unsaturated monomers having a functional group such as an amino group, and one or more of them are selected and used depending on the purpose of use. In this invention, it is necessary that the weight average molecular weight of the acidic group-containing copolymer synthesized by various polymerization methods is set in the range of 10 4 to 10 6 . The reason for this is as follows, 10 4
If it is less than 10 6 , the physical properties such as cohesive force and physical strength will be poor when used as a coating or other molded product, and if it exceeds 10 6 , the viscosity will be high and will interfere with the alkaline treatment. This is because it becomes difficult to generate hydrosol. In this invention, the copolymer having the molecular weight as described above and containing no medium or unreacted substances is mixed with methanol, ethanol, n-ethanol, etc., if necessary, in order to facilitate hydrosolization. ―
Propanol, isopropyl alcohol, sec-
After adding an alcohol-based water-soluble solvent such as butanol, an alkali or an aqueous alkali solution is added while stirring for neutralization. The treatment temperature at this time is kept at a constant temperature depending on the type and properties of the copolymer, but is generally 40 to 95°C. The alkali or alkaline aqueous solution used for the neutralization treatment includes ammonia, aqueous ammonia, caustic soda, caustic alkali aqueous solution such as caustic potash, etc., and usually has a concentration of about 1/2 with respect to acidic groups such as carboxyl groups and sulfonic groups of the copolymer. It may be used at a ratio of 50 to 2 equivalents. After this neutralization treatment, if water is gradually added while stirring and mixing well, a so-called phase inversion phenomenon will occur at regular intervals, and the water will form a continuous layer, in which the copolymer will be formed. An O/W type dispersion in which particles are dispersed is produced. After this dispersion is produced, a necessary amount of water is gradually added to adjust the viscosity and solid content concentration of the dispersion. The viscosity is generally 30 to 1000 poise at 25°C, and the solids concentration is usually 10 to 60% by weight. The dispersion thus obtained is a hydrosol in which the copolymer particles as dispersed particles have an average particle diameter of 0.01 to 0.1 μm, and the copolymer particles are uniformly and stably dispersed in water. Alternatively, when a crosslinking agent or the like is added, the composition is cast onto a carrier and dried to form a coating film, or when it is cured and molded into other molded articles, it exhibits the excellent performance as described above. Examples of this invention will be described below. In addition,
In the following, parts mean parts by weight. Example 1 n-butyl methacrylate 60g ethyl acrylate 60g methacrylic acid 15g azobisisobutyronitrile 0.15g benzene 200g The above raw material composition was placed in flask 1, reacted at 65°C for 4 hours with stirring, and the weight average A copolymer with a molecular weight of 3×10 5 (according to GPC) was synthesized. Toluene and unreacted monomers were distilled off from this polymerization reaction product by vacuum distillation. Next, 1/4 equivalent of a caustic soda aqueous solution (20% by weight) was added to the carboxyl groups of this copolymer to neutralize it at a temperature of 80°C, and then 100 parts of the copolymer was added with further stirring. However, when 250 parts of water was gradually added dropwise over a period of about 2 hours, a phase inversion phenomenon occurred in which the continuous phase became water when 55 parts of water was added, and a translucent hydrosol was finally obtained. . The hydrosol thus obtained has a viscosity (at 25°C) of 100 poise and a solids concentration of 29% by weight.
The average particle diameter was 0.06 μm (according to Nanosizer). This hydrosol was cast onto a 75 μm thick polyester film and heated and dried at 110° C. for 10 minutes to form a 50 μm thick film. The results of examining the water resistance and other properties of this film are shown in Table 1 below.
【表】【table】
【表】
参考例
実施例１にて合成しかつ合成後トルエンおよび
未反応のモノマーを留去した共重合体100部を１
のフラスコに入れ、この共重合体のカルボキシ
ル基に対して1/4当量の苛性ソーダ水溶液（20重
量％）と共重合体100部に対して250部の水を同時
に加え、80℃の温度にて２時間強力に撹拌したと
ころ、撹拌の剪断力により共重合体が分断されて
米粒大の粒子が生成し、この粒子が水中に浮遊し
た混濁液となつた。しかし、撹拌をやめると上記
の粒子はすぐに沈澱し、共重合体沈澱物と透明な
水相との２相に分離し、分離した共重合体粒子は
すぐに自己ゆう着した。
このように、共重合体とアルカリ水溶液とを一
度に加熱混合する方法では、共重合体が水中にコ
ロイド状粒子として安定に分散した水分散体を得
ることはできなかつた。
実施例 ２
アクリル酸ｎ―オクチル 65ｇ
メタクリル酸メチル 35ｇ
メタクリル酸 10ｇ
ラウリルメルカプタン 0.15ｇ
ポリオキシエチレンアルキルフエノールエーテ
ル ３ｇ
水 160ｇ
上記組成物を１のフラスコに仕込み、撹拌し
ながら70℃に加熱し、その後、過硫酸カリウム
0.1ｇを５ｇの水に溶解した重合開始剤溶液を加
え、70℃で３時間反応させ、重量平均分子量5.2
×105（GPCによる）の共重合体エマルジヨンを
合成した。この共重合体エマルジヨンを塩析し、
沈殿した共重合体を過、水洗乾燥した。
つぎに、この共重合体のカルボキシル基に対し
て1/4当量のアンモニア水溶液（25重量％）を加
えて80℃の温度下で中和処理し、その後、さらに
撹拌しながら共重合体100部に対して250部の水を
約２時間要して徐々に滴下したところ、83部の水
を加えた時点で連続相が水となる転相現象が生
じ、最終的に半透明のヒドロゾルを得た。
このようにして得られたヒドロゾルは、その粘
度（25℃）が150ポイズ、固形分濃度が30重量％
で、平均粒子径が0.05μｍであつた。このヒドロ
ゾルを用いて、以下実施例１にしたがつて皮膜を
作成し、実施例１と同様に特性評価を行なつた結
果は、後記の第２表に示されるとおりであつた。
実施例 ３
アクリル酸ｎ―ブチル 65ｇ
アクリル酸メチル 35ｇ
アクリル酸 ７ｇ
ベンゾイルパーオキサイド 0.1ｇ
４×10-4重量％のポリビニルアルコール水溶液
250ｇを１のフラスコに仕込み、上記原料組成
物を加えて撹拌しながら70℃で４時間反応させ重
量平均分子量6.5×105（GPCによる）の共重合体
で平均粒子径１mmのパール粒子を得た。この共重
合体粒子を過、水洗、乾燥した。
つぎに、この共重合体100部に対して15部のｎ
―プロピルアルコールを添加して充分に溶解させ
た後、実施例１と同様にして半透明のヒドロゾル
を得た。
このようにして得られたヒドロゾルは、その粘
度（25℃）が170ポイズ、固形分濃度が29重量％
で、平均粒子径が0.05μｍであつた。このヒドロ
ゾルを用いて、以下実施例１にしたがつて皮膜を
形成し、実施例１と同様に特性評価を行なつた結
果は、後記の第２表に示されるとおりであつた。
実施例 ４
アクリル酸ｎ―オクチル 65ｇ
メタクリル酸メチル 35ｇ
アクリル酸 10ｇ
ベンゾイルパーオキサイド 0.2ｇ
sec―ブタノール ５ｇ
上記組成のうち、モノマー混合物10ｇとsec―
ブタノール５ｇとを１のフラスコに仕込み、撹
拌しながら80℃に加熱し、次いで残りのモノマー
混合物を約２時間で滴下し、重量平均分子量5.0
×105（GPCによる）の共重合体を合成した。こ
の共重合体から蒸留によつて未反応のモノマー成
分とsec―ブタノールを留去した。つぎにこの共
重合体より実施例２と同様にして半透明のヒドロ
ゾルを得た。
このようにして得られたヒドロゾルは、その粘
度（25℃）が200ポイズ、固形分濃度が31重量％
で、平均粒子径が0.07μｍであつた。このヒドロ
ゾルを用いて実施例１に従つて皮膜を形成し、実
施例１と同様に特性評価を行なつた結果は、次の
第２表の通りであつた。[Table] Reference example: 100 parts of the copolymer synthesized in Example 1 and with toluene and unreacted monomers distilled off after synthesis.
into a flask, add 1/4 equivalent of a caustic soda aqueous solution (20% by weight) to the carboxyl group of this copolymer, and 250 parts of water to 100 parts of the copolymer at a temperature of 80°C. When the mixture was vigorously stirred for 2 hours, the copolymer was fragmented by the shear force of the stirring to form particles the size of rice grains, which became a turbid liquid in which the particles were suspended in water. However, when the stirring was stopped, the particles immediately precipitated and separated into two phases, a copolymer precipitate and a transparent aqueous phase, and the separated copolymer particles immediately self-agglomerated. As described above, by the method of heating and mixing the copolymer and the alkaline aqueous solution at once, it has not been possible to obtain an aqueous dispersion in which the copolymer is stably dispersed in water as colloidal particles. Example 2 65 g of n-octyl acrylate 35 g of methyl methacrylate 10 g of methacrylic acid 0.15 g of lauryl mercaptan 3 g of polyoxyethylene alkyl phenol ether 160 g of water The above composition was placed in flask 1, heated to 70°C with stirring, and then, potassium persulfate
A polymerization initiator solution of 0.1g dissolved in 5g of water was added and reacted at 70°C for 3 hours, resulting in a weight average molecular weight of 5.2.
A copolymer emulsion of ×10 5 (by GPC) was synthesized. Salting out this copolymer emulsion,
The precipitated copolymer was filtered, washed with water and dried. Next, 1/4 equivalent of ammonia aqueous solution (25% by weight) was added to the carboxyl group of this copolymer to neutralize it at a temperature of 80°C, and then 100 parts of the copolymer was added while stirring. When 250 parts of water was gradually added dropwise over a period of about 2 hours, a phase inversion phenomenon occurred in which the continuous phase became water when 83 parts of water was added, and a translucent hydrosol was finally obtained. Ta. The hydrosol thus obtained has a viscosity (25°C) of 150 poise and a solid content concentration of 30% by weight.
The average particle diameter was 0.05 μm. Using this hydrosol, a film was prepared according to Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results were as shown in Table 2 below. Example 3 n-Butyl acrylate 65g Methyl acrylate 35g Acrylic acid 7g Benzoyl peroxide 0.1g 4 x 10 -4 % by weight polyvinyl alcohol aqueous solution
250 g was placed in flask 1, and the above raw material composition was added and reacted at 70°C for 4 hours with stirring to obtain pearl particles with a weight average molecular weight of 6.5 x 10 5 (according to GPC) and an average particle size of 1 mm. Ta. The copolymer particles were filtered, washed with water, and dried. Next, 15 parts of n per 100 parts of this copolymer.
- After adding propyl alcohol and sufficiently dissolving it, a translucent hydrosol was obtained in the same manner as in Example 1. The hydrosol thus obtained has a viscosity (25°C) of 170 poise and a solids concentration of 29% by weight.
The average particle diameter was 0.05 μm. Using this hydrosol, a film was formed according to Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results were as shown in Table 2 below. Example 4 N-octyl acrylate 65g Methyl methacrylate 35g Acrylic acid 10g Benzoyl peroxide 0.2g sec-butanol 5g Among the above compositions, 10g of monomer mixture and sec-
5 g of butanol was charged into flask 1, heated to 80°C while stirring, and then the remaining monomer mixture was added dropwise over about 2 hours.The weight average molecular weight was 5.0.
A copolymer of ×10 5 (by GPC) was synthesized. Unreacted monomer components and sec-butanol were removed from this copolymer by distillation. Next, a translucent hydrosol was obtained from this copolymer in the same manner as in Example 2. The hydrosol obtained in this way has a viscosity (at 25°C) of 200 poise and a solid content concentration of 31% by weight.
The average particle diameter was 0.07 μm. A film was formed using this hydrosol according to Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2 below.
【表】
以上の試験結果から明らかなように、この発明
法により得たヒドロゾルによれば、耐水性にすぐ
れる皮膜を形成でき、また皮膜の機械的特性も充
分に満足できるものであることが判る。[Table] As is clear from the above test results, the hydrosol obtained by the method of this invention can form a film with excellent water resistance, and the mechanical properties of the film are also sufficiently satisfactory. I understand.
Claims (1)
これと共重合可能な他の不飽和単量体98〜80重量
％とからなる重量平均分子量104〜106の共重合体
を合成した後、未反応物もしくは未反応物と媒体
とを除去して実質的に未反応物および媒体を含ま
ぬ固形物を調製し、これにアルカリないしアルカ
リ水溶液を加えて上記共重合体分子中の酸性基の
一部または全部を中和し、その後さらに水を加え
て転相させることにより、上記共重合体が平均粒
子径0.01〜0.1μｍの範囲で安定に分散されたヒ
ドロゾルを得ることを特徴とするヒドロゾルの製
造方法。1 A copolymer with a weight average molecular weight of 10 4 to 10 6 consisting of 2 to 20% by weight of an unsaturated monomer having an acidic group and 98 to 80% by weight of another unsaturated monomer that can be copolymerized with this. After the synthesis, unreacted substances or unreacted substances and the medium are removed to prepare a solid substance substantially free of unreacted substances and medium, and an alkali or aqueous alkali solution is added to this to form a solid substance in the copolymer molecules. By neutralizing some or all of the acidic groups of the copolymer and then further adding water for phase inversion, it is possible to obtain a hydrosol in which the above copolymer is stably dispersed with an average particle size in the range of 0.01 to 0.1 μm. Characteristic method for producing hydrosol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1794582A JPS58136647A (en) | 1982-02-07 | 1982-02-07 | Production of hydrosol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1794582A JPS58136647A (en) | 1982-02-07 | 1982-02-07 | Production of hydrosol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58136647A JPS58136647A (en) | 1983-08-13 |
| JPS6150482B2 true JPS6150482B2 (en) | 1986-11-05 |
Family
ID=11957908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1794582A Granted JPS58136647A (en) | 1982-02-07 | 1982-02-07 | Production of hydrosol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58136647A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3159550B2 (en) * | 1992-12-10 | 2001-04-23 | ライオン株式会社 | Process for producing self-dispersing, salt-sensitive polymers |
| JP5944798B2 (en) * | 2012-09-05 | 2016-07-05 | ジャパンコーティングレジン株式会社 | Aqueous dispersion and floor brightener using the same |
| JP2016106172A (en) * | 2016-03-23 | 2016-06-16 | ジャパンコーティングレジン株式会社 | Aqueous dispersion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4936942A (en) * | 1972-08-26 | 1974-04-05 | ||
| JPS5536281A (en) * | 1978-09-08 | 1980-03-13 | Sanyo Chem Ind Ltd | Agent for imparting high electric resistance |
| JPS55135174A (en) * | 1979-04-09 | 1980-10-21 | Mitsui Petrochem Ind Ltd | Aqueous dispersion composition for coating |
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1982
- 1982-02-07 JP JP1794582A patent/JPS58136647A/en active Granted
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4936942A (en) * | 1972-08-26 | 1974-04-05 | ||
| JPS5536281A (en) * | 1978-09-08 | 1980-03-13 | Sanyo Chem Ind Ltd | Agent for imparting high electric resistance |
| JPS55135174A (en) * | 1979-04-09 | 1980-10-21 | Mitsui Petrochem Ind Ltd | Aqueous dispersion composition for coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58136647A (en) | 1983-08-13 |
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