CA1109756A - Liquid detergent composition - Google Patents
Liquid detergent compositionInfo
- Publication number
- CA1109756A CA1109756A CA318,100A CA318100A CA1109756A CA 1109756 A CA1109756 A CA 1109756A CA 318100 A CA318100 A CA 318100A CA 1109756 A CA1109756 A CA 1109756A
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- CA
- Canada
- Prior art keywords
- alkyl
- carbon atoms
- weight
- composition
- group
- 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.)
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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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
-
- 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
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
Abstract
Abstract of the Invention An aqueous liquid detergent composition especially adapted for dishwashing, comprising 5-60% by weight of an organic synthetic surfactant system of at least two surfactants, and 5-50% by weight of a citrus juice, said organic synthetic surfactant system consist-ing of 1) from about 30-90 parts by weight of the surfactant system of a Ca-sensitive first surfactant selected from the group consisting Water-soluble C8-16 alkyl benzene sulphonates; alkane sulphonates having 8-20 car-bon atoms; olefin sulphonates having from 8-20 carbon atoms; di-C8-20-alkyl sulpho-succinates; di-C6-12-alkyl phenol sulphosuccinates; primary and secondary alkyl suphates having 8-20 carbon atoms; C8-20 alkyl poly-ethoxy sulphates having 1-25 ethoxy groups and mixtures thereof, and 2) from about 70-10 parts by weight of said system of a less Ca-sensitive second surfactant selected from the group consisting of water-soluble nonionic condensation products obtained by condensing from 5-30 moles of an alkylene oxide, preferably ethylene or propylene oxide with one mole of an organic hydrophobic compound, aliphatic or alkyl aromatic in nature, having 8 to 24 carbon atoms and at least one reactive hydrogen atom, particularly a reactive hydroxyl, amino, amido or carboxyl group; C8-20-alkylsulphobetaines; amines oxides containing one long chain alkyl moiety of from 10-28 carbon atoms and two moieties which can be either alkyl radicals or hydroxyalkyl radicals having from 1-4 carbon atoms; C8-20 alkyl-polyethoxy sulphates having from 1-25 ethoxy groups, and mixtures thereof, said surfactants of group (1) and the ion-active surfactants of group (2) being present in the form of their alkalimetal salts, ammonium salts, or mixtures thereof.
The composition is an effective liquid dishwashing composition with improved cleaning performance on difficult soils.
The composition is an effective liquid dishwashing composition with improved cleaning performance on difficult soils.
Description
,, 1~
- 1 - C 557 (R) LIQUID DETERGENT COMPOSITION
This invention relates to a liquid detergent composition with improved c~eaning performance. More particularly the invention relates to an improved liquid detergent composition which is especially suitable for the manual cleaning of dishes, glasses, kitchen utensils, cutlery and the like. The liquid detergent composition of the invention contains juice of a citrusfruit, such as lemon juice.
!
Liquid detergent compositions containing lemon juice are known in the art. US Patent Specification No. 3,650,968 describes cleaning compositions for removing fish odours comprising 30-80% by weight of water, 0.1-35% by weight of detergent and 0.1-15~ by weight of citrus (lemon) juice. These li~uid detergent compositions, however, have very poor dishwashing properties and cannot therefore be used satisfactorily for the cleaning of dishes, glasses, kitchen utensils, cutlery and the like.
It is an object of the present invention to provide an effective liquid dishwashing detergent composition which is moreover particularly effective against difficult soils.
It is a further object of the present invention to provide a method for the removal of difficult soils from dishes, pots and pans and other kitchen utensils.
.
;' ~ ' -.
. ~ :
, ~ 7 3 ~j .,
- 1 - C 557 (R) LIQUID DETERGENT COMPOSITION
This invention relates to a liquid detergent composition with improved c~eaning performance. More particularly the invention relates to an improved liquid detergent composition which is especially suitable for the manual cleaning of dishes, glasses, kitchen utensils, cutlery and the like. The liquid detergent composition of the invention contains juice of a citrusfruit, such as lemon juice.
!
Liquid detergent compositions containing lemon juice are known in the art. US Patent Specification No. 3,650,968 describes cleaning compositions for removing fish odours comprising 30-80% by weight of water, 0.1-35% by weight of detergent and 0.1-15~ by weight of citrus (lemon) juice. These li~uid detergent compositions, however, have very poor dishwashing properties and cannot therefore be used satisfactorily for the cleaning of dishes, glasses, kitchen utensils, cutlery and the like.
It is an object of the present invention to provide an effective liquid dishwashing detergent composition which is moreover particularly effective against difficult soils.
It is a further object of the present invention to provide a method for the removal of difficult soils from dishes, pots and pans and other kitchen utensils.
.
;' ~ ' -.
. ~ :
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-2- C 557 (R) By "difficult soils" is meant here the difficult end of the dish-washing spectrum, such as baked-on proteins and starch soils.
These and other objects of the invention, which will be apparent hereinafter, can be achieved by combining an organic synthetic surfactant system of at least two surfactants as defined below with a citrus juice at a level of from 5% by weight based on the total composition. Any juice of a citrus fruit belonging to the general class of citrus fruits can be used, such as:
sweet oranges (citrus sinensis); sour or bitter oranges (citrus auranticum); mandarins (citrus reticulata); grapefruits (citrus paradisi); pumelos (citrus grandis); lemons (citrus limon~; limes (citrus aurantifolia); citrons (citrus medica);
papeda (citrus hystrix) and trifoliate oranges (citrus trifoliata), though lemon juice in view of its established consumer's acceptance will be preferred in the invention.
Unless otherwise indicated the percentages of fruit juices given in this specification refer to fruit juices of single strength.
The term "single strength" is used here to indicate the average strength of fruit juice sgueezed out from fruit.
If concentrated juices are used, these will be indicated by ; designating the strength factor, e.g. "4x concentrate".
The compositions of the present invention are therefore especially designed for general use in conventional dishwashing, which can be used in the concentrated aqueous form or in the conventional hi~hly dilute dishwashing operation, producing a good cleaning effect combined with a consumer-acceptable foam level and foam stability.
Accordingly the liquid detergent composition of the invention comprises from about 5-60% by weight of an organic synthetic surfactant system of at least two surfactants as defined below, and at least 5% by weight of a citrus juice.
The organic synthetic surfactant system consists of 1) from about 30-90 parts by weight of the surfactant system of _ 3 _ .
7;~6 a Ca-sensitive first surfactant selected from the group consisting of water-soluble C -C16-alkyl benzene sulphonates, alkane sulphonates having 8-20 carbon atoms, olefin sulphonates having from 8-20 carbon atoms, di-C8 20-alkyl sulpho-succinates, di-C6 12-alkyl phenol sulphosuccinates, primary and secondary alkyl sulphates having 8-20 carbon atoms, C8 20-alkyl polyethoxy sulphates having 1-25 ethoxy groups, and mixtures thereof,and 2) from about 70-10 parts by weight of said system of a less Ca-sensitive second surfactant selected from the group consisting of water-soluble nonionic condensation products obtained by condens-ing from 5-30 moles of an alkylene oxide, preferably ethylene or propylene oxide, with one mole of an organic hydrophobic compound, aliphatic or alkyl aromatic in nature, having 8-24 carbon atoms and at least one reactive hydrogen atom, particularly a reactive hydroxyl, amino, amido or carboxyl group; C8 20-alkyl sulphobetaines;
amine oxides containing one long chain alkyl moiety of from 10-28 carbon atoms and two moieties which can be either alkyl radicals or hydroxyalkyl radicals having from 1 to 4 carbon atoms; C8 20-alkyl polyethoxy sulphates having 1-25 ethylene oxide groups, and mixtures thereof, said surfactants (1) and the ion-active surfactants of group (2) being present in the form of their alkali metal salts, ammonium salts, or mixtures thereof.
Examples of nonionic water-soluble condensation products obtained by condensing 5-30 moles of an alkylene oxide with one mole of an organic hydrophobic compound are:
a) the condensates of ethylene oxide with aliphatic straight chain or branched chain, primary or secondary alcohols of more than 8 carbon atoms such as those derived from tallow or coconut fatty acids, containing 5-20 ethylene oxide groups, and branched chained 97~
- 3a -Cl1-C15 alcohols condensed with 5-20 ethylene oxide groups.
b) the condensates of ethylene oxide with alkylphenols, in which the phenols may be mono- or polyalkylated and the -4- C 557 (R) total number of carbon atoms in the side chain or chains is from 5 to 18. Specific examples are condensates of one mole nonyl phenol with 8 to 15 moles of ethylene oxide.
c) the condensates of ethylene oxide with fatty acid esters, preferably mono-fatty acid esters of the sugar alcohols, sorbitol and manitol.
d) polyethenoxyesters obtained by reacting ethylene oxide with carboxylic acids, the latter being natural fatty acids or synthetic fatty acids made from oxidised paraffin wax having from 8-20 carbon atoms or alkylbenzoic or naphthenic acids having from 5-18 carbon atoms in the alkyl chain.
e) the condensation products of fatty acyl alkanolamides of the type C7 17 alkyl-C0-NHC2H40H, C7_17 alkyl-CO-N(C2H40H)2 with ethylene oxide.
f) the condensation products of C8 18 alkyl-, C8 18 alkenyl-and C8 18 alkylaryl amines with ethylene oxide.
A specific example is the condensation product of one mole of a dodecylamine with 9-12 moles of ethylene oxide.
Specific examples of amine oxides are dimethyl dodecyl amine oxide, diethyl tetradecyl amine oxide, bis-(2-hydroxyethyl)-dodecyl amine oxide, and dimethyl-2-hydroxydodecyl amine oxide.
It has been discovered that the above defined surfactant system can be utilised effectively in combination with citrus juice, particularly lemon juice, in the above stated proportions, to provide the desirable combined effect of good detergency, good ; foam behaviour and enhanced per'ormance on difficult soils, particularly baked-on or dried-on proteins or starchy soils, over a wide pH range from practically acid pH to alkaline pH, e.g. from 4-10. A preferred pH range of the composition of the invention is from about 5.5 to 9, particuarly from 6-8.5, more particularly from 7-8.5.
Any combination of the above-described first and second sur-factants can be used to form the organic synthetic surfactant system in the composition of the invention.
' .
`9 7~jti -S- C 557 (R) Typical examples of surfactant systems are alkyl benzene sulphonate/alkyl polyethoxy sulphate mixtures; alkyl benzene sulphonate/alkyl polyethoxy sulphate/nonionic mixtures; alkyl sulphate/alkyl benzene sulphonate/alkyl polyethoxy sulphate mi~tures and alkyl sulphate/alkyl polyethoxy sulphate/amine oxide mixtures.
As explained above, any type of citrus juice at a level of from 5~0 by weight can be used in the present invention, lemon, lime, orange and grapefruit juices being representative of the general class. The minimum amount of 5% by weight of citrus juice is taken since at lower levels the effect is insignificant to practically zero. Although any proportion above 5% of citrus juice as practically possible can in principle be used, it was found that high levels are not necessary to achi~e the desired benefit. Besides, as there is a clear fall-off in the increase in performance improvements with increasing juice content above 10%, and a quick fall-off especially in the higher percentage region, the use of too high levels of juice will not justify the extra high expenses incurred. Advantageously 50~, preferably 25%,can be taken as a convenient practical upper level of single strength citrus juice in the composition of the invention, as at concentrations above these percentages citrus iuice provides no further advantages that would compensate the high costs of extra citrus juice.
A citrus juice level most advantageously used in the liquid detergent composition of the invention is from 5% to about 10%
by weight.
Accordingly the invention provides an aqueous liquid detergent composition especially adapted for dishwashing and having improved cleaning performance particularly on difficult soils, comprising 5-60% by weight of an organic synthetic surfactant system consisting of at least two surfactants as defined here-inbefore, and 5-50% weight of a citrus juice.
t~ J
.'. ' -6- C 557 (R) Citrus juices are availble on the market. They are generally presented as either single strength juices or as concentrates of various strengths, i.e. from 2x concentrates up to 10x concentrates. Lemon juice contains a number of different classes of chemical compounds including acids, sugars, amino acids, oils and trace elements. Analytical data on citrus juices can be found in the following literature references:
a) "Chemical Constituents of Citrus Fruits", SUPD. 2 (1970) by Kefford and Chandler;
2) "Biochemistry of Fruits and their Products", Vol. 1 (1970) Ed. A.C.Hulme.
Within each class there are several different constituents each separately capable of being determined analytically. The main acid in citrus juice is citric acid, which is present at a level of about 5-6% by weight.
It is not known exactly which of the constituents present in citrus juice are responsible for improving the cleaning effect, but it is believed that a synergistic effect is produced by the combination of one or more constituents present in citrus juice and the active system used in the composition of the invention.
In addition to the above-described essential ingredients the liquid detergent composition of the invention can optionally contain other nOn-essential materials. Such optional ingredients include additional surfactants other than those specified as first and second surfactants of the organic synthetic surfactant system; builder salts which can be added to promote the cleaning and soil-removal efficiency of the surfactants of the composition, e.g. phosphates, polyphosphates, phosphonates, carbonates, polyacetates and polycarboxylates;
lather promoting agents, such as coconut fatty acid diethanol amide; hydrotropes and solubilising agents, such as the lower alkanols containing 2-4 carbon atoms, especially ethanol, urea, sodium or potassium toluene sulphonate and sodium or potassium xylene sulphonate, which are generally added to promote phase stability especially of compositions with high concentrations .
, ~, . . .
-7- C 557 (R) of surfactants; preservatives; perfume and colouring agents.
Furthermore, as desired, acid or alkaline substances for pH
adjustment and also scouring agents may be incorporated in the detergent composition of the invention.
Preferred compositions are those which contain 10-50% by weight of the above-described organic synthetic surfactant system, 5-25% by weight of lemin juice and about 15-75% by weight of water. Particularly preferred are those having an active detergent content of more than 35% by weight.
The invention will now be illustrated by the following Examples:
Examples I-III
The following compositions were prepared:
Composition I II III A B
/O by weight sodium dodecyl benzene 29.0 29.0 29.0 29.0 29.0 sodium lauryl-(ethXY)3-14.0 14.0 14.0 14-0 14-0 sodium citrate - - - - 1.0 lemon juice 1.25 2.5 5.0 0.25 0.25 (4x concentrate) ethanol 5.5 5.5 5.5 8.0 7.0 urea 5.5 5.5 5.5 7.5 8.0 water + preservatives44.7543.5 41.0 41.25 40.75 To determine the relative ease of cleaning of baked-on soils from substrates after soaking, the following half-tile comparison test method was used:
Soiled substrates, in the form of square enamel tiles (10 x 10 cm) are immersed in solutions of the test products (1 litre) at 0.15% concentrations. The solution is at 45C
at the start of the test and is reheated when it drops to 40C (use a small immersion coil). The tiles are checked for the first indications that the soil on one of them has ....
~ 97~
" .
-8- C 557 (R) softened and then all are removed from the test solution and cleaned (immersion time varies between 5-50 mins). Cleaning is carried out for 30 seconds using a Brillo Swish sponge dipped in the appropriate test solution.
The soil and soiling method:
The testswere carried out using Fruit Pie filling (Cherry and Apricot) and a mixture of flour and fruit pie filling (1:4~.
The pie filling is finely mushed by pressing it through a 240 micron sieve and a fine paste is produced from the flour/pie filling mixture.
The soil is applied to the substrate by screen printing, using two passes. The s~il is then baked in the centre of a large oven (Gallenkamp Oven Model OV330) for 4 minutes. Temperature should be 250C before putting the soiled substrates into the oven and speed in putting them into the oven is desirable to avoid the temperature dropping below 220C.
Results:
These are set out fully in Table 1 below.
Assessment was made by a technician panel rating the degree of soil removal on the following basis:
O = completely clean 1 = still slightly soiled 2 = moderately soiled
These and other objects of the invention, which will be apparent hereinafter, can be achieved by combining an organic synthetic surfactant system of at least two surfactants as defined below with a citrus juice at a level of from 5% by weight based on the total composition. Any juice of a citrus fruit belonging to the general class of citrus fruits can be used, such as:
sweet oranges (citrus sinensis); sour or bitter oranges (citrus auranticum); mandarins (citrus reticulata); grapefruits (citrus paradisi); pumelos (citrus grandis); lemons (citrus limon~; limes (citrus aurantifolia); citrons (citrus medica);
papeda (citrus hystrix) and trifoliate oranges (citrus trifoliata), though lemon juice in view of its established consumer's acceptance will be preferred in the invention.
Unless otherwise indicated the percentages of fruit juices given in this specification refer to fruit juices of single strength.
The term "single strength" is used here to indicate the average strength of fruit juice sgueezed out from fruit.
If concentrated juices are used, these will be indicated by ; designating the strength factor, e.g. "4x concentrate".
The compositions of the present invention are therefore especially designed for general use in conventional dishwashing, which can be used in the concentrated aqueous form or in the conventional hi~hly dilute dishwashing operation, producing a good cleaning effect combined with a consumer-acceptable foam level and foam stability.
Accordingly the liquid detergent composition of the invention comprises from about 5-60% by weight of an organic synthetic surfactant system of at least two surfactants as defined below, and at least 5% by weight of a citrus juice.
The organic synthetic surfactant system consists of 1) from about 30-90 parts by weight of the surfactant system of _ 3 _ .
7;~6 a Ca-sensitive first surfactant selected from the group consisting of water-soluble C -C16-alkyl benzene sulphonates, alkane sulphonates having 8-20 carbon atoms, olefin sulphonates having from 8-20 carbon atoms, di-C8 20-alkyl sulpho-succinates, di-C6 12-alkyl phenol sulphosuccinates, primary and secondary alkyl sulphates having 8-20 carbon atoms, C8 20-alkyl polyethoxy sulphates having 1-25 ethoxy groups, and mixtures thereof,and 2) from about 70-10 parts by weight of said system of a less Ca-sensitive second surfactant selected from the group consisting of water-soluble nonionic condensation products obtained by condens-ing from 5-30 moles of an alkylene oxide, preferably ethylene or propylene oxide, with one mole of an organic hydrophobic compound, aliphatic or alkyl aromatic in nature, having 8-24 carbon atoms and at least one reactive hydrogen atom, particularly a reactive hydroxyl, amino, amido or carboxyl group; C8 20-alkyl sulphobetaines;
amine oxides containing one long chain alkyl moiety of from 10-28 carbon atoms and two moieties which can be either alkyl radicals or hydroxyalkyl radicals having from 1 to 4 carbon atoms; C8 20-alkyl polyethoxy sulphates having 1-25 ethylene oxide groups, and mixtures thereof, said surfactants (1) and the ion-active surfactants of group (2) being present in the form of their alkali metal salts, ammonium salts, or mixtures thereof.
Examples of nonionic water-soluble condensation products obtained by condensing 5-30 moles of an alkylene oxide with one mole of an organic hydrophobic compound are:
a) the condensates of ethylene oxide with aliphatic straight chain or branched chain, primary or secondary alcohols of more than 8 carbon atoms such as those derived from tallow or coconut fatty acids, containing 5-20 ethylene oxide groups, and branched chained 97~
- 3a -Cl1-C15 alcohols condensed with 5-20 ethylene oxide groups.
b) the condensates of ethylene oxide with alkylphenols, in which the phenols may be mono- or polyalkylated and the -4- C 557 (R) total number of carbon atoms in the side chain or chains is from 5 to 18. Specific examples are condensates of one mole nonyl phenol with 8 to 15 moles of ethylene oxide.
c) the condensates of ethylene oxide with fatty acid esters, preferably mono-fatty acid esters of the sugar alcohols, sorbitol and manitol.
d) polyethenoxyesters obtained by reacting ethylene oxide with carboxylic acids, the latter being natural fatty acids or synthetic fatty acids made from oxidised paraffin wax having from 8-20 carbon atoms or alkylbenzoic or naphthenic acids having from 5-18 carbon atoms in the alkyl chain.
e) the condensation products of fatty acyl alkanolamides of the type C7 17 alkyl-C0-NHC2H40H, C7_17 alkyl-CO-N(C2H40H)2 with ethylene oxide.
f) the condensation products of C8 18 alkyl-, C8 18 alkenyl-and C8 18 alkylaryl amines with ethylene oxide.
A specific example is the condensation product of one mole of a dodecylamine with 9-12 moles of ethylene oxide.
Specific examples of amine oxides are dimethyl dodecyl amine oxide, diethyl tetradecyl amine oxide, bis-(2-hydroxyethyl)-dodecyl amine oxide, and dimethyl-2-hydroxydodecyl amine oxide.
It has been discovered that the above defined surfactant system can be utilised effectively in combination with citrus juice, particularly lemon juice, in the above stated proportions, to provide the desirable combined effect of good detergency, good ; foam behaviour and enhanced per'ormance on difficult soils, particularly baked-on or dried-on proteins or starchy soils, over a wide pH range from practically acid pH to alkaline pH, e.g. from 4-10. A preferred pH range of the composition of the invention is from about 5.5 to 9, particuarly from 6-8.5, more particularly from 7-8.5.
Any combination of the above-described first and second sur-factants can be used to form the organic synthetic surfactant system in the composition of the invention.
' .
`9 7~jti -S- C 557 (R) Typical examples of surfactant systems are alkyl benzene sulphonate/alkyl polyethoxy sulphate mixtures; alkyl benzene sulphonate/alkyl polyethoxy sulphate/nonionic mixtures; alkyl sulphate/alkyl benzene sulphonate/alkyl polyethoxy sulphate mi~tures and alkyl sulphate/alkyl polyethoxy sulphate/amine oxide mixtures.
As explained above, any type of citrus juice at a level of from 5~0 by weight can be used in the present invention, lemon, lime, orange and grapefruit juices being representative of the general class. The minimum amount of 5% by weight of citrus juice is taken since at lower levels the effect is insignificant to practically zero. Although any proportion above 5% of citrus juice as practically possible can in principle be used, it was found that high levels are not necessary to achi~e the desired benefit. Besides, as there is a clear fall-off in the increase in performance improvements with increasing juice content above 10%, and a quick fall-off especially in the higher percentage region, the use of too high levels of juice will not justify the extra high expenses incurred. Advantageously 50~, preferably 25%,can be taken as a convenient practical upper level of single strength citrus juice in the composition of the invention, as at concentrations above these percentages citrus iuice provides no further advantages that would compensate the high costs of extra citrus juice.
A citrus juice level most advantageously used in the liquid detergent composition of the invention is from 5% to about 10%
by weight.
Accordingly the invention provides an aqueous liquid detergent composition especially adapted for dishwashing and having improved cleaning performance particularly on difficult soils, comprising 5-60% by weight of an organic synthetic surfactant system consisting of at least two surfactants as defined here-inbefore, and 5-50% weight of a citrus juice.
t~ J
.'. ' -6- C 557 (R) Citrus juices are availble on the market. They are generally presented as either single strength juices or as concentrates of various strengths, i.e. from 2x concentrates up to 10x concentrates. Lemon juice contains a number of different classes of chemical compounds including acids, sugars, amino acids, oils and trace elements. Analytical data on citrus juices can be found in the following literature references:
a) "Chemical Constituents of Citrus Fruits", SUPD. 2 (1970) by Kefford and Chandler;
2) "Biochemistry of Fruits and their Products", Vol. 1 (1970) Ed. A.C.Hulme.
Within each class there are several different constituents each separately capable of being determined analytically. The main acid in citrus juice is citric acid, which is present at a level of about 5-6% by weight.
It is not known exactly which of the constituents present in citrus juice are responsible for improving the cleaning effect, but it is believed that a synergistic effect is produced by the combination of one or more constituents present in citrus juice and the active system used in the composition of the invention.
In addition to the above-described essential ingredients the liquid detergent composition of the invention can optionally contain other nOn-essential materials. Such optional ingredients include additional surfactants other than those specified as first and second surfactants of the organic synthetic surfactant system; builder salts which can be added to promote the cleaning and soil-removal efficiency of the surfactants of the composition, e.g. phosphates, polyphosphates, phosphonates, carbonates, polyacetates and polycarboxylates;
lather promoting agents, such as coconut fatty acid diethanol amide; hydrotropes and solubilising agents, such as the lower alkanols containing 2-4 carbon atoms, especially ethanol, urea, sodium or potassium toluene sulphonate and sodium or potassium xylene sulphonate, which are generally added to promote phase stability especially of compositions with high concentrations .
, ~, . . .
-7- C 557 (R) of surfactants; preservatives; perfume and colouring agents.
Furthermore, as desired, acid or alkaline substances for pH
adjustment and also scouring agents may be incorporated in the detergent composition of the invention.
Preferred compositions are those which contain 10-50% by weight of the above-described organic synthetic surfactant system, 5-25% by weight of lemin juice and about 15-75% by weight of water. Particularly preferred are those having an active detergent content of more than 35% by weight.
The invention will now be illustrated by the following Examples:
Examples I-III
The following compositions were prepared:
Composition I II III A B
/O by weight sodium dodecyl benzene 29.0 29.0 29.0 29.0 29.0 sodium lauryl-(ethXY)3-14.0 14.0 14.0 14-0 14-0 sodium citrate - - - - 1.0 lemon juice 1.25 2.5 5.0 0.25 0.25 (4x concentrate) ethanol 5.5 5.5 5.5 8.0 7.0 urea 5.5 5.5 5.5 7.5 8.0 water + preservatives44.7543.5 41.0 41.25 40.75 To determine the relative ease of cleaning of baked-on soils from substrates after soaking, the following half-tile comparison test method was used:
Soiled substrates, in the form of square enamel tiles (10 x 10 cm) are immersed in solutions of the test products (1 litre) at 0.15% concentrations. The solution is at 45C
at the start of the test and is reheated when it drops to 40C (use a small immersion coil). The tiles are checked for the first indications that the soil on one of them has ....
~ 97~
" .
-8- C 557 (R) softened and then all are removed from the test solution and cleaned (immersion time varies between 5-50 mins). Cleaning is carried out for 30 seconds using a Brillo Swish sponge dipped in the appropriate test solution.
The soil and soiling method:
The testswere carried out using Fruit Pie filling (Cherry and Apricot) and a mixture of flour and fruit pie filling (1:4~.
The pie filling is finely mushed by pressing it through a 240 micron sieve and a fine paste is produced from the flour/pie filling mixture.
The soil is applied to the substrate by screen printing, using two passes. The s~il is then baked in the centre of a large oven (Gallenkamp Oven Model OV330) for 4 minutes. Temperature should be 250C before putting the soiled substrates into the oven and speed in putting them into the oven is desirable to avoid the temperature dropping below 220C.
Results:
These are set out fully in Table 1 below.
Assessment was made by a technician panel rating the degree of soil removal on the following basis:
O = completely clean 1 = still slightly soiled 2 = moderately soiled
3 = considerably soiled
4 = no visible cleaning.
The ratings were averaged from 8 results for each product and control. Product A was used as control.
' .
7~
-9- C 557 (R) Average Rating Difference (control-sample) Product in 5H water in 26H water in 5H water in 26H water I 2.13 2.93 + 0.81 + 0.81 5control (A) 2.94 3.74 II 1.25 3.31 + 0.44 + 0.32 control (A) 1.69 3.63 10III 1.00 2.18 + 0.88 + 0.44 control (A) 1.88 2.62 B 0.75 2.62 - 0.12 - 0.37 control (A) 0.63 2.25 From the above results it is clear that the lemon juice compositions I, II and III of the invention are superior to compositions A and B outside the invention.
Example IV
The influence of pH was investigated from assessing the perfor-mance of the following liquid composition in a soaking test.
Composition sodium dodecyl benzene sulphonate 29.0%
C12 alkyl ether sulphate containing 3 ethylene oxide 14.0%
lemon juice 10.0%
ethanol . 5.5%
urea 5.5%
water + preservatives 36.0%
Comparisons were carried out by using the standard (10 x 10 cm) enamel tiles soiled with Apricot pie filling/flour and baked as in Examples I-III. Half tile comparisons in water of 11.3 German Hardness were carried out at 45C.
Test products were tested in a random manner and all tests were ~97~6 , -10- C 557 (R) duplicated.
pH Adjustments were carried out at 45C using dilute sulphuric acid (0.1 M) and dilute sodium hydroxide (0.1 M) solutions and measurement of the pH at the end of each test was also made.
A product of the above nominal composition without lemon juice was used as control.
Assessment was made by a technician panel to assess the degree of soil remaining on each half tile using the following ratings:
0 = completely clean 1 = still slightly soiled 2 = moderately soiled 3 = considerably soiled 4 = no visible cleaning.
These ratings have been averaged ( 6 results for each test product andcontrol at each pH value) and a soil difference between the control and the test product calculated.
TABLE I
Results of soaking ~st - a comparison of product with and without 10% lemon juice.
pH Product Ratings Average Difference control-sample
The ratings were averaged from 8 results for each product and control. Product A was used as control.
' .
7~
-9- C 557 (R) Average Rating Difference (control-sample) Product in 5H water in 26H water in 5H water in 26H water I 2.13 2.93 + 0.81 + 0.81 5control (A) 2.94 3.74 II 1.25 3.31 + 0.44 + 0.32 control (A) 1.69 3.63 10III 1.00 2.18 + 0.88 + 0.44 control (A) 1.88 2.62 B 0.75 2.62 - 0.12 - 0.37 control (A) 0.63 2.25 From the above results it is clear that the lemon juice compositions I, II and III of the invention are superior to compositions A and B outside the invention.
Example IV
The influence of pH was investigated from assessing the perfor-mance of the following liquid composition in a soaking test.
Composition sodium dodecyl benzene sulphonate 29.0%
C12 alkyl ether sulphate containing 3 ethylene oxide 14.0%
lemon juice 10.0%
ethanol . 5.5%
urea 5.5%
water + preservatives 36.0%
Comparisons were carried out by using the standard (10 x 10 cm) enamel tiles soiled with Apricot pie filling/flour and baked as in Examples I-III. Half tile comparisons in water of 11.3 German Hardness were carried out at 45C.
Test products were tested in a random manner and all tests were ~97~6 , -10- C 557 (R) duplicated.
pH Adjustments were carried out at 45C using dilute sulphuric acid (0.1 M) and dilute sodium hydroxide (0.1 M) solutions and measurement of the pH at the end of each test was also made.
A product of the above nominal composition without lemon juice was used as control.
Assessment was made by a technician panel to assess the degree of soil remaining on each half tile using the following ratings:
0 = completely clean 1 = still slightly soiled 2 = moderately soiled 3 = considerably soiled 4 = no visible cleaning.
These ratings have been averaged ( 6 results for each test product andcontrol at each pH value) and a soil difference between the control and the test product calculated.
TABLE I
Results of soaking ~st - a comparison of product with and without 10% lemon juice.
pH Product Ratings Average Difference control-sample
5.5 lemon 1.5 2.5 1. 0.5 1. 0.5 1.17 +0.75 control 2.5 3. 1.5 1.5 2. 1. 1.92 7.0 lemon 3. 3.5 2.5 0 0 0 1.5 +0.67 control 3.5 4. 3. 0.5 1. 0.5 2.17 .5 lemon 0.5 0.5 0.5 0.5 1. 0.5 0.58 +1.42 control 1.5 2. 1. 2.5 3. 2. 2.0 10.0 lemon 1.5 2.5 1. 1.5 2.5 1. 1.67 +0.50 control 3. 3. 1.5 2. 2.5 1. 2.17 The above Table shows that the composition of the invention shows a consistent superiority at pH 5.5, 7.0, 8.5 and 10.0, with : .- . . - : ~ .
- ~.
9~6 -11- C 557 (R) results at pH 8.5 being particularly good.
Example V
The following compositions were assessed:
% by weight Composition C V1 V2 V3 V4 V5 V6 sodium dodecyl ben- 29 0 29.0 29.0 29.0 29.0 29-0 29-0 zene sulphonate lauryl-3-ethoxy- 14.0 14.0 14.0 14.0 14.0 14.0 14.0 lemon juice 0.25 1.25 2.5 3.75 5.06.25 12.5 (4x concentrate) ethanol 10.0 10.0 10.0 10.0 10.010.0 10.0 urea 10.0 10.0 10.0 10.0 10.010.0 10.0 - 15 water+ to to to to to to to preservative100.0 100.0 100.0 100.0 100.0 100.0 100.0 nominal lemon1 5 10 15 20 25 50 juice level The method employed was as follows:
1. An egg soiling was prepared by carefully mixing dried egg powder and water in a ratio of 1:1.
2. A 5 cm strip of soil was screen-printed on to the centre of a 30 x 25 cm glass tile.
3. Tiles were baked for 30 mins at 20nc.
Five assessments could then be carried out across each tile. At least two control assessments were carried out on each tile.
4. Five 5 cm wells were built across the tile using plasticine strips. 6 mls of solution (0.15%) were placed in a well.
Using a J cloth covered head and a 1.5 kg weight, the number of rubs to clean the 5 cm strip of soil was recorded.
5. Results for the test solution were calculated as a per-centage of the performance of the nearest control in the tile.
!9~
-12- C 557 (R) The results of the tests using water of 5H are tabulated below:
Composition /0 Lemon juice Average performance as % control Control (C) 1 100 V6 50 . 60.5 The above results clearly show the superior performance of the compositions V1 to V6 of the invention, containing 5' to 50%
lemon juice respectively, on cleanin~ baked-on egg, over the control.
Example VI
The following compositions were compared in a standard plate washing test for their dishwashing performance as well as in a test to determine the relative ease of cleaning baked-on soils from substrates after soaking, using the test method as described in Examples I-III.
Composition Vl Composition D
- 25 10~ sodium dodecylbenzene sulphonate 15' Empilan~LP 10 5' sodium lauryl (ethoxy)3-sulphate 30~c glycerin 5o lemon juice 5% lemon juice 2'~, urea 2% urea balance water balance water Empilan LP10 is a nonionic fatty amide condensate, comparable to Nopco 1179 of the Nopco Chemical comPany~
Empilan is a Registered Trade Mark of Marchon Products Ltd.
The standard plate washing tests were carried out using the following test conditions:
7~
-13- C 557 (R) Product concentrations: 0.15% and 0.45%
Temperature of solution: 45C
Standard gravy soil at 5g/plate: fat, starch, oleic and stearic acids.
The results are tabulated below:
Number of plates washed Water hardness 5H 26H
Product concentration 0.15% 0.45% 0.15% 0.45%
Composition VI (pH 7) 30 63 27 59 Composition D (pH 5.8) 3 7 2 4 Results of the test to determine the relative ease of cleaning baked-on soils from substrates. The ratings were arranged from 5 results for each product used at 0.75% concentrations.
Average rating Difference Composition in 5Hwater in 26H water in 5Hwater in 26Hwater VI (pH 7) 0.2 2.4 D (pH 5-8) 0 72.4 + 0.5 + 0.0 VI (pH 7) 0.73.0 D (pH 7) 1.13.3 + 0.4 + 0 3 VI (pH 7) 2.4 D (pH 5.8) 2.7 ~ + 0.3 VI (pH 7) 1.5 D (pH 7) 2.1 + 0.6 The above results clearly show the superior properties of composition VI of the invention over comDosition D of the art in both dishwashing and baked-on soil performance.
Examples VII-IX
The following liquid dishwashing formulations are within the scope - -14- C 557 (R) of the invention:
Composition VII % by weight sodium dodecyl benzene sulphonate 16.0 nonyl phenol-7 ethylene oxide 7.0 ethanol 2.0 urea 4.0 lemon juice 8.0 water + preservatives to 100.0 Composition VIII % by weight ammonium dodecyl benzene sulphonate32.0 nonyl phenol-10 ethylene oxide 8.0 ethanol 3.0 15 urea 3.0 sodium xylene sulphonate 9.0 lemon juice 7.5 magnesium sulphate 1.2 water + preservatives to 100.0 Composition IX
sodium lauryl (ethoxy)3-sulphate 24.0 dimethyl dodecyl amine oxide 5.0 lemon juice 10.0 25 sodium citrate 1.0 urea 3.0 ethanol 3.0 water + preservatives to 100.0
- ~.
9~6 -11- C 557 (R) results at pH 8.5 being particularly good.
Example V
The following compositions were assessed:
% by weight Composition C V1 V2 V3 V4 V5 V6 sodium dodecyl ben- 29 0 29.0 29.0 29.0 29.0 29-0 29-0 zene sulphonate lauryl-3-ethoxy- 14.0 14.0 14.0 14.0 14.0 14.0 14.0 lemon juice 0.25 1.25 2.5 3.75 5.06.25 12.5 (4x concentrate) ethanol 10.0 10.0 10.0 10.0 10.010.0 10.0 urea 10.0 10.0 10.0 10.0 10.010.0 10.0 - 15 water+ to to to to to to to preservative100.0 100.0 100.0 100.0 100.0 100.0 100.0 nominal lemon1 5 10 15 20 25 50 juice level The method employed was as follows:
1. An egg soiling was prepared by carefully mixing dried egg powder and water in a ratio of 1:1.
2. A 5 cm strip of soil was screen-printed on to the centre of a 30 x 25 cm glass tile.
3. Tiles were baked for 30 mins at 20nc.
Five assessments could then be carried out across each tile. At least two control assessments were carried out on each tile.
4. Five 5 cm wells were built across the tile using plasticine strips. 6 mls of solution (0.15%) were placed in a well.
Using a J cloth covered head and a 1.5 kg weight, the number of rubs to clean the 5 cm strip of soil was recorded.
5. Results for the test solution were calculated as a per-centage of the performance of the nearest control in the tile.
!9~
-12- C 557 (R) The results of the tests using water of 5H are tabulated below:
Composition /0 Lemon juice Average performance as % control Control (C) 1 100 V6 50 . 60.5 The above results clearly show the superior performance of the compositions V1 to V6 of the invention, containing 5' to 50%
lemon juice respectively, on cleanin~ baked-on egg, over the control.
Example VI
The following compositions were compared in a standard plate washing test for their dishwashing performance as well as in a test to determine the relative ease of cleaning baked-on soils from substrates after soaking, using the test method as described in Examples I-III.
Composition Vl Composition D
- 25 10~ sodium dodecylbenzene sulphonate 15' Empilan~LP 10 5' sodium lauryl (ethoxy)3-sulphate 30~c glycerin 5o lemon juice 5% lemon juice 2'~, urea 2% urea balance water balance water Empilan LP10 is a nonionic fatty amide condensate, comparable to Nopco 1179 of the Nopco Chemical comPany~
Empilan is a Registered Trade Mark of Marchon Products Ltd.
The standard plate washing tests were carried out using the following test conditions:
7~
-13- C 557 (R) Product concentrations: 0.15% and 0.45%
Temperature of solution: 45C
Standard gravy soil at 5g/plate: fat, starch, oleic and stearic acids.
The results are tabulated below:
Number of plates washed Water hardness 5H 26H
Product concentration 0.15% 0.45% 0.15% 0.45%
Composition VI (pH 7) 30 63 27 59 Composition D (pH 5.8) 3 7 2 4 Results of the test to determine the relative ease of cleaning baked-on soils from substrates. The ratings were arranged from 5 results for each product used at 0.75% concentrations.
Average rating Difference Composition in 5Hwater in 26H water in 5Hwater in 26Hwater VI (pH 7) 0.2 2.4 D (pH 5-8) 0 72.4 + 0.5 + 0.0 VI (pH 7) 0.73.0 D (pH 7) 1.13.3 + 0.4 + 0 3 VI (pH 7) 2.4 D (pH 5.8) 2.7 ~ + 0.3 VI (pH 7) 1.5 D (pH 7) 2.1 + 0.6 The above results clearly show the superior properties of composition VI of the invention over comDosition D of the art in both dishwashing and baked-on soil performance.
Examples VII-IX
The following liquid dishwashing formulations are within the scope - -14- C 557 (R) of the invention:
Composition VII % by weight sodium dodecyl benzene sulphonate 16.0 nonyl phenol-7 ethylene oxide 7.0 ethanol 2.0 urea 4.0 lemon juice 8.0 water + preservatives to 100.0 Composition VIII % by weight ammonium dodecyl benzene sulphonate32.0 nonyl phenol-10 ethylene oxide 8.0 ethanol 3.0 15 urea 3.0 sodium xylene sulphonate 9.0 lemon juice 7.5 magnesium sulphate 1.2 water + preservatives to 100.0 Composition IX
sodium lauryl (ethoxy)3-sulphate 24.0 dimethyl dodecyl amine oxide 5.0 lemon juice 10.0 25 sodium citrate 1.0 urea 3.0 ethanol 3.0 water + preservatives to 100.0
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous detergent composition especially adapted for dish-washing, comprising 5-60% by weight of an organic synthetic surfac-tant system of at least two surfactants and 5-50% by weight of a citrus juice, said organic synthetic surfactant system consisting of 1) from about 30-90 parts by weight of the surfactant system of a Ca-sensitive first surfactant selected from the group consisting of water soluble C8-16 alkyl benzene sulphonates; alkane sulphonates having from 8-20 carbon atoms; olefin sulphonates having from 8-20 carbon atoms; di-C8-20-alkyl sulphosuccinates;
d-C6-12-alkylphenol sulphosuccinates; primary and secondary alkyl sulphates having 8-20 carbon atoms; C8-20 alkyl polyethoxy sulphates having 1-25 ethoxy groups and mixtures thereof, and 2) from about 70-10 parts by wieght of said system of a less Ca-sensitive second surfactant selected from the group consisting of water-soluble nonionic condensation products obtained by condens-ing from 5-30 moles of an alkylene oxide, preferably ethylene or propylene oxide with one mole of an organic hydrophobic compound, aliphatic or alkyl aromatic in nature, having 8 to 24 carbon atoms and at least one reactive hydrogen atom, particularly a reactive hydroxyl, amino, amido or carboxyl group; C8-20-alkylsulphobetaines;
amine oxides containing one long chain alkyl moiety of from 10-28 carbon atoms and two moieties which can be either alkyl radicals or hydroxyalkyl radicals having from 1-4 carbon atoms; C8-20-alkyl-polyethoxy sulphates having from 1-25 ethoxy groups, and mixtures thereof, said surfactants of group (1) and the ion-active surfactants of group (2) being present in the form of their alkalimetal salts, ammonium salts, or mixtures thereof.
d-C6-12-alkylphenol sulphosuccinates; primary and secondary alkyl sulphates having 8-20 carbon atoms; C8-20 alkyl polyethoxy sulphates having 1-25 ethoxy groups and mixtures thereof, and 2) from about 70-10 parts by wieght of said system of a less Ca-sensitive second surfactant selected from the group consisting of water-soluble nonionic condensation products obtained by condens-ing from 5-30 moles of an alkylene oxide, preferably ethylene or propylene oxide with one mole of an organic hydrophobic compound, aliphatic or alkyl aromatic in nature, having 8 to 24 carbon atoms and at least one reactive hydrogen atom, particularly a reactive hydroxyl, amino, amido or carboxyl group; C8-20-alkylsulphobetaines;
amine oxides containing one long chain alkyl moiety of from 10-28 carbon atoms and two moieties which can be either alkyl radicals or hydroxyalkyl radicals having from 1-4 carbon atoms; C8-20-alkyl-polyethoxy sulphates having from 1-25 ethoxy groups, and mixtures thereof, said surfactants of group (1) and the ion-active surfactants of group (2) being present in the form of their alkalimetal salts, ammonium salts, or mixtures thereof.
2. A composition according to claim 1, wherein said organic synthetic surfactant system ir present in an amount of 10-50% by weight of the composition.
3. A composition according to claim 1, wherein the citrus juice is present in an amount of 5-25% by weight of the composition.
4. A composition according to claim 3, wherein the citrus juice is present in an amount of 5-10% by wieght of the composition.
5. A composition according to claim 1, wherein the citrus juice is lemon juice.
6. A composition according to claim 5, having a pH of from 5.5-9.
7. A composition according to claim 6, wherein the pH is 6-8.5.
8. A composition according to claim 1, claim 2 or claim 3, wherein the organic surfactant system is present in an amount of more than 35% by weight of the composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5347277 | 1977-12-22 | ||
| GB53,472/77 | 1977-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109756A true CA1109756A (en) | 1981-09-29 |
Family
ID=10467944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA318,100A Expired CA1109756A (en) | 1977-12-22 | 1978-12-18 | Liquid detergent composition |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS5850680B2 (en) |
| AT (1) | ATA910978A (en) |
| AU (1) | AU520258B2 (en) |
| BE (1) | BE873051A (en) |
| BR (1) | BR7808426A (en) |
| CA (1) | CA1109756A (en) |
| CH (1) | CH641836A5 (en) |
| DE (1) | DE2855778B2 (en) |
| DK (1) | DK574778A (en) |
| FI (1) | FI63056C (en) |
| FR (1) | FR2412610A1 (en) |
| GR (1) | GR66577B (en) |
| IT (1) | IT1109668B (en) |
| NL (1) | NL7812439A (en) |
| NO (1) | NO152014C (en) |
| PT (1) | PT68972A (en) |
| SE (1) | SE442019B (en) |
| ZA (1) | ZA787143B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6081781U (en) * | 1983-11-14 | 1985-06-06 | 第一精工株式会社 | fishing weights |
| JP2668388B2 (en) * | 1988-05-16 | 1997-10-27 | ライオン株式会社 | Liquid polishing composition |
| DE19927936B4 (en) * | 1999-06-18 | 2009-04-09 | Predinal Gmbh | Use of juices of naturally grown citrus fruits as a microbicidal component in disinfectants |
| EP1111031A1 (en) * | 1999-12-22 | 2001-06-27 | The Procter & Gamble Company | cleaning composition |
| US6551984B1 (en) * | 2002-04-09 | 2003-04-22 | Colgate-Palmolive Company | High foaming, grease cutting light duty liquid composition containing at least one natural extract |
| DE102005056289A1 (en) * | 2005-11-24 | 2007-05-31 | Predinal Gmbh | Disinfecting agent for combating harmful arthropod comprises citrus juice of the family Rutaceae as active agent, surfactant, alcohols, hydrotropic agents and further auxiliary materials |
-
1978
- 1978-12-18 NO NO784258A patent/NO152014C/en unknown
- 1978-12-18 CA CA318,100A patent/CA1109756A/en not_active Expired
- 1978-12-18 FI FI783879A patent/FI63056C/en not_active IP Right Cessation
- 1978-12-19 GR GR57926A patent/GR66577B/el unknown
- 1978-12-20 AT AT0910978A patent/ATA910978A/en unknown
- 1978-12-20 ZA ZA787143A patent/ZA787143B/en unknown
- 1978-12-21 BR BR7808426A patent/BR7808426A/en unknown
- 1978-12-21 DK DK574778A patent/DK574778A/en not_active Application Discontinuation
- 1978-12-21 NL NL7812439A patent/NL7812439A/en not_active Application Discontinuation
- 1978-12-21 FR FR7835882A patent/FR2412610A1/en active Granted
- 1978-12-21 SE SE7813213A patent/SE442019B/en unknown
- 1978-12-21 JP JP53156958A patent/JPS5850680B2/en not_active Expired
- 1978-12-21 CH CH1303278A patent/CH641836A5/en not_active IP Right Cessation
- 1978-12-21 AU AU42795/78A patent/AU520258B2/en not_active Expired
- 1978-12-21 IT IT69927/78A patent/IT1109668B/en active
- 1978-12-22 DE DE2855778A patent/DE2855778B2/en not_active Ceased
- 1978-12-22 BE BE192548A patent/BE873051A/en not_active IP Right Cessation
- 1978-12-22 PT PT68972A patent/PT68972A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5850680B2 (en) | 1983-11-11 |
| PT68972A (en) | 1979-01-01 |
| JPS5499108A (en) | 1979-08-04 |
| SE442019B (en) | 1985-11-25 |
| AU4279578A (en) | 1979-06-28 |
| ATA910978A (en) | 1981-07-15 |
| CH641836A5 (en) | 1984-03-15 |
| IT7869927A0 (en) | 1978-12-21 |
| ZA787143B (en) | 1980-07-30 |
| FI63056B (en) | 1982-12-31 |
| NO152014B (en) | 1985-04-09 |
| GR66577B (en) | 1981-03-27 |
| FR2412610A1 (en) | 1979-07-20 |
| FI63056C (en) | 1983-04-11 |
| FI783879A (en) | 1979-06-23 |
| BR7808426A (en) | 1979-08-21 |
| DE2855778A1 (en) | 1979-06-28 |
| BE873051A (en) | 1979-06-22 |
| NO152014C (en) | 1985-07-17 |
| SE7813213L (en) | 1979-06-23 |
| DE2855778B2 (en) | 1980-03-27 |
| NO784258L (en) | 1979-06-25 |
| AU520258B2 (en) | 1982-01-21 |
| NL7812439A (en) | 1979-06-26 |
| IT1109668B (en) | 1985-12-23 |
| DK574778A (en) | 1979-06-23 |
| FR2412610B1 (en) | 1982-12-17 |
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