US3679589A - Low-foaming rinsing,washing and cleaning compositions - Google Patents

Low-foaming rinsing,washing and cleaning compositions Download PDF

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Publication number
US3679589A
US3679589A US837369A US3679589DA US3679589A US 3679589 A US3679589 A US 3679589A US 837369 A US837369 A US 837369A US 3679589D A US3679589D A US 3679589DA US 3679589 A US3679589 A US 3679589A
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Prior art keywords
washing
foaming
melamines
agents
compounds
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US837369A
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Harald Schnegelberger
Theodor Altenschopfer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions

Definitions

  • non-ionic detergent substances especially those based on polyglycol ethers, have a low-foaming power and beyond that are suitable for suppressing foam formation caused by anionic basic detergent substances. These properties are of particular importance in the case of washing and cleaning agents which are intended for use in automatic dishwashing machines and rotating drum washing machines.
  • the most active known compounds of this class of nonionic detergent substances include the ethoxylated polypropylene glycols such as the Pluronics (registered trademark) and the ethoxylated polypropylene glycol ether derivatives of ethylenediamine such as the Tetronics (registered trademark).
  • Their anti-foaming properties are not sufiicient in some cases.
  • foam-producing impurities such as protein substances, carbohydrates and other high polymers, such as those from label adhesives
  • foam suppression properties are not sufiicient.
  • the said compounds possess relatively poor running-off properties. When dishes are rinsed, the rinsing solutions frequently runs otf the glass, metal or plastic surface not as a uniform film, but remain in the form of drops or streaks and after drying leave a cloudiness and spots.
  • An object of the present invention is to provide washing, rinsing and cleaning agents which, compared with the known agents, have an improved anti-foaming action and do not have the disadvantages mentioned above.
  • Another object of the present invention is the obtention of low-foaming rinsing, washing and cleaning compo- 'ice sitions comprising (a) a content of at least one compound having a cleaning action selected from the group consisting of (1) anionic surface-active compounds, amphoteric surface-active compounds, non-ionic surface-active compounds and mixtures thereof, (2) organic builder salts and inorganic builder salts, and (3) mixtures of (1) and (2), and (b) a content of at least one alkoxylated melamine having a molecular weight of from 700 to 20,000 selected from the group consisting of propoxylated melamines, butoxylated melamines and propoxylated-butoxylated melamines, where the weight ratio of components (a) to components (b) is from 999 to 1 to 3 to 1.
  • the invention therefore, comprises low-foaming washing, rinsing and cleaning agents which are characterized in that they contain (a) a content of at least one substance having a cleaning action from the class of (1) anionic, amphoteric and non-ionic surface-active basic detergent substances, (2) inorganic and organic builder salts, and (3) mixtures of (l) and (2), and (b) a content of at least one compound from the class of propoxylated and/or butoxylated melamines having a molecular weight of from 700 to 20,000, where the weight ratio of the compounds mentioned in (a) and (b) is from 999:1 to 3:1.
  • the preparation of the alkoxylated melamines to be used according to the invention may be carried out in known manner, for example, by reacting melamine, dispersed in water or dissolved in a solvent such as dimcthyl sulfoxide, with propylene oxide or butylene oxide or mixtures thereof.
  • the melamine may also first be reacted with one of the two alkylene oxides mentioned, for example, propylene oxide, and the reaction with the other alkylene oxide, for example, butylene oxide, may be carried out until the desired molecular weight is obtained.
  • Alkoxylated melamines are preferably used whose molecular Weight amounts to 1,200 to 12,000. Such compounds preferably contain 20 or more oxypropylene units (abbreviated to PrO groups) or 16 or more oxybutylene units (abbreviated to B0 groups), or a corresponding number of PrO and B0 groups.
  • PrO groups oxypropylene units
  • B0 groups oxybutylene units
  • PrO and B0 groups oxypropylene units
  • B0 groups oxybutylene units
  • Alkoxylated melamines have been found specially active in the preparation of which, per mol of melamine, first 4 to 25 mols of propylene oxide and then 10 to 50 mols of butylene oxide are utilized. Mixtures of differently alkoxylated melamines may also be used.
  • the alkoxylated melamine containing up to 30 PrO groups are water-soluble. More highly propoxylated compounds dissolve in dilute acids such as acetic acid or phosphoric acid. Butoxylated melamines and alkoxylated melamines containing PrO and B0 groups are sparingly soluble or insoluble in water and dilute acids, but can be easily dispersed in the usual aqueous concentrates containing the basic basic detergent substances.
  • the washing, rinsing and cleaning agents according to the invention contain at least one substance with a cleaning action.
  • This may consist of an inorganic or organic builder salt or a surface-active basic detergent substance or a combination of these.
  • the agents usually contain several such substances having a cleaning action.
  • Suitable inorganic builder salt components having a cleaning action are phosphates, such as orthophosphates, pyrophosphates, triphosphates and more highly condensed phosphates in the form of their neutral or acid alkali metal salts such as the sodium or potassium salt, or ammonium salts.
  • Alkali metal silicates are also suitable, especially sodium silicate, in which the ratio of Na O to SiO amounts to 1:35 to 1:1.
  • Suitable organic builder salt components having a cleaning action are the complex-forming alkali metal or ammonium salts of aminopolycarboxylic acids and/or aminopolyphosphonic acids, especially the sodium or potassium salts of aminotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentacetic acid, triethylenetetraaminehexaacetic acid and higher homologues thereof, ethylenediaminehydroxyethanetriacetic acid, aminotri-(methyleuephosphonic acid), ethylenediaminetetra-(methylenephosphonic acid), l-hydroxyethane-1,1-diphosphonic acid, methylenediphosphonic acid and the higher homologues of the said polyphosphonic acids.
  • suitable components of the mixture include neutral salts, such as sodium sulfate and sodium chloride, compounds regulating the pH value, such as the bicarbonates, carbonates, borates and hydroxides of the alkali metals, such as sodium or potassium, and acids such as lactic acid and citric acid.
  • the amount of alkaline-reacting substances including the alkali metal silicates and phosphates should be such that the pH of a liquor utilizable for mechanical dishwashing machines amounts to to 14, and in laundry machines for coarse washing, 9 to 12, and for fine washing, 6 to 9.
  • Cleaning and rinsing agents for manual use preferably have a weakly acidic, neutral or weakly basic reaction.
  • the agents may also contain oxygen-yielding or active chlorine-containing bleaching agents such as alkali metal perborates, alkali metal percarbonates, alkali metal perphosphates, urea perhydrate, alkali metal hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid and its alkali metal salts as Well as bleaching agent activator and stabilizers such as magnesium silicate.
  • oxygen-yielding or active chlorine-containing bleaching agents such as alkali metal perborates, alkali metal percarbonates, alkali metal perphosphates, urea perhydrate, alkali metal hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid and its alkali metal salts as Well as bleaching agent activator and stabilizers such as magnesium silicate.
  • the most important substances for all fields of application in which development of foam has to be entirely or largely excluded are weakly foaming compounds, especially the non-io'nic polyglycol ether derivatives of alcohols, fatty acids and alkylphenols which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon residue.
  • Polyglycol ether derivatives in which the number of ethyleneglycol ether groups amounts to 5 to and the hydrocarbon residues of which are derived from straight-chain primary alcohols with 12 to 18 carbon atoms or from alkylphenols with a straight-chain alkyl chain having 6 to 14 carbon atoms are specially suitable.
  • non-ionic basic detergent substances are the water-soluble adducts of polyethylene oxide to polypropyleneglycol containing to 250 ethyleneglycol ether groups and 10 to 100 propyleneglycol ether groups, ethylenediaminepolypropyleneglycol and alkylpolypropyleneglycol with 1 to 10 carbon atoms in the alkyl chain.
  • the said compounds usually contain 1 to 5 ethyleneglycol units per propyleneglycol unit.
  • Washing and cleaning agents in which an insignificant development of foam is not harmful may also contain anionic basic detergent substances of the sulfonate or sulfate type.
  • basic detergent substances are olefin sulfonates, such as are obtained, for example,
  • alkyl sulfonates such as are obtainable from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, or by bisulfite addition to olefins.
  • alkylbenzenesulfonates, a-sulfo-fatty acid esters, primary and secondary alkylsulfates, and the sulfates of ethoxylated or propoxylated alcohols are suitable.
  • sulfated partial ethers and partial esters of polyhydric alcohols such as the alkali metal salts of the monoalkyl ethers or monofatty acid esters of glycerine monosulfuric acid esters or of l,2-dihydroxypropanesulfonic acid.
  • sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols, and fatty acid taurides and fatty acid isothionates are suitable.
  • the agents may also contain alkali metal soaps of fatty acids, amphoteric surfaceactive compounds such as alkylbetaines and alkylsulfobetaines, and non-ionic surface-active compounds of the amineoxide and sulfoxide type.
  • the anionic basic detergents may be present in the form of their sodium, potassium and ammonium salts as well as salts of organic bases, such as mono-, dior triethanolamine. If the said detergent compounds possess an aliphatic hydrocarbon residue, this should preferably have a straight-chain and contain 8 to 22 carbon atoms. In the compounds with araliphatic hydrocarbon residues, the preferably unbranched alkyl chains in the agent contain 6 to 16 carbon atoms.
  • the washing and cleaning agents may also contain enzymes from the class of the proteases, lipases and amylases, which may be obtained from animal and vegetable origin, for example, from digestive ferments or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase.
  • enzymes from the class of the proteases, lipases and amylases which may be obtained from animal and vegetable origin, for example, from digestive ferments or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase.
  • enzymic active substances are obtained from strains of bacteria or fungi, such as Bacillus subtilis and Streptomyces griseus, which substances are relatively stable towards, alkalis, per-compounds and anionic detergent substances and are not appreciably inactivated even at temperatures between 45 C. and 70 C. Their relatively great stability towards oxidizing agents is possibly due to their low content of free sulfhydryl groups.
  • greying inhibitors such as sodium cellulose glycollate, disinfectant and brightening agents, fillers, such as urea, abrasives, dyestuffs and perfumes, and also optical brighteners, for example, those of the diaminostilbenedisulfonic acid type according to the following formula:
  • optical brighteners of the diarylpyrazoline type according to the following formula may be present:
  • R represents a hydrogen atom or an alkyl or aryl residue, which if desired may be substituted
  • Ar and Ar represent aryl residues, such as phenyl, diphenyl or naphthyl, which may carry further substituents such acrylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms.
  • 1,3-diarylpyrazolines are preferably used in which R represents a hydrogen atom.
  • foam-inhibiting agents as, for example, preferably saturated fatty acids having 20 to 24 carbon atoms or their alkali metal soaps or triazine derivatives which are obtainable by reacting 1 mol of cyanuric chloride with 2 to 3 mols of an aliphatic, straight or branched chain, or cyclic primary monoamine.
  • the washing and cleaning agents may be present in liquid, pasty or solid form, for example, pulverulent, granulated or lump form.
  • liquid preparations may contain solvents miscible with water, especially ethanol and isopropanol, as Well as solution aids such as the alkali metal salts of benzene-, toluene-, xyleneor ethylbenzene-sulfonic acids.
  • Skin protecting substances, such as fatty acid monoand di-alkylolamides may be added to the rinsing and cleaning agents intended for manual use.
  • the propoxylated and/ or butoxylated melamine derivatives to be used according to the invention have to a great extent an anti-foaming action in hard and soft water and solutions containing the same have good run-01f properties with respect to glass, ceramic, metal and plastic articles. In this property they considerably surpass the known polyglycol ether derivatives of the type of Pluronics (registered trademark) and Tetronics (registered trademark). In contrast to anti-foaming agents with a fatty character such as parafiins, fatty acid esters and N-substituted amines, amides and polyamines, they leave behind no fatty film on the rinsed or washed objects and do not lessen the cleaning power of the basic detergent substances.
  • the foam inhibitors may first be mixed with a part of the pulverulent components, for example, polymeric phosphates, active-oxygen containing substances, non-ionic basic detergent substances, enzymes or perfumes and then these mixtures may be united with the remaining pulverulent components.
  • Mixing the alkoxylated melamines with the powder or the powder components has the advantage that fine-grained constituents and the enzymes are bonded with the other particles of powder, so that the mixtures have no tendency to form dust or to separate into their components.
  • the invention therefore, relates to mixtures which contain surface-active compounds and also those which are free from surface-active compounds.
  • Mixtures containing surface-active compounds may have the following oomposition.
  • the following figures, in percentages by weight, are based on a water-free recipe.
  • washing agent constituents such as greying inhibitors, skin-protective substances, biocides, optical brighteners, enzymes, solution aids as well as dyestuffs and perfumes.
  • Mixtures free from surface-active compounds may contain the following mix components (data in percentage by weight) 0.1% to 25%, preferably 0.2% to 5%, of alkoxylated melamine,
  • the sulfate and sulfonate basic surface-active washing components and soaps are generally used as the sodium salts although other alkali metal salts may be employed. If liquid preparations are used, the anionic detergent substances may advantageously be used in the form of the mono-, dior tri-ethanolammonium salts.
  • alkylpolyglycol ethers C to C -alkyl
  • alkylphenolpolyglycol ethers C to C -alkyl
  • soap C to C 0.5% to 5% of anti-forming agent consisting of propoxylated and/or butoxylated melamine or its mixture with fatty acids or their alkali metal soaps, containing 20 to 24 carbon atoms,
  • an inorganic salt from the class of the carbonates, bicarbonates, borates, sulfates and chlorides of alkali metals,
  • alkylpolyglycol ether sulfate (C to C -alkyl
  • fatty acid amide-glycol ether condensate (C to C -fatty acid, 1 to 10 ethyleneglycol ether p 0 to 10% of solution aids from the class of alkali metal salts of benzene-, toluene-, or xylene-sulfonic acids,
  • optical brightener 0 to 1% of optical brightener
  • Pulverulent fine washing agent 1% to 30% of sulfonate basic surface-active washing component
  • alkylpolyglycol ether sulfate (C to C -alkyl
  • alkylpolyglycol ether C to C -alkyl
  • alkylphenolpolyglycol ether C to C -alkyl
  • alkylpolyglycol ether (C to C -alkyl) with 5 to 12 ethyleneglycol ether groups
  • magnesium silicate 0 to 5%
  • washing assistant and softening agent 0.2% to 5% of propoxylated and/or butoxylated melamine
  • washing agent was tested once without an anti-foaming agent and once with a commercial anti-foaming agent (Pluronic L 61, registered trademark) known to be very active.
  • Pluronic L 61 commercial anti-foaming agent
  • the apparatus used consisted of several 20 vertical cylinders filled with the solution to be tested up to a predetermined height, and each containing a plunger provided with a perforated plate which, driven by a motor, was periodically immersed in the solution and lifted out again. The height of foam obtained after a 25 specified number of oscillating movements is a measure of the foaming tendency of the solution.
  • the anti-foaming properties of a melamine reacted with 7.5 mols of propylene oxide and then with 34 mols of butylene oxide were investigated in a series of foaming solutions.
  • the cleaner used was a mixture intended for an automatic dishwater and consisted of:
  • component (b) is obtained by the reaction of 1 mol of Varying amounts of surface-active compounds were also melamine i from 4 to 25 mols of propylene oxide and utilized as indicated. The results are collected in the folthereafter wlth from 10 to mols of butylene oxide lowing Table II.
  • condensation .prod- A low'foaming rinsing, Washing and Cleaning C0111- uct fr 30 l of propylene oxide and 45 mols of position of claim 1 having a further content of up to 5% ethylene oxide, known as a foam inhibitor, was again y Weight of enzymes Selected from the group Consisting used.
  • the symbol X in the table indicate that the soluof proteases, lipases and amylases.
  • a low-foaming rinsing, washing and cleaning com- 100% by weight of components (a) of a surface-active position of claim 1 consisting essentially of from 40% to compound selected from the group consisting of anionic 99.9% of component (a) (2), from 0.1% to 25% of comsurface-active compounds, amphoteric surface-active component (b), and additionally containing from 0 to 50% of an alkali metal hydroxide, and further from '0 to 30% of an active chlorine bleaching agent.
  • a low-foaming rinsing, washing and cleaning composition of claim 7 consisting essentially of from 50% to 9 0% of component (a) (2) and from 0.2% to 5% of component (b).
  • Foaming solution 11 2 Foaming agent 1 12 3 Cleaner -2 Foaming agent 13 Cleaner O.' )6 C12 to C b elkyldiglyool 1 ether sulfate 2 Foaming agent 14 3 Cleaner 0.06 Na dodecylbonzenesulionat 2 Foaming agent I 15 1 3 01w.

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  • 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)
US837369A 1968-08-17 1969-06-27 Low-foaming rinsing,washing and cleaning compositions Expired - Lifetime US3679589A (en)

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DE19681792308 DE1792308A1 (de) 1968-08-17 1968-08-17 Schwachschaeumende Wasch-,Spuel- und Reinigungsmittel

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US (1) US3679589A (en, 2012)
AT (1) AT292896B (en, 2012)
BE (1) BE737445A (en, 2012)
BR (1) BR6911522D0 (en, 2012)
CH (1) CH527899A (en, 2012)
DE (1) DE1792308A1 (en, 2012)
DK (2) DK128213B (en, 2012)
ES (1) ES370567A1 (en, 2012)
FR (1) FR1598688A (en, 2012)
GB (1) GB1272607A (en, 2012)
NL (1) NL6911087A (en, 2012)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898351A (en) * 1972-05-26 1975-08-05 Ibm Substrate cleaning process
US3920645A (en) * 1972-03-28 1975-11-18 Ciba Geigy Ag Carbamide-formaldehyde condensation products
US4000082A (en) * 1975-10-02 1976-12-28 Basf Wyandotte Corporation Defoaming compositions based on lithium salts
US4123395A (en) * 1975-11-28 1978-10-31 The Procter & Gamble Company Compositions containing nonionic surfactant and sulfonated aromatic compatibilizing agent
US4151127A (en) * 1977-03-10 1979-04-24 Basf Aktiengesellschaft Process for suppressing the foaming of detergents
US4356304A (en) * 1980-11-10 1982-10-26 American Cyanamid Company Synthesis of oxyalkylated polyamino-1,3,5-triazines
US4390441A (en) * 1980-04-11 1983-06-28 Lever Brothers Company Machine dishwashing composition
US4408045A (en) * 1981-03-31 1983-10-04 Chemie Linz Aktiengesellschaft Process for the preparation of partially etherified methylolmelamines
US4539145A (en) * 1983-09-15 1985-09-03 The Clorox Company Outside window cleaner containing polyvinyl alcohol and amine-containing polymer
US4826930A (en) * 1988-04-22 1989-05-02 Texaco Chemical Company Melamine-diamine condensates and the cure of 1,2-epoxide resins therewith
US4871483A (en) * 1987-04-16 1989-10-03 Gaf Corporation Novel non-depositing defoaming compositions
US4946625A (en) * 1989-03-27 1990-08-07 Siltech Inc. Particulate defoaming compositions
US20060111261A1 (en) * 2004-11-19 2006-05-25 The Procter & Gamble Company Acidic laundry detergent compositions

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920645A (en) * 1972-03-28 1975-11-18 Ciba Geigy Ag Carbamide-formaldehyde condensation products
US3898351A (en) * 1972-05-26 1975-08-05 Ibm Substrate cleaning process
US4000082A (en) * 1975-10-02 1976-12-28 Basf Wyandotte Corporation Defoaming compositions based on lithium salts
US4123395A (en) * 1975-11-28 1978-10-31 The Procter & Gamble Company Compositions containing nonionic surfactant and sulfonated aromatic compatibilizing agent
US4151127A (en) * 1977-03-10 1979-04-24 Basf Aktiengesellschaft Process for suppressing the foaming of detergents
US4390441A (en) * 1980-04-11 1983-06-28 Lever Brothers Company Machine dishwashing composition
US4356304A (en) * 1980-11-10 1982-10-26 American Cyanamid Company Synthesis of oxyalkylated polyamino-1,3,5-triazines
US4408045A (en) * 1981-03-31 1983-10-04 Chemie Linz Aktiengesellschaft Process for the preparation of partially etherified methylolmelamines
US4539145A (en) * 1983-09-15 1985-09-03 The Clorox Company Outside window cleaner containing polyvinyl alcohol and amine-containing polymer
US4871483A (en) * 1987-04-16 1989-10-03 Gaf Corporation Novel non-depositing defoaming compositions
US4826930A (en) * 1988-04-22 1989-05-02 Texaco Chemical Company Melamine-diamine condensates and the cure of 1,2-epoxide resins therewith
US4946625A (en) * 1989-03-27 1990-08-07 Siltech Inc. Particulate defoaming compositions
US20060111261A1 (en) * 2004-11-19 2006-05-25 The Procter & Gamble Company Acidic laundry detergent compositions

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Publication number Publication date
NL6911087A (en, 2012) 1970-02-19
ES370567A1 (es) 1971-04-16
DE1792308A1 (de) 1970-06-04
FR1598688A (en, 2012) 1970-07-06
CH527899A (de) 1972-09-15
DK128213A (en, 2012)
AT292896B (de) 1971-09-10
DK128213B (da) 1974-03-18
BE737445A (en, 2012) 1970-02-13
BR6911522D0 (pt) 1973-01-16
GB1272607A (en) 1972-05-03

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