NO139225B - DETERGENT MIXTURE. - Google Patents
DETERGENT MIXTURE. Download PDFInfo
- Publication number
- NO139225B NO139225B NO3326/72A NO332672A NO139225B NO 139225 B NO139225 B NO 139225B NO 3326/72 A NO3326/72 A NO 3326/72A NO 332672 A NO332672 A NO 332672A NO 139225 B NO139225 B NO 139225B
- Authority
- NO
- Norway
- Prior art keywords
- washing
- acid
- building
- substances
- detergent
- Prior art date
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- 239000003599 detergent Substances 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 title claims description 16
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 description 31
- 239000000126 substance Substances 0.000 description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000004566 building material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- VIGOAHUTMBFPMD-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O VIGOAHUTMBFPMD-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VXRUADVCBZMFSV-UHFFFAOYSA-N 2-acetyloxypropane-1,2,3-tricarboxylic acid Chemical compound CC(=O)OC(CC(O)=O)(CC(O)=O)C(O)=O VXRUADVCBZMFSV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004348 Glyceryl diacetate Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 238000003287 bathing Methods 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
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- -1 butanecarboxylic acid adipic acid Chemical compound 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 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
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- LBGVCGUWUIQOJR-UHFFFAOYSA-N ethane-1,2-diol;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OCCO.OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O LBGVCGUWUIQOJR-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 235000019443 glyceryl diacetate Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 210000003371 toe Anatomy 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
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Oppfinnelsens gjenstand er en vaskemiddelblanding som inneholder anioniske eller ikke-ioniske tensider og byggesalter, samt eventuelt ytterligere tilsetningsstoffer. The object of the invention is a detergent mixture containing anionic or non-ionic surfactants and building salts, as well as possibly further additives.
Det er kjent at rensekraften av såper og syntetiske vaskemidler i vaske- og rensemidler økes ved tilsetning av bestemte produkter. Slike rensningsforsterkere betegnes som byggestoffer eller "Builder". Byggestoffer-inneholdende vaske- <p>g rensemidler er mer virksomme og enda mer prisgunstigere enn de tilsvarende byggestoffrie formuleringer. It is known that the cleaning power of soaps and synthetic detergents in washing and cleaning products is increased by adding certain products. Such cleansing enhancers are referred to as building substances or "Builder". Building material-containing washing <p>g cleaners are more effective and even more cost-effective than the corresponding building material-free formulations.
Mekanismen og detaljer ved "bygger-virkningen" er The mechanism and details of the "builder effect" are
ennu ikke helt avklaret . Det er flere prosesser som spiller en rolle ved funksjonen av byggere som stabilisering av pigmentsmuss-suspensjonene, emulgering av smusspartikler, påvirkning av over-flate- og grenseflateegenskaper av vandige tensidoppløsninger, solubilisering av vahnuoppløselige bestanddeler av rensebadet, peptisering av smussagglomerater, nøytralisering av sure stoffer og inaktivering av mineralstoffer i vaskebadet. not yet completely settled. There are several processes that play a role in the function of builders such as stabilization of the pigment dirt suspensions, emulsification of dirt particles, influence of surface and interface properties of aqueous surfactant solutions, solubilization of water-insoluble components of the cleaning bath, peptization of dirt agglomerates, neutralization of acidic substances and inactivation of mineral substances in the washing bath.
For å få opplysning om kvaliteten og egenskapene av enkelte produkter som byggere, undersøker man hensiktsmessig deres forholdsmåter og deres virkningsgrad ved vaske- eller renseprosesser Dermed sikres at alle i bygger-virkningen deltagende faktorer tas hensyn til kvalitativt og kvantitativt. In order to obtain information about the quality and properties of certain products as builders, their ratios and their effectiveness during washing or cleaning processes are appropriately examined. This ensures that all factors participating in the builder effect are taken into account qualitatively and quantitatively.
Klassiske byggere er de vannoppløselige uorganiske alkalisalter, som alkalikarbonater,-borater, -fosfater, -polyfosfater, -bikarbonater og -silikater. Classic builders are the water-soluble inorganic alkali salts, such as alkali carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates.
Av de tallrike produkter som foreslås som byggere an-vendes i de vanlige vaske-og rensemidler omtrent utelukkende de lineære kondenserte fosfater eller polyfosfater, spesielt penta-natriumtrifosfat eller natriumtripolyfosfat. Innholdet av vaske-og rensemiddel av disse byggerstoffer utgjør inntil ca. 50 vekt%. Of the numerous products that are proposed as builders, the usual detergents and cleaners use almost exclusively the linear condensed phosphates or polyphosphates, especially penta-sodium triphosphate or sodium tripolyphosphate. The detergent and cleaning agent content of these building materials amounts to approx. 50% by weight.
På grunn av den betraktelige forbruksøkning av fosfat-holdige vaske- og rensemidler, såvel i husholding som også i indu-strien, har også fosfatinnholdet av naturlig avvann øket. Ved diskusjonen om den økende vanneutrofering er i den siste tid nitra-tene og fosfatene tilskrevet egenskaper som befordrer veksten av bestemte algetyper under bestemte betingelser og således på denne måte kan bidra til vanneutrofiering. Enskjønt en entydig av-klaring av betydningen av vaske- og rensemiddel for vanneutrofiering ennu ikke er mulig, synes det imidlertid å skulle til-strebes å utvikle potensielle nitrogen- og fosforfrie erstatnings-stoffer i stedet for de for tiden i vanlige vaskemiddelformuleringer anvendte bærerstoffer, nemlig polyfosfåtene. Due to the considerable increase in consumption of phosphate-containing detergents and cleaning agents, both in households and in industry, the phosphate content of natural waste water has also increased. In the discussion about the increasing water neutrofation, the nitrates and phosphates have recently been attributed with properties that promote the growth of certain types of algae under certain conditions and thus can contribute to water neutrofation in this way. Although an unequivocal clarification of the importance of detergents and cleaning agents for water eutrophication is not yet possible, it seems that efforts should be made to develop potential nitrogen- and phosphorus-free replacement substances instead of the carrier substances currently used in normal detergent formulations, namely the polyphosphates.
Anvendelsen av nitrogen- og fosforfrie byggerstoffer for vaskemiddelformuleringer er kjent. Som slike ble det tidligere eksempelvis anvendt stivelsesderivater, som dikarboksyl- og kar-boksymetylstivelse, polykarboksylsyrer som polymaleinsyre og deres blandingspolymerisater, oksydieddiksyre, oksydiravsyre, estere av polyetylenglykol og adipinsyre resp. maleinsyre som inneholder sulfonatgrupper, samt estere av etylenglykol og tri- resp. tetra-karboksylsyrer. Anvendelsen av ovennevnte stoffer som bærestoffer er forbundet med ulemper som består i at disse stoffer enten ikke er tilstrekkelig biologisk nedbrytbare eller ikke har tilstrekkelig dispergeringsevne for hydrofil smuss. Dessuten mangler delvis også øknonomiske fremgangsmåter til fremstilling av disse for-bindelser. The use of nitrogen- and phosphorus-free builders for detergent formulations is known. As such, starch derivatives, such as dicarboxyl and carboxymethyl starch, polycarboxylic acids such as polymaleic acid and their mixed polymers, oxydiacetic acid, oxydiacetic acid, esters of polyethylene glycol and adipic acid resp. maleic acid containing sulfonate groups, as well as esters of ethylene glycol and tri- or tetra-carboxylic acids. The use of the above-mentioned substances as carriers is associated with disadvantages which consist in the fact that these substances are either not sufficiently biodegradable or do not have sufficient dispersing power for hydrophilic dirt. In addition, economical methods for the production of these compounds are also partially lacking.
I komplettering til tensidbestanddelen av en vaske-middelf ormulering , hvorved bare hydrofobt smuss som sot og fett-partikler dispergeres og/eller peptiseres, må det i vaskemidlet imidlertid også være en komponent som er egnet til å fjerne hydro-filt smuss. Denne oppgave tilkommer byggerstoffene. Ved mangel av et slikt byggerstoff, opptas de på vevnaden befinnende smuss-avleiringer bare ufullstendig fra vaskebadet eller det kommer til avleiring av smusspartikler på vasken, således at det ikke oppnås noen tilfredsstillende vaskeeffekt. However, in addition to the surfactant component of a detergent formulation, whereby only hydrophobic dirt such as soot and fat particles are dispersed and/or peptized, the detergent must also contain a component which is suitable for removing hydrophilic dirt. This task belongs to the building materials. In the absence of such a building material, the dirt deposits on the fabric are only incompletely removed from the washing bath or there is a deposit of dirt particles on the sink, so that no satisfactory washing effect is achieved.
Ifølge US-patent 3.692.684 er det kjent å fremstille vaskemiddelkomposisjoner som ved siden av vanlige vaskemiddel-komponenter som byggere inneholder et alkalisalt av en karboksylsyre som melkesyre, eddiksyre, vinsyre, sitronsyre, butandikarboksylsyre adipinsyre og lignende. According to US patent 3,692,684, it is known to produce detergent compositions which, in addition to usual detergent components, contain an alkali salt of a carboxylic acid such as lactic acid, acetic acid, tartaric acid, citric acid, butanecarboxylic acid adipic acid and the like.
Videre kan i henhold til spalte 3, 2.. avsnitt i ovennevnte patent byggereffekten av ovennevnte salter forbedres ved tilsetning av 0,5-25 vekt% sorbitol eller pentaerytritol referert til mengden byggersalt. Furthermore, according to column 3, paragraph 2.. of the above-mentioned patent, the building effect of the above-mentioned salts can be improved by adding 0.5-25% by weight of sorbitol or pentaerythritol, referred to the amount of building salt.
Da sorbitol som pentaerytritol er relativt dyre produkter og si-tronsyre resp. dens trinatriumsalt alene ikke har noen optimal byggeregenskap, kan de i US-patent 3.692.684 nevnte byggere ikke tilskrives teknisk og økonomisk betydning. As sorbitol and pentaerythritol are relatively expensive products and citric acid resp. its trisodium salt alone has no optimal building properties, the builders mentioned in US patent 3,692,684 cannot be attributed technical and economic importance.
Ved de i US-patént 2.311.008 og 2.264.103 omtalte byggere som sorbitolacetat resp.acetylsitronsyre er det en ulempe at eddiksyrekomponentene ikke har byggeregenskaper og således bare sorbitol resp. sitronsyren i begrenset grad er virksom som bygger. With the builders mentioned in US patents 2,311,008 and 2,264,103 such as sorbitol acetate or acetylcitric acid, it is a disadvantage that the acetic acid components do not have building properties and thus only sorbitol or the citric acid to a limited extent is active as a builder.
Oppfinnelsen vedrører nu en vaskemiddelblanding som inneholder anioniske eller ikke-ioniske tensider og byggersalter, samt eventuelt ytterligere tilsetningsstoffer, idet blandingen er karakterisert ved at den som byggersalt inneholder 15-60 .vekt% referert til mengden tørt stoff av vaske- og rensemidlet, av et vannoppløselig salt av glycerol-tri-citrat. Vaskemiddelblandingen ifølge oppfinnelsen gir i vandig miljø av vaskebadet en pH-verdi fra 8 til 12. The invention now relates to a detergent mixture containing anionic or non-ionic surfactants and building salts, as well as possibly further additives, the mixture being characterized in that the building salt contains 15-60% by weight, referred to the amount of dry matter of the washing and cleaning agent, of a water-soluble salt of glycerol tri-citrate. The detergent mixture according to the invention gives a pH value of from 8 to 12 in the aqueous environment of the washing bath.
Tilsetningsstoffer, som eventuelt kan inneholdes ved .siden av ioneaktive og/eller ikke-ionogene tensider i vaskemiddel-formuleringen omfatter stoffer som alkali- eller ammoniumsalter av svovelsyre, kiselsyre, di- og trikiselsyre, karbonsyre, borsyre, iminodieddiksyre, nitrilotrieddiksyre, etylendiamintetraeddiksyre, alkylenfosfonsyre, hydroksyalkylénfosfosyre og/eller aminoalkylen-r fosfonsyre, eller stabilisatorer og aktivatorer for perborater samt hvittonere, karboksymetylcellulose, magnesiumsilikat, desin-feksjonsmidler og/eller enzymer. Additives, which may possibly be contained alongside ion-active and/or non-ionic surfactants in the detergent formulation, include substances such as alkali or ammonium salts of sulfuric acid, silicic acid, di- and trisilicic acid, carbonic acid, boric acid, iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, alkylenephosphonic acid , hydroxyalkylene phosphonic acid and/or aminoalkylene-r phosphonic acid, or stabilizers and activators for perborates as well as white toners, carboxymethyl cellulose, magnesium silicate, disinfectants and/or enzymes.
Den til byggersalt ifølge oppfinnelsen til grunn liggende karboksylsyreester kan fremstilles etter kjente forest-.' ringsfremgangsmåter, eksempelvis ved omsetning av karboksylsyre med alkoholen ved samtidig destillativ fjerning av reaksjonsvannet ved hjelp av et slepemiddel. Molforholdet mellom karboksylsyre og-alkohol velges vanligvis således at pr. alkoholisk hydroksylgruppé■ står det til disposisjon et molekyl karboksylsyre. Inneholder selve karboksylsyren en eller flere alkoholiske hydroksylgrupper, kan også disse forestres. Viktig er at ved forestringen fjernes pr. mol anvendt karboksylsyre et mol reaksjonsvann fra forestringsblan-dingen. Den dannede sure karboksylsyreester overføres ved tilsetning av støkiometriske mengder alkali i det tilsvarende vann-oppløselige salt av karboksylsyreesteren. The carboxylic acid ester underlying the building salt according to the invention can be prepared according to known methods. ring procedures, for example by reaction of carboxylic acid with the alcohol by simultaneous distillation removal of the reaction water with the help of a drag agent. The molar ratio between carboxylic acid and alcohol is usually chosen so that per alcoholic hydroxyl group■ a molecule of carboxylic acid is available. If the carboxylic acid itself contains one or more alcoholic hydroxyl groups, these can also be esterified. It is important that the esterification removes per mole of carboxylic acid used one mole of reaction water from the esterification mixture. The acidic carboxylic acid ester formed is transferred by adding stoichiometric amounts of alkali in the corresponding water-soluble salt of the carboxylic acid ester.
Bærerstoff ifølge oppfinnelsen er å betegne som teknisk fremskritt, da det i betraktelig grad forsinker utfelling av kalsiumioner i vaskebadet og dessuten danner stabile dispersjoner med hydrofile pigmentpartikler. En ytterligere fordel er å se i dets gode biologiske nedbrytbarhet, hvorved det unngås en anrik-ning av bærerstoffer i avvannet. The carrier substance according to the invention can be described as technical progress, as it significantly delays the precipitation of calcium ions in the washing bath and also forms stable dispersions with hydrophilic pigment particles. A further advantage is to be seen in its good biological degradability, whereby an enrichment of carrier substances in the waste water is avoided.
For vurdering av byggeregenskaper av byggerstoffene ifølge oppfinnelsen, er eksempelvis dets dispergeringsevne for jern-(III)-oksyd, bindeevnen for kalsiumioner samt vaskekraften ved vasking av en kunstig tilsmusset vevnad egnet. Tilsvarende forsøk ble gjort med byggerstoffer ifølge oppfinnelsen og resul- . tåtene sammenlignet med egenskapene av kjente byggerstoffer. Gjen-nomføring av forsøkene forklares i følgende eksempler: For assessing the building properties of the building materials according to the invention, for example its dispersing ability for iron (III) oxide, the binding ability for calcium ions and the washing power when washing an artificially soiled fabric are suitable. Similar experiments were carried out with building materials according to the invention and the results the toes compared to the properties of known building materials. Implementation of the experiments is explained in the following examples:
Forsøk 1 Attempt 1
Det ble bestemt dispergeringsvirkningen av natriumsaltet av glyserol-tri-citrat (A) i en vandig 4 vekt%-ig oppslem-ming av tørr, pulverisert jern-(III)-oksyd med en partikkelstør-relse på under 0,058 mm og sammenlignet med virkningen av kjente bærerstoffer som The dispersing effect of the sodium salt of glycerol tricitrate (A) in an aqueous 4% by weight slurry of dry, powdered iron (III) oxide with a particle size of less than 0.058 mm was determined and compared to the effect of known carrier substances such as
B: trinatriumcitrat B: trisodium citrate
C: glycerol C: glycerol
D: diacetin D: diacetin
D: natriumsalt av etylenglykol-di-citrat D: sodium salt of ethylene glycol dicitrate
Den eventuelle konsentrasjon av byggerstoffer i oppslemmingen utgjorde 0,16 vekt-%, referert til den vandige oppløsning. Som grad for dispergeringsvirkningen ble det hver gang fastslått avsetningstiden av jernoksyd-partiklene i 25 ml målesylindre, samt sedimentasjonsvolumet etter 24 timer, idet oppslemmingen har en pH-verdi på 10. De oppnådde resultater er sammenfattet i Tabell 1: The possible concentration of building materials in the slurry amounted to 0.16% by weight, referred to the aqueous solution. As a measure of the dispersing effect, the deposition time of the iron oxide particles in 25 ml measuring cylinders was determined each time, as well as the sedimentation volume after 24 hours, as the slurry has a pH value of 10. The results obtained are summarized in Table 1:
Av tabell 1 fremgår at det nye bærerstoff (A) bedre dispergerer hydrofile smusspartikler enn de kjente bærerstoffer, Table 1 shows that the new carrier substance (A) disperses hydrophilic dirt particles better than the known carrier substances,
da sedimentasjonsvolumene er mindre og avsetningstiden lenger enn for de to kjente bærerstoffer. as the sedimentation volumes are smaller and the deposition time longer than for the two known carrier substances.
Forsøk 2 Attempt 2
Det ble av de i Eksempel 1 omtalte bærerstoffer fastslått bindeevnen for kalsiumioner. Bindeevnen for kalsiumioner i vandige oppløsninger er definert ved det tall som angir hvor mange gram kalsiumioner som holdes i oppløsning av 100 g bærerstoff under bestemte betingelser. Bestemmelsen av dette tall foregår ved titrering med natriumkarbonat, idet det titrerer den til pH 10 innstilte 1%-ige prøveoppløsning med 0,1 normal kalsiumklorid-oppløsning til opptredende uklarhet. For de enkelte bærerstoffer ble det fastslått i Tabell 2 oppførte måletall for bindeevnen av kalsiumioner: The binding capacity for calcium ions was determined from the carrier substances mentioned in Example 1. The binding capacity for calcium ions in aqueous solutions is defined by the number indicating how many grams of calcium ions are held in solution by 100 g of carrier substance under certain conditions. The determination of this number takes place by titration with sodium carbonate, titrating the 1% sample solution adjusted to pH 10 with 0.1 normal calcium chloride solution until cloudiness appears. For the individual carrier substances, the measured figures listed in Table 2 for the binding capacity of calcium ions were determined:
Av Tabell 2 fremgår at det nye bærerstoff (A) ved siden av den i Tabell 1 påviste gode dispergerbarhet også har en Table 2 shows that the new carrier substance (A) in addition to the good dispersibility demonstrated in Table 1 also has a
god bindeevne for Ca<++->ioner, mens de kjente bærerstoffer ikke samtidig har begge egenskaper i ovennevnte grad. good binding capacity for Ca<++-> ions, while the known carrier substances do not simultaneously have both properties to the above-mentioned extent.
Forsøk 3 Attempt 3
Det ble ved hjelp av vaskeforsøk fastslått vaske-kraftkvotienten av vaskebad med en konstant konsentrasjon av vaskeaktivt stoff, imidlertid med forskjellige mengder av det i Eks. 1 nevnte bærerstoff (A) ifølge oppfinnelsen og de dannede resultater grafisk oppstilt i fig. 1 i form av kurve A. Til sammenligning ble de gjennomførte analoge vaskeforsøk under anvendelse av de i Eks. 1 oppførte kjente bærerstoffer og de derved dannede vaske-kraftkvotienter likeledes vist på fig. 1 i form av kurvene B, D og E. The washing power quotient of washing baths with a constant concentration of washing active substance, however with different amounts of it in Ex. 1 said carrier substance (A) according to the invention and the resulting results graphically displayed in fig. 1 in the form of curve A. For comparison, the analogous washing tests were carried out using those in Ex. 1 listed known carrier substances and the thereby formed washing power quotients likewise shown in fig. 1 in the form of curves B, D and E.
Vaskeforsøkene ble gjennomført med en standard-bomulls-vevnad med Krefelder-tilsmussing i et Launder-O-meter ved en vaske-badtemperatur på 90°C. Standardvevnad med Krefelder-tilsmussin er definert i boken av Kurt Lindner "Tenside, Textilhilfsmittel-Wasch-rohstoffe", Wissenschafti. Verlagsgesellschaft Stuttgart (1964), bind II, side 1837. The washing tests were carried out with a standard cotton fabric with Krefelder soiling in a Launder-O meter at a washing bath temperature of 90°C. Standard weaving with Krefelder soil is defined in the book by Kurt Lindner "Tenside, Textilhilfsmittel-Wasch-rohstoffe", Wissenschafti. Verlagsgesellschaft Stuttgart (1964), Volume II, page 1837.
Vaskevannet har 20° tysk hårdhetsgrad og en pH-verdi på 10. Vasketiden utgjorde 30 minutter og badforholdet karakterisert ved forholdet av (kg) vaskegods til (liter) vaskebad, 1:50 i nærvær av 10 stålkuler. Vaskebadet inneholdt som vaskeaktivt stoff 0,4 5 g/l dodecylbenzensulfonat The washing water has a German hardness of 20° and a pH value of 10. The washing time was 30 minutes and the bathing conditions characterized by the ratio of (kg) laundry to (litres) washing bath, 1:50 in the presence of 10 steel balls. The washing bath contained 0.45 g/l dodecylbenzene sulphonate as washing active substance
0,15 g/l talgfett-alkohol og 0.15 g/l tallow fat alcohol and
0,15 g/l herdet talgsåpe. 0.15 g/l hardened tallow soap.
Konsentrasjonen av bærerstoffene utgjorde i vaskebadet The concentration of the carrier substances constituted in the washing bath
0,2-2 g/l vaskebad. 0.2-2 g/l washing bath.
Etter forløp av den ovennevnte vasketid ble standard-bomullsvevnaden skylt, en gang varmt og en gang koldt, og deretter målt i remisjonsfotometer Elrepho fra firmaet Zeiss for hvithets-grad under anvendelse av filter R 53. Vaskekraften ble fastslått etter differensmetoden, hvortil følgende ligning ligger til grunn: After the above-mentioned washing time, the standard cotton fabric was rinsed, once hot and once cold, and then measured in the emission photometer Elrepho from the company Zeiss for the degree of whiteness using filter R 53. The washing power was determined according to the difference method, for which the following equation is to reason:
I denne ligning betyr: In this equation means:
% WK = % vaskekraft . % WK = % washing power.
% WG = % hvithetsinnhold av det vaskede stoff %WGb = % hvithetsinnhold i uvasket stoff.. % WG = % whiteness content of the washed fabric %WGb = % whiteness content in unwashed fabric..
Av kurveforløpet for kurve A på fig. 1 sees at bærer-, stoffet ifølge oppfinnelsen gir vaskebadet en høyere vaskekraft enn de kjente bærerstoffer B, D og E. Of the curve sequence for curve A in fig. 1 shows that the carrier substance according to the invention gives the washing bath a higher washing power than the known carrier substances B, D and E.
Eksempel Example
Det ble gått frem analogt Forsøk 3, imidlertid ble det i vaskebadet i tillegg innført følgende ingredienser: 0,15 g magnesiumsilikat/1 vaskebad 0,15 g natriumsilikat/1 vaskebad The procedure was analogous to Trial 3, however the following ingredients were additionally introduced into the wash bath: 0.15 g magnesium silicate/1 wash bath 0.15 g sodium silicate/1 wash bath
1,25 g "natriumperborat-tetrahydrat/1 vaskebad 0,45 g natriumsulfat/l vaskebad 1.25 g "sodium perborate tetrahydrate/1 wash bath 0.45 g sodium sulfate/l wash bath
0,05 g karboksymetylGeilulose/1 vaskebad. 0.05 g carboxymethylgeilulose/1 wash bath.
De oppnådde vaskeeffekter er vist i form av kurver på fig. 2, idet av kurveforløpet for kurve A fremgår overlegenheten av bærerstoffet ifølge oppfinnelsen i forhold til de kjente bærerstoffer som ble representert ved kurvene B, D og E. The achieved washing effects are shown in the form of curves in fig. 2, as the curve progression for curve A shows the superiority of the carrier substance according to the invention in relation to the known carrier substances which were represented by curves B, D and E.
Fremstilling av bærerstoffet A ifølge oppfinnelsen: Det ble fra en blanding bestående av 92 vektdeler glycerol og 768 vektdeler vannfri sitronsyre med 250 vektdeler toluen under stadig kretsløpsføring av toluenet azeotrop avdestil-lert 72 vektdeler reaksjonsvann, som oppsto under forestringen. Etter blandingens avkjøling, ble toluenet adskilt fra esteren. For fremstilling av natriumsaltet ble den sure esteren nøytrali-sert med 800 vektdeler 40%-ig natronlut og nøytralisasjonsblan- - dingen tørket i vakuum. Det dannede produkt ble anvendt i eksem-plet som bærerstoff A. Preparation of the carrier substance A according to the invention: From a mixture consisting of 92 parts by weight of glycerol and 768 parts by weight of anhydrous citric acid with 250 parts by weight of toluene under constant circulation of the toluene, 72 parts by weight of reaction water, which arose during the esterification, were azeotropically distilled. After the mixture cooled, the toluene was separated from the ester. To prepare the sodium salt, the acidic ester was neutralized with 800 parts by weight of 40% caustic soda and the neutralization mixture was dried in a vacuum. The product formed was used in the example as carrier substance A.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2147778A DE2147778C3 (en) | 1971-09-24 | 1971-09-24 | Washing and cleaning agents containing water-soluble salts of acidic carboxylic acid esters |
Publications (2)
Publication Number | Publication Date |
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NO139225B true NO139225B (en) | 1978-10-16 |
NO139225C NO139225C (en) | 1979-01-24 |
Family
ID=5820495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO3326/72A NO139225C (en) | 1971-09-24 | 1972-09-18 | DETERGENT MIXTURE. |
Country Status (14)
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US (1) | US3859224A (en) |
AT (1) | AT322713B (en) |
BE (1) | BE789135A (en) |
CA (1) | CA1010058A (en) |
CH (1) | CH577453A5 (en) |
DE (1) | DE2147778C3 (en) |
DK (1) | DK139438C (en) |
FI (1) | FI53834C (en) |
FR (1) | FR2153448B1 (en) |
GB (1) | GB1397957A (en) |
IT (1) | IT965461B (en) |
NL (1) | NL7212868A (en) |
NO (1) | NO139225C (en) |
SE (1) | SE399906B (en) |
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US3919107A (en) * | 1973-03-23 | 1975-11-11 | Procter & Gamble | Built detergent compositions containing dextrin esters of poly carboxylic acids |
IT1213330B (en) * | 1986-08-28 | 1989-12-20 | Rol Spa | SURFACTANTS DERIVED FROM BI- OR TRI-CARBOXYL HYDROXIACIDS. |
US4983315A (en) * | 1989-08-10 | 1991-01-08 | The Procter & Gamble Company | N,N'-(1-oxo-1,2-ethanediyl)-bis(aspartic acid), salts and use in detergent compositions |
DE4108626A1 (en) * | 1991-03-16 | 1992-09-17 | Basf Ag | CITRONIC ACID ESTERS OF POLYHYDROXY COMPOUNDS AND THEIR USE IN DETERGENTS AND CLEANERS |
DE4142131A1 (en) * | 1991-12-20 | 1993-06-24 | Basf Ag | POLYCONDENSATES FROM BUTANTETRACARBONIC ACID AND POLYHYDROXY COMPOUNDS AND THEIR USE IN DETERGENT AND CLEANING AGENTS |
US5531939A (en) * | 1994-03-23 | 1996-07-02 | Amway Corporation | Concentrated glass and window cleaning composition and method of use |
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US3083188A (en) * | 1959-06-22 | 1963-03-26 | California Research Corp | Detergent condensation polymers |
SE352652B (en) * | 1969-10-01 | 1973-01-08 | Hentschel V | |
US3717616A (en) * | 1970-08-11 | 1973-02-20 | Fmc Corp | Polymers of 1-butene-2,3,4-tricarboxylic acid |
US3763047A (en) * | 1971-05-03 | 1973-10-02 | Procter & Gamble | Detergent compositions |
-
0
- BE BE789135D patent/BE789135A/en unknown
-
1971
- 1971-09-24 DE DE2147778A patent/DE2147778C3/en not_active Expired
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- 1972-08-31 FI FI2398/72A patent/FI53834C/en active
- 1972-09-14 GB GB4270672A patent/GB1397957A/en not_active Expired
- 1972-09-18 NO NO3326/72A patent/NO139225C/en unknown
- 1972-09-20 CA CA152,135A patent/CA1010058A/en not_active Expired
- 1972-09-21 US US291044A patent/US3859224A/en not_active Expired - Lifetime
- 1972-09-22 NL NL7212868A patent/NL7212868A/xx not_active Application Discontinuation
- 1972-09-22 DK DK470872A patent/DK139438C/en not_active IP Right Cessation
- 1972-09-22 IT IT52897/72A patent/IT965461B/en active
- 1972-09-22 CH CH1384872A patent/CH577453A5/xx not_active IP Right Cessation
- 1972-09-22 SE SE7212278A patent/SE399906B/en unknown
- 1972-09-22 AT AT818772A patent/AT322713B/en not_active IP Right Cessation
- 1972-09-22 FR FR7233770A patent/FR2153448B1/fr not_active Expired
Also Published As
Publication number | Publication date |
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BE789135A (en) | 1973-03-22 |
DK139438C (en) | 1979-07-16 |
US3859224A (en) | 1975-01-07 |
GB1397957A (en) | 1975-06-18 |
DK139438B (en) | 1979-02-19 |
DE2147778A1 (en) | 1973-03-29 |
NL7212868A (en) | 1973-03-27 |
DE2147778B2 (en) | 1974-07-25 |
FI53834B (en) | 1978-05-02 |
NO139225C (en) | 1979-01-24 |
DE2147778C3 (en) | 1975-03-27 |
SE399906B (en) | 1978-03-06 |
CH577453A5 (en) | 1976-07-15 |
FR2153448A1 (en) | 1973-05-04 |
FR2153448B1 (en) | 1977-03-18 |
IT965461B (en) | 1974-01-31 |
CA1010058A (en) | 1977-05-10 |
AT322713B (en) | 1975-06-10 |
FI53834C (en) | 1978-08-10 |
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