US3793228A - Detergent compositions containing maleic acid vinyl alcohol copolymers as builders - Google Patents
Detergent compositions containing maleic acid vinyl alcohol copolymers as builders Download PDFInfo
- Publication number
- US3793228A US3793228A US00299821A US3793228DA US3793228A US 3793228 A US3793228 A US 3793228A US 00299821 A US00299821 A US 00299821A US 3793228D A US3793228D A US 3793228DA US 3793228 A US3793228 A US 3793228A
- Authority
- US
- United States
- Prior art keywords
- builders
- maleic acid
- detergent
- builder
- vinyl alcohol
- 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.)
- Expired - Lifetime
Links
- 239000003599 detergent Substances 0.000 title abstract description 27
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title abstract description 20
- 229920001577 copolymer Polymers 0.000 title abstract description 18
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title abstract description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000011976 maleic acid Substances 0.000 title abstract description 14
- 239000000203 mixture Substances 0.000 title description 23
- 239000012459 cleaning agent Substances 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 14
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 6
- 229920000388 Polyphosphate Polymers 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000001205 polyphosphate Substances 0.000 description 6
- 235000011176 polyphosphates Nutrition 0.000 description 6
- -1 MALEIC ACID VINYL Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910019142 PO4 Inorganic materials 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
- 238000000034 method Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 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
- 239000007788 liquid Substances 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
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 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
- 235000019794 sodium silicate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000459170 Maleae Species 0.000 description 1
- 208000025370 Middle East respiratory syndrome Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000007244 Zea mays Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010936 aqueous wash Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 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
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
Definitions
- the builders are comprised of water-soluble salts of cotelomers or copolymers of vinyl alcohol with maleic acid.
- the present invention provides builders foridetcrgen't and cleaning agents, the builders comprising organic polymer compounds.
- V y s theeffect onlthefs'urface and interfacial properties" (if aqueous surfactant" solutions; the solubilization of waterinsoluble ingredients of the cleaning bath; the pepti zati'on of agglomerat'e d dirt; the neutralization of acid-substances; and the inactivation of mineral matter in the cleaning bath.
- Classical builders comprise water-soluble inorganic alkali metal salts, such as alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, and silicates.
- liquid detergent formulations may be Claims 3,793,228 Patented Feb. 19, 1974 1 rendered turbid, or precipitation may occur therein, which is undesirable.
- watersoluble alkali metal, ammonium and substituted ammonium salts of homopolymers and copolymers of aliphaticpolycarboxylic acids be used as builders in detergent and cleaning compositions.
- the comonomers include primarly short chain olefins and unsaturated carboxylic acids.
- Representatives of these builders, which are termed polyelectrolyte builders, include for example, the sodium salt of polymaleic acid or copolymers of propylene or styrene with maleic acid. These builders either have no satisfactory builder properties or are too costly for mass production.
- the present invention now unexpectedly provides watersoluble'salts of cotelomers or copolymers of vinyl alcohol withymaleic-acid, which can be used with particular advantage as buildersin detergent and cleaning compositions.
- Me stands for an alkali metal or ammonium ion
- n is a whole number within a range of which the lower limit is 3 and of which the upper limit is defined by the solubility of the polymer in water
- the copolymer builders have a preferred molecular weight of between 1,500 and 3,000.
- the maleic acid fraction in the copolymer or cotelomer should preferably be limited to a value of between about 25 and 50 mol percent.
- the copolymer builders of the present invention into conventional detergent and cleaning agent formulations, such as those which are based on ionactive and/ or non-ionic surfactants, and which may op- 3 tionally be used in combination with further addends
- the builder is generally used in a proportion of between about 10 and 80 Weight percent, preferably between about 15 and 60 weight percent, based on the drysubstance of the detergent and cleaning agent.
- the detergent and cleaning agents may contain an alkali metal polyphosphate as a further builder.
- Detergent and cleaning compositions prepared in accordance with the present invention give a pH-value of between 8 and 12 in the aqueous medium of the wash bath. I
- the addends which may be present together with the ion-active and/or non-ionic surfactants in the detergent formulation, comprise substances, such as sodium silicate, magnesium silicate, sodium sulfate, sodiumf'perborate, optical brighteners, carboxymethyl cellulose and/ or enzymes, for example.
- the builders of the present invention are produced in conventional manner, for example, by subjecting a copolymer or telomer of maleic anhydride and vinyl acetate to saponification by means of a sodium hydroxide solution.
- the properties of the builders of the persent invention can be evaluated, for example, in dispersing tests. Starting with an aqueous suspension, which contained either hydrophilic particles, such as iron (III) oxide, or hydrophobic particles, for example graphite particles, it was possible by the addition of the builders of the present invention to produce stable dispersions. This is demonstrated in the table hereinafter. As results from the tabulated test results, the builder substances of the present invention can be said to have the properties required of a builder. On comparing Table 1 with Table 2, it will readily be seen that hydrophilic dirt particles are particularly well dispersed by a vinyl alcohol/maleate cotelomer.
- EXAMPLE 1 The sodium salt of a vinyl alcohol/melic acid copolymer was tested as to its dispersing effect in an aqueous suspension of 4 weight percent graphite powder at various pH-values, and the eifect produced was compared with that produced by a conventional styrene/maleic acid copolymer builder, in a corresponding suspension.
- the settling time of the graphite particles in 25 cc. mixing cylinders, and the volume of sedimentation were determined in each case as an index of the dispersing effect.
- the builder was used in the suspension in a concentration of 0.1 weight percent, based on the aqueous solution. Th results obtained are summarized in Table 1 below.
- the wash water had a hardness of 20 (German degrees of hardness) and a pH of 10.
- the wash period was 30 minutes and the bath ratio, expressed by the ratio of material to be washed in kg. to wash liquor in liter was 1:50, and the wash operation was carried out in the presence of 10 steel balls.
- the wash liquor contained a alkylaryl sulfonate as a surface-active substance as well as Pluronic which is a non-ionic polyoxypropylene glykol.
- the cleansing power quotient was calculated along the following formula:
- Percent WG Percent whiteness of unwashed fabric
- Percent WG Percent whiteness of unsoiled fabric
- Me stands for an alkali metal or ammonium ion
- n is a whole number with a range of which the lower limit is 3 and of which the upper limit is defined by the solubility of the polymer in water.
- a detergent composition according to claim 1 producing a pH value of between 8 and 12 in an aqueous wash or cleaning liquor.
Landscapes
- Chemical & Material Sciences (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)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1950702A DE1950702B2 (de) | 1969-10-08 | 1969-10-08 | Gerüststoffe für Wasch- und Reinigungsmittel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3793228A true US3793228A (en) | 1974-02-19 |
Family
ID=5747636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00299821A Expired - Lifetime US3793228A (en) | 1969-10-08 | 1972-10-24 | Detergent compositions containing maleic acid vinyl alcohol copolymers as builders |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3793228A (fr) |
| JP (1) | JPS4823646B1 (fr) |
| AT (1) | AT302515B (fr) |
| BE (1) | BE757034A (fr) |
| CH (1) | CH537454A (fr) |
| DE (1) | DE1950702B2 (fr) |
| DK (1) | DK135543B (fr) |
| FR (1) | FR2065219A5 (fr) |
| GB (1) | GB1284815A (fr) |
| NL (1) | NL7014532A (fr) |
| SE (1) | SE369607B (fr) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021376A (en) * | 1972-05-17 | 1977-05-03 | Lever Brothers Company | Detergent compositions with nonphosphate builders containing two or more carboxyl groups |
| US4288327A (en) * | 1975-09-08 | 1981-09-08 | Betz Laboratories, Inc. | Copolymers for the control of the formation and deposition of materials in aqueous mediums |
| US4797223A (en) * | 1988-01-11 | 1989-01-10 | Rohm And Haas Company | Water soluble polymers for detergent compositions |
| US5332519A (en) * | 1992-05-22 | 1994-07-26 | Church & Dwight Co., Inc. | Detergent composition that dissolves completely in cold water, and method for producing the same |
| US5637444A (en) * | 1994-10-14 | 1997-06-10 | Fuji Photo Film Co., Ltd. | Composition for lithographic printing fountain solution |
| WO2007039554A1 (fr) * | 2005-10-05 | 2007-04-12 | Basf Se | Procede pour produire des compositions detergentes en granules ou en poudre |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55501147A (fr) * | 1978-11-28 | 1980-12-18 | ||
| ES2140667T5 (es) † | 1994-03-31 | 2004-07-16 | Unilever N.V. | Composiciones detergentes. |
| JPWO2005005090A1 (ja) * | 2003-07-10 | 2007-09-20 | Tdk株式会社 | 超音波溶着装置、情報記録媒体製造装置、超音波溶着方法、物体およびカートリッジケース |
-
0
- BE BE757034D patent/BE757034A/fr unknown
-
1969
- 1969-10-08 DE DE1950702A patent/DE1950702B2/de active Pending
-
1970
- 1970-08-28 CH CH1293970A patent/CH537454A/de not_active IP Right Cessation
- 1970-09-16 GB GB44267/70A patent/GB1284815A/en not_active Expired
- 1970-10-02 NL NL7014532A patent/NL7014532A/xx not_active Application Discontinuation
- 1970-10-07 AT AT903370A patent/AT302515B/de not_active IP Right Cessation
- 1970-10-07 DK DK510470AA patent/DK135543B/da not_active IP Right Cessation
- 1970-10-07 SE SE13603/70A patent/SE369607B/xx unknown
- 1970-10-08 JP JP45088720A patent/JPS4823646B1/ja active Pending
- 1970-10-08 FR FR7036449A patent/FR2065219A5/fr not_active Expired
-
1972
- 1972-10-24 US US00299821A patent/US3793228A/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021376A (en) * | 1972-05-17 | 1977-05-03 | Lever Brothers Company | Detergent compositions with nonphosphate builders containing two or more carboxyl groups |
| US4288327A (en) * | 1975-09-08 | 1981-09-08 | Betz Laboratories, Inc. | Copolymers for the control of the formation and deposition of materials in aqueous mediums |
| US4797223A (en) * | 1988-01-11 | 1989-01-10 | Rohm And Haas Company | Water soluble polymers for detergent compositions |
| US5332519A (en) * | 1992-05-22 | 1994-07-26 | Church & Dwight Co., Inc. | Detergent composition that dissolves completely in cold water, and method for producing the same |
| US5637444A (en) * | 1994-10-14 | 1997-06-10 | Fuji Photo Film Co., Ltd. | Composition for lithographic printing fountain solution |
| WO2007039554A1 (fr) * | 2005-10-05 | 2007-04-12 | Basf Se | Procede pour produire des compositions detergentes en granules ou en poudre |
| US20080255022A1 (en) * | 2005-10-05 | 2008-10-16 | Basf Se | Method for Producing Granular or Powdery Detergent Compositions |
| CN101278038B (zh) * | 2005-10-05 | 2012-11-28 | 巴斯夫欧洲公司 | 生产粒状或粉状洗涤剂组合物的方法 |
| US8486884B2 (en) | 2005-10-05 | 2013-07-16 | Basf Aktiengesellschaft | Method for producing granular or powdery detergent compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| DK135543C (fr) | 1977-10-24 |
| NL7014532A (fr) | 1971-04-14 |
| DK135543B (da) | 1977-05-16 |
| DE1950702B2 (de) | 1976-01-08 |
| BE757034A (fr) | 1971-04-05 |
| DE1950702A1 (de) | 1971-04-15 |
| AT302515B (de) | 1972-10-25 |
| SE369607B (fr) | 1974-09-09 |
| FR2065219A5 (fr) | 1971-07-23 |
| CH537454A (de) | 1973-05-31 |
| JPS4823646B1 (fr) | 1973-07-16 |
| GB1284815A (en) | 1972-08-09 |
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