JPH036235A - Reactive resin particle - Google Patents
Reactive resin particleInfo
- Publication number
- JPH036235A JPH036235A JP1137385A JP13738589A JPH036235A JP H036235 A JPH036235 A JP H036235A JP 1137385 A JP1137385 A JP 1137385A JP 13738589 A JP13738589 A JP 13738589A JP H036235 A JPH036235 A JP H036235A
- Authority
- JP
- Japan
- Prior art keywords
- resin particles
- reactive resin
- meth
- acrylate
- parts
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 42
- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 8
- 239000000839 emulsion Substances 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- -1 as flow regulators Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NUTJVZGIRRFKKI-UHFFFAOYSA-N (2-oxo-1,3-dioxolan-4-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1COC(=O)O1 NUTJVZGIRRFKKI-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 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
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-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
- 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000282344 Mellivora capensis Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 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
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- 239000000463 material 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000007519 polyprotic acids 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
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Medicinal Preparation (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は新規な反応性樹脂粒子に関し、更に詳細には塗
料、インク、接着剤、医療、医薬材料又は高分子凝集剤
等の分野で有用な反応性樹脂粒子に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a novel reactive resin particle, and more specifically, it is useful in the fields of paints, inks, adhesives, medicine, pharmaceutical materials, polymer flocculants, etc. This invention relates to reactive resin particles.
〈従来の技術〉
反応性樹脂粒子は塗料、インク、接着剤等の工業分野に
おいて、流動調整剤、増量剤、あるいは物性向上用の添
加剤として、さらには、医療、医薬品の機能性担体材料
として広く使用され注目を集めている。特に最近では上
記分野において、低公害、省資源化への要望が高まって
きており、従来の有機媒体を主体とする組成物から、水
を媒体とし、かつ低温で反応する組成物への転化が強く
望まれている。しかしながら、従来の反応性樹脂粒子は
、有機媒体中での反応を中心としたものであり、樹脂粒
子に担持される官能基としては水酸基、カルボキシル基
、アミノ基、エポキシ基、イソシアネート基が主体であ
る。これらの官能基は。<Prior art> Reactive resin particles are used in industrial fields such as paints, inks, and adhesives, as flow regulators, extenders, or additives to improve physical properties, and as functional carrier materials for medical and pharmaceutical products. It is widely used and attracts attention. Particularly in recent years, demands for low pollution and resource conservation have been increasing in the above fields, and there has been a shift from conventional compositions based on organic media to compositions that use water as a medium and react at low temperatures. Highly desired. However, conventional reactive resin particles mainly undergo reactions in organic media, and the functional groups supported on resin particles are mainly hydroxyl groups, carboxyl groups, amino groups, epoxy groups, and isocyanate groups. be. These functional groups are.
脱水縮合あるいは付加重合により他の官能基と化学結合
を形成するものであるが、いずれの反応系も水の存在が
反応の妨げとなり、上記要望を必ずしも満足するもので
はないのが現状である。Chemical bonds are formed with other functional groups through dehydration condensation or addition polymerization, but the presence of water in any of these reaction systems hinders the reaction, and the above requirements are not necessarily met at present.
〈発明が解決しようとする課題〉
本発明の目的は、低温及び水媒体中においても高反応性
を有する新規な反応性樹脂粒子を提供することにある。<Problems to be Solved by the Invention> An object of the present invention is to provide novel reactive resin particles that have high reactivity even at low temperatures and in an aqueous medium.
く課題を解決するための手段〉
本発明によれば、平均粒径が０．０１〜１００μｍの樹
脂粒子であって、該樹脂粒子に下記一般式（Ｉ）
♂
（式中Ｒ工、Ｒ２及びＲ１は、各々水素原子又は炭素数
１〜４のアルキル基を示す）で表わされるシクロカーボ
ネート基を担持させてなることを特徴とする反応性樹脂
粒子が提供される。Means for Solving the Problems> According to the present invention, resin particles having an average particle diameter of 0.01 to 100 μm, the resin particles having the following general formula (I) ♂ (in the formula R, R2 and Reactive resin particles are provided, characterized in that each R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明の反応性樹脂粒子は、特定の粒径を有し。The reactive resin particles of the present invention have a specific particle size.
且つ特定のシクロカーボネート基を担持させてなること
を特徴とする。It is also characterized by supporting a specific cyclocarbonate group.
本発明において、担持させるシクロカーボネート基は下
記一般式（Ｉ）で表わすことができ♂
式中Ｒ工、Ｒ２及びＲ１は、各々水素原子又は炭素数１
〜４のアルキル基を示す。前記Ｒ□、Ｒ２及びＲ３の炭
素数が５以上の場合には、得られる反応性樹脂粒子の反
応性が低下する恐れがある。前記一般式（りで表わされ
るシクロカーボネート基は、水媒体中で極めて安定であ
り、かつアミノ基と低温で反応し、カーバメートを形成
することが知られている。尚シクロカーボネート基とア
ミノ基との反応に関しては、フランス国特許第６２６１
７号明細書；Ｈ，Ｎａｊｅｒ、 Ｐ、 Ｃｈａｂｂｉｅ
ｒ ａｔｅｌ。In the present invention, the supported cyclocarbonate group can be represented by the following general formula (I) ♂ In the formula, R, R2 and R1 are each a hydrogen atom or a carbon number of 1
~4 alkyl group is shown. When the number of carbon atoms in R□, R2, and R3 is 5 or more, the reactivity of the resulting reactive resin particles may decrease. It is known that the cyclocarbonate group represented by the general formula (RI) is extremely stable in an aqueous medium and reacts with an amino group at low temperatures to form a carbamate. Regarding the reaction, French Patent No. 6261
Specification No. 7; H, Najer, P, Chabbie
ratel.
Ｃｏｍｐｔ、 Ｒｅｎｄ、、２３８．６９０〜６９２．
１９５４等の報文に記載されている。Compt, Rend, 238.690-692.
It is described in reports such as 1954.
本発明において前記一般式（１）で表ねされるシクロカ
ーボネート基を担持させるには、前記シクロカーボネー
ト基を有するα、β−エチレン性不飽和単量体と乳化重
合、懸濁重合またはＮＡＤ重合等の公知の重合方法によ
り行うか、または前記シクロカーボネート基を有するポ
リマーを界面活性剤及び／又は高分子界面活性剤の存在
下、機械的に水系又は非水系媒体中に乳化する強制乳化
法により行うことができる。In the present invention, in order to support the cyclocarbonate group represented by the general formula (1), emulsion polymerization, suspension polymerization or NAD polymerization with the α,β-ethylenically unsaturated monomer having the cyclocarbonate group is performed. or by a forced emulsification method in which the polymer having a cyclocarbonate group is mechanically emulsified in an aqueous or non-aqueous medium in the presence of a surfactant and/or a polymeric surfactant. It can be carried out.
前記シクロカーボネート基を有するα、β−エチレン性
不飽和単量体としては１例えば４−（メタ）アクリロイ
ルオキシメチル−１，３−ジオキソラン−２−オン、４
−（メタ）アクリロイルオキシエチル−１，３−ジオキ
ソラン−２−オン、４−（メタ）アクリロイルオキシプ
ロピレン−１゜３−ジオキソラン−２−オン、４−（メ
タ）アクリロイルオキシブチル−１，３−ジオキソラン
−２−オン等を挙げることができ、これらの単量体はオ
キソシラン化合物と、炭酸ガスとを公知の方法（例えば
＾、 Ｂａｂａ、 Ｔ、 Ｎｏｚａｋｉ、 Ｂｕｌｌ、
Ｃｈｅｗ。Examples of the α,β-ethylenically unsaturated monomer having a cyclocarbonate group include 1, for example, 4-(meth)acryloyloxymethyl-1,3-dioxolan-2-one, 4
-(meth)acryloyloxyethyl-1,3-dioxolan-2-one, 4-(meth)acryloyloxypropylene-1゜3-dioxolan-2-one, 4-(meth)acryloyloxybutyl-1,3- Dioxolan-2-one, etc. can be mentioned, and these monomers can be prepared by combining an oxosilane compound and carbon dioxide gas by a known method (for example, Baba, T., Nozaki, Bull,
Chew.
Ｓｏｃ、Ｊｐｎ、、６０．１５５２〜１５４４（１９８
７））により反応させることによって容易に得ることが
できる。また前記α、β−エチレン性不飽和単量体と共
に、所望により用いる他の重合性単量体としては１例え
ばアクリル酸、メタクリル酸、イタコン酸、マレイン酸
、フマル酸又はこれらのエステル類等を挙げることがで
き、スチレン、ビニルトルエン、アクリロニトリル、酢
酸ビニル等を含ませることもできる。またここで特にア
クリル酸エステル類、メタクリル酸エステル類を使用す
る場合には、下記一般式（ｎ）
ＣＨ，＝Ｃ−Ｃｏｏ−Ｒ。Soc, Jpn, 60.1552-1544 (198
7)) can be easily obtained by reaction. In addition to the α,β-ethylenically unsaturated monomer, other polymerizable monomers that may be used as desired include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, or esters thereof. Styrene, vinyltoluene, acrylonitrile, vinyl acetate and the like can also be included. Moreover, especially when using acrylic esters and methacrylic esters here, the following general formula (n) CH,=C-Coo-R is used.
Ｉ ・・・ （ＩＩ）Ｒ４
（式中Ｒ４は水素原子又はメチル基を示し、Ｒ６は炭素
数１〜１５の飽和炭化水素基、水酸基又はエポキシ基を
示す）で表わす化合物が好ましく、式中Ｒ６が飽和炭化
水素基の場合としては、例えば（メタ）アクリル酸メチ
ル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブ
チル、（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等を挙げることができ、また式
中Ｒ９が水酸基又はエポキシ基の場合には、例えば（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−ヒドロキシエチル、グリシジルアクリレ
ート、グリシジルメタクリレート等を挙げることができ
る。一方前記シクロカーボネート基を有するポリマーは
、例えば西ドイツ特許第３５２９２６３号明細書等に記
載される方法により得られる他、通常重版されているビ
スフェノールＡ又はビスフェノールＦ型のエポキシ樹脂
、さらには、グリシジル基を有するポリマーと炭酸ガス
を反応させることにより容易に得ることが可能である。I ... (II) A compound represented by R4 (in the formula, R4 represents a hydrogen atom or a methyl group, and R6 represents a saturated hydrocarbon group having 1 to 15 carbon atoms, a hydroxyl group, or an epoxy group) is preferred, and in the formula, R6 Examples of saturated hydrocarbon groups include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc. In the formula, when R9 is a hydroxyl group or an epoxy group, examples include 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl acrylate, glycidyl methacrylate, etc. be able to. On the other hand, the polymer having a cyclocarbonate group can be obtained, for example, by the method described in West German Patent No. 3,529,263, etc., and can also be obtained by a bisphenol A or bisphenol F type epoxy resin which is usually reprinted, and further by a glycidyl group-containing epoxy resin. It can be easily obtained by reacting a polymer containing carbon dioxide with carbon dioxide gas.
本発明において、前記各方法により得られる反応性樹脂
粒子の平均粒径は０．０１μｍ未満の場合、製造の際の
系の粘度が高くなり作業性が低下し、また１００μｍを
超える場合、塗料又はインク等に使用する際に良好な平
滑性が得られず、更には沈降安定性が低下するので０．
０１〜１００μｍの範囲とする必要がある０反応性樹脂
粒子の粒径を前記範囲内に調製するには、前記製造方法
により一般に用いる方法により行うことができる。In the present invention, when the average particle size of the reactive resin particles obtained by each of the above methods is less than 0.01 μm, the viscosity of the system during production increases and workability decreases, and when it exceeds 100 μm, the paint or When used in ink, etc., good smoothness cannot be obtained, and furthermore, sedimentation stability is reduced, so 0.
In order to adjust the particle size of the zero-reactive resin particles, which needs to be in the range of 0.01 to 100 μm, to within the above range, it can be carried out by the method generally used in the production method described above.
即ち、使用する界面活性剤１分散安定剤、高分子界面活
性剤の種類と使用量、分散媒、単量体の種類、更には滴
下速度１重合温度等の合成条件を適時選択することによ
り行うことができる。That is, it is carried out by appropriately selecting the synthesis conditions such as the surfactant 1 dispersion stabilizer used, the type and amount of polymeric surfactant used, the dispersion medium, the type of monomer, and also the dropping rate 1 polymerization temperature. be able to.
さらに本発明の反応性樹脂粒子は、必要に応じて架橋さ
せることも可能であって、例えば分子内に２個以上のラ
ジカル重合可能なエチレン性不飽和基を有する単量体等
を用いて公知の方法により架橋させることができる。前
記エチレン性不飽和基を有する単量体としては、例えば
多価アルコールの重合性不飽和モノカルボン酸エステル
、多価塩基酸の重合性不飽和アルコールエステル又は２
個以上のビニル基で置換された芳香族化合物等を挙げる
ことができ、具体的には、エチレングリコールジ（メタ
）アクリレート、トリエチレングリコールジ（メタ）ア
クリレート、テトラエチレングリコールジ（メタ）アク
リレート、１．３−ブチレングリコールジ（メタ）アク
リレート、トリメチロールプロパントリ（メタ）アクリ
レート、１．４−ブタンジオールジ（メタ）アクリレー
ト、ネオペンチルグリコールジ（メタ）アクリレート。Furthermore, the reactive resin particles of the present invention can be crosslinked if necessary, for example by using a known monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule. Crosslinking can be carried out by the method described in the following. Examples of the monomer having an ethylenically unsaturated group include a polymerizable unsaturated monocarboxylic acid ester of a polyhydric alcohol, a polymerizable unsaturated alcohol ester of a polybasic acid, or a monomer having an ethylenically unsaturated group.
Examples include aromatic compounds substituted with more than one vinyl group, specifically ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1.3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate.
１．６−ヘキサンシオールジ（メタ）アクリレート、ペ
ンタエリスリトールジ（メタ）アクリレート、ペンタエ
リスリトールトリ（メタ）アクリレート、ペンタエリス
リトールテトラ（メタ）アクリレート、グリシジル基（
メタ）アクリレート、グリセロールアリロキシジメタク
リレート、１゜１．１−トリスヒドロキシメチルエタン
ジ（メタ）アクリレート、１，１．１−トリスヒドロキ
シメチルエタントリ（メタ）アクリレート、１，１゜１
−トリスヒドロキシメチルプロパンジ（メタ）アクリレ
ート、１，１．１−トリスヒドロキシメチルプロパント
リ（メタ）アクリレート、トリアリルシアヌレート、ト
リアリルイソシアヌレート。1.6-hexanethiol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycidyl group (
meth)acrylate, glycerol allyloxy dimethacrylate, 1゜1.1-trishydroxymethylethane di(meth)acrylate, 1,1.1-trishydroxymethylethane tri(meth)acrylate, 1,1゜1
- Trishydroxymethylpropane di(meth)acrylate, 1,1.1-trishydroxymethylpropane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate.
トリアリルトリメリテート、ジアリルテレフタレート、
ジアリルフタレート又はジビニルベンゼン等を挙げるこ
とができる。triallyl trimellitate, diallyl terephthalate,
Examples include diallylphthalate and divinylbenzene.
本発明の反応性樹脂粒子は、シクロカーボネート基を担
持させてなるので、使用に際しては、該シクロカーボネ
ート基と反応して化学結合を形成するアミノ基、フェノ
ール、カルボキシル基等の活性水素を有する化合物との
反応を各種用途に利用して用いることができるが、該反
応の際の温度を低温で行うためには、脂肪族モノ又はポ
リアミン、芳香族モノ又はポリアミン、ポリアミド、ア
ミノ酸化合物、天然タンパク質等のアミノ基含有化合物
を用いるのが好ましい。該アミノ基含有化合物と、反応
性樹脂粒子との反応は、水媒体、非水系媒体のいずれに
おいても低温で定量的に進行することから、本発明の反
応性樹脂粒子は水性。Since the reactive resin particles of the present invention carry a cyclocarbonate group, when used, a compound having active hydrogen such as an amino group, phenol, or carboxyl group that reacts with the cyclocarbonate group to form a chemical bond is required. The reaction can be used for various purposes, but in order to carry out the reaction at a low temperature, aliphatic mono- or polyamines, aromatic mono- or polyamines, polyamides, amino acid compounds, natural proteins, etc. It is preferable to use an amino group-containing compound. Since the reaction between the amino group-containing compound and the reactive resin particles proceeds quantitatively at low temperatures in both aqueous and non-aqueous media, the reactive resin particles of the present invention are aqueous.
有機溶剤系のいずれの組成物にも応用可能である。It is applicable to any organic solvent-based composition.
〈発明の効果〉
本発明の反応性樹脂粒子は、従来型の反応性樹脂粒子の
欠点を大巾に改善し、低温で、しかも水媒体中又は有機
媒体中においても反応可能であるので、塗料、インク、
接着剤等の流動調整剤、増量剤あるいは物性向上用の添
加剤として、さらには医療、医薬品の機能性担体材料及
び高分子凝集剤等として極めて有用である。<Effects of the Invention> The reactive resin particles of the present invention greatly improve the drawbacks of conventional reactive resin particles, and can react at low temperatures even in an aqueous medium or an organic medium, so they can be used in paints. ,ink,
It is extremely useful as a flow regulator for adhesives, a filler, or an additive for improving physical properties, and as a functional carrier material and polymer flocculant for medical and pharmaceutical products.
〈実施例〉
以下、実施例により本発明をさらに詳細に説明するが１
本発明はこれらの例によってなんら限定されるものでは
ない。<Example> The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited in any way by these examples.
尚、例中の部は重量部を示す。In addition, parts in the examples indicate parts by weight.
笑舊１
攪拌機、冷却器、温度制御装置、窒素導入管および滴下
ロートを備えた２Ｑの反応容器に脱イオン水８３０部、
ジオクチルスルホコハク酸ナトリウム４．５部、ロンガ
リット０．７部、リン酸三ナトリウム１２水塩３．５部
、エチレンジアミン四酢酸４ナトリウム０．３部を仕込
み、窒素ガス気流下昇温して４０℃に保った。次いで硫
酸第一鉄７水塩０．２部を脱イオン水４４部に溶解した
水溶液およびｔ−ブチルヒドロペルオキシド０．５部を
脱イオン水４４部に溶解した水溶液を仕込んだ後、メチ
ルメタクリレート３０４．４部、４−メタクリロイルオ
キシメチル−１，３−ジオキソラン−２−オン１３１．
４部及びエチレングリコールジメタクリレート２．２部
の混合物を３時間かけて滴下した。該モノマー混合物の
滴下終了後。1. 830 parts of deionized water was added to a 2Q reaction vessel equipped with a stirrer, a cooler, a temperature control device, a nitrogen inlet tube, and a dropping funnel.
4.5 parts of sodium dioctyl sulfosuccinate, 0.7 parts of Rongalite, 3.5 parts of trisodium phosphate dodecahydrate, and 0.3 parts of tetrasodium ethylenediaminetetraacetate were charged, and the temperature was raised to 40°C under a stream of nitrogen gas. I kept it. Next, an aqueous solution of 0.2 part of ferrous sulfate heptahydrate dissolved in 44 parts of deionized water and an aqueous solution of 0.5 part of t-butyl hydroperoxide dissolved in 44 parts of deionized water were charged, and then methyl methacrylate 304 was added. .4 parts, 4-methacryloyloxymethyl-1,3-dioxolan-2-one 131.
A mixture of 4 parts and 2.2 parts of ethylene glycol dimethacrylate was added dropwise over 3 hours. After the completion of dropping the monomer mixture.
温度を６０℃に昇温し、２時間攪拌を継続して反応を終
了したところ、加熱残分は３２．１重量％、平均粒径は
０．２４６μｍであった。反応条件及び加熱残分、平均
粒径並びに反応性の尺度となるゲル化時間の結果を表１
に示し、また該ゲル化時間の測定方法を下記に示す。When the temperature was raised to 60° C. and stirring was continued for 2 hours to complete the reaction, the heating residue was 32.1% by weight and the average particle size was 0.246 μm. Table 1 shows the results of reaction conditions, heating residue, average particle size, and gelation time, which is a measure of reactivity.
The method for measuring the gelation time is shown below.
ヱ土似薩■立夾定
１００ｍＱのビーカー中に実施例１で得られた反応性樹
脂粒子を含む水分散液２０ｇを採り、ヘキサメチレンジ
アミンを水中濃度が０．２モル／Ｉｌとなるように添加
した。次いでビーカーを５０℃の温湯中に浸し、ビーカ
ーと温湯の液面が一致するように固定した後攪拌を開始
し、内容物がゲル化するまでの時間を測定した。該ゲル
化時間を測定することによって、得られた樹脂粒子の反
応性を確認することができる。Take 20 g of the aqueous dispersion containing the reactive resin particles obtained in Example 1 into a 100 mQ beaker, and add hexamethylene diamine to a concentration of 0.2 mol/Il in the water. Added. Next, the beaker was immersed in hot water at 50° C., and after fixing the beaker and the hot water so that the liquid levels were the same, stirring was started, and the time until the contents gelled was measured. By measuring the gelation time, the reactivity of the obtained resin particles can be confirmed.
夾庭銖主
攪拌機、冷却器、温度制御装置、窒素導入管および滴下
ロートを備えたＩＱの反応容器に脱イオン水４８０部及
びジオクチルスルホコハク酸ナトリウム０．８部を仕込
み、窒素気流下昇温し６０℃に保った。次いでチオ硫酸
ナトリウム０．３部と脱イオン水１５部および過硫酸カ
リウム０．２５部と脱イオン水１５部の水溶液を仕込ん
だ後、メチルメタクリレート１０３部、４−メタクリロ
イルオキシメチル−１，３−ジオキソラン−２−オン４
４．４部及びエチレングリコールジメタクリレート０．
７５部を混合し、モノマー混合物を得、該モノマー混合
物の１／１ｏ量を仕込み、次いで重合反応が生じたこと
を確認した後、該モノマー混合物の残りを３時間かけて
滴下した。七ツマー混合物の滴下を開始した時点から３
０分ごとにチオ硫酸ナトリウム０．３部と脱イオン水１
５部および過硫酸カリウム０．２５部と脱イオン水１５
部の各水溶液の１／７量ずつを順次添加した。モノマー
混合物の滴下終了後、６０℃で３時間攪拌を継続し反応
を終了したところ、加熱残分は２１．４重量％、平均粒
径は０．０８５μｍであった。反応条件及び加熱残分、
平均粒径並びにゲル化時間の結果を表１に示す。480 parts of deionized water and 0.8 parts of sodium dioctyl sulfosuccinate were charged into an IQ reaction vessel equipped with a main stirrer, a cooler, a temperature control device, a nitrogen introduction tube, and a dropping funnel, and the mixture was heated under a nitrogen stream. It was kept at 60°C. Next, after charging an aqueous solution of 0.3 parts of sodium thiosulfate, 15 parts of deionized water, and 0.25 parts of potassium persulfate and 15 parts of deionized water, 103 parts of methyl methacrylate, 4-methacryloyloxymethyl-1,3- Dioxolan-2-one 4
4.4 parts and 0.4 parts of ethylene glycol dimethacrylate.
75 parts were mixed to obtain a monomer mixture, 1/10 of the monomer mixture was charged, and after confirming that a polymerization reaction had occurred, the remainder of the monomer mixture was added dropwise over 3 hours. 3 from the time of starting the dripping of the 7-mer mixture
0.3 parts of sodium thiosulfate and 1 part of deionized water every 0 min.
5 parts and 0.25 parts of potassium persulfate and 15 parts of deionized water.
1/7 of each aqueous solution was sequentially added. After the monomer mixture was added dropwise, stirring was continued at 60° C. for 3 hours to complete the reaction, and the heating residue was 21.4% by weight and the average particle size was 0.085 μm. Reaction conditions and heating residue,
Table 1 shows the results of average particle size and gelation time.
失斑五主five masters of spotting
Claims (1)
て、該樹脂粒子に下記一般式（ I ） ▲数式、化学式、表等があります▼…（ I ） （式中Ｒ＿１、Ｒ＿２及びＲ＿３は、各々水素原子又は
炭素数１〜４のアルキル基を示す）で表わされるシクロ
カーボネート基を担持させてなることを特徴とする反応
性樹脂粒子。 ２）前記反応性樹脂粒子が、架橋されていることを特徴
とする請求項１記載の反応性樹脂粒子。[Claims] 1) Resin particles having an average particle diameter of 0.01 to 100 μm, the resin particles having the following general formula (I) ▲ mathematical formula, chemical formula, table, etc. ▼...(I) (formula Reactive resin particles, characterized in that R_1, R_2 and R_3 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 2) The reactive resin particles according to claim 1, wherein the reactive resin particles are crosslinked.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1137385A JP2623832B2 (en) | 1989-06-01 | 1989-06-01 | Reactive resin particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1137385A JP2623832B2 (en) | 1989-06-01 | 1989-06-01 | Reactive resin particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH036235A true JPH036235A (en) | 1991-01-11 |
| JP2623832B2 JP2623832B2 (en) | 1997-06-25 |
Family
ID=15197453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1137385A Expired - Fee Related JP2623832B2 (en) | 1989-06-01 | 1989-06-01 | Reactive resin particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2623832B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402564C (en) * | 2006-02-20 | 2008-07-16 | 四川大学 | Water-soluble organic amphoteric polymer copolymer and preparation method thereof |
| JP2022134369A (en) * | 2021-03-03 | 2022-09-15 | 共栄社化学株式会社 | Polymer, water-insoluble resin particle, material for medical use, material for biochemical experiment, and immobilized physiologically active substance |
| WO2025028203A1 (en) * | 2023-07-28 | 2025-02-06 | リンテック株式会社 | Emulsion, fine particles, and resin composition |
-
1989
- 1989-06-01 JP JP1137385A patent/JP2623832B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402564C (en) * | 2006-02-20 | 2008-07-16 | 四川大学 | Water-soluble organic amphoteric polymer copolymer and preparation method thereof |
| JP2022134369A (en) * | 2021-03-03 | 2022-09-15 | 共栄社化学株式会社 | Polymer, water-insoluble resin particle, material for medical use, material for biochemical experiment, and immobilized physiologically active substance |
| WO2025028203A1 (en) * | 2023-07-28 | 2025-02-06 | リンテック株式会社 | Emulsion, fine particles, and resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2623832B2 (en) | 1997-06-25 |
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