JPS6239162B2 - - Google Patents
Info
- Publication number
- JPS6239162B2 JPS6239162B2 JP12705679A JP12705679A JPS6239162B2 JP S6239162 B2 JPS6239162 B2 JP S6239162B2 JP 12705679 A JP12705679 A JP 12705679A JP 12705679 A JP12705679 A JP 12705679A JP S6239162 B2 JPS6239162 B2 JP S6239162B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- solution
- organic solvent
- group
- soluble organic
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 48
- 239000000178 monomer Substances 0.000 claims description 46
- 229920002554 vinyl polymer Polymers 0.000 claims description 46
- 229920001577 copolymer Polymers 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 36
- 239000004815 dispersion polymer Substances 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 150000002978 peroxides Chemical class 0.000 claims description 15
- 229920001400 block copolymer Polymers 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 6
- 125000005717 substituted cycloalkylene group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000005650 substituted phenylene group Chemical group 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 239000006185 dispersion Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- -1 2-hydroxypropyl Chemical group 0.000 description 7
- 238000012661 block copolymerization Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 238000007665 sagging Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は水または水と水溶性有機溶剤との溶液
中にブロツク共重合体を均一に分散させた分散安
定性のすぐれた水性重合体分散液の製造法に関す
るものである。
水性重合体分散液は塗料、印刷インキ、繊維加
工、紙加工、皮革加工、接着剤、粘着剤など広い
用途に用いられている。特に無公害化の面からも
省資源の面からも安全で、かつ、衛生的であり、
枯渇の心配のない原料である水を溶剤として使用
する水系塗料は今後の塗料として大きい意義をも
つものである。
従来このような水性重合体分散液の製造法の一
つとして水または水と水溶性有機溶剤との溶液に
おいて、この液体に可溶性の分散安定剤にこの液
体に不溶性の重合体を形成するビニル型単量体を
グラフト重合させて製造する方法がある。
たとえば、分散安定剤としてマレイン化ポリブ
タジエン（特公昭49−43381号公報）、水溶性の不
飽和ポリエステル（特公昭53−9795号公報）、重
合性ビニル基を分子中に導入した水溶性重合体
（特開昭53−17680号公報）などを用い、水または
水と水溶性有機溶剤との溶液中において、これら
の分散安定剤存在下にこの液体に不溶性の重合体
となるビニル型単量体のグラフト重合を行うこと
が提案されている。
これらの方法は工程が複雑であるばかりか、グ
ラフト工程における重合収率が低いため反応時間
が長く生産性が低いこと、またグラフト効率が低
いために得られた分散液の機械的安定性および保
存安定性が劣るという欠点があつた。またマレイ
ン化ポリブタジエンや不飽和ポリエステルなどを
分散安定剤として使用した場合にはアクリル系共
重合体との相溶性が悪いため、たとえば塗料用塗
において塗膜面の均一性が得られにくく、かつ耐
侯性が劣るという欠点があつた。
以上のように従来の水性重合体分散液の製造法
には種々の欠点があり、いまだ満足すべき結果は
得られていない。本発明の目的は前記のような従
来法の欠点を解消した新しい水性重合体分散液の
工業的製造法を提供することにある。
すなわち、本発明の製造方法の概要は次のよう
である。まず本発明に用いる主な原料化合物をあ
げるとポリメリツクペルオキシドと下記(イ)および
(ロ)に示す２つの型のビニル型単量体および水また
は(ハ)で示す水と水溶性有機溶剤との溶液がある。
本発明に用いるポリメリツクペルオキシドは一
般式（）
〔式中、R1は炭素数１〜18のアルキレン基もしく
は置換アルキレン基、炭素数３〜15のシクロアル
キレン基もしくは置換シクロアルキレン基または
フエニレン基もしくは置換フエニレン基を表わ
し、R2は炭素数２〜10のアルキレン基または置
換アルキレン基、
（式中R3は水素原子またはメチル基であり、R4は
炭素数２〜10のアルキレン基または置換アルキレ
ン基である。またｍ＝１〜13である。）。
The present invention relates to a method for producing an aqueous polymer dispersion having excellent dispersion stability, in which a block copolymer is uniformly dispersed in water or a solution of water and a water-soluble organic solvent. Aqueous polymer dispersions are used in a wide range of applications, including paints, printing inks, textile processing, paper processing, leather processing, adhesives, and pressure-sensitive adhesives. In particular, it is safe and sanitary in terms of pollution-free and resource saving.
Water-based paints that use water as a solvent, a raw material that is not subject to depletion, are of great significance as future paints. Conventionally, one of the methods for producing such aqueous polymer dispersions is to form a vinyl-type polymer in a solution of water or water and a water-soluble organic solvent with a dispersion stabilizer soluble in this liquid to form a polymer insoluble in this liquid. There is a method of manufacturing by graft polymerizing monomers. For example, as a dispersion stabilizer, maleated polybutadiene (Japanese Patent Publication No. 49-43381), water-soluble unsaturated polyester (Japanese Patent Publication No. 53-9795), water-soluble polymers with polymerizable vinyl groups introduced into the molecule ( In water or a solution of water and a water-soluble organic solvent, in the presence of these dispersion stabilizers, vinyl monomers become polymers that are insoluble in this liquid. It has been proposed to carry out graft polymerization. These methods not only have complicated steps, but also have long reaction times and low productivity due to low polymerization yields in the grafting process, and low grafting efficiency that leads to poor mechanical stability and storage of the resulting dispersion. The drawback was poor stability. Furthermore, when maleated polybutadiene or unsaturated polyester is used as a dispersion stabilizer, it has poor compatibility with acrylic copolymers, making it difficult to obtain uniformity on the coating surface in coatings, for example, and poor weather resistance. It had the disadvantage of being inferior in quality. As described above, conventional methods for producing aqueous polymer dispersions have various drawbacks, and satisfactory results have not yet been obtained. An object of the present invention is to provide a new method for industrially producing aqueous polymer dispersions, which eliminates the drawbacks of the conventional methods as described above. That is, the outline of the manufacturing method of the present invention is as follows. First, the main raw material compounds used in the present invention are polymeric peroxide, the following (a) and
There are two types of vinyl monomers shown in (b) and solutions of water or water and a water-soluble organic solvent shown in (c). The polymer peroxide used in the present invention has the general formula () [In the formula, R 1 represents an alkylene group or substituted alkylene group having 1 to 18 carbon atoms, a cycloalkylene group or substituted cycloalkylene group having 3 to 15 carbon atoms, or a phenylene group or substituted phenylene group, and R 2 represents an alkylene group having 2 to 18 carbon atoms or a substituted cycloalkylene group, ~10 alkylene groups or substituted alkylene groups, (In the formula, R 3 is a hydrogen atom or a methyl group, and R 4 is an alkylene group or substituted alkylene group having 2 to 10 carbon atoms. Also, m = 1 to 13.)
【式】または[expression] or
【式】
を表わす。またｎ＝２〜20である〕。
および一般式（）
〔式中、R1およびｎは前記一般式（）の場合と
同じである。〕からなる群から選ばれた１種また
は２種以上のポリメリツクペルオキシドである。
その他の原料化合物としては、
(イ) 前記のポリメリツクペルオキシドと共重合さ
せる１種または２種以上のビニル型単量体で、
その重合体が水または水と水溶性有機溶剤との
溶液に溶解性を有するビニル型単量体。
(ロ) (イ)で定義されるビニル型単量体と異なる１種
または２種以上の他のビニル型単量体で、その
重合体が水または水と水溶性有機溶剤との溶液
に溶解しないビニル型単量体。
(ハ) 水と水溶性有機溶剤との溶液で、ペルオキシ
結合含有共重合体の構成成分であるビニル型単
量体の重合体を溶解し、かつペルオキシ結合含
有共重合体にブロツク共重合させる他のビニル
型単量体の重合体を溶解しない溶液、である。
本発明の製造法は、ポリメリツクペルオキシド
と(イ)に示すビニル型単量体とを共重合させてペル
オキシ結合含有共重合体を製造し、次いでこのペ
ルオキシ結合含有共重合体と(ロ)に示すビニル型単
量体とを水または水と水溶性有機溶剤との溶液中
でブロツク共重合させて水性重合体分散液を製造
する方法である。
一般式（）で示されるポリメリツクペルオキ
シドとは、具体的にはたとえば、
などをあげることができる。
前記の一般式（）で示されるポリメリツクペ
ルオキシドとは具体的にはたとえば、
などをあげることができる。
これらのポリメリツクペルオキシドとビニル型
単量体の共重合機構およびそれにより得られるペ
ルオキシ結合含有共重合体と他のビニル型単量体
とのブロツク共重合の機構は次のように説明する
ことができる。
まずポリメリツクペルオキシドと(イ)に示すビニ
ル型単量体との共重合を行うと、連鎖中にペルオ
キシ結合が導入された共重合体が得られる。これ
に水または水と水溶性有機溶剤との溶液中で、(ロ)
に示すビニル型単量体を加えて重合を行うと、ペ
ルオキシ結合含有共重合体がペルオキシ結合にお
いて開裂し、効率よくブロツク共重合体が得られ
る。
このブロツク共重合体は水または水と水溶性有
機溶剤との溶液に可溶性の重合体部分と水または
水と水溶性有機溶剤との溶液に不溶性の重合体部
分とからなり、水または水と水溶性有機溶剤との
溶液中において、不溶性重合体部分は凝集して粒
子状となり、可溶性重合体部分はこの液体中に伸
びており、全体的には粒子状のものが分散してい
る状態となる。
本発明に用いられる水溶性有機溶剤には、たと
えば、メチルアルコール、エチルアルコール、ｎ
−プロピルアルコール、iso−プロピルアルコー
ル、tert−ブチルアルコール、メチルセロソル
ブ、エチルセロソルブ、ブチルセロソルブ、メト
キシブチルアルコール、メチルカルビトール、エ
チルカルビトール、アセトン、ジオキサン、酢酸
メチルセロソルブ、酢酸カルビトール、ジアセト
ンアルコールなどのように、常温で水と任意の割
合で溶解するもの、またはたとえばｎ−ブチルア
ルコール、iso−ブチルアルコール、sec−ブチル
アルコール、メチルエチルケトン、酢酸メチル、
酢酸エチル、酢酸セロソルブなどのように常温で
水に対する溶解度が７〜25％であるものがある。
これらを使用するにあたつては本発明のブロツク
共重合体の水可溶性重合体部分および水不溶性重
合体部分の溶解性に応じ適宜選択しなければなら
ない。
本発明におけるポリメリツクペルオキシドと共
重合させる前記(イ)で定義されるビニル型単量体と
しては、たとえば（メタ）アクリル酸ヒドロキシ
エチル（アクリル酸ヒドロキシエチル、メタアク
リル酸ヒドロキシエチルをいう。以下同様）、（メ
タ）アクリル酸−２−ヒドロキシプロピル、（メ
タ）アクリル酸−２−ヒドロキシブチルやモノ
（メタ）アクリル酸ジエチレングリコールエステ
ル、モノ（メタ）アクリル酸トリエチレングリコ
ールエステル、モノ（メタ）アクリル酸ペンタエ
チレングリコールエステルなどのようなモノ（メ
タ）アクリル酸ポリエチレングリコールエステル
類、モノ（メタ）アクリル酸ジプロピレングリコ
ールエステル、モノ（メタ）アクリル酸トリプロ
ピレングリコールエステル、モノ（メタ）アクリ
ル酸ペンタプロピレングリコールエステルなどの
ようなモノ（メタ）アクリル酸ポリプロピレング
リコールエステル類、（メタ）アクリルアミド、
Ｎ−メチロール（メタ）アクリルアミド、ジアセ
トンアクリルアミドなどの（メタ）アクリルアミ
ド誘導体、酢酸ビニルなどがあり、これらの１種
または２種以上のビニル型単量体が用いられる。
この場合、水または水と水溶性有機溶剤との溶
液に目的とするペルオキシ結合含有共重合体のビ
ニル型単量体に基づく重合体部分が溶解する範囲
内で、前記(ロ)で定義される他のビニル型単量体を
前記(イ)で定義されるビニル型単量体に加えること
ができる。
なお、このような前記(イ)で定義されるビニル型
単量体に前記(ロ)で定義されるビニル型単量体を加
えた混合物における混合割合は両者のビニル型単
量体の組合わせによつて異なり、一様に特定でき
ないが、前記(ロ)で定義されるビニル型単量体の混
合物中における含有率は通常0.1〜50重量％の範
囲で用いられる。
また、本発明における前記のペルオキシ結合含
有共重合体とブロツク共重合させる前記(ロ)で定義
される他のビニル型単量体としては、たとえば、
ブタジエン、スチレン、プロピオン酸ビニル、塩
化ビニル、塩化ビニリデン、（メタ）アクリロニ
トリル、（メタ）アクリル酸メチル、（メタ）アク
リル酸エチル、（メタ）アクリル酸ｎ−プロピ
ル、（メタ）アクリル酸イソプロピル、（メタ）ア
クリル酸ブチル、（メタ）アクリル酸イソブチ
ル、（メタ）アクリル酸tert−ブチル、（メタ）ア
クリル酸ｎ−ヘキシル、（メタ）アクリル酸シク
ロヘキシル、（メタ）アクリル酸オクチル、（メ
タ）アクリル酸ベンジル、（メタ）アクリル酸２
−エチルヘキシル、（メタ）アクリル酸ラウリ
ル、（メタ）アクリル酸ステアリル、（メタ）アク
リル酸グリシジルエステル、（メタ）アクリル酸
メチルグリシジルエステル、（メタ）アリルグリ
シジルエーテル、ビニルトルエン、ビニルピロリ
ドン、フマル酸ジブチルなどがあげられ、これら
の１種または２種以上のビニル型単量体が用いら
れる。この場合、水または水と水溶性有機溶剤と
の溶液に目的とするブロツク共重合体のビニル型
単量体に基づくブロツク共重合体部分が溶解しな
い範囲内で、前記(イ)で定義されるビニル型単量体
を前記(ロ)で定義されるビニル型単量体に加えるこ
とができる。
なお、このような前記(ロ)で定義されるビニル型
単量体に前記(イ)で定義されるビニル型単量体を加
えた混合物中における混合割合は両者のビニル型
単量体の組合わせによつて異なり、一様に特定で
きないが、前記(イ)で定義されるビニル型単量体の
混合物中における含有率は通常0.1〜50重量％の
範囲で用いられる。
本発明に用いるペルオキシ結合含有共重合体は
水溶性有機溶剤中で一般式（）および一般式
（）からなる群から選ばれた１種または２種以
上のポリメリツクペルオキシドと１種または２種
以上のビニル型単量体とを共重合させることによ
つて容易に得られる。
この場合、ポリメリツクペルオキシドの使用量
はそのビニル型単量体100重量部に対して0.5〜20
重量部、重合温度は60〜130℃、重合時間は２〜
５時間がそれぞれ好適な範囲である。
本発明の実施に際して、前記のペルオキシ結合
含有共重合体の水溶性有機溶剤溶液に、水とブロ
ツク共重合させるビニル型単量体とを混合し、こ
の水と水溶性有機溶剤との溶液中でブロツク共重
合反応を行えば目的とする水性重合体分散液が得
られる。また、前記のペルオキシ結合含有共重合
体溶液から水溶性有機溶剤を除去して、水および
ブロツク共重合させるビニル型単量体とを混合
し、この水中でブロツク共重合反応を行えば、目
的の水のみを分散媒体とする水性重合体分散液が
得られる。
ここでブロツク共重合反応の重合温度は60〜
140℃、重合時間は３〜６時間が好適である。
この際、水と水溶性有機溶剤の混合比率は水溶
性有機溶剤が80％以下が好ましい。そして水また
は水と水溶性有機溶剤との溶液の使用量は、生成
する水性重合体分散液中の固形分濃度が30〜70％
となるような範囲、すなわち、全体の70〜30％が
好適である。また、ブロツク共重合体における可
溶性重合体部分と不溶性重合体部分との比率は特
に限定するものではないが、本発明の分散液の安
定性の面から可溶性重合体部分の量は不溶性重合
体部分と可溶性重合体部分との総量に対して５〜
70重量％が適当である。
本発明の水性重合体分散液は被覆組成物として
有用であり、必要に応じて他の樹脂、顔料、充て
ん剤、各種添加剤を添加することが可能である。
添加可能な樹脂としては、メラミン樹脂、エポキ
シ樹脂、ビニル樹脂などがその代表例である。
以上のように本発明の水性重合体分散液の製造
法は従来法にくらべて次の利点を有し、その工業
的価値は極めて高い。
(1) 従来法によれば可溶性重合体を合成し、さら
にその重合体分子中にビニル基などの官能基を
導入してから不溶性重合体部分をグラフトある
いはブロツク共重合により生成するという三段
階にわたる製造工程をとつていたのに比べ、本
発明によればポリメリツクペルオキシドとビニ
ル型単量体を共重合してペルオキシ結合含有共
重合体を合成し、直接その重合体分子中のペル
オキシ結合の開裂によつて、不溶性重合体部分
をブロツク共重合により生成するという二段階
の製造工程のため、製造工程が簡便で工業的に
有利である。
(2) 生成重合体のほとんどが水または水と水溶性
有機溶剤との溶液に可溶性の重合体部分と不溶
性の重合体部分とからなるブロツク共重合体で
あるため、固形分が高濃度に含有され、しかも
低粘度の極めて分散安定性の優れた水性重合体
分散液が得られる。
(3) 本発明の水性重合体分散液を用いて調製され
た被覆組成物は、その硬化被膜の平滑性が優
れ、光沢に富む連続被覆層を形成することがで
きる。
次に実施例により本発明の有効性をさらに詳し
く述べるが、本発明はこの実施例に限定されるも
のではない。なお、実施例における「部」はすべ
て重量部を表わす。
実施例 １
(A) ペルオキシ結合含有共重合体の製造
温度計、撹拌器および還流冷却器をそなえた
反応器にエチルセロソルブ20部を仕込み、窒素
ガスを吹き込みながら、75℃に加熱し、第１表
に示す組成からなる混合液（）を１時間かけ
て徐々に仕込んだ。[Formula] represents. In addition, n=2 to 20]. and general expression () [In the formula, R 1 and n are the same as in the above general formula (). ] One or more polymeric peroxides selected from the group consisting of: Other raw material compounds include (a) one or more vinyl monomers to be copolymerized with the polymeric peroxide;
A vinyl monomer whose polymer is soluble in water or a solution of water and a water-soluble organic solvent. (b) One or more other vinyl monomers different from the vinyl monomer defined in (a), the polymer of which is dissolved in water or a solution of water and a water-soluble organic solvent. No vinyl type monomer. (c) Dissolving a polymer of vinyl monomer, which is a component of the peroxy bond-containing copolymer, in a solution of water and a water-soluble organic solvent, and then block copolymerizing it into a peroxy bond-containing copolymer. It is a solution that does not dissolve the polymer of vinyl type monomer. In the production method of the present invention, a peroxy bond-containing copolymer is produced by copolymerizing a polymeric peroxide and the vinyl monomer shown in (a), and then this peroxy bond-containing copolymer and (b) are copolymerized. This is a method for producing an aqueous polymer dispersion by block copolymerizing the vinyl type monomers shown below in water or a solution of water and a water-soluble organic solvent. Specifically, the polymeric peroxide represented by the general formula () is, for example, etc. can be given. Specifically, the polymeric peroxide represented by the above general formula () is, for example, etc. can be given. The copolymerization mechanism of these polymeric peroxides and vinyl monomers and the block copolymerization mechanism of the resulting peroxy bond-containing copolymer and other vinyl monomers can be explained as follows. can. First, by copolymerizing polymeric peroxide with the vinyl type monomer shown in (a), a copolymer in which peroxy bonds are introduced into the chain is obtained. In water or a solution of water and a water-soluble organic solvent, (b)
When polymerization is carried out with the addition of the vinyl monomers shown in , the peroxy bond-containing copolymer is cleaved at the peroxy bond, and a block copolymer can be efficiently obtained. This block copolymer consists of a polymer part that is soluble in water or a solution of water and a water-soluble organic solvent, and a polymer part that is insoluble in water or a solution of water and a water-soluble organic solvent. In a solution with a soluble organic solvent, the insoluble polymer portion aggregates into particles, and the soluble polymer portion extends into this liquid, resulting in an overall state of dispersed particles. . The water-soluble organic solvent used in the present invention includes, for example, methyl alcohol, ethyl alcohol, n
-Propyl alcohol, iso-propyl alcohol, tert-butyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methoxybutyl alcohol, methyl carbitol, ethyl carbitol, acetone, dioxane, methyl cellosolve acetate, carbitol acetate, diacetone alcohol, etc. Those that dissolve in any proportion with water at room temperature, such as n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, methyl ethyl ketone, methyl acetate,
Some substances, such as ethyl acetate and cellosolve acetate, have a solubility in water of 7 to 25% at room temperature.
When using these, they must be appropriately selected depending on the solubility of the water-soluble polymer portion and the water-insoluble polymer portion of the block copolymer of the present invention. The vinyl type monomer defined in (a) above to be copolymerized with the polymeric peroxide in the present invention includes, for example, hydroxyethyl (meth)acrylate (hydroxyethyl acrylate, hydroxyethyl methacrylate. The same applies hereinafter). ), 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, mono(meth)acrylic acid Mono(meth)acrylic acid polyethylene glycol esters such as pentaethylene glycol ester, mono(meth)acrylic acid dipropylene glycol ester, mono(meth)acrylic acid tripropylene glycol ester, mono(meth)acrylic acid pentapropylene glycol ester Mono(meth)acrylic acid polypropylene glycol esters such as esters, (meth)acrylamide,
Examples include (meth)acrylamide derivatives such as N-methylol (meth)acrylamide and diacetone acrylamide, and vinyl acetate, and one or more of these vinyl type monomers are used. In this case, within the range where the vinyl monomer-based polymer portion of the desired peroxy bond-containing copolymer is dissolved in water or a solution of water and a water-soluble organic solvent, as defined in (b) above. Other vinyl type monomers can be added to the vinyl type monomers defined in (a) above. The mixing ratio in such a mixture of the vinyl monomer defined in (a) above and the vinyl monomer defined in (b) above is the combination of both vinyl monomers. The content of the vinyl monomer defined in (b) above in the mixture is usually used in the range of 0.1 to 50% by weight, although it cannot be specified uniformly. In addition, other vinyl monomers defined in (b) above to be block copolymerized with the peroxy bond-containing copolymer in the present invention include, for example,
Butadiene, styrene, vinyl propionate, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( Butyl meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid Benzyl, (meth)acrylic acid 2
-Ethylhexyl, lauryl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, (meth)allyl glycidyl ether, vinyltoluene, vinylpyrrolidone, dibutyl fumarate etc., and one or more types of vinyl monomers are used. In this case, the vinyl monomer-based block copolymer portion of the target block copolymer does not dissolve in water or a solution of water and a water-soluble organic solvent, as defined in (a) above. A vinyl type monomer can be added to the vinyl type monomer defined in (b) above. The mixing ratio in a mixture of the vinyl monomer defined in (b) above and the vinyl monomer defined in (a) above is determined by the combination of both vinyl monomers. Although it varies depending on the combination and cannot be specified uniformly, the content of the vinyl monomer defined in (a) above in the mixture is usually used in the range of 0.1 to 50% by weight. The peroxy bond-containing copolymer used in the present invention is prepared by combining one or more polymeric peroxides selected from the group consisting of general formula () and general formula () in a water-soluble organic solvent. It can be easily obtained by copolymerizing with a vinyl type monomer. In this case, the amount of polymer peroxide used is 0.5 to 20 parts by weight per 100 parts by weight of the vinyl monomer.
Parts by weight, polymerization temperature 60~130℃, polymerization time 2~
5 hours is a suitable range for each. In carrying out the present invention, water and a vinyl monomer to be block copolymerized are mixed in a water-soluble organic solvent solution of the above-mentioned peroxy bond-containing copolymer, and the copolymer is mixed in a solution of water and a water-soluble organic solvent. By carrying out the block copolymerization reaction, the desired aqueous polymer dispersion can be obtained. Furthermore, if the water-soluble organic solvent is removed from the peroxy bond-containing copolymer solution, water and the vinyl monomer to be block copolymerized are mixed, and the block copolymerization reaction is carried out in this water, the desired result can be achieved. An aqueous polymer dispersion using only water as a dispersion medium is obtained. Here, the polymerization temperature of the block copolymerization reaction is 60~
A temperature of 140°C and a polymerization time of 3 to 6 hours are suitable. At this time, the mixing ratio of water and water-soluble organic solvent is preferably 80% or less. The amount of water or a solution of water and a water-soluble organic solvent used is such that the solid content concentration in the aqueous polymer dispersion produced is 30 to 70%.
A suitable range is such that 70 to 30% of the total. Further, the ratio of the soluble polymer portion to the insoluble polymer portion in the block copolymer is not particularly limited, but from the viewpoint of stability of the dispersion of the present invention, the amount of the soluble polymer portion is smaller than the insoluble polymer portion. 5 to 5 for the total amount of and soluble polymer portion
70% by weight is suitable. The aqueous polymer dispersion of the present invention is useful as a coating composition, and other resins, pigments, fillers, and various additives can be added as necessary.
Typical examples of resins that can be added include melamine resin, epoxy resin, and vinyl resin. As described above, the method for producing an aqueous polymer dispersion of the present invention has the following advantages over conventional methods, and its industrial value is extremely high. (1) Conventional methods involve a three-step process in which a soluble polymer is synthesized, a functional group such as a vinyl group is introduced into the polymer molecule, and an insoluble polymer portion is generated by grafting or block copolymerization. In contrast to conventional manufacturing processes, according to the present invention, a peroxy bond-containing copolymer is synthesized by copolymerizing polymeric peroxide and a vinyl monomer, and the peroxy bonds in the polymer molecule are directly removed. Since the production process is a two-step process in which an insoluble polymer portion is produced by block copolymerization by cleavage, the production process is simple and industrially advantageous. (2) Most of the produced polymers are block copolymers consisting of a polymer part that is soluble in water or a solution of water and a water-soluble organic solvent, and a polymer part that is insoluble, so the solid content is high. Furthermore, an aqueous polymer dispersion with low viscosity and extremely excellent dispersion stability can be obtained. (3) The coating composition prepared using the aqueous polymer dispersion of the present invention has a cured film with excellent smoothness and can form a continuous coating layer with high gloss. Next, the effectiveness of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, all "parts" in Examples represent parts by weight. Example 1 (A) Production of peroxy bond-containing copolymer 20 parts of ethyl cellosolve was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 75°C while blowing nitrogen gas. A mixed solution () having the composition shown in the table was gradually added over 1 hour.
【表】
仕込終了後引続き1.5時間重合反応を行つ
た。生成物はペルオキシ結合含有共重合体を
37.3重量％含み、25℃における粘度が1.5ポイ
ズである透明な溶液であつた。
(B) 水性重合体分散液の製造
温度計、撹拌器および還流冷却器をそなえた
反応器に、水80部を仕込み窒素ガスを吹込みな
がら80℃に加熱し、そこに第２表に示す混合液
（）を２時間かけて滴下した。
第２表 混合液（）の組成
(A)で得られたペルオキシ結合含有共重合体溶液
60部
メタアクリル酸メチル 20部
アクリル酸ブチル 20部
スチレン 20部
水 60部
反応物を引続き80℃で３時間保つことにより
ブロツク共重合体を31.4重量％含み、25℃にお
ける粘度が0.5ポイズであり、乳白色である水
およびエチルセロソルブを分散媒とする水性重
合体分散液を得た。
この分散液は25℃で６カ月の放置後も安定で
粒子の沈降、相分離、粘度の変化も全く見られ
なかつた。
この分散液を鋼板上に乾燥膜厚が30〜40μに
なるように塗布して140℃で30分間強制乾燥さ
せたところ、塗膜は平滑で光沢に富み、発泡や
ダレの現象はまつたく見られなかつた。
実施例 ２
(A) ペルオキシ結合含有共重合体の製造
実施例１と同様な方法でペルオキシ結合含有
共重合体を製造した。ただし、実施例１におい
て最初反応器に仕込んだエチルセロソルブにか
えてイソプロピルアルコールを用い、また、混
合液（）の代りに第３表に示す混合液（）
を用い、共重合反応の重合温度を90℃とした。[Table] After the completion of the preparation, the polymerization reaction was continued for 1.5 hours. The product is a peroxy bond-containing copolymer.
It was a clear solution containing 37.3% by weight and a viscosity of 1.5 poise at 25°C. (B) Production of aqueous polymer dispersion 80 parts of water was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 80°C while blowing nitrogen gas. The mixture () was added dropwise over 2 hours. Table 2 Composition of mixture () Peroxy bond-containing copolymer solution obtained from (A)
60 parts Methyl methacrylate 20 parts Butyl acrylate 20 parts Styrene 20 parts Water 60 parts The reaction mixture was kept at 80°C for 3 hours to obtain a block copolymer containing 31.4% by weight and a viscosity of 0.5 poise at 25°C. A milky-white aqueous polymer dispersion containing water and ethyl cellosolve as dispersion media was obtained. This dispersion remained stable even after being left at 25°C for 6 months, with no particle sedimentation, phase separation, or viscosity change observed. When this dispersion was applied to a steel plate to a dry film thickness of 30 to 40μ and force-dried at 140°C for 30 minutes, the film was smooth and glossy, with no visible foaming or sagging. I couldn't help it. Example 2 (A) Production of peroxy bond-containing copolymer A peroxy bond-containing copolymer was produced in the same manner as in Example 1. However, in Example 1, isopropyl alcohol was used instead of the ethyl cellosolve initially charged in the reactor, and the mixture () shown in Table 3 was used instead of the mixture ().
was used, and the polymerization temperature for the copolymerization reaction was set at 90°C.
【表】【table】
【表】
また、生成物はペルオキシ結合含有共重合体
を36.7重量％含み、25℃における粘度が1.9ポ
イズの透明な溶液であつた。
(B) 水性重合体分散液の製造
撹拌器をそなえた容器中で前記(A)で得られた
ペルオキシ結合含有共重合体溶液60部を500部
のｎ−ヘキサン中に常温で撹拌しながら加えて
放置し、白色の沈澱物を得た。この沈澱物を分
離し、常温で減圧乾燥し、ペルオキシ結合含有
共重合体の白色粉末を得た。次に温度計、撹拌
器および還流冷却器をそなえた反応器に水60部
を仕込み、窒素ガスを吹込みながら95℃に加熱
し第４表に示す混合液（）を２時間かけて仕
込んだ。
第４表 混合液（）の組成
上記により得られたペルオキシ結合含有共重合
体粉末 20部
メタアクリル酸メチル 30部
アクリル酸ブチル 40部
スチレン 30部
水 40部
反応物を引続き80℃で３時間保つことによ
り、ブロツク共重合体を55.1重量％含み、25℃
における粘度が5.8ポイズであり、色が乳白色
である水のみを分散媒とする水性重合体分散液
を得た。
この分散液は25℃で６カ月の放置後も安定で
粒子の沈降、相分離、粘度の変化は全く見られ
なかつた。この分散液を実施例１と同様な方法
で塗布試験をしたところ、塗膜は平滑で光沢に
富み、発泡やダレの現象は見られなかつた。
実施例 ３
(A) ペルオキシ結合含有共重合体
実施例２の(A)で得られたペルオキシ結合含有
共重合体溶液を用いた。
(B) 水性重合体分散液の製造
実施例２の(B)と同様な方法で水性重合体分散
液を製造した。ただし、実施例２で用いた混合
液（）の代りに第５表に示す混合液（）を
用いた。
第５表 混合液（）の組成
ペルオキシ結合含有共重合体粉末 20部
メタアクリル酸メチル 30部
メタアクリル酸ブチル 30部
スチレン 30部
メタアクリル酸ヒドロキシエチル 10部
水 40部
生成物はブロツク共重合体を54.5重量％含む
ものであり、25℃の粘度が6.1ポイズであり、
色は乳白色であり、水のみを分散媒とする水性
重合体分散液である。
この水性重合体分散液は25℃で６カ月の放置
後も安定であり、粒子の沈降、相分離、粘度の
変化などが全く見られなかつた。
この水性重合体分散液を実施例１の(B)と同様
な方法で塗布試験を行つたところ、塗膜は平滑
で光沢に富み、発泡やダレの現象は全くみられ
なかつた。
実施例 ４
(A) ペルオキシ結合含有共重合体
実施例１の(A)で得られたペルオキシ結合含有
共重合体溶液を用いた。
(B) 水性重合体分散液の製造
実施例１の(B)と同様な方法で製造した。ただ
し実施例１の(B)の混合液（）に代えて第６表
に示す組成の混合液（）を用いた。
第６表 混合液（）の組成
ペルオキシ結合含有共重合体溶液 60部
メタアクリル酸メチル 25部
アクリル酸エチル 25部
メタアクリル酸ヒドロキシエチル ９部
アクリル酸 １部
水 60部
得られた水性重合体分散液はブロツク共重合
体を31.4重量％含み、25℃における粘度が0.5
ポイズであり、色は乳白色であつた。この水性
重合体分散液は25℃で６カ月の放置後も安定で
粒子の沈降、相分離、粘度の変化は全く見られ
なかつた。
また、この水性重合体分散液を実施例１と同
様な方法で塗布試験を行つたところ、塗膜は平
滑で光沢に富み、発泡やダレの現象は全く見ら
れなかつた。
実施例 ５〜９
(A) ペルオキシ結合含有共重合体の製造
実施例１の(A)と同様な方法で製造を行つた。
ただし実施例１の(A)のエチルセロソルブ20部に
代えて第７表に示す溶剤を用い、実施例１の混
合液（）にかえて第７表に示す混合液を用
い、また共重合反応の重合温度を実施例６にお
いては100℃とし実施例７においては90℃とし
た。また、生成物中のペルオキシ結合含有共重
合体の重量％および25℃におけるペルオキシ結
合含有共重合体溶液の粘度は第７表に示すとお
りである。[Table] The product contained 36.7% by weight of the peroxy bond-containing copolymer and was a transparent solution with a viscosity of 1.9 poise at 25°C. (B) Production of aqueous polymer dispersion In a container equipped with a stirrer, add 60 parts of the peroxy bond-containing copolymer solution obtained in (A) above to 500 parts of n-hexane at room temperature while stirring. The mixture was left to stand to obtain a white precipitate. This precipitate was separated and dried under reduced pressure at room temperature to obtain a white powder of a peroxy bond-containing copolymer. Next, 60 parts of water was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 95°C while blowing nitrogen gas, and the mixture () shown in Table 4 was charged over 2 hours. . Table 4 Composition of the mixed solution () Peroxy bond-containing copolymer powder obtained above 20 parts Methyl methacrylate 30 parts Butyl acrylate 40 parts Styrene 30 parts Water 40 parts The reaction mixture was kept at 80°C for 3 hours. It contains 55.1% by weight of block copolymer and is heated at 25°C.
An aqueous polymer dispersion having a viscosity of 5.8 poise and a milky white color using only water as a dispersion medium was obtained. This dispersion remained stable even after being left at 25°C for 6 months, with no particle sedimentation, phase separation, or viscosity change observed. When this dispersion was subjected to a coating test in the same manner as in Example 1, the coating film was smooth and glossy, and no phenomena of foaming or sagging were observed. Example 3 (A) Peroxy bond-containing copolymer The peroxy bond-containing copolymer solution obtained in Example 2 (A) was used. (B) Production of aqueous polymer dispersion An aqueous polymer dispersion was produced in the same manner as in Example 2 (B). However, instead of the mixed solution () used in Example 2, the mixed solution () shown in Table 5 was used. Table 5 Composition of mixed solution () Peroxy bond-containing copolymer powder 20 parts Methyl methacrylate 30 parts Butyl methacrylate 30 parts Styrene 30 parts Hydroxyethyl methacrylate 10 parts Water 40 parts The product is a block copolymer It contains 54.5% by weight, and its viscosity at 25℃ is 6.1 poise.
It is milky white in color and is an aqueous polymer dispersion using only water as a dispersion medium. This aqueous polymer dispersion remained stable even after being left at 25° C. for 6 months, with no particle sedimentation, phase separation, or viscosity change observed. When this aqueous polymer dispersion was subjected to a coating test in the same manner as in Example 1 (B), the coating film was smooth and glossy, with no phenomena of foaming or sagging observed. Example 4 (A) Peroxy bond-containing copolymer The peroxy bond-containing copolymer solution obtained in Example 1 (A) was used. (B) Production of aqueous polymer dispersion A dispersion was produced in the same manner as in Example 1 (B). However, in place of the mixed solution (B) of Example 1, a mixed solution (2) having the composition shown in Table 6 was used. Table 6 Composition of mixed solution () Peroxy bond-containing copolymer solution 60 parts Methyl methacrylate 25 parts Ethyl acrylate 25 parts Hydroxyethyl methacrylate 9 parts Acrylic acid 1 part Water 60 parts Obtained aqueous polymer dispersion The liquid contains 31.4% by weight of block copolymer and has a viscosity of 0.5 at 25°C.
It was poise and had a milky white color. This aqueous polymer dispersion remained stable even after being left at 25°C for 6 months, with no particle sedimentation, phase separation, or viscosity change observed. Further, when this aqueous polymer dispersion was subjected to a coating test in the same manner as in Example 1, the coating film was smooth and glossy, and no phenomena of foaming or sagging were observed. Examples 5 to 9 (A) Production of peroxy bond-containing copolymers Production was carried out in the same manner as in Example 1 (A).
However, in place of 20 parts of ethyl cellosolve in (A) of Example 1, the solvent shown in Table 7 was used, and in place of the mixture () of Example 1, the mixture shown in Table 7 was used, and the copolymerization reaction The polymerization temperature was 100°C in Example 6 and 90°C in Example 7. Further, the weight percent of the peroxy bond-containing copolymer in the product and the viscosity of the peroxy bond-containing copolymer solution at 25°C are as shown in Table 7.
【表】【table】
【表】
(B) 水性重合体分散液の製造
実施例１の(B)の混合液（）の代りに第８表
に示す組成の混合液を用い、またブロツク共重
合反応の重合温度を実施例６においては105℃
とし実施例７においては95℃とした以外は実施
例１の(B)の方法に準じて各水性重合体分散液を
製造した。ただし実施例７においては、第８表
の混合液中のペルオキシ結合含有共重合体溶液
に代り、前記(A)の工程で得られたペルオキシ結
合含有共重合体溶液60部を常温で500部のｎ−
ヘキサン中に撹拌しながら加えて放置し、白色
の沈澱物を得、その上澄液を除去した後常温で
減圧下で乾燥して得たペルオキシ結合含有共重
合体粉末を混合液の原料としたものである。
また、得られた水性重合体分散液中のブロツ
ク共重合体の含有量および25℃における水性重
合体分散液の粘度は第８表に示すとおりであ
る。[Table] (B) Production of aqueous polymer dispersion A mixture having the composition shown in Table 8 was used in place of the mixture () in (B) of Example 1, and the polymerization temperature of the block copolymerization reaction was carried out. 105℃ in example 6
Each aqueous polymer dispersion was produced according to the method (B) of Example 1, except that in Example 7, the temperature was 95°C. However, in Example 7, instead of the peroxy bond-containing copolymer solution in the mixture shown in Table 8, 60 parts of the peroxy bond-containing copolymer solution obtained in step (A) was added to 500 parts of the peroxy bond-containing copolymer solution at room temperature. n-
A white precipitate was obtained by adding it to hexane with stirring and leaving it to stand. After removing the supernatant liquid, the obtained peroxy bond-containing copolymer powder was used as the raw material for the mixed liquid. It is something. Further, the content of the block copolymer in the obtained aqueous polymer dispersion and the viscosity of the aqueous polymer dispersion at 25°C are as shown in Table 8.
【表】【table】
【表】
実施例５〜９で得られた水性重合体分散液はい
ずれも25℃で６カ月の放置後も安定で粒子の沈
降、相分離、粘度の変化は全く見られなかつた。
また、実施例１と同様な方法で塗布試験を行つ
た結果、いずれの塗膜も平滑で光沢に富み、発泡
やダレの現象は全く見られなかつた。[Table] The aqueous polymer dispersions obtained in Examples 5 to 9 were all stable even after being left at 25°C for 6 months, with no particle sedimentation, phase separation, or viscosity change observed. Further, as a result of conducting a coating test in the same manner as in Example 1, all coating films were smooth and glossy, and no phenomena of foaming or sagging were observed.
Claims (1)
は置換アルキレン基、炭素数３〜15のシクロアル
キレン基もしくは置換シクロアルキレン基または
フエニレン基もしくは置換フエニレン基を表わ
し、R2は炭素数２〜10のアルキレン基または置
換アルキレン基、 【式】 （式中、R3は水素原子またはメチル基であり、R4
は炭素数２〜10のアルキレン基または置換アルキ
レン基である。またｍ＝１〜13である）、
【式】 または【式】を表わ す。また、ｎ＝２〜20である〕 および一般式（） 〔式中、R1およびｎは前記一般式（）の場合と
同じである〕 からなる群から選ばれた１種または２種以上のポ
リメツリクペルオキシドと、下記(イ)で定義される
１種または２種以上のビニル型単量体とを共重合
させてなるペルオキシ結合含有共重合体を、下記
(ロ)で定義される１種または２種以上のビニル型単
量体と、水または水と水溶性有機溶剤との溶液中
でブロツク共重合させることを特徴とするブロツ
ク共重体が前記水または水と水溶性有機溶剤との
溶液中に分散している水性重合体分散液の製造
法。 (イ) 前記のポリメリツクペルオキシドと共重合さ
せる１種または２種以上のビニル型単量体と
は、その重合体が水または水と水溶性有機溶剤
との溶液に溶解性を有するものである。 (ロ) (イ)で定義されるビニル型単量体と異なる１種
または２種以上の他のビニル型単量体とは、そ
の重合体が水または水と水溶性有機溶剤との溶
液に溶解しないものである。 (ハ) 前記の水と水溶性有機溶剤との溶液とは、前
記のペルオキシ結合含有共重合体の構成成分で
あるビニル型単量体の重合体を溶解し、かつ、
前記のペルオキシ結合含有共重合体にブロツク
共重合させる前記の他のビニル型単量体の重合
体を溶解しない溶液である。[Claims] 1 General formula () [In the formula, R 1 represents an alkylene group or substituted alkylene group having 1 to 18 carbon atoms, a cycloalkylene group or substituted cycloalkylene group having 3 to 15 carbon atoms, or a phenylene group or substituted phenylene group, and R 2 represents an alkylene group having 2 to 18 carbon atoms or a substituted cycloalkylene group, ~10 alkylene groups or substituted alkylene groups, [Formula] (wherein R 3 is a hydrogen atom or a methyl group, R 4
is an alkylene group or substituted alkylene group having 2 to 10 carbon atoms. Also, m = 1 to 13),
Represents [formula] or [formula]. In addition, n = 2 to 20] and general formula () [In the formula, R 1 and n are the same as in the above general formula ()] One or more polymetrylic peroxides selected from the group consisting of: and 1 defined in (a) below. A peroxy bond-containing copolymer obtained by copolymerizing a species or two or more vinyl monomers is as follows.
A block copolymer characterized in that it is block copolymerized with one or more vinyl monomers defined in (b) in water or a solution of water and a water-soluble organic solvent. A method for producing an aqueous polymer dispersion in a solution of water and a water-soluble organic solvent. (b) The one or more vinyl monomers to be copolymerized with the polymeric peroxide mentioned above are those whose polymer is soluble in water or a solution of water and a water-soluble organic solvent. . (b) One or more other vinyl monomers different from the vinyl monomer defined in (a) means that the polymer is dissolved in water or in a solution of water and a water-soluble organic solvent. It does not dissolve. (c) The above-mentioned solution of water and a water-soluble organic solvent dissolves a polymer of a vinyl monomer that is a constituent component of the above-mentioned peroxy bond-containing copolymer, and
This is a solution that does not dissolve the polymer of the other vinyl monomer to be block copolymerized with the peroxy bond-containing copolymer.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12705679A JPS5650908A (en) | 1979-10-02 | 1979-10-02 | Manufacture of aqueous polymer dispersion |
| US06/192,161 US4318834A (en) | 1979-10-02 | 1980-09-29 | Method for producing an aqueous liquid dispersion of polymers |
| CA000361266A CA1157176A (en) | 1979-10-02 | 1980-09-30 | Method for producing an aqueous liquid dispersion of polymers |
| GB8031603A GB2065672B (en) | 1979-10-02 | 1980-10-01 | Process for producing an aqueous polymer dispersion |
| DE3037162A DE3037162C2 (en) | 1979-10-02 | 1980-10-01 | Process for the preparation of an aqueous polymer dispersion |
| DE3050841A DE3050841C2 (en) | 1979-10-02 | 1980-10-01 | Process for the preparation of an aqueous polymer dispersion |
| DE3050850A DE3050850C2 (en) | 1979-10-02 | 1980-10-01 | Process for the preparation of an aqueous polymer dispersion |
| IT25067/80A IT1133830B (en) | 1979-10-02 | 1980-10-01 | PROCEDURE FOR THE PRODUCTION OF A WATER LIQUID DISPERSION OF POLYMERS |
| NLAANVRAGE8005474,A NL187977C (en) | 1979-10-02 | 1980-10-02 | METHOD FOR PREPARING AN AQUEOUS LIQUID POLYMER DISPERSION |
| FR8021103A FR2466479B1 (en) | 1979-10-02 | 1980-10-02 | PROCESS FOR THE PREPARATION OF AN AQUEOUS LIQUID DISPERSION OF POLYMERS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12705679A JPS5650908A (en) | 1979-10-02 | 1979-10-02 | Manufacture of aqueous polymer dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5650908A JPS5650908A (en) | 1981-05-08 |
| JPS6239162B2 true JPS6239162B2 (en) | 1987-08-21 |
Family
ID=14950499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12705679A Granted JPS5650908A (en) | 1979-10-02 | 1979-10-02 | Manufacture of aqueous polymer dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5650908A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61152714A (en) * | 1984-12-26 | 1986-07-11 | Ube Saikon Kk | Thermoplastic elastomer resin and production thereof |
-
1979
- 1979-10-02 JP JP12705679A patent/JPS5650908A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5650908A (en) | 1981-05-08 |
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