JPS62177007A - Production of high-concentration reactive microgel - Google Patents
Production of high-concentration reactive microgelInfo
- Publication number
- JPS62177007A JPS62177007A JP1835786A JP1835786A JPS62177007A JP S62177007 A JPS62177007 A JP S62177007A JP 1835786 A JP1835786 A JP 1835786A JP 1835786 A JP1835786 A JP 1835786A JP S62177007 A JPS62177007 A JP S62177007A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- meth
- reactive
- microgel
- monomers
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 7
- 229920002601 oligoester Polymers 0.000 claims abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 10
- 239000011882 ultra-fine particle Substances 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000010949 copper Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000002245 particle Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- -1 ester acrylate Chemical class 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010024229 Leprosy Diseases 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- TXHIDIHEXDFONW-UHFFFAOYSA-N benzene;propan-2-one Chemical compound CC(C)=O.C1=CC=CC=C1 TXHIDIHEXDFONW-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 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
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 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
- 239000004575 stone Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はアクリル酸エステル類などのエチレン性二重結
合を有する単量体を主成分とし、さらに１〜５重量％の
それと共重合し得るＮ−メチロールアクリルアミド、２
−ヒドロキシエチル（メタ）アクリレート、グリシジル
（メタ）アクリレートなどの官能性単量体を水性媒体中
で乳化共重合するに当って１分子中に２ｇｉ以上の（メ
タ）アクリロイル基をもつ水溶性のオリゴエステルアク
リレート系の反応性乳化剤を用いて粒子径が５０ｎｍ以
下の超微粒子で、かつ、粒子内に３次元網目構造を有す
る反応性ミクロゲルを高濃度に分散安定性良く製造する
方法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention has a monomer having an ethylenic double bond such as acrylic acid ester as a main component, and can be further copolymerized with 1 to 5% by weight of the monomer having an ethylenic double bond. N-methylol acrylamide, 2
- For emulsion copolymerization of functional monomers such as hydroxyethyl (meth)acrylate and glycidyl (meth)acrylate in an aqueous medium, water-soluble oligomers having 2 gi or more (meth)acryloyl groups in one molecule are used. The present invention relates to a method for producing highly concentrated reactive microgels with good dispersion stability, which are ultrafine particles with a particle size of 50 nm or less and have a three-dimensional network structure within the particles, using an ester acrylate-based reactive emulsifier.
（従来の技術）
最近の学説によると耐久性のある塗膜、たとえばうるし
膜や不飽和ポリエステル樹脂、アルキッド樹脂塗膜など
は塗膜形成過程においてミクロゲルを形成しつつ硬化反
応し、架橋密度の低いポリマー中に架橋密度の高い部分
のはめ込まれたような輪郭構造をもった不均一な網目構
造をもった石垣構造を持っていると考えられている。し
たがって反応性ミクロゲルは塗料材料として理想的なも
のと考えられている。(Prior art) According to recent theories, durable coatings such as lacquer coatings, unsaturated polyester resin coatings, and alkyd resin coatings undergo a curing reaction while forming microgels during the coating film formation process, resulting in low crosslinking density. It is thought to have a stone wall structure with a non-uniform network structure with a contour structure in which parts with high crosslink density are embedded in the polymer. Therefore, reactive microgels are considered ideal as paint materials.
しかしながら、従来の技術ではこのような反応性ミクロ
ゲルの合成において系全体をゲル化させることなく、高
濃度反応性ミクロゲルの安定な分散体を得ることは非常
に困難であった。特に粒子径が５０ｎｍ以下の超微粒子
の反応性ミクロゲルを高濃度で合成する方法は知られて
いない。However, with conventional techniques, it has been extremely difficult to obtain a stable dispersion of highly concentrated reactive microgels without gelling the entire system in the synthesis of such reactive microgels. In particular, there is no known method for synthesizing ultrafine reactive microgels with a particle diameter of 50 nm or less at high concentrations.
従来、反応性ミクロゲルの製造法としては、放射線照射
による架橋やジビニルベンゼン、フタル醇ジアリル、ジ
メタクリル酸エチレングリコール、トリアクリル酸エス
テル、アリルアクリレートなどの４官能性以上の架橋性
単量体を重合もしくは共重合する方法が知られている。Conventionally, methods for producing reactive microgels include crosslinking by radiation irradiation and polymerization of tetrafunctional or higher crosslinkable monomers such as divinylbenzene, diallyl phthalate, ethylene glycol dimethacrylate, triacrylate, and allyl acrylate. Alternatively, a method of copolymerization is known.
（発明が解決しようとする問題点）
しかしながら、これらの架橋性単量体を用いた場合には
、硫酸ドデシルナトリウムなどの性能の良いアニオン性
界面活性剤を乳化剤として多量に使用しても重合安定性
が悪く、高濃度の分散液を得ることはできないという欠
点を有していた。これはジビニルベンゼンなどの４官能
性の架橋性単量体を用いるために未反応のペンダントビ
ニル基が残存してポリマーラテックス（ミクロゲル）粒
子表面が反応性に富むために重合過程でアグロメリゼー
ションを生じ系全体がゲル化したり、白色の凝集粒子を
生じるためである。したがってポリマー濃度は固型分で
８〜１６重量％の低濃度で重合を止めなければならない
欠点があって実用上必要な４０重量％以上の高濃度の反
応性ミクロゲルを生成させることは非常に困難であった
。(Problem to be solved by the invention) However, when these crosslinking monomers are used, polymerization does not stabilize even if a large amount of a high-performance anionic surfactant such as sodium dodecyl sulfate is used as an emulsifier. However, it has the disadvantage that it has poor properties and cannot obtain a highly concentrated dispersion. This is because unreacted pendant vinyl groups remain due to the use of a tetrafunctional crosslinking monomer such as divinylbenzene, making the polymer latex (microgel) particle surface highly reactive, resulting in agglomerization during the polymerization process. This is because the entire system gels or white agglomerated particles are generated. Therefore, polymerization must be stopped at a low polymer concentration of 8 to 16% by weight in terms of solid content, making it extremely difficult to produce a reactive microgel with a high concentration of 40% by weight or more, which is necessary for practical use. Met.
またジビニルベンゼンなどの多官能性単量体は共重合し
にくく重合速度も著しく遅＜１０〜３０時間を要し、乳
化剤も著しく多量に用いるため乳化剤の副作用が大きな
問題となるなど工業的用途への実用化には大きな問題が
あった。In addition, polyfunctional monomers such as divinylbenzene are difficult to copolymerize, and the polymerization rate is extremely slow, requiring 10 to 30 hours. Emulsifiers are also used in extremely large amounts, which causes side effects of emulsifiers to become a major problem. There were major problems in its practical application.
（問題点を解決するための手段）
本発明者らは上記従来の方法がジビニルベンゼンなどの
架橋性単量体を重合もしくは共重合する方法であるため
に粒子内架橋だけでなく同時に粒子表面にも反応性を付
与できるという利点もあるが、一方この利点である反応
性に富むペンダントビニル基が生成した反応性ミクロゲ
ルの凝集を著しく促進する欠点ともなっていることがら
、これらの架橋性単量体を用いないでもポリマーラテッ
クス粒子内に架橋構造を導入しうる方法を開発するため
鋭意研究を進めた結果、ジビニルベンゼンなどの公知の
架橋性単量体のかわりに、ある種の特殊な化学構造をも
った反応性乳化剤を用い、かつ、重合開始剤、単量体組
成比、重合温度などの重合条件を特定することによって
ポリマー固型分濃度が３０〜５０重量％という高濃度で
も凝集することなく粒子径が５０ｎｍ以下の透明性のあ
る超微粒子が形成でき、しかも粒子内に３次元網目構造
を生成しうることを見出し、この知見に基づき本発明を
なすに至った。(Means for Solving the Problems) The present inventors found that because the above-mentioned conventional method involves polymerizing or copolymerizing a crosslinking monomer such as divinylbenzene, it not only crosslinks within the particle but also forms a polymer on the surface of the particle at the same time. These crosslinkable monomers have the advantage of being able to impart reactivity, but this advantage also has the disadvantage that the highly reactive pendant vinyl groups significantly accelerate the aggregation of the generated reactive microgels. As a result of intensive research to develop a method that can introduce a crosslinked structure into polymer latex particles without using By using a reactive emulsifier and specifying polymerization conditions such as the polymerization initiator, monomer composition ratio, and polymerization temperature, it is possible to achieve polymer solid content without agglomeration even at a high concentration of 30 to 50% by weight. It was discovered that transparent ultrafine particles having a particle diameter of 50 nm or less can be formed, and a three-dimensional network structure can be generated within the particles, and based on this knowledge, the present invention was accomplished.
すなわち本発明は、アクリル酸もしくはメタクリル酸の
低級アルキルエステルの中から選ばれた単量体とこれら
単量体と共重合可能な他の重合性単量体との混合物から
なる単量体にさらに単官能性の反応性単量体を単量体全
量に対して５重量％以下含有させて水性媒体中で乳化共
重合させるに当り、系中濃度１０−８ｍ０１Ｚ文〜ｌ０
−６ｍ ｏ ｌ ／ ｌの範囲の２価の銅イオンの存在
下レドックス触媒を用い、かつ、乳化剤として１分子中
に２個以上の（メタ）アクリロイル基を有するオリゴエ
ステルアクリレート系の反応性乳化剤を用いて反応させ
ることを特徴とする高濃度反応性ミクロゲルの製造方法
を提供するものである。That is, the present invention further provides a monomer consisting of a mixture of a monomer selected from lower alkyl esters of acrylic acid or methacrylic acid and another polymerizable monomer copolymerizable with these monomers. When carrying out emulsion copolymerization in an aqueous medium containing 5% by weight or less of a monofunctional reactive monomer based on the total amount of monomers, the concentration in the system is 10-8m01Z~10
- Using a redox catalyst in the presence of divalent copper ions in the range of 6 mol/l, and using an oligoester acrylate-based reactive emulsifier having two or more (meth)acryloyl groups in one molecule as an emulsifier. The present invention provides a method for producing a highly concentrated reactive microgel, which is characterized in that the reaction is carried out using a microgel.
本発明によって製造される反応性ミクロゲルとは通常の
乳化重合法によって製造されるポリマーラテックスをよ
り高性能化したポリマー微粒子の水性媒体分散体であり
、外観は通常のポリマーラテックスが乳白色から白色で
あるのと異なり、反射光に対しては青白色で、透過光に
対しては黄赤色に見える透明性のやや粘稠性を帯びた超
微粒子の水分散体である。この反応性ミクロゲルは粒子
表面にはヒドロキシル基、アミド基、エポキシ基などの
反応性の官能基を有し、かつ、粒子内は３次元網目構造
をもついわゆる超微粒子の反応性成架橋ポリマーラテッ
クスの形態を示している。The reactive microgel produced by the present invention is an aqueous dispersion of fine polymer particles, which is a higher-performance polymer latex produced by ordinary emulsion polymerization, and has a milky to white appearance than that of ordinary polymer latex. It is a transparent, slightly viscous water dispersion of ultrafine particles that appears blue-white to reflected light and yellow-red to transmitted light. This reactive microgel has reactive functional groups such as hydroxyl groups, amide groups, and epoxy groups on the particle surface, and a three-dimensional network structure inside the particle. It shows the form.
本発明において重合開始剤としては１．０×１０ 〜１
．０Ｘ１０−−ｏ１／ｎの等モル濃度からなる過硫酸カ
リウムとチオ硫酸ナトリウムなどの公知のレドックス触
媒が用いられるが、透明性のある超微粒子のポリマーラ
テックスの生成のためには、重合促進剤として系中濃度
５．０×１０−８−７．５Ｘ １０−６ｍｏ １／Ｍの
微量の２価の銅イオンの添加が不可欠である。In the present invention, the polymerization initiator is 1.0×10 ~1
．． A known redox catalyst such as potassium persulfate and sodium thiosulfate having an equimolar concentration of 0x10--o1/n is used, but in order to produce a transparent ultrafine particle polymer latex, it is necessary to use it as a polymerization accelerator. It is essential to add a trace amount of divalent copper ions at a concentration of 5.0 x 10-8-7.5 x 10-6 mo 1/M in the system.
重合温度は重合触媒を活性化させる温度範囲で使用が可
能であるが、８０’Ｃ以上では生成ポリマー分散液の安
定性が悪くなる他、開始剤の失活がおこるので重合温度
をコントロールするために単量体は少量ずつ連続的に滴
下しながら５０〜７０’Ｏで重合を行うのが好ましい。The polymerization temperature can be used within a temperature range that activates the polymerization catalyst, but if it exceeds 80'C, the stability of the resulting polymer dispersion will deteriorate and the initiator will be deactivated, so the polymerization temperature must be controlled. It is preferable to carry out the polymerization at 50 to 70'O while continuously adding the monomer dropwise little by little.
本発明で用いられる反応性乳化剤は１分子中に２個以上
の（メタ）アクリロイル基を持ったオリゴエステル（メ
タ）アクリレートのリン酸エステルのアルカリ塩もしく
は分子中に親水性のエチレンオキサイド基をもったポリ
エチレングリコール誘導体のオリゴエステルアクリレー
トで次のような化学構造の成分を含むものをいう。The reactive emulsifier used in the present invention is an alkali salt of an oligoester (meth)acrylate phosphate having two or more (meth)acryloyl groups in one molecule or a hydrophilic ethylene oxide group in the molecule. This refers to oligoester acrylates of polyethylene glycol derivatives containing components with the following chemical structure.
オリゴエステル（メタ）アクリレート類は原料および合
成方法によって非常に多数のものがあり、また単一化合
物として得ることは困難で、一般には種々の化合物から
なる混合物として製造されるものが多く混合物をもって
単一化合物的に扱うことが広く行われている。本発明の
方法では市販品のニューフロンティアＡ−２２９Ｅ及び
ニューフロンティアＮ−２５０７（いずれも商品名、第
一工業製薬社製）を単独もしくは通常乳化重合に用いら
れる公知のアニオン性界面活性剤例えば長鎖α−オレフ
ィンスルホン酸ナトリウム、アルキルジフェニルオキシ
エチレンアルキルアリルエーテル硫酸エステル塩、より
望ましくはアニオン性の反応性乳化剤エレミノールＪＳ
−２（商品名、三洋化成社製）ラテムルＳ−１８０（商
品名、花王社製）などのスルホコハク酸系反応性乳化剤
との組み合わせで使用し、その重量組成比としては１：
３〜３：１の割合にするのが好ましい。また単独もしく
は混合乳化剤の濃度は水性媒体に対して０．５〜２０重
量％望ましくは２〜１０重量％の範囲で用いるのがよい
。There are a large number of oligoester (meth)acrylates depending on the raw materials and synthesis methods, and it is difficult to obtain them as a single compound.In general, many of them are produced as a mixture of various compounds. It is widely used as a single compound. In the method of the present invention, commercially available New Frontier A-229E and New Frontier N-2507 (both trade names, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) are used alone or with known anionic surfactants commonly used in emulsion polymerization, such as Sodium chain α-olefin sulfonate, alkyldiphenyloxyethylene alkyl allyl ether sulfate salt, more preferably anionic reactive emulsifier Eleminol JS
-2 (trade name, manufactured by Sanyo Chemical Co., Ltd.) is used in combination with a sulfosuccinic acid-based reactive emulsifier such as Latemul S-180 (trade name, manufactured by Kao Corporation), and the weight composition ratio is 1:
A ratio of 3 to 3:1 is preferred. The concentration of the emulsifier alone or in combination is preferably 0.5 to 20% by weight, preferably 2 to 10% by weight, based on the aqueous medium.
本発明方法において重合により生成した反応性ミクロゲ
ルはアセトンに不溶であり、アセトン中で低粘性のミク
ロゲル分散液を形成する。また自然乾燥生成皮膜はベン
ゼンに不溶であり、架橋度合は反応性乳化剤の種類およ
びその濃度、単量体組成中のＮ−メチロールアクリルア
ミドなどの官能性単量体の存在比および重合促進剤とし
て添加されている２価の銅イオン（硫酸銅水溶液）濃度
などの重合条件によって架橋密度が自由にコントロール
される。The reactive microgel produced by polymerization in the method of the present invention is insoluble in acetone and forms a low viscosity microgel dispersion in acetone. Furthermore, the air-dried film is insoluble in benzene, and the degree of crosslinking is determined by the type and concentration of the reactive emulsifier, the abundance ratio of functional monomers such as N-methylolacrylamide in the monomer composition, and the amount added as a polymerization accelerator. The crosslinking density can be freely controlled by polymerization conditions such as the concentration of divalent copper ions (copper sulfate aqueous solution).
本発明で使用される単量体としては重合性のエチレン結
合を有するアクリル酸エチル、メタクリル酸メチル、メ
タクリル酸ブチルなどのアクリル系ビニル単量体、アク
リロニトリル、酢酸ビニル、スチレンなどの工業的に広
く使われている単量体などがあり、上記単量体に共重合
して生成ミクロゲルに反応性を付与する単量体としては
Ｎ−メチロール（メタ）アクリルアミド、２−ヒドロキ
シ（メタ）アクリレート、（メタ）アクリル酸、無水マ
レイン酸、アクリルアミド、グリシジル（メタ）アクリ
レートなどの一般に使用にされている単官能性の反応性
単量体が例示される。The monomers used in the present invention include acrylic vinyl monomers having polymerizable ethylene bonds such as ethyl acrylate, methyl methacrylate, and butyl methacrylate, acrylonitrile, vinyl acetate, and styrene, which are widely used industrially. The monomers that are used are N-methylol (meth)acrylamide, 2-hydroxy (meth)acrylate, ( Commonly used monofunctional reactive monomers such as meth)acrylic acid, maleic anhydride, acrylamide, and glycidyl (meth)acrylate are exemplified.
（発明の効果）
本発明の方法によって得られる反応性ミクロゲルは粒子
径が５０ｎｍ以下の超微粒子で水性媒体中の固型分濃度
が４０〜４５重量％でも分散安定性は著しく良好であり
、また重合速度も著しく速く単量体組成比、乳化剤濃度
、乳化剤の組み合せ、銅（ＩＩ）イオン濃度などの重合
条件をコントロールすることによって広い範囲の硬度と
架橋密度を持った反応性ミクロゲルを容易に合成し得る
ため工業的な反応性ミクロゲルの製造方法として好適で
ある。(Effects of the Invention) The reactive microgel obtained by the method of the present invention has ultrafine particles with a particle size of 50 nm or less, and has extremely good dispersion stability even when the solid content concentration in the aqueous medium is 40 to 45% by weight. The polymerization rate is extremely fast, and reactive microgels with a wide range of hardness and crosslinking density can be easily synthesized by controlling polymerization conditions such as monomer composition ratio, emulsifier concentration, emulsifier combination, and copper (II) ion concentration. Therefore, it is suitable as an industrial method for producing reactive microgels.
また、本発明の方法は反応性ミクロゲルの架橋度と硬度
が任意にコントロールできるのが特徴で、硬度が低い場
合は自然乾燥によって粒子は相互に融着して連続皮膜を
形成し初期モジュラス値の大きい弾力性に富んだ皮膜を
形成させることができる。また、硬度や架橋密度が高く
なると透膜性は悪くなり多数の網目様のスジや亀裂が生
じるが透膜助剤（例えば酢酸ジエチレングリコールモノ
エチルエーテルなど）を併用するか乾燥温度を高くする
ことによって均一フラットな皮膜を生成し得る。In addition, the method of the present invention is characterized in that the degree of crosslinking and hardness of the reactive microgel can be controlled arbitrarily; if the hardness is low, the particles will fuse together by air drying to form a continuous film, and the initial modulus value will decrease. A highly elastic film can be formed. In addition, as the hardness and crosslinking density increase, the membrane permeability deteriorates and many mesh-like streaks and cracks occur, but by using a membrane auxiliary agent (for example, diethylene glycol monoethyl ether acetate, etc.) or increasing the drying temperature, A uniform flat film can be produced.
本発明の方法によって製造される反応性ミクロゲルはそ
のまま塗膜を形成するエマルジョン塗料のビヒクルとし
て用いることも可能であるが、好ましくはメチロール化
メラミン樹脂のようなアミノプラスト樹脂と混合して焼
付硬化を行う水性焼付塗料の素材として用いる。また、
粉末化した反応性ミクロゲルは粉体塗料に添加してブロ
ッキング性および塗膜物性の向上に有用であるし、有機
溶剤中に分散しても低粘性であることからハイソリッド
系塗料素材としても有用である。その他既存の溶媒型塗
料、水溶性塗料、エマルジョン塗料に混合して当該塗料
の性能を向上させるのに使用できる。Although the reactive microgel produced by the method of the present invention can be used as it is as a vehicle for an emulsion paint to form a coating film, it is preferably mixed with an aminoplast resin such as a methylolated melamine resin and cured by baking. Used as a material for water-based baking paints. Also,
Powdered reactive microgels are useful for improving blocking properties and coating film properties when added to powder coatings, and are also useful as high-solid coating materials because they have low viscosity even when dispersed in organic solvents. It is. It can be used to improve the performance of existing solvent-based paints, water-soluble paints, and emulsion paints by mixing with them.
本発明方法により得られる反応性ミクロゲルはまた、浸
透性のよい充填材、バインダーとして用いることができ
る。さらにヘキサキスメトキシメチロールメラミンなど
のアミノプラスト樹脂を混合して焼付硬化による粒子間
の架橋により接着剤などの性能を著しく向上させること
ができる。The reactive microgel obtained by the method of the present invention can also be used as a filler or binder with good permeability. Furthermore, by mixing an aminoplast resin such as hexakismethoxymethylolmelamine, the performance of adhesives and the like can be significantly improved by crosslinking between particles through baking hardening.
本発明の方法によって製造される反応性ミクロゲルは、
粒子径が５０ｎｍ以下の超微粒子であるため、金属面な
どの微細な凹凸面に対する密着性や、コンクリート、木
材などに対する浸透性が優れており、また従来のポリマ
ーラテックスの欠点であったアミノプラスト樹脂などの
硬化剤との混合が溶液タイプの分子分散に近い形でより
均一に行われるなどの特徴を有する。The reactive microgel produced by the method of the present invention is
Since it is an ultrafine particle with a particle size of 50 nm or less, it has excellent adhesion to finely uneven surfaces such as metal surfaces, and permeability to concrete, wood, etc., and has improved aminoplast resin, which has overcome the drawbacks of conventional polymer latex. It has the characteristics that mixing with curing agents such as etc. is carried out more uniformly in a form similar to solution-type molecular dispersion.
また、反応性ミクロゲル粒子内が３次元網目構造となっ
ているために、より少ない架橋反応によって塗膜全体が
高次の３次元網目の構造をとることができるため耐溶剤
性で、初期モジュラス値の大きい特異な皮膜が容易に形
成される。In addition, because the reactive microgel particles have a three-dimensional network structure, the entire coating film can take on a high-order three-dimensional network structure with fewer crosslinking reactions, resulting in excellent solvent resistance and an initial modulus value. A unique film with a large amount is easily formed.
さらに本発明方法によって製造される反応性ミクロゲル
においては粒子表面の反応性基間どうし、あるいは反応
性基と硬化剤との間に橋かけ結合による３次元網目が可
能で耐久性と熱安定性、衝撃性強度の優れた皮膜が得ら
れるなどの特徴を有する。Furthermore, in the reactive microgel produced by the method of the present invention, a three-dimensional network can be formed by cross-bonding between the reactive groups on the particle surface or between the reactive groups and the curing agent, resulting in durability, thermal stability, It has the characteristics of producing a film with excellent impact strength.
（実施例） 次に実施例によって本発明をさらに詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例１〜１７
ガス導入管還流冷却器、ＰＨ測定用複合ガス電極および
かきまぜ装置を備えた１００１００Ｏの四つロセパラブ
ルフラスコを用い蒸留水４０ＯｍＫＬ中に乳化剤として
固型分換算濃度で系中濃度が１ 、０〜５ 、０ （ｇ
／ｌ ００ｍＪＬ）に相当するニューフロンティアＡ２
２９Ｅ （第一工業製薬社製）単独、もしくはこれに反
応性乳化剤、エレミノールＪＳ−２（三洋化成工業社製
）あるいはニューフロンティアＮ−２５０２との混合物
を溶解し５０℃に保つ。重合単量体としてアクリル酸エ
チルとメタクリル酸メチルの混合単量体３００ｇ（混合
比６０：４０）に３ｇ〜１５ｇのＮ−メチロールアクリ
ルアミド（Ｎ−ＭＡＭあるいは２−ヒドロキシエチルア
クリレート（２−ＨＥＭＡ）、もしくはグリシジルメタ
クリレ−） （ＧＭＡ）を加えたものを最初的５０ｇだ
け重合フラスコ中に分散乳化させ一定のかきまぜ状態に
保ちながら微量の硫酸銅（系中濃度２．５Ｘ１０−６も
しくは５ 、ＯＸＩ ０−７ｎｏ ｌ／Ｊｌ）の存在下
で過硫酸カリウム−チオ硫酸ナトリウムの等モル量から
なるレドックス開始剤（系中濃度３．０Ｘ１０−３ｍｏ
１／Ｊｌ）で５０〜６０℃、ｐＨ４〜７で重合を開始さ
せる。ついで残りの混合単量体約２５０ｇを徐々に滴下
しつつ重合熱による昇温を防ぎながら重合を行った。Examples 1 to 17 Using a 100,100O four separable flask equipped with a gas inlet pipe reflux condenser, a composite gas electrode for PH measurement, and a stirring device, the system concentration was determined as an emulsifier in 400mKL of distilled water in terms of solid content. is 1,0~5,0 (g
/l 00mJL) equivalent to New Frontier A2
29E (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) alone or a mixture with a reactive emulsifier, Eleminol JS-2 (manufactured by Sanyo Chemical Industries, Ltd.) or New Frontier N-2502 is dissolved therein and maintained at 50°C. 3 g to 15 g of N-methylolacrylamide (N-MAM or 2-hydroxyethyl acrylate (2-HEMA), Initially, 50 g of glycidyl methacrylate (GMA) was dispersed and emulsified in a polymerization flask, and while keeping constant stirring, a trace amount of copper sulfate (concentration in the system: 2.5 x 10-6 or 5, OXI 0 A redox initiator consisting of equimolar amounts of potassium persulfate-sodium thiosulfate (concentration in the system: 3.0 x 10-3 mo
1/Jl) at 50-60°C and pH 4-7. Then, about 250 g of the remaining mixed monomer was gradually added dropwise to carry out polymerization while preventing temperature rise due to polymerization heat.
なお、重合の経過とともに系の粘度が上昇してきて単量
体の分散やかきまぜが困難となる場合は重合系の粘度が
上貸し始める前に２〜４ｍＭの２８％アンモニア水を少
量ずつ添加するか、あらかじめ重合開始前に０．５ｇ前
後のリン酸ニアンモニウム塩を添加して粘度の調整を行
う。In addition, if the viscosity of the system increases as the polymerization progresses and it becomes difficult to disperse or stir the monomers, add 2-4mM 28% ammonia water little by little before the viscosity of the polymerization system starts to increase. The viscosity is adjusted by adding approximately 0.5 g of ammonium phosphate salt before the start of polymerization.
重合は３０分程で完了し、反射光に対しては青白色、透
過光では黄赤色にみえる透明性のある超微粒子ポリマー
の分散体が得られた。Polymerization was completed in about 30 minutes, and a transparent ultrafine particle polymer dispersion was obtained that appeared blue-white to reflected light and yellow-red to transmitted light.
単量体の組成比及び乳化剤の種類、濃度を変えて行った
実験結果を第１表にまとめて示した。Table 1 summarizes the results of experiments conducted by changing the composition ratio of monomers and the type and concentration of emulsifier.
生成したポリマー微粒子の分散体（反応性ミクロゲル）
の外観の透明性は、分光光度計で８００ｎｍの光線透過
率を１ｃｍのガラスセルで測定した値で示した。平均粒
子径はコールタ−社の光子相関法によるナノサイザーＮ
−４Ｇで測定した数平均の粒子径で水和層を含む流体力
学半径であす、電子顕微鏡法で求めた乾燥粒子径の値よ
りも１．５〜２倍大きな値を示している。Dispersion of generated polymer particles (reactive microgel)
The transparency of the appearance was determined by measuring the light transmittance at 800 nm with a spectrophotometer using a 1 cm glass cell. The average particle diameter was determined by Coulter's Nanosizer N using the photon correlation method.
The number average particle diameter measured at -4G and the hydrodynamic radius including the hydrated layer is 1.5 to 2 times larger than the value of the dry particle diameter determined by electron microscopy.
反応性ミクロゲルをガラス板上で自然乾燥して得られた
皮膜の透明性は、一般に良好でフラットな皮膜の場合は
光沢性も非常に良好であった。The films obtained by air-drying the reactive microgels on a glass plate generally had good transparency, and in the case of flat films, the gloss was also very good.
皮膜の硬度が高い場合と架橋度合が高い場合には自然乾
燥条件では透膜性が悪くなって皮膜全体に網目状のスジ
と亀裂を生じたが造膜助剤を添加した場合は均一フラッ
トな皮膜を形成することが認められた。When the hardness of the film is high or the degree of crosslinking is high, the film permeability deteriorates under air drying conditions, resulting in network-like streaks and cracks throughout the film, but when a film-forming agent is added, it becomes uniform and flat. It was observed that a film was formed.
自然乾燥で生成した皮膜はすべてベンゼンアセトンに不
溶であり、ゲル分率はいずれも９５％以上であった。皮
膜のベンゼンに対する膨潤度合は０．１ｇ＜らいの皮膜
を１００メツシ為網製のカゴに入れベンゼン中に４８時
間以上浸漬した重合増加から膨潤比を求めて表示した。All the films formed by air drying were insoluble in benzeneacetone, and the gel fractions were all 95% or more. The degree of swelling of the film in benzene was determined by calculating the swelling ratio from the increase in polymerization when 0.1 g <100 of the film was placed in a mesh basket and immersed in benzene for 48 hours or more.
膨潤比が２０倍以下の場合は皮膜の形態は保持されてお
り、膨潤比が３０倍以上の場合は皮膜は変形し流動性の
ゲル軟塊となった。When the swelling ratio was 20 times or less, the form of the film was maintained, and when the swelling ratio was 30 times or more, the film was deformed and became a fluid gel mass.
（注） 月Ａ−２９９Ｅ、オリゴエステルアクリレート
系反応性乳化剤 市販品 第一工業製薬
ニューフロンティアＡ−２２９Ｅ
ＪＳ−２；スルホコハク酸系反応性乳化剤市販品 三洋
化成 エレミノールＪＳ−２＊２ 水相中濃度 エレミ
ノールＪＳ−２は固型分換算す３ＥＡ；アクリル酸エチ
ル
ＨＭＡ 、メタクリル酸メチル
Ｎ−ＭＡＭ、Ｎ−メチロールアクリルアミド２−ＨＥＭ
Ａ 、 ２−ヒドロキシエチルメタアクリレートＧＭＡ
、グリシジルメタアクリレート＊４ 系中濃度５．０
Ｅ−７＋ｆ ５．ＯＸｌｏ−７ｍｏｌ／ＪＪオ５ 外観
の透明性を示す。分光光度計で８００ｎｍ波長（１ｃｍ
がラスセル使用）の光線透過率＊６ コールタ−社 ナ
ノサイザーＮ４Ｇで測定した流体力学半径
＊７ がラス板上で自然乾燥したクリヤー皮膜の外観網
目スジ； ２〜３ｍｍの網目状のスジが全体にある
フラット；均一平滑な高光沢透明性皮膜２８ ０、１ｇ
＜らい皮膜を１００メツシユの金網製カゴに入れベン
ゼン中４８時間以上浸漬し浸漬前後の重量比で比較した
。(Note) Moon A-299E, oligoester acrylate-based reactive emulsifier (commercial product) Daiichi Kogyo Seiyaku New Frontier A-229E JS-2; sulfosuccinic acid-based reactive emulsifier (commercial product) Sanyo Kasei Eleminol JS-2*2 Concentration in aqueous phase Eleminol JS-2 is 3EA in terms of solid content; ethyl acrylate HMA, methyl methacrylate N-MAM, N-methylolacrylamide 2-HEM
A, 2-hydroxyethyl methacrylate GMA
, glycidyl methacrylate *4 Concentration in the system 5.0
E-7+f 5. OXlo-7mol/JJo5 Indicates transparency of appearance. 800 nm wavelength (1 cm) using a spectrophotometer
(using a lath cell) *6 Hydrodynamic radius measured with Coulter Nanosizer N4G *7 Appearance of clear film air-dried on a lath plate: mesh streaks of 2 to 3 mm across the entire surface Flat: Uniform and smooth high gloss transparent film 28 0.1g
<The leprosy membrane was placed in a 100-mesh wire mesh basket and immersed in benzene for 48 hours or more, and the weight ratio before and after immersion was compared.
＊９ ５ｍｍＸ ２０＋ａｍ位の皮膜を水中に浸漬し白
化して新聞活字が密着で読めなくなるまでの時間一般に
２０日以上の場合はその後殆ど変化なく ８ケ月以上放
置しても変化が認められなかった。*9 The time it takes for a film of about 5mm x 20+am to become white and become unreadable due to adhesion after being soaked in water for more than 20 days.No change was observed even after leaving it for more than 8 months.
Claims (1)
ルの中から選ばれた単量体とこれら単量体と共重合可能
な他の重合性単量体との混合物からなる単量体にさらに
単官能性の反応性単量体を単量体全量に対して５重量％
以下含有させて水性媒体中で乳化共重合させるに当り、
系中濃度１０＾−＾８ｍｏｌ／ｌ〜１０＾−＾６ｍｏｌ
／ｌの範囲の２価の銅イオンの存在下レドックス触媒を
用い、かつ、乳化剤として１分子中に２個以上の（メタ
）アクリロイル基を有するオリゴエステルアクリレート
系の反応性乳化剤を用いて反応させることを特徴とする
高濃度反応性ミクロゲルの製造方法。Monofunctional reaction of a monomer consisting of a mixture of monomers selected from lower alkyl esters of acrylic acid or methacrylic acid and other polymerizable monomers copolymerizable with these monomers. 5% by weight of monomer based on the total amount of monomers
When carrying out emulsion copolymerization in an aqueous medium by containing the following:
Concentration in the system: 10^-^8 mol/l ~ 10^-^6 mol
The reaction is carried out using a redox catalyst in the presence of divalent copper ions in the range of /l and an oligoester acrylate-based reactive emulsifier having two or more (meth)acryloyl groups in one molecule as an emulsifier. A method for producing a highly concentrated reactive microgel, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1835786A JPH0780971B2 (en) | 1986-01-30 | 1986-01-30 | Method for producing highly concentrated reactive microgel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1835786A JPH0780971B2 (en) | 1986-01-30 | 1986-01-30 | Method for producing highly concentrated reactive microgel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62177007A true JPS62177007A (en) | 1987-08-03 |
| JPH0780971B2 JPH0780971B2 (en) | 1995-08-30 |
Family
ID=11969436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1835786A Expired - Lifetime JPH0780971B2 (en) | 1986-01-30 | 1986-01-30 | Method for producing highly concentrated reactive microgel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0780971B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6480942A (en) * | 1987-09-23 | 1989-03-27 | Chiaki Azuma | Photosensitive microgel particles |
| JPH0362843A (en) * | 1989-07-31 | 1991-03-18 | Hoechst Gosei Kk | Aqueous dispersion composition of internally crosslinked acrylic copolymer and its production |
| JPH03504775A (en) * | 1988-12-20 | 1991-10-17 | ウニヴェルザーレ グルントバウ ゲゼルシャフト エムベーハー | Method for measuring the inclination of the wall of a slotted hole |
| JPH06509606A (en) * | 1992-06-04 | 1994-10-27 | ソシエテ・プロラボ | Functionalized polymer ultrafine particles, their manufacturing method and uses |
-
1986
- 1986-01-30 JP JP1835786A patent/JPH0780971B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6480942A (en) * | 1987-09-23 | 1989-03-27 | Chiaki Azuma | Photosensitive microgel particles |
| JPH03504775A (en) * | 1988-12-20 | 1991-10-17 | ウニヴェルザーレ グルントバウ ゲゼルシャフト エムベーハー | Method for measuring the inclination of the wall of a slotted hole |
| JPH0362843A (en) * | 1989-07-31 | 1991-03-18 | Hoechst Gosei Kk | Aqueous dispersion composition of internally crosslinked acrylic copolymer and its production |
| JPH0717807B2 (en) * | 1989-07-31 | 1995-03-01 | ヘキスト合成株式会社 | Internally cross-linked acrylic copolymer aqueous dispersion composition and method for producing the same |
| JPH06509606A (en) * | 1992-06-04 | 1994-10-27 | ソシエテ・プロラボ | Functionalized polymer ultrafine particles, their manufacturing method and uses |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0780971B2 (en) | 1995-08-30 |
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| EXPY | Cancellation because of completion of term |