(19)
(11) EP 0 145 065 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Mention of the grant of the patent:
11.04.1990 Bulletin 1990/15

(21) Application number: 84201677.6

(22) Date of filing: 20.11.1984
(51) International Patent Classification (IPC)5C11D 1/83, C11D 1/14, C11D 1/22, C11D 1/72

(54)

Detergents

Reinigungsmittel

Compositions détergentes


(84) Designated Contracting States:
AT BE CH DE FR GB IT LI NL SE

(30) Priority: 02.12.1983 NL 8304144

(43) Date of publication of application:
19.06.1985 Bulletin 1985/25

(73) Proprietor: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
2596 HR Den Haag (NL)

(72) Inventors:
  • Jones, Neville Earl
    London (GB)
  • Craven, Sheila Mairi
    NL-1921 XK Akersloot (NL)

(74) Representative: Aalbers, Onno et al
P.O. Box 162
2501 AN Den Haag
2501 AN Den Haag (NL)


(56) References cited: : 
EP-A- 123 423
EP-A- 0 125 854
BE-A- 623 882
FR-A- 1 189 134
FR-A- 1 361 839
FR-A- 2 316 324
EP-A- 0 039 110
BE-A- 623 881
DE-A- 3 124 549
FR-A- 1 251 853
FR-A- 1 535 855
   
       
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description


    [0001] The invention relates to aqueous detergent concentrates which, after dilution, preferably after mixing with the desired quantity of water, can be used for cleaning, amongst other things, dishes and fabrics. The concentrates consist of an aqueous solution containing at least three components with cleansing action. These components, which will be specified in greater detail below, are collectively referred to by the term "active detergent".

    [0002] As is known, it is necessary in practice for both the concentrate and the ready-to-use washing liquid to meet certain requirements in respect of viscosity and transparency point, which is the temperature at which turbidity, caused by precipitation of solids after strong cooling, completely disappears.

    [0003] Concentrates are convenient for storage and transport, but for the final users it is of course the properties of the washing liquid obtained by dilution that are important. There is a danger that dilution can cause the viscosity to drop excessively, especially if the active detergent consists of alkylaryl sulphonate and one or more polyethyleneglycol ethers of primary or secondary higher alcohols and/or of alkylphenols. A large viscosity drop on dilution is unacceptable for buyers of the detergent concentrates, especially housewives, and should therefore be avoided.

    [0004] It has now been found that by adding a salt of a sulphate alcohol to a detergent concentrate of the above-mentioned sort, the undesired viscosity drop on dilution can be greatly reduced while retaining a low transparency point.

    [0005] The invention therefore relates to an aqueous detergent concentrate, characterized in that in addition to water it contains an active detergent comprising the following components.

    [0006] 

    (a) 50 to 70% wt of one or more salts of an alkylaryl sulphonic acid,

    (b) 5 to 30% wt of one or more polyethyleneglycol ethers of primary or secondary alcohols with the general formulae (R(OC2H4)n―OH, in which R represents an alkyl group with 8-18 carbon atoms and n is an integer varying from 5 to 12, and

    (c) 0.1 to 25% wt of one or more salts of sulphated alkanols with 6-16 carbon atoms per molecule.



    [0007] The detergent concentrate preferably contains at least 10% wt, and in most cases not more than 70% wt, relative to the weight of the concentrate, of the active detergent.

    [0008] The salts of component (a) and (c) are preferably alkali, ammonium and/or amine salts. Alkali salts are most preferred, especially sodium salts.

    [0009] Component (a) is preferably a salt of an alkylbenzene sulphonic acid, especially one with 8-16 carbon atoms in the alkyl group. The carbon atoms in the alkyl group in component (a) preferably form a straight chain.

    [0010] The polyethyleneglycol ethers of primary or secondary alcohols in component (b) satisfy the general formula (R-(OC2H4)"OH, in which R is an alkyl group with 8-18 carbon atoms and n represents an integer varying from 5 to 12. The carbon atoms in the alkyl group R preferably form a straight chain.

    [0011] The salts of components (c) are preferably alkali, ammonium and/or amine salts. Alkali salts are most preferred, especially sodium salts. The alcohol from which component (c) is derived is preferably a primary or secondary alcohol. The carbon atoms in this alkanol preferably form a straight chain.

    [0012] The previous mentioned undesirable viscosity drop on dilution while retaining a low transparency point is reduced even more if the active detergent also contains a component (d) consisting of one or more salts of sulphated alcohol ethoxylates and/or of sulphated alkylphenolethoxylates. The salts of component (d) are preferably alkali, ammonium and/or amine salts. Alkali salts are most preferred, especially sodium salts. Component (d) is preferably a sulphated alcohol ethoxylate, such as the sulphated ethoxylate of primary or secondary alcohols with straight or branched chains, especially of alcohol mixtures. Component (d) is preferably a sulphated ethoxylate of Ce-C,8 alkanols, especially of C,2-C,e alkanols. The alkanols are preferably primary and have mainly straight chains, i.e. they are less than 30% branched. The most satisfactory alcohols are obtained by hydroformylation of olefins. The sulphated ethoxylates are prepared from these alcohols by first reaching them with ethylene oxide, suitably in such a quantity that on average 1 to 15, especially 2 to 4 mol ethylene oxide per mol alcohol (or alcohol mixture) is added, followed by sulphation of the ethoxylate and neutralization to the sulphated alcohol ethoxylate. Suitable sulphated alkylphenolethoxylates are sulphated C4-C,s alkylphenolethoxylates with an average of 1 to 12, especially 1 to 5 mol ethylene oxide per mol alkylphenol. Mixtures of sulphated alcohol ethoxylates and sulphated alkylphenolethoxylates can be used.

    [0013] The composition of the aqueous detergent concentrate according to the invention contains an active detergent comprising 50-70% wt of component (a) 5-30% wt of component (b) and 0.1-25% wt of component (c). Component (d), if present, is preferably present in a quantity of 0.1-25% wt. The most preferred concentrates contain 50-70% wt of component (a), 15-25% wt of component (b), 1-25% wt of component (c) and 5-25% wt of component (d). All weight percentages are calculated as activce detergent component on the total of the active detergent.

    [0014] The previously mentioned viscosity drop on dilution while retaining a low transparency point is reduced even more by the presence of MgS04 in the concentrate. The quantity of MgS04 absorbed in the detergent concentrates depends on the nature and the quantities of the other constituents, as well as on the desired viscosity in undiluted and diluted state. In general, preference is given to quantities between 0.05 and 10% wt relative to the weight of the aqueous concentrate.

    [0015] An additional advantage of the present invention is that in general no solubilizing agent needs to be added to this aqueous detergent concentrate in order to improve the solubility of the active detergent, so that the composition of the concentrates remains homogeneous during transport and storage, provided that the temperature does not drop to abnormally low levels. A useful criterion in practice is to assume that the transparency point should not be above about 5°C. If it is nevertheless desired to add a solubilizing agent, use can be made of, for example, urea, alkanols with 1-4 carbon atoms per molecule, e.g. 2-propanol, and the sodium, potassium, and ammonium salts of arylsulphonic acids substituted with one or more alkyl groups having 1-4 carbon atoms, such as toluene sulphonic acid and xylene sulphonic acid. When using an alkali salt of an alkyl-substituted aryl sulphonic acid, e.g. sodium xylene sulphonate, it can be favourable also to add a lower alcohol, e.g. 2-propanol. The content of solubilizing agent in the concentrates is preferably between 0 and 30% wt, calculated on the total quantity of active detergent.

    [0016] The invention will be further illustrated with the aid of the following examples.

    Examples 1-8 and Comparative Examples A-C



    [0017] Eleven detergent concentrates were prepared by mixing, at room temperature, water and components (a), (b), (c) and (d) listed in Table I. Component (a) was the sodium salt of "DOBANIC ACID". "DOBANIC ACID" is a trade mark for a mixture of n-alkylbenze sulphonic acids with 8-13 carbon atoms in the alkyl group. The intermediate product used for its preparation, CS-C13 alkylbenzene, was obtained by alkylation of benzene with a mixture of CS-C13 olefins obtained by thermal cracking of paraffin wax. These olefins consisted mainly of olefins with a terminal double carbon-carbon bond. Component (b) was "DOBANOL" 91-8. "DOBANOL" 91-8 is a trade mark for a mixture of polyethyleneglycol ethers obtained by ethoxylation linear primary alkanols with 9-11 carbon atoms per molecule and which contain an average of 8 ethylene oxide groups per molecule. The alkanols consist mainly of 80% straight-chained and 20% alkyl (mainly 2-methyl) isomers. Component (c) was "TEEPOL:HB6". "TEEPOL:HB6" is a trademark for an aqueous solution of a mixture of sodium salts of sulphated primary alkanols. Component (d) was "DOBANOL" 25-3S". "DOBANOL" 25―3S" is a trade mark for a mixture of polyethyleneglycol ethers obtained by ethoxylation of linear primary alkanols with 12-15 carbon atoms per molecule and which contains an average of 3 ethylene oxide groups per molecule.

    [0018] From each of the eleven concentrates were prepared three diluted aqueous solutions, containing 37, 35 and 30 weight per cent of active detergent. The viscosity (in mm2/s at 20°C) and the transparency point of the thus obtained solutions were determined. The results are given in Table I. It can be seen that for examples 1-8 according to the invention the viscosity drop on dilution is considerably less than for the comparative examples A-C, which are not in accordance with the invention. It can also be seen that a much lower transparency point was observed for the examples than for the comparative examples.



    Examples 9-12

    [0019] Four detergent concentrates were prepared by mixing, at room temperature, water and the components listed in Table II. Component (a) contained for the sodium salt of "DOBANIC ACID". The intermediate product used for its preparation, C8―C13 alkylbenzene, was obtained by alkylation of benzene with a mixture of linear C8―C13 olefins with mainly non-terminal double carbon-carbon bonds. Components (b), (c) and (d) were the same as those used in examples 1-8. From each of these concentrates were prepared three diluted aqueous solutions, containing 37, 35 and 30 weight per cent active detergent. Of each of the diluted solutions thus obtained, the viscosity was measured in mm2/s at 20°C and the transparency point was determined, this being done with the solutions as such and also after addition of 0.2 and after addition of 0.4% wt MgS04, calculated on the diluted solution. Table II shows the results obtained. It can be seen that the viscosity drop of the diluted solutions was considerably reduced, especially for the ones to which MgS04 was added. Moreover, a low transparency point was observed.




    Claims

    1. Aqueous detergent concentrate, characterized in that in addition to water it contains an active detergent comprising the following components.

    (a) 50 to 70% wt of one or more salts of an alkylaryl sulphonic acid,

    (b) 5 to 30% wt of one or more polyethyleneglycol ethers of primary or secondary alcohols with the general formula (R(OC2H4)n-OH, in which R represents an alkyl group with 8-18 carbon atoms and n is an integer varying from 5 to 12, and

    (c) 0.1 to 25% wt of one or more salts of sulphated alkanols with 6-16 carbon atoms per molecule.


     
    2. Detergent concentrate according to claim 1, characterized in that component (a) consists of one or more salts of an alkylbenzene sulphonic acid.
     
    3. Detergent concentrate according to claim 1 or 2, characterized in that the alkylbenzene sulphonic acid contains 8-16 carbon atoms in the alkyl group.
     
    4. Detergent concentrate according to one or more of the previous claims, characterized in that the active detergent also contains a component (d) consisting of one or more salts of sulphated alcohol- ethoxylates and/or of sulphated alkylphenolethoxylates.
     
    5. Detergent concentrate according to claim 4, characterized in that component (d) is a salt of sulphated ethoxylate of Cs-C1s-alkanols.
     
    6. Detergent concentrate according to claim 4 or 5, characterized in that component (d) is a sulphate or an alcohol ethoxylate, prepared by reacting 1 mol of an alcohol with 1 to 15 mol ethylene oxide.
     
    7. Detergent concentrate according to one or more of the previous claims, characterized in that the salts in the components (a), (c) and (d) are alkali, ammonium and/or amine salts.
     
    8. Detergent concentrate according to one or more of the previous claims, characterized in that it contains at least 10% wt, relative to the weight of the concentrate, of the active detergent.
     
    9. Detergent concentrate according to claim 4, characterized in that the active detergent also contains 1.5-25% wt of component (d).
     
    10. Detergent concentrate according to claims 4 to 9, characterized in that the active detergent contains 15-25% wt of component (b), 1-25% of component (c) and 5-25% wt of component (d).
     
    11. Detergent concentrate according to one or more of the previous claims, characterized in that the alkyl groups present are mainly n-alkyl groups.
     
    12. Detergent concentrate according to one or more of the previous claims, characterized in that the aqueous solution also contains MgS04.
     
    13. Detergent concentrate according to claim 12, characterized in that the aqueous solution contains 0.05 to 10% wt, relative to the weight of the solution, of MgS04.
     


    Ansprüche

    1. Wäßriges Detergenskonzentrat, dadurch gekennzeichnet, daß es zusätzlich zu Wasser ein wirksames Detergens enthält, das die folgenden Komponenten umfäßt:

    (a) 50 bis 70 Gew.-% eines oder mehrerer Salze einer Alkylarylsulfonsäure,

    (b) 5 bis 30 Gew.-% eines oder mehrerer Polyethylenglykolether von primären oder sekundären Alkoholen mit der allgemeinen Formel R(OCH4)n-OH, worin R eine Alkylgruppe mit 8 bis 18 Kohlenstoffatomen darstellt und n eine von 5 bis 12 variierende ganze Zahl ist, und

    (c) 0,1 bis 25 Gew.-% eines oder mehrerer Salze von sulfatierten Alkanolen mit 6 bis 16 Kohlenstoffatomen je Molekül.


     
    2. Detergenskonzentrat nach Anspruch 1, dadurch gekennzeichnet, daß die Komponente (a) aus einem oder mehreren Salzen einer Alkylbenzolsulfonsäure besteht.
     
    3. Detergenskonzentrat nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Alkylbenzolsulfonsäure 8 bis 16 Kohlenstoffatome in der Alkylgruppe enthält.
     
    4. Detergenskonzentrat nach einem oder mehreren der vorherstehenden Ansprüche, dadurch gekennzeichnet, daß das wirksame Detergens auch eine Komponente (d) enthält, die aus einem oder mehreren Salzen von sulfatierten Alkoholethoxylaten und/oder sulfatierten Alkylphenolethoxylaten besteht.
     
    5. Detergenskonzentrat nach Anspruch 4, dadurch gekennzeichnet, daß die Komponente (d) ein Salz eines sulfatierten Ethoxylats von Ce-C,8 Alkanolen ist.
     
    6. Detergenskonzentrat nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß die Komponente (d) ein Sulfat eines Alkoholethoxylats ist, welches durch Umsetzen von 1 Mol eines Alkohols mit 1 bis 15 Mol Ethylenoxid hergestellt wird.
     
    7. Detergenskonzentrat nach einem oder mehreren der vorherstehenden Ansprüche, dadurch gekennzeichnet, daß die Salze in den Komponenten (a), (c) und (d) Alkali-, Ammonium- und/oder Aminsalze sind.
     
    8. Detergenskonzentrat nach einem oder mehreren der vorherstehenden Ansprüche, dadurch gekennzeichnet, daß es mindestens 10 Gew.-% des wirksamen Detergens, bezogen auf das Gewicht des Konzentrats, enthält.
     
    9. Detergenskonzentrat nach Anspruch 4, dadurch gekennzeichnet, daß das wirksame Detergens auch 1,5 bis 25 Gew.-% der Komponente (d) enthält.
     
    10. Detergenskonzentrat nach den Ansprüchen 4 bis 9, dadurch gekennzeichnet, daß das wirksame Detergens

    15 bis 25 Gew.-% der Komponente (b),

    1 bis 25 Gew.-% der Komponente (c), und

    5 bis 25 Gew.-% der Komponente (d) enthält.


     
    11. Detergenskonzentrat nach einem oder mehreren der vorherstehenden Ansprüche, dadurch gekennzeichnet, daß die vorliegenden Alkylgruppen hauptsächlich n-Alkylgruppen sind.
     
    12. Detergenskonzentrat nach einem oder mehreren der vorherstehenden Ansprüche, dadurch gekennzeichnet, daß die wäßrige Lösung auch MgS04 enthält.
     
    13. Detergenskonzentrat nach Anspruch 12, dadurch gekennzeichnet, daß die wäßrige Lösung 0,05 bis 10 Gew.-% MgS04, bezogen auf das Gewicht der Lösung enthält.
     


    Revendications

    1. Concentré aqueux de détergent, caractérisé en ce que, outre l'eau, il renferme un détergent actif comportant les constituants suivants:

    (a) de 50 à 70% en poids d'un ou de plus d'un sel d'un acide alkylaryl sulfonique,

    (b) de 5 à 30% d'un ou de plus d'un éther polyéthylène glycolique d'alcools, primaires ou secondaire, de formule générale R(OC2H4)n-OH, dans laquelle R représente un groupe alkyle de 8 à 18 atomes de carbone et n est un nombre entier pouvant varier de 5 à 12, et

    (c) de 0,1 à 25% en poids d'un ou de plus d'un sel d'alcanols sulfatés de 6 à 16 atomes de carbone par molécule.


     
    2. Concentré détergent selon la revendication 1, caractérisé en ce que le composant (a) est constitué d'un ou de plus d'un sels d'acide alkylbenzène sulfonique.
     
    3. Concentré détergent selon la revendication 1 ou 2, caractérisé en ce que l'acide alkylbenzène sulfonique contient de 8 à 16 atomes de carbone dans le groupe alkyle.
     
    4. Concentré détergent selon une ou plus d'une revendications précédentes, caractérisé en ce que le détergent actif contient également un composé (d) constitué d'un ou de plus d'un sels d'éthoxylates d'aclools sulfatés et/ou d'alkylphénoléthoxylates sulfatés.
     
    5. Concentré de détergent selon la revendication 4, caractérisé en ce que le composant (d) est un sel d'éthoxylate sulfaté d'alcanol en Ce à C18.
     
    6. Concentré de détergent selon la revendication 4 ou 5, caractérisé en ce que le composant (d) est un sulfate d'un éthoxylate d'alcool préparé en faisant réagir une mole d'alcool avec de 1 à 15 moles d'oxyde d'éthylène.
     
    7. Concentré de détergent selon une ou plus d'une des revendications précédentes, caractérisé en ce que les sels dans les composants (a), (c) et (d) sont des sels alcalins, d'ammonium et/ou d'amine.
     
    8. Concentré de détergent selon une ou plus d'une des revendications précédentes, caractérisé en ce qu'il contient au moins 10% en poids, par rapport au poids du concentré, de détergent actif.
     
    9. Concentré. de détergent selon la revendication 4, caractérisé en ce que le détergent actif contient également 1,5 à 25% en poids de composant (d).
     
    10. Concentré de détergent selon les revendications 4 à 9, caractérisé en ce que le détergent actif contient de 15 à 25% en poids de composant (b), de 1 à 25% en poids de composant (c) et 5 à 25% en poids de composant (d).
     
    11. Concentré de détergent selon une ou plus d'une des revendications précédentes, caractérisé en ce que les groupes alkyles présents sont principalement des groupes n-alkyles.
     
    12. Concentré de détergent selon une ou plus d'une des revendications précédentes, caractérisé en ce lque la solution aqueuse contient également du MgS04.
     
    13. Concentré de détergent selon la revendication 12, caractérisé en ce que la solution aqueuse contient 0,05 à 10% en poids, par rapport au poids de la solution, de MgS04.