JP4580156B2 - Dispersion - Google Patents
Dispersion Download PDFInfo
- Publication number
- JP4580156B2 JP4580156B2 JP2003291713A JP2003291713A JP4580156B2 JP 4580156 B2 JP4580156 B2 JP 4580156B2 JP 2003291713 A JP2003291713 A JP 2003291713A JP 2003291713 A JP2003291713 A JP 2003291713A JP 4580156 B2 JP4580156 B2 JP 4580156B2
- Authority
- JP
- Japan
- Prior art keywords
- dispersion
- meth
- particles
- resin particles
- acrylic resin
- 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 - Lifetime
Links
- 239000006185 dispersion Substances 0.000 title claims description 150
- 239000002245 particle Substances 0.000 claims description 201
- 229920000178 Acrylic resin Polymers 0.000 claims description 56
- 239000004925 Acrylic resin Substances 0.000 claims description 56
- 239000011347 resin Substances 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 53
- -1 fatty acid esters Chemical class 0.000 claims description 50
- 239000000178 monomer Substances 0.000 claims description 48
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 26
- 239000000194 fatty acid Substances 0.000 claims description 26
- 229930195729 fatty acid Natural products 0.000 claims description 26
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000007900 aqueous suspension Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 37
- 239000007787 solid Substances 0.000 description 30
- 229920001213 Polysorbate 20 Polymers 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 13
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000975 dye Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000000113 methacrylic resin Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MKWJZTFMDWSRIH-UHFFFAOYSA-N (4-fluoro-3-nitrophenyl)methanol Chemical compound OCC1=CC=C(F)C([N+]([O-])=O)=C1 MKWJZTFMDWSRIH-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
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- PFRGXCVKLLPLIP-UHFFFAOYSA-N diallyl disulfide Chemical compound C=CCSSCC=C PFRGXCVKLLPLIP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- YVLJEXBGMVDKBR-UHFFFAOYSA-N 1,10-dichloro-7-methyldec-1-ene Chemical compound ClCCCC(C)CCCCC=CCl YVLJEXBGMVDKBR-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- FVHAWXWFPBPFOS-UHFFFAOYSA-N 1,2-dimethyl-3-nitrobenzene Chemical group CC1=CC=CC([N+]([O-])=O)=C1C FVHAWXWFPBPFOS-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 1
- LEPIMHWWCATZTP-UHFFFAOYSA-N 2-[(2-cyano-3,3-dimethylbutan-2-yl)diazenyl]-2,3,3-trimethylbutanenitrile Chemical compound CC(C)(C)C(C)(C#N)N=NC(C)(C#N)C(C)(C)C LEPIMHWWCATZTP-UHFFFAOYSA-N 0.000 description 1
- FRFPIUXEUZICHA-UHFFFAOYSA-N 2-[(2-cyano-3-methylbutan-2-yl)diazenyl]-2,3-dimethylbutanenitrile Chemical compound CC(C)C(C)(C#N)N=NC(C)(C#N)C(C)C FRFPIUXEUZICHA-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- WWKWBIGDIHXKFW-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C(C)=C WWKWBIGDIHXKFW-UHFFFAOYSA-N 0.000 description 1
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- CKSAKVMRQYOFBC-UHFFFAOYSA-N 2-cyanopropan-2-yliminourea Chemical compound N#CC(C)(C)N=NC(N)=O CKSAKVMRQYOFBC-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BJOAMCSNLUKBSK-UHFFFAOYSA-N 2h-dibenzo-p-dioxin-1-one Chemical compound O1C2=CC=CC=C2OC2=C1C(=O)CC=C2 BJOAMCSNLUKBSK-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- FLROJJGKUKLCAE-UHFFFAOYSA-N 3-amino-2-methylphenol Chemical compound CC1=C(N)C=CC=C1O FLROJJGKUKLCAE-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
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Description
本発明は、長時間経過したのちに再分散させたときでも樹脂粒子の全量が分散して全量を有効に使用できる、定量性に優れた（メタ）アクリル系樹脂粒子の分散体に関する。 The present invention relates to a dispersion of (meth) acrylic resin particles having excellent quantitativeness, in which the entire amount of resin particles can be dispersed and used effectively even after being redispersed after a long time.
有機樹脂粒子は、樹脂フィルム用の添加剤（例えば、耐ブロッキング剤、易滑剤、つや消し剤、光拡散剤など）、水分散型コーティング剤、研磨剤、潤滑液用添加剤等の用途において有用であることが知られているが、なかでも、（メタ）アクリル系樹脂粒子は、透明性や耐光性に優れる等の利点があることから汎用されている。その製造方法も種々知られている（例えば、特許文献１〜２参照）。
Organic resin particles are useful in applications such as additives for resin films (for example, anti-blocking agents, lubricants, matting agents, light diffusing agents, etc.), water-dispersed coating agents, abrasives, additives for lubricating liquids, etc. Among them, it is known that (meth) acrylic resin particles are widely used because they have advantages such as excellent transparency and light resistance. Various manufacturing methods are also known (see, for example,
（メタ）アクリル系樹脂粒子は、用途に応じて、粉体状態で樹脂と混練して使用されるか、水や溶剤に分散した状態で使用される。コーティング剤などの用途においては分散体として用いられるのが一般的であった。 The (meth) acrylic resin particles are used by being kneaded with a resin in a powder state or used in a state dispersed in water or a solvent depending on the application. In applications such as a coating agent, it was generally used as a dispersion.
ところが、（メタ）アクリル系樹脂粒子を分散体の状態にしておくと、粒子が経時的に沈降する傾向があるため、分散体を数日間放置しておくと、粒子が容器底部において固まりとなってしまうことが多い。 However, if the (meth) acrylic resin particles are kept in a dispersion state, the particles tend to settle over time, so if the dispersion is left for several days, the particles become agglomerated at the bottom of the container. It often happens.
このような問題の発生を避けるためには、（メタ）アクリル系樹脂粒子は、乾燥体のままで貯蔵しておき、使用する直前にこれを分散体とすることが望ましいのであるが、使用する直前に分散体とすることは、工業的には効率が悪く、用途によっては適用しにくい場合があった。 In order to avoid the occurrence of such a problem, it is desirable to store the (meth) acrylic resin particles in a dry state, and use it as a dispersion immediately before use. Making a dispersion immediately before is industrially inefficient and sometimes difficult to apply depending on the application.
そのため、多くの製造現場においては、あらかじめ分散体としておくのではあるが、使用直前に攪拌機を用いて沈降した粒子を再分散させるようにしている。
しかし、沈降した粒子（とりわけ粒子径が０．５〜５００μｍの範囲にある粒子）の中には強固な固まりを作るものがあり、強固な固まりとなった粒子は、通常の攪拌手段では再分散させにくく、有用な粒子としては働かない。このような強固な固まりとなる粒子の量も、粒子の種類や貯蔵状態で異なり、一定しない。つまり、樹脂粒子の全量を有効に使うことができず、しかも、どれだけの量の樹脂粒子が再分散するかと言う点で、再分散量が一定しないと言う問題があった。すなわち、定量性に問題があったのである。なお、樹脂粒子の全量を有効に使用するためには、粒子の全量を再分散させる必要があるが、強固な固まりとなった粒子を再分散させるには非常に大きな労力を要し、工業的には実質的に困難である。また、再分散した粒子だけを分散体として用いるようにすることは、樹脂粒子の固形分濃度を再度算出し直さなければならず工程が煩雑になるといった問題や、沈降してしまった粒子を有効利用することが難しく廃棄せざるを得ないといった問題がある。 However, some of the settled particles (particularly particles having a particle diameter in the range of 0.5 to 500 μm) form a strong mass, and the particles that have become a firm mass are redispersed by ordinary stirring means. It is hard to make and does not work as a useful particle. The amount of particles that form such a solid mass also varies depending on the type and storage state of the particles and is not constant. That is, there is a problem that the total amount of the resin particles cannot be used effectively, and the amount of resin particles to be redispersed is not constant. In other words, there was a problem in quantitativeness. In order to effectively use the entire amount of resin particles, it is necessary to re-disperse the entire amount of particles. Is practically difficult. In addition, using only re-dispersed particles as a dispersion makes it necessary to recalculate the solid content concentration of the resin particles, and the process becomes complicated, and particles that have settled are effective. There is a problem that it is difficult to use and must be discarded.
（メタ）アクリル系樹脂粒子の分散体は、上に見たように、どの分散体が固まりを作るか、そして、固まりの程度はどのようであるか、固まりの量はどのようであるかが分からないため、厳密な定量性を必要とする用途に供することには問題がある。 As seen above, the dispersion of (meth) acrylic resin particles shows which dispersion forms a lump, what is the degree of lump, and what is the amount of lump. Since it is not known, there is a problem in using it for applications that require strict quantitativeness.
そこで、本発明の課題は、定量性に優れた（メタ）アクリル系樹脂粒子の分散体を提供することにある。 Then, the subject of this invention is providing the dispersion of the (meth) acrylic-type resin particle excellent in quantitative property.
本発明者は、上記のように、分散体に関して定量性というこれまでに注目されていなかった新たな課題を見出し、この課題を解決すべく鋭意検討を行った。その結果、分散体が示す物性として特定の試験方法によって求められる再分散指数を定義し、該再分散指数が特定範囲である分散体は、使用の直前において従来の攪拌手段を用いて再分散させた場合においても、沈降した粒子の固まりを再分散させることができ、常に定量性に優れることに着想し、この着想を実現する優れた再分散性の試験方法を見いだして、本発明を完成した。 As described above, the present inventor has found a new problem that has not been noticed so far regarding the quantitativeness of the dispersion, and has intensively studied to solve this problem. As a result, the redispersion index required by a specific test method is defined as a physical property of the dispersion, and the dispersion having the redispersion index in a specific range is redispersed using a conventional stirring means immediately before use. In this case, it was possible to re-disperse the lump of settled particles, and the idea was always excellent in quantification, and the present invention was completed by finding an excellent re-dispersibility test method that realizes this idea. .
本発明者の知見によれば、分散体は７２時間放置すると殆どの樹脂粒子が沈降して固まりを作るが、この固まりを実験室レベルの小さな攪拌装置を用いて再分散させたときにある基準以上の再分散性を示すものであれば、その後さらに長期間放置しておいても、工場レベルの実機（攪拌機）で強力な攪拌力を与えると、樹脂粒子のほぼ全量が再度、きれいに分散するようになり、そのまま、新鮮な分散体と同様に、定量性をもって使用することができる。本発明者が見出した試験方法はこのような知見に基づき案出されたものである。 According to the knowledge of the present inventor, when the dispersion is allowed to stand for 72 hours, most of the resin particles settle to form a lump. However, when the lump is redispersed using a small stirrer at the laboratory level, there is a certain standard. As long as it exhibits the above redispersibility, even if it is allowed to stand for a longer period of time, if a strong stirring force is applied with an actual machine (stirrer) at the factory level, almost all of the resin particles are dispersed again cleanly. As it is, it can be used as it is with the same quantitative quality as a fresh dispersion. The test method found by the present inventors has been devised based on such knowledge.
これまで、このような分散体の再分散性に着目した技術の報告はなかった。例えば、前記した特許文献１には、（メタ）アクリル系樹脂粒子を懸濁重合により得る際に、懸濁粒子の安定化を図るための分散安定剤としてソルビタン系界面活性剤を用いる技術が開示されてはいるが、該技術は、耐熱安定性など樹脂粒子自体の物性向上や、懸濁重合時の乳化重合の発生を抑制すること等を目指したものであり、該技術によって得られた分散体を分離したとしても前述した定量性を有するものではない。特許文献２には、光拡散性の（メタ）アクリル系樹脂組成物を得る技術の中で、製造方法の一形態として樹脂粒子の分散体を界面活性剤としてのソルビタントリステアレートを用いて得る技術が開示されてはいるが、分散体自体を製造する思想や分散体を反応系から分離する思想はなく、該技術によって得られた分散体を分離したとしても前述した定量性を有するものではない。
Until now, there has been no report of a technique focusing on the redispersibility of such a dispersion. For example,
したがって、本発明にかかる分散体は、溶媒中に乾燥工程を経て得られた平均粒子径が１．０〜１００μｍの（メタ）アクリル系樹脂粒子が分散してなる分散体であって、該（メタ）アクリル系樹脂粒子が水系懸濁重合により得られた粒子であり、ＨＬＢが８以上であるポリオキシエチレンソルビタン脂肪酸エステル類を含み、かつ、ｐＨが５〜１０である、樹脂フィルム用添加剤用分散体である。
本発明において、再分散指数とは、下記で定義されるものである。
Accordingly, the dispersion according to the present invention is a dispersion average particle diameter obtained through the drying step in a solvent is 1.0～100Myuemu (meth) acrylic resin particles are dispersed, the ( Additives for resin films , wherein the ( meth) acrylic resin particles are particles obtained by aqueous suspension polymerization , contain polyoxyethylene sorbitan fatty acid esters having an HLB of 8 or more, and have a pH of 5 to 10 Dispersion for use .
In the present invention, the redispersion index is defined as follows.
再分散指数：
内径１００ｍｍのガラス製ビーカーに、沈降粒子のない分散状態で固形分濃度（Ａ）の分散体を５００ｍＬ秤り取り、２３±２℃で７２時間放置したのち、下記の攪拌羽根を用いて２００ｒｐｍで３０分間攪拌し、前記ビーカー中の液体部分をデカンテーションにより採取して、その固形分濃度（Ｂ）を測定し、下記式に基づき求める。
Redispersion index:
In a glass beaker having an inner diameter of 100 mm, 500 mL of a dispersion having a solid content concentration (A) in a dispersion state without precipitated particles is weighed and allowed to stand at 23 ± 2 ° C. for 72 hours, and then at 200 rpm using the following stirring blade. The mixture is stirred for 30 minutes, and the liquid portion in the beaker is collected by decantation, and the solid content concentration (B) is measured and determined based on the following formula.
再分散指数（％）＝［（Ｂ）／（Ａ）］×１００
攪拌羽根の構造と設置：攪拌羽根は、攪拌軸とこれに結合された４枚の平板を備え、各平板は攪拌軸の中心からの長さ（ａ）３４ｍｍ、幅（ｂ）１６ｍｍ、厚み（ｃ）２ｍｍのほぼ長方形であり、それぞれの長さ方向を水平とし、それぞれの面が垂直面から同じ向きに４５度傾くとともに、それぞれの長さ方向中心線が攪拌軸に対して９０度の角度を持つようにし、かつ、それぞれの長さ方向中心線が互いに９０度の角度を持つような配置で、それぞれの平板の根元を攪拌軸に結合してなるものであり、該攪拌羽根は、その平板の下端縁がビーカーの底から１０ｍｍの高さ位置になるようにして、かつ、その攪拌軸が前記ビーカーの中心に垂直に位置するようにして、前記ビーカー内に設置されている。
Redispersion index (%) = [(B) / (A)] × 100
Structure and installation of stirring blade: The stirring blade includes a stirring shaft and four flat plates connected to the stirring shaft. Each flat plate has a length (a) 34 mm, a width (b) 16 mm, a thickness (from the center of the stirring shaft) c) It is a substantially 2 mm rectangle, each length direction is horizontal, each surface is inclined 45 degrees in the same direction from the vertical plane, and each length direction center line is an angle of 90 degrees with respect to the stirring axis And the bases of the respective flat plates are coupled to the stirring shafts in such an arrangement that the respective longitudinal centerlines have an angle of 90 degrees with each other. The flat plate is installed in the beaker so that the lower edge of the flat plate is at a height of 10 mm from the bottom of the beaker and the stirring shaft is positioned perpendicular to the center of the beaker.
本発明において、前記再分散指数を求めるに際しては、前述した試験（所定量を秤り取り、特定の条件で放置した後、特定の条件で攪拌し、液体部分をデカンテーションにより採取する試験）に供する分散体は、「沈降粒子のない分散状態で秤り取る」ことが必要である。すなわち、製造直後の分散体は通常、沈降粒子のない分散状態にあるし、製造後しばらく時間が経過したのちでも、通常、沈降粒子が生じていない。このように、製造直後の場合または製造後貯蔵状態に入っていても沈降粒子が生じていない場合はそのまま、前記ビーカーに秤り取るようにする。他方、製造後ある程度の時間が経過すると、分散体中の粒子がドラム缶などの貯蔵容器の底に沈降してしまうことがある。ときには、沈降粒子が固まりとなってしまうこともある。このように沈降粒子が生じている分散体について前記再分散指数を求めようとする場合には、いったん攪拌機で攪拌するなど、あらかじめ状況に応じた手段で沈降粒子のない分散状態にしてから、前記ビーカーに秤り取るようにするのである。 In the present invention, when obtaining the redispersion index, the above-described test (a test in which a predetermined amount is weighed and left under a specific condition and then stirred under a specific condition and a liquid part is collected by decantation). The dispersion to be provided needs to be “weighed out in a dispersed state free of precipitated particles”. That is, the dispersion immediately after production is usually in a dispersed state free of precipitated particles, and usually no precipitated particles are generated even after a while has passed after the production. As described above, when the precipitated particles are not generated even immediately after the production or in the storage state after the production, they are weighed in the beaker as they are. On the other hand, when a certain amount of time has elapsed after production, particles in the dispersion may settle to the bottom of a storage container such as a drum. Sometimes the settled particles become agglomerated. When trying to obtain the redispersion index for a dispersion in which precipitated particles are generated in this manner, the dispersion state without precipitated particles is previously obtained by means according to the situation, such as once stirring with a stirrer. Weigh it in a beaker.
本発明にかかる上記分散体は、前記ポリオキシエチレンソルビタン脂肪酸エステル類の含有量が前記（メタ）アクリル系樹脂粒子に対して０．１〜１５重量％であることが好ましい。
本発明にかかる上記分散体は、分散体中の（メタ）アクリル系樹脂粒子濃度が０．０５〜６０重量％であることが好ましい。
本発明にかかる上記分散体は、上記溶媒が水または水と相溶性のある溶媒であるであることが好ましい。
本発明にかかる上記分散体は、上記（メタ）アクリル系樹脂粒子が、（メタ）アクリル系モノマーを主成分とする重合性単量体（Ａ）を、水に対して実質的に不溶性で、かつ、該重合性単量体（Ａ）に対して難溶性である化合物（Ｂ）の存在下で水系懸濁重合させることにより得られた樹脂粒子であることが好ましい。
本発明はまた、上記分散体を用いた樹脂フィルム用の添加剤に関する。
本発明はまた、樹脂フィルム用の添加剤に用いられる分散体の調製方法に関する。該分散体の調製方法は、水系懸濁重合により得られた平均粒子径が１．０〜１００μｍである乾燥工程を経て得られた（メタ）アクリル系樹脂粒子、溶媒、および、ＨＬＢが８以上であるポリオキシエチレンソルビタン脂肪酸エステル類を混合する工程、ならびに、ｐＨを５〜１０に調整する工程を含む。
In the dispersion according to the present invention, the content of the polyoxyethylene sorbitan fatty acid esters is preferably 0.1 to 15% by weight with respect to the (meth) acrylic resin particles.
The dispersion according to the present invention preferably has a (meth) acrylic resin particle concentration in the dispersion of 0.05 to 60% by weight.
In the dispersion according to the present invention, the solvent is preferably water or a solvent compatible with water.
In the dispersion according to the present invention, the (meth) acrylic resin particles are substantially insoluble in water with respect to the polymerizable monomer (A) mainly composed of a (meth) acrylic monomer, And it is preferable that it is the resin particle obtained by carrying out the aqueous suspension polymerization in presence of the compound (B) which is sparingly soluble with respect to this polymerizable monomer (A).
The present invention also relates to an additive for a resin film using the above dispersion.
The present invention also relates to a method for preparing a dispersion used as an additive for a resin film . The method for preparing the dispersion is such that (meth) acrylic resin particles obtained by a drying step in which the average particle size obtained by aqueous suspension polymerization is 1.0 to 100 μm, the solvent, and the HLB is 8 or more. A step of mixing polyoxyethylene sorbitan fatty acid esters, and a step of adjusting the pH to 5-10.
本発明によれば、定量性に優れた（メタ）アクリル系樹脂粒子の分散体を提供することができる。 According to the present invention, it is possible to provide a dispersion of (meth) acrylic resin particles having excellent quantitativeness.
本発明の分散体は、（メタ）アクリル系樹脂粒子の分散体である。（メタ）アクリル系樹脂粒子は、透明性に優れる粒子であるので、本発明の分散体を例えば透明フィルムに対する添加剤やコーティング剤として用いた場合に、フィルムの透明性を損なうことがない。 The dispersion of the present invention is a dispersion of (meth) acrylic resin particles. Since the (meth) acrylic resin particles are particles having excellent transparency, the transparency of the film is not impaired when the dispersion of the present invention is used, for example, as an additive or a coating agent for a transparent film.
本発明における（メタ）アクリル系樹脂粒子の組成等は用途に応じて適宜設定すればよい。前記（メタ）アクリル系樹脂粒子としては、例えば、（メタ）アクリル系モノマーを主成分とする重合性単量体（Ａ）を、水に対して実質的に不溶性でかつ前記重合性単量体（Ａ）に対して難溶性である化合物（Ｂ）の存在下で水系懸濁重合させることにより得られる樹脂粒子が好ましく挙げられる。以下、該方法で得られる（メタ）アクリル系樹脂粒子について詳しく説明するが、本発明における（メタ）アクリル系樹脂粒子は、もちろんこれに限定されるものではなく、例えば、機械的粉砕による方法、他の懸濁重合による方法、もしくは乳化重合による方法などにより得られたものであってもよい。なお、（メタ）アクリル系樹脂粒子は、１種のみを用いてもよいし、２種以上を併用してもよい。 What is necessary is just to set suitably the composition of the (meth) acrylic-type resin particle in this invention according to a use. Examples of the (meth) acrylic resin particles include a polymerizable monomer (A) containing a (meth) acrylic monomer as a main component, substantially insoluble in water and the polymerizable monomer. Preferred examples include resin particles obtained by aqueous suspension polymerization in the presence of a compound (B) that is sparingly soluble in (A). Hereinafter, the (meth) acrylic resin particles obtained by the method will be described in detail. Of course, the (meth) acrylic resin particles in the present invention are not limited to this, for example, a method by mechanical pulverization, It may be obtained by another suspension polymerization method or emulsion polymerization method. In addition, only 1 type may be used for a (meth) acrylic-type resin particle, and 2 or more types may be used together.
前記重合性単量体（Ａ）は、（メタ）アクリル系モノマーを主成分とするものであり、好ましくは（メタ）アクリル系モノマーを５０〜１００重量％、より好ましくは６０〜１００重量％含有するものである。また、重合性単量体（Ａ）のＳＰ（溶解パラメータ）値は９．０以下であることが好ましい。 The polymerizable monomer (A) contains a (meth) acrylic monomer as a main component, and preferably contains a (meth) acrylic monomer in an amount of 50 to 100% by weight, more preferably 60 to 100% by weight. To do. The SP (solubility parameter) value of the polymerizable monomer (A) is preferably 9.0 or less.
前記（メタ）アクリル系モノマーとしては、特に制限されないが、例えば、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ドデシル、アクリル酸ステアリル、アクリル酸２−エチルヘキシル、アクリル酸テトラヒドロフルフリル、アクリルアミド、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸２−エチルヘキシル、メタクリル酸ステアリル、メタクリルアミド等が挙げられる。なお、（メタ）アクリル系モノマーは複数種組合せて用いることも可能である。 The (meth) acrylic monomer is not particularly limited. For example, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-acrylic acid 2- Ethylhexyl, tetrahydrofurfuryl acrylate, acrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate , Stearyl methacrylate, methacrylamide and the like. The (meth) acrylic monomers can be used in combination.
前記重合性単量体（Ａ）としては、前記（メタ）アクリル系モノマーのほかに、重合性二重結合基を分子中に複数個有する架橋性（メタ）アクリル系モノマーを用いることが、分子間に架橋構造を有する架橋樹脂粒子を得ようとする場合には有効である。架橋性（メタ）アクリル系モノマーとしては、例えば、トリアクリル酸トリメチロールプロパン、ジメタクリル酸エチレングリコール、ジメタクリル酸ジエチレングリコール、ジメタクリル酸トリエチレングリコール、ジメタクリル酸デカエチレングリコール、ジメタクリル酸ペンタデカエチレングリコール、ジメタクリル酸ペンタコンタヘクタエチレングリコール、ジメタクリル酸１，３−ブチレン、メタクリル酸アリル、トリメタクリル酸トリメチロールプロパン、テトラメタクリル酸ペンタエリスリトール、ジメタクリル酸フタル酸ジエチレングリコール等の（メタ）アクリル系モノマーが挙げられる。なお、架橋性（メタ）アクリル系モノマーは複数種組合せて用いることも可能である。 As the polymerizable monomer (A), in addition to the (meth) acrylic monomer, a crosslinkable (meth) acrylic monomer having a plurality of polymerizable double bond groups in the molecule is used. This is effective for obtaining crosslinked resin particles having a crosslinked structure therebetween. Examples of the crosslinkable (meth) acrylic monomer include trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, and pentadecamethacrylate. (Meth) acrylics such as ethylene glycol, pentamethacrylate dimethacrylate ethylene glycol, 1,3-butylene dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, diethylene glycol dimethacrylate Based monomers. Note that a plurality of crosslinkable (meth) acrylic monomers can be used in combination.
前記架橋性（メタ）アクリル系モノマーを用いる場合には、その使用量は、重合性単量体（Ａ）中、０．５〜２０重量％、より好ましくは１〜１５重量％とするのがよい。架橋性（メタ）アクリル系モノマーが０．５重量％未満であると、架橋結合量が少なくなり、得られる粒子に充分な架橋構造を導入できなくなり、一方、２０重量％を越えると、架橋結合量が多くなりすぎて、得られる粒子の架橋密度が高くなりすぎるとともに、架橋性（メタ）アクリル系モノマーは比較的高価であるので必要以上の使用は得られる粒子のコストを上昇させることになる。 When the crosslinkable (meth) acrylic monomer is used, the amount used is 0.5 to 20% by weight, more preferably 1 to 15% by weight in the polymerizable monomer (A). Good. If the crosslinkable (meth) acrylic monomer is less than 0.5% by weight, the amount of cross-linking decreases, and it becomes impossible to introduce a sufficient cross-linking structure into the resulting particles. The amount is too high, resulting in a too high crosslink density of the resulting particles and the use of more than necessary crosslinkable (meth) acrylic monomers increases the cost of the resulting particles. .
前記重合性単量体（Ａ）としては、前記（メタ）アクリル系モノマーのほかに、（メタ）アクリル系モノマーと共重合可能な他のモノマーを（メタ）アクリル系モノマーの配合量を阻害しない範囲内において用いることができる。（メタ）アクリル系モノマーと共重合可能な他のモノマーとしては、具体的には、例えば、スチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、ｐ−メトキシスチレン、ｐ−ｔ−ブチルスチレン、ｐ−フェニルスチレン、ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン等のスチレン系モノマー、エチレン、プロピレン、ブチレン、塩化ビニル、酢酸ビニル、アクリロニトリル、Ｎ−ビニルピロリドン等が挙げられる。また、例えば、ジビニルベンゼン、ジビニルナフタレン、これらの誘導体等の芳香族ジビニル化合物、Ｎ，Ｎ−ジビニルアニリン、ジビニルエーテル、ジビニルサルファイド、ジビニルスルホン酸等の架橋剤、さらに、ポリブダジエン、ポリイソプレン不飽和ポリエステルおよび特公昭５７−５６５０７号公報、特開昭５９−２２１３０４号公報、特開昭５９−２２１３０５号公報、特開昭５９−２２１３０６号公報、特開昭５９−２２１３０７号公報等に記載される反応性重合体等も使用可能である。なお、前記他のモノマーは複数種組合せて用いることも可能である。 As the polymerizable monomer (A), in addition to the (meth) acrylic monomer, other monomers copolymerizable with the (meth) acrylic monomer do not inhibit the blending amount of the (meth) acrylic monomer. It can be used within the range. Specific examples of other monomers copolymerizable with (meth) acrylic monomers include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, and p-methoxystyrene. , Styrene monomers such as pt-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, N-vinyl Examples include pyrrolidone and the like. In addition, for example, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof, cross-linking agents such as N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfonic acid, polybutadiene, polyisoprene unsaturated Polyester and described in JP-B-57-56507, JP-A-59-221304, JP-A-59-221305, JP-A-59-221306, JP-A-59-221307, etc. A reactive polymer or the like can also be used. The other monomers can be used in combination.
前記（メタ）アクリル系モノマーと共重合可能な他のモノマーを用いる場合には、その使用量は、重合性単量体（Ａ）中、５０重量％以下、より好ましくは４０重量％以下、さらに好ましくは３０重量％以下、さらに好ましくは２０重量％以下、最も好ましくは１０重量％以下とするのがよい。 In the case of using another monomer copolymerizable with the (meth) acrylic monomer, the amount used is 50% by weight or less in the polymerizable monomer (A), more preferably 40% by weight or less, It is preferably 30% by weight or less, more preferably 20% by weight or less, and most preferably 10% by weight or less.
前記化合物（Ｂ）は、重合時に使用される乳化剤や界面活性剤の作用によって生成する粒子界面に存在し、生成する粒子界面で起きる可能性がある乳化重合を抑制するとともに、生成する粒子の連鎖移動を阻害して重合度を上げ、得られる粒子の耐熱性を向上させるといった作用をするものもある。前記化合物（Ｂ）は、水に対して実質的に不溶性でかつ重合性単量体（Ａ）に対しても難溶性であるものであればよく、例えば、−ＳＨ、−Ｓ−Ｓ−、−ＣＯＯＨ、−ＮＯ２および−ＯＨからなる群から選ばれる構造単位を少なくとも１種以上有する化合物が好ましく用いられる。−ＳＨを有する化合物の具体例としては、例えば、チオクレゾール、チオフェノール、チオグリコール酸メチル、チオグリコール酸エチル、チオグリコール酸ブチル、チオグリコール酸２−エチルヘキシル、トリチオグリコール酸トリメチロールプロパン、ジチオヒドロキノン、キシレンジチオール、２−メルカプトナフタリンなどが挙げられ、−Ｓ−Ｓ−を有する化合物の具体例としては、例えば、ジアリルジスルフィド、ジチオジプロピオン酸ジオクチルエステル等が挙げられ、−ＣＯＯＨを有する化合物の具体例としては、例えば、ケイ皮酸、安息香酸、クロル安息香酸、フタル酸、イソフタル酸等が挙げられ、−ＮＯ２を有する化合物の具体例としては、例えば、ニトロベンゼン、ニトロトルエン、ニトロキシレン、ニトロナフタリン、ニトロアニリン等が挙げられ、−ＯＨを有する化合物の具体例としては、例えば、アミノクレゾール、アミノナフトール、ｍ−クレゾール、オキシアントラセン、オキシアントラキノン、オキサントロン、３−オキシ−９−アントロン、オキシナフトキノン、ジオキシアントラセン、ジオキシアントラキノン、１，５−ジオキシナフタリン、１，８−ジオキシナフタリン、２，６−ジオキシナフタリン、３，５−ジメチルフェノール、ナフトール等が挙げられる。さらに、−ＳＨ、−Ｓ−Ｓ−、−ＣＯＯＨ、−ＮＯ２および−ＯＨからなる群から選ばれる構造単位を２種以上有する化合物の具体例としては、例えば、サリチル酸、チオサリチル酸、ジチオサリチル酸、ニトロ安息香酸、３，４−ジニトロ安息香酸、ニトロフェノール等が挙げられる。 The compound (B) is present at the particle interface generated by the action of the emulsifier and surfactant used at the time of polymerization, suppresses emulsion polymerization that may occur at the generated particle interface, and generates a chain of particles. Some have the effect of inhibiting the movement to increase the degree of polymerization and improving the heat resistance of the resulting particles. The compound (B) may be any compound that is substantially insoluble in water and hardly soluble in the polymerizable monomer (A). For example, -SH, -SS-, A compound having at least one structural unit selected from the group consisting of —COOH, —NO 2 and —OH is preferably used. Specific examples of the compound having —SH include, for example, thiocresol, thiophenol, methyl thioglycolate, ethyl thioglycolate, butyl thioglycolate, 2-ethylhexyl thioglycolate, trimethylolpropane trithioglycolate, dithio Hydroquinone, xylenedithiol, 2-mercaptonaphthalene and the like are mentioned, and specific examples of the compound having -SS- include, for example, diallyl disulfide, dithiodipropionic acid dioctyl ester, etc. Specific examples include, for example, cinnamic acid, benzoic acid, chlorobenzoic acid, phthalic acid, isophthalic acid, etc. Specific examples of the compound having —NO 2 include, for example, nitrobenzene, nitrotoluene, nitroxylene, nitro Naphtali Specific examples of the compound having —OH include, for example, aminocresol, aminonaphthol, m-cresol, oxyanthracene, oxyanthraquinone, oxanthrone, 3-oxy-9-anthrone, and oxynaphthoquinone. , Dioxyanthracene, dioxyanthraquinone, 1,5-dioxynaphthalene, 1,8-dioxynaphthalene, 2,6-dioxynaphthalene, 3,5-dimethylphenol, naphthol and the like. Furthermore, specific examples of the compound having two or more structural units selected from the group consisting of —SH, —SS—, —COOH, —NO 2 and —OH include, for example, salicylic acid, thiosalicylic acid, dithiosalicylic acid, Examples thereof include nitrobenzoic acid, 3,4-dinitrobenzoic acid, and nitrophenol.
前記化合物（Ｂ）の使用量は、化合物（Ｂ）の種類および重合性単量体（Ａ）の組成等に応じて適宜設定すればよいのであるが、例えば、前記重合性単量体（Ａ）に対して２０〜０．０００１重量％、より好ましくは１０〜０．００１重量％、さらに好ましくは５〜０．０１重量％程度とするのがよい。なお、化合物（Ｂ）は、例えば、前記重合性単量体（Ａ）中に添加するようにしてもよいし、水相に添加するようにしてもよいし、メタノール等の溶媒に溶解したのち水相中に分散させるようにしてもよい。 What is necessary is just to set the usage-amount of the said compound (B) suitably according to the kind of compound (B), a composition of a polymerizable monomer (A), etc., for example, the said polymerizable monomer (A ) To 20 to 0.0001% by weight, more preferably 10 to 0.001% by weight, and still more preferably about 5 to 0.01% by weight. The compound (B) may be added, for example, to the polymerizable monomer (A), may be added to the aqueous phase, or dissolved in a solvent such as methanol. You may make it disperse | distribute in an aqueous phase.
懸濁重合の際に用いる重合開始剤としては、通常該反応に用いられる油溶性の過酸化物系開始剤あるいはアゾ系開始剤を用いればよい。例えば、過酸化ベンゾイル、過酸化ラウロイル、過酸化オクタノイル、オルソクロロ過酸化ベンゾイル、オルソメトキシ過酸化ベンゾイル、メチルエチルケトンパーオキサイド、ジイソプロピルパーオキシジカーボネート、キュメンハイドロパーオキサイド、シクロヘキサノンパーオキサイド、ｔ−ブチルハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド等の過酸化物系開始剤、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，３−ジメチルブチロニトリル）、２，２’−アゾビス（２−メメチルブチロニトリル）、２，２’−アゾビス（２，３，３−トリメチルブチロニトリル）、２，２’−アゾビス（２−イソプロピルブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス（４−メチキシ−２，４−ジメチルバレロニトリル）、２−（カルバモイルアゾ）イソブチロニトリル、４，４’−アゾビス（４−シアノバレリン酸）、ジメチル−２，２’−アゾビスイソブチレート等が挙げられる。重合開始剤の使用量は、重合性単量体（Ａ）に対して０．０１〜２０重量％、好ましくは０．１〜１０重量％程度とするのが適当である。 As the polymerization initiator used in suspension polymerization, an oil-soluble peroxide-based initiator or azo-based initiator that is usually used in the reaction may be used. For example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide , Peroxide initiators such as diisopropylbenzene hydroperoxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2,3-dimethylbutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,3,3-trimethylbutyronitrile), 2,2'- Azobis (2-isopropylbutyronitrate ), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 4 , 4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobisisobutyrate and the like. The amount of the polymerization initiator used is suitably 0.01 to 20% by weight, preferably about 0.1 to 10% by weight, based on the polymerizable monomer (A).
懸濁重合の際の重合温度は、特に限定されないが、例えば、１０〜９０℃、好ましくは３０〜８０℃程度が適当である。 Although the polymerization temperature in suspension polymerization is not specifically limited, For example, 10-90 degreeC, Preferably about 30-80 degreeC is suitable.
懸濁重合は、重合性単量体（Ａ）懸濁粒子の粒子径の規制を行なった後、あるいは粒子径の規制を行ないながら、行なうことが好ましいが、特に粒子径の規制を行なった後に懸濁重合を行なうことが好ましい。この粒子径の規制は、例えば、所定の成分を水性媒体に分散させた懸濁液をＴ．Ｋ．ホモミキサーにより撹拌して行なうか、あるいはラインミキサー（例えばエバラマイルダー）等の高速撹拌機に１回ないし数回通過させることにより行うことができる。 The suspension polymerization is preferably carried out after regulating the particle size of the polymerizable monomer (A) suspended particles or while regulating the particle size, but especially after regulating the particle size. It is preferable to perform suspension polymerization. The regulation of the particle diameter is, for example, that a suspension in which a predetermined component is dispersed in an aqueous medium is T.D. K. It can be carried out by stirring with a homomixer or by passing it once or several times through a high-speed stirrer such as a line mixer (eg, Ebara Milder).
懸濁重合の際には、懸濁粒子の安定化を図るために、分散安定剤を添加することができる。分散安定剤としては、例えば、ポリビニルアルコール、ゼラチン、トラガント、デンプン、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸ナトリウム、ポリメタクリル酸ナトリウム等の水溶性高分子；オレイン酸ナトリウム、ヒマシ油カリ等の脂肪酸油、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム等のアルキル硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルカンスルホン酸塩、ジアルキルスルホコハク酸塩、アルキルリン酸エステル塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩、ポリオキシエチレンアルキル硫酸エステル塩等のアニオン性界面活性剤；ラウリルアミンアセテート、ステアリルアミンアセテート等のアルキルアミン塩、ラウリルトリメチルアンモニウムクロライド等の第四級アンモニウム塩等のカチオン性界面活性剤；ラウリルジメチルアミンオキサイド等の両性イオン性界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルアミン、グリセリン脂肪酸エステル、オキシエチレン−オキシプロピレンブロックポリマー等のノニオン性界面活性剤；等が挙げられ、その他に、アルギン酸塩、ゼイン、カゼイン、硫酸バリウム、硫酸カルシウム、炭酸バリウム、炭酸マグネシウム、リン酸カルシウム、タルク、粘土、ケイソウ土、ベントナイト、水酸化チタン、水酸化トリウム、金属酸化物粉末等を用いることもできる。分散安定剤の使用量は、その組成や得ようとする樹脂粒子の粒子径等に応じて、適宜設定すればよいのであるが、例えば、重合性単量体（Ａ）に対して０．０１〜２９重量％、好ましくは０．１〜１０重量％とするのが好ましい。 During suspension polymerization, a dispersion stabilizer can be added in order to stabilize the suspended particles. Examples of the dispersion stabilizer include water-soluble polymers such as polyvinyl alcohol, gelatin, tragacanth, starch, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, sodium polyacrylate, and sodium polymethacrylate; sodium oleate, castor oil potash, etc. Fatty acid oils, alkyl sulfate salts such as sodium lauryl sulfate, ammonium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonates, alkane sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, Naphthalenesulfonic acid formalin condensate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl sulfate, etc. Anionic surfactants; cationic amines such as alkylamine salts such as laurylamine acetate and stearylamine acetate; quaternary ammonium salts such as lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene-oxypropylene block polymer, etc. Nonionic surfactants; etc. In addition, alginate, zein, casein, barium sulfate, calcium sulfate, barium carbonate Magnesium carbonate, calcium phosphate, talc, clay, diatomaceous earth, bentonite, titanium hydroxide, thorium hydroxide, also possible to use a metal oxide powder or the like. The amount of the dispersion stabilizer used may be appropriately set according to the composition, the particle size of the resin particles to be obtained, and the like. For example, the amount of the dispersion stabilizer is 0.01 with respect to the polymerizable monomer (A). It is preferable to set it to -29 weight%, Preferably it is 0.1-10 weight%.
さらに、懸濁重合の際には、前記重合性単量体（Ａ）中あるいは水相中に、必要に応じて、顔料や染料などの着色剤、あるいはその他の添加剤等を添加することもできる。顔料としては、例えば、鉛白、鉛丹、黄鉛、カーボンブラック、群青、酸化亜鉛、酸化コバルト、二酸化チタン、酸化鉄、シリカ、チタン黄、チタンブラック等の無機顔料、イソインドリノン、キナクリドン、ジオキサンバイオレット、フタロシアニンブルー、ペリノン顔料、ペリレン顔料、不溶性アゾ顔料、溶性アゾ顔料、染色レーキ等の有機顔料が挙げられる。染料としては、例えば、ニトロソ染料、ニトロ染料、アゾ染料、スチルベンアゾ染料、ジフェニルメタン染料、トリフェニルメタン染料、キサンテン染料、アクリジン染料、キノリン染料、メチン染料、ポリメチン染料、チアゾール染料、インダミン染料、インドフェノール染料、アジン染料、オキサジン染料、チアジン染料、硫化染料等が挙げられる。また、その他の添加剤としては、可塑剤、重合安定剤、蛍光増白剤、磁性粉、紫外線吸収剤、帯電防止剤、難燃剤等が挙げられる。なお、これらの着色剤やその他の添加剤は、重合性単量体（Ａ）への分散性の向上を目的として、種々の方法により表面処理されたものであってもよい。表面処理方法としては、例えば、ステアリン酸、オレイン酸等の長鎖の炭化水素で処理する方法、アクリル酸、メタクリル酸等の極性基を有する重合性単量体で処理する方法、トリメチロールプロパン等の多価アルコールで処理する方法、トリエタノールアミン等のアミン類等で処理する方法、各種カップリング剤で処理する方法、あるいは着色剤やその他の添加剤とこれらの表面の官能基と反応し得る反応基（アジリジン基、オキサゾリン基、Ｎ−ヒドロキシアルキルアミド基、エポキシ基、チオエポキシ基、イソシアネート基、ビニル基、ケイ素系加水分解基、アミノ基等）を有する重合体とを２０〜３５０℃の温度で反応させ、着色剤やその他の添加剤の表面に重合体をグラフト化する方法などを挙げることができる。 Furthermore, in the case of suspension polymerization, a colorant such as a pigment or a dye or other additives may be added to the polymerizable monomer (A) or the aqueous phase as necessary. it can. Examples of the pigment include inorganic pigments such as lead white, red lead, yellow lead, carbon black, ultramarine, zinc oxide, cobalt oxide, titanium dioxide, iron oxide, silica, titanium yellow, and titanium black, isoindolinone, quinacridone, Examples thereof include organic pigments such as dioxane violet, phthalocyanine blue, perinone pigment, perylene pigment, insoluble azo pigment, soluble azo pigment, and dye lake. Examples of the dye include nitroso dye, nitro dye, azo dye, stilbene azo dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye, polymethine dye, thiazole dye, indamine dye, indophenol And dyes, azine dyes, oxazine dyes, thiazine dyes, sulfur dyes and the like. Other additives include plasticizers, polymerization stabilizers, fluorescent brighteners, magnetic powders, ultraviolet absorbers, antistatic agents, flame retardants, and the like. These colorants and other additives may be surface-treated by various methods for the purpose of improving dispersibility in the polymerizable monomer (A). Examples of the surface treatment method include a method of treating with a long-chain hydrocarbon such as stearic acid and oleic acid, a method of treating with a polymerizable monomer having a polar group such as acrylic acid and methacrylic acid, trimethylolpropane and the like. A method of treating with polyhydric alcohols, a method of treating with amines such as triethanolamine, a method of treating with various coupling agents, or a colorant or other additive and can react with functional groups on these surfaces A polymer having a reactive group (aziridine group, oxazoline group, N-hydroxyalkylamide group, epoxy group, thioepoxy group, isocyanate group, vinyl group, silicon hydrolyzable group, amino group, etc.) and a temperature of 20 to 350 ° C. And a method of grafting a polymer onto the surface of a colorant or other additives.
本発明の分散体は、再分散指数が５０％以上であることが重要である。本発明において、再分散指数とは、下記で定義されるものである。 It is important that the dispersion of the present invention has a redispersion index of 50% or more. In the present invention, the redispersion index is defined as follows.
再分散指数：
この指数は図１に示す装置を用いて測定することができる。
Redispersion index:
This index can be measured using the apparatus shown in FIG.
内径１００ｍｍのガラス製ビーカーに、沈降粒子のない分散状態で固形分濃度（Ａ）の分散体を５００ｍＬ秤り取り、２３±２℃で７２時間放置したのち、下記の攪拌羽根２を用いて２００ｒｐｍで３０分間攪拌し、ビーカー１中の液体部分をデカンテーションにより採取して、その固形分濃度（Ｂ）を測定し、下記式に基づき求める。なお、前記デカンテーションにより採取した液体部分は、再分散指数が高い分散体であるほど、通常、沈降粒子のないほぼ均一な分散状態の液となり、再分散指数が低い分散体であるほど、通常、ほとんどの粒子が沈降してしまったクリヤーな液になる。
In a glass beaker having an inner diameter of 100 mm, 500 mL of the dispersion having a solid content concentration (A) in a dispersion state without precipitated particles is weighed and left at 23 ± 2 ° C. for 72 hours, and then 200 rpm using the following
再分散指数（％）＝［（Ｂ）／（Ａ）］×１００
攪拌羽根の構造と設置：攪拌羽根２は、攪拌軸２１とこれに結合された平板２２を４枚備え、各平板２２は攪拌軸（直径８ｍｍ）２１の中心２１ａからの長さ（ａ）３４ｍｍ、幅（ｂ）１６ｍｍ、厚み（ｃ）２ｍｍのほぼ長方形であり、それぞれの長さ方向を水平とし、それぞれの面が垂直面から同じ向きに４５度の角度（Ｐ１）で傾くとともに、それぞれの長さ方向中心線が攪拌軸２１に対して９０度の角度を持つようにし、かつ、それぞれの長さ方向中心線が互いに９０度の角度（Ｐ２）を持つような配置で、それぞれの平板の根元を、直径１４ｍｍのブッシュ２３を介して、攪拌軸２１に結合してなるものであり、該攪拌羽根２は、その平板２２の下端縁がビーカー１の底から１０ｍｍの高さ位置になるようにして、かつ、その攪拌軸２１が前記ビーカー１の中心に垂直に位置するようにして、前記ビーカー１内に設置されている。この攪拌装置においては、攪拌軸２１の直径やブッシュ２３の直径が多少変化しても、その攪拌能力に影響はない。
Redispersion index (%) = [(B) / (A)] × 100
Structure and installation of stirring blades: The stirring
実験室レベルのこの小さな攪拌装置を用いて再分散させたときの、７２時間放置前後の分散性を見ることで、貯蔵などで長時間放置したのちでも、樹脂粒子の全量がきれいに再分散するか否かを予測することができるのである。 Whether the total amount of resin particles can be redispersed neatly even after storage for a long time by observing the dispersibility before and after 72 hours of redispersion using this small stirrer at the laboratory level. It is possible to predict whether or not.
なお、固形分濃度は、分散体をアルミカップに精秤し（アルミカップの大きさにもよるが、通常１〜２ｇを精秤すればよい）、１１０℃に加温したホットプレート上で重量が変化しなくなるまで乾固させたのち、残存固形分（乾固物）の重量を測定し、前記精秤した分散体の重量に対する残存固形分の重量の割合（重量％）を算出することにより求める。 In addition, solid content concentration is weighted on a hot plate heated to 110 ° C. by accurately weighing the dispersion in an aluminum cup (depending on the size of the aluminum cup, usually 1 to 2 g may be precisely weighed). By drying until solids no longer change, and then measuring the weight of the remaining solids (dried product) and calculating the ratio (% by weight) of the weight of the remaining solids to the weight of the precisely weighed dispersion. Ask.
詳しくは、従来、分散体を数日間放置しておくと、分散体中の粒子が容器底部に沈降し、その一部または全部が強固な固まりとなってしまい、定量性に欠けることがあったが、再分散指数が前記範囲である分散体は、粒子が沈降してしまっている場合であっても粒子の全てを容易に再分散させることができるため、定量性を有するのである。再分散指数が５０％未満である分散体は、沈降して強く固まった粒子を通常の攪拌手段で再分散させることが困難となる。再分散指数は、好ましくは６０％以上、より好ましくは７０％以上、最も好ましくは８０％以上である。 Specifically, conventionally, if the dispersion is left for several days, particles in the dispersion settle to the bottom of the container, and part or all of the dispersion becomes a solid mass, which sometimes lacks quantitativeness. However, a dispersion having a redispersion index in the above range has quantitativeness because all of the particles can be easily redispersed even when the particles have settled. A dispersion having a redispersion index of less than 50% makes it difficult to redisperse particles that have settled and become hardened by a normal stirring means. The redispersion index is preferably 60% or more, more preferably 70% or more, and most preferably 80% or more.
本発明の分散体の好ましい態様は、ＨＬＢが８以上であるポリオキシエチレンソルビタン脂肪酸エステル類を含む分散体である。これにより、本発明の分散体は、前記範囲の再分散指数を有し、定量性に優れたものとなる。これは、前記ポリオキシエチレンソルビタン脂肪酸エステル類が共存することにより、分散した状態において数個の樹脂粒子同士が非常にゆるやかに凝集し、このようにゆるやかに凝集した状態で沈降するようにしておくことで、個々の粒子が密に詰まり樹脂粒子全体が強固な固まりになることを阻止することができる、からであると推測される。このように、ＨＬＢが特定範囲のポリオキシエチレンソルビタン脂肪酸エステル類が再分散性能の向上に寄与するということは、これまで全く知られておらず、本発明は、この新たに見出した前記ポリオキシエチレンソルビタン脂肪酸エステル類の特性を利用したものである。ポリオキシエチレンソルビタン脂肪酸エステル類のＨＬＢが８未満であると、疎水性が強すぎ、（メタ）アクリル系樹脂粒子を充分に再分散させることができず、充分な定量性を発現させることができない。ポリオキシエチレンソルビタン脂肪酸エステル類のＨＬＢは、好ましくは１０以上、さらに好ましくは１２以上であるのがよい。 A preferred embodiment of the dispersion of the present invention is a dispersion containing polyoxyethylene sorbitan fatty acid esters having an HLB of 8 or more. As a result, the dispersion of the present invention has a redispersion index in the above range, and has excellent quantitativeness. This is because the coexistence of the polyoxyethylene sorbitan fatty acid esters causes several resin particles to aggregate very gently in a dispersed state, and settles in such a gently aggregated state. Thus, it is presumed that it is possible to prevent the individual particles from being tightly packed and the entire resin particles from becoming a solid mass. Thus, it has not been known so far that polyoxyethylene sorbitan fatty acid esters having a specific range of HLB contribute to the improvement of the redispersion performance, and the present invention is not limited to the newly found polyoxyethylene sorbitan fatty acid esters. It utilizes the characteristics of ethylene sorbitan fatty acid esters. When the HLB of the polyoxyethylene sorbitan fatty acid esters is less than 8, the hydrophobicity is too strong, the (meth) acrylic resin particles cannot be sufficiently redispersed, and sufficient quantitative properties cannot be expressed. . The HLB of the polyoxyethylene sorbitan fatty acid esters is preferably 10 or more, more preferably 12 or more.
前記ポリオキシエチレンソルビタン脂肪酸エステル類としては、例えば、炭素数１０〜２０の飽和もしくは不飽和脂肪酸からなるエステルが好ましく、具体的には、例えば、ポリオキシエチレンソルビタンモノ（ジ、セスキ、またはトリ）ラウレート、ポリオキシエチレンソルビタンモノ（ジ、セスキ、またはトリ）パルミテート、ポリオキシエチレンソルビタンモノ（ジ、セスキ、またはトリ）ステアレート、ポリオキシエチレンソルビタンモノ（ジ、セスキ、またはトリ）オレエート等が挙げられる。なお、前記ポリオキシエチレンソルビタン脂肪酸エステル類は、１種のみを用いてもよいし、２種以上を併用してもよい。 As the polyoxyethylene sorbitan fatty acid esters, for example, esters composed of saturated or unsaturated fatty acids having 10 to 20 carbon atoms are preferable, and specifically, for example, polyoxyethylene sorbitan mono (di, sesqui, or tri). Examples include laurate, polyoxyethylene sorbitan mono (di, sesqui, or tri) palmitate, polyoxyethylene sorbitan mono (di, sesqui, or tri) stearate, polyoxyethylene sorbitan mono (di, sesqui, or tri) oleate It is done. In addition, the said polyoxyethylene sorbitan fatty acid ester may use only 1 type, and may use 2 or more types together.
前記ポリオキシエチレンソルビタン脂肪酸エステル類の分散体中に占める含有量は、特に制限されないが、例えば、（メタ）アクリル系樹脂粒子に対して０．１〜１５重量％とすることが好ましく、０．５〜１０重量％とすることがより好ましく、１〜８重量％とすることがさらに好ましい。０．１重量％未満であると、充分な再分散性能を付与できず、充分な定量性を発現できない恐れがあり、一方、１５重量％を越えて使用しても、さらなる効果が期待できず経済的に不利となると同時に、ポリオキシエチレンソルビタン脂肪酸エステル類の使用量が多すぎると、分散時の泡立ちが顕著になり、泡が消えにくくなるため、得られた分散体を例えばコーティング用途に使用した場合に泡の混入により塗膜の外観不良を招くこととなる。 The content of the polyoxyethylene sorbitan fatty acid ester in the dispersion is not particularly limited, but is preferably 0.1 to 15% by weight with respect to the (meth) acrylic resin particles, for example. It is more preferable to set it as 5 to 10 weight%, and it is still more preferable to set it as 1 to 8 weight%. If it is less than 0.1% by weight, sufficient redispersion performance cannot be imparted, and there is a possibility that sufficient quantitative properties cannot be expressed. On the other hand, even if it exceeds 15% by weight, no further effect can be expected. At the same time as being economically disadvantageous, if the amount of polyoxyethylene sorbitan fatty acid esters used is too large, foaming at the time of dispersion becomes prominent and foam is difficult to disappear, so the resulting dispersion is used for coating applications, for example In such a case, the appearance of the coating film is deteriorated due to the mixing of bubbles.
本発明の分散体のさらに好ましい態様は、ｐＨが５〜１０である分散体である。これにより、本発明の分散体は、より良好な再分散性能を有し、定量性に優れたものとなる。分散体のｐＨを前記範囲に調整する方法は、特に制限されるものではないが、例えば、ｐＨを測定しながらアルカリや酸等を添加することにより行うことが好ましい。用いることのできるアルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア等の水溶液が挙げられる。用いることのできる酸としては、例えば、硫酸、塩酸等の公知の酸が挙げられる。 A further preferred embodiment of the dispersion of the present invention is a dispersion having a pH of 5 to 10. Thereby, the dispersion of the present invention has better redispersion performance and excellent quantitativeness. The method for adjusting the pH of the dispersion to the above range is not particularly limited, but for example, it is preferably performed by adding an alkali or an acid while measuring the pH. Examples of the alkali that can be used include aqueous solutions of sodium hydroxide, potassium hydroxide, ammonia, and the like. Examples of the acid that can be used include known acids such as sulfuric acid and hydrochloric acid.
本発明の分散体は、溶媒中に（メタ）アクリル系樹脂粒子が分散してなるものであり、前記（メタ）アクリル系樹脂粒子を分散させるための溶媒を含むものであるが、該溶媒は用途に応じて適宜選択すればよく、特に制限されるものではない。溶媒としては、水を単独で用いることが好ましいが、水と相溶性のある溶媒であれば、用途に応じて適宜用いることもできる。但し、水と相溶性のある溶媒を用いる場合には、該水以外の溶媒が分散体１００重量部中、３０重量部以下、好ましくは２０重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下となるようにするのがよい。 The dispersion of the present invention is obtained by dispersing (meth) acrylic resin particles in a solvent, and contains a solvent for dispersing the (meth) acrylic resin particles. It may be appropriately selected depending on the case, and is not particularly limited. As the solvent, it is preferable to use water alone, but any solvent that is compatible with water can be used as appropriate depending on the application. However, when a solvent compatible with water is used, the solvent other than water is 30 parts by weight or less, preferably 20 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 100 parts by weight of the dispersion. Is preferably 5 parts by weight or less.
前記（メタ）アクリル系樹脂粒子と溶媒との含有割合は、特に制限されるものではないが、分散体の固形分濃度（分散体中の（メタ）アクリル系樹脂粒子濃度）が０．０５〜６０重量％となるようにするのが好ましく、０．５〜５０重量％となるようにするのがより好ましい。分散体中の（メタ）アクリル系樹脂粒子濃度が０．０５重量％未満であると、生産効率が悪くなる傾向があり、一方、６０重量％を越えると、粘度が上昇して分散し難くなり、未分散物が増加する恐れがある。前記再分散指数を満足する本発明の分散体は、良好な再分散性能を有するものであるので、その固形分濃度を６０重量％以下と比較的高い範囲で設定することが可能となるのである。 The content ratio of the (meth) acrylic resin particles and the solvent is not particularly limited, but the solid content concentration of the dispersion ((meth) acrylic resin particle concentration in the dispersion) is 0.05 to. It is preferably 60% by weight, more preferably 0.5 to 50% by weight. When the concentration of the (meth) acrylic resin particles in the dispersion is less than 0.05% by weight, the production efficiency tends to deteriorate. On the other hand, when the concentration exceeds 60% by weight, the viscosity increases and it becomes difficult to disperse. The undispersed material may increase. Since the dispersion of the present invention that satisfies the redispersion index has good redispersion performance, the solid content concentration can be set within a relatively high range of 60% by weight or less. .
本発明においては、前記（メタ）アクリル系樹脂粒子は、乾燥工程を経て得られたものであることが好ましい。すなわち、本発明においては、前述のような懸濁重合で得られた反応物から固形分を分離し、乾燥工程と必要に応じて粉砕工程とを経て得られる乾燥状態の（メタ）アクリル系樹脂粒子と、前記溶媒および前記ポリオキシエチレンソルビタン脂肪酸エステル類とを混合分散させることにより得られる分散体が好ましい態様となる。このように乾燥工程を経て得られた（メタ）アクリル系樹脂粒子を用いる態様の場合、必要に応じて（メタ）アクリル系樹脂粒子を洗浄する洗浄工程をも経ることができ、該洗浄工程や乾燥工程において樹脂粒子製造時の残存モノマーなどの不純物を洗浄もしくは揮発させて低減することができるので、結果として、不純物の少ない（メタ）アクリル系樹脂粒子の分散体とすることができるからである。もちろん、本発明の分散体は、前記乾燥工程を経て得られた樹脂粒子を用いる態様に限定されるものではなく、（メタ）アクリル系樹脂粒子を得る際の懸濁重合で用いる分散安定剤として前記ポリオキシエチレンソルビタン脂肪酸エステル類を用い、得られた反応物をそのまま分散体とした態様であってもよい。 In the present invention, the (meth) acrylic resin particles are preferably obtained through a drying process. That is, in the present invention, a (meth) acrylic resin in a dry state obtained by separating a solid content from the reaction product obtained by suspension polymerization as described above and passing through a drying step and, if necessary, a pulverization step A dispersion obtained by mixing and dispersing particles, the solvent, and the polyoxyethylene sorbitan fatty acid ester is a preferred embodiment. In the case of the embodiment using the (meth) acrylic resin particles obtained through the drying step in this way, a washing step for washing the (meth) acrylic resin particles can be performed as necessary. This is because impurities such as residual monomers at the time of producing the resin particles can be reduced by washing or volatilizing in the drying step, and as a result, a dispersion of (meth) acrylic resin particles with few impurities can be obtained. . Of course, the dispersion of the present invention is not limited to the embodiment using the resin particles obtained through the drying step, but as a dispersion stabilizer used in suspension polymerization when obtaining (meth) acrylic resin particles. The polyoxyethylene sorbitan fatty acid ester may be used and the obtained reaction product may be used as a dispersion.
本発明の分散体が乾燥工程を経て得られた（メタ）アクリル系樹脂粒子を用いる態様の場合、乾燥工程における具体的な手法や条件については、特に制限はなく、得られる樹脂粒子の水分含量が３０重量％以下となるように従来公知の方法により行えばよい。 In the case where the dispersion of the present invention uses the (meth) acrylic resin particles obtained through the drying step, there are no particular restrictions on the specific technique and conditions in the drying step, and the water content of the resin particles obtained May be carried out by a conventionally known method so that the amount becomes 30% by weight or less.
本発明の分散体が乾燥工程を経て得られた（メタ）アクリル系樹脂粒子を用いる態様の場合、（メタ）アクリル系樹脂粒子と前記溶媒および前記ポリオキシエチレンソルビタン脂肪酸エステル類とを混合して分散体とする際の具体的な手法や条件等については、特に制限されないが、例えば、前記溶媒に前記ポリオキシエチレンソルビタン脂肪酸エステル類を溶解させた溶液中に乾燥工程を経て得られた（メタ）アクリル系樹脂粒子を添加して、ホモジナイザー等の公知の攪拌手段を用いて、例えば、１５００〜１２０００ｒｐｍで０．１〜２．０時間程度攪拌するようにすればよい。 In the case where the dispersion of the present invention uses the (meth) acrylic resin particles obtained through the drying step, the (meth) acrylic resin particles are mixed with the solvent and the polyoxyethylene sorbitan fatty acid esters. There are no particular restrictions on the specific method and conditions for making the dispersion, but for example, it was obtained through a drying step in a solution in which the polyoxyethylene sorbitan fatty acid esters were dissolved in the solvent (meta ) Acrylic resin particles may be added and stirred using a known stirring means such as a homogenizer at, for example, 1500 to 12000 rpm for about 0.1 to 2.0 hours.
本発明の分散体中の（メタ）アクリル系樹脂粒子の平均粒子径は０．５〜５００μｍであることが好ましい。（メタ）アクリル系樹脂粒子の平均粒子径がこの範囲にある分散体は、特に粒子の沈降が起こりやすい（例えば、室温で７２時間放置するとおのずと粒子の沈降が起こる）ので、再分散が必要になることが多く、本発明の技術を有効に活用しうるからである。（メタ）アクリル系樹脂粒子の平均粒子径が０．５μｍ未満であると、粒子の沈降が起こりにくくなり、再分散の必要がなく本発明の技術を適応する必然性が低くなるとともに、このように平均粒子径の小さい粒子は懸濁重合では製造しにくい。一方、５００μｍを超えると、分散体になりにくい傾向がある。また、平均粒子径が前記範囲である（メタ）アクリル系樹脂粒子の分散体は、耐ブロッキング性、光拡散性、易滑性などの性能を付与するのに好適であり、フィルムに対する添加剤やコーティング剤として用いた場合に、得られた表面がざらつくこともない。より好ましくは０．５〜３００μｍの範囲、さらに好ましくは０．５〜２００μｍの範囲、さらに好ましくは０．５〜１００μｍの範囲、最も好ましくは１．０〜１００μｍの範囲であるのがよい。また、特に、本発明の分散体が乾燥工程を経て得られた（メタ）アクリル系樹脂粒子を用いる態様の場合には、分散体中の（メタ）アクリル系樹脂粒子の平均粒子径は用いた（メタ）アクリル系樹脂粒子の平均粒子径±１．０μｍの範囲であるのが好ましい。なお、前記（メタ）アクリル系樹脂粒子の平均粒子径は、例えば、実施例で後述ように、所定のアパチャーを使用したコールターカウンターを用いて測定することができる。 The average particle diameter of the (meth) acrylic resin particles in the dispersion of the present invention is preferably 0.5 to 500 μm. Dispersions in which the average particle diameter of (meth) acrylic resin particles is in this range are particularly likely to cause sedimentation of the particles (for example, the sedimentation of the particles naturally occurs after standing for 72 hours at room temperature), so redispersion is necessary. This is because the technique of the present invention can be effectively utilized. When the average particle diameter of the (meth) acrylic resin particles is less than 0.5 μm, it is difficult for the particles to settle, and there is no need for redispersion. Particles having a small average particle size are difficult to produce by suspension polymerization. On the other hand, when it exceeds 500 μm, it tends to be difficult to form a dispersion. Further, a dispersion of (meth) acrylic resin particles having an average particle diameter in the above range is suitable for imparting performance such as blocking resistance, light diffusibility, and slipperiness, When used as a coating agent, the obtained surface does not become rough. More preferably, it is in the range of 0.5 to 300 μm, more preferably in the range of 0.5 to 200 μm, still more preferably in the range of 0.5 to 100 μm, and most preferably in the range of 1.0 to 100 μm. In particular, in the case where the dispersion of the present invention uses the (meth) acrylic resin particles obtained through the drying step, the average particle diameter of the (meth) acrylic resin particles in the dispersion was used. The average particle diameter of the (meth) acrylic resin particles is preferably in the range of ± 1.0 μm. In addition, the average particle diameter of the (meth) acrylic resin particles can be measured, for example, using a Coulter counter using a predetermined aperture as described later in Examples.
本発明の分散体中の（メタ）アクリル系樹脂粒子の標準偏差値は２．０μｍ以下であることが好ましい。特に、本発明の分散体が乾燥工程を経て得られた（メタ）アクリル系樹脂粒子を用いる態様の場合には、分散体中の（メタ）アクリル系樹脂粒子の標準偏差値は用いた（メタ）アクリル系樹脂粒子の標準偏差値±０．５μｍの範囲であるのが好ましい。 The standard deviation value of the (meth) acrylic resin particles in the dispersion of the present invention is preferably 2.0 μm or less. In particular, in the case where the dispersion of the present invention uses (meth) acrylic resin particles obtained through a drying step, the standard deviation value of (meth) acrylic resin particles in the dispersion was used (meta ) The standard deviation value of acrylic resin particles is preferably in the range of ± 0.5 μm.
本発明の分散体は、例えば、樹脂フィルム用の添加剤（例えば、耐ブロッキング剤、易滑剤、つや消し剤、光拡散剤など）、水分散型塗料、研磨剤、潤滑液用添加剤等の用途において好適に用いることができる。 The dispersion of the present invention is used for, for example, additives for resin films (for example, anti-blocking agents, easy-to-lubricants, matting agents, light diffusing agents, etc.), water-dispersed paints, abrasives, additives for lubricating liquids, etc. Can be suitably used.
なお、本発明の分散体は（メタ）アクリル系樹脂粒子を分散させたものであるが、本発明において再分散性能を得るための前述した各態様は、例えば、スチレン系樹脂粒子やベンゾグアナミン系樹脂粒子等のような他の有機樹脂粒子にも適用できるものであり、特に乾燥工程を経て得られた有機樹脂粒子には好ましく適用することできる。したがって、用途に応じて最適な特性を有する有機樹脂粒子を選択し、本発明の分散体における各態様とすることにより、幅広い用途に好適な再分散性能に優れた分散体を得ることができる。 The dispersion of the present invention is obtained by dispersing (meth) acrylic resin particles. In the present invention, the above-described embodiments for obtaining redispersion performance include, for example, styrene resin particles and benzoguanamine resins. The present invention can also be applied to other organic resin particles such as particles, and can be preferably applied to organic resin particles obtained through a drying process. Therefore, a dispersion excellent in redispersion performance suitable for a wide range of uses can be obtained by selecting organic resin particles having optimum characteristics according to the use and making each aspect of the dispersion of the present invention.
以下に、実施例および比較例によって本発明をより具体的に説明するが、本発明は実施例に限定されるものではない。なお、特に断りのない限り、実施例および比較例に記載の「部」および「％」はそれぞれ「重量部」および「重量％」を示している。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples. Unless otherwise specified, “parts” and “%” described in Examples and Comparative Examples represent “parts by weight” and “% by weight”, respectively.
〔実施例１〕
攪拌機、不活性ガス導入管、還流冷却器および温度計を備えたフラスコに、ポリオキシエチレンアルキルスルフォアンモニウム（「ハイテノールＮ−０８」第一工業製薬（株）製）０．５部を溶解した脱イオン水９００部を仕込んだ。そこへ予め調製しておいたメタクリル酸メチル９０部、トリメタクリル酸トリメチロールプロパン１０部、アゾイソブチロニトリル１部および３，４−ジニトロ安息香酸１部を配合した混合物を仕込み、Ｔ．Ｋ．ホモジナイザー（特殊機化工業（株）製）により８０００ｒｐｍで５分間攪拌して均一な懸濁液とした。次いで、窒素ガスを吹き込みながら７５℃に加熱し、この温度で５時間攪拌を続けて懸濁重合反応を行なった後冷却した。この懸濁液を瀘過した後乾燥して、乾燥状態のメタクリル系樹脂粒子（１）を得た。得られた粒子（１）についてコールターカウンター（アパーチャ１００μｍ）で測定した結果、平均粒子径は３．４７μｍ、標準偏差値は１．４０μｍであった。
[Example 1]
In a flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser, and a thermometer, 0.5 part of polyoxyethylene alkyl sulfoammonium (“Hitenol N-08”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved. 900 parts of deionized water was charged. A mixture containing 90 parts of methyl methacrylate, 10 parts of trimethylolpropane trimethacrylate, 1 part of azoisobutyronitrile and 1 part of 3,4-dinitrobenzoic acid prepared in advance was charged. K. The mixture was stirred for 5 minutes at 8000 rpm with a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a uniform suspension. Next, the mixture was heated to 75 ° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to conduct a suspension polymerization reaction, followed by cooling. This suspension was filtered and then dried to obtain dried methacrylic resin particles (1). The obtained particles (1) were measured with a Coulter counter (aperture 100 μm). As a result, the average particle size was 3.47 μm, and the standard deviation value was 1.40 μm.
次に、ポリオキシエチレンソルビタンモノラウレート（「ソルゲンＴＷ２０」第一工業製薬製：ＨＬＢ１６．７）２．１部を水１４４．９部に溶解させた溶液の中に、前記樹脂粒子（１）６３部を加え（樹脂粒子固形分に対するポリオキシエチレンソルビタンモノラウレート量は３．３重量％）、Ｔ．Ｋ．ホモジナイザー（特殊機化工業（株）製）により７０００ｒｐｍで４０分間攪拌した。その後、回転数を５００ｒｐｍにし、ｐＨメーターで確認しながら０．１Ｎ水酸化ナトリウム水溶液１１．４部を添加してｐＨを９に調整して、固形分濃度３０％の分散体（１）を得た。 Next, in the solution in which 2.1 parts of polyoxyethylene sorbitan monolaurate (“Sorgen TW20”, manufactured by Daiichi Kogyo Seiyaku: HLB16.7) is dissolved in 144.9 parts of water, the resin particles (1) 63 parts are added (the amount of polyoxyethylene sorbitan monolaurate based on the solid content of the resin particles is 3.3% by weight). K. The mixture was stirred at 7000 rpm for 40 minutes with a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Thereafter, the rotational speed was set to 500 rpm, and 11.4 parts of a 0.1N sodium hydroxide aqueous solution was added while checking with a pH meter to adjust the pH to 9, whereby a dispersion (1) having a solid content concentration of 30% was obtained. It was.
得られた分散体（１）中の粒子の平均粒子径は３．６３μｍ、標準偏差値は１．５０μｍ、分散体（１）の再分散指数は９５％であった。なお、分散体中の粒子の平均粒子径は、粒子径測定装置（ベックマンコールター社製「マルチサイザーＩＩ」）により所定のアパーチャーを用いて測定した（以下の実施例・比較例も同様）。 The average particle size of the particles in the obtained dispersion (1) was 3.63 μm, the standard deviation value was 1.50 μm, and the redispersion index of the dispersion (1) was 95%. The average particle size of the particles in the dispersion was measured using a predetermined aperture with a particle size measuring device (“Multisizer II” manufactured by Beckman Coulter, Inc.) (the same applies to the following examples and comparative examples).
〔実施例２〕
実施例１で用いたポリオキシエチレンソルビタンモノラウレートの代わりに、ポリオキシエチレンソルビタンモノステアレート（「レオドールＰＷ−Ｓ１０６」花王製：ＨＬＢ９．６）を用いたこと以外は、実施例１と同様にして、固形分濃度３０％の分散体（２）を得た。
[Example 2]
The same as Example 1 except that polyoxyethylene sorbitan monostearate (“Rheodor PW-S106” manufactured by Kao: HLB9.6) was used instead of the polyoxyethylene sorbitan monolaurate used in Example 1. Thus, a dispersion (2) having a solid content concentration of 30% was obtained.
得られた分散体（２）中の粒子の平均粒子径は３．５８μｍ、標準偏差値は１．５２μｍ、分散体（２）の再分散指数は７５％であった。 The average particle diameter of the particles in the obtained dispersion (2) was 3.58 μm, the standard deviation value was 1.52 μm, and the redispersion index of the dispersion (2) was 75%.
〔実施例３〕
実施例１で用いたポリオキシエチレンソルビタンモノラウレートの代わりに、ポリオキシエチレンソルビタンモノラウレート（「レオドールＴＷ−Ｌ１０６」花王製：ＨＬＢ１３．３）を用いたこと以外は、実施例１と同様にして、固形分濃度３０％の分散体（３）を得た。
Example 3
The same as Example 1 except that polyoxyethylene sorbitan monolaurate (“Leodol TW-L106” manufactured by Kao: HLB13.3) was used instead of the polyoxyethylene sorbitan monolaurate used in Example 1. Thus, a dispersion (3) having a solid content concentration of 30% was obtained.
得られた分散体（３）中の粒子の平均粒子径は３．６２μｍ、標準偏差値は１．４９μｍ、分散体（３）の再分散指数は８１％であった。 The average particle diameter of the particles in the obtained dispersion (3) was 3.62 μm, the standard deviation value was 1.49 μm, and the redispersion index of the dispersion (3) was 81%.
〔実施例４〕
実施例１と同様にして、乾燥状態のメタクリル系樹脂粒子（１）を得た。得られた粒子（１）についてコールターカウンター（アパーチャ１００μｍ）で測定した結果、平均粒子径は３．４７μｍ、標準偏差値は１．４０μｍであった。
Example 4
In the same manner as in Example 1, dry methacrylic resin particles (1) were obtained. The obtained particles (1) were measured with a Coulter counter (aperture 100 μm). As a result, the average particle size was 3.47 μm, and the standard deviation value was 1.40 μm.
次に、樹脂粒子（１）の量を９８部に変更した（樹脂粒子固形分に対するポリオキシエチレンソルビタンモノラウレート量は２．１重量％）こと以外は、実施例１と同様にして、固形分濃度４０％の分散体（４）を得た。 Next, in the same manner as in Example 1, except that the amount of the resin particles (1) was changed to 98 parts (the amount of polyoxyethylene sorbitan monolaurate based on the solid content of the resin particles was 2.1% by weight). A dispersion (4) having a partial concentration of 40% was obtained.
得られた分散体（４）中の粒子の平均粒子径は３．６８μｍ、標準偏差値は１．５２μｍ、分散体（４）の再分散指数は８９％であった。 The average particle diameter of the particles in the obtained dispersion (4) was 3.68 μm, the standard deviation value was 1.52 μm, and the redispersion index of the dispersion (4) was 89%.
〔実施例５〕
実施例１と同様にして、乾燥状態のメタクリル系樹脂粒子（１）を得た。得られた粒子（１）についてコールターカウンター（アパーチャ１００μｍ）で測定した結果、平均粒子径は３．４７μｍ、標準偏差値は１．４０μｍであった。
Example 5
In the same manner as in Example 1, dry methacrylic resin particles (1) were obtained. The obtained particles (1) were measured with a Coulter counter (aperture 100 μm). As a result, the average particle size was 3.47 μm, and the standard deviation value was 1.40 μm.
次に、樹脂粒子（１）の量を１．５部に、ポリオキシエチレンソルビタンモノラウレートの量を０．０７５部にそれぞれ変更した（樹脂粒子固形分に対するポリオキシエチレンソルビタンモノラウレート量は５．０重量％）こと以外は、実施例１と同様にして、固形分濃度１％の分散体（５）を得た。 Next, the amount of resin particles (1) was changed to 1.5 parts and the amount of polyoxyethylene sorbitan monolaurate was changed to 0.075 parts (the amount of polyoxyethylene sorbitan monolaurate relative to the solid content of the resin particles is A dispersion (5) having a solid content concentration of 1% was obtained in the same manner as in Example 1, except that 5.0 wt%).
得られた分散体（５）中の粒子の平均粒子径は３．６０μｍ、標準偏差値は１．４５μｍ、分散体（５）の再分散指数は９２％であった。 The average particle diameter of the particles in the obtained dispersion (5) was 3.60 μm, the standard deviation value was 1.45 μm, and the redispersion index of the dispersion (5) was 92%.
〔実施例６〕
実施例１と同様にして、乾燥状態のメタクリル系樹脂粒子（１）を得た。得られた粒子（１）についてコールターカウンター（アパーチャ１００μｍ）で測定した結果、平均粒子径は３．４７μｍ、標準偏差値は１．４０μｍであった。
Example 6
In the same manner as in Example 1, dry methacrylic resin particles (1) were obtained. The obtained particles (1) were measured with a Coulter counter (aperture 100 μm). As a result, the average particle size was 3.47 μm, and the standard deviation value was 1.40 μm.
次に、ポリオキシエチレンソルビタンモノラウレートの量を５部に変更した（樹脂粒子固形分に対するポリオキシエチレンソルビタンモノラウレート量は７．９重量％）こと以外は、実施例１と同様にして、固形分濃度３０％の分散体（６）を得た。 Next, the amount of polyoxyethylene sorbitan monolaurate was changed to 5 parts (the amount of polyoxyethylene sorbitan monolaurate with respect to the solid content of the resin particles was 7.9% by weight). A dispersion (6) having a solid content concentration of 30% was obtained.
得られた分散体（６）中の粒子の平均粒子径は３．２３μｍ、標準偏差値は１．３０μｍ、分散体（６）の再分散指数は９０％であった。 The average particle diameter of the particles in the obtained dispersion (6) was 3.23 μm, the standard deviation value was 1.30 μm, and the redispersion index of the dispersion (6) was 90%.
〔実施例７〕
実施例１において、懸濁重合時に用いたポリオキシエチレンアルキルスルフォアンモニウム（「ハイテノールＮ−０８」第一工業製薬（株）製）０．５部をポリオキシエチレンソルビタンモノラウレート（「ソルゲンＴＷ２０」第一工業製薬製：ＨＬＢ１６．７）３部に変更したこと以外は、実施例１と同様にして、懸濁重合反応を行なった後冷却した。この懸濁液を瀘過した後、乾燥させることなく、Ｔ．Ｋ．ホモジナイザー（特殊機化工業（株）製）により５００ｒｐｍで攪拌し、ｐＨメーターで確認しながら０．１Ｎ水酸化ナトリウム水溶液１１．４部を添加してｐＨを９に調整して、固形分濃度９．８％の分散体（７）を得た。該分散体（７）は、樹脂粒子固形分に対して３重量％のポリオキシエチレンソルビタンモノラウレートを含有するものであった。
Example 7
In Example 1, 0.5 part of polyoxyethylene alkyl sulfoammonium (“Hitenol N-08”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) used during suspension polymerization was added to polyoxyethylene sorbitan monolaurate (“Sorgen”). TW20 ”(Daiichi Kogyo Seiyaku Co., Ltd .: HLB 16.7) Except for changing to 3 parts, the suspension polymerization reaction was carried out in the same manner as in Example 1 and then cooled. This suspension was filtered and then dried without drying. K. The mixture was stirred at 500 rpm with a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and adjusted to pH 9 by adding 11.4 parts of 0.1N aqueous sodium hydroxide while confirming with a pH meter. 8% of dispersion (7) was obtained. The dispersion (7) contained 3% by weight of polyoxyethylene sorbitan monolaurate with respect to the solid content of the resin particles.
得られた分散体（７）中の粒子の平均粒子径は４．６２μｍ、標準偏差値は１．５８μｍ、分散体（７）の再分散指数は８５％であった。 The average particle diameter of the particles in the obtained dispersion (7) was 4.62 μm, the standard deviation value was 1.58 μm, and the redispersion index of the dispersion (7) was 85%.
〔実施例８〕
実施例１において、懸濁重合時に用いたポリオキシエチレンアルキルスルフォアンモニウム（「ハイテノールＮ−０８」第一工業製薬（株）製）の量を０．３部に変更し、均一な懸濁液とする際の攪拌条件を８０００ｒｐｍ５分間から４０００ｒｐｍ３分間としたこと以外は、実施例１と同様にして、乾燥状態のメタクリル系樹脂粒子（８）を得た。得られた粒子（８）についてコールターカウンター（アパーチャ１００μｍ）で測定した結果、平均粒子径は２８．５μｍ、標準偏差値は１．７５μｍであった。
Example 8
In Example 1, the amount of polyoxyethylene alkyl sulfoammonium ("Haitenol N-08", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) used during suspension polymerization was changed to 0.3 part to obtain a uniform suspension Dry methacrylic resin particles (8) were obtained in the same manner as in Example 1 except that the stirring condition for preparing the liquid was 8000 rpm for 5 minutes to 4000 rpm for 3 minutes. The obtained particles (8) were measured with a Coulter counter (aperture 100 μm). As a result, the average particle diameter was 28.5 μm and the standard deviation value was 1.75 μm.
次に、樹脂粒子（１）の代わりに樹脂粒子（８）を用いたこと以外は、実施例１と同様にして、固形分濃度３０％の分散体（８）を得た。 Next, a dispersion (8) having a solid content concentration of 30% was obtained in the same manner as in Example 1 except that the resin particles (8) were used instead of the resin particles (1).
得られた分散体（８）中の粒子の平均粒子径は２９．８μｍ、標準偏差値は１．７０μｍ、分散体（８）の再分散指数は９８％であった。 The average particle diameter of the particles in the dispersion (8) obtained was 29.8 μm, the standard deviation value was 1.70 μm, and the redispersion index of the dispersion (8) was 98%.
〔比較例１〕
実施例１で用いたポリオキシエチレンソルビタンモノラウレートの代わりに、ポリオキシエチレンノニルフェニルエーテル（「ノイゲンＥＡ１５０」第一工業製薬製：ＨＬＢ１５．０）を用いたこと以外は、実施例１と同様にして、固形分濃度３０％の比較用の分散体（Ｃ１）を得た。
[Comparative Example 1]
The same as Example 1 except that polyoxyethylene nonylphenyl ether ("Neugen EA150" manufactured by Daiichi Kogyo Seiyaku: HLB 15.0) was used instead of the polyoxyethylene sorbitan monolaurate used in Example 1. Thus, a comparative dispersion (C1) having a solid content concentration of 30% was obtained.
得られた分散体（Ｃ１）中の粒子の平均粒子径は３．６０μｍ、標準偏差値は１．４８μｍ、分散体（Ｃ１）の再分散指数は１０％であった。 The average particle diameter of the particles in the obtained dispersion (C1) was 3.60 μm, the standard deviation value was 1.48 μm, and the redispersion index of the dispersion (C1) was 10%.
〔比較例２〕
実施例１において、ｐＨ調整（回転数を５００ｒｐｍにし、ｐＨメーターで確認しながら０．１Ｎ水酸化ナトリウム水溶液１１．４部を添加してｐＨを９に調整すること）を行なわないこと以外は、実施例１と同様にして、固形分濃度３０％の比較用の分散体（Ｃ２）を得た。
[Comparative Example 2]
In Example 1, except that pH adjustment (rotation speed is 500 rpm, pH is adjusted to 9 by adding 11.4 parts of 0.1N aqueous sodium hydroxide while checking with a pH meter), In the same manner as in Example 1, a comparative dispersion (C2) having a solid content concentration of 30% was obtained.
得られた分散体（Ｃ２）中の粒子の平均粒子径は３．５９μｍ、標準偏差値は１．４７μｍ、分散体（Ｃ２）の再分散指数は７％であった。 The average particle diameter of the particles in the obtained dispersion (C2) was 3.59 μm, the standard deviation value was 1.47 μm, and the redispersion index of the dispersion (C2) was 7%.
上記実施例１〜８の分散体（１）〜（８）および比較例（１）〜（２）の分散体（Ｃ１）〜（Ｃ２）は、いずれも製造直後に再分散指数の測定を行なったものであった。
つぎに、これらの分散体を１ヶ月貯蔵しておいて、実用レベルでの再分散性を以下のようにして評価してみた。
The dispersions (1) to (8) of Examples 1 to 8 and the dispersions (C1) to (C2) of Comparative Examples (1) to (2) all measured the redispersion index immediately after production. It was.
Next, these dispersions were stored for one month, and the redispersibility at a practical level was evaluated as follows.
１ヶ月経過後の分散体は、いずれも粒子の沈降が認められたので、いずれもに対して、工場レベルの実機（攪拌機）も用いて同じ攪拌条件で強力に攪拌した。その結果、分散体（１）〜（８）については、沈降した粒子を短時間で再分散させることができ、再分散させた後の分散体の固形分濃度は製造直後の固形分濃度に比べて殆ど変化することがないことから、実用上問題のないことを確認した。すなわち、分散体（１）〜（８）は定量性に優れた分散体であると言える。一方、分散体（Ｃ１）〜（Ｃ２）については、分散体（１）〜（８）と同じ攪拌条件、すなわち、実用レベルでの強い攪拌条件で攪拌しているにもかかわらず、沈降した粒子を再分散させることができず、さらに、実用レベルよりも強い攪拌力で長時間攪拌しても沈降した粒子の一部が再分散しただけで、製造直後の状態に戻すことはできなかった。このことから、分散体（Ｃ１）〜（Ｃ２）は、定量性に欠ける分散体であると言える。 Since all of the dispersions after one month had particles settled, they were vigorously stirred under the same stirring conditions using a factory-level actual machine (stirrer). As a result, for dispersions (1) to (8), the settled particles can be redispersed in a short time, and the solid content concentration of the dispersion after redispersion is compared with the solid content concentration immediately after production. Therefore, it was confirmed that there was no problem in practical use. That is, it can be said that the dispersions (1) to (8) are dispersions excellent in quantitative properties. On the other hand, for dispersions (C1) to (C2), particles that settled despite stirring under the same stirring conditions as dispersions (1) to (8), that is, strong stirring conditions at a practical level. Furthermore, even when stirred for a long time with a stirring force stronger than the practical level, only a part of the settled particles were redispersed, and it was not possible to return to the state immediately after production. From this, it can be said that the dispersions (C1) to (C2) are dispersions lacking in quantitativeness.
１ ビーカー平板
２ 攪拌羽根
２１ 平板
２２ 攪拌軸
1 beaker
Claims (7)
該（メタ）アクリル系樹脂粒子が水系懸濁重合により得られた粒子であり、
ＨＬＢが８以上であるポリオキシエチレンソルビタン脂肪酸エステル類を含み、かつ、
ｐＨが５〜１０である、樹脂フィルム用の添加剤用分散体。 A dispersion formed by dispersing (meth) acrylic resin particles having an average particle diameter of 1.0 to 100 μm obtained through a drying step in a solvent,
The (meth) acrylic resin particles are particles obtained by aqueous suspension polymerization,
Polyoxyethylene sorbitan fatty acid esters having an HLB of 8 or more, and
Dispersion for additive for resin film having a pH of 5 to 10.
ｐＨを５〜１０に調整する工程を含む、樹脂フィルム用の添加剤に用いられる分散体の調製方法。
(Meth) acrylic resin particles obtained through a drying step having an average particle diameter of 1.0 to 100 μm obtained by aqueous suspension polymerization , a solvent, and a polyoxyethylene sorbitan fatty acid ester having an HLB of 8 or more Mixing steps, and
The preparation method of the dispersion used for the additive for resin films including the process of adjusting pH to 5-10.
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| JPH02158605A (en) * | 1988-12-12 | 1990-06-19 | Kyoritsu Yuki Co Ltd | Preservation of fluidity of acrylic polymer dispersion |
| JPH02245062A (en) * | 1989-03-17 | 1990-09-28 | Arakawa Chem Ind Co Ltd | Homogeneous dispersion of water-absorbing resin |
| JPH0453834A (en) * | 1990-06-21 | 1992-02-21 | Dainippon Ink & Chem Inc | Aqueous resin dispersion and production thereof |
| JPH11181300A (en) * | 1997-12-22 | 1999-07-06 | Konica Corp | Production of dispersion of finely divided polymer particles and image recording material using finely divided polymer particles |
| JP2000159969A (en) * | 1998-11-25 | 2000-06-13 | Hymo Corp | Emulsion and its use |
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