JPS6129601B2 - - Google Patents
Info
- Publication number
- JPS6129601B2 JPS6129601B2 JP12900480A JP12900480A JPS6129601B2 JP S6129601 B2 JPS6129601 B2 JP S6129601B2 JP 12900480 A JP12900480 A JP 12900480A JP 12900480 A JP12900480 A JP 12900480A JP S6129601 B2 JPS6129601 B2 JP S6129601B2
- Authority
- JP
- Japan
- Prior art keywords
- emulsion polymerization
- parts
- weight
- emulsion
- polymerization
- 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
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000010556 emulsion polymerization method Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 17
- 239000000839 emulsion Substances 0.000 description 14
- -1 alkyl ether sulfates Chemical class 0.000 description 13
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 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
- 229920003169 water-soluble polymer Polymers 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002675 Polyoxyl 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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 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
- 150000005673 monoalkenes Chemical class 0.000 description 1
- ISGLTJLASMFGMP-UHFFFAOYSA-N octoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCOC1=CC=CC=C1 ISGLTJLASMFGMP-UHFFFAOYSA-N 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は耐水性の著しく改善された皮膜（フイ
ルム）の形成に好適なエマルジヨンを製造するの
に適した乳化剤を用いる乳化重合法に関する。
従来、乳化重合に際し乳化剤として、アニオン
界面活性剤を用いることは知られている。乳化重
合用アニオン界面活性剤にはアルキル硫酸塩、ア
ルキルエーテル硫酸塩、アルキルベンゼンスルホ
ン酸塩などが主としてナトリウム塩の形で用いら
れている。しかしながら、これらの界面活性剤を
用いて乳化重合を行なつた場合、得られるエマル
ジヨンは耐水性に劣り、塗料や接着剤などに用い
た場合、接着不良や塗膜のふくれ、はがれを生じ
やすいという欠点を有し、また乳化重合中にエマ
ルジヨン粘度が上昇し、作業性が著しく低下する
という問題もある。
本発明者らは、従来の乳化重合用乳化剤に見ら
れる前記欠点を改良すべく鋭意研究した結果、あ
る種のエーテルサルフエートの多価金属塩がすぐ
れた乳化剤特性を有することを見出した。即ち本
発明はポリオキシアルキレンアルキルフエニルエ
ーテル硫酸エステル多価金属塩を必須成分として
含有する乳化剤の存在下で重合させることを特徴
とする乳化重合法を提供せんとするものである。
本発明の方法で用いるポリオキシアルキレンア
ルキルフエニルエーテル硫酸エステル多価金属塩
は、アルキル基の炭素数は４〜20、好ましくは８
〜15の範囲であり、アルキレンオキシドはエチレ
ンオキシド、プロピレンオキシド及びブチレンオ
キシドから選ばれ、平均付加モル数は３〜60であ
り、好ましくは、アルキレンオキシドの50重量％
以上はエチレンオキシドである。多価金属塩には
マグネシウム塩、カルシウム塩、バリウム塩など
のアルカリ土類金属塩、アルミニウム塩、亜鉛
塩、錫塩、鉛塩などの多価金属塩が含まれる。
本発明の方法に用いる重合用乳化剤はポリオキ
シルアルキレンアルキルフエニルエーテル硫酸エ
ステル多価金属塩単独でもよく、非イオン界面活
性剤、他のアニオン界面活性剤、水溶性高分子な
どを併用してもよい。非イオン界面活性剤を併用
する場合、例えばポリオキシエチレンアルキルエ
ーテル、ポリオキシエチレンアルキルフエニルエ
ーテル、ポリオキシエチレン脂肪酸エステル、プ
ルロニツク型非イオン活性剤などが挙げられる
が、特に酸化エチレン付加モル数10〜100、好ま
しくは10〜50のポリオキシエチレン系非イオン界
面活性剤が適している。又アニオン界面活性剤を
併用する場合には、例えば、長鎖アルキル硫酸
塩、長鎖アルキルベンゼンスルホン酸塩などが挙
げられる。水溶性高分子の例として、ポリビニル
アルコール、ヒドロキシエチルセルロースなどが
挙げられる。これらの化合物を併用する場合に
は、ポリオキシアルキレンアルキルフエニルエー
テル硫酸エステル多価金属塩１重量部に対し、
0.05〜20重量部が適当である。
本発明乳化重合法が適用できる乳化重合用ビニ
ル単量体としては、アクリル酸メチル、アクリル
酸エチル、アクリル酸ブチル、アクリル酸２―エ
チルヘキシル、メタクリル酸メチルなどのアクリ
ル酸又はメタクリル酸のエステル；臭化ビニル、
塩化ビニル、塩化ビニリデンなどのハロゲン化ビ
ニル；酢酸ビニル、プロピオン酸ビニルなどのビ
ニルエステル；スチレン、ビニルトルエンなどの
ビニル芳香族単量体；エチレン、ブタジエンなど
のモノオレフイン又は共役ジオルフイン類；アク
リロニトリルなどのシアン化ビニル類；アクリル
アミドなどのα，β不飽和アミド類；アクリル
酸、メタクリル酸、イタコン酸、マレイン酸、フ
マール酸などのα，β―不飽和カルボン酸類があ
り、各々単独であるいは二種以上が併用して用い
られる。好ましいビニル単量体の例はアクリル酸
エステル、メタクリル酸エステル、酢酸ビニルな
どである。
本発明の乳化重合に際し、使用される重合開始
剤には過酸化水素、過硫酸カリウム、過硫酸アン
モニウムなどがあり、必要に応じ亜硫酸水素ナト
リウム、チオ硫酸ナトリウムなどの還元剤を併用
してもよい。
本発明の乳化重合法には、乳化重合手段自体は
従来公知の乳化手段が適用できる。例えば、ビニ
ル単量体の濃度は20〜70重量％、乳化剤はビニル
単量体100重量部当り0.2〜10重量部、重合開始剤
はビニル単量体100重量部当り、0.1〜２重量部な
どの条件が採用できる。さらに、必要に応じてPH
調整剤、重合度調節剤、その他の補助添加剤を使
用してもよい。
本発明に用いる乳化重合用乳化剤は従来のナト
リウム塩系のものより著しくすぐれた効果を奏
し、本発明の乳化剤を用いた乳化重合によつて得
られるエマルジユヨンから形成されるフイルムは
水に浸漬した際にふくれやたるみの程度が大幅に
改善され、吸水率も低いという効果がある。また
乳化重合時には粗大粒子の生成がなく、エマルジ
ヨンの粘度上昇も少なく、作業性にすぐれた低粘
度のエマルジヨンが得られ、更に、このエマルジ
ヨンは貯蔵安定性、機械安定性、凍結安定性にお
いても良好である。
次に本発明を実施例により更に詳細に説明す
る。
実施例 １
温度計、撹拌棒、還流冷却器及び滴下ロートを
備えた反応容器に、ポリオキシエチレン（＝
22）オクチルフエニル―テルサルフエートのマグ
ネシウム塩5.0重量部と水137.5部重量部を加えて
溶解し、系内を窒素ガスで置換する。これにアク
リル酸エチル10重量部と2.4％過硫酸カリウム水
溶液6.25部を加え、70℃で重合を開始する。残り
のアクリル酸エチル90重量部を１時間20分かけて
反応容器内に滴下し、別に2.4％過硫酸カリウム
水溶液6.25部を２回に分けて添加する。滴下終了
後、70℃で１時間熟成する。
得られたエマルジヨンをＩAとする。
実施例 ２
実施例１と同様にして、マグネシウム塩の代り
にカルシウム塩を用いて乳化重合を行つた。得ら
れたエマルジヨンをＩBとする。
比較例
また、比較のために、ポリオキシエチレン（Ｐ
＝22）オクチルフエニルエーテルサルフエートの
ソーダ塩を用いて、実施例１と同様にして乳化重
合を行つた。得られたエマルジヨンをＩCとす
る。
エマルジヨンＩA，ＩB，ＩCをそれぞれガラス
板上に展開し、風乾してフイルムを作り、耐水性
を評価した。この結果を次の第１表に示す。
The present invention relates to an emulsion polymerization process using a suitable emulsifier for producing an emulsion suitable for forming a film with significantly improved water resistance. Conventionally, it has been known to use an anionic surfactant as an emulsifier during emulsion polymerization. As anionic surfactants for emulsion polymerization, alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, and the like are mainly used in the form of sodium salts. However, when emulsion polymerization is carried out using these surfactants, the resulting emulsion has poor water resistance, and when used in paints or adhesives, it tends to cause poor adhesion, blistering, and peeling of the paint film. In addition, there is also the problem that the viscosity of the emulsion increases during emulsion polymerization, resulting in a significant decrease in workability. The present inventors have conducted intensive research to improve the above-mentioned drawbacks found in conventional emulsifiers for emulsion polymerization, and have discovered that certain polyvalent metal salts of ether sulfates have excellent emulsifier properties. That is, the present invention provides an emulsion polymerization method characterized in that polymerization is carried out in the presence of an emulsifier containing a polyoxyalkylene alkyl phenyl ether sulfate polyvalent metal salt as an essential component. The polyoxyalkylene alkyl phenyl ether sulfate polyvalent metal salt used in the method of the present invention has an alkyl group having 4 to 20 carbon atoms, preferably 8 carbon atoms.
~15, the alkylene oxide is selected from ethylene oxide, propylene oxide and butylene oxide, and the average number of moles added is 3 to 60, preferably 50% by weight of the alkylene oxide.
The above is ethylene oxide. Polyvalent metal salts include alkaline earth metal salts such as magnesium salts, calcium salts, and barium salts, and polyvalent metal salts such as aluminum salts, zinc salts, tin salts, and lead salts. The emulsifier for polymerization used in the method of the present invention may be a polyoxyl alkylene alkyl phenyl ether sulfate polyvalent metal salt alone, or may be used in combination with a nonionic surfactant, another anionic surfactant, a water-soluble polymer, etc. good. When a nonionic surfactant is used in combination, examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, Pluronic type nonionic surfactant, but in particular, when the number of moles of ethylene oxide added is 10 ~100, preferably 10-50 polyoxyethylene nonionic surfactants are suitable. When an anionic surfactant is used in combination, examples thereof include long-chain alkyl sulfates and long-chain alkylbenzenesulfonates. Examples of water-soluble polymers include polyvinyl alcohol and hydroxyethyl cellulose. When these compounds are used together, for 1 part by weight of polyoxyalkylene alkyl phenyl ether sulfate polyvalent metal salt,
0.05 to 20 parts by weight is suitable. Vinyl monomers for emulsion polymerization to which the emulsion polymerization method of the present invention can be applied include esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate; vinyl chloride,
Vinyl halides such as vinyl chloride and vinylidene chloride; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl aromatic monomers such as styrene and vinyltoluene; Monoolefins or conjugated diorphins such as ethylene and butadiene; Acrylonitrile, etc. Vinyl cyanides; α, β-unsaturated amides such as acrylamide; α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, etc., each used singly or in combination are used in combination. Examples of preferred vinyl monomers include acrylic esters, methacrylic esters, and vinyl acetate. Polymerization initiators used in the emulsion polymerization of the present invention include hydrogen peroxide, potassium persulfate, ammonium persulfate, and the like, and reducing agents such as sodium bisulfite and sodium thiosulfate may be used in combination, if necessary. In the emulsion polymerization method of the present invention, conventionally known emulsification means can be applied as the emulsion polymerization means itself. For example, the concentration of vinyl monomer is 20 to 70 parts by weight, the emulsifier is 0.2 to 10 parts by weight per 100 parts by weight of vinyl monomer, and the polymerization initiator is 0.1 to 2 parts by weight per 100 parts by weight of vinyl monomer. conditions can be adopted. In addition, if necessary, PH
Regulators, degree of polymerization regulators, and other auxiliary additives may also be used. The emulsifier for emulsion polymerization used in the present invention has a significantly superior effect than conventional sodium salt-based emulsifiers, and the film formed from the emulsion obtained by emulsion polymerization using the emulsifier of the present invention does not change when immersed in water. The effect is that the degree of swelling and sagging on the skin is greatly improved, and the water absorption rate is also low. In addition, during emulsion polymerization, no coarse particles are generated, and the viscosity of the emulsion increases little, resulting in a low-viscosity emulsion with excellent workability.Furthermore, this emulsion has good storage stability, mechanical stability, and freezing stability. It is. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Polyoxyethylene (=
22) Add and dissolve 5.0 parts by weight of magnesium salt of octylphenyl-tersulfate and 137.5 parts by weight of water, and replace the inside of the system with nitrogen gas. Add 10 parts by weight of ethyl acrylate and 6.25 parts of a 2.4% potassium persulfate aqueous solution to this, and start polymerization at 70°C. The remaining 90 parts by weight of ethyl acrylate was dropped into the reaction vessel over 1 hour and 20 minutes, and 6.25 parts of a 2.4% potassium persulfate aqueous solution was added in two portions. After the addition is complete, the mixture is aged at 70°C for 1 hour. The obtained emulsion is designated as IA . Example 2 Emulsion polymerization was carried out in the same manner as in Example 1, using calcium salt instead of magnesium salt. The obtained emulsion is designated as IB . Comparative Example Also, for comparison, polyoxyethylene (P
=22) Emulsion polymerization was carried out in the same manner as in Example 1 using the soda salt of octyl phenyl ether sulfate. The obtained emulsion is designated as I C. Each of the emulsions I A , I B , and I C was spread on a glass plate and air-dried to form a film, and its water resistance was evaluated. The results are shown in Table 1 below.
【表】
実施例３，４及び比較例
ビニル単量体として、アクリル酸エチル95重量
部とアクリル酸５重量部の混合物を用いた以外は
実施例１と同様にして乳化重合を行つた。[Table] Examples 3 and 4 and Comparative Example Emulsion polymerization was carried out in the same manner as in Example 1 except that a mixture of 95 parts by weight of ethyl acrylate and 5 parts by weight of acrylic acid was used as the vinyl monomer.
【表】
エマルジヨンA，B，Cを30％アンモニア
水にてPH７に調整したのち、ガラス板上に展開
し、風乾してフイルムをつくつた。その評価結果
は第２表の通りである。[Table] Emulsions A , B , and C were adjusted to pH 7 with 30% ammonia water, spread on a glass plate, and air-dried to form a film. The evaluation results are shown in Table 2.
【表】
実施例５，６及び比較例
ビニル単量体としてアクリル酸エチル66重量部
とメタクリル酸メチル34重量部の混合物を用いた
以外は実施例１と同様にして乳化重合を行つた。[Table] Examples 5, 6 and Comparative Example Emulsion polymerization was carried out in the same manner as in Example 1, except that a mixture of 66 parts by weight of ethyl acrylate and 34 parts by weight of methyl methacrylate was used as the vinyl monomer.
【表】【table】
【表】
エマルジヨンA，B，Cをガラス板上に展開
し、風乾してフイル ムを作り、耐水性評価し
た。この結果を第３表に示す。[Table] Emulsions A , B , and C were spread on a glass plate and air-dried to form a film, and the water resistance was evaluated. The results are shown in Table 3.
【表】
実施例７，８及び比較例
ビニル単量体として、アクリル酸エチル66重量
部、メタクリル酸メチル32.8重量部、アクリル酸
1.2重量部の混合物を用いた以外は、実施例１と
同様にして乳化重合を行つた。[Table] Examples 7, 8 and comparative examples As vinyl monomers, 66 parts by weight of ethyl acrylate, 32.8 parts by weight of methyl methacrylate, acrylic acid
Emulsion polymerization was carried out in the same manner as in Example 1, except that 1.2 parts by weight of the mixture was used.
【表】
エマルジヨンA，B，Cを30％アンモニア
水にてPH８〜９に調整したのちガラス板上に展開
し、風乾してフイルムを作り、耐水性評価した。
この結果を第４表に示す。[Table] Emulsions A , B , and C were adjusted to pH 8-9 with 30% ammonia water, spread on a glass plate, air-dried to form a film, and evaluated for water resistance.
The results are shown in Table 4.
Claims (1)
テル硫酸エステル多価金属塩を必須成分として含
有する乳化剤の存在下で重合させることを特徴と
する乳化重合法。 ２ 反応終了後PHの調整を行なう特許請求の範囲
第１項記載の方法。[Scope of Claims] 1. An emulsion polymerization method characterized in that polymerization is carried out in the presence of an emulsifier containing a polyoxyalkylene alkyl phenyl ether sulfate polyvalent metal salt as an essential component. 2. The method according to claim 1, wherein the PH is adjusted after the reaction is completed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12900480A JPS5753503A (en) | 1980-09-17 | 1980-09-17 | Method for emulsion polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12900480A JPS5753503A (en) | 1980-09-17 | 1980-09-17 | Method for emulsion polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5753503A JPS5753503A (en) | 1982-03-30 |
| JPS6129601B2 true JPS6129601B2 (en) | 1986-07-08 |
Family
ID=14998766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12900480A Granted JPS5753503A (en) | 1980-09-17 | 1980-09-17 | Method for emulsion polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5753503A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6315901A (en) * | 1986-07-07 | 1988-01-23 | 株式会社カカイ | Slipper sole and its production |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59179640A (en) * | 1983-03-31 | 1984-10-12 | Japan Synthetic Rubber Co Ltd | Carpet packing material |
| JP6648938B2 (en) * | 2016-03-16 | 2020-02-14 | 関西ペイント株式会社 | Paint composition |
-
1980
- 1980-09-17 JP JP12900480A patent/JPS5753503A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6315901A (en) * | 1986-07-07 | 1988-01-23 | 株式会社カカイ | Slipper sole and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5753503A (en) | 1982-03-30 |
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