IE52291B1 - Amphoteric fatty acid,amino acid salts and their use in detergent compounds and compositions - Google Patents
Amphoteric fatty acid,amino acid salts and their use in detergent compounds and compositionsInfo
- Publication number
- IE52291B1 IE52291B1 IE512/82A IE51282A IE52291B1 IE 52291 B1 IE52291 B1 IE 52291B1 IE 512/82 A IE512/82 A IE 512/82A IE 51282 A IE51282 A IE 51282A IE 52291 B1 IE52291 B1 IE 52291B1
- Authority
- IE
- Ireland
- Prior art keywords
- compound
- carbon atoms
- alkyl
- fatty acid
- formula
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- 239000000194 fatty acid Substances 0.000 title claims description 36
- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 22
- 229930195729 fatty acid Natural products 0.000 title claims description 22
- 150000004665 fatty acids Chemical class 0.000 title claims description 18
- 239000003599 detergent Substances 0.000 title abstract description 23
- -1 amino acid salts Chemical class 0.000 title description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 9
- 244000060011 Cocos nucifera Species 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 4
- 239000003760 tallow Substances 0.000 claims description 4
- 101710178035 Chorismate synthase 2 Proteins 0.000 claims 1
- 101710152694 Cysteine synthase 2 Proteins 0.000 claims 1
- 239000006260 foam Substances 0.000 description 16
- 229940126062 Compound A Drugs 0.000 description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 8
- 230000007794 irritation Effects 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000004166 Lanolin Substances 0.000 description 7
- 229940039717 lanolin Drugs 0.000 description 7
- 235000019388 lanolin Nutrition 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- XYYUAOIALFMRGY-UHFFFAOYSA-N 3-[2-carboxyethyl(dodecyl)amino]propanoic acid Chemical compound CCCCCCCCCCCCN(CCC(O)=O)CCC(O)=O XYYUAOIALFMRGY-UHFFFAOYSA-N 0.000 description 4
- 241000283973 Oryctolagus cuniculus Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 231100001254 ocular irritant Toxicity 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) 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
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 231100000021 irritant Toxicity 0.000 description 2
- 239000002085 irritant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000344 non-irritating Toxicity 0.000 description 2
- 239000003921 oil Substances 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
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 2
- 239000001570 sorbitan monopalmitate Substances 0.000 description 2
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 2
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 208000006069 Corneal Opacity Diseases 0.000 description 1
- 231100000635 Draize test Toxicity 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910006127 SO3X Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 101150093710 clec-87 gene Proteins 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 231100000269 corneal opacity Toxicity 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- UKHVLWKBNNSRRR-ODZAUARKSA-M dowicil 200 Chemical compound [Cl-].C1N(C2)CN3CN2C[N+]1(C\C=C/Cl)C3 UKHVLWKBNNSRRR-ODZAUARKSA-M 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 210000000554 iris Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 208000013441 ocular lesion Diseases 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- XMMDYIZEXRYOSV-UHFFFAOYSA-N tetradecoxycarbonylcarbamic acid Chemical compound CCCCCCCCCCCCCCOC(=O)NC(=O)O XMMDYIZEXRYOSV-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/74—Biological properties of particular ingredients
- A61K2800/75—Anti-irritant
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Detergent compounds of the formula wherein R1 is alkyl or substituted alkyl containing from about 6 to 18 carbon atoms and mixtures thereof; R2 is alkyl containing from about 8 to 18 carbon atoms and mixtures thereof or alkyl amido of the formula wherein R3 is alkyl containing from about 8 to 18 carbon atoms; Z is H or lower alkyl containing from 1 to 4 carbon atoms; and Y is alkylene containing from 1 to 4 carbon atoms; A1 and A2 are the same or different and are -[-CH2CH2-COOX]n -[-CH2-COOX]n -[-CH2CHOH-CH2SO3X]n or -[-CH2-CHOH-CH2-OPO3X]n wherein X is a water soluble cation and n is 1 or 2 with the proviso that if only one of A1 and A2 are selected from the anionic salt moieties above, the other is alkyl or hydroxyalkyl with 1-4 C atoms. Detergent compositions comprise, as about 1-50% by weight of the total, at least one detergent compound as specified above.
Description
The present invention relates to amphoteric-fatty acid complexes. More specifically, the invention relates to amphoteric-fatty acid complexes which exhibit unexpected foam properties and low ocular irritancy. The invention further relates to detergent compositions containing the novel amphoteric-fatty acid complexes in combination with other surfactants and/or detergent components.
Nonirritating detergent compositions have been known in the art and have been in use for some time. United States Patent Nos. 3,299,069 and 3,055,836 are merely two representative examples of such prior art nonirritating detergent compositions. Likewise, amphoteric compounds have been well known in the art and have been disclosed ir. use with various other detergent compounds. United States Patent No. 2,528,380, discloses a ring structured amphoteric compound with a fatty acid attached to the ring nitrogen. None of the disclosures in the prior art disclose the amphoteric-fatty acid complexes of the present invention nor the advantages provided by same. 2o It is an object of the present invention to provide novel detergent compounds.
It is another object of the present invention to provide novel detergent compounds which exhibit good foam properties and low ocular irritancy. 53391 It is a further object of the present invention to enable detergent compositions which exhibit good foam properties and low ocular irritancy to be provided.
These and other objects of the present invention will become apparent to one skilled in the art from the detailed description given hereinafter.
This invention encompasses non-zwitterionic, amphoteric-fatty acid complexes of the formula 0 Θ r «« ii RlC-0 ^A1 «2- The present invention relates to novel non-zwitterionic, amphoteric-fatty acid complexes of the formula 0 Θ a XA1 RjC-0R2-<, - 1 A2 H J wherein Rl is alkyl or substituted alkyl containing from 6 to 18 carbon atoms and mixtures thereof; R2 is alkyl containing from 8 to 18 carbon atoms and mixtures thereof or alkyl amido alkylene c-f the formula IL-CO-NZ-Y3 I wherein R3 is alkyl containing from 8 to 18 carbon atoms, Z is H or lower alkyl containing from 1 to 4 carbon atoms; and Y is alkylene containing from 1 to 4 carbon atoms; Aj and A2 are the same or different and are each selected from the following anionic salt moieties; fCH2CH2-COOX] -fCH2-COOX] wherein X is a water-soluble cation such as Na+, K+, Ca++, Hg** and the like with the proviso that if only one of Aj_ and A2 are selected from the anionic salt moieties above the other can be lower alkyl or lower hydroxyalkyl containing from 1 to 4 15 carbon atoms; or R is tallow fatty acid' alkyl, R2 is C12H25’ A1 is H’ A2 is CH2CH2C00Na.
The non-zwitterionic, amphoteric compounds which are useful in the complexes of the present invention give ions of the formula: wherein A1 and A 2 are as defined above These compounds can be prepared in accordance with thp teachings of the art, see for example, United States Patent No. 2,970,160, which is incorporated herein by reference.
The fatty acid compounds which are useful in the complexes of the present invention give ions of the formula: II Χχ-C-O wherein Rj is as defined above. These compounds are readily available commercially from numerous sources such as the fatty acids available from Emery Industries Inc.; Cincinnati, Ohio Procter & Gamble, Cincinnati, Ohio anc various other commercial suppliers.
The amphoteric-fatty acid complexes of the present invention can be prepared by admixing a suitable non-zwitterionic amphoteric and a suitable fatty acid, utilizing heat, if necessary, to facilitate the blending and adding water, if needed. The ratio of fatty acid to amphoteric can be in the range of (e.g.) 0.5:1 to 1.5:1, preferably about 1:1. The pH of the resulting complex should be within the range of 6.5-8.5, preferably within the rance of 7.0-7.5, to minimize potential irritation problems.
Specific examples of the novel amphoteric-fatty acid complexes of the present invention include: (A) Rl-C-0 ? 1® wherein ?.χ is a C11H23 - CX8H37 mixture. (Β) 0 II Θ CHjCHjCOONa Rl-C-0 Cl4H29-Nx ’ - pCH2CH2COONa Θ wherein Rj_ is an 80%/20% tallow coconut mixture.
© (C) 0 1 RlC-0 Θ H 1 Ci2H25"N’CH2CK2-COONa H 0 II Θ H CH2CH2COONac12h25c_0c14h29-n\^ -J CH2CH2COONa_ O H Θ CH2CH2C00Na c12h25-n\' (E) RXC-0 |^CH2CH2COONa H wherein Ri is a C5H13 - C18H37 mixture.
Another specific example of the present complexes is that homolog of complex (D) above wherein the C12H25 is rePlaced by a CilH23' The amphoteric-fatty acid complexes of the present invention exhibit excellent surfactant properties. In particular, these complexes exhibit good foam properties and low ocular irritancy. The good foam properties are unexpected because fatty acids do not normally exhioit such properties. It has further been found within the pH range of 7.0-7.2 that the amphoteric-fatty acids complexes exhibit unexpected foam synergism.
These complexes can be utilized in detergent compositions either alone or in combination with other surfactants in a range of from about 1.0 to 50.0% by weight Of the total compositions.
The amphoteric surfactants which may be used in these compositions include betaines, n-alkylamino propionates, n-alkylimino dipropionates and imidazolines. The betaine surfactants useful here are described in U.S. Patent No. 3,950,417 issued April 13, 1976, which is incorporated herein by reference. The n-alkylamino propionates and n-alkylimino dipropionates are sold under the tradename Deriohats by General Mills. The imidazolines which are useful in the compositions mentioned are described in U.S. Patent No. 2,970,160, which is incorporated herein by reference.
The preferred betaine amphoteric surfactants include the alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylcarboxyethylbetaine, cetyld imethylcarboxymethylbetaine, lauryl-bis-(2-hyaroxyethyi, carboxymethvlbetaine, oleyldimethyl-ganuna-carboxypropvlbetaine. lauryl-bis(2-hydroxypropyl)-carboxyethylbetaine, and the like.
The preferred n-alkylamino propionates and n-alkylimino dipropionates include those having the following structures: Θ Θ R - NH2CH2CH2COO and θ 7CH2C&2C00 R - NH \ CH2C32COO Ma wherein R is from about 8 to 22 carbon atoms and mixtures thereof.
The amphoteric detergents may be present in an amount from about 2 to 10% by weight of the total composition.
It is envisioned that any anionic surfactant may be used in the compositions containing the present complexes,e.g. an alkyl sulfate of the formula R-CH2-OSO3X, an alkylether sulfate of the formula R(OCH2CH2)p-OSO X, an alkylmonoglyceryl ether sulfonate of the formula R-OCH2-CH-CH2-SO3X, OH an alkylmonoglyceride sulfate of the formula RCOOCH2-CH-CH2OSO3X OH an alkylmonoglyceride sulfonate of the formula RCOOCH2CH-CH2SO3X I OH an alkyl sulfonate of the formula RSO3X and an alkylaryl sulfonate of the formula wherein R is alkyl having from 7 to 17 carbon atoms; X is selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from 1 to 3 lower alkyls and p is an integer from 1 to 6.
The anionic detergent may be present in an amount of from about 2 to 10% by weight of the total composition.
Nor.ionic detergents which are useful include the alkylene oxide ethers of phenols, fatty alcohols, and alkyl mercapta.ns; the alkylene oxide esters of fatty acid amides; the condensation products of ethylene oxide with partial fatty acid esters, and mixtures thereof. The polyoxyalkvlene chain in such agents may contain from 5 to 100 alkylene oxide units in which each alkylene unit has from 2 to 3 carbon atoms.
The nonionic surfactant may be present in an amount of from about 1 to 30% by weight of the total composition.
Cationic surfactants suitable in these compositions include mono-and bis-quaternary ammonium halides, such as stearyldimethylbenzylammoniura chloride, cetyltrimethylammonium chloride, N,N-dioctadecyl-N,N,N', N‘-tetramethyl1,5-(3-oxapentylene)di-ammonium bromide; tertiary amine salts such as cocoamidopropyldimethylamine hydrochloride stearylamidopropyldimethylamine citrate; cationic polymers such as hydroxytthyl cellulose reacted with epichlorohydrin and then quaternized with trimethylamine (Polymers of this type are sold by Union Carbide under the tradename Polymer JR) and specific triesters of phosphoric acid.
The specific triesters of phosphoric acid are described in copending patent application Serial No. 59,838 filed July 23, 1979, which is incorporated herein by reference. The cationic surfactants should be present in an amount of from about 0.5 to 3.0% by weight of the total composition. 2o The total amount of the active surfactant ingredients in the composition should not be greater than about 50% by weight of the total composition in order to avoid ocular irritation problems, preferably from about 5 to 20% by weight of the total composition with the proviso that the total amount of anionic surfactant and amphoteric surfactant should not exceed 20% by weight of the total composition. In addition, other ingredients conventionally added to surfactant compositions for personal use. such as ayes, preservatives, perfumes, thickeners, opacifiers, conditioners, emollients, buffering agents, and the like, may be added in minor amounts. Ingredients such as dyes, preservatives and perfumes together usually constitute less than 2% by weight of the total composition and thickeners may be added to the composition in an η amount of from about 1 to about 3» by weight of the total composition.
The detergent compositions under discussion here should have a pH in the range of about 6.5 to 8.5, preferably from about 7.0-7.5.
Liquid detergent compositions utilizing the complexes of the present invention can be prepared by admixing the amphoteric-fatty acid complex with the other surfactant(s) at room temperature or slightly elevated temperatures (about 50eC) and then sufficient deionized water is added to bring the composition to about three quarters of itsintended weight. Other ingredients such as various detergency adjuncts, fillers, carriers, perfumes, preservatives, gelling agents and the like are added as required followed by the balance of the water. The pH is then- adjusted to within the desired range by the addition of strong acid, e.g., HCl, or strong base NaOH, as needed.
Detergent bar compositions utilizing the complexes of the present invention can be prepared by admixing the amphoteric - fatty acid complex with the other surfactant(s) in a steam jacketed rotary mixer at temperatures within the range of 60-80eC. Fillers, whitening agents and processing oils can be added, as needed, to the hot slurry. After adequate mixing to assure homogeneity and moisture balance the product is chill rolled or drum dried into flakes. Dyes and fragrances are added to the flakes in a standard amalgamator together with additional water to provide proper bar formation. After adequate mixing the flakes are milled and plodded into logs which are then cut into blanks prior to stamping into bar form.
The detergent compositions described can be tested for ocular irritation by the following modified Draize Test (J.H. Draize et al., Toilet Goods Assn. No. 17, May 1952, No. 1, Proc. Sci. Sect.).
An 0.1 ml. sample of a neutral composition under test is dropped into one eye of an albino rabbit, the other eye serving as a control. Six rabbits are employed for each composition. Observations are made after 1, 24, 48, 72 and 96 hours and 7 days after initial instillation; second and third instillations are made after the 24 and 48 hour readings. Results may vary from substantially no change or only a slight irritation in the appearance of the rabbit's eye after 7 days to severe irritation and/or complete corneal opacity. Ocular lesions are scored for the cornea, iris and conjunctiva with a higher number indicating greater ocular irritation and the scores are added to give a total numerical value for each, reading for six rabbits and averaged. The averaged score is an indication of the irritation potential of the composition under test. Based on the averaged score, descriptive irritation evaluation may be given, e.g., none, slight, moderate, severe, as the case may be.
The above-described detergent conpcsitions provide high foan volume and moreover outstanding foam staoility as measured by an adaption of the well-known Ross-Miles foam test principle "Oil and Soap 18.9-102 (1941) : Lanolin, anhydrous, cosmetic grade is mixed with dioxane (technical grade) in the proportion of 2.5 grams lanolin and 100 grams of dioxane. The lanolin is first mixed with cc. of dioxane. This mixture is heated over a steam bath to 454C in order to dissolve the lanolin in the dioxane. The remainder of the dioxane is then added and mixed. This lanolin dioxane solution, which is stored in 53291 an ambef bottle, should be prepared fresh on the day that the tests are run.
The composition to be tested is diluted by adding 376 cc. of distilled water to 4 grams of the composition, and then by adding 20 cc. of the lanolin-dioxane solution described above while mixing. Heat is produced when the lanolindioxane solution is added to the solution of the composition in water and care must be taken in adjusting the temperature of this solution to 24°-25eC. Both of these intermediate solutions should therefore be adjusted to 23°C before mixing. The cooling of the lanolin-dioxane solution should be gradual in order to avoid precipitation of the lanolin. This will produce a final solution with a temperature of 24°-25°C.
The final solution of the composition to be tested, water, cioxane and lanolin described above, is then run in a modified Ross-Miles foam column in the usual way. All tests are conducted in duplicate, and the average of the two results is taken. Foam stability is determined by measuring the decay in foam height after two minutes, expressed as a percentage of the original height.
The use of the compounds of the invention is illustrated by the following representative examples. It will be understood, however, that the invention is not confined to the specific applications set forth in the individual examples.
Example I 320.2 grams (.19g/moles) of a 24% active solution of an amphoteric of the formula H C2H4OH cuh23JJ-,ch2,2-»( _ H are mixed with 47 grams (.24 g/moles) of preraelted coconut fatty acids of the following chain length percentage distribution: Cg-0.3, Cg-7.3, Cxq-6.5, Ci2"50.7, C14-18.9, C16-8.6, Ci8-7.7.
The resulting product is an opaque, viscous slurry containing 34% solids with a pH of 7.1 and is an amphoteric-fatty acid complex of the structure shown as compound E in the specification. The complex foams copiously in both soft and hard water and is a slight •ocular irritant.
Example II The slurry obtained in Example I is freeze-dried by known procedures to yield about 95% solids. The solids are ground to a slightly tacky powder which can be utilized to form a bar soap and is a slight to moderate ocular irritant.
Example III Following the procedures of Example I, the amphoteric of Example I is mixed with stripped hydrogenated coconut fatty acids of the following chain length percentage distribution: Cg-1, Cig-1, Ci2-56, Ci4-24, Cig-12.5 and Cpg-5; to form an amphoteric-fatty acid complex shown as compound A in the specification. The resultant dried powder is found to be a slight ocular irritant.
Example IV Following the procedures of Example 1, 227 grams 5 (.15 g/moles) of a 22) active solution of tetradecyl iminodicarboxylate are dissolved in 450 grams of deionized water at a temperature of about 5O’-6O*C. 30 grams (.15 g/reoles) of the coconut fatty acid of Example I are added to form the resulting amphoteric-fatty acid complex which is a moderate irritant and is of the following structure: RjC-0 c14k29-Nv CH2CH2COONa wherein Rj is a C6K13_C18H37 fixture.
EXAMPLE V 360 grans (0.19 g./moles) of a 19.1% active solution of an amphoteric of the formula ^xC^COONa J '*''»CH2COONa H wherein R has an alkyl chain length percent distribution as follows: Cjq-2, Ci2"53, Οχ4-24, Cjg—11 Cia-10,· are mixed with 40 grams (0.19 g./moles) of premelted coconut fatty acids having the alkyl chain length distribution set forth in Example I. The resulting product is a thin, opaque slurry containing 27% solids having a pH of 7.5 and is an amphoteric fatty acid complex of the formula: CH2C00Na R2H CH2COONa Example VI A clear gel hair care product is prepared as follows: 200 grams of deionized water are charged to a vessel equipped with an agitator and steam. 50 grams of a phosphate ester hydrotrope are added and the pH is adjusted to 7.0. 150 grams of Compound A are added and the solution is mixed until clear. 20 grams of polyethylene glycol 6000 distearate are added and heat is applied to the solution to 70°C for twenty minutes. The solution is cooled to -30eC and 1.0 grams of preservative, 2.0 grains of fragrance and sufficient deionized water is added to bring the total weight to 1000 grams.
The resulting product has the following compositions: wt./wt. % Compound A 15.00 phosphate ester hydrotrope 5.00 polyethylene glycol 6000 distearate 2.00 preservative 0.10 fragrance 0.20 20 deionized water q.s. to 100% Example VII A clear, liquid hair cleanser composition is prepared having the following formulation: wt. /wt. % Compound A 5.00 polyoxyethylene 80 sorbitan monolaurate 10.00 Deriphat (tradename for salt of N-alkvl 5.00 beta-iminoprooionic acid available from General Mills Inc., Kankekee, Illinois) polyethylene glycol 6000 distearate 2.00 benzyl alcohol 0.10 Dowicil 200 (tradename for the cis isomer 0.10 of 1-(3-chloroalkyI)-3,5,7-triaza-lazoniaadamantine chloride) fragrance 0.20 deionized water q.s. to 100% The above formulation is adjusted to a pH of 7.1 with 15% HC1 and has a viscosity of 413 cps. at 25°C and is a slight ocular irritant. The formulation also exhibits good foam properties.
Example VIII A detergent bar composition is prepared as follows: 50 parts of Compound A are mixed with 20 parts of Deriphat in a steam jacketed mixer at a temperature of 70°C. After the slurry is homogeneous, 10 parts of polyoxyethylene (8u) sorbitan monopalmitate are added followed by the addition of 10 parts each of talc and dextrin. The catch is mixed 20 minutes, cooled, milled into ribbons and pressed into detergent bars.
The resulting bars have the following formulation. wt./wt.t Compound A 50.00 Deriphat 20.00 polyoxyethylene (80) 10.00 sorbitan monopalmitate talc 10.00 dextrin 10.00 100.00 and has a pH of 7.0. This product is a moderate irritant and exhibits excellent foaming properties.
EXAMPLE IX In order to demonstrate the synergism of the amphotericfatty acid complexes of the present invention with respect to foam characteristics, compounds A and B, the amphoteric portion thereof and the coconut fatty acid portion thereof were individually tested in accordance with the modified Ross-Miles foam test set forth hereinbefore.
The results are shown in Table I below: TABLE I Compound % Active Initial foam Normal Water and Grease He ight (nun) Hard Water 200 ppm CaCOi amphoteric of compound A 5.0 295 343 coconut fatty acid 5.0 0 0 compound A 5.0 353 358 amphoteric of compound 3 5.0 - 295 coconut fatty acid 5.0 - 0 compound B 5.0 - 360 Xn addition to the preferred embodiments described herein, other embodiments, arrangements and variations within the 15 ambit of the invention and the scope of the appended claim will occur to those skilled in the art.
The words Deriphat and Dowicil appearing in the foregoing description are Trade Marks.
Claims (5)
1. A compound of the formula 0 Θ ‘ β η 0 RyC-0 L i M wherein Rj is alkyl or substituted alkyl containing from 6 to 18 carbon atoms ana mixtures thereof; R 2 is alkyl containing from 8 to 18 carbon atoms and mixtures thereof or alkyl amido alkylene of the formula R -CO-IIZ-Y10 wherein R3 is alkyl containing from 8 to 18 carbon atoms; Z is H or lower alkyl containing from 1 to 4 carbon atoms; and Y is alkylene containing from 1 to 4 carbon atoms; Aj, and A 2 are the same or different and are each 15 selected from the following anionic salt moieties: fCH 2 CH 2 -COOX] -:CS 2 -COOXl wherein X is a water soluble cation with the proviso that if only one of A3. and A 2 are selected from the anionic salt moieties above, the other can be lower alkyl or lower hydroxyalkyl containing from 1 to 4 carbon atoms; or R^ is tallow fatty acid alkyl, R 2 is C 12 H 25 , A [ is H, and A 2 is CH 2 CH 2 C00Na.
2. The compound of claim 1 wherein R 2 is a coconut 5 fatty acid mixture.
3. The compound of claim 1 wherein R 2 is ^14^29·
4. The compound of claim 1 wherein R2 is ^ι 2 Η 2 5· 5. The compound of claim 1 wherein R 2 is a tallow fatty acid mixture. 10 6. The compound of claim 1 wherein and A2 are each fCHoCOOX). 7. The compound of claim 1 of the formula 0 II Rl-C-0 C2H4OH Ο,,Η ,-C-N(CH 2 ) 2 -N 11 23 l X CH 2 C00K H wherein Rj. is a Ci 2 H 2 3 - Cl8 H 37 mixture. 8. The compound of claim 1 of the formula 0 II R3.C-0 m© CH 2 CH 2 COONa c 12 h 25 _ N ' s CH 2 CH 2 COONa wherein R 2 is a C5H13 - CygH37 mixture. 10. A compound as claimed in claim 1 prepared by a procedure substantially as set forth in any of the
5. Foregoing Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US24186281A | 1981-03-09 | 1981-03-09 |
Publications (2)
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| IE820512L IE820512L (en) | 1982-09-09 |
| IE52291B1 true IE52291B1 (en) | 1987-09-02 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE512/82A IE52291B1 (en) | 1981-03-09 | 1982-03-08 | Amphoteric fatty acid,amino acid salts and their use in detergent compounds and compositions |
Country Status (22)
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| JP (1) | JPS57159737A (en) |
| AU (1) | AU554101B2 (en) |
| BE (1) | BE892426A (en) |
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| CH (1) | CH648823A5 (en) |
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| SE (1) | SE452018B (en) |
| ZA (1) | ZA821528B (en) |
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|---|---|---|---|---|
| US4069875A (en) * | 1976-03-01 | 1978-01-24 | The Hamby Company | Rolling ring |
| US4820447A (en) * | 1985-12-02 | 1989-04-11 | The Proctor & Gamble Company | Mild skin cleansing soap bar with hydrated cationic polymer skin conditioner |
| US5064555A (en) * | 1985-12-02 | 1991-11-12 | The Procter & Gamble Company | Mild skin cleansing soap bar with hydrated cationic polymer skin conditioner |
| US4946618A (en) * | 1988-11-02 | 1990-08-07 | The Procter & Gamble Company | Toilet bar composition containing cationic guar gum |
| FR2639635B1 (en) * | 1988-11-30 | 1992-06-12 | Sandoz Sa | AMPHOTERIC SURFACTANTS CONTAINING ALKYLENE OXIDE |
| US6138769A (en) * | 1998-05-15 | 2000-10-31 | Breyer; Stephen R. | Root cutting tool |
| JP4729782B2 (en) * | 2000-10-16 | 2011-07-20 | 日油株式会社 | Cleaning composition |
| JP4792628B2 (en) * | 2000-10-16 | 2011-10-12 | 日油株式会社 | Cleaning composition |
| DE102010001686A1 (en) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Composition for the alkaline passivation of zinc surfaces |
| ES2428290T3 (en) | 2011-03-22 | 2013-11-06 | Henkel Ag & Co. Kgaa | Multi-step anticorrosive treatment for metal components, which at least partially have zinc or zinc alloy surfaces |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3055836A (en) * | 1957-12-24 | 1962-09-25 | Johnson & Johnson | Detergent composition |
| US2970160A (en) * | 1959-02-11 | 1961-01-31 | Johnson & Johnson | Process for making amphoteric surface active agents |
| DE1245971B (en) * | 1962-05-30 | 1967-08-03 | Ciba Aktiengesellschaft, Basel (Schweiz) | Process for the preparation of new tetrahydro-imidazoles |
| US3452065A (en) * | 1966-08-11 | 1969-06-24 | Hans S Mannheimer | Sulfate or sulfonate amphoteric amine salts |
| US4215064A (en) * | 1978-11-30 | 1980-07-29 | Johnson & Johnson | Phosphobetaines |
| MX155752A (en) * | 1980-01-14 | 1988-04-22 | Kao Corp | THE NEW USE OF INDUSTRIAL CHARACTER OF A QUATERNARY AMMONIUM SALT AS AN ANTI-STATIC AGENT |
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1982
- 1982-02-26 NZ NZ199856A patent/NZ199856A/en unknown
- 1982-02-26 SE SE8201214A patent/SE452018B/en not_active IP Right Cessation
- 1982-03-03 MX MX022604A patent/MX174108B/en unknown
- 1982-03-04 GR GR67487A patent/GR76365B/el unknown
- 1982-03-05 CA CA000397740A patent/CA1179683A/en not_active Expired
- 1982-03-05 FR FR8203688A patent/FR2501200B1/en not_active Expired
- 1982-03-05 IT IT47924/82A patent/IT1186673B/en active
- 1982-03-08 BR BR8201233A patent/BR8201233A/en not_active IP Right Cessation
- 1982-03-08 FI FI820796A patent/FI80013C/en not_active IP Right Cessation
- 1982-03-08 GB GB8206774A patent/GB2094307B/en not_active Expired
- 1982-03-08 NO NO820731A patent/NO155881C/en unknown
- 1982-03-08 ZA ZA821528A patent/ZA821528B/en unknown
- 1982-03-08 NL NL8200946A patent/NL8200946A/en not_active Application Discontinuation
- 1982-03-08 DE DE19823208311 patent/DE3208311A1/en not_active Ceased
- 1982-03-08 DK DK100082A patent/DK100082A/en not_active Application Discontinuation
- 1982-03-08 IE IE512/82A patent/IE52291B1/en not_active IP Right Cessation
- 1982-03-08 ES ES510232A patent/ES510232A0/en active Granted
- 1982-03-09 PH PH26965A patent/PH18432A/en unknown
- 1982-03-09 JP JP57035970A patent/JPS57159737A/en active Granted
- 1982-03-09 MX MX191714A patent/MX162869B/en unknown
- 1982-03-09 CH CH1453/82A patent/CH648823A5/en not_active IP Right Cessation
- 1982-03-09 AU AU81194/82A patent/AU554101B2/en not_active Ceased
- 1982-03-09 BE BE0/207517A patent/BE892426A/en not_active IP Right Cessation
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| MX162869B (en) | 1991-07-02 |
| NZ199856A (en) | 1984-08-24 |
| PH18432A (en) | 1985-07-08 |
| CH648823A5 (en) | 1985-04-15 |
| ES8305685A1 (en) | 1983-04-16 |
| ZA821528B (en) | 1983-10-26 |
| GR76365B (en) | 1984-08-06 |
| DK100082A (en) | 1982-09-10 |
| IE820512L (en) | 1982-09-09 |
| ES510232A0 (en) | 1983-04-16 |
| SE8201214L (en) | 1982-09-10 |
| CA1179683A (en) | 1984-12-18 |
| GB2094307B (en) | 1985-02-06 |
| NO155881B (en) | 1987-03-09 |
| AU554101B2 (en) | 1986-08-07 |
| BE892426A (en) | 1982-09-09 |
| NO155881C (en) | 1987-06-17 |
| FI80013C (en) | 1990-04-10 |
| FR2501200B1 (en) | 1986-05-02 |
| BR8201233A (en) | 1983-01-18 |
| FR2501200A1 (en) | 1982-09-10 |
| FI820796L (en) | 1982-09-10 |
| IT8247924A0 (en) | 1982-03-05 |
| MX174108B (en) | 1994-04-21 |
| NL8200946A (en) | 1982-10-01 |
| AU8119482A (en) | 1982-09-16 |
| NO820731L (en) | 1982-09-10 |
| GB2094307A (en) | 1982-09-15 |
| FI80013B (en) | 1989-12-29 |
| DE3208311A1 (en) | 1982-12-30 |
| JPH0561259B2 (en) | 1993-09-06 |
| JPS57159737A (en) | 1982-10-01 |
| IT1186673B (en) | 1987-12-04 |
| SE452018B (en) | 1987-11-09 |
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