CN105199863B - A kind of water-soluble unit dose articles suitable for fabric washing application - Google Patents
A kind of water-soluble unit dose articles suitable for fabric washing application Download PDFInfo
- Publication number
- CN105199863B CN105199863B CN201510540655.2A CN201510540655A CN105199863B CN 105199863 B CN105199863 B CN 105199863B CN 201510540655 A CN201510540655 A CN 201510540655A CN 105199863 B CN105199863 B CN 105199863B
- Authority
- CN
- China
- Prior art keywords
- water
- soluble film
- unit dose
- soluble
- dose articles
- 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
- 238000005406 washing Methods 0.000 title claims abstract description 99
- 239000004744 fabric Substances 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 132
- 239000003599 detergent Substances 0.000 claims abstract description 72
- -1 washing assisant a Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 239000007844 bleaching agent Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 21
- 102000004190 Enzymes Human genes 0.000 claims description 20
- 108090000790 Enzymes Proteins 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 239000002736 nonionic surfactant Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 238000005538 encapsulation Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000009994 optical bleaching Methods 0.000 claims description 11
- 238000013459 approach Methods 0.000 claims description 10
- 239000000686 essence Substances 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002979 fabric softener Substances 0.000 claims description 7
- 239000003755 preservative agent Substances 0.000 claims description 7
- 230000002335 preservative effect Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000004061 bleaching Methods 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000004375 Dextrin Substances 0.000 claims description 5
- 229920001353 Dextrin Polymers 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 235000010980 cellulose Nutrition 0.000 claims description 5
- 235000019425 dextrin Nutrition 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 235000010981 methylcellulose Nutrition 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 230000000474 nursing effect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 104
- 125000000217 alkyl group Chemical group 0.000 description 23
- 239000002253 acid Substances 0.000 description 22
- 229940088598 enzyme Drugs 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 238000007046 ethoxylation reaction Methods 0.000 description 12
- 238000007792 addition Methods 0.000 description 11
- 239000003945 anionic surfactant Substances 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 150000002191 fatty alcohols Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
- 229960003237 betaine Drugs 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000004900 laundering Methods 0.000 description 5
- 150000001451 organic peroxides Chemical group 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 108010059892 Cellulase Proteins 0.000 description 3
- 108090001060 Lipase Proteins 0.000 description 3
- 102000004882 Lipase Human genes 0.000 description 3
- 239000004367 Lipase Substances 0.000 description 3
- 229920002774 Maltodextrin Polymers 0.000 description 3
- 239000005913 Maltodextrin Substances 0.000 description 3
- 108091005804 Peptidases Proteins 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 239000004365 Protease Substances 0.000 description 3
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 229940106157 cellulase Drugs 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 235000019421 lipase Nutrition 0.000 description 3
- 229940035034 maltodextrin Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 235000019419 proteases Nutrition 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 230000003019 stabilising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 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
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N Indigo Chemical group N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 108010005400 cutinase Proteins 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229940070721 polyacrylate Drugs 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- IKYKEVDKGZYRMQ-PDBXOOCHSA-N (9Z,12Z,15Z)-octadecatrien-1-ol Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCCO IKYKEVDKGZYRMQ-PDBXOOCHSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- AUVBKWQJMSXELH-UHFFFAOYSA-N 3-propylsulfanylpropan-1-ol Chemical compound CCCSCCCO AUVBKWQJMSXELH-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical class CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 108010001682 Dextranase Proteins 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- 239000004258 Ethoxyquin Substances 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- 102000004317 Lyases Human genes 0.000 description 1
- 108090000856 Lyases Proteins 0.000 description 1
- HPTULVAFZQXKIS-UHFFFAOYSA-N NC1=C(C=CC=C1)C=CC1=CC=CC=C1.N1=NN=CC=C1 Chemical compound NC1=C(C=CC=C1)C=CC1=CC=CC=C1.N1=NN=CC=C1 HPTULVAFZQXKIS-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 206010033546 Pallor Diseases 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 244000272264 Saussurea lappa Species 0.000 description 1
- 235000006784 Saussurea lappa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001294 alanine derivatives Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 102000004139 alpha-Amylases Human genes 0.000 description 1
- 108090000637 alpha-Amylases Proteins 0.000 description 1
- 229940024171 alpha-amylase Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 108010089934 carbohydrase Proteins 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- MORMPWNLQJTSOT-UHFFFAOYSA-L disodium;4-dodecyl-2-(4-sulfonatophenoxy)benzenesulfonate Chemical compound [Na+].[Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C(OC=2C=CC(=CC=2)S([O-])(=O)=O)=C1 MORMPWNLQJTSOT-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- YERABYSOHUZTPQ-UHFFFAOYSA-P endo-1,4-beta-Xylanase Chemical compound C=1C=CC=CC=1C[N+](CC)(CC)CCCNC(C(C=1)=O)=CC(=O)C=1NCCC[N+](CC)(CC)CC1=CC=CC=C1 YERABYSOHUZTPQ-UHFFFAOYSA-P 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 229940093500 ethoxyquin Drugs 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002332 glycine derivatives Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010412 laundry washing Methods 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- LBIYNOAMNIKVKF-FPLPWBNLSA-N palmitoleyl alcohol Chemical compound CCCCCC\C=C/CCCCCCCCO LBIYNOAMNIKVKF-FPLPWBNLSA-N 0.000 description 1
- LBIYNOAMNIKVKF-UHFFFAOYSA-N palmitoleyl alcohol Natural products CCCCCCC=CCCCCCCCCO LBIYNOAMNIKVKF-UHFFFAOYSA-N 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 108010038851 tannase Proteins 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
Abstract
The invention discloses a kind of water-soluble unit dose articles suitable for fabric washing application.The water-soluble unit dose articles include：A) at least one the first enclosure portion made of water-soluble film a；Described its content of first enclosure portion is main detergent composition a；The weight average molecular weight range of the water-soluble film a is 5000~120000, and thickness range is 25~100 μm；B) at least one the second enclosure portion made of water-soluble film b；Described its content of second enclosure portion is detergent auxiliary composition b；The weight average molecular weight range 40000~250000 of the water-soluble film b, thickness range are 25~120 μm.The thickness and molecular weight that the present invention passes through control water-soluble film, achieve the purpose that main body detergent composition pouch and washing assisant pouch are ruptured in different time, to realize that scrubbed component discharges in different time points, the advantageous effect that each scrubbed component plays maximum washing or nursing role is obtained.
Description
Technical field
The invention belongs to daily-use chemical industry technical fields, and in particular to one kind being suitable for fabric washing application, at least by two kinds
Or the solvable unit dose articles of two or more water-soluble film encapsulatings.
Background technology
In daily life, clothing is easy to wear after repeatedly washing to be hardened.In order to solve the problems, such as that clothing wears, especially
It is white or light-colored clothing, and the bleaching agent of solid or liquid would generally be added in consumer in laundering process, to real
Existing clothing brightens the effect of blast.In order to reach best bleaching effect, the washing stage in laundering process is needed to add
Enter bleaching agent to play best blanching effect；However in order to effectively remove protide spot, in the market in most detergent
It is added to enzyme preparation, however the addition of bleaching agent can cause enzyme preparation to inactivate, and can weaken the washing effect of detergent.If adding simultaneously
Enter bleaching agent and enzyme detergent, it will cause the losses of respective washing functions.Therefore in practical laundering process, it is proposed that
Way be：After enzyme preparation plays one's part to the full, bleaching agent is added.
In order to solve the problems, such as that clothing is hardened, usual consumer can be additionally added clothing softness in laundering process
Agent.But the main functional component of most of clothing softening agents is cationic surface active agent, and most of laundry detergent compositions
Main functional component be anionic surfactant, will also result in the losses of respective washing functions if being added simultaneously, therefore
In practical laundering process, it is proposed that way be rinse stage be added clothing softening agent.
In order to reach better laundry washing effects, consumer's moment is needed to pay close attention to washing process, in the different washing stages
Corresponding detergent is added.But for today's society, rhythm of life is increasingly accelerated, this is more for ordinary consumer
Clothes laundry and protection articles for use cumbersome and time-consuming therefore easy to use, that process is simple, environmental-friendly become particularly urgent.
The patent CN1344214A of Unilever's application discloses a kind of water soluble package of packaging flowing material,
Flowing material therein is released when the packaging bag is dissolved；The patent passes through the characteristics masters such as the shape of change packaging bag
Improve the rupture resistivity of water soluble package.The patent CN101153241A of Unilever's application discloses one
Kind includes the water soluble package of basic non aqueous liquid rinse conditioning composition wherein, which follows in the rinsing of washing operation
It is added in ring.
But a common defects of the above technology are：Different functional components is discharged into aqueous solution simultaneously, but by
In the incompatible problem of different chemical constituents, the effect of respective component can be caused to reduce and even failed.How different function is realized
Property component the washing stage different time points substep discharge technology, be industry problem in the urgent need to address.
Invention content
The purpose of the present invention is to provide a kind of fabric washing shields to use, water-soluble unit dose articles, by controlling thin, water soluble
The thickness and molecular weight of film achieve the purpose that main body detergent composition pouch and washing assisant pouch are ruptured in different time,
To realize that different time points substep of the different scrubbed components in the washing stage discharges.
A kind of water-soluble unit dose articles suitable for fabric washing application, the product include at least more than two closings
Part,
A) at least one the first enclosure portion made of water-soluble film a；Based on described its content of first enclosure portion
Detergent composition a；The weight average molecular weight range of the water-soluble film a is 5000~120000, and thickness range is 25~100
μm；
B) at least one the second enclosure portion made of water-soluble film b；Described its content of second enclosure portion is to wash
Wash assistant composition b；The weight average molecular weight range 40000~250000 of the water-soluble film b, thickness range are 25~120 μ
m。
The water-soluble film a thickness is preferably 25~80 μm, more preferably 40~80 μm；The water-soluble film b is thick
Preferably 25~110 μm, more preferably 50~110 μm of degree.
The water-soluble unit dose articles for being suitable for fabric washing application, the Weight-average molecular of the water-soluble film a
Amount ranges preferably from 10000~100000 and is more preferably, and 20000~70000；The weight average molecular weight model of the water-soluble film b
It encloses preferably 50000~200000 to be more preferably, 70000~150000.
The water-soluble unit dose articles for being suitable for fabric washing application, at normal temperatures, first enclosure portion
Volume ratio with water is 125：1~1：After ∝ contacts water, rupture within 0.5 minute to 2 minutes；Second enclosure portion and water
Volume ratio be 2：1~1：After ∝ contacts water, rupture within 6 minutes to 10 minutes.
The water-soluble film a be selected from polyvinyl alcohol, polyvinyl alcohol copolymer, polyacrylic acid and its salt, polyacrylic acid and
Copolymer, methylcellulose, sodium carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose, the hydroxypropyl methyl fiber of its salt
Element, dextrin, maltodextrin and their mixture, preferably polyvinyl alcohol, polyvinyl alcohol copolymer and they
Mixture；
The water-soluble film b be selected from polyvinyl alcohol, polyvinyl alcohol copolymer, polyacrylic acid and its salt, polyacrylic acid and
Copolymer, methylcellulose, sodium carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose, the hydroxypropyl methyl fiber of its salt
Element, dextrin, maltodextrin and their mixture, preferably polyvinyl alcohol, polyvinyl alcohol copolymer and they
Mixture.
The main detergent composition a include surfactant, deionized water, washing assisant a, cosolvent and they
Mixture.
The water-soluble unit dose articles for being suitable for fabric washing application, by weight hundred in detergent compositions
Divide than meter, the main body detergent composition a includes raw material components：
0.05%~20.0% fatty acid salt, preferably 1.5%~15.0%；
0.05%~25.0% linear alkylbenzene sulfonate (LAS), preferably 5.0%~20.0%；
10.0%~40.0% nonionic surfactant；
1.0%~40.0% cosolvent；
1.0%~15.0% washing assisant a；
The water-soluble unit dose articles of the present invention, the main detergent composition a are selected from liquid form, powder type or cream
Body form.
The water-soluble unit dose articles of the present invention, the washing assisant a are selected from：Enzyme preparation, Optical Bleaching Agent, is prevented essence
Rotten agent, chelating agent, alkaline agent, salt, pigment, anti redeposition agent and their mixture etc..
The water-soluble unit dose articles of the present invention, detergent auxiliary composition b are selected from：It is fabric softener, enzyme preparation, antistatic
Agent, essence, solid or liquid bleaching system, surfactant and their mixture etc..
The water-soluble unit dose articles of the present invention, can be prepared by processing step below：
1) using water-soluble film b as counterdie；
2) after film being heated or soaked, vacuum can be used to be sucked in grinding tool appropriate (mold), to counterdie
It is vacuumized, fitting grinding tool (mold) is handled；
3) filling of washing assisant is completed by approach appropriate, addition is adjusted according to grinding tool size；
4) it does and heats in counterdie and upper film sealing part using water-soluble film b as upper film, or spraying is appropriate molten
Agent, and carry out encapsulation process；
5) water-soluble film a is put in the packaging motor spindle of unit dose articles, which is counterdie；
6) it repeats the above steps 2), and completes the filling of main body detergent composition, addition root by approach appropriate
It is adjusted according to grinding tool size；
7) it using the water-soluble film b for containing washing assisant pouch obtained by step 4) as upper film, is sealed in counterdie and upper film
Place, does and heats, or the appropriate solvent of spraying, and carries out encapsulation process, obtains at least by the water-soluble of two or more
The solvable unit dose articles of property thin film encapsulation.
In addition, the water-soluble unit dose articles of the present invention, can also be prepared by processing step below：
1) using water-soluble film b as counterdie；
2) after film being heated or soaked, vacuum can be used to be sucked in grinding tool appropriate (mold), to counterdie
It is vacuumized, fitting grinding tool (mold) is handled；
3) filling of washing assisant is completed by approach appropriate, addition is adjusted according to grinding tool size；
4) it does and heats in counterdie and upper film sealing part using water-soluble film b as upper film, or spraying is appropriate molten
Agent, and encapsulation process is carried out, obtain being encapsulated in the washing assisant pouch in water-soluble film, and be cut into independent small
Bag；
If 5) there is more than one detergent auxiliary composition, step 1)~4 are repeated) it can be obtained and be encapsulated in water-soluble film
Different, independent washing assisant pouches；
6) using water-soluble film a as counterdie；
7) it repeats the above steps 2), and completes the filling of main body detergent composition, addition root by approach appropriate
It is adjusted according to grinding tool size, while independent washing assisant pouch obtained above is added；
8) it does and heats in counterdie and upper film sealing part using water-soluble film a as upper film, or spraying is appropriate molten
Agent, and encapsulation process is carried out, obtain the solvable unit dose articles of the water-soluble film encapsulating at least by two or more.
For those skilled in the art, feature of the invention, beneficial by reading the disclosure of the specification
Effect and advantage will become obvious.
Unless otherwise specified, all percentages, score and ratio are calculated by the total weight of the present composition.It removes
Non- otherwise indicated, all wt in relation to ingredients listed gives the content of active material, thus they be not included in it is commercially available
The solvent or by-product that may include in the material of acquisition.This paper terms " weight content " available symbols " % " indicate.
Unless otherwise specified, all molecular weight herein are all the weight average molecular weight indicated as unit of dalton.
Unless otherwise specified, all preparations and test herein are happened at 25 DEG C of environment.
Herein "include", "comprise", " containing ", " containing ", " having " or other variants be intended to it is non-enclosed include,
It is not distinguished between these terms.Term "comprising" refers to that the other steps and ingredient that influence final result can be added not.Term
"comprising" further includes term " Consists of " and "consisting essentially of ...".The compositions and methods of the invention/technique may include,
It is made from it and substantially by essential elements described herein and limit entry and described herein any additional or optional
Ingredient, component, step or limit entry composition.
Water-soluble film
Preferred film is polymer material, preferably can be shaped as the polymer of film or sheet material.Such as this field, oneself knows, can be with
It cast, be blow molded by polymer material, extruding acquisition water-soluble film.The material packet of water-soluble film can preferably be prepared
Include polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, cellulose, cellulose ether, cellulose esters, cellulose
Amide, polyvinyl acetate, polycarboxylic acids and its salt, polyaminoacid or peptide, polyacrylamide, maleic acid/acrylic acid copolymer,
Polysaccharide includes starch and gelatin, natural gum such as xanthans and carrageenan and their mixture.It is highly preferred that comprising poly-
Acrylate and water-soluble acrylic ester copolymer, methylcellulose, carboxymethyl cellulose, dextrin, ethyl cellulose, ethoxy
Cellulose, hydroxypropyl methyl cellulose, maltodextrin, polymethacrylates and their mixture.Most preferably, it wraps
Containing polyvinyl alcohol, polyvinyl alcohol copolymer and their mixture.
The molecular weight and thickness of water-soluble film and its rupture time in water are closely related.
The thin, water soluble film thickness of used encapsulating main body detergent composition is 25~100 μm in the present invention, preferably
It is 25~80 μm, more preferably 40~80 μm, the water-soluble film for being 20000~70000 in combination with weight average molecular weight range,
The water-soluble film rupture time of control encapsulating main body detergent composition is 0.2min~2min.
The water-solubility membrane thickness of the described encapsulating washing assisant is 25~120 μm, preferably 25~110 μm, more preferably
50~110 μm.The water-soluble film for being 70000~150000 in combination with weight average molecular weight range, control encapsulating washing assisant
Water-soluble film rupture time be 6min~10min.
The present invention is by regulating and controlling the molecular weight and thickness of water-soluble film, to make main body detergent composition pouch and to wash
It washs auxiliary agent pouch to rupture in different time, scrubbed component discharges in different times, reaches different functionalities component different
Washing stage or wash time release, to provide different function profit points.
The molecule measuring method for testing of water-soluble film
With ultrapure water dissolution water-soluble film, and the polyethylene glycol standard sample for choosing different molecular weight is as a contrast, makes
The molecular weight of thin, water soluble membrane sample is tested with gel permeation chromatograph.Concrete operations are as follows：
The accurate polyethylene glycol standard sample 20mg for weighing different molecular weight is settled in 10mL volumetric flasks with ultra-pure water
Series standard solution is made in scale, spare after filtering；Water-soluble film 20mg to be measured is accurately weighed in 10mL volumetric flasks, is added
Enter ultra-pure water and be settled to scale, sample solution is made, it is spare after filtering；Show poor folding using high performance liquid chromatograph, and by selection
Photodetector selects the model of chromatographic column：Agilent PL aquagel-OH 40(4.6×250mm,8μm)；(this place
The similar other chromatographic columns of property can be used to substitute with chromatographic column), select 0.1mol/L NaNO3+0.01mol/L NaH2PO4It is water-soluble
Liquid is as mobile phase, and the flow rate set of mobile phase is 1.0mL/min, and the sample size of sample is set as 5 μ L.In above-mentioned chromatographic condition
Under, after instrument is ready, difference bioassay standard solution series and sample solution.Draw the song of standard items appearance time and molecular weight
The weight average molecular weight and molecular weight distribution of sample are calculated by instrument software according to sample to be tested appearance time for line.
Water-soluble film thickness testing method
The test of thin, water soluble film thickness uses the digital display calibrator of Beijing cities Zhong Huitian Science and Technology Ltd., specific experiment side
Method is as follows：
Power supply is opened, " mm/in " key selection system of unit (having the appearance of " mm " character when metric system) is pressed, screws gauge rod, press " 0 " key
Make numerical value zero setting.Film is sandwiched among two gauge rods by unscrewing gauge rod, waits for that film is not fallen vertically, and gauge rod is not applied to film
Pressure, the thickness of reading as film at this time.
Unit dose articles rupture time test containing functional pouch
At 25 DEG C, 800mL tap water will be added in the beaker of standard 1000mL, and use magnetic stirrer, make
The bottom for obtaining whirlpool (adjusts mixing speed until being about water column one third height at the one third of the beaker liquid level
Whirlpool show).
Into the water by the unit dose articles containing functional pouch, start timing, it is to be encapsulated in water-soluble film
Content start leakage when, record the time, as the rupture time of the water-soluble film of encapsulation compositions.
Unit dose articles
Unit dose articles refer to：Solid a certain amount of, compared with low water content or fluid composition are encapsulated in certain
In material, obtained easy-to-use, convenient product.Used encapsulating material is water-soluble film in the present invention.
Unit dose articles can have the composition for the relatively low water content for being suitable for accommodating any form, shape and material.
Do not allow to discharge any composition and any annexing ingredient from unit dose articles before unit dose articles are contacted with water.
Unit dose articles containing functional pouch
The heretofore described unit dose articles containing functional pouch refer to：Contain cationic polymer, non-
Ionic surface active agent, anion surfactant liquid composition be encapsulated in unit dose articles.Wherein main body is washed
Agent composition is encapsulated in water-soluble film, and contains at least one washing assisant pouch, is helped wherein the pouch is washing
Agent is encapsulated in the pouch of water-soluble film composition.Encapsulate the water solubility of the water-soluble film and encapsulating washing assisant of main body detergent
The molecular weight of film and thickness difference.
The unit dose articles include being completely enclosed in water-soluble film and water-soluble film encapsulating relatively low water
The composition of content.Liquid and/or solid component of the unit dose articles optionally containing washing assisant pouch.Containing functional
The unit dose articles of property pouch due to following the reason is that desired, it is expected that obtaining following result：
Since the water-soluble film a of encapsulating main body detergent composition touches water, after 0.5-2 minutes, the water
Soluble film ruptures, and main body detergent composition releases；Water is touched from the water-soluble film b of encapsulating washing assisant to open
Begin, after 6-10 minutes, water-soluble film rupture, washing assisant pouch is slower to be released, different to reach
Functional component substep discharges, while realizing the purpose of the multi-efficiencies such as clothes cleaning, laundry care.
Main body detergent composition
The main body detergent composition refers to the content being encapsulated in water-soluble film a.It is in detergent
Main cleaning function is played in the process.
The main body detergent composition is the liquid detergent composition or powder detergent for including surfactant
Composition or lotion detergent composition.Main body detergent composition is selected from：Surfactant, deionized water, washing assisant (remove
Be encapsulated in other than the washing assisant in washing assisant pouch, other washing assisants), cosolvent and their mixing
Object.
Surfactant system
Suitable surfactant system includes, but is not limited to：Anion surfactant, non-ionic surface active
Agent, cationic surfactant, one kind of zwitterionic surfactant and its a variety of mixtures.Preferred surfactant
System includes the mixture of anion surfactant and nonionic surfactant.
Anion surfactant
The content of anion surfactant is the 1% to 40% of detergent composition, with detergent composition total weight
It calculates.
Anion surfactant be selected from linear alkylbenzene sulfonate (LAS), alpha-alkene sulfonate, fatty acid alkyl ester sulfonate,
The ethoxylation of alkyl sulfate, the fatty acid salt of C8 to C18, the ethoxylated fatty alcohol sulfate of C8 to C18, C8 to C18
One or more mixtures in aliphatic alcohol sulfate, ethoxylized fatty alcohol ether carboxylate.
In some embodiments, the mixture of anion surfactant preferably comprise linear alkylbenzene sulfonate (LAS) and its
Derivative.The linear alkylbenzene sulfonate (LAS) meets following general formula：
Wherein R1It is the alkyl that carbon number is 6 to 24, M+For cation, such as potassium ion, sodium ion, ammonium ion etc..R1It can be with
It is the alkyl of straight chain；It can be the alkyl of saturation, can also be the alkyl containing one or more unsaturated double-bonds.It is further excellent
Select R1It is the straight chained alkyl that carbon number is 8 to 18.Suitable example is neopelex.
In some embodiments, anion surfactant contains the aliphatic alcohol sulfate of ethoxylation.Ethoxylation
Aliphatic alcohol sulfate is the derivative of ethoxylate fatty alcohol, has following general formula：
Wherein R1It is the alkyl that carbon number is 6 to 24；X is 0.5 to 30；Wherein M+For cation, for example, potassium ion, sodium ion,
Ammonium ion etc..R1It can be the alkyl of straight chain, can also be the alkyl of branch；Can be saturation alkyl, can also be containing
The alkyl of one or more unsaturated double-bonds.It is preferred that R1It is the straight chained alkyl that carbon number is 8 to 18.X represents average ethoxylation journey
Degree is 0.5 to 30, preferably 0.5 to 10, more preferable 0.5 to 3.Suitable example is the TexaponN70 of BASF AG.
In some embodiments, containing alkyl sulfate, alkyl segment can be straight chain, or branch, it can
Can also be the alkyl containing one or more unsaturated double-bonds to be the alkyl of saturation.The alkane that optimizing alkyl carbon number is 6 to 24
Base sulfate, the alkyl sulfate that further preferred carbon number is 8 to 18.Suitable example is lauryl sodium sulfate.
In some embodiments, containing alpha-alkene sulfonate, there is following general formula：
Wherein a is 0 to 2, R1It is the alkyl that carbon number is 6 to 24, preferably R1It is the alkyl that carbon number is 8 to 18.M+For sun from
Son, such as potassium ion, sodium ion, ammonium ion etc..
In some embodiments, anion surfactant contains fatty acid salt, the fat that preferably carbon number is 8 to 18
Fat hydrochlorate.The alkyl segment of aliphatic acid can be straight chain, or branch, it can be the alkyl of saturation, can also be to contain
There are one or multiple unsaturated double-bonds alkyl.Fatty acid salt can be single composition, can also be what a variety of aliphatic acid formed
Mixture.Suitable example is enuatrol, sodium laurate.The fatty acid salt also includes ethoxylized fatty alcohol ether carboxylate,
The carbon number of fatty alcohol preferably 8 to 18, average ethoxylation degree is preferably 2.0 to 10.
The anion surfactant can also include one kind of alkyl sodium disulfonate or derivatives thereof and a variety of mixing
Object, optimizing alkyl diphenyl oxide disulfonate, suitable example are disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt, the Dowfax of DOW companies
Series of products.Fatty acid alkyl esters sulfate, preferably fatty acid methyl ester sulfate (MES), aliphatic acid carbon number can also be contained
It is preferred that 8 to 18.Can also include sulfosuccinate, preferably fatty alcohol polyoxyethylene ether sulfosuccinic acid monoesters disodium
Salt, the carbon number of fatty alcohol preferably 8 to 18, average ethoxylation degree is preferably 2.0.
Nonionic surfactant
The content of nonionic surfactant is the 1% to 40% of detergent composition, with detergent composition total weight
It calculates.
Nonionic surfactant is selected from alkyl polyglycoside, ethoxylated fatty acid ester, alkanolamide and its polyoxyethylene
Ether, polyol ester, fatty acid polyglycol polyester, sucrose ester, one or more mixtures of ethoxylated sorbitan acid alcohol ester.
In some embodiments, nonionic surfactant preferably comprises fatty alcohol alkoxy compound, the fatty alcohol
Alcoxylates have following general formula：
Wherein, n is 6 to 24；X is that 0.5 to 30, y is 0 to 10.
The fatty alcohol alkoxy compound is the ring-opening polymerisation under basic catalyst effect of fatty alcohol and epoxyalkane
Product, substantially mixture.Fatty alcohol includes the isomery alcohol of straight chain alcohol or branch.Alkoxy grp includes ethyoxyl (such as above formula)
With propoxyl group group.The fatty alcohol that the preferred carbon number of fatty alcohol is 8 to 18, preferred alcohol includes but is not limited to hexanol, octanol, the last of the ten Heavenly stems
Alcohol, 2-ethylhexanol, 3- propyl enanthols, laruyl alcohol, different three decyl alcohol, tridecanol, tetradecanol, hexadecanol, Palmitoleyl alcohol,
One kind and its mixture of stearyl alcohol, isooctadecanol, oleyl alcohol, sub- oleyl alcohol, linolenyl alcohol.Average ethoxylation degree x preferably 2 to
12.Preferred example is SHELL companies NEODOL series linear primary alcohol ethoxylate products, ECOSURF EH systems of DOW companies
Row ethoxylation and the third oxidation 2-ethylhexanol product, the ethoxylation of BASF AG LutensolXL series and the third oxidation 3- propyl
Enanthol product and BASF AG's Lutensol XP series ethoxylation 3- propyl enanthol products.
In some embodiments, nonionic surfactant preferably comprises alkyl polyglycoside, has following general formula：
Wherein, it is 1.1 to 3 that n, which is 6 to 24, p,.It is preferred that n is 8 to 16.Suitable alkyl polyglycoside such as BASF AG
Glucopon series alkyl glycosides products.
Nonionic surfactant can contain fatty acid ester alkoxylating object, preferably be selected from ethoxylation C8 to C18 fat
Acid esters, average ethoxylation degree are 2 to 10.Can contain ethoxylated sorbitan acid alcohol Arrcostab, alkyl carbon number be 6 to
18, average ethoxyquin degree is 4 to 20；Suitable example is Croda company's T ween series of products.
Nonionic surfactant can contain fatty acid alkyl alcohol amide, and the carbon number of aliphatic acid is 6 to 24, can be straight
The aliphatic acid of chain can also be the aliphatic acid of branch, can be the aliphatic acid of saturation, can also be undersaturated aliphatic acid；Alkane
Base alcohol number is 0 to 2.The glycollic amide that preferred fatty acid carbon number is 8 to 18, diglycollic amide, isopropanol amide, suitably
Example is coconut acid diethanolamide.
Nonionic surfactant can contain fatty acid methyl ester ethoxylate, and general formula is as follows：
Wherein, n is 6 to 24；X is 0.5 to 30.It is preferred that it is 2 to 20 that n, which is 8 to 18, x,.
Nonionic surfactant can contain polyether surfactant.Polyether surfactant is a kind of polymerization
Object, the nonionic surfactant containing ethyoxyl and/or propoxy repeating units, suitable example such as BASF AG
Pluronic series of products.
Other surfactants
Surfactant system of the present invention can contain other surfaces activating agent, be selected from：0.5%~30% both sexes
Ionic surface active agent, the group of 0.1%~30% cationic surface active agent composition.Zwitterionic surfactant is selected from ammonia
Base acid type surfactant, betaine type amphoteric surfactant, one or more mixtures of Imidazoline Surfactants；Including
But it is not limited to：Alkyl betaine, fatty acid amide glycine betaine, fattyamidopropyl betaine, fatty amide propyl hydroxypropyl sulphur
Acidic group glycine betaine, including acetate alkyl sodium form imidazoline, fatty acid type imidazoline, sulfonic acid type imidazoline；Alanine derivatives,
Glycine derivative etc..Cationic surfactant includes quaternary ammonium salt surface active agent, heterocyclic surfactant, polymer
Type cationic surfactant；Including：Single long linear quaternary ammonium salt, double long linear quaternary ammonium salts, benzyl quaternary ammonium salt, hydroxyalkyl quaternary ammonium
Salt, fatty amide propyl hydroxyalkyl quaternary ammonium salt, has vinyl pyrrolidone and unsaturated amides or unsaturated quaternary ammonium salt to be copolymerized
The multi-quaternary ammonium salt arrived.
Optical Bleaching Agent
Detergent composition of the present invention preferably comprises Optical Bleaching Agent.Optical Bleaching Agent is in detergent compositions
Application be technology known in the art, and have many commercially available Optical Bleaching Agent commodity.The use of usual Optical Bleaching Agent
Amount is the 0.01% to 2% of total composition, preferably 0.01% to 0.1%.Optical Bleaching Agent (is mostly sodium with its alkali metal salt
Salt) form presence.Preferred Optical Bleaching Agent including but not limited to：Distyryl biphenyl compound.Suitable example is
4,4 '-bis- (2- sodium sulfonates styryl) biphenyl, such as the product of BASF AG's CBS-X trades mark；Double triazine amino-stilbene classes,
Suitable example is 4,4 '-bis- { [(4- phenylamino 6- morpholino -1,3,5-, triazine -2- base)] amino } stilbenes -2,
2 '-disulfonates.
It can include the group selected from following compound composition：2- (4- styryl -3- sulfo groups phenyl) -2H- naphtho-s [1,2-
D] 1-Sodium-1,2,4-Triazole, 4,4 '-bis- { [(4- phenylaminos 6- (N- methyl-N-2- ethoxys) amino -1,3,5-, triazine -2- bases)] amino }
2,2 '-disulfonate of stilbene -, 4,4 '-bis- { [(4- phenylamino 6- morpholinoes -1,3,5-, triazine -2- bases)] ammonia
Base } 2,2 '-disulfonate of stilbene-, 4,4 '-bis- (2- sulfostyryls) biphenyl disodiums.
Enzyme preparation
Detergent composition of the present invention can include that one or more of enzyme preparations are knitted with providing clean-up performance
Object is nursed and/or other beneficial effects.The enzyme preparation is selected from following enzyme and different combinations：Protease, alpha-amylase,
Cellulase, hemicellulase, phosphatidase, esterase, lipase, peroxidase/oxidizing ferment, pectase, lyases, sweet dew are poly-
Carbohydrase, cutinase, reductase, zytase, amylopectase, tannase, pentosanase, maltosan, arabinase, β-
Dextranase.Common enzyme preparation is protease, amylase, lipase, cutinase and/or cellulase.Enzyme preparation content is
The 0.001% to 5% of detergent composition, preferably 0.01% to 2%.
The detergent composition of the present invention can include the enzyme stabilising system for accounting for composition weight 0.001% to 10%.Institute
Stating enzyme stabilising system can be compatible with detergent composition, may include calcium ion, boric acid, borax, propylene glycol, glycerine, polyalcohol
One kind and its mixture.The weight and dosage of enzyme stabilising system are according to the form and composition and enzyme preparation of detergent composition
Type be adjusted.
Anti redeposition agent
Can include to resist to sink again in detergent composition of the present invention from the viewpoint of effectively improving washing effect
Product agent.The anti redeposition agent includes but is not limited to the group of following compound composition：Cellulose derivative, such as carboxymethyl are fine
Dimension element, ethylhydroxyethylcellulose, methylcellulose；The homopolymer and copolymer of vinyl pyrrolidone, such as the poly- second of straight chain
The copolymer of vinyl pyrrolidone, n-vinyl pyrrolidone and vinyl acetate, n-vinyl pyrrolidone and N- vinyl
The copolymer of imidazoles, polyvinyl oxazolidone, polyethylene glycol and polyethyleneterephthalate block copolymer, polypropylene
Acid or polyacrylate, alkoxylate polyethyleneimine etc..
Washing assisant a
Washing assisant a mentioned in the present invention refers to the washing assisant being present in main body detergent composition, washing
Auxiliary agent a can be selected from：Enzyme preparation, essence, Optical Bleaching Agent, anti redeposition agent and their mixture etc..
Washing assisant b
The washing assisant b, refers to the content being encapsulated in water-soluble film b.It is played in washing process
Additional laundry care function.
Washing assisant described herein can include fabric softener, enzyme preparation, antistatic agent, essence, solid or liquid
Body bleach system.
Bleach system
Bleaching agent can be independently selected from many different activities substances as disclosed below：
In this paper preferred embodiment, bleaching agent includes oxygen source and/or oxygen release bleaching agent.This oxygen release bleaching
Agent includes hydrogen peroxide source, such as hydrogen peroxide itself；Perborate, such as sodium perborate；SODIUM PERCARBONATE or the mistake being equal with it
Carbonate；Sodium pyrophosphate per-compound, persulfate, sodium peroxide and their mixture.Wherein preferred sodium perborate
Monohydrate and SODIUM PERCARBONATE.
When bleaching active is organic peroxide acid bleach precursor compound, pass through the precursor and hydrogen peroxide source
Situ reaction can carry out the preparation of organic peroxide acid.Furthermore it is possible to which preformed organic peroxide acid is directly incorporated into composition
In, the blend compositions can be used when bleaching active is pre-formed peracids or bleaching catalyst, regardless of whether with
Hydrogen peroxide source mixes.
Inorganic peroxy compounds bleaching agent, and containing the organic peroxide acid combined with preformed organic peroxide acid before
The composition of the mixture of body and hydrogen peroxide source is also applied for the present invention.
The coating material of per-compound can provide stable solid bleach system, be also applied for the present invention.
Fabric softener
The fabric softener that the present invention is previously mentioned is selected from：Water-insoluble clay, nonionic, amphoteric ion and both sexes nitrogen-free silicon
Oxygen alkane polymer, nitrogenous siloxane polymer, Cationic silicone polymer, anion siloxane polymer, long-chain fatty alcohol,
One or more mixtures of water-insoluble quaternary ammonium fabric softener active or their corresponding amine precursors.
Optional member
Detergent composition of the present invention includes following optional additive：Alkaline agent, viscosity modifier, preservative,
Colorant, essence etc..
Detergent composition of the present invention can include one or more alkaline agents, and alkaline agent is selected from sodium hydroxide, hydrogen-oxygen
The compound of change potassium, alkali carbonate, the silicate of alkali metal, alcamine compound and other organic base types.
In some embodiments, detergent composition of the present invention preferably comprises preservative, and suitable example is
Phenoxy group alcohol, sodium benzoate；Isothiazolinone and its derivative such as methylisothiazolinone, methylchloroisothiazandnone, benzo
One kind or mixture of isothiazolinone.Preservative dosage is 0.001% to 5%, preferably 0.01% to 2%.
In some embodiments, detergent composition of the present invention contains colorant, and the colorant includes dye
Material and pigment.Colorant can include the colorant applied in be used in cleaning product, suitable example such as acid red G, alkali
Property pinkish red, Methanil Yellow G, Acid Light Yellow G, alkaline yolk, direct fast blue B2RL, it is indigo-blue etc..
Detergent composition of the present invention preferably comprises fragrance, and the fragrance includes that all are suitable for cleaning product
Fragrance component.The fragrance used of the present invention can be natural origin, can also be the mixed of chemically synthesized product or the two
Close object.Suitable example such as lemon, rose, jasmine, lavender, citrus is fragrant, green fragrant, root of Aucklandia lappa Decne etc..
In addition to above-mentioned optional member, detergent composition of the invention also may include water, organic solvent, cosolvent, solubilising
Agent, gelling agent promote infusion, foam inhibitor, fabric softener, the various common and conventional additives such as anti wrinkling agent.These additions
Agent and associated method of use are all well-known to those skilled in the art, and the selection of specific type and dosage can be according to reality
Border needs to be adjusted.
Preparation and application method
The detergent composition of the present invention is prepared using various methods well-known to those skilled in the art.The composition
Preparation can be carried out by conventional means, specifically should be according to the state of component in the solution and effect and the stabilization of component
Property selection suitable charging sequence, charge temperature and feed time.
By above-mentioned technical proposal, the present invention has the advantage that is with advantageous effect：
1) present invention is reached main body detergent composition pouch and is washed by the thickness and molecular weight of control water-soluble film
The purpose that auxiliary agent pouch is ruptured in different time is washed, to realize that scrubbed component discharges in different time points so that each washing
Component plays the advantageous effect of maximum washing or nursing role；
2) during clothes washing, only in the solvable unit dose system of the primary present invention of washing incipient stage addition
Product, you can reach while cleaning clothing, the profit point of care of laundry items, to reduce in laundry processes hydroelectric resources and manpower,
Waste of time；
3) present invention be it is a kind of it is convenient, be easy use, simplify laundry processes, save water power fabric washing shield use, water-soluble list
Position dosage formulation.
Description of the drawings
Fig. 1 is the display diagram of the unit dose articles containing functional pouch of the present invention.
Specific implementation mode
The unit dose articles containing functional pouch of the present invention are suitable for fabric washing application.The pouch is suitable for
Hand washing, washing machine wash automatically.When hand washing, the unit dose articles can be put into water, wait for that pouch and content are complete
After dissolving, start to wash；When washing machine washs automatically, the unit dose articles are placed into the fixed delivery apparatus of machine
In, or can also be added directly into the rotating cylinder of washing machine.
Refering to Figure 1, Fig. 1 is the display diagram of the unit dose articles containing functional pouch of the present invention.Wherein,
Detergent composition a, water-soluble film b based on water-soluble film a encapsulatings1Encapsulating is washing assisant b1, water-soluble film
b2Encapsulating is washing assisant b2。
The following examples purpose is to be further described and show specific embodiment within the scope of the present invention.Cause
This, embodiment is interpreted as being only used for showing the present invention in more detail, without the content limiting the invention in any way.
In following embodiment, unless otherwise specified, all contents are weight percentages, and related ingredients listed contains
Amount is the content of the active material by conversion.
In the described embodiment, following abbreviations will be used, and have the function of being indicated.
Enzyme：Protease, cellulase, pectase, lipase and its mixture.
Brightening agent：4,4 '-bis- (2- sodium sulfonates styryl) biphenyl, Optical Bleaching Agent, BASF AG's product, the trade mark are
CBS-X。
Preservative：Methylisothiazolinone and chlormethylisothiazo,ine alcohol/ketone mixtures.
A kind of solvable unit applied suitable for fabric washing, at least encapsulated by two or more water-soluble film
Dosage formulation can be prepared by following processing step：
1) it is 70000~150000 by molecular weight, the water-soluble film b that thickness is 50~110 μm is as counterdie；
2) after film being heated or soaked, vacuum can be used to be sucked in grinding tool appropriate (mold), to counterdie
It is vacuumized, fitting grinding tool (mold) is handled；
3) filling of washing assisant is completed by approach appropriate, addition is adjusted according to grinding tool size；
4) it is 70000~150000 by molecular weight, the water-soluble film b that thickness is 50~110 μm is as upper film, in counterdie
It with upper film sealing part, does and heats, or the appropriate solvent of spraying, and carry out encapsulation process.
5) it is 20000~70000 to put molecular weight in the packaging motor spindle of unit dose articles, and thickness is 40~80 μm
Water-soluble film a, the water-soluble film are counterdie；
6) it repeats the above steps 2), and completes the filling of main body detergent composition, addition root by approach appropriate
It is adjusted according to grinding tool size；
7) it using the water-soluble film b for containing washing assisant pouch obtained by step 4) as upper film, is sealed in counterdie and upper film
Place, does and heats, or the appropriate solvent of spraying, and carries out encapsulation process, obtains at least by the water-soluble of two or more
The solvable unit dose articles of property thin film encapsulation.
In addition, it is a kind of suitable for fabric washing application, at least by two or more water-soluble film encapsulating can
Molten unit dose articles can also be prepared by second of processing step：
1) it is 70000~150000 by molecular weight, the water-soluble film b that thickness is 50~110 μm is as counterdie；
2) after film being heated or soaked, vacuum can be used to be sucked in grinding tool appropriate (mold), to counterdie
It is vacuumized, fitting grinding tool (mold) is handled；
3) filling of washing assisant is completed by approach appropriate, addition is adjusted according to grinding tool size；
4) it is 70000~150000 by molecular weight, the water-soluble film b that thickness is 50~110 μm is as upper film, in counterdie
It with upper film sealing part, does and heats, or the appropriate solvent of spraying, and carry out encapsulation process, obtain being encapsulated in water-soluble film
In washing assisant pouch, and be cut into independent pouch；
If 5) there is more than one detergent auxiliary composition, repetition step 1~5, which can be obtained, is encapsulated in water-soluble film
Different, independent washing assisant pouch；
6) it is 20000~70000 by molecular weight, the water-soluble film a that thickness is 40~80 μm is as counterdie；
7) it repeats the above steps 2), and completes the filling of main body detergent composition, addition root by approach appropriate
It is adjusted according to grinding tool size, while independent washing assisant pouch obtained above is added,
8) be 20000~70000 by molecular weight, the water-soluble film a that thickness is 40~80 μm as upper film, counterdie with
Upper film sealing part, does and heats, or the appropriate solvent of spraying, and carries out encapsulation process, obtain at least by two kinds or two kinds with
On water-soluble film encapsulating solvable unit dose articles.
The preparation method of main body detergent composition a, includes the following steps：
1) water is added into batch tank；
2) glycerine, propylene glycol are added into batch tank；
3) 60 DEG C~70 DEG C are warming up to, is under alkaline condition fatty acid salt, stirring to dissolving by aliphatic acid heating saponification
Completely；
4) stop heating, temperature is down to 50 DEG C hereinafter, other anion surfactants, nonionic surfactant is added
And amphoteric surfactant, stirring are complete to dissolving；
5) balance deionized water is added into batch tank, accelerates cooling；
6) after temperature is down to 45 DEG C or less, brightening agent is added, essence, pigment, the other compositions such as preservative, stirring and dissolving is complete
Entirely；
7) metal or semimetal salt is added, adjusts pH, stirring is complete to dissolving；
The following preferred embodiment further illustrated by specific preferred embodiment in the scope of the invention.These
Embodiment is merely illustrative, rather than is limited the scope of the invention, as long as because without departing from the spirit with the item of range
Under part, many variations can be carried out to the present invention.
The preparation process of washing assisant b1, includes the following steps：
1) deionized water is added into batch tank；
2) 50 DEG C~60 DEG C are warming up to, cationic polymer is added, stirring is complete or uniformly mixed to dissolving；
3) glycerine, propylene glycol are added into batch tank；
4) wait for that temperature is down to 50 DEG C hereinafter, other anion surfactants, nonionic surfactant and both sexes are added
Surfactant, stirring are complete to dissolving；
5) balance deionized water is added into batch tank, accelerates cooling；
6) after temperature is down to 45 DEG C or less, essence is added, pigment, the other compositions such as preservative, stirring and dissolving is complete；
7) metal or semimetal salt is added, adjusts pH, stirring is complete to dissolving.
The preparation process of washing assisant b2, includes the following steps：
1) in advance using percarbonic acid compound as kernel, external apply successively is covered with sodium carbonate, sodium sulphate, Boratex, sodium metasilicate
Or sodium metasilicate；
2) applicator obtained above is added in ingredients pot；
3) anhydrous sodium sulphate is added in ingredients pot, and is uniformly mixed；
4) zeolite is added in ingredients pot, and is uniformly mixed；
5) color masterbatch is added in ingredients pot, and is uniformly mixed；
6) anti redeposition agent is added in ingredients pot, and is uniformly mixed；
7) when temperature in ingredients pot is less than 40 DEG C, essence, catalase is added.
The main body detergent group that the solvable unit dose articles described in the invention are coated is listed in following table 1-table 3
Close the raw material composition of object a, detergent auxiliary composition b1, detergent auxiliary composition b2.
The composition example of 1 main body detergent composition a of table
2 detergent auxiliary composition b of table1Composition example
3 detergent auxiliary composition b of table2Composition example
Table 4 lists water-soluble film a, the water-soluble film b for forming the solubility unit dose articles1, thin, water soluble
Film b2Thickness and the parameters such as molecular weight, and test respectively the solubility unit dose articles main body detergent pouch and
Washing assisant pouch encounters the rupture time after water.
4 unit dose articles solubility property of table is tested
It can be obtained by data above, since the water-soluble film a of encapsulating main body detergent composition touches water, warp
After spending 0.5-2 minutes, water-soluble film rupture, main body detergent composition releases；From the water-soluble of encapsulating washing assisant
Property film b touch water and start, after 6-10 minutes, water-soluble film rupture, washing assisant pouch is slower to be released
Come, to which the functional component substep for reaching different discharges, while realizing the mesh of the multi-efficiencies such as clothes cleaning, laundry care
's.
Dimension disclosed herein and numerical value should not be construed as the stringent limitation of the exact value.Unless otherwise stated, often
A such dimension is intended to indicate that described value and the functionally equivalent range around the value.For example, being disclosed as the amount of " 40mm "
Guiding principle is intended to indicate that " about 40mm ".
The All Files quoted in invention content are included in herein by reference all in relevant portion.For any
The reference of file is not construed as recognizing that it is the prior art for the present invention.
Although specific embodiments of the present invention have had been illustrated and described, for those skilled in the art
For it is readily apparent that a number of other modification and change can be made without departing substantially from spirit and scope of the present invention
Type.These modifications and variations are included within protection scope of the present invention.
Claims (13)
1. a kind of water-soluble unit dose articles suitable for fabric washing application, it is characterised in that：The product includes at least two
Above enclosure portion,
A) at least one the first enclosure portion made of water-soluble film a；It is washed based on described its content of first enclosure portion
Agent composition a；The weight average molecular weight range of the water-soluble film a is 5000~120000, and thickness range is 25~100 μm；
B) at least one the second enclosure portion made of water-soluble film b；Described its content of second enclosure portion is that washing helps
Agent composition b；The weight average molecular weight range 40000~250000 of the water-soluble film b, thickness range are 25~120 μm；
Above-mentioned water-soluble unit dose articles are prepared by processing step below：
1) using water-soluble film b as counterdie；
2) after film being heated or soaked, it vacuum can be used to be sucked in mold appropriate, counterdie vacuumized,
It is bonded die treatment；
3) filling of washing assisant is completed by approach appropriate, addition is adjusted according to grinding tool size；
4) it does and heats in counterdie and upper film sealing part using water-soluble film b as upper film, or the appropriate solvent of spraying, and
It is sealed processing；
5) water-soluble film a is put in the packaging motor spindle of unit dose articles, which is counterdie；
6) it repeats the above steps 2), and completes the filling of main body detergent composition by approach appropriate, addition is according to mill
Has size adjustment；
7) the water-soluble film b for containing washing assisant pouch obtained by step 4) is done as upper film in counterdie and upper film sealing part
Heat treatment, or the appropriate solvent of spraying, and encapsulation process is carried out, obtain the water-soluble film at least by two or more
The solvable unit dose articles of encapsulating.
2. the water-soluble unit dose articles suitable for fabric washing application as described in claim 1, it is characterised in that：The water
Soluble film's a thickness is 25~80 μm；The water-soluble film b thickness is 25~110 μm.
3. the water-soluble unit dose articles suitable for fabric washing application as claimed in claim 2, it is characterised in that：The water
Soluble film's a thickness is 40~80 μm；The water-soluble film b thickness is 50~110 μm.
4. the water-soluble unit dose articles suitable for fabric washing application as described in claim 1, it is characterised in that：The water
The weight average molecular weight range of soluble film a is 10000~100000；The weight average molecular weight range of the water-soluble film b is
50000~200000.
5. the water-soluble unit dose articles suitable for fabric washing application as claimed in claim 4, it is characterised in that：The water
The weight average molecular weight range of soluble film a is 20000~70000；The weight average molecular weight range of the water-soluble film b is
70000~150000.
6. the water-soluble unit dose articles suitable for fabric washing application as described in claim 1, it is characterised in that：In room temperature
Under, the volume ratio of first enclosure portion and water is 125：1~1：After ∝ contacts water, rupture within 0.5 minute to 2 minutes；
Second enclosure portion and the volume ratio of water are 2：1~1：After ∝ contacts water, rupture within 6 minutes to 10 minutes.
7. the water-soluble unit dose articles suitable for fabric washing application as described in claim 1, it is characterised in that：The water
Soluble film a is selected from polyvinyl alcohol, polyvinyl alcohol copolymer, polyacrylic acid and its salt, the copolymer of polyacrylic acid and its salt, first
Base cellulose, sodium carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, dextrin and it
Mixture；
The water-soluble film b is selected from polyvinyl alcohol, polyvinyl alcohol copolymer, polyacrylic acid and its salt, polyacrylic acid and its salt
Copolymer, methylcellulose, sodium carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose,
Dextrin and their mixture.
8. the water-soluble unit dose articles suitable for fabric washing application as described in claim 1, it is characterised in that：The master
Detergent composition a includes surfactant, deionized water, washing assisant a, cosolvent and their mixture.
9. the water-soluble unit dose articles suitable for fabric washing application as claimed in claim 8, it is characterised in that：By washing
The weight percent meter in agent composition is washed, the main body detergent composition a includes raw material components：
0.05%~20.0% fatty acid salt；
0.05%~25.0% linear alkylbenzene sulfonate (LAS)；
10.0%~40.0% nonionic surfactant；
1.0%~40.0% cosolvent；
1.0%~15.0% washing assisant a.
10. the water-soluble unit dose articles suitable for fabric washing application as claimed in claim 9, it is characterised in that：It is described
The content range of fatty acid salt is 1.5%~15.0%；The content range of the linear alkylbenzene sulfonate (LAS) be 5.0%~
20.0%.
11. the water-soluble unit dose articles suitable for fabric washing application as described in claim 1, it is characterised in that：It is described
Main detergent composition a is selected from liquid form, powder type or paste.
12. the water-soluble unit dose articles suitable for fabric washing application as claimed in claim 8, it is characterised in that：It is described
Washing assisant a includes：Enzyme preparation, essence, Optical Bleaching Agent, preservative, chelating agent, alkaline agent, salt, pigment, anti redeposition agent with
And their mixture.
13. the water-soluble unit dose articles suitable for fabric washing application as described in claim 1, it is characterised in that：It is described
Detergent auxiliary composition b includes：Fabric softener, enzyme preparation, antistatic agent, essence, solid or liquid bleaching system, surface are lived
Property agent and their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510540655.2A CN105199863B (en) | 2015-08-27 | 2015-08-27 | A kind of water-soluble unit dose articles suitable for fabric washing application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510540655.2A CN105199863B (en) | 2015-08-27 | 2015-08-27 | A kind of water-soluble unit dose articles suitable for fabric washing application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105199863A CN105199863A (en) | 2015-12-30 |
| CN105199863B true CN105199863B (en) | 2018-10-19 |
Family
ID=54947826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510540655.2A Active CN105199863B (en) | 2015-08-27 | 2015-08-27 | A kind of water-soluble unit dose articles suitable for fabric washing application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105199863B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694322A (en) * | 2016-01-20 | 2016-06-22 | 广州立白企业集团有限公司 | Water-soluble thin film with good water dissolving performance and small bag prepared from water-soluble thin film |
| JP7120999B2 (en) * | 2016-06-13 | 2022-08-17 | モノソル リミテッド ライアビリティ カンパニー | USING A WATER-SOLUBLE UNIT DOSE ARTICLE TO IMPROVE USERS' DOSING EXPERIENCE |
| EP3668961A1 (en) | 2017-08-17 | 2020-06-24 | The Procter and Gamble Company | Method for reducing gelling between a liquid laundry detergent and a liquid fabric enhancer |
| CN113913249A (en) * | 2021-11-18 | 2022-01-11 | 广州立白企业集团有限公司 | Unit dose degerming product with high PCMX content and preparation method thereof |
| CN115404137A (en) * | 2022-09-23 | 2022-11-29 | 深圳市减化生物科技有限公司 | Washing gel bead and preparation method thereof |
| WO2024130588A1 (en) * | 2022-12-21 | 2024-06-27 | L'oreal | Capsule for caring for keratin material and mask containing the same |
| US20240209295A1 (en) * | 2022-12-22 | 2024-06-27 | Henkel Ag & Co. Kgaa | Unit dose product comprising a liquid composition with encapsulated fragrance and a powder composition with pigment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1444644A (en) * | 2000-07-24 | 2003-09-24 | 宝洁公司 | Articles containing encapsulated compositions |
-
2015
- 2015-08-27 CN CN201510540655.2A patent/CN105199863B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1444644A (en) * | 2000-07-24 | 2003-09-24 | 宝洁公司 | Articles containing encapsulated compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105199863A (en) | 2015-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105199863B (en) | A kind of water-soluble unit dose articles suitable for fabric washing application | |
| CN106795353B (en) | Product and correlation technique comprising water-soluble poval film and plasticizer blends | |
| US4972017A (en) | Rinse soluble polymer film composition for wash additives | |
| US4801636A (en) | Rinse soluble polymer film composition for wash additives | |
| CN104781381B (en) | Laundry composition | |
| JP6246891B2 (en) | Water-soluble film for delayed release | |
| CA1151496A (en) | Built liquid detergent compositions and method of preparation | |
| ES2272543T3 (en) | PORTIONS OF DETERGENT, WASHING AGENT OR CLEANING AGENT MECHANICALLY STABLE, OF LIQUID FORMULATION. | |
| CN104531406B (en) | A kind of fabric detergent compositions and the method for promoting its color protection performance | |
| CN106536702A (en) | Unit dose detergent compositions | |
| CN105874048B (en) | Laundry composition | |
| CN108130215A (en) | A kind of low-viscosity (mobile) liquid detergent composition with yield stress and preparation method thereof | |
| KR102211162B1 (en) | Sheet for laundry | |
| KR20100066447A (en) | Associative thickener dispersion | |
| CN101153241A (en) | Water soluble package and liquid contents thereof | |
| KR20120127174A (en) | Sheet for laundry | |
| CN109135960B (en) | Application of polymer as protease stabilizer in detergent and detergent composition | |
| CN110343580A (en) | A kind of unit dose detergent product of high-moisture | |
| CZ20012187A3 (en) | Laundry detergent in the form of a paste | |
| CN113980749A (en) | Liquid detergent composition | |
| EP4001385A1 (en) | Automatic dishwashing composition | |
| JP5199614B2 (en) | Viscous liquid detergent composition and method for producing the same | |
| PL188031B1 (en) | Stable liquid washing agents of increased viscosity | |
| KR20130124261A (en) | Sheet for laundry | |
| JP4588722B2 (en) | Cleaning composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |