JP6247093B2 - Method for suppressing adhesion of solid particles to hydrophilic hard material - Google Patents
Method for suppressing adhesion of solid particles to hydrophilic hard material Download PDFInfo
- Publication number
- JP6247093B2 JP6247093B2 JP2013270438A JP2013270438A JP6247093B2 JP 6247093 B2 JP6247093 B2 JP 6247093B2 JP 2013270438 A JP2013270438 A JP 2013270438A JP 2013270438 A JP2013270438 A JP 2013270438A JP 6247093 B2 JP6247093 B2 JP 6247093B2
- Authority
- JP
- Japan
- Prior art keywords
- hard material
- less
- solid particles
- hydrophilic hard
- adhesion
- 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.)
- Active
Links
- 239000002245 particle Substances 0.000 title claims description 59
- 239000000463 material Substances 0.000 title claims description 47
- 239000007787 solid Substances 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229920006317 cationic polymer Polymers 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 125000002091 cationic group Chemical group 0.000 claims description 13
- 230000003068 static effect Effects 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims 1
- -1 alkali metal salt Chemical class 0.000 description 16
- 239000000178 monomer Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- 229920006318 anionic polymer Polymers 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000021186 dishes Nutrition 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000019503 curry powder Nutrition 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 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
- 238000000691 measurement method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- CNMOBBVPWQZHRP-UHFFFAOYSA-N (3-bromo-2-hydroxypropyl)-triethylazanium Chemical compound CC[N+](CC)(CC)CC(O)CBr CNMOBBVPWQZHRP-UHFFFAOYSA-N 0.000 description 1
- WZRGAJKOIRJGHX-UHFFFAOYSA-N (3-bromo-2-hydroxypropyl)-trimethylazanium Chemical compound C[N+](C)(C)CC(O)CBr WZRGAJKOIRJGHX-UHFFFAOYSA-N 0.000 description 1
- BDJKOPKKCLQDEQ-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-triethylazanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC(O)CCl BDJKOPKKCLQDEQ-UHFFFAOYSA-M 0.000 description 1
- XIUCEANTZSXBQQ-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl)-trimethylazanium Chemical compound C[N+](C)(C)CC(O)CCl XIUCEANTZSXBQQ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 1
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- HDFYUONVRIMVSN-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(CCN)N Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(CCN)N HDFYUONVRIMVSN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 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
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 244000269722 Thea sinensis Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 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 1
- 230000001133 acceleration Effects 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 150000001649 bromium compounds Chemical class 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- WZAPMUSQALINQD-UHFFFAOYSA-M potassium;ethenyl sulfate Chemical compound [K+].[O-]S(=O)(=O)OC=C WZAPMUSQALINQD-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 235000019419 proteases Nutrition 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- UDDGCPMRVYLGCU-UHFFFAOYSA-N triethyl(oxiran-2-ylmethyl)azanium Chemical compound CC[N+](CC)(CC)CC1CO1 UDDGCPMRVYLGCU-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
Description
本発明は、親水性硬質材料への固体粒子の付着抑制方法に関する。 The present invention relates to a method for suppressing adhesion of solid particles to a hydrophilic hard material.
自動食器洗浄機は、手洗いに比べて少量の洗浄水で洗浄することができ、また、家事の負担を軽減することができるため広く普及しており、これに伴って自動食器洗浄機用洗浄剤組成物の開発も盛んに行われている。したがって、洗浄力に優れた自動食器洗浄機用洗浄剤組成物が多く市販されており、これらを用いることにより、食器に付着した汚れを容易に洗浄することができる。
しかしながら、自動食器洗浄機を用いた洗浄においては、一度洗浄された汚れが再度食器に付着する、汚れの再付着の問題があり、この問題を解消するための自動食器洗浄機用洗浄剤組成物が提案されている。
例えば、特許文献1には、(a)炭素数が8〜22である脂肪酸と多価アルコールとのエステル、(b)漂白活性化剤を含有し、特定のpHを示す自動食器洗浄機用洗浄剤組成物が提案されている。
また、特許文献2には、(A)トリポリリン酸カリウム、(B)トリポリリン酸ナトリウム、(C)ケイ酸カリウム、及び(D)次亜塩素酸アルカリ金属塩を含有すると共に、水を含有する自動洗浄機用液体洗浄剤組成物が提案されている。
Automatic dishwashers are widely used because they can be washed with a small amount of washing water compared to hand washing, and can reduce the burden of housework. Development of the composition is also actively performed. Therefore, many cleaning compositions for automatic dishwashers having excellent detergency are commercially available, and by using these, it is possible to easily clean dirt adhered to tableware.
However, in washing using an automatic dishwasher, there is a problem of reattachment of dirt, in which dirt once washed again adheres to the dish, and a cleaning composition for an automatic dishwasher to solve this problem Has been proposed.
For example, Patent Document 1 discloses (a) an ester of a fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol, and (b) a washing agent for automatic dishwashing that contains a bleach activator and exhibits a specific pH. Agent compositions have been proposed.
In addition, Patent Document 2 includes (A) potassium tripolyphosphate, (B) sodium tripolyphosphate, (C) potassium silicate, and (D) an alkali metal salt of hypochlorite and water. Liquid cleaning compositions for cleaning machines have been proposed.
特許文献1、2に記載された自動洗浄機用洗浄剤組成物によれば、固体粒子からなる汚れの再付着をある程度抑制することができるものの、更なる改善が望まれている。
そこで、本発明者らが汚れの再付着を抑制する技術について検討を行ったところ、汚れの再付着の要因が以下に記載のとおりであることを知見した。
一般に家庭の自動食器洗浄機で洗浄される食器の材質は、ポリプロピレン、ポリエチレンなどから構成される疎水性硬質材料と、ガラス、陶器などで構成される親水性硬質材料に大別される。また、食器に付着する洗浄対象の汚れとしては、糖質、無機物などに代表される水溶性汚れと、その他の水不溶性の汚れが挙げられる。水溶性の汚れは、自動食器洗浄機での洗浄時に溶解又は分散しやすい性質を有しており、洗浄後に残留することは稀である。これに対して、水不溶性の汚れは粒子汚れとして洗浄時の槽内に存在し、一旦食器から除去された後、再び他の食器に付着残留しやすい性質を有する。特に、洗浄水、すすぎ水が当たりにくい場所に置かれた食器には、槽内に存在する粒子汚れが少量であったとしても再付着してしまい、すすぎ工程を経た後も除去されなかった粒子汚れが食器に残留する場合がある。
水不溶性汚れを更に分類すると、油などの疎水性汚れと、茶葉、スパイスなどの親水性汚れが挙げられる。疎水性汚れは疎水性硬質材料に吸着残留しやすい性質を有するが、自動食器洗浄機用洗浄剤に含まれる界面活性剤の乳化力により除去することが可能である。一方、親水性汚れは親水性硬質材料との親和性が高く、固体粒子として残留しやすいため汚れの再付着の問題が生じる。
According to the cleaning composition for an automatic cleaning machine described in Patent Documents 1 and 2, further improvement is desired, although it is possible to suppress the reattachment of dirt composed of solid particles to some extent.
Then, when the present inventors examined the technique which suppresses the reattachment of dirt, it discovered that the factor of the reattachment of dirt was as follows.
In general, the materials of tableware to be washed by an automatic dishwasher at home are roughly classified into a hydrophobic hard material composed of polypropylene, polyethylene and the like, and a hydrophilic hard material composed of glass, ceramics and the like. In addition, examples of dirt to be cleaned that adheres to tableware include water-soluble dirt typified by carbohydrates and inorganic substances, and other water-insoluble dirt. Water-soluble soil has a property of easily dissolving or dispersing during washing in an automatic dishwasher, and rarely remains after washing. On the other hand, water-insoluble dirt exists in the tank at the time of washing as particle dirt, and once removed from the tableware, it has a property of easily remaining on other tableware. In particular, in dishes placed in places where washing water and rinsing water are difficult to hit, even if a small amount of particle dirt is present in the tank, it will reattach, and particles that have not been removed after the rinsing process. Dirt may remain on the dishes.
Water-insoluble stains can be further classified into hydrophobic stains such as oil and hydrophilic stains such as tea leaves and spices. Hydrophobic soil has the property of easily adsorbing and remaining on the hydrophobic hard material, but can be removed by the emulsifying power of the surfactant contained in the detergent for automatic dishwashers. On the other hand, hydrophilic dirt has a high affinity with the hydrophilic hard material and tends to remain as solid particles, thus causing the problem of redeposition of dirt.
そこで本発明者らが、親水性硬質材料に対する固体粒子の付着抑制方法について更に検討を重ねた結果、自動食器洗浄機の洗浄水中に含まれる固体粒子のうち、平均粒子径が50μm以上、1,000μm以下である固体粒子が食器に対して付着残留しやすいことを知見した。そして、前記平均粒子径を有する固体粒子に対しては、前記特定のカチオン性ポリマーの水溶液を接触させることにより、親水性硬質材料への固体粒子の付着を抑制できることを見出した。 Therefore, as a result of further investigations on the method for suppressing the adhesion of solid particles to the hydrophilic hard material, the present inventors have determined that the average particle diameter of the solid particles contained in the washing water of the automatic dishwasher is 50 μm or more, 1, It was found that solid particles having a size of 000 μm or less are likely to remain attached to tableware. And it discovered that adhesion of the solid particle to a hydrophilic hard material can be suppressed by making the aqueous solution of the said specific cationic polymer contact the solid particle which has the said average particle diameter.
本発明は、食器等の親水性硬質材料の表面に対して、平均粒子径が50μm以上、1,000μm以下である固体粒子の付着を抑制することができる、親水性硬質材料への固体粒子の付着抑制方法を提供する。 The present invention can suppress the adhesion of solid particles having an average particle diameter of 50 μm or more and 1,000 μm or less to the surface of a hydrophilic hard material such as tableware, and the like. An adhesion suppression method is provided.
すなわち、本発明の要旨は以下のとおりである。
親水性硬質材料の表面に対して平均粒子径が50μm以上、1,000μm以下である固体粒子が付着することを抑制する方法であり、下記一般式(a−1)〜(a−5)から選ばれる1種又は2種以上のカチオン性基を有し、カチオン化度が0.25mol%以上、5.0mol%以下であるカチオン性ポリマーの水溶液を前記親水性硬質材料の表面に接触させる、親水性硬質材料への固体粒子の付着抑制方法。
That is, the gist of the present invention is as follows.
This is a method for suppressing the adhesion of solid particles having an average particle size of 50 μm or more and 1,000 μm or less to the surface of the hydrophilic hard material. From the following general formulas (a-1) to (a-5) Contacting the surface of the hydrophilic hard material with an aqueous solution of a cationic polymer having one or two or more selected cationic groups and having a degree of cationization of 0.25 mol% or more and 5.0 mol% or less, A method for suppressing adhesion of solid particles to a hydrophilic hard material.
本発明によれば、食器等の親水性硬質材料の表面に対して、平均粒子径が50μm以上、1,000μm以下である固体粒子の付着を抑制することができる親水性硬質材料への固体粒子の付着抑制方法を提供することができる。 According to the present invention, solid particles on a hydrophilic hard material that can suppress adhesion of solid particles having an average particle size of 50 μm or more and 1,000 μm or less to the surface of a hydrophilic hard material such as tableware. Can be provided.
[親水性硬質材料への固体粒子の付着抑制方法]
本発明の親水性硬質材料への固体粒子の付着抑制方法は、親水性硬質材料の表面に対して平均粒子径が50μm以上、1,000μm以下である固体粒子が付着することを抑制する方法であり、前記一般式(a−1)〜(a−5)から選ばれる1種又は2種以上のカチオン性基を有し、カチオン化度が0.25mol%以上、5.0mol%以下であるカチオン性ポリマーの水溶液を前記親水性硬質材料の表面に接触させるものである。
なお、本明細書において、固体粒子の平均粒子径は、株式会社堀場製作所製レーザー解析式粒径測定装置「LA−950」を用いて測定した値をいう。
また、本発明において、「親水性硬質材料」とは水の静止接触角が20°以下の条件を満たす硬質材料であり、親水性硬質材料としては、陶器、ガラスを挙げることができる。
[Method of suppressing adhesion of solid particles to hydrophilic hard material]
The method for suppressing the adhesion of solid particles to the hydrophilic hard material of the present invention is a method for suppressing the adhesion of solid particles having an average particle diameter of 50 μm or more and 1,000 μm or less to the surface of the hydrophilic hard material. Yes, having one or two or more cationic groups selected from the general formulas (a-1) to (a-5), and having a degree of cationization of 0.25 mol% or more and 5.0 mol% or less. An aqueous solution of a cationic polymer is brought into contact with the surface of the hydrophilic hard material.
In addition, in this specification, the average particle diameter of a solid particle means the value measured using Horiba Ltd. laser analysis type particle size measuring apparatus "LA-950".
In the present invention, the “hydrophilic hard material” is a hard material that satisfies the condition that the static contact angle of water is 20 ° or less, and examples of the hydrophilic hard material include pottery and glass.
<(a)成分>
前記(a)成分は、下記一般式(a−1)〜(a−5)から選ばれる1種又は2種以上のカチオン性基を有し、カチオン化度が0.25mol%以上、5mol%以下であるカチオン性ポリマーである。
<(A) component>
The component (a) has one or more cationic groups selected from the following general formulas (a-1) to (a-5), and has a degree of cationization of 0.25 mol% or more and 5 mol%. The following is a cationic polymer.
R1〜R14は、炭素数1以上、6以下のアルキル基であり、該アルキル基の炭素数は、固体粒子の付着を抑制する観点から、好ましくは1以上であり、そして、好ましくは4以下、より好ましくは3以下、更に好ましくは2以下である。
具体的なアルキル基としては、メチル基、エチル基、プロピル基、各種ブチル基、各種ペンチル基、及び各種ヘキシル基が挙げられ、これらの中でもメチル基が好ましい。なお、前記「各種」とは、n−、sec−、tert−、iso−を含む各種異性体を意味する。
R 1 to R 14 are each an alkyl group having 1 to 6 carbon atoms, and the carbon number of the alkyl group is preferably 1 or more from the viewpoint of suppressing adhesion of solid particles, and preferably 4 Below, more preferably 3 or less, and still more preferably 2 or less.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, various butyl groups, various pentyl groups, and various hexyl groups. Among these, a methyl group is preferable. The “various” means various isomers including n-, sec-, tert-, and iso-.
Z-は、陰イオンであり、陰イオンとしては、ヒドロキシイオン;塩化物イオン、臭化物イオン又はヨウ化物イオン等のハロゲン化物イオン;酢酸イオン、プロピオン酸イオン、又は酪酸イオン等の炭素数2以上、4以下の低級脂肪酸イオン;メチル硫酸イオン、エチル硫酸イオン等の炭素数1以上、3以下の低級アルキル硫酸イオン等が挙げられる。これらの中でも、固体粒子の付着を抑制する観点から、ヒドロキシイオン及びハロゲン化物イオンが好ましく、ヒドロキシイオン、塩化物イオン及び臭化物イオンがより好ましく、塩化物イオンが更に好ましい。 Z − is an anion, and the anion includes a hydroxy ion; a halide ion such as a chloride ion, a bromide ion, or an iodide ion; and two or more carbon atoms such as an acetate ion, a propionate ion, or a butyrate ion, Lower fatty acid ions of 4 or less; lower alkyl sulfate ions of 1 to 3 carbon atoms such as methyl sulfate ion and ethyl sulfate ion. Among these, from the viewpoint of suppressing adhesion of solid particles, hydroxy ions and halide ions are preferable, hydroxy ions, chloride ions and bromide ions are more preferable, and chloride ions are still more preferable.
mは、1以上10以下の整数を示す。mが1以上10以下であれば、洗浄性能が向上する。mは、洗浄性能の観点から、好ましくは2以上であり、そして、好ましくは8以下、より好ましくは6以下、更に好ましくは4以下、より更に好ましくは3以下である。
nは、0以上10以下の整数を示す。nが0以上10以下であれば、洗浄性能が向上する。nは、洗浄性能の観点から、好ましくは1以上、より好ましくは2以上であり、そして、好ましくは8以下、より好ましくは6以下、更に好ましくは4以下、より更に好ましくは3以下である。
m represents an integer of 1 or more and 10 or less. When m is 1 or more and 10 or less, the cleaning performance is improved. From the viewpoint of cleaning performance, m is preferably 2 or more, and is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and even more preferably 3 or less.
n represents an integer of 0 or more and 10 or less. If n is 0 or more and 10 or less, the cleaning performance is improved. From the viewpoint of cleaning performance, n is preferably 1 or more, more preferably 2 or more, and is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and even more preferably 3 or less.
前記一般式(a−1)〜(a−5)で表されるカチオン性基を有するカチオン性ポリマーは、例えば、前記カチオン性基を有するモノマーと重合性モノマーとを重合させることにより得ることができる。
前記重合性モノマーとしては、例えば、プロピレン、1−ブテン、1−ペンテン、1−ヘキセン等のオレフィン類、スチレン、p−メチルスチレン等のスチレン類、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステル誘導体類、酢酸ビニル、酢酸イソプロペニル等の脂肪酸ビニル類等が挙げられる。
また、ヒドロキシエチルセルロース、及び可溶性澱粉等の半合成水溶性高分子に対して前記カチオン性基を有する化合物を反応させることにより製造することもできる。
本発明においては、汚れの再付着性能を向上させる観点、及び入手容易性の観点から、酢酸ビニルと前記カチオン性基を有するモノマーとを重合して製造したカチオン変性ポリビニルアルコール、及びヒドロキシエチルセルロースと前記カチオン性基を有する化合物とを反応させたカチオン変性ヒドロキシルエチルセルロースが好ましい。
The cationic polymer having a cationic group represented by the general formulas (a-1) to (a-5) can be obtained, for example, by polymerizing a monomer having the cationic group and a polymerizable monomer. it can.
Examples of the polymerizable monomer include olefins such as propylene, 1-butene, 1-pentene and 1-hexene, styrenes such as styrene and p-methylstyrene, and acrylic esters such as ethyl acrylate and butyl acrylate. Derivatives, fatty acid vinyls such as vinyl acetate and isopropenyl acetate, and the like.
Moreover, it can also manufacture by making the compound which has the said cationic group react with semisynthetic water-soluble polymers, such as hydroxyethyl cellulose and soluble starch.
In the present invention, from the viewpoint of improving the reattachment performance of soil, and from the viewpoint of availability, cationically modified polyvinyl alcohol produced by polymerizing vinyl acetate and the monomer having the cationic group, hydroxyethyl cellulose, and the above A cation-modified hydroxyl ethyl cellulose obtained by reacting a compound having a cationic group is preferred.
(カチオン変性ポリビニルアルコール)
カチオン変性ポリビニルアルコールは、前記カチオン性基を主鎖あるいは側鎖に有するポリビニルアルコールのことである。前記カチオン変性ポリビニルアルコールは、原料の酢酸ビニルを重合する際に、ジアリルジメチルアンモニウムクロリド、(3−アクリルアミドプロピル)トリメチルアンモニウムクロリド等と酢酸ビニルとを共重合し、得られたコポリマーを常法によりケン化することにより得られる。
また、酢酸ビニルと他の反応性基を有するモノマーとを共重合しておき、ケン化後前記反応性基を利用して、前記カチオン性基を含有する化合物を反応させてポリビニルアルコールをカチオン化してもよい。
(Cation-modified polyvinyl alcohol)
Cationic modified polyvinyl alcohol is polyvinyl alcohol having the cationic group in the main chain or side chain. The cation-modified polyvinyl alcohol is obtained by copolymerizing diallyldimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, and the like with vinyl acetate when polymerizing the raw material vinyl acetate. Can be obtained.
In addition, vinyl acetate is copolymerized with a monomer having another reactive group, and after saponification, the reactive group is used to react with the compound containing the cationic group to cationize polyvinyl alcohol. May be.
(カチオン変性ヒドロキシエチルセルロース)
カチオン変性ヒドロキシルエチルセルロースは、例えば、原料セルロースとエチレンオキシドとを反応させてヒドロキシエチルセルロースを得た後、このヒドロキシエチルセルロースをカチオン化剤と反応させてカチオン化する方法により得ることができる。
(Cation-modified hydroxyethyl cellulose)
The cation-modified hydroxyl ethyl cellulose can be obtained, for example, by a method in which raw material cellulose and ethylene oxide are reacted to obtain hydroxyethyl cellulose, and then this hydroxyethyl cellulose is reacted with a cationizing agent to be cationized.
原料セルロースとして用いられるセルロースとしては、化学的に純粋なセルロースの他、各種木材チップ等の木材類;木材から製造される木材パルプ等のパルプ類;新聞紙、段ボール等の紙類;稲わら、とうもろこし茎等の植物茎・葉類;籾殻、パーム殻、ココナッツ殻等の植物殻類等、種々のセルロース含有原料を用いることができる。 Cellulose used as raw material cellulose includes chemically pure cellulose, wood such as various wood chips; pulps such as wood pulp produced from wood; papers such as newspaper and cardboard; rice straw and corn Various cellulose-containing raw materials such as plant stems and leaves such as stems; plant shells such as rice husks, palm shells, and coconut shells can be used.
カチオン化剤としては、入手性の観点から、グリシジルトリメチルアンモニウム又はグリシジルトリエチルアンモニウムの塩化物又は臭化物、3−クロロ−2−ヒドロキシプロピルトリメチルアンモニウム、3−クロロ−2−ヒドロキシプロピルトリエチルアンモニウム等の塩化物、3−ブロモ−2−ヒドロキシプロピルトリメチルアンモニウム、3−ブロモ−2−ヒドロキシプロピルトリエチルアンモニウム等の臭化物が好ましく、グリシジルトリメチルアンモニウム塩化物又は3−クロロ−2−ヒドロキシプロピルトリメチルアンモニウム塩化物がより好ましく、3−クロロ−2−ヒドロキシプロピルトリメチルアンモニウム塩化物が更に好ましい。これらのカチオン化剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。 As a cationizing agent, from the viewpoint of availability, chlorides or bromides of glycidyltrimethylammonium or glycidyltriethylammonium, chlorides such as 3-chloro-2-hydroxypropyltrimethylammonium and 3-chloro-2-hydroxypropyltriethylammonium Bromide such as 3-bromo-2-hydroxypropyltrimethylammonium and 3-bromo-2-hydroxypropyltriethylammonium, glycidyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride is more preferable, More preferred is 3-chloro-2-hydroxypropyltrimethylammonium chloride. These cationizing agents may be used alone or in combination of two or more.
カチオン性ポリマーのカチオン化度は、汚れの再付着を抑制する観点から、0.25mol%以上、好ましくは0.35mol%以上、より好ましくは0.45mol%以上、更に好ましくは0.6mol%以上、より更に好ましくは0.8mol%以上、より更に好ましくは1.0mol%以上であり、そして、食器に対してポリマーを均一に吸着させ、汚れの再付着を抑制する観点から、5mol%以下、好ましくは4mol%以下、より好ましくは3mol%以下、更に好ましくは2mol%以下である。
なお、カチオン化度は、ポリビニル硫酸カリウム(PVSK)を用いたコロイド滴定により求めることができる。
The degree of cationization of the cationic polymer is 0.25 mol% or more, preferably 0.35 mol% or more, more preferably 0.45 mol% or more, further preferably 0.6 mol% or more, from the viewpoint of suppressing the reattachment of dirt. More preferably 0.8 mol% or more, still more preferably 1.0 mol% or more, and 5 mol% or less from the viewpoint of uniformly adsorbing the polymer to the tableware and suppressing the reattachment of dirt, Preferably it is 4 mol% or less, More preferably, it is 3 mol% or less, More preferably, it is 2 mol% or less.
The degree of cationization can be determined by colloid titration using potassium polyvinyl sulfate (PVSK).
カチオン性ポリマーの平均分子量は、洗浄性を向上させる観点から、好ましくは10,000Da以上、より好ましくは30,000Da以上、更に好ましくは50,000Da以上、より更に好ましくは70,000Da以上であり、そして、汚れの再付着を抑制する観点から、好ましくは2,000,000Da以下、より好ましくは1,500,000Da以下、更に好ましくは1,000,000Da以下、より更に好ましくは800,000Da以下である。
なお、カチオン性ポリマーの平均分子量は、ゲルパーミテーションクロマトグラフィーでポリスチレンを標準物質として求めることができる。
The average molecular weight of the cationic polymer is preferably 10,000 Da or more, more preferably 30,000 Da or more, still more preferably 50,000 Da or more, and even more preferably 70,000 Da or more, from the viewpoint of improving detergency. From the viewpoint of suppressing the reattachment of dirt, it is preferably 2,000,000 Da or less, more preferably 1,500,000 Da or less, still more preferably 1,000,000 Da or less, and still more preferably 800,000 Da or less. is there.
The average molecular weight of the cationic polymer can be determined by gel permeation chromatography using polystyrene as a standard substance.
カチオン性ポリマーの水溶液の濃度は、固体粒子の付着を抑制する観点から、好ましくは1ppm以上、好ましくは10ppm以上、より好ましくは20ppm以上、更により好ましくは50ppm以上、更に好ましくは100ppm以上である。そして、洗浄性能とコスト増加とのバランスの観点から、好ましくは1,000ppm以下、より好ましくは900ppm以下、更に好ましくは850ppm以下である。
カチオン性ポリマーの水溶液を構成する水としては、水道水、蒸留水、又は脱イオン水を用いることができる。これらの中でも、蒸留水又は脱イオン水が好ましい。
The concentration of the aqueous solution of the cationic polymer is preferably 1 ppm or more, preferably 10 ppm or more, more preferably 20 ppm or more, still more preferably 50 ppm or more, and still more preferably 100 ppm or more, from the viewpoint of suppressing the adhesion of solid particles. And from a viewpoint of the balance of washing | cleaning performance and cost increase, Preferably it is 1,000 ppm or less, More preferably, it is 900 ppm or less, More preferably, it is 850 ppm or less.
As the water constituting the aqueous solution of the cationic polymer, tap water, distilled water, or deionized water can be used. Among these, distilled water or deionized water is preferable.
本発明において、カチオン性ポリマーの水溶液と親水性硬質材料とを接触させる方法に制限はないが、例えば、カチオン性ポリマーの水溶液に親水性硬質材料を浸漬させる方法、カチオン性ポリマーの水溶液を親水性硬質材料に対して噴霧する方法等を挙げることができる。また、カチオン性ポリマーの水溶液を自動食器洗浄機の洗浄剤として投入し、親水性硬質材料を洗浄することにより接触させてもよい。 In the present invention, there is no limitation on the method of bringing the aqueous solution of the cationic polymer into contact with the hydrophilic hard material. For example, the method of immersing the hydrophilic hard material in the aqueous solution of the cationic polymer, the aqueous solution of the cationic polymer being hydrophilic. The method etc. which spray with respect to a hard material can be mentioned. Alternatively, an aqueous solution of a cationic polymer may be introduced as a cleaning agent for an automatic dishwasher, and contact may be made by cleaning the hydrophilic hard material.
<水の静的接触角、及び水の後退接触角>
本発明の方法によれば、通常20°以下である親水性硬質材料表面の水の静的接触角を40°以上に変化させることができる。また、親水性硬質材料表面の水の後退接触角を10°以上に変化させることができる。
本発明においては、特定構造のカチオン性ポリマーが親水性硬質材料表面に吸着し、その吸着状態の特徴により、効果が発現すると推定される。静的接触角及び後退接触角が前記範囲以上であると、固体粒子の付着を抑制することができる。
前記水の静的接触角は、好ましくは45°以上、より好ましくは50°以上、更に好ましくは55°以上であり、そして、好ましくは80°以下である。水の静的接触角が前記範囲内であれば、親水性硬質材料の表面が疎水化され、固体の粒子径よりも大きい水滴が付着するようになり、当該水滴と共に固体粒子が除去されやすくなると推定している。また、水の静的接触角の処理前からの変化量は、好ましくは10°以上、より好ましくは20°以上、更に好ましくは30°以上である。
後退接触角は、好ましくは13°以上、より好ましくは16°以上、更に好ましくは19°以上であり、そして、好ましくは80°以下である。水の後退接触角が前記範囲内であれば、被処理面に付着した水滴が垂直面等を移動する際に、水滴の末端が薄膜化しにくくなり、水滴中に固体粒子が包含されるようになるため、水滴と共に固体粒子が親水性硬質材料の表面から除去されると推定される。
なお、静的接触角及び後退接触角は、実施例に記載の方法により測定することができる。
<Static contact angle of water and receding contact angle of water>
According to the method of the present invention, the static contact angle of water on the hydrophilic hard material surface, which is usually 20 ° or less, can be changed to 40 ° or more. Moreover, the receding contact angle of water on the surface of the hydrophilic hard material can be changed to 10 ° or more.
In the present invention, it is presumed that a cationic polymer having a specific structure is adsorbed on the surface of the hydrophilic hard material, and the effect is exhibited by the characteristics of the adsorbed state. When the static contact angle and the receding contact angle are equal to or greater than the above range, the adhesion of solid particles can be suppressed.
The static contact angle of water is preferably 45 ° or more, more preferably 50 ° or more, still more preferably 55 ° or more, and preferably 80 ° or less. If the static contact angle of water is within the above range, the surface of the hydrophilic hard material is hydrophobized, and water droplets larger than the particle size of the solid are attached, and solid particles are easily removed together with the water droplets. Estimated. Moreover, the amount of change of the static contact angle of water from before the treatment is preferably 10 ° or more, more preferably 20 ° or more, and further preferably 30 ° or more.
The receding contact angle is preferably 13 ° or more, more preferably 16 ° or more, still more preferably 19 ° or more, and preferably 80 ° or less. If the receding contact angle of water is within the above range, when the water droplets adhering to the surface to be treated move on a vertical surface or the like, it becomes difficult for the ends of the water droplets to become thin, and solid particles are included in the water droplets. Therefore, it is presumed that solid particles are removed from the surface of the hydrophilic hard material together with water droplets.
The static contact angle and the receding contact angle can be measured by the methods described in the examples.
<pH>
カチオン性ポリマーの水溶液の20℃におけるpHは、固体粒子の付着を抑制する観点から、好ましくは6.5以上、より好ましくは7以上であり、そして、カチオン性ポリマーの水溶液の取り扱い性の観点から、好ましくは8.6以下、より好ましくは8.2以下、更に好ましくは7.8以下である。
<PH>
The pH of the aqueous solution of the cationic polymer at 20 ° C. is preferably 6.5 or more, more preferably 7 or more from the viewpoint of suppressing adhesion of solid particles, and from the viewpoint of the handleability of the aqueous solution of the cationic polymer. , Preferably 8.6 or less, more preferably 8.2 or less, still more preferably 7.8 or less.
なお、本発明の親水性硬質材料への固体粒子の付着抑制方法に供される組成物は、液体、粉末、固体等、いずれの形態であってもよいが、自動食器洗浄機での溶解性の観点から、液体組成物であることが好ましい。一方、内容成分の保存安定性の観点からは、粉末組成物であることが好ましい。
本発明の親水性硬質材料への固体粒子の付着抑制方法に供される組成物は、自動食器洗浄機用洗浄剤組成物であることが好ましい。
The composition used for the method for suppressing the adhesion of solid particles to the hydrophilic hard material of the present invention may be in any form such as liquid, powder, solid, etc., but is soluble in an automatic dishwasher. From the viewpoint of the above, a liquid composition is preferable. On the other hand, from the viewpoint of storage stability of the content component, a powder composition is preferable.
It is preferable that the composition used for the method for suppressing the adhesion of solid particles to the hydrophilic hard material of the present invention is a cleaning composition for an automatic dishwasher.
<任意成分>
前記カチオン性ポリマーの水溶液は、例えば、アニオン性ポリマー、キレート剤、界面活性剤、pH調整剤、アルカリ剤、漂白剤、漂白活性化剤、吸油性粉体、溶媒、カルシウム塩や蟻酸等の酵素安定化剤、香料、防菌剤、防黴剤、及び色素等を含有していてもよい。
<Optional component>
Examples of the aqueous solution of the cationic polymer include an anionic polymer, a chelating agent, a surfactant, a pH adjuster, an alkali agent, a bleaching agent, a bleaching activator, an oil-absorbing powder, a solvent, an enzyme such as a calcium salt and formic acid. It may contain stabilizers, fragrances, antibacterial agents, antifungal agents, dyes and the like.
(アニオン性ポリマー)
アニオン性ポリマーとしては、アクリル酸塩、メタクリル酸塩、及びマレイン酸塩から選ばれるアニオン性基含有モノマーに由来する構成単位を有するアニオン性ポリマーを挙げることができる。前記アクリル酸、メタクリル酸、又はマレイン酸の塩としては、ナトリウム塩、カリウム塩、アンモニウム塩、アルカノールアンモニウム塩が挙げられる。
前記アニオン性ポリマーは、前記アニオン性基含有モノマーのみで構成されるポリマーであってもよく、アニオン性基含有モノマーと、アニオン性基含有モノマー以外のモノマーとの共重合体であってもよい。
(Anionic polymer)
Examples of the anionic polymer include an anionic polymer having a constitutional unit derived from an anionic group-containing monomer selected from acrylate, methacrylate, and maleate. Examples of the salt of acrylic acid, methacrylic acid, or maleic acid include sodium salt, potassium salt, ammonium salt, and alkanol ammonium salt.
The anionic polymer may be a polymer composed only of the anionic group-containing monomer, or may be a copolymer of an anionic group-containing monomer and a monomer other than the anionic group-containing monomer.
アニオン性ポリマーを用いる場合のアニオン性ポリマーの含有量は、カチオン性ポリマー100質量部に対して、好ましくは1質量部以上、より好ましくは5質量部以上であり、そして、好ましくは60質量部以下、より好ましくは50質量部以下である。 When the anionic polymer is used, the content of the anionic polymer is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and preferably 60 parts by mass or less with respect to 100 parts by mass of the cationic polymer. More preferably, it is 50 parts by mass or less.
(キレート剤)
キレート剤としては、クエン酸、リンゴ酸、酒石酸、コハク酸、メチルグリシン二酢酸、グルタミン酸二酢酸、ヒドロキシエチルイミノ二酢酸、エチレンジアミン二コハク酸、ニトリロ三酢酸、1,3−プロパンジアミン三酢酸、1,3−ジアミノ−2−ヒドロキシプロパン四酢酸、グリコールエーテルジアミン四酢酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラアミン六酢酸、ジヒドロキシエチルグリシン、及びヒドロキシエチルエチレンジアミンジカルボキシメチルグルタミン酸等のポリカルボン酸又はその塩、トリポリリン酸又はその塩を用いることができる。これらのキレート剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
(Chelating agent)
Examples of chelating agents include citric acid, malic acid, tartaric acid, succinic acid, methylglycine diacetic acid, glutamic acid diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, 1,3-propanediamine triacetic acid, 1 , 3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, and hydroxyethylethylenediaminedicarboxymethylglutamic acid Alternatively, a salt thereof, tripolyphosphoric acid or a salt thereof can be used. These chelating agents may be used individually by 1 type, and may be used in combination of 2 or more type.
キレート剤を用いる場合のキレート剤の含有量は、カチオン性ポリマー100質量部に対して、好ましくは1質量部以上、より好ましくは5質量部以上であり、そして、好ましくは25質量部以下、より好ましくは20質量部以下である。 When the chelating agent is used, the content of the chelating agent is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and preferably 25 parts by mass or less, based on 100 parts by mass of the cationic polymer. Preferably it is 20 mass parts or less.
(ノニオン性界面活性剤)
カチオン性ポリマーの水溶液を洗浄剤組成物として使用する場合は、ノニオン性界面活性剤を含有していることが好ましく、ノニオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ソルビタンモノステアレート、ポリオキシエチレンアルキルアミン類等が好ましい。
これらの中でも、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンラウリルエーテルが好ましい。これらのノニオン性界面活性剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
(Nonionic surfactant)
When an aqueous solution of a cationic polymer is used as a cleaning composition, it preferably contains a nonionic surfactant. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl Ethers, sorbitan monostearate, polyoxyethylene alkylamines and the like are preferable.
Among these, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, and polyoxyethylene lauryl ether are preferable. One of these nonionic surfactants may be used alone, or two or more thereof may be used in combination.
ノニオン性界面活性剤を用いる場合のノニオン性界面活性剤の含有量は、カチオン性ポリマー100質量部に対して、好ましくは2質量部以上、より好ましくは3質量部以上であり、そして、好ましくは100質量部以下、より好ましくは90質量部以下である。
なお、カチオン性ポリマーの水溶液は、前記ノニオン性界面活性剤の他に、陰イオン性界面活性剤、両性界面活性剤、陽イオン性界面活性剤を含有していてもよい。
When the nonionic surfactant is used, the content of the nonionic surfactant is preferably 2 parts by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the cationic polymer, and preferably 100 parts by mass or less, more preferably 90 parts by mass or less.
The aqueous solution of the cationic polymer may contain an anionic surfactant, an amphoteric surfactant, and a cationic surfactant in addition to the nonionic surfactant.
(酵素)
カチオン性ポリマーの水溶液を洗浄剤組成物として使用する場合は、酵素を含有していることが好ましい。酵素としては、アミラーゼ、プロテアーゼ、リパーゼ、セルラーゼ、エステラーゼ、及びペルオキシダーゼから選ばれる1種又は2種以上を用いることができ、市販品として粒状化されたものを用いることができる。いずれの酵素も他成分との保存安定性等を考慮して適宜選択すればよい。これらの中でも、他の界面活性剤では除去が難しい糊化したデンプンへの作用が期待されるアミラーゼが好ましい。また、界面活性剤等では除去が困難な変性タンパク質等に対して著しい効果を示すことからプロテアーゼも好ましい。
酵素を用いる場合の酵素の含有量は、カチオン性ポリマー100質量部に対して、好ましくは1質量部以上、より好ましくは2質量部以上であり、そして、好ましくは100質量部以下、より好ましくは90質量部以下である。
(enzyme)
When an aqueous solution of a cationic polymer is used as a cleaning composition, it preferably contains an enzyme. As the enzyme, one or more selected from amylase, protease, lipase, cellulase, esterase, and peroxidase can be used, and a commercially available product can be used. Any enzyme may be appropriately selected in consideration of storage stability with other components. Among these, amylases are preferred because they are expected to act on gelatinized starch that is difficult to remove with other surfactants. A protease is also preferable because it exhibits a remarkable effect on a denatured protein that is difficult to remove with a surfactant or the like.
When the enzyme is used, the content of the enzyme is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 100 parts by mass or less, more preferably 100 parts by mass of the cationic polymer. 90 parts by mass or less.
<実施例1〜5、比較例1〜5>
・固体粒子の調製
カレーパウダーを篩いにかけて50〜1,000μmの粒径を採取し、乾燥させたものを固体粒子とした。
<Examples 1-5, Comparative Examples 1-5>
-Preparation of solid particles The particle size of 50-1,000 micrometers was extract | collected with the curry powder and sieved, and it was set as the solid particle.
・親水性硬質材料の表面に対する処理
前記カレーパウダーを食器洗い乾燥機(パナソニック株式会社、型番「NP−P45M1WS」(ビルトインタイプ))の洗剤投入口の部分に200mg投入した。食器を自動食器洗浄機内の皿立て等の全てにセットし次いで、表1に記載の配合にしたがって洗浄液中のポリマー成分の濃度が100ppmとなるようにポリマーの水溶液を投入後、標準コースで運転を行った。洗浄終了後、陶器製の食器及びガラス製の食器のそれぞれに付着した粒子を回収し乾燥させた。評価は、乾燥した粒子の質量を測定し、下記評価基準にしたがって行った。結果を表1に示す。
・評価基準
A:固体粒子の付着量が1.5mg未満であった。
B:固体粒子の付着量が1.5mg以上、2.5mg未満であった。
C:固体粒子の付着量が2.5mg以上であった。
Treatment of hydrophilic hard material surface 200 mg of the curry powder was added to the detergent inlet of a dishwasher (Panasonic Corporation, model number “NP-P45M1WS” (built-in type)). Set the dishes in all dishes such as a dish stand in an automatic dishwasher, and then add the polymer aqueous solution so that the concentration of the polymer component in the washing liquid becomes 100 ppm according to the composition shown in Table 1, and then operate on the standard course. went. After washing, the particles adhering to the ceramic tableware and glass tableware were collected and dried. The evaluation was performed according to the following evaluation criteria by measuring the mass of the dried particles. The results are shown in Table 1.
Evaluation criteria A: The amount of solid particles adhered was less than 1.5 mg.
B: The adhesion amount of solid particles was 1.5 mg or more and less than 2.5 mg.
C: The adhesion amount of solid particles was 2.5 mg or more.
(水の静的接触角、及び水の後退接触角の測定)
・サンプルプレートの作成
サンプルプレート(76mm×26mm×1mm)のスライドガラス(松浪硝子製)の上部をクリップで挟み、食器洗い乾燥機(パナソニック株式会社、型番「NP−P45M1WS」(ビルトインタイプ))の上カゴの両端に設置した。
洗浄時のポリマー濃度が100ppmとなるように標準コースで運転を開始し、洗浄開始25分後(洗浄工程終了直前)にサンプルプレートを取り出し、イオン交換水で3回すすいだ後、自然乾燥させたものを接触角測定のサンプルプレートとした。
(Measurement of static contact angle of water and receding contact angle of water)
・ Creation of the sample plate The upper part of the slide glass (made by Matsunami Glass) of the sample plate (76 mm x 26 mm x 1 mm) is sandwiched between clips, above the dishwasher (Panasonic Corporation, model number "NP-P45M1WS" (built-in type)) Installed at both ends of the basket.
Operation was started on a standard course so that the polymer concentration at the time of washing was 100 ppm, the sample plate was taken out 25 minutes after washing was started (immediately before the end of the washing step), rinsed three times with ion-exchanged water, and then naturally dried. This was used as a sample plate for contact angle measurement.
・水の静的接触角の測定
測定機器:協和界面科学株式会社製「Drop Master DM700」
測定方法:液滴法に従って測定した。
測定条件:液量を2mLとし、滴下から3秒後の液滴を測定した。これを5回繰り返し、平均値を測定値とした。
なお、未処理のスライドガラスの測定値は5°以下であり、本発明の方法によりスライドガラスが改質されていることが実施例よりわかる。
・ Measurement of static contact angle of water Measuring instrument: “Drop Master DM700” manufactured by Kyowa Interface Science Co., Ltd.
Measurement method: Measured according to the droplet method.
Measurement conditions: The liquid volume was 2 mL, and the liquid droplets 3 seconds after dropping were measured. This was repeated 5 times, and the average value was taken as the measured value.
In addition, the measured value of an untreated slide glass is 5 degrees or less, and it can be seen from the Examples that the slide glass is modified by the method of the present invention.
・水の後退接触角の測定
測定機器:KRuSS社製 表面張力計「K−100」
測定方法:液体試料として水を用い、Wilhelmyプレート法にしたがって測定した。
測定条件:浸漬深さを5mm、浸漬速さを3mm/minとした。1プレートにつき浸漬及び引き上げを3回ずつ行い、3回の平均値を1プレートの測定値とした。更にプレート2枚分の測定を行い、計3プレート分の平均値を測定値とした。
なお、後退接触角は以下の式により求めることができる。
・ Measurement of receding contact angle of water Measuring instrument: Surface tension meter “K-100” manufactured by KRuSS
Measurement method: Measured according to the Wilhelmy plate method using water as a liquid sample.
Measurement conditions: The immersion depth was 5 mm, and the immersion speed was 3 mm / min. One plate was dipped and pulled three times, and the average of the three times was taken as the measured value for one plate. Further, two plates were measured, and the average value for a total of three plates was taken as the measured value.
The receding contact angle can be obtained by the following formula.
θ:後退接触角(プレートを引き上げる時の接触角θが後退接触角となる。)
F:張力(表面張力計にて測定)
S:プレートの断面積(26mm×1mm)
h:プレートの浸漬距離(<5mm)
ρ:水の密度(1g/cm3)
g:重力加速度(9.8m/s2)
L:プレートの周囲長(1mm×2+26mm×2)
γ:水の表面張力(73mN/m)
なお、未処理のスライドガラスの水の後退接触角の測定値は約0°であり、本発明の方法によりスライドガラスが改質されていることが実施例よりわかる。
θ: receding contact angle (the contact angle θ when the plate is pulled up is the receding contact angle)
F: Tension (measured with a surface tension meter)
S: Plate cross-sectional area (26 mm x 1 mm)
h: Immersion distance of plate (<5mm)
ρ: density of water (1 g / cm 3 )
g: Gravity acceleration (9.8 m / s 2 )
L: Perimeter of the plate (1 mm x 2 + 26 mm x 2)
γ: Surface tension of water (73 mN / m)
In addition, the measured value of the receding contact angle of water of the untreated slide glass is about 0 °, and it can be seen from the Examples that the slide glass is modified by the method of the present invention.
表に記載の化合物の詳細は以下のとおりである。
<カチオン性ポリマー>
・カチオン変性ポリビニルアルコール
CM−318、株式会社クラレ製、平均分子量90kDa、カチオン化度1.7mol%、下記式(I)中のp:q:rは88.5:9.8:1.7
Details of the compounds described in the table are as follows.
<Cationic polymer>
Cation-modified polyvinyl alcohol CM-318, manufactured by Kuraray Co., Ltd., average molecular weight 90 kDa, cationization degree 1.7 mol%, p: q: r in the following formula (I) is 88.5: 9.8: 1.7
HP−1、日本合成化学工業株式会社製、平均分子量90kDa、カチオン化度0.9mol%、下記式(II)中のp:q:rは86.8:12.3:0.9 HP-1, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average molecular weight 90 kDa, cationization degree 0.9 mol%, p: q: r in the following formula (II) is 86.8: 12.3: 0.9
・カチオン変性ヒドロキシエチルセルロース
Poiz−C60H、花王株式会社製
Poiz−C80M、花王株式会社製
Poiz−C150M、花王株式会社製
Cation-modified hydroxyethyl cellulose Poiz-C60H, Kao Corporation Poiz-C80M, Kao Corporation Poiz-C150M, Kao Corporation
<カチオン性基含有ポリビニルアルコール>
OSK−6225、日本合成化学工業株式会社製、平均分子量90kDa、カチオン化度0.15mol%、下記式(II)中のp:q:rは87.0:12.9:0.15
<Cationic group-containing polyvinyl alcohol>
OSK-6225, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average molecular weight 90 kDa, cationization degree 0.15 mol%, p: q: r in the following formula (II) is 87.0: 12.9: 0.15
Marquat 740、Lubrizol社製、平均分子量120kDa、アクリルアミド/ジアリルジメチルアンモニウムクロリド共重合体、下記式(III)中のm:nは76:24、カチオン化度24mol% Marquat 740, manufactured by Lubrizol, average molecular weight 120 kDa, acrylamide / diallyldimethylammonium chloride copolymer, m: n in the following formula (III) is 76:24, cationization degree 24 mol%
ポリマーA、平均分子量20kDa、下記式(IV)中のm:nは60:40、カチオン化度60mol% Polymer A, average molecular weight 20 kDa, m: n in the following formula (IV) is 60:40, cationization degree 60 mol%
<ノニオン性ポリビニルアルコール>
PVA−424、株式会社クラレ製、平均分子量120kDa、下記式(V)中のp:qは80.0:20.0、カチオン化度0mol%
<Nonionic polyvinyl alcohol>
PVA-424, manufactured by Kuraray Co., Ltd., average molecular weight 120 kDa, p: q in the following formula (V) is 80.0: 20.0, cationization degree 0 mol%
PVA−205、株式会社クラレ製、平均分子量25kDa、下記式(V)中のp:qは88.0:12.0、カチオン化度0mol% PVA-205, manufactured by Kuraray Co., Ltd., average molecular weight 25 kDa, p: q in the following formula (V) is 88.0: 12.0, cationization degree 0 mol%
表1より明らかなように、本発明の親水性硬質材料への固体粒子の付着抑制方法は、食器等の親水性硬質材料の表面に対して、平均粒子径が50μm以上、1,000μm以下である固体粒子の付着を抑制することができる。 As is clear from Table 1, the method for suppressing solid particle adhesion to the hydrophilic hard material of the present invention has an average particle diameter of 50 μm or more and 1,000 μm or less with respect to the surface of the hydrophilic hard material such as tableware. Adhesion of certain solid particles can be suppressed.
Claims (5)
(式中、R1〜R14はそれぞれ独立に炭素数1以上、6以下のアルキル基を示し、Z−はそれぞれ独立に陰イオンを示し、mはそれぞれ独立に1以上、10以下の整数を示し、nはそれぞれ独立に0以上、10以下の整数を示す。) This is a method for suppressing the adhesion of solid particles having an average particle diameter of 50 μm or more and 1,000 μm or less to the surface of a hydrophilic hard material that satisfies the condition that the static contact angle of water is 20 ° or less. A cationic polymer having one or more cationic groups selected from formulas (a-1) to (a-5) and having a degree of cationization of 0.25 mol% or more and 5.0 mol% or less. A method for inhibiting solid particles from adhering to a hydrophilic hard material by bringing the aqueous solution into contact with the surface of the hydrophilic hard material, the cleaning composition for an automatic dishwasher containing the aqueous solution of the cationic polymer for automatic tableware A method for suppressing the adhesion of solid particles to a hydrophilic hard material, wherein the aqueous solution of the cationic polymer is brought into contact with the surface of the hydrophilic hard material by putting it in a washing machine and washing the hydrophilic hard material .
(Wherein R 1 to R 14 each independently represents an alkyl group having 1 to 6 carbon atoms, Z − represents an anion independently, and m represents an integer of 1 to 10 independently. N represents an integer of 0 or more and 10 or less independently.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013270438A JP6247093B2 (en) | 2013-12-26 | 2013-12-26 | Method for suppressing adhesion of solid particles to hydrophilic hard material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013270438A JP6247093B2 (en) | 2013-12-26 | 2013-12-26 | Method for suppressing adhesion of solid particles to hydrophilic hard material |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2015124314A JP2015124314A (en) | 2015-07-06 |
JP6247093B2 true JP6247093B2 (en) | 2017-12-13 |
Family
ID=53535267
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013270438A Active JP6247093B2 (en) | 2013-12-26 | 2013-12-26 | Method for suppressing adhesion of solid particles to hydrophilic hard material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6247093B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019146374A1 (en) * | 2018-01-26 | 2019-08-01 | 第一工業製薬株式会社 | Hard surface treatment agent |
JP6960510B1 (en) * | 2020-09-29 | 2021-11-05 | 株式会社Adeka | Detergent composition for hard surface and cleaning method for hard surface |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001049230A (en) * | 1999-08-11 | 2001-02-20 | Eagle Star:Kk | Stainproofing protectant and treatment therewith |
JP2003155499A (en) * | 2001-11-20 | 2003-05-30 | Lion Corp | Liquid detergent composition |
JP4145865B2 (en) * | 2004-11-18 | 2008-09-03 | 花王株式会社 | Hard surface cleaner |
JP4979908B2 (en) * | 2005-08-12 | 2012-07-18 | 花王株式会社 | Hard surface drainage imparting agent |
JP4975317B2 (en) * | 2005-12-22 | 2012-07-11 | 花王株式会社 | Detergent composition for dishwasher |
JP5197927B2 (en) * | 2006-05-17 | 2013-05-15 | 花王株式会社 | Hard surface cleaner |
JP5234701B2 (en) * | 2006-05-17 | 2013-07-10 | 花王株式会社 | Cleaning composition for hard surface |
JP5188709B2 (en) * | 2006-12-25 | 2013-04-24 | 花王株式会社 | Dishwasher finish composition |
JP2010013616A (en) * | 2007-09-28 | 2010-01-21 | Toto Ltd | Coating composition |
JP5349783B2 (en) * | 2007-10-05 | 2013-11-20 | 花王株式会社 | Liquid detergent composition |
BRPI0918813A2 (en) * | 2008-09-19 | 2015-12-01 | Procter & Gamble | modified lignin biopolymer useful in cleaning compositions |
JP5642465B2 (en) * | 2009-09-10 | 2014-12-17 | ライオン株式会社 | Liquid detergent composition for automatic dishwashers |
JP5575466B2 (en) * | 2009-12-15 | 2014-08-20 | 花王株式会社 | Cleaning composition for hard surface |
EP2622053A1 (en) * | 2010-10-01 | 2013-08-07 | Rhodia Operations | Cleaning composition for hard surface |
JP6228005B2 (en) * | 2013-12-26 | 2017-11-08 | 花王株式会社 | Method for producing detergent composition for automatic dishwasher, and method for suppressing adhesion of solid particles to hydrophilic hard material |
JP6247092B2 (en) * | 2013-12-26 | 2017-12-13 | 花王株式会社 | Liquid detergent composition for automatic dishwasher and dishwashing method |
-
2013
- 2013-12-26 JP JP2013270438A patent/JP6247093B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2015124314A (en) | 2015-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2364350B1 (en) | Ware washing system containing cationic starch | |
KR101564117B1 (en) | Rinse aid | |
KR101621115B1 (en) | Cleaning of a cooking device or appliance with a composition comprising a built-in rinse aid | |
US10301577B2 (en) | Composition | |
CN104508106B (en) | Tableware cleanser compositions | |
JP2012510342A5 (en) | ||
US20130326824A1 (en) | Laundry detergents | |
CA2688030A1 (en) | Ware washing system containing polysaccharide | |
JP4975317B2 (en) | Detergent composition for dishwasher | |
JP2012520910A5 (en) | ||
US20140352076A1 (en) | Laundry detergents | |
JP6247093B2 (en) | Method for suppressing adhesion of solid particles to hydrophilic hard material | |
JP6247092B2 (en) | Liquid detergent composition for automatic dishwasher and dishwashing method | |
JP2016526056A (en) | Formulations, their use as dishwashing detergents, or their use for the production of dishwashing detergents, and their production | |
JP6228005B2 (en) | Method for producing detergent composition for automatic dishwasher, and method for suppressing adhesion of solid particles to hydrophilic hard material | |
JP5435906B2 (en) | Liquid detergent composition for dishwashers | |
ES2884253T3 (en) | Cleaning agent and dishwashing procedure | |
JP2014129493A (en) | Detergent composition for automatic dishwasher | |
CN110042016A (en) | A kind of use in dishwasher solid cleaning agent and preparation method thereof | |
JP5836104B2 (en) | How to wash textile products | |
WO2006061957A1 (en) | Cleansing agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160913 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170628 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170704 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170828 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20171107 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20171116 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 6247093 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |