JP6053109B2 - Water-insoluble polymer builder - Google Patents
Water-insoluble polymer builder Download PDFInfo
- Publication number
- JP6053109B2 JP6053109B2 JP2012151420A JP2012151420A JP6053109B2 JP 6053109 B2 JP6053109 B2 JP 6053109B2 JP 2012151420 A JP2012151420 A JP 2012151420A JP 2012151420 A JP2012151420 A JP 2012151420A JP 6053109 B2 JP6053109 B2 JP 6053109B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- insoluble polymer
- monomer
- polymer builder
- producing
- 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.)
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- 229920003176 water-insoluble polymer Polymers 0.000 title claims description 65
- 239000000178 monomer Substances 0.000 claims description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 239000002904 solvent Substances 0.000 claims description 60
- 230000002209 hydrophobic effect Effects 0.000 claims description 51
- 239000006185 dispersion Substances 0.000 claims description 41
- -1 sucrose ester Chemical class 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 230000008961 swelling Effects 0.000 claims description 13
- 125000002091 cationic group Chemical group 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 31
- 230000008569 process Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 230000002265 prevention Effects 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000003445 sucroses Chemical class 0.000 description 7
- 239000012085 test solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ONAIRGOTKJCYEY-XXDXYRHBSA-N CCCCCCCCCCCCCCCCCC(O)=O.O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 ONAIRGOTKJCYEY-XXDXYRHBSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 229960003237 betaine Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000003405 preventing effect Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BUFQZEHPOKLSTP-UHFFFAOYSA-M sodium;oxido hydrogen sulfate Chemical compound [Na+].OS(=O)(=O)O[O-] BUFQZEHPOKLSTP-UHFFFAOYSA-M 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 2
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 108010082455 Sebelipase alfa Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- FNYLWPVRPXGIIP-UHFFFAOYSA-N Triamterene Chemical compound NC1=NC2=NC(N)=NC(N)=C2N=C1C1=CC=CC=C1 FNYLWPVRPXGIIP-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229940041615 kanuma Drugs 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Description
本発明は、水不溶性高分子ビルダー及びその製造方法に関する。 The present invention relates to a water-insoluble polymer builder and a method for producing the same.
近年、環境意識の高まりにより節水タイプの洗濯機が普及しており、また、１回あたりの洗濯物量の増加に伴って洗濯機の浴比が低下していることから、洗濯物から分離した汚れが洗濯液中に十分に分散せずに洗濯物に再び付着する、いわゆる再汚染の問題が顕著となりつつある。
この問題に対して、水難溶性無機物と、水溶性ポリマー及び水溶性塩類から選ばれる一種以上の水溶性成分とを含有してなるベース顆粒群に、界面活性剤が担持されてなる洗剤粒子群を含有する粉粒状洗剤が提案されている（特許文献１参照）。
一方、水難溶性物質と膨潤性高分子化合物とを含有する組成物により被処理水中の泥を凝集させ、被処理水から泥を除去する方法が提案されている（特許文献２参照）。
また、膨潤性高分子化合物の製造方法としては、逆送懸濁重合法が知られている（特許文献３）。
In recent years, water-saving washing machines have become widespread due to increased environmental awareness, and since the bath ratio of the washing machine has decreased with an increase in the amount of laundry per wash, dirt separated from the laundry The problem of so-called recontamination is becoming more prominent in that the powder does not sufficiently disperse in the washing liquid and adheres again to the laundry.
In order to solve this problem, a detergent particle group in which a surfactant is supported on a base granule group containing a poorly water-soluble inorganic substance and one or more water-soluble components selected from water-soluble polymers and water-soluble salts. A granular detergent to be contained has been proposed (see Patent Document 1).
On the other hand, a method for aggregating mud in water to be treated with a composition containing a poorly water-soluble substance and a swellable polymer compound and removing the mud from the water to be treated has been proposed (see Patent Document 2).
As a method for producing a swellable polymer compound, a reverse suspension polymerization method is known (Patent Document 3).
特許文献１に記載される粉状洗浄剤は、洗浄力と再汚染防止性能とを両立することができるが、その性能は十分とは言えず、更なる改善が望まれている。
特許文献２には、効率的な泥の除去方法が記載されているが、再汚染防止性能に関する具体的な記載はない。
特許文献３には、膨潤性高分子化合物の調製方法が記載されているが、再汚染防止性能に関する具体的な記載はない。
本発明は、優れた洗浄力と再汚染防止性能とを兼ね備える水不溶性高分子ビルダー、及び水不溶性高分子ビルダーの製造方法を提供する。
Although the powdery cleaning agent described in Patent Document 1 can achieve both cleaning power and recontamination prevention performance, the performance is not sufficient, and further improvement is desired.
Patent Document 2 describes an efficient method for removing mud, but there is no specific description regarding recontamination prevention performance.
Patent Document 3 describes a method for preparing a swellable polymer compound, but there is no specific description regarding re-contamination prevention performance.
The present invention provides a water-insoluble polymer builder having both excellent detergency and re-contamination prevention performance, and a method for producing a water-insoluble polymer builder.
本発明は、下記［１］，［２］を要旨とするものである。
［１］有機カルボン酸モノマーと架橋性モノマーとの共重合体で構成される水不溶性高分子ビルダーであって、乾燥時の体積平均粒子径（ｄ１）と水による膨潤時の体積平均粒子径（ｄ２）との比（ｄ２／ｄ１）が５〜１００である水不溶性高分子ビルダー。
［２］下記工程１〜３を含む水不溶性高分子ビルダーの製造方法。
工程１：有機カルボン酸モノマー、架橋性モノマー、及び重合開始剤を含む水性混合液を調製する工程
工程２：工程１で得られた水性混合液を疎水性溶媒（Ａ）に分散させて分散液（ａ）を調製する工程
工程３：温度が５０℃以上沸点以下である疎水性溶媒（Ｂ）に、前記工程２で得られた分散液（ａ）を滴下して重合を行う工程
The gist of the present invention is the following [1] and [2].
[1] A water-insoluble polymer builder composed of a copolymer of an organic carboxylic acid monomer and a crosslinkable monomer, wherein the volume average particle size (d1) when dried and the volume average particle size when swollen with water ( A water-insoluble polymer builder having a ratio (d2 / d1) to d2) of 5 to 100.
[2] A method for producing a water-insoluble polymer builder comprising the following steps 1 to 3.
Step 1: Preparing an aqueous mixed solution containing an organic carboxylic acid monomer, a crosslinkable monomer, and a polymerization initiator Step 2: Dispersing the aqueous mixed solution obtained in Step 1 in a hydrophobic solvent (A) Step (3) for preparing (a): a step of performing polymerization by dropping the dispersion (a) obtained in Step 2 above into a hydrophobic solvent (B) having a temperature of 50 ° C. or higher and a boiling point or lower.
本発明によれば、優れた洗浄力と再汚染防止性能とを兼ね備える水不溶性高分子ビルダー、及びその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the water-insoluble polymer builder which has the outstanding detergency and recontamination prevention performance, and its manufacturing method can be provided.
［水不溶性高分子ビルダー］
本発明の水不溶性高分子ビルダーは、有機カルボン酸モノマーと架橋性モノマーとの共重合体で構成される水不溶性高分子ビルダーであって、乾燥時の体積平均粒子径（ｄ１）と水による膨潤時の体積平均粒子径（ｄ２）との比（ｄ２／ｄ１）が５〜１００であるため、洗浄力と再汚染防止性能とを高い水準で兼ね備えるものである。なお、本明細書において比（ｄ２／ｄ１）を膨潤度という場合がある。
[Water-insoluble polymer builder]
The water-insoluble polymer builder of the present invention is a water-insoluble polymer builder composed of a copolymer of an organic carboxylic acid monomer and a crosslinkable monomer, and has a volume average particle diameter (d1) at the time of drying and swelling with water. Since the ratio (d2 / d1) to the volume average particle diameter (d2) at the time is 5 to 100, the cleaning power and the recontamination prevention performance are combined at a high level. In this specification, the ratio (d2 / d1) may be referred to as the degree of swelling.
＜膨潤度＞
本発明の水不溶性高分子ビルダーは、乾燥時の体積平均粒子径（ｄ１）と水による膨潤時の体積平均粒子径（ｄ２）との比（ｄ２／ｄ１）で表される膨潤度が５〜１００である。膨潤時に汚れを吸着し、洗浄力、及び再汚染防止性能を向上させる観点から、比（ｄ２／ｄ１）は５以上であり、汚れを吸着した高分子ビルダーを洗濯液中で効率的に分散させる観点から１００以下である。
前記比（ｄ２／ｄ１）は、洗浄力、及び再汚染防止性能を向上させる観点から、５以上であり、６以上が好ましく、７以上がより好ましく、１０以上が更に好ましい。そして、前記比（ｄ２／ｄ１）は、汚れを吸着した高分子ビルダーを洗濯液中で効率的に分散させる観点から、４０以下が好ましく、３０以下がより好ましく、２０以下が更に好ましい。
<Swelling degree>
The water-insoluble polymer builder of the present invention has a swelling degree represented by a ratio (d2 / d1) of a volume average particle diameter (d1) at the time of drying and a volume average particle diameter (d2) at the time of swelling by water of 5 to 5. 100. The ratio (d2 / d1) is 5 or more from the viewpoint of adsorbing dirt at the time of swelling and improving detergency and performance of preventing recontamination, and the polymer builder adsorbing dirt is efficiently dispersed in the washing liquid. 100 or less from the viewpoint.
The ratio (d2 / d1) is 5 or more, preferably 6 or more, more preferably 7 or more, and still more preferably 10 or more, from the viewpoint of improving detergency and recontamination prevention performance. The ratio (d2 / d1) is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less, from the viewpoint of efficiently dispersing the polymer builder having adsorbed dirt in the washing liquid.
乾燥時の体積平均粒子径（ｄ１）は、洗浄力を向上させる観点から、１μｍ以上が好ましく、２μｍ以上がより好ましく、３μｍ以上が更に好ましく、そして、洗浄剤組成物に配合する観点から、５０μｍ以下が好ましく、２０μｍ以下がより好ましく、１０μｍ以下が更に好ましい。
なお、本発明における乾燥時の体積平均粒子径は、８０℃、２５ｋＰａ（絶対圧力）で１２時間乾燥を行った後に測定した体積平均粒子径を指し、具体的には後述の乾燥工程を行った後に測定することができる。乾燥時の体積平均粒子径については、実施例に記載の方法により測定することができる。
The volume average particle diameter (d1) at the time of drying is preferably 1 μm or more, more preferably 2 μm or more, further preferably 3 μm or more from the viewpoint of improving the cleaning power, and 50 μm from the viewpoint of blending into the cleaning composition. Or less, more preferably 20 μm or less, and even more preferably 10 μm or less.
In addition, the volume average particle diameter at the time of drying in the present invention refers to the volume average particle diameter measured after drying for 12 hours at 80 ° C. and 25 kPa (absolute pressure). Specifically, the drying step described below was performed. It can be measured later. About the volume average particle diameter at the time of drying, it can measure by the method as described in an Example.
水による膨潤時の体積平均粒子径（ｄ２）は、再汚染防止性能を向上させる観点から、２０μｍ以上が好ましく、３０μｍ以上がより好ましく、３５μｍ以上が更に好ましく、４０μｍ以上がより更に好ましく、５０μｍ以上がより更に好ましく、そして、洗浄力の観点から、１００μｍ以下が好ましく、８０μｍ以下がより好ましく、７０μｍ以下が更に好ましく、６０μｍ以下がより更に好ましい。
なお、本発明における水による膨潤時の体積平均粒子径とは、水不溶性高分子ビルダーを２５℃の水に３０分以上浸漬させた後に測定した体積平均粒子径を指す。水による膨潤時の体積平均粒子径については、実施例に記載の方法により測定することができる。
The volume average particle diameter (d2) during swelling with water is preferably 20 μm or more, more preferably 30 μm or more, still more preferably 35 μm or more, still more preferably 40 μm or more, and even more preferably 50 μm or more, from the viewpoint of improving the recontamination prevention performance. Further, from the viewpoint of detergency, it is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 70 μm or less, and even more preferably 60 μm or less.
In addition, the volume average particle diameter at the time of swelling with water in the present invention refers to the volume average particle diameter measured after immersing the water-insoluble polymer builder in water at 25 ° C. for 30 minutes or more. The volume average particle diameter when swollen with water can be measured by the method described in Examples.
＜水不溶性高分子ビルダーを構成するモノマー＞
前記水不溶性高分子ビルダーは、洗剤に配合したときの汚れ分散性の観点から、前記有機カルボン酸モノマー及び架橋性モノマーを必須とし、必要に応じて共重合可能な他のモノマーとの共重合体としてもよい。
（必須モノマー）
（ａ）：有機カルボン酸モノマー
有機カルボン酸モノマーは、重合性の不飽和基を有するカルボン酸やその酸無水物を挙げることができる。具体的には、（メタ）アクリル酸、マレイン酸、イタコン酸及び／又はその無水物から選ばれる１種又は２種以上が好ましい。ここで、（メタ）アクリル酸とは、アクリル酸、メタクリル酸又はそれらの混合物を意味する。
<Monomer constituting water-insoluble polymer builder>
From the viewpoint of soil dispersibility when blended in a detergent, the water-insoluble polymer builder essentially comprises the organic carboxylic acid monomer and the crosslinkable monomer, and a copolymer with other monomers that can be copolymerized as necessary. It is good.
(Essential monomer)
(A): Organic carboxylic acid monomer Examples of the organic carboxylic acid monomer include carboxylic acids having a polymerizable unsaturated group and acid anhydrides thereof. Specifically, one or more selected from (meth) acrylic acid, maleic acid, itaconic acid and / or anhydrides thereof are preferable. Here, (meth) acrylic acid means acrylic acid, methacrylic acid or a mixture thereof.
（ｂ）：架橋性モノマー
架橋性モノマーとしては、１分子中に２個以上の二重結合を持った多官能性モノマーが挙げられ、多価アルコールの（メタ）アクリル酸エステル、アクリルアミド、ジビニル化合物、ポリアリル化合物、不飽和アルコールの（メタ）アクリル酸エステルから選ばれる１種又は２種以上が好ましい。具体的には、メチレンビスアクリルアミドが好ましい。
(B): Crosslinkable monomer Examples of the crosslinkable monomer include polyfunctional monomers having two or more double bonds in one molecule, (meth) acrylic acid ester of polyhydric alcohol, acrylamide, divinyl compound 1 type or 2 types or more chosen from the (meth) acrylic acid ester of a polyallyl compound and unsaturated alcohol are preferable. Specifically, methylene bisacrylamide is preferable.
（その他のモノマー）
本発明においては、前記必須モノマーの他に、本発明の効果を阻害しない範囲でその他のモノマーを用いてもよい。その他のモノマーとしては、モノマー（ａ）を除くアニオン性モノマー（ｃ）、カチオン性モノマー（ｄ）、両性モノマー（ｅ）、及びノニオン性モノマー（ｆ）から選ばれる１種又は２種以上が好ましい。
(Other monomers)
In the present invention, in addition to the essential monomers, other monomers may be used as long as the effects of the present invention are not impaired. The other monomer is preferably one or more selected from the anionic monomer (c) excluding the monomer (a), the cationic monomer (d), the amphoteric monomer (e), and the nonionic monomer (f). .
（ｃ）：（ａ）を除くアニオン性モノマー
アニオン性モノマーとしては、スルホン酸モノマー、及びリン酸モノマーが挙げられる。具体的には、スチレンスルホン酸、アルキル基の炭素数が１〜４の２−（メタ）アクリルアミド−２−アルキルプロパンスルホン酸、アルキル基の炭素数が１〜４の（メタ）アクリロイロキシアルキルリン酸から選ばれる１種又は２種以上が好ましい。
(C): Anionic monomer excluding (a) Examples of the anionic monomer include a sulfonic acid monomer and a phosphoric acid monomer. Specifically, styrenesulfonic acid, 2- (meth) acrylamide-2-alkylpropanesulfonic acid having 1 to 4 carbon atoms in the alkyl group, and (meth) acryloyloxyalkyl having 1 to 4 carbon atoms in the alkyl group One or more selected from phosphoric acid are preferred.
（ｄ）：カチオン性モノマー
カチオン性モノマーとしては、一般式（Ｉ）及び（II）で表されるカチオン性ビニルモノマーから選ばれる１種が好ましい。
（一般式（Ｉ）で表されるカチオン性モノマー）
(D): Cationic monomer The cationic monomer is preferably one selected from cationic vinyl monomers represented by the general formulas (I) and (II).
(Cationic monomer represented by formula (I))
（式中、Ｒ1は水素原子又はメチル基を示し、Ｒ2及びＲ3は同一又は異なっていてもよく、炭素数１〜４のアルキル基又はアルケニル基を示し、Ｒ4は水素原子又は炭素数１〜４のアルキル基を示し、Ｙは−Ｏ−、−ＮＨ−又は−Ｏ−ＣＨ2ＣＨ(ＯＨ)−基を示し、Ｚは炭素数１〜４の直鎖又は分岐鎖のアルキレン基を示し、Ｘは酸の共役塩基、ハロゲン原子又は炭素数１〜４の硫酸エステルを示す。） (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 may be the same or different, each represents an alkyl group or an alkenyl group having 1 to 4 carbon atoms, and R 4 represents a hydrogen atom or carbon. 1 represents an alkyl group having 1 to 4; Y represents an —O—, —NH— or —O—CH 2 CH (OH) — group, and Z represents a linear or branched alkylene group having 1 to 4 carbon atoms. X represents an acid conjugate base, a halogen atom or a C 1-4 sulfate ester.)
一般式（Ｉ）で表されるカチオン性ビニルモノマーの具体例としては、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリルアミド、ジエチルアミノプロピル（メタ）アクリルアミド等のアルキル基の総炭素数２〜８がジアルキルアミノ基を有する（メタ）アクリル酸エステル又は（メタ）アクリルアミドを酸で中和した酸中和物、あるいは４級化剤を反応させた４級アンモニウム塩が挙げられる。 Specific examples of the cationic vinyl monomer represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide. A quaternary ammonium salt obtained by reacting an acid neutralized product obtained by neutralizing a (meth) acrylic acid ester or (meth) acrylamide having an alkyl group with 2 to 8 carbon atoms having a dialkylamino group with an acid, or a quaternizing agent. Is mentioned.
（式中、Ｒ5及びＲ6は同一又は異なり、水素原子又はメチル基を示し、Ｒ7及びＲ8は同一又は異なり、水素原子又は炭素数１〜４のアルキル基を示し、Ｘは前記の意味を示す。）
一般式（II）で表されるカチオン性モノマーの具体例としては、ジアリルジメチルアンモニウムクロライド、ジアリルジエチルアンモニウムクロライド等のジアリル型４級アンモニウム塩が挙げられる。
(In the formula, R 5 and R 6 are the same or different and each represents a hydrogen atom or a methyl group; R 7 and R 8 are the same or different; each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Show meaning.)
Specific examples of the cationic monomer represented by the general formula (II) include diallyl quaternary ammonium salts such as diallyldimethylammonium chloride and diallyldiethylammonium chloride.
酸中和物を得るための好ましい酸としては、塩酸、硫酸、硝酸、リン酸等の無機酸；酢酸、ギ酸、マレイン酸、フマル酸、クエン酸、酒石酸、トルエンスルホン酸、乳酸、コハク酸等の有機酸から選ばれる１種又は２種以上が好ましい。
４級アンモニウム塩を得るための好ましい４級化剤としては、塩化メチル、塩化エチル、臭化メチル、ヨウ化メチル等の炭素数１〜４のハロゲン化アルキル、硫酸ジメチル、硫酸ジエチル、硫酸ジ−ｎ−プロピル等の一般的なアルキル化剤から選ばれる１種又は２種以上が好ましい。
Preferred acids for obtaining the acid neutralized product include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid; acetic acid, formic acid, maleic acid, fumaric acid, citric acid, tartaric acid, toluenesulfonic acid, lactic acid, succinic acid, etc. 1 type (s) or 2 or more types chosen from organic acids of these are preferable.
Preferred quaternizing agents for obtaining a quaternary ammonium salt include alkyl halides having 1 to 4 carbon atoms such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate, di-sulfate. One or more selected from general alkylating agents such as n-propyl are preferred.
上記一般式（Ｉ）又は（II）で表されるカチオン性モノマーの中で好ましいものとしては、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリルアミド、ジエチルアミノプロピル（メタ）アクリルアミドを前記の４級化剤で４級化した４級アンモニウム塩、あるいはジアリルジメチルアンモニウムクロライドが挙げられる。
酸中和物型のモノマーとしては、ポリマー構造の安定性を確保し、再汚染防止性能を確保する観点から、４級アンモニウム塩型モノマーがより好ましく、ジメチルアミノプロピル（メタ）アクリルアミド、ジエチルアミノプロピル（メタ）アクリルアミドの４級アンモニウム塩、あるいはジアリルジメチルアンモニウムクロライドが更に好ましい。
Among the cationic monomers represented by the general formula (I) or (II), dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl are preferable. A quaternary ammonium salt obtained by quaternizing (meth) acrylamide with the above quaternizing agent, or diallyldimethylammonium chloride can be used.
As the acid neutralized monomer, a quaternary ammonium salt monomer is more preferable from the viewpoint of ensuring the stability of the polymer structure and ensuring anti-recontamination performance, and dimethylaminopropyl (meth) acrylamide, diethylaminopropyl ( More preferred are quaternary ammonium salts of (meth) acrylamide or diallyldimethylammonium chloride.
（ｅ）：両性モノマー
両性モノマーとしては、Ｎ−（３−スルホプロピル）−Ｎ−（メタ）アクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウムベタイン、Ｎ−（３−スルホプロピル）−Ｎ−（メタ）アクリロイルアミドプロピル−Ｎ，Ｎ−ジメチルアンモニウムベタイン、Ｎ−（カルボキシメチル）−Ｎ−（メタ）アクリロイルアミドプロピル−Ｎ，Ｎ−ジメチルアンモニウムベタイン、Ｎ−カルボキシメチル−Ｎ−（メタ）アクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウムベタイン等のベタイン構造を有するビニルモノマーから選ばれる１種又は２種以上が好ましい。
(E): Amphoteric monomer Amphoteric monomers include N- (3-sulfopropyl) -N- (meth) acryloyloxyethyl-N, N-dimethylammonium betaine, N- (3-sulfopropyl) -N- (meta ) Acryloylamidopropyl-N, N-dimethylammonium betaine, N- (carboxymethyl) -N- (meth) acryloylamidopropyl-N, N-dimethylammonium betaine, N-carboxymethyl-N- (meth) acryloyloxyethyl One or more selected from vinyl monomers having a betaine structure such as -N, N-dimethylammonium betaine are preferred.
（ｆ）：ノニオン性モノマー
ノニオン性モノマーとしては、アルキル基の炭素数が１〜８のＮ−アルキル（メタ）アクリルアミド、アルキル基の総炭素数が２〜８のＮ，Ｎ−ジアルキル（メタ）アクリルアミド、アルキル基の炭素数が１〜８のＮ−ヒドロキシアルキル（メタ）アクリルアミド、Ｎ−（メタ）アクリロイルモルホリンから選ばれる１種又は２種以上が好ましい。
(F): Nonionic monomer As the nonionic monomer, N-alkyl (meth) acrylamide having 1 to 8 carbon atoms in the alkyl group, N, N-dialkyl (meth) having 2 to 8 total carbon atoms in the alkyl group. One or more selected from acrylamide, N-hydroxyalkyl (meth) acrylamide having 1 to 8 carbon atoms in the alkyl group, and N- (meth) acryloylmorpholine are preferable.
水不溶性高分子ビルダーを構成する全モノマー中の（ａ）〜（ｆ）の合計量は、７０質量％以上が好ましく、８５質量％以上がより好ましく、そして、１００質量％以下が好ましい。
水不溶性高分子ビルダーを構成する全モノマー中の有機カルボン酸モノマー（ａ）の量は、３０質量％以上が好ましく、３５質量％以上がより好ましく、４０質量％以上が更に好ましく、そして、９９質量％以下が好ましく、８０質量％以下がより好ましく、６０質量％以下が更に好ましい。
The total amount of (a) to (f) in all monomers constituting the water-insoluble polymer builder is preferably 70% by mass or more, more preferably 85% by mass or more, and preferably 100% by mass or less.
The amount of the organic carboxylic acid monomer (a) in the total monomer constituting the water-insoluble polymer builder is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and 99% by mass. % Or less is preferable, 80 mass% or less is more preferable, and 60 mass% or less is still more preferable.
水不溶性高分子ビルダーを構成する全モノマー中の架橋性モノマー（ｂ）のモノマー量は、０．００５質量％以上が好ましく、０．０１質量％以上がより好ましく、そして、５質量％以下が好ましく、１質量％以下がより好ましい。 The monomer amount of the crosslinkable monomer (b) in all monomers constituting the water-insoluble polymer builder is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 5% by mass or less. 1 mass% or less is more preferable.
水不溶性高分子ビルダーを構成する全モノマー中の（ａ）を除くアニオン性モノマー（ｃ）の量は、１〜６９質量％が好ましく、４０〜６０質量％がより好ましい。
水不溶性高分子ビルダーを構成する全モノマー中のカチオン性モノマー（ｄ）の量は、１〜６９質量％が好ましく、４０〜６０質量％がより好ましい。
水不溶性高分子ビルダーを構成する全モノマー中の両性モノマー（ｅ）の量は、１〜６９質量％が好ましく、４０〜６０質量％がより好ましい。
水不溶性高分子ビルダーを構成する全モノマー中のノニオンモノマー（ｆ）の量は、１〜６９質量％が好ましく、４０〜６０質量％がより好ましい。
1-69 mass% is preferable and, as for the quantity of the anionic monomer (c) except (a) in all the monomers which comprise a water-insoluble polymer builder, 40-60 mass% is more preferable.
1-69 mass% is preferable and, as for the quantity of the cationic monomer (d) in all the monomers which comprise a water-insoluble polymer builder, 40-60 mass% is more preferable.
The amount of the amphoteric monomer (e) in all monomers constituting the water-insoluble polymer builder is preferably 1 to 69% by mass, and more preferably 40 to 60% by mass.
1-69 mass% is preferable and, as for the quantity of the nonionic monomer (f) in all the monomers which comprise a water-insoluble polymer builder, 40-60 mass% is more preferable.
[水不溶性高分子ビルダーの製造方法]
本発明の水不溶性高分子ビルダーの製造方法は、下記工程１〜３を含むものである。
工程１：有機カルボン酸モノマー、架橋性モノマー、及び重合開始剤を含む水性混合液を調製する工程
工程２：工程１で得られた水性混合液を疎水性溶媒（Ａ）に分散させて分散液（ａ）を調製する工程
工程３：温度が５０℃以上沸点以下である疎水性溶媒（Ｂ）に、前記工程２で得られた分散液（ａ）を滴下して重合を行う工程
[Method for producing water-insoluble polymer builder]
The method for producing a water-insoluble polymer builder of the present invention includes the following steps 1 to 3.
Step 1: Preparing an aqueous mixed solution containing an organic carboxylic acid monomer, a crosslinkable monomer, and a polymerization initiator Step 2: Dispersing the aqueous mixed solution obtained in Step 1 in a hydrophobic solvent (A) Step (3) for preparing (a): a step of performing polymerization by dropping the dispersion (a) obtained in Step 2 above into a hydrophobic solvent (B) having a temperature of 50 ° C. or higher and a boiling point or lower.
（工程１）
本発明における工程１は、有機カルボン酸モノマー、架橋性モノマー、及び重合開始剤を含む水性混合液を調製する工程である。
工程１において、有機カルボン酸モノマーは、水への溶解性を向上させる観点から、その一部又は全部が工程１の終了時に中和されていることが好ましい。なお、有機カルボン酸モノマー以外のアニオン性モノマーを併用する場合は、有機カルボン酸モノマーとアニオン性モノマーとの両方の一部又は全部が中和されていることが好ましい。
(Process 1)
Step 1 in the present invention is a step of preparing an aqueous mixed solution containing an organic carboxylic acid monomer, a crosslinkable monomer, and a polymerization initiator.
In Step 1, the organic carboxylic acid monomer is preferably partially or completely neutralized at the end of Step 1 from the viewpoint of improving the solubility in water. In addition, when using together anionic monomers other than an organic carboxylic acid monomer, it is preferable that some or all of both the organic carboxylic acid monomer and the anionic monomer are neutralized.
前記有機カルボン酸モノマーのカルボキシ基の中和に用いるアルカリ量は、水への溶解性を高め、重合反応を円滑に行う観点から、カルボキシ基に対して０．３〜１．３当量が好ましく、０．５〜１．２当量がより好ましい。
前記中和は、工程１の前、又は工程１の途中で行うことができるが、生産性の観点から、工程１の途中で行うことが好ましく、重合開始剤の添加前に行うことが更に好ましい。
中和に用いるアルカリとしては、水酸化ナトリウムや水酸化カリウム及びそれらの水溶液が好ましい。
The alkali amount used for neutralization of the carboxy group of the organic carboxylic acid monomer is preferably 0.3 to 1.3 equivalents relative to the carboxy group from the viewpoint of increasing the solubility in water and performing the polymerization reaction smoothly. 0.5-1.2 equivalent is more preferable.
The neutralization can be performed before Step 1 or in the middle of Step 1, but is preferably performed in the middle of Step 1 and more preferably performed before the addition of the polymerization initiator from the viewpoint of productivity. .
As the alkali used for neutralization, sodium hydroxide, potassium hydroxide and an aqueous solution thereof are preferable.
工程１で得られる水性混合液中の有機カルボン酸モノマー、架橋性モノマー及びその他のモノマー（以下、これらのモノマーを「原料モノマー」ともいう）の濃度は、重合後の水除去工程の負荷を軽くし、生産効率を高める観点から、２０質量％以上が好ましく、３０質量％以上がより好ましく、３５質量％以上が更に好ましい。また、原料モノマーの濃度は、得られる水性混合液の均一性、粘度等の安定性の観点から、８０質量％以下が好ましく、７０質量％以下がより好ましく、６５質量％以下が更に好ましい。 The concentration of the organic carboxylic acid monomer, the crosslinkable monomer and other monomers (hereinafter, these monomers are also referred to as “raw material monomers”) in the aqueous mixture obtained in Step 1 reduces the load of the water removal step after polymerization. And from a viewpoint of improving production efficiency, 20 mass% or more is preferable, 30 mass% or more is more preferable, and 35 mass% or more is still more preferable. In addition, the concentration of the raw material monomer is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 65% by mass or less, from the viewpoint of the stability of the aqueous mixture obtained, such as uniformity and viscosity.
水性混合液を調製するにあたっては、溶媒に対して原料モノマーの全てを一括して同時に添加してもよく、溶媒に対して各モノマーを個別に添加してもよい。各モノマーを個別に添加する場合の順序に制限はない。
原料モノマーの添加は、得られる水性混合液の安定性の観点から、水を添加したのち重合開始剤の添加前に行うことが好ましい。
In preparing the aqueous mixture, all the raw material monomers may be added simultaneously to the solvent, or each monomer may be added individually to the solvent. There is no restriction | limiting in the order in the case of adding each monomer separately.
From the viewpoint of the stability of the aqueous mixture obtained, the addition of the raw material monomer is preferably carried out after adding water and before adding the polymerization initiator.
重合開始剤としては、過硫酸ナトリウム、過硫酸カリウム、過酸化ベンゾイル等の過酸化物、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩等のアゾ化合物が挙げられ、これらの中では過硫酸ナトリウム、過硫酸カリウム等の水溶性のものが好ましい。
重合開始剤の添加量は、再汚染防止性能に優れる水不溶性高分子ビルダーを得る観点から、全モノマー１００質量部に対して、０．０１〜５質量部が好ましく、０．０５〜３質量部がより好ましく、０．１〜１質量部が更に好ましく、０．２〜０．５質量部がより更に好ましい。
重合開始剤は、水に溶解させて水溶液とした後に水性混合液に対して添加することが好ましい。
本発明の工程１で使用される水の量は、原料モノマー及び重合開始剤の濃度が好ましい範囲になるような量を使用することが好ましい。
As polymerization initiators, peroxides such as sodium persulfate, potassium persulfate, benzoyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride Among them, water-soluble compounds such as sodium persulfate and potassium persulfate are preferable.
The addition amount of the polymerization initiator is preferably 0.01 to 5 parts by mass, and 0.05 to 3 parts by mass with respect to 100 parts by mass of all monomers, from the viewpoint of obtaining a water-insoluble polymer builder having excellent anti-recontamination performance. Is more preferable, 0.1-1 mass part is still more preferable, and 0.2-0.5 mass part is still more preferable.
The polymerization initiator is preferably added to the aqueous mixture after dissolving in water to form an aqueous solution.
The amount of water used in step 1 of the present invention is preferably such that the concentration of the raw material monomer and the polymerization initiator is within a preferred range.
工程１の水性混合液を調製する際の温度は、工程１においてモノマーが重合してしまうことを回避する観点から、０〜５０℃が好ましく、０〜３０℃がより好ましい。
また、工程１は回分式、半回分式、連続式のいずれの反応装置であっても行うことができる。モノマーの中和も含め、系を均一に混合可能であれば、撹拌翼や静止型混合機等、一般的に用いられている混合装置、手段を用いることができる。
From the viewpoint of avoiding the polymerization of the monomer in Step 1, the temperature when preparing the aqueous mixed solution in Step 1 is preferably 0 to 50 ° C, and more preferably 0 to 30 ° C.
Further, Step 1 can be carried out in any of batch, semi-batch and continuous reactors. As long as the system can be uniformly mixed, including neutralization of monomers, generally used mixing devices and means such as a stirring blade and a static mixer can be used.
（工程２）
本発明では、工程１で得られた水性混合液を疎水性溶媒（Ａ）に分散させる。工程２で用いられる疎水性溶媒（Ａ）とは、２５℃における水に対する溶解度が１質量％以下のものであり、具体的には、シクロヘキサン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレン、エチルベンゼン、イソパラフィン等の炭化水素系溶媒、四塩化炭素、ジクロルエタン等のハロゲン化炭化水素系溶媒から選ばれる１種又は２種以上が好ましい。これらの中では、炭化水素系溶媒が好ましく、シクロヘキサン、ヘキサンがより好ましい。
(Process 2)
In the present invention, the aqueous mixed solution obtained in step 1 is dispersed in the hydrophobic solvent (A). The hydrophobic solvent (A) used in Step 2 is one having a solubility in water at 25 ° C. of 1% by mass or less, specifically, cyclohexane, hexane, heptane, octane, benzene, toluene, xylene, ethylbenzene. One or more selected from hydrocarbon solvents such as isoparaffin and halogenated hydrocarbon solvents such as carbon tetrachloride and dichloroethane are preferred. Among these, hydrocarbon solvents are preferable, and cyclohexane and hexane are more preferable.
工程２における疎水性溶媒（Ａ）の使用量は、疎水性溶媒（Ａ）に分散させた前記水性混合液の液滴の安定性を向上させる観点から、工程１で得られた水性混合液１００質量部に対して５０質量部以上が好ましく、９０質量部以上がより好ましく、９５質量部以上が更に好ましく、１００質量部以上がより更に好ましい。
また、前記疎水性溶媒（Ａ）の使用量は、精製工程での負荷を低減し、円滑に生産する観点から、水性混合液１００質量部に対して２００質量部以下が好ましく、１５０質量部以下がより好ましく、１３０質量部以下が更に好ましく、１２０質量部以下がより更に好ましい。
工程２における疎水性溶媒（Ａ）の具体的な使用量としては、水性混合液１００質量部に対して５０〜２００質量部が好ましく、９０〜１５０質量部がより好ましく、９５〜１３０質量部が更に好ましく、１００〜１２０質量部がより更に好ましい。
The amount of the hydrophobic solvent (A) used in the step 2 is selected from the viewpoint of improving the stability of the droplets of the aqueous mixture dispersed in the hydrophobic solvent (A). 50 mass parts or more are preferable with respect to mass parts, 90 mass parts or more are more preferable, 95 mass parts or more are still more preferable, and 100 mass parts or more are still more preferable.
In addition, the amount of the hydrophobic solvent (A) used is preferably 200 parts by mass or less, and 150 parts by mass or less with respect to 100 parts by mass of the aqueous mixture from the viewpoint of reducing the load in the purification step and producing smoothly. Is more preferable, 130 mass parts or less are still more preferable, and 120 mass parts or less are still more preferable.
As a specific usage-amount of the hydrophobic solvent (A) in process 2, 50-200 mass parts is preferable with respect to 100 mass parts of aqueous mixture, 90-150 mass parts is more preferable, 95-130 mass parts is More preferably, 100-120 mass parts is still more preferable.
工程２において疎水性溶媒（Ａ）に分散させた水性混合液の液滴の体積平均分散径は、液滴の安定性、及び工程３で得られる高分子ビルダーの再汚染防止性能を向上させる観点から、１〜５０μｍが好ましく、５〜３０μｍがより好ましい。
前記液滴の体積平均分散径は、例えば、コールターＬＳ―２３０（ベックマンコールター社製）等でレーザー回折法によって測定することができる。
The volume average dispersion diameter of the droplets of the aqueous mixed liquid dispersed in the hydrophobic solvent (A) in the step 2 is a viewpoint of improving the stability of the droplets and the anti-contamination performance of the polymer builder obtained in the step 3. Therefore, 1 to 50 μm is preferable, and 5 to 30 μm is more preferable.
The volume average dispersion diameter of the droplets can be measured by a laser diffraction method with, for example, Coulter LS-230 (manufactured by Beckman Coulter).
分散液を調製する際に使用する分散機としては、一般的に分散、混合に用いられている高圧ホモジナイザー、ラインミキサー、静止型混合器等を用いることができる。ラインミキサーを使用する場合の回転数は、上述した分散径の油中水型分散液滴を得る観点から、７，０００〜５００，０００ｒ／ｍｉｎが好ましく、８，０００〜１００，０００ｒ／ｍｉｎがより好ましく、９，０００〜２０，０００ｒ／ｍｉｎが更に好ましい。
なお、これら分散機での処理に先立って、簡便な撹拌槽等を用い、予め疎水性溶媒（Ａ）と水性混合液を予備分散しておくことが好ましい。
As a disperser used for preparing the dispersion, a high-pressure homogenizer, a line mixer, a static mixer, or the like generally used for dispersion and mixing can be used. The rotational speed when using a line mixer is preferably 7,000 to 500,000 r / min, and preferably 8,000 to 100,000 r / min from the viewpoint of obtaining water-in-oil dispersed droplets having the above-mentioned dispersion diameter. More preferred is 9,000 to 20,000 r / min.
Prior to treatment with these dispersers, it is preferable to preliminarily disperse the hydrophobic solvent (A) and the aqueous mixed solution in advance using a simple stirring tank or the like.
工程２の水分散液を調製する際の温度としては、工程２においてモノマーが重合することを回避する観点から、０〜５０℃が好ましく、０〜３０℃がより好ましい。 The temperature for preparing the aqueous dispersion in step 2 is preferably 0 to 50 ° C, more preferably 0 to 30 ° C from the viewpoint of avoiding the polymerization of the monomer in step 2.
工程２においては、工程１で得られた水性混合液からなる液滴の疎水性溶媒中（Ａ）での安定性を向上させる観点から、疎水性溶媒（Ａ）に分散剤を含有させることが好ましい。
分散剤としては、乳化性の観点から親水性−親油性バランス（ＨＬＢ）が、好ましくは４〜３０、より好ましくは５〜２０、更に好ましくは６〜１０である界面活性剤が挙げられる。なお、ＨＬＢ値は、デービスの式に基づき、「ＨＬＢ＝７＋Σ（親水基の基数）−Σ（疎水基の基数）」により算出することができる［（参考）「界面活性剤」竹内節著、米田出版（１９９９年）］。
また、分散剤としては、例えば、ショ糖エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル等の脂肪酸エステル；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等のポリオキシアルキレン誘導体；メチルセルロース、カルボキシメチルセルロース等のセルロース誘導体；ポリビニルアルコール等の合成ポリマー；アルキル硫酸塩等のアニオン性界面活性剤から選ばれる１種又は２種以上が好ましい。
これらの中では、工程１で得られた水性混合液からなる液滴の疎水性溶媒中での安定性を向上させる観点から、脂肪酸エステルが好ましく、ショ糖エステル、ソルビタンエステルがより好ましく、ショ糖エステルが更に好ましい。ショ糖エステルの中では、ショ糖ステアリン酸エステル（ＨＬＢ＝７）が好ましい。
In step 2, from the viewpoint of improving the stability of the droplets comprising the aqueous mixture obtained in step 1 in the hydrophobic solvent (A), the hydrophobic solvent (A) may contain a dispersant. preferable.
Examples of the dispersant include surfactants having a hydrophilic-lipophilic balance (HLB) of preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 10 from the viewpoint of emulsification. The HLB value can be calculated by “HLB = 7 + Σ (the number of hydrophilic groups) −Σ (the number of hydrophobic groups)” based on the Davis equation [(Reference) “Surfactant” by Takeuchi Takeshi, Yoneda Publishing (1999)].
Examples of the dispersant include sucrose esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters and the like; polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers 1 type or 2 types or more chosen from anionic surfactants, such as polyoxyalkylene derivatives, such as; cellulose derivatives, such as methylcellulose and carboxymethylcellulose; synthetic polymers, such as polyvinyl alcohol; alkyl sulfate.
Among these, fatty acid esters are preferable, sucrose esters and sorbitan esters are more preferable, and sucrose is preferable from the viewpoint of improving the stability of droplets made of the aqueous mixture obtained in Step 1 in a hydrophobic solvent. Esters are more preferred. Among the sucrose esters, sucrose stearate (HLB = 7) is preferable.
工程２で使用する分散剤は、疎水性溶媒（Ａ）中における液滴の安定性を向上させる観点から、原料モノマー１００質量部に対し、０．１〜２０質量部が好ましく、０．１５〜１０質量部がより好ましく、０．２〜１質量部が更に好ましい。
工程２で使用する分散剤は、疎水性溶媒（Ａ）中における液滴の安定性を向上させる観点から、工程１で得られた水性混合液を疎水性溶媒に分散させる前に、疎水性溶媒（Ａ）に添加、溶解させておくことが好ましい。
From the viewpoint of improving the stability of droplets in the hydrophobic solvent (A), the dispersant used in Step 2 is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the raw material monomer, and 0.15 to 10 mass parts is more preferable, and 0.2-1 mass part is still more preferable.
From the viewpoint of improving the stability of the droplets in the hydrophobic solvent (A), the dispersant used in the step 2 is a hydrophobic solvent before the aqueous mixture obtained in the step 1 is dispersed in the hydrophobic solvent. It is preferable to add and dissolve in (A).
（工程３）
本発明における工程３では、原料モノマーを前記工程２で得られた分散液（ａ）を滴下することにより重合を行う工程である。
工程３で使用することができる疎水性溶媒（Ｂ）とは、２５℃における水に対する溶解度が１質量％以下のものであり、具体的にはシクロヘキサン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレン、エチルベンゼン等の炭化水素系溶媒、四塩化炭素、ジクロルエタン等のハロゲン化炭化水素系溶媒、アイソバー等の鉱油から選ばれる１種又は２種以上が好ましい。これらの中では、生産性の観点から、炭化水素系溶媒が好ましく、シクロヘキサン、ヘキサンがより好ましい。
なお、生産性の観点から疎水性溶媒（Ｂ）は、工程１で用いる疎水性溶媒（Ａ）と同一の溶媒であることが好ましい。
(Process 3)
In step 3 of the present invention, the raw material monomer is polymerized by dropping the dispersion liquid (a) obtained in step 2 above.
The hydrophobic solvent (B) that can be used in Step 3 is one having a solubility in water at 25 ° C. of 1% by mass or less, specifically cyclohexane, hexane, heptane, octane, benzene, toluene, xylene. One or more selected from hydrocarbon solvents such as ethylbenzene, halogenated hydrocarbon solvents such as carbon tetrachloride and dichloroethane, and mineral oils such as isobar are preferred. Of these, hydrocarbon solvents are preferred from the viewpoint of productivity, and cyclohexane and hexane are more preferred.
From the viewpoint of productivity, the hydrophobic solvent (B) is preferably the same solvent as the hydrophobic solvent (A) used in Step 1.
工程３における重合反応の温度は５０℃以上、疎水性溶媒（Ｂ）の沸点以下である。反応温度が５０℃以上であると重合反応が生じ、沸点以下とすると製造エネルギーを徒に消費することがないため好ましい。
前記重合反応の温度としては、モノマーの反応性の観点から、５０℃以上であり、６０℃以上が好ましく、６５℃以上がより好ましい。また、前記反応温度は、安定的に水不溶性高分子ビルダーを生産する観点から、９５℃以下が好ましく、９０℃以下がより好ましく、８０℃以下が更に好ましい。
なお、本製造方法においては、疎水性溶媒（Ｂ）及び水を還流させながら反応を行うことが好ましい。
The temperature of the polymerization reaction in Step 3 is 50 ° C. or higher and lower than the boiling point of the hydrophobic solvent (B). When the reaction temperature is 50 ° C. or higher, a polymerization reaction occurs. When the reaction temperature is lower than the boiling point, production energy is not consumed easily, which is preferable.
The temperature of the polymerization reaction is 50 ° C. or higher, preferably 60 ° C. or higher, and more preferably 65 ° C. or higher from the viewpoint of monomer reactivity. The reaction temperature is preferably 95 ° C. or lower, more preferably 90 ° C. or lower, and still more preferably 80 ° C. or lower, from the viewpoint of stably producing a water-insoluble polymer builder.
In this production method, it is preferable to carry out the reaction while refluxing the hydrophobic solvent (B) and water.
工程３における分散液（ａ）の滴下時間は、急激な反応温度の上昇を抑止し、反応を制御する観点から、０．１時間以上が好ましく、０．５時間以上がより好ましく、１時間以上が更に好ましい。また、前記滴下時間は、生産性の観点から、１０時間以下が好ましく、５時間以下がより好ましく、２時間以下が更に好ましい。 The dropping time of the dispersion liquid (a) in step 3 is preferably 0.1 hours or more, more preferably 0.5 hours or more, and more preferably 1 hour or more from the viewpoint of suppressing a rapid increase in reaction temperature and controlling the reaction. Is more preferable. The dropping time is preferably 10 hours or less, more preferably 5 hours or less, and even more preferably 2 hours or less from the viewpoint of productivity.
工程３において用いる疎水性溶媒（Ｂ）と分散液（ａ）との質量比（分散液（ａ）／疎水性溶媒（Ｂ））は、反応に使用する溶媒量を低減する観点から、２００／１００以上が好ましく、２５０／１００以上がより好ましく、２７０／１００以上が更に好ましい。また、前記質量比は、再汚染防止性能に優れた疎水性高分子ビルダーを得る観点から、４００／１００以下が好ましく、３５０／１００以下がより好ましく、３１０／１００以下が更に好ましい。 The mass ratio (dispersion liquid (a) / hydrophobic solvent (B)) between the hydrophobic solvent (B) and the dispersion liquid (a) used in Step 3 is 200 / 100 or more are preferable, 250/100 or more are more preferable, and 270/100 or more are still more preferable. The mass ratio is preferably 400/100 or less, more preferably 350/100 or less, and still more preferably 310/100 or less, from the viewpoint of obtaining a hydrophobic polymer builder excellent in recontamination prevention performance.
分散液（ａ）の滴下速度は、水不溶性高分子ビルダーの生産性の観点から、工程３において使用する疎水性溶媒（Ｂ）１００質量部に対して、１．５質量部／ｍｉｎ以上が好ましく、２質量部／ｍｉｎ以上がより好ましく、２．５質量部／ｍｉｎ以上が更に好ましい。
また、前記分散液（ａ）の滴下速度は、急激な反応温度の上昇を抑止し、反応を制御する観点から、工程３で使用する疎水性溶媒（Ｂ）１００質量部に対して、３０質量部／ｍｉｎ以下が好ましく、１５質量部／ｍｉｎ以下がより好ましく、１０質量部／ｍｉｎ以下が更に好ましく、５質量部／ｍｉｎ以下がより更に好ましい。
The dropping rate of the dispersion liquid (a) is preferably 1.5 parts by mass / min or more with respect to 100 parts by mass of the hydrophobic solvent (B) used in Step 3 from the viewpoint of productivity of the water-insoluble polymer builder. 2 mass parts / min or more is more preferable, and 2.5 mass parts / min or more is still more preferable.
Moreover, the dropping rate of the dispersion liquid (a) is 30 masses with respect to 100 parts by mass of the hydrophobic solvent (B) used in step 3 from the viewpoint of suppressing a rapid increase in reaction temperature and controlling the reaction. Parts / min or less, more preferably 15 parts by mass / min or less, still more preferably 10 parts by mass / min or less, and even more preferably 5 parts by mass / min or less.
疎水性溶媒（Ｂ）は、重合反応を速やかに進行させ、再汚染防止性能に優れる高分子ビルダーを得る観点から、重合反応開始前に昇温することが好ましく、工程２で得られた分散液（ａ）を疎水性溶媒（Ｂ）に対して滴下する前に５０℃から疎水性溶媒等の反応溶液の沸点の間の温度に昇温することがより好ましい。 The hydrophobic solvent (B) is preferably heated before the start of the polymerization reaction from the viewpoint of obtaining a polymer builder that allows the polymerization reaction to proceed rapidly and has excellent anti-contamination performance, and the dispersion obtained in step 2 It is more preferable to raise the temperature from 50 ° C. to the temperature between the boiling points of the reaction solution such as the hydrophobic solvent before dropping (a) to the hydrophobic solvent (B).
工程３では、再汚染防止性能に優れる疎水性高分子ビルダーを得る観点から、疎水性溶媒（Ｂ）に分散剤を含有させることが好ましい。
分散剤としては、ショ糖エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル等の脂肪酸エステル、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等のポリオキシアルキレン誘導体、メチルセルロース、カルボキシメチルセルロース等のセルロース誘導体、ポリビニルアルコール等の合成ポリマー、アルキル硫酸塩等のアニオン性界面活性剤から選ばれる１種又は２種以上が好ましい。
これらの中で、更に好ましくは脂肪酸エステル、更に好ましくはショ糖エステル、又はソルビタンエステル、更に好ましくはショ糖エステルである。ショ糖エステルの中では、ショ糖ステアリン酸エステルが好ましい。
In Step 3, it is preferable to contain a dispersant in the hydrophobic solvent (B) from the viewpoint of obtaining a hydrophobic polymer builder excellent in recontamination prevention performance.
Dispersants include sucrose esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters and other fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers and other polyoxyethylene alkyl esters. One or more types selected from alkylene derivatives, cellulose derivatives such as methylcellulose and carboxymethylcellulose, synthetic polymers such as polyvinyl alcohol, and anionic surfactants such as alkyl sulfates are preferred.
Among these, fatty acid esters are more preferable, sucrose esters or sorbitan esters are more preferable, and sucrose esters are more preferable. Among the sucrose esters, sucrose stearate is preferable.
工程３において用いる分散剤は、生産性の観点から、工程２で用いる分散剤と同一であることが好ましく、工程２において疎水性溶媒（Ａ）に対して分散剤を溶解させ、この疎水性溶媒（Ａ）を工程３において疎水性溶媒（Ｂ）として用いることが更に好ましい。
また、工程３は回分式反応装置で行うことが好ましい。系を均一に混合可能であれば、撹拌翼や静止型混合機等、一般的に用いられている混合装置、手段を用いることができる。
The dispersant used in step 3 is preferably the same as the dispersant used in step 2 from the viewpoint of productivity. In step 2, the dispersant is dissolved in the hydrophobic solvent (A), and the hydrophobic solvent is used. More preferably, (A) is used as the hydrophobic solvent (B) in step 3.
Moreover, it is preferable to perform the process 3 with a batch type reactor. If the system can be uniformly mixed, generally used mixing devices and means such as a stirring blade and a static mixer can be used.
（水除去工程）
本発明においては、工程３における重合反応の後、分散液（ｂ）から水を留去する水除去工程を設けることが好ましい。
工程３で得られた分散液（ｂ）から、水を留去する際の温度は、エネルギー効率、及び水不溶性高分子ビルダーの凝集を防ぐ観点から、５０〜１００℃が好ましく、７０〜９０℃がより好ましく、７５〜８５℃が更に好ましい。また、減圧下又は大気圧下で、０．５〜２０時間行うことが好ましい。
水の除去量は、水不溶性高分子ビルダーの凝集を防ぐ観点から、工程３で得られた分散液（ｂ）に含まれる水のうち、３０質量％以上が好ましく、４０質量％以上がより好ましく、８０質量％以上が更に好ましく、８５質量％以上がより更に好ましい。また、前記水の除去量は、優れた泥捕捉性を得る観点から、９５質量％以下が好ましい。
なお、工程３で得られた分散液（ｂ）に含まれる水に対し、除去する水の割合を、以下、脱水率という場合がある。
(Water removal process)
In the present invention, it is preferable to provide a water removal step of distilling off water from the dispersion (b) after the polymerization reaction in step 3.
From the viewpoint of preventing energy aggregation and aggregation of the water-insoluble polymer builder, the temperature at which water is distilled off from the dispersion (b) obtained in Step 3 is preferably 50 to 100 ° C, and 70 to 90 ° C. Is more preferable, and 75-85 degreeC is still more preferable. Moreover, it is preferable to carry out for 0.5 to 20 hours under reduced pressure or atmospheric pressure.
From the viewpoint of preventing aggregation of the water-insoluble polymer builder, the amount of water removed is preferably 30% by mass or more, more preferably 40% by mass or more, of the water contained in the dispersion liquid (b) obtained in Step 3. 80 mass% or more is still more preferable, and 85 mass% or more is still more preferable. Moreover, the removal amount of the water is preferably 95% by mass or less from the viewpoint of obtaining excellent mud trapping properties.
In addition, the ratio of the water to remove with respect to the water contained in the dispersion liquid (b) obtained at the process 3 may be hereinafter referred to as a dehydration rate.
水除去工程の具体的な方法としては、以下に示す方法が挙げられる。
疎水性溶媒及び水を共沸させて反応容器から得られた留分を回収する。回収した留分から静置分離等により水を分離し排出する一方で、疎水性溶媒を反応容器の分散液（ｂ）に戻す操作を繰り返すことにより、分散液（ｂ）から水を除去し、上記の好ましい量の水を除去する。
水除去工程後の疎水性溶媒中の水不溶性高分子ビルダーのレーザー回折法による体積平均粒子径は１〜５０μｍが好ましく、５〜３０μｍが更に好ましい。
Specific methods for the water removal step include the following methods.
A fraction obtained from the reaction vessel is recovered by azeotropic distillation of the hydrophobic solvent and water. While separating and discharging water from the collected fraction by standing separation or the like, water is removed from the dispersion (b) by repeating the operation of returning the hydrophobic solvent to the dispersion (b) in the reaction vessel, The preferred amount of water is removed.
The volume average particle diameter of the water-insoluble polymer builder in the hydrophobic solvent after the water removal step is preferably from 1 to 50 μm, more preferably from 5 to 30 μm, by the laser diffraction method.
（乾燥工程）
本発明においては、前記水除去工程後、水不溶性高分子ビルダーを乾燥させる乾燥工程を設けることが好ましい。
乾燥工程の具体的な方法としては、以下に示す方法が挙げられる。
すなわち、前記水除去工程において一定量の水を回収した後、分散液（ｂ）から固形分をろ別し、ろ別した固形分を棚型乾燥機や噴霧乾燥機等の乾燥機にて乾燥させることにより行う方法が好ましい。
前記乾燥工程は、減圧下又は大気圧下、好ましくは減圧下で行うことが好ましい。
乾燥工程における温度は、６０〜１５０℃が好ましく、７０〜１２０℃がより好ましく、７５〜１１０℃が更に好ましい。
乾燥時間は０．５〜２０時間が好ましく、１〜１０時間がより好ましい。
すなわち、水除去工程においては、水分等を含む水不溶性高分子ビルダーを６０〜１００℃に保持し、減圧下、０．５〜２０時間程度乾燥を行うことが好ましい。
(Drying process)
In this invention, it is preferable to provide the drying process which dries a water-insoluble polymer builder after the said water removal process.
Specific examples of the drying process include the following methods.
That is, after collecting a certain amount of water in the water removal step, the solid content is filtered off from the dispersion (b), and the filtered solid content is dried in a dryer such as a shelf dryer or a spray dryer. The method performed by making it preferable is preferable.
The drying step is preferably performed under reduced pressure or atmospheric pressure, preferably under reduced pressure.
60-150 degreeC is preferable, the temperature in a drying process has more preferable 70-120 degreeC, and 75-110 degreeC is still more preferable.
The drying time is preferably 0.5 to 20 hours, and more preferably 1 to 10 hours.
That is, in the water removal step, it is preferable that the water-insoluble polymer builder containing moisture and the like is kept at 60 to 100 ° C. and dried under reduced pressure for about 0.5 to 20 hours.
以下の実施例、比較例における体積平均分散径、及び水不溶性高分子ビルダーの体積平均粒子径は以下の方法で測定した。
＜体積平均分散径、及び体積平均粒子径の測定方法＞
測定装置としては、(株)堀場製作所製レーザー回折/散乱式粒度分布測定装置「ＬＡ−９２０」を用いた。
乾燥時の体積平均粒子径は、水不溶性高分子ビルダーを８０℃、２５ｋＰａ（絶対圧力）で１２時間乾燥を行った後、分散媒をシクロヘキサン、相対屈折率を１．１２として測定を行った。
水による膨潤時の体積平均粒子径は、水不溶性高分子ビルダーを水に３０分以上浸漬させることにより膨潤させ、分散媒を４．５（ｍＭ）Ｎａ2ＣＯ3、４[°ｄＨ]の水とし、相対屈折率を１．１２として測定を行った。
The volume average dispersion diameter in the following Examples and Comparative Examples and the volume average particle diameter of the water-insoluble polymer builder were measured by the following methods.
<Measurement method of volume average dispersion diameter and volume average particle diameter>
As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” manufactured by Horiba, Ltd. was used.
The volume average particle size at the time of drying was measured by drying the water-insoluble polymer builder at 80 ° C. and 25 kPa (absolute pressure) for 12 hours, and then setting the dispersion medium as cyclohexane and the relative refractive index as 1.12.
The volume average particle size during swelling with water is such that the water-insoluble polymer builder is immersed in water for 30 minutes or more to swell, and the dispersion medium is 4.5 (mM) Na 2 CO 3 , 4 [° dH] water. And the relative refractive index was 1.12.
実施例１
（工程１）
２Ｌフラスコに３２質量％水酸化ナトリウム水溶液１５８ｇを仕込み、次いで２−アクリルアミド−２−メチルプロパンスルホン酸（東亜合成化学（株）製）１００ｇ、８０質量％アクリル酸水溶液を１００ｇ加えて中和した後に、メチレンビスアクリルアミド０．２９５ｇを添加して、混合した。これにペルオキソ硫酸ナトリウム０．３８０ｇを脱イオン水７０．０ｇに溶解させたものを添加し、溶解させた（水性混合液（１））。
（工程２）
３Ｌの丸型フラスコにシクロヘキサン７１２ｇをとり、ショ糖ステアリン酸エステル（ＨＬＢ＝７）２．１０ｇを撹拌混合しながら添加し、５０℃まで昇温し、５０℃を１時間保つことで完全に溶解させた（疎水性溶媒（Ａ１））。
前記疎水性溶媒（Ａ１）を４３０ｇとり、これに前記水性混合液（１）を添加し、ホモミキサーを用い９０００ｒ／ｍｉｎで８分間混合分散を行い分散液（ａ）を得た。
（工程３）
残りの疎水性溶媒（Ａ１）２８４ｇを疎水性溶媒（Ｂ１）として４Ｌフラスコにとり、窒素ガスを５０ｍｌ／ｍｉｎ流し、１８０ｒ／ｍｉｎで撹拌混合し、７０℃まで到達したのち還流させ、このフラスコ中に前記分散液（ａ）を９０分間かけて滴下し重合を行った。
Example 1
(Process 1)
After charging 158 g of a 32% by mass sodium hydroxide aqueous solution into a 2 L flask, and then neutralizing by adding 100 g of 2-acrylamido-2-methylpropanesulfonic acid (manufactured by Toa Gosei Chemical Co., Ltd.) and 100 g of an 80% by mass acrylic acid aqueous solution. Then, 0.295 g of methylenebisacrylamide was added and mixed. A solution obtained by dissolving 0.380 g of sodium peroxosulfate in 70.0 g of deionized water was added and dissolved (aqueous mixture (1)).
(Process 2)
Take 712 g of cyclohexane in a 3 L round flask, add 2.10 g of sucrose stearate (HLB = 7) with stirring and mixing, raise the temperature to 50 ° C., and keep at 50 ° C. for 1 hour to completely dissolve (Hydrophobic solvent (A1)).
430 g of the hydrophobic solvent (A1) was taken, the aqueous mixed solution (1) was added thereto, and the mixture was dispersed at 9000 r / min for 8 minutes using a homomixer to obtain a dispersion (a).
(Process 3)
Take 284 g of the remaining hydrophobic solvent (A1) as a hydrophobic solvent (B1) in a 4 L flask, flow nitrogen gas at 50 ml / min, stir and mix at 180 r / min, reach 70 ° C. and then reflux, The dispersion (a) was added dropwise over 90 minutes for polymerization.
（水除去工程）
工程３の後、フラスコに脱水管を取り付けて分散液（ｂ）の共沸脱水を行った。１９５ｇの水を回収した。脱水率は８９質量％であった。
（乾燥工程）
水除去工程後の分散液（ｂ）を室温まで冷却後、この分散液（ｂ）から固形分をろ別して固形分を平バットにとり、棚型乾燥器で８０℃、２５ｋＰａ（絶対圧力）で１２時間乾燥を行い、水不溶性高分子ビルダーを得た。
この水不溶性高分子ビルダーの平均体積粒子径はレーザー回折式粒度分布測定装置「ＬＡ−９５０」にてバッチ式で測定したところ、乾燥時で５．３μｍ、膨潤時で４０μｍ、膨潤度は７．４であった。
(Water removal process)
After step 3, a dehydrating tube was attached to the flask to perform azeotropic dehydration of the dispersion (b). 195 g of water was recovered. The dehydration rate was 89% by mass.
(Drying process)
After the dispersion (b) after the water removal step is cooled to room temperature, the solid content is separated from the dispersion (b) by filtration, and the solid content is taken into a flat bat. The solid content is 12 ° C. at 80 ° C. and 25 kPa (absolute pressure) in a shelf dryer. Time drying was performed to obtain a water-insoluble polymer builder.
The average volume particle size of the water-insoluble polymer builder was measured by a batch method using a laser diffraction particle size distribution analyzer “LA-950”. The dry particle size was 5.3 μm when dried, 40 μm when swollen, and the degree of swelling was 7. 4.
実施例２
（工程１）
２Ｌフラスコに８０質量％アクリル酸水溶液１００ｇを仕込み、３２質量％水酸化ナトリウム水溶液９７．１ｇを加えて中和し、次いでメタクリロイルオキシエチレントリメチルアンモニウムクロライド７０質量％水溶液１４３ｇを加えた後にメチレンビスアクリルアミド０．２９５ｇを添加して、均一混合した。これにペルオキソ硫酸ナトリウム０．３８０ｇを脱イオン水２０．０ｇに溶解させたものを添加し、均一溶解させた（水性混合液（２））。
（工程２）
３Ｌの丸型フラスコにシクロヘキサン７１２ｇをとり、ショ糖ステアリン酸エステル２．１０ｇを撹拌混合しながら添加し、５０℃まで昇温し、５０℃を１時間保つことで完全に溶解させた（疎水性溶媒（Ａ２））。
前記疎水性溶媒（Ａ２）を４３０ｇとり、これに前記水性混合液（２）を添加し、ホモミキサーを用い９０００ｒ／ｍｉｎで８分間混合分散を行い分散液（ａ）を得た。
（工程３）
残りの疎水性溶媒（Ａ２）２８４ｇを疎水性溶媒（Ｂ２）として４Ｌフラスコにとり、反応容器中の雰囲気を窒素に置換した後、窒素ガスを５０ｍｌ／ｍｉｎ流し、１８０ｒ／ｍｉｎで撹拌混合し、７０℃まで到達したのち還流させ、このフラスコ中に分散液（ａ）を９０分間かけて滴下し重合を行った。
Example 2
(Process 1)
A 2 L flask was charged with 100 g of an 80% by weight aqueous acrylic acid solution, neutralized by adding 97.1 g of a 32% by weight aqueous sodium hydroxide solution, and then added with 143 g of a 70% by weight aqueous solution of methacryloyloxyethylenetrimethylammonium chloride. .295 g was added and mixed uniformly. A solution obtained by dissolving 0.380 g of sodium peroxosulfate in 20.0 g of deionized water was added and dissolved uniformly (aqueous mixed solution (2)).
(Process 2)
712 g of cyclohexane was added to a 3 L round flask, and 2.10 g of sucrose stearate was added with stirring and mixing. The mixture was heated to 50 ° C. and kept at 50 ° C. for 1 hour for complete dissolution (hydrophobic properties Solvent (A2)).
430 g of the hydrophobic solvent (A2) was taken, the aqueous mixed solution (2) was added thereto, and the mixture was dispersed for 8 minutes at 9000 r / min using a homomixer to obtain a dispersion (a).
(Process 3)
284 g of the remaining hydrophobic solvent (A2) as a hydrophobic solvent (B2) was placed in a 4 L flask, and the atmosphere in the reaction vessel was replaced with nitrogen. Then, nitrogen gas was flowed at 50 ml / min, and the mixture was stirred and mixed at 180 r / min. After reaching to ° C., the mixture was refluxed, and the dispersion (a) was dropped into the flask over 90 minutes for polymerization.
（水除去工程）
実施例１と同じ操作により水除去工程を行った。１３０ｇの水を回収した。脱水率は８７質量％であった。
（乾燥工程）
実施例１と同じ操作により乾燥工程を行った。この水不溶性高分子ビルダーの平均体積粒子径はレーザー回折式粒度分布測定装置「ＬＡ−９５０」にてバッチ式で測定したところ、乾燥時で５．３μｍ、膨潤時で５６μｍであった。
(Water removal process)
A water removal step was performed by the same operation as in Example 1. 130 g of water was recovered. The dehydration rate was 87% by mass.
(Drying process)
The drying step was performed by the same operation as in Example 1. The average volume particle size of the water-insoluble polymer builder was measured by a batch method using a laser diffraction particle size distribution analyzer “LA-950” and found to be 5.3 μm when dried and 56 μm when swollen.
比較例１
３Ｌの丸型フラスコにシクロヘキサン１０５０ｇをとり、ショ糖ステアリン酸エステル１．０５ｇを撹拌混合しながら添加し、５０℃まで昇温し、５０℃を１時間保つことで完全に溶解させた。
また、２Ｌフラスコに脱イオン水１０７ｇ、４８質量％水酸化ナトリウム水溶液５２．５ｇを仕込み、次いで２−アクリルアミド−２−メチルプロパンスルホン酸５０．２ｇ、８０質量％アクリル酸水溶液を５０．０ｇ加えて中和した後に、メチレンビスアクリルアミド０．１４８ｇを添加して、均一混合した。
これにペルオキソ硫酸ナトリウム０．１９０ｇを脱イオン水３．００ｇに溶解させたものを添加し、均一溶解させた。
これを、前記のショ糖ステアリン酸エステルを溶解させたシクロヘキサン中に添加し、ホモミキサーを用い９０００ｒ／ｍｉｎで８分間混合分散を行い、微細粒子径の分散液を得た。
反応容器中の雰囲気を窒素に置換した後、窒素ガスを５０ｍｌ／ｍｉｎ流しながら分散液を１８０ｒ／ｍｉｎで撹拌混合し、１℃／ｍｉｎで昇温し、６５℃に到達した後、４０分間保持し、その後１℃／ｍｉｎのペースで７０℃まで昇温し重合を行った。
Comparative Example 1
To a 3 L round flask, 1050 g of cyclohexane was added, 1.05 g of sucrose stearate was added with stirring and mixing, the temperature was raised to 50 ° C., and the solution was completely dissolved by maintaining 50 ° C. for 1 hour.
In addition, 107 g of deionized water and 52.5 g of a 48% by mass aqueous sodium hydroxide solution were charged into a 2 L flask, and then 50.2 g of 2-acrylamido-2-methylpropanesulfonic acid and 50.0 g of an 80% by mass acrylic acid aqueous solution were added. After neutralization, 0.148 g of methylene bisacrylamide was added and mixed uniformly.
A solution obtained by dissolving 0.190 g of sodium peroxosulfate in 3.00 g of deionized water was added and dissolved uniformly.
This was added into cyclohexane in which the sucrose stearate was dissolved, and mixed and dispersed at 9000 r / min for 8 minutes using a homomixer to obtain a dispersion with a fine particle size.
After replacing the atmosphere in the reaction vessel with nitrogen, the dispersion was stirred and mixed at 180 r / min while flowing nitrogen gas at 50 ml / min, heated at 1 ° C./min, reached 65 ° C., and held for 40 minutes Thereafter, the temperature was raised to 70 ° C. at a rate of 1 ° C./min to carry out polymerization.
（水除去工程）
実施例１と同じ操作により水除去工程を行った。１３０ｇの水を回収した。脱水率は９２質量％であった。
（乾燥工程）
実施例１と同じ操作により乾燥工程を行った。この水不溶性高分子ビルダーの平均体積粒子径はレーザー回折式粒度分布測定装置「ＬＡ−９５０」にてバッチ式で測定したところ、乾燥時で５．３μｍ、膨潤時で２４μｍであった。
(Water removal process)
A water removal step was performed by the same operation as in Example 1. 130 g of water was recovered. The dehydration rate was 92% by mass.
(Drying process)
The drying step was performed by the same operation as in Example 1. The average volume particle size of the water-insoluble polymer builder was measured by a batch method using a laser diffraction particle size distribution analyzer “LA-950” to be 5.3 μm when dried and 24 μm when swollen.
実施例、及び比較例で得られた水不溶性高分子ビルダーを試験用高分子ビルダーとして、下記の方法で洗浄性試験を行った。
＜洗浄試験＞
泥汚染布は特開平１０−２０４７６９記載の製法により、木綿メリヤスに鹿沼赤玉土を付着させることにより調製した。
表１に示す組成の試験液を１００ｍＬ調製し、これに直径が１５μｍのスチール球１５個、木綿メリヤス白布（６×６ｃｍ）５枚、泥汚染布（４×５ｃｍ）５枚を添加後、１５分間撹拌した。水温は２０℃とした。撹拌終了後、白布、泥汚染布を取出し、脱水、乾燥後、白布の反射率、及び汚染布の反射率を測定し（日本電色工業(株)製分光色差計、型番「ＳＥ２０００」）、汚染布の反射率の平均値を洗浄率、白布の反射率の平均値を再付着防止率とした。結果を表２に示す。なお、前記試験液の硬度成分は塩化カルシウム二水和物／塩化マグネシウム六水和物＝８／２（ｍｏｌ比）であり、硬度は４［°ｄＨ］とした。
The water-insoluble polymer builder obtained in Examples and Comparative Examples was used as a test polymer builder, and a detergency test was performed by the following method.
<Cleaning test>
The mud-contaminated cloth was prepared by adhering Kanuma Akadama to cotton knitted fabric according to the method described in JP-A-10-204769.
100 mL of a test solution having the composition shown in Table 1 was prepared. After adding 15 steel balls having a diameter of 15 μm, 5 cotton knitted white cloths (6 × 6 cm), and 5 mud-contaminated cloths (4 × 5 cm), 15 Stir for minutes. The water temperature was 20 ° C. After stirring, take out the white cloth and mud-contaminated cloth, and after dehydration and drying, measure the reflectance of the white cloth and the reflectance of the contaminated cloth (Nippon Denshoku Co., Ltd. spectrophotometric color difference meter, model number "SE2000"), The average value of the reflectance of the contaminated fabric was defined as the cleaning rate, and the average value of the reflectance of the white fabric was defined as the reattachment prevention rate. The results are shown in Table 2. The hardness component of the test solution was calcium chloride dihydrate / magnesium chloride hexahydrate = 8/2 (mol ratio), and the hardness was 4 [° dH].
実施例１と比較例１との対比から、本発明の水不溶性高分子ビルダーは再汚染防止性に優れていることが分かった。また、実施例２により、カチオン性モノマーとの共重合体である水不溶性高分子ビルダーも、水に対する膨潤度が高く、衣料用の高分子ビルダーとして再汚染防止性能に優れていることが分る。 From the comparison between Example 1 and Comparative Example 1, it was found that the water-insoluble polymer builder of the present invention was excellent in recontamination preventing property. In addition, Example 2 shows that the water-insoluble polymer builder, which is a copolymer with a cationic monomer, also has a high degree of swelling with respect to water and is excellent in anti-recontamination performance as a polymer builder for clothing. .
実施例３〜５
水除去工程において表３に示す脱水率になるまで脱水を行ったこと以外は、実施例１と同様に水不溶性高分子ビルダーを製造した。各水不溶性高分子ビルダーの物性を表３に示す。
Examples 3-5
A water-insoluble polymer builder was produced in the same manner as in Example 1 except that dehydration was performed until the dehydration rate shown in Table 3 was reached in the water removal step. Table 3 shows the physical properties of each water-insoluble polymer builder.
実施例３〜５により得られた水不溶性高分子ビルダーについて、以下の方法により泥捕捉率を測定した。
＜泥捕捉率の測定方法＞
５０ｍｌスクリュー管（（株）マルエム製）に表４に記載の泥溶液を約４０ｍｌ入れ、この泥試験液中に分散している泥の濃度（Ｔ1）を下記方法で測定した。
更に前記泥試験液に対して実施例３〜５の水不溶性高分子ビルダーをそれぞれ泥試験液の濃度が２０ｍｇ／ｋｇになるように添加した。このスクリュー管に３０ｍｍスターラーチップを投入し、５００ｒ／ｍで１５分間撹拌した。
次いで、泥試験液を孔径１０μｍポリカーボネート製フィルターに通すことにより固液分離を行い、ろ液中に分散している泥の濃度（Ｔ2）を測定した。
なお、前記泥試験液の硬度成分は塩化カルシウム二水和物／塩化マグネシウム六水和物＝８／２（ｍｏｌ比）であり、硬度は４［°ｄＨ］とした。
＜泥濃度の測定方法＞
分散している泥の濃度は、(株)日立製作所製分光光度計、型番「Ｕ―３３００」を用いて５７５ｎｍの吸光度を測定して算出した。検量線は、表４に記載の試験液の泥分散濃度を変えて５７５ｎｍの吸光度より作成した。
泥捕捉率は下記計算式にしたがって算出した。
泥捕捉率（％）＝（１−Ｔ2／Ｔ1）×１００
About the water-insoluble polymer builder obtained by Examples 3-5, the mud capture rate was measured with the following method.
<Measurement method of mud catch rate>
About 40 ml of the mud solution described in Table 4 was put into a 50 ml screw tube (manufactured by Marum Co., Ltd.), and the concentration (T 1 ) of mud dispersed in this mud test solution was measured by the following method.
Further, the water-insoluble polymer builders of Examples 3 to 5 were added to the mud test solution so that the concentration of the mud test solution was 20 mg / kg. A 30 mm stirrer tip was put into this screw tube and stirred at 500 r / m for 15 minutes.
Next, solid-liquid separation was performed by passing the mud test liquid through a polycarbonate filter having a pore size of 10 μm, and the concentration (T 2 ) of mud dispersed in the filtrate was measured.
The hardness component of the mud test solution was calcium chloride dihydrate / magnesium chloride hexahydrate = 8/2 (mol ratio), and the hardness was 4 [° dH].
<Measurement method of mud concentration>
The concentration of the dispersed mud was calculated by measuring the absorbance at 575 nm using a spectrophotometer manufactured by Hitachi, Ltd., model number “U-3300”. The calibration curve was prepared from the absorbance at 575 nm by changing the mud dispersion concentration of the test solution described in Table 4.
The mud trapping rate was calculated according to the following formula.
Mud capture rate (%) = (1−T 2 / T 1 ) × 100
上記実施例３〜５の結果より、膨潤度が高いほど泥捕捉性が高いことが分かる。 From the results of Examples 3 to 5, it can be seen that the higher the degree of swelling, the higher the mud trapping property.
Claims (13)
水不溶性高分子ビルダーを構成する全モノマー中の有機カルボン酸モノマー（ａ）の量は３５〜６０質量％であり、
水不溶性高分子ビルダーを構成する全モノマー中の架橋性モノマー（ｂ）の量は０．０１〜１質量％であり、
水不溶性高分子ビルダーを構成する全モノマー中のアニオン性モノマー（ｃ）、カチオン性モノマー（ｄ）、両性モノマー（ｅ）、及びノニオン性モノマー（ｆ）よりなる群から選択されるモノマーの含有量が４０〜６０質量％であり、
乾燥時の体積平均粒子径（ｄ１）と水による膨潤時の体積平均粒子径（ｄ２）との比（ｄ２／ｄ１）が５〜１００である、水不溶性高分子ビルダーの製造方法。
工程１：有機カルボン酸モノマー（ａ）と、架橋性モノマー（ｂ）と、有機カルボン酸モノマー（ａ）を除くアニオン性モノマー（ｃ）、カチオン性モノマー（ｄ）、両性モノマー（ｅ）、及びノニオン性モノマー（ｆ）よりなる群から選択される１種又は２種以上のモノマーと、重合開始剤とを含む水性混合液を調製する工程
工程２：工程１で得られた水性混合液を疎水性溶媒（Ａ）に分散させて分散液（ａ）を調製する工程
工程３：温度が５０℃以上沸点以下である疎水性溶媒（Ｂ）に、前記工程２で得られた分散液（ａ）を滴下して重合を行う工程 A method for producing a water-insoluble polymer builder comprising the following steps 1 to 3 ,
The amount of the organic carboxylic acid monomer (a) in all monomers constituting the water-insoluble polymer builder is 35 to 60% by mass,
The amount of the crosslinkable monomer (b) in all monomers constituting the water-insoluble polymer builder is 0.01 to 1% by mass,
Content of monomer selected from the group consisting of anionic monomer (c), cationic monomer (d), amphoteric monomer (e), and nonionic monomer (f) in all monomers constituting the water-insoluble polymer builder Is 40-60 mass%,
A method for producing a water-insoluble polymer builder, wherein a ratio (d2 / d1) of a volume average particle diameter (d1) during drying to a volume average particle diameter (d2) during swelling with water is 5 to 100 .
Step 1: an organic carboxylic acid monomer (a), the crosslinking monomer (b), the anionic monomer excluding the organic carboxylic acid monomer (a) (c), cationic monomer (d), amphoteric monomer (e), and and one or more monomers selected from the group consisting of nonionic monomer (f), the step step 2 of preparing an aqueous mixture containing a heavy initiator: aqueous mixture obtained in the step 1 Step 3 for preparing the dispersion liquid (a) by dispersing in the hydrophobic solvent (A): The dispersion liquid (a) obtained in Step 2 above is added to the hydrophobic solvent (B) having a temperature of 50 ° C. or higher and a boiling point or lower. ) Is added dropwise to perform polymerization
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